B Y t V khoa hc v o to

Hp cht hu c n chc v a chc

(Sch dng o to dc s i hc) M s: .20.Y.13 Tp I

Nh xut bn Y hc H ni - 2006 1

Ch bin: PGS. TS. Trng Th K Tham gia bin son: ThS. Nguyn Anh Tun TS. Phm Khnh Phong Lan ThS. Th Thu PGS. TS. ng Vn Tnh ThS. Trng Ngc Tuyn Tham gia t chc bn tho

TS. Nguyn Mnh Pha ThS. Ph Vn Thm

Bn quyn thuc B Y t (V khoa hc v o to)

Li gii thiu
Thc hin Ngh nh 43/2000/N-CP ngy 30/08/2000 ca Chnh ph quy nh chi tit v hng dn trin khai Lut Gio dc, B Gio dc v o to v B Y t ph duyt, ban hnh cc chng trnh khung cho o to Dc s i hc. B Y t t chc thm nh sch v ti liu dy hc cc mn hc c s v chuyn mn theo chng trnh mi nhm tng bc xy dng b sch chun trong cng tc o to Dc s i hc ngnh Y t. B sch Ho hu c c bin son theo chng trnh o to mn Ho hc hu c thuc chng trnh gio dc ca i hc Y Dc thnh ph H Ch Minh trn c s chng trnh khung c B Gio dc v o to, B Y t ph duyt. Ni dung b sch ch cp nhng kin thc l thuyt v ho hu c, gm 40 chng v chia lm 2 tp trnh by nhng kin thc c bn v danh php, cu trc, c ch phn ng, tnh cht l hc v tnh cht ho hc ca cc hp cht hydrocarbon, cc hp cht n chc, cc hp cht a chc, hp cht tp chc, hp cht thin nhin v hp cht cao phn t. i tng s dng chnh ca b sch ny l cc sinh vin ang theo hc ti Trng i hc Dc khoa Dc cc trng i hc ngnh Y t. ng thi cng l ti liu tham kho tt cho nhng hc vin sau i hc. Sch c bin son da theo chng trnh c B Y t ban hnh. Ni dung sch ch cp nhng kin thc l thuyt v Ho hu c. Sch Ho hu c c cc ging vin giu kinh nghim ca Khoa Dc - i hc Y Dc Thnh ph H Ch Minh bin son. Sch c Hi ng chuyn mn thm nh sch gio khoa v ti liu dy hc chuyn ngnh Dc ca B Y t thm nh v c B Y t ban hnh lm ti liu dy hc chnh thc dng o to dc s i hc ca Ngnh Y t trong giai on hin nay. Trong thi gian t 3 n 5 nm, sch cn c chnh l, b sung v cp nht. V Khoa hc v o to, B Y t xin chn thnh cm n Khoa Dc - i hc Y Dc Thnh ph H Ch Minh cng cc tc gi b nhiu cng sc bin son cun sch ny. V l ln u xut bn nn chc chn cn nhiu thiu st, chng ti mong nhn c kin ng gp ca ng nghip v bn c cun sch ngy cng hon thin.

V khoa hc v o to B Y t

MC LC
Li gii thiu M u Chng1: Cu trc in t ca nguyn t carbon v s to thnh cc lin kt trong hp cht hu c ThS. Nguyn Anh Tun 1. Cu trc in t (electron) ca nguyn t carbon 2. S to thnh cc lin kt Chng 2: Cc hiu ng in t trong ha hu c ThS. Nguyn Anh Tun 1. Hiu ng cm ng 2. Hiu ng lin hp (cng hng) 3. Hiu ng siu lin hp (Hyperconjugate effeet) Chng 3: Cu trc phn t hp cht hu c. ng phn v cu dng ThS. Nguyn Anh Tun 1. ng phn phng 2. ng phn lp th - ng phn khng gian Chng 4: Khi nim acid -base trong ha hu c ThS. Nguyn Anh Tun 1. Khi nim acid -base theo Bronsted-Lowry (1923) 2. Khi nim acid -base theo Lewis (1923) 3. Hng s cn bng acid base 4. Yu t nh hng n tnh acid -base ca cht hu c Chng 5: Cc loi phn ng trong ha hu c v khi nim v c ch phn ng ThS. Nguyn Anh Tun 1. Cc loi phn ng trong ha hu c 2. Khi nim v c ch phn ng Chng 6: Cc phng php ha hc v vt l xc nh cu to hp cht hu c ThS. Nguyn Anh Tun 1. Phng php ha hc 2. Phng php vt l Chng 7: Alkan - Hydrocarbon no ThS. Th Thy 1. Ngun gc thin nhin - Cu to, ng phn, cu dng 82 67 68 54 57 67 49 51 51 53 54 31 33 49 22 25 29 3 9 11 11 13 22

2. Danh php 3. Phng php iu ch alkan 4. Tnh cht l hc 5. Tnh cht ha hc 6. Cht in hnh Chng 8: Cycloalkan ThS. Th Thy 1. Monocycloalkan 2. Hp cht a vng Chng 9: Alken - Hydrocarbon etylenic ThS. Th Thy 1. Cu to ca alken 2. ng phn 3. Danh php 4. Phng php iu ch 5. Tnh cht l hc 6. Tnh cht ha hc 7. Cht in hnh Chng 10: Alkyn - Hydrocarbon acetylenic ThS. Th Thy 1. Cu trc in t 2. Danh php v ng phn 3. Phng php iu ch 4. Tnh cht l hc 5. Tnh cht ha hc 6. Cht in hnh Chng 11: Aren - Hydrocarbon thm PGS. TS. ng Vn Tnh 1. Benzen v nhn thm 2. Danh php v ng phn 3. Phng php iu ch 4. Tnh cht l hc 5. Tnh cht ha hc Chng 12: Hydrocarbon a nhn thm PGSTS. ng Vn Tnh 1. Cu to v danh php 2. Biphenyl 3. Biphenylmetan v triphenylmetan 4. Naphtalen 5. Anthracen 6. Phenanthren

85 86 88 89 93

95 100 102 102 102 104 105 109 110 118 120 120 121 121 123 123 127 129 129 132 133 134 135 150 150 151 153 154 155 156

Chng13: H thng lin hp v alkadien PGS. TS. ng Vn Tnh 1. H thng allylic 2. Dien 3. H thng lin hp bc cao 4. Phn ng Diels Alder Chng 14: Dn xut halogen ThS. Trng Ngc Tuyn 1. Danh php 2. ng phn 3. Phng php iu ch 4. Tnh cht l hc 5. Tnh cht ha hc Chng 15: Hp cht c kim ThS. Trng Ngc Tuyn 1. Cu to 2. Danh php 3.Tnh cht l hc 4. Phng php iu ch cc hp cht c kim 5. Cc phn ng ca hp cht c kim Chng 16: Alcol ThS. Trng Ngc Tuyn 1. Monoalcol 2. Alcol cha no 3. Alcol vng 4. Polyalcol alcohol a chc Chng 17: Phenol ThS. Trng Ngc Tuyn 1. Monophenol 2. Polyphenol Chng 18: Ether ThS. Trng Ngc Tuyn 1. Ether mch h 2. Ether vng Chng 19: Aldehyd , Ceton v Quinon ThS. Nguyn Anh Tun 1. Aldehyd v ceton 2. Aldehyd - ceton cha no

158 158 161 164 165 168 168 169 169 173 173 181 181 181 182 182 184 189 189 200 201 201 207 207 215 219 219 223 224 224 245

3. Aldehyd - ceton a chc 4. Quinon Chng 20: Acid carboxylic ThS. Nguyn Anh Tun 1. Cu to 2. Danh php 3. Phng php iu ch 4. Tnh cht l hc 5. Tnh cht ha hc 6. Acid carboxylic cha no 7. Acid a chc polyacid Chng 21: Cc dn xut ca acid carboxylic ThS. Nguyn Anh Tun 1. Ester 2. Anhydrid acid 3. Ceten 4. Halogenid acid - acyl halogenid 5. Amid 6. Nitril Chng 22: Amin TS. Phm Khnh Phong Lan 1. Cu to 2. Danh php 3. iu ch 4. Tnh cht l hc 5. Tnh base ca amin 6. Cc phn ng ca amin 7. Amin cha no c mt lin kt i Enamin 8. Amin a chc - polyamin Chng 23: Cc hp cht khc cha nit TS. Phm Khnh Phong Lan 1. Hp cht nitro 2. Isocyanat, carbamat v ure 3. Hp cht diazo v mui diazoni Chng 24: Hp cht c lu hunh v phosphor ThS. Th Thy 1. Hp cht hu c c lu hunh 2. Hp cht cha phosphor Ti liu tham kho

250 253 257 257 258 259 261 262 268 270 273 274 279 280 281 283 285 288 288 289 290 292 292 295 300 301 303 303 306 308 313 313 317 319

M U

i tng ca ha hc hu c: Ha hc hu c l mn khoa hc nghin cu thnh phn v tnh cht cc hp cht ca carbon. Trong thnh phn hp cht hu c, ngoi carbon cn c nhiu nguyn t khc nh H, O, N, S, P, halogen... nhng carbon c xem l nguyn t c bn cu to nn hp cht hu c. S lc lch s pht trin ca Ha hc hu c T xa xa ngi ta bit iu ch v s dng mt s cht hu c trong i sng nh gim (acid acetic long), ru (ethanol), mt s cht mu hu c. Thi k gi kim thut cc nh ha hc iu ch c mt s cht hu c nh ur, ether etylic... Cui th k 18 u th k 19, cc nh ha hc chit tch t ng, thc vt nhiu acid hu c nh acid oxalic, acid citric, acid lactic ... v mt s base hu c (alcaloid). Nm 1806 ln u tin nh ha hc ngi Thy in Berzelius dng danh t Ha hc hu c ch ngnh ha hc nghin cu cc hp cht c ngun gc ng vt v thc vt. Thi im ny c th xem nh ct mc nh du s ra i ca mn ha hc hu c. Nm 1815 Berzelius a ra thuyt Lc sng cho rng cc hp cht hu c ch c th c to ra trong c th ng vt v thc vt nh mt lc sng ch con ngi khng th iu ch c. Thuyt duy tm ny tn ti trong nhiu nm nhng dn dn b nh bi cc cng trnh tng hp cc cht hu c t cc cht v c. Nm 1824, nh ha hc ngi c Wohler tng hp c acid oxalic bng cch thy phn dixian l mt cht v c. Nm 1828 cng chnh ng, t cht v c amoni cyanat tng hp c ur. Tip theo Bertholet (Php) tng hp c cht bo nm 1854 v Bulerov (Nga) tng hp ng glucose t formalin nm 1861. Cho n nay hng triu cht hu c c tng hp trong phng th nghim v trn quy m cng nghip. Con ngi khng ch bt chc tng hp cc cht ging thin nhin m cn sng to ra nhiu cht hu c, nhiu vt liu hu c cc k quan trng v qu gi m t nhin khng c. Tuy nhin tn gi hp cht hu c vn c duy tr, nhng khng phi ch vi ngha l cc cht c ngun gc ng vt v thc vt m mang ni dung mi: l cc hp cht ca carbon.

c im ca cc hp cht hu c v phn ng hu c Mc d ra i mun hn ha hc v c nhng cc hp cht hu c rt phong ph v s lng, chng loi. S lng cht hu c cho n nay nhiu gp vi chc ln cc cht v c bit. Nguyn nhn c bn l do carbon c kh nng to thnh mch di v tn theo nhiu kiu khc nhau. Ni cch khc hin tng ng phn (tc l cc cht c cng thnh phn phn t nhng khc nhau v cu to) l cc k ph bin v c trng trong ha hc hu c. Cu trc phn t ca hp cht hu c c th n gin nhng cng c th rt phc tp, vic xc nh cu trc ca chng nhiu khi rt kh khn, phi s dng nhiu phng php ha hc v vt l hc hin i. Nu nh lin kt ion kh ph bin trong hp cht v c th lin kt ch yu gia cc nguyn t trong phn t hu c li l lin kt cng ha tr. c im ny nh hng nhiu n tnh cht l ha v c bit l kh nng phn ng ca chng. Cc phn ng hu c thng xy ra vi tc chm, khng hon ton v thng theo nhiu hng khc nhau, v vy vai tr ca nhit ng hc, ng hc v xc tc trong ha hu c rt quan trng. Vai tr ca ha hc hu c Cc cht hu c c vai tr rt quan trng trong i sng ca con ngi. Khng nhng hu ht thc phm chng ta n (glucid, protid, lipid), vt dng hng ngy (cellulose, si tng hp, cao su, cht do . . .) l cc cht hu c m nhiu cht hu c cn l c s ca s sng (protid, acid nucleic..). Nhin liu cho ng c t trong, cho nh my nh xng, du l hn hp hydrocarbon mch di ngn khc nhau. Cc vt liu hu c nh, khng han g, tin s dng, nhiu mu sc a dng ang ngy mt thay th cho cc kim loi, hp kim trong nhiu lnh vc, k c nhng lnh vc tng nh khng th thay th c nh bn dn, siu dn. . . Do tt c nhng c im trn, ha hc hu c c tch ra nh mt ngnh khoa hc ring i hi nhng phng php nghin cu v thit b ngy cng hin i hn, i hi n lc khng ngng ca cc nh ha hc khng nhng bt chc thin nhin tng hp nn cc cht phc tp phc v cho nhiu lnh vc ca cuc sng m cn vt xa hn c thin nhin. T c s ha hc hu c, c rt nhiu ngnh nghin cu ng dng ra i: ha cng nghip, ha du, cng nghip dt, ha thc phm, dc phm v ha m phm.

10

Chng 1

CU TRC in t CA NGUYN T CARBON V S TO THNH CC LIN KT TRONG HP CHT HU C

Mc tiu 1. Trnh by c cu to in t carbon cc trng thi lai ha sp3, sp2 v sp. 2. Gii thch c cch hnh thnh cc loi lin kt: Cng ha tr Lin kt phi tr Lin kt hydro Ni dung 1. Cu trc in t (electron) ca nguyn t carbon 1.1. Thuyt carbon t din (Vant Hoff- Le Bel 1874) Nguyn t carbon c 4 ha tr. Bn ha tr ca carbon hng ra bn nh ca mt t din. Tm ca t din l nguyn t carbon.
o C 109 28'

Cc gc ha tr tm u bng nhau v bng 10928'. Khi nguyn t carbon lin kt vi 4 nguyn t hoc 4 nhm th ng nht ta c mt t din u. 1.2. Cu trc in t ca nguyn t carbon 1.2.1. Carbon trng thi c bn
2 2 1 1 Carbon c c cu hnh in t C 1S 2S 2px2py 1S22S22p2

1s22s22p2 2 in t n c l px v py. Cn c mt orbital 2pz trng khng c in t 1.2.2. Carbon trng thi kch thch C *
1 1 1 1 1S22S 2px2py2pz

1S22S12p3

11

Carbon hp thu nng lng 60-70 kcal/mol, mt in t 2s2 chuyn ln trng thi 2p (orbital 2pz).
1s2 2s2 2p2 1s2 2s

2px 2py 2pz

C 1s22s22p2

C 1s22s12p3

Carbon c cu hnh in t 1s22s12p3 l carbon kch thch (1s22s12px2py2pz). Kt qu l carbon c 4 in t n c to lin kt. Carbon lun c ha tr 4. Bn in t ca carbon kch thch c nng lng khc nhau do cc lin kt ca carbon phi khc nhau. Thc t phn t metan c 4 lin kt C _H hon ton ging nhau . 1.2.3. Carbon trng thi lai ha Khi to thnh cc lin kt, orbital 2s v mt s orbital 2p c th t hp li to thnh nhng orbital c dng khc cc orbital ban u v c kh nng xen ph cao hn do lin kt c hnh thnh cng bn hn. S t hp c gi l s lai ha. Lai ha sp3 Kiu lai ha th nht gi l lai ho sp3 (cn gi l lai ha t din). Mt orbital 2s v 3 orbital p t hp vi nhau to thnh 4 orbital lai ha sp3.

SS hp 2s v 2p 2p t to hp 2s va

Orbital ho sp Orbital lailai hoa sp

Carbon lai hoa sp3 Carbon lai ho sp3

Cc kt qu tnh ton cho thy rng nu xem kh nng xen ph ca orbital s l 1 th ca orbital p l 3 v ca orbital sp3 l 2.

Lai ha sp2. S t hp orbital 2s vi 2 orbital 2p (2px, 2py) to thnh 3 orbital lai ha sp2 hay cn gi l lai ha tam gic. Trc i xng ca 3 orbital sp2 nm trong mt mt phng v to nn nhng gc 120. Kh nng xen ph tng i ca orbital sp2 l 1,99. 12

120o

Pz

S t hp 2s2s va 2p S to hp v 2p

Carbon lai ho 2sp 2 Carbon lai hoa2sp

Orbital 2pz khng lai ho Orbital 2pz khonglai ho

Nh vy trn carbon lai ha sp2 cn c mt in t trn orbital 2pz khng lai ha. Orbital ny c dng hnh khi s 8 ni . Lai ha sp T hp mt orbital s v mt orbital 2px to thnh 2 orbital lai ha sp vi kh nng xen ph tng i 1, 93 v gc to bi trc i xng ca 2 orbital l 180o hay cn gi l lai ha ng thng. Trn carbon lai ha sp cn c 2 in t p khng tham gia lai ha 2py v 2pz

S to h 2s v 2p S t hpp 2s va 2p

Orbital lai ho sp Orbital lai ho a sp

2 Orbital 2py v 2pz 2 Orbital 2pyva 2pz

S lai ha gia orbital s v p cng xy ra trong cc nguyn t oxy, nit ... 2. S to thnh cc lin kt 2.1. S to thnh lin kt cng ha tr - Lin kt v lin kt Lin kt c to thnh do s xen ph cc i ca cc orbital nguyn t thnh orbital phn t. Khi vng xen ph ca cc orbital nguyn t cng ln th lin kt (orbital phn t) c to thnh cng bn v nng lng thot ra khi hnh thnh lin kt cng ln. Khuynh hng ca s xen ph l tin ti cc i, l ni dung ca nguyn l xen ph cc i . Cc orbital nguyn t tng tc c hiu qu vi nhau thnh orbital phn t chng phi tha mn 3 iu kin: Nng lng ca chng gn nhau . S xen ph mc ln. Chng phi c cng mt kiu i xng i vi trc ni hai ht nhn nguyn t. Nh vy 2 orbital s, hoc 1 orbital s v 1 orbital p no c trc i xng trng vi trc ni 2 ht nhn c th tham gia xen ph nhau thnh orbital phn t.

13

Ty theo c im i xng ca cc orbital nguyn t, s xen ph ca chng c th theo trc hay bn trc ni gia 2 nguyn t. S xen ph theo trc orbital to lin kt . S xen ph bn xy ra s to thnh lin kt . Xen ph trc - To lin kt

Orbital s

Lin kt

Orbital s

Orbital p

Lin kt

Orbital p

Orbital p

Lin kt

Xen ph bn - To lin kt
+ Orbital p Lien ket

Orbital p

2.2. Lin kt v lin kt trong cc hp cht hu c 2.2.1. Trong cc hp cht hu c lin kt to thnh do s xen ph Orbital s ca nguyn t hydro vi cc orbital lai ha ca carbon sp3, sp2, sp. Orbital lai ha ca carbon xen ph vi nhau. Orbital lai ha s v p ca nguyn t oxy hoc ca nit vi orbital s ca hydro hoc vi cc orbital lai ha ca carbon sp3, sp2, sp trong cc hp cht c lin kt O-H hoc C-O v trong cc hp cht c lin kt N-H hoc C-N. 2.2.2. Lin kt

c to thnh do s xen ph

Orbital Py hoc Pz ca cc nguyn t carbon xen ph vi nhau tng i mt to thnh lin kt trong C=C hoc trong C C. Orbital p ca nguyn t oxy, nit xen ph vi orbital p ca nguyn t carbon to thnh lin kt trong C=O hoc trong C =N, CN. V d: S to thnh lin kt trong cc hp cht etan, ethylen, acetylen, alcol ethylic c th c minh ha nh sau:

14


Cac lien ket Cc lin kt trong trongphn t etan etan phan t

HH H-C-C-H H H

H H Cc lin kt trong phn Cac lien ket C C trong t ethylen etylen H H phan t

Caclin ktket Cc lien trong phn tt acetylen H acetylen trong phan

C C H

Cc lin kt trong Cac lien ket phn t alcol ethylic trong phan t

H H C H

H C H O H

c-c H o-

alccol etylic

c-o

S to thnh lin kt trong phn t ethylen, acetylen c th minh ha nh sau:

Lin kt trong ethylen c to thnh do s xen ph cc i v 2 pha ca cc orbital Pz khng lai ha. Lin kt (orbital phn t ) nm trong mt phng thng gc vi mt phng cha cc nguyn t C v H. H H H H Lin kt Lien ket trong ethylen H H trong etylen H H Hai lin kt trong acetylen c to thnh do s xen ph cc i v 2 pha ca cc orbital py v pz tng ng. Cc orbital lin kt nm trong 2 mt phng thng gc vi nhau.

H
H

Cac trong phan t acetylen

Lin kt trong acetyle lien ket n

15

 S to thnh lin kt trong h thng alen C=C=C .

H H C

S to thnh lin kt trong h thng lin hp C =CC=C.

H H

H thng lin hp thng thng v n gin l nhng h m hai lin kt v mt lin kt (hoc mt cp in t cha s dng) phn b cnh nhau (lun phin, tip cch). CH2=CH_CH=CH_CH=O ; CH2=CH_CH=CH_CH =CH_OCCH3 Trong h thng lin hp s xen ph bn ca cc orbital p to thnh mt orbital phn t bao trm ln ton b phn t.

S to thnh cc lin kt v trong h thng lin hp lm cho di lin kt ngn i v di ca lin kt di ra. H thng lin hp thng c trong cc cht thuc loi hydrocarbon thm, d vng thm. Cc lin kt trong h thng lin hp lun nm trong cng mt mt phng. 2.3. Tnh cht ca cc lin kt v 2.3.1. S phn cc ca lin kt Khi phn t c dng A _ A ng nht th phn t khng c s phn cc. Ngha l cp in t lin kt hay l orbital phn t lin kt c phn b u gia 2 nguyn t v momen lng cc ()bng khng. V d: H_H ; Cl_Cl ; O=O ; CH3_CH3 ; Cl3C_CCl3 ; CH2=CH2 ; HCCH .

Khi hai nguyn t lin kt vi nhau khng ng nht (phn t c dng A _B) nh H _Cl, CH3_Cl ... cp in t lin kt s lch v pha nguyn t c m in ln hn. Do trng tm in dng v m khng trng nhau v lin kt s c momen lng cc khc khng ( 0). l lin kt cng ha tr phn cc.
S phn cc khng nhng xy ra cc lin kt kt (phn t c dng A =B hoc A B).

m cn xy ra cc lin

16

Trong cc phn t H2C =O v CH3 _CN, v.v .. c s phn cc ca lin kt . ch s phn cc ca lin kt ngi ta dng mi tn thng ()v s phn cc ca lin kt ngi ta dng mi tn cong ( ). Chiu chuyn dch ca mi tn l chiu chuyn dch in t. Hoc dng k hiu +, - nhm biu th cc phn in tch nh nhng nguyn t tham gia lin kt . V d: CH3 Cl ; CH Cl ; H2C=O ; H2C=O hoc: H2C==O 3 2.3.2. tan Cc hp cht hu c c lin kt cng ha tr (l nhng lin kt c phn cc khng ln) rt t hoc khng tan trong nc, tri li tan nhiu trong cc dung mi hu c. Dung dch cc cht hu c thng l khng dn in. Cc cht c lin kt ion d tan trong nc v khng hoc t tan trong dung mi hu c, dung dch ca chng dn in. 2.3.3. di lin kt Khong cch gia 2 ht nhn nguyn t lin kt thng gi theo quy c l di lin kt. di lin kt c o bng cc phng php vt l hin i nh: phng php nhiu x tia X, ntron, electron, phng php ph hng ngoi. Ngi ta nhn thy rng:

di lin kt cng ha tr gia carbon v mt nguyn t khc trong cng mt phn nhm ca h thng tun hon tng theo s th t ca nguyn t .
C_F < C_Cl < C_Br < C_I

di ca lin kt cng ha tr gia carbon v mt nguyn t khc trong cng mt chu k gim khi s th t tng.
C _ C > C_ N > C _ O > C_ F

di ca lin kt cng ha tr gia 2 nguyn t cng gim nu s orbital lin kt cng ln.
C_C > C= C > CC ; C_O > C=O > CO C_N > C=N > C N ; N_N > N=N > NN

di lin kt gia carbon vi mt nguyn t khc ph thuc trng thi lai ha ca carbon. T l orbital s trong orbital lai ha cng cao th di lin kt cng ngn.

C__H 3
sp

C__H 2
sp

C__H
sp

17

2.3.4. Nng lng lin kt

Nng lng ca lin kt A _B l s nng lng thot ra khi hnh thnh lin kt t 2 nguyn t hay 2 gc A v B. cng chnh l nng lng cn thit lm t lin kt A _B thnh 2 nguyn t hay 2 gc A v B.
Bng 1.1: Nng lng lin kt (kcal/mol)
Lin kt H-H F-F Cl-Cl Br-Br I-I N-N N=N NN P-P C-C C=C CC Si-Si O-H N-H Nng lng lin kt 104,2 36,4 58,0 46,1 36,1 38,4 100,0 226,0 51,3 83,1 147,2 194,0 42,2 110,6 93,6 Lin kt C-H C-F C-Cl C-Br C-I C-O C=O C -O C-N C=N CN H-F H-Cl H-Br H-I
+

Nng lng lin kt 98,8 105,4 78,5 65,9 57,4 84,0 171,0 255,8 69,7 147,0 213,0 134,6 103,2 87,5 71,5

Nng lng lin kt l gi tr trung bnh gn ng. Khi dng khi nim nng lng lin kt c ngha l tt c cc lin kt C_H trong phn t alkan u ging nhau (thc t nng lng ph thuc vo cu to phn t). Qua bng 1-1 c th thy rng cc lin kt bi (i = ; ba ) khng c tnh cht bi v nng lng. Nng lng lin kt C =C v C C khng ln gp i v gp 3 ln lin kt C _C. Tri li nng lng ca cc lin kt N =N v N N li gp 3 v gp 6 ln nng lng lin kt N _N. Trong cc phn t c h thng lin hp th gi tr sinh nhit ca n thp hn tng gi tr nng lng lin kt ca cc lin kt c trong phn t c h thng khng lin hp. chnh lch gi l nng lng lin hp hoc nng lng cng hng ca h thng lin hp. Cn phn bit nng lng lin kt v nng lng phn ly. Nng lng phn ly l nhng i lng c trng cho cc lin kt trong phn t. Nng lng cn lm t lin kt CH th nht khng phi bng 1/4 nng lng chung phn ct phn t metan thnh carbon v hydro, cng khng hon ton bng nng lng ca mi lin kt CH trong cc phn t etan v benzen. Mi lin kt trong phn t c mc nng lng phn ly khc nhau (bng 1-2). 18

Bng 1.2: Nng lng phn ly lin kt R-X (kcal/mol)

R CH3 CH3CH2 (CH3)2CH (CH3)3C C6H5 C6H5CH2 X H 102 98 89 85 104 77,5 Br 67 65 65 61 71 48 51 52 47 45 57 39 I OH 86,5 87, 84,5 85, 85, 85, CH3 83 82 74 74 91 63 R 83 82 82 60 103 47

HO-OH ---------------------------------

52 (CH3)2 C N = N C (CH3)2 31 CN CN

C6H5COO-OCC6H5 -----------------

30

(C6H5)3C N = N C(C6H5)3 27

2.4. S to thnh lin kt yu hn lin kt cng ha tr 2.4.1. Lin kt hydro Lin kt hydro c bn cht tnh in. Nng lng lin kt nh ( 5kcal/mol).

X___H+ ... Y ; X
iu kin hnh thnh lin kt hydro:

H+ ... Y

X c m in ln hn hydro sao cho X __H phn cc . Y c cp in t t do e . Kch thc ca X v Y u khng ln .

X v Y thng l nhng nguyn t ph bin nh F, O, N . Trng hp Y l Cl, S, lin kt th lin kt hydro to thnh s rt yu. C hai loi lin kt hydro:

Lin kt hydro lin phn t

Lin kt hydro c to thnh gia cc phn t vi nhau. Khi pha long hp cht c lin kt hydro lin phn t trong dung mi tr (khng phn cc), lin kt hydro b ct t dn.
Et Et O...H H O ... ...H ... H O O Et Et H__C O ... H O O H ... O C__H

Lin kt hydro ni phn t

Lin kt hydro c to thnh trong cng mt phn t. Khi pha long hp cht c lin kt hydro ni phn t, lin kt hydro vn c bo ton. hnh thnh lin kt hydro ni phn t ngoi cc iu kin 19

trn, XH v Y phi gn nhau sao cho khi to lin kt hydro s hnh thnh nhng vng 5 hoc 6 cnh. Cc hp cht vng c nhm chc v tr 1, 2 thng d hnh thnh lin kt hydro ni phn t.
OH C O O. H H .. . NH2 CH2

. .

O CH2

2.4.2. nh hng ca lin kt hydro n tnh cht l -ha hc v sinh hc S to thnh lin kt hydro nh hng n tnh cht ca hp cht hu c.

Nhit nng chy v nhit si

Lin kt hydro lin phn t lm tng nhit nng chy tc v tng nhit si tos nhng lin kt hydro ni phn t khng c nh hng ny. V d. Hp cht nitrophenol c 3 ng phn th ng phn p-nitrophenol c lin kt hydro lin phn t c toc l 144C v toc l 241C. ng phn o-nitrophenol (c lin kt hydro ni toc phn t) c toc l 44C v tos l 114C .
O N O ... H O N O OH ...O N O OH ...O N O OH

...

Lin kt hydro gia cc phn t p -nitrophenol

Lin kt hydro ni phn t o -nitrophenol

tan
Cc cht c kh nng to lin kt hydro vi nc th rt d tan vo nc. Lin kt hydro lin phn t gia cht tan v dung mi lm tng tan trong dung mi phn cc. Lin kt hydro ni phn t lm tng tan trong dung mi khng phn cc. V d: Alcol methanol, ethanol rt d tan trong nc. p-nitrophenol tan c trong nc, cn o -nitrophenol khng tan trong nc. V vy c th phn ring o -nitrophenol ra khi hn hp bng phng php ct li cun hi nc.

bn ca phn t
S to thnh lin kt hydro ni phn t, c bit khi lin kt c kh nng to vng, lm cho ng phn tr nn bn vng hn. V d: Khi 1,2 -dicloethan dng anti bn vng hn dng syn th ethylenglycol dng syn li bn hn dng anti. V syn-ethylenglycol c kh nng to lin kt hydro ni phn t. 20

Anti-dicloetan

Syn-dicloetan

Anti-ethylenglycol

Syn-ethylenglycol

* Thut ng anti v syn s c trnh by chng ng phn.

nh hng n mt s tnh cht khc

Lin kt hydro lm thay i cc vch c trng trong quang ph hng ngoi (IR), t ngoi (UV), cng hng t ht nhn (NMR), momen lng cc, di lin kt. Lin kt hydro cng c tc dng lm thay i s tng tc ca cc cht trong qu trnh chuyn ha sinh hc trong c th ng vt v thc vt. 2.4.3. Lin kt trong phc chuyn in tch Phc chuyn in tch to thnh do s chuyn dch mt phn mt in t t phn t cho in t sang phn t hay ion nhn in t. Phc chuyn in tch do s chuyn dch mt in t gi l phc .
CH 3 NO2 Phc to thnh gia toluen v trinitrobenzen O2N NO2 Phn t nhn

Lin kt trong phc chuyn in tch l lin kt yu. Khong cch gia 2 hp phn vo khong 3 - 3,5 ln hn nhiu so vi lin kt cng ha tr. Phc chuyn in tch c s thay i v phn cc v mu sc ca cc cht ban u. Bi tp 1. V m hnh orbital nguyn t trng thi xen ph cho cc hp cht sau: a- Propan, propylen, methylacetylen, ceten (HC2=C=O). b- Cyclobutan, Cyclopentan, Cyclohexan. c- 1,3-Butadien 2. Hy trnh by mt s nh ngha: a- Th no l lin kt cng ha tr, lin kt hydro ? b- Th no l nng lng lin kt v nng lng phn ly, nng lng cng hng ? 3. Trong hn hp phenol - methanol c bao nhiu "dng" lin kt hydro. Dng no bn nht ? Dng no km bn nht ? Ti sao ? 4. Alcol v ether, cht no d tan trong nc hn. Gii thch ?

21

Chng 2

Cc HIU NG IN T TRONG HA HU C

Mc tiu 1. Nu c cc loi hiu ng cm ng, hiu ng lin hp, hiu ng siu lin hp v tnh cht ca chng. 2. Bit c mt s ng dng ca cc hiu ng trn. Ni dung Mt in t trong lin kt cng ha tr thng c phn b khng ng u gia 2 nguyn t ca lin kt, khi y phn t cht hu c b phn cc. S phn cc c th xy ra ngay trng thi tnh hoc cng c th ch xut hin nht thi trng thi ng (khi phn t b tc ng bi cc yu t ca mi trng). Bn cht ca s phn cc khc nhau cn tu thuc vo cu to phn t (phn t c h thng lin kt nh th no). Nh vy cu to phn t c nh hng n s phn b mt in t. nh hng gi l hiu ng in t trong phn t. C cc loi hiu ng:

Hiu ng cm ng I Hiu ng lin hp C, M Hiu ng siu lin hp H

1. Hiu ng cm ng (Inductive effect): K hiu l I Kho st phn t n -propan C3H8 v phn t n-propylclorid C3H7Cl
H H H H H

C3 C 2 C1 H n-propan n-propan
H

H H + + + 3 2 1 H C C C Cl 3 2 1 H

n-propylclorur n-propyclorid

Trong phn t n -propylclorid, lin kt C1 Cl b phn cc v pha nguyn t clor v nguyn t clor c m in ln hn. Nguyn t clor mang mt phn in tch m v nguyn t carbon mang mt phn in tch dng +. V C1 mang in tch dng nn cp in t lin kt ca lin kt C2 C1 b dch chuyn v pha carbon C1. Kt qu l lin kt C2 C1 cng b phn cc theo. Nguyn t C2 mang mt phn in tch dng. n lt lin kt C3 C2 cng chu nh hng nh vy v kt qu nguyn t carbon C3 mang mt phn in tch dng. Nhng 1+ >2+ >3+. Cc lin kt cng chu nh hng nh th v kt qu c s phn cc 22

ca lin kt C H. Hydro tr nn linh ng hn. Hin tng ny khng ch xy ra vi phn t propan. Nh vy nh hng s phn cc ca lin kt C -Cl lm cho cc lin kt khc b phn cc theo v ton phn t b phn cc. Nguyn t clor l nguyn t gy nh hng cm ng. S phn cc hay s chuyn dch mt in t trong cc lin kt gi l hiu ng cm ng. Hiu ng cm ng k hiu l I hoc I (ch u ca inductive) phn loi cc nhm nguyn t theo hiu ng cm ng ngi ta quy c rng nguyn t hydro lin kt vi carbon trong C __ H c hiu ng I = 0. Nhng nguyn t hay nhm nguyn t X c kh nng ht in t (CX) mnh hn hydro c coi l c hiu ng - I (hiu ng cm ng m). Nhng nguyn t hay nhm nguyn t Y c kh nng y in t (YC) mnh hn hydro c coi l nhng nhm c hiu ng +I (hiu ng cm ng dng)

Y +I
1.1. Hiu ng cm ng + I

H I=0

-I

Thng thy cc nhm alkyl (R-) v cc nhm mang in tch m. Trong dy cc nhm alkyl, hiu ng cm ng +I tng theo phn nhnh hay l bc ca nhm .

+I

CH3

CH2 CH3

CH CH3 CH3

CH3 C CH3 CH3

Trong dy cc nhm mang in tch m, nhm c m in nh hn l nhm c hiu ng + I ln hn . -O- < -S- < -Se1.2. Hiu ng cm ng - I L hiu ng rt ph bin cc nhm khng no, cc nhm mang in tch dng v cc nhm ng vi nhng nguyn t c m in ln (nh cc halogen, oxy, nit). S bin thin mc mnh yu ca hiu ng - I trong cc nhm nguyn t tun theo mt s quy lut:

Nguyn t carbon lai ha sp c -I ln hn nguyn t carbon lai ha sp2 v sp3

-CCR > -CR1=CR2 > -CR2_CR3.

Nhm mang in tch dng c hiu ng -I ln hn nhm c cng cu to nhng khng mang in tch.
-OR2 > -OR
+

-NR3 > -NR2

23

 Cc nguyn t ca nhng nguyn t trong cng mt chu k nh hay trong cng mt phn nhm chnh ca h thng tun hon, hiu ng -I cng ln khi nguyn t tng ng cng bn phi (trong cng chu k) hoc cng pha trn trong cng phn nhm).
-F > -Cl > -Br > -I -F > -OR > -NR2 > -CH3. -OR > -SR > -SeR m in cng tng th hiu ng cm ng - I cng ln Biu hin c th ca hiu ng cm ng l nh hng ca cc nhm th khc nhau n lc acid v lc base ca cc acid carboxylic no v ca cc amin. Trn bng 2-1, ngi ta nhn thy rng nu thay th hydro ca acid formic bng cc gc alkyl c + I tng th kh nng phn ly ca acid gim. Cn ln lt thay th cc hydro ca amoniac bng cc gc alkyl c +I tng th tnh base tng ln. Hiu ng + I tng lm cho lin kt O __ H km phn ly.
H_COOH CH3 C O O H

Khi thay th hydro ca amoniac bng cc nhm c hiu ng + I, mt in t trn nguyn t nit tng ln do tnh base ca amin tng.
CH3 CH3 N: CH3

H_NH2

..

CH3 NH2

..

Bng 2.1. nh hng hiu ng cm ng n tnh acid base

Lc acid giam khi +I tang Acid hu c

HCOOH CH3COOH CH3CH2COOH CH3CH2CH2COOH (CH3)2CHCOOH pKa (H2O.25o) 3,75 4,76 4,87 4,82 4,86

Lc base tang khi +I tang Base hu c pKa (H2O.25o)

NH3 CH3NH2 CH3CH2NH2 (CH3)2NH (CH3)3N 9,10 10,62 10,63 10.77 9,8*

Ch : *S d tnh base ca trimethylamin khng tng l do hiu ng khng gian.

Hiu ng - I tng, lc acid tng. Khi thay th hydro ca CH3 trong acid acetic bng cc halogen c m in khc nhau th tnh acid thay i. Nguyn t halogen c hiu ng -I ht in t nh hng n s phn ly ca nhm O _H.
F CH2 C O H O pKa 2,58 Cl CH2C O H O 2,85 Br CH2C O H O 2,9 I CH2 C O H O 3,16 H CH2 C O H O 4,76

24

c im quan trng ca hiu ng cm ng l hiu ng cm ng lan truyn trn mch lin kt v yu dn khi chiu di ca mch carbon tng ln.
CH3CH2CH2COOH 4,82 pKa CH3CH2CHClCOOH 2,86

CH3CHClCH2COOH 4,05

CH2ClCH2CH2COOH 4,42

2. Hiu ng lin hp (cng hng) 2.1. H thng lin hp H thng lin hp l mt h thng:

Cc lin kt bi (i, ba) lun phin vi lin kt n.

C=C-C=C-C=C( - ) C=C-C=C-C=O(- ).

H thng cha nguyn t cn cp in t p t do khng lin kt trc tip vi nguyn t carbon c lin kt bi.

-C=C-O-R

..

-C=C-Cl

..

( p- )

Phn t cha h thng lin hp l phn t lin hp. 2.1.1. Phn loi h thng lin hp nh sau:

H thng lin hp - H thng lin hp khng vng

CH2=CH_CH=CH2 1,3-Butadien CH2=C_CH=CH2 CH3 2-methyl-1,3-butadien (izopren)

CH2 = CH CH = O
Aldehyd acrylic

CH2 = CH C N
Acrylonitril

CH2 = CH C = O
Acid acrylic OH

H thng vng
.. O

H thng lin hp p - H thng lin kt lin hp do tng tc gia in t p t do vi lin kt .

CH2=CH_Cl Vinylclorid

..

CH2=CH_OCH3 Methylvinyl ether Phenol Anilin

..

:OH

:NH2

2.1.2. c im ca h thng lin hp Trong phn t khng ch c lin kt i hoc lin kt n ring: 25

CH2=CH_CH2_CH=CH2 ;
Khng lin hp

CH2=CH_CH=CH_CH3 ;
Lin hp

CH=CH_CH2_OCH3
Khng lin hp

Cc nguyn t to h lin hp lun nm trong mt mt phng v trc ca cc oirbtal p song song vi nhau v thng gc vi mt phng cha cc lin kt .

Butadien

Benzen

phenol

Phn t lin hp bao gi cng c nng lng thp hn nng lng ca nhng phn t khng lin hp tng ng. V mt in t gn nh gii ta ng u trn cc nguyn t to h thng lin hp v to thnh mt orbital phn t gii ta trn ton b phn t.
C C C C

Orbital phn t trong h thng lin hp rt d bin dng v d phn cc khi cu to ca phn t lin hp c mt nguyn t chnh lch v m in. Nh vy trong h lin hp c s tng tc gia cc orbital p vi nhau. S tng tc gi l hiu ng lin hp. 2.2. Hiu ng lin hp C (M) Hiu ng lin hp l hiu ng sinh ra do s phn cc ca lin kt c lan truyn trong h thng lin hp Hiu ng lin hp c k hiu l C (Conjugate effect) hoc M (Mesomeric effect) 2.2.1. Phn loi hiu ng lin hp Cn c vo s dch chuyn in t ca cc in t . C hai loi hiu ng lin hp: Hiu ng lin hp + C v Hiu ng lin hp - C

Hiu ng lin hp - C
Nu thay th nguyn t hydro trong nhm CH2 ca butadien bng nhm CH = O, nhm ny tham gia lin hp vi orbital phn t ca butadien. Nh c c tnh phn cc ca nhm CH =O nn ton b orbital mi hnh thnh ca phn t b dch chuyn mt phn v pha nguyn t oxy.
CH2 CH CH CH CH O

Nhm CH = O c hiu ng lin hp theo c ch ht in t nn c gi l nhm c hiu ng - C.

26

Cc nhm c hiu ng - C l nhng nhm khng no c cng thc chung C =Y, CZ v mt s nhm khc khng cha carbon nh - NO2, - SO3H... Hng chuyn dch in t trong h thng c nhm vi hiu ng - C c m t bng mi tn cong. Nhm c hiu ng -C thng c thm hiu ng cm ng - I. Cc nhm chc c hiu ng -C :
C .. O : Cl : ..

..

C O .. H

..

C O .. CH3

..

C O .. : OR ..

..

:OH ..

C O ..

..

: NH2 ..

C O ..

..

C O .. :O ..

..

CR = O > CR > CR = CR2 NO2 > O N > O CR Hiu ng lin hp +C Cc nguyn t hay nhm nguyn t c hiu ng lin hp +C l nhng nhm c kh nng y in t. Cc nhm ny thng c nguyn t mang cp in t p t do. Chnh cp in t p ny lin hp vi cc lin kt trong h thng lin hp.
CH2=CH_OCH3

..

CH2=CH_Cl: ..

..

Cc nhm c hiu ng + C :

-NH2 > -OH ; -O- > -OH

-F > -Cl > -Br > -I -NR2 > -OR > -SR > -SeR

Cc nhm c hiu ng + C thng c thm hiu ng cm ng - I.

Hiu ng lin hp c ng dng rng ri gii thch c ch phn ng, cc cu to trung gian, bn ca cc ion, tnh acid -base ...

Hiu ng lin hp c nh hng n s dch chuyn in t. Chng c cc cng thc trung gian hay cn gi l cng thc gii hn nh sau:
V d: Butadien-1,3:
CH2 CH CH CH2 CH2 CH + CH CH2 + CH2 CH CH CH2

Aldehyd crotonic:
CH3 CH CH CH O + CH3 CH CH CH O

CH3

+ CH

CH

CH O

Phenol

:OH
-

+OH

+OH

+OH -

OH

Hp cht c h thng lin hp cng di th c nhiu cng thc gii hn. bn ca cc cng thc gii hn ph thuc vo khong cch gia 2 in tch tri du. in tch tri du cng xa nhau th cng thc gii hn cng bn. 27

 Khc vi hiu ng cm ng, nh hng ca hiu ng lin hp khng b gim i khi h lin hp ko di.
V d: Nguyn t hydro trong nhm CH3 ca aldehyd crotonic linh ng do nh hng ca hiu ng lin hp.
H

: CH3 CH CH CH aldehid crotonic Aldehyd crotonic

Nu ko di mch aldehyd crotonic bng cc nhm vinyl th hydro ca nhm CH3 vn cn linh ng.
H

: CH2

CH

CH

CH

CH

CH

CH CH

Hiu ng lin hp lm thay i trung tm phn ng:

V d: C hp cht sau:
..
C O CH CH NH2 C OCH CH + NH2

Trong h thng lin hp p -, cp in t p khng lin kt trn nguyn t N lin hp vi h thng lin kt . Nhm NH2 gy hiu ng lin hp + C. Nhm NH2 c tnh base c kh nng tc dng vi proton H+. Nhng do hiu ng lin hp, H+ khng tc dng vo nhm amin NH2 m tc dng vo nguyn t oxy ca nhm carbonyl.
C CH CH O + NH 2 + H+ C CH CH OH + NH 2

nh hng ca hiu ng lin hp ch xy ra trong h thng phng:

V d: Phenol (I) c tnh acid v nhm OH c hiu ng lin hp +C. p-Nitrophenol (II) c tnh acid mnh hn phenol v nhm -NO2 c hiu ng lin hp - C. Thay 2 nhm CH3 vo v tr orto so vi nhm OH c cht (III). Cht (III) c tnh acid gim cht t so vi (II). Nhng a 2 nhm CH3 vo v tr orto so vi nhm NO2 c cht (IV). Cht (IV) c tnh acid yu hn (II). iu chng t 2 nhm CH3 lm cho nhm NO2 khng c hiu ng lin hp - C nh hng n chc phenol.
OH OH CH3 OH CH3 CH3 I OH

pKa

9.98

NO2 II 7,16

NO2 III 7,21

CH3 NO2 IV 8,24

S d c iu v trong (III) nhm NO2 khng nm trong cng mt phng vi vng benzen. Hai nhm CH3 c cn tr khng gian lm cho nhm NO2 b lch ra khi mt phng ca vng benzen. Hiu ng lin hp ca nhm NO2 khng pht huy tc dng. 28

CH3 HO II

..

N O O

HO IV

..

N O O CH3

3. Hiu ng siu lin hp (Hyperconjugate effect) Ngoi s lin hp - v p - nu trn cn c s lin hp - gia cc orbital ca cc lin kt C H trong nhm alkyl v orbital ca ni i, ni ba hay vng thm.
H H H C C C CH3 H 3 lin kt 3 lien ket H H C C C CH3 H 22 lien ket lin kt H H C C C CH3 CH3 H C H

1 lin kt 1lien ket

3 lin kt 3 lien ket

S tng tc lin hp gia orbital ca lin kt C - H vi orbital ca lin kt i, ba hoc h thng lin hp gi l hiu ng siu lin hp.

Hiu ng siu lin hp c k hiu l H. Hiu ng siu lin hp khng nhng lm thay i bn cht ca lin kt i m cn lm thay i c tnh cht ca lin kt n C - H. Hiu ng siu lin hp lm thay i hng cng hp vo lin kt i.
V d: Trong phn t 2-penten, nhm C2H5 c hiu ng + I ln hn nhm CH3. Phn t 2-penten cng hp vi HBr ng l phi to thnh 3-bromopentan. Nhng thc t thu c 2-bromopentan. iu chng t nh hng siu lin hp ca nhm CH3 ln hn nh hng siu lin hp ca nhm C2H5 nh hng n hng cng hp.
H H C CH CH H CH2 CH3 + HBr H H C CHBr CH2 H CH2 CH3

Hiu ng siu lin hp nh hng n tnh cht linh ng ca lin kt C H trong gc alkyl.
V d: Nguyn t hydro trong nhm CH3 ca aldehyd acetic d dng b ct t trong mi trng kim to carbanion.
H H C CH H O

HO -

H H C CH Carbanion

O + H2 O

Carbanion to thnh c h thng lin hp p - . V vy carbanion ny c th c cng thc gii hn:

H H C CH

H H C CH

Hin tng trn cn th hin trong hp cht ester ethylacetoacetat CH3COCH2COOC2H5. Lin kt C H ca nhm CH2 c siu lin hp vi nhm 29

carbonyl C =O. Hydro ca CH2 tr nn linh ng v d dng b ct t trong mi trng base to thnh carbanion.
CH3 C O H. . C C H O OC2H5

+ OH -

CH3 C

C C OC2H5 + H2O O H O Carbanion

Carbanion to thnh c h thng lin hp p - do c th c cc cng thc gii hn.

CH3 C C C OC2H5 O: H O .. Carbanion CH3 C

:O : ..

C H

C O

OC2H5

Hiu ng siu lin hp tng theo s lng lin kt C _H v tr .

CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C -

Hiu ng siu lin hp v hiu ng cm ng +I lun xy ra cng hng. Hin tng phn b li mt in t cn c th c trong cc trng hp h thng carbanion v carbocation.
V d: Carbocation allylic CH2=CHCH+ v carbanion allylic CH2=CHCH-.
+ CH2=CH_CH2

CH2=CH_CH2

Trong carbocation c hin tng dch chuyn in t t lin kt n orbital trng ca nguyn t carbon. Trong carbanion c hin tng dch chuyn cp in t t do ca carbon n lin kt .

Bi tp
1. Pht biu nh ngha v hiu ng cm ng, hiu ng lin hp v siu lin hp. 2. So snh hiu ng cm ng v hiu ng lin hp v bn cht, c tnh v quy lut. 3. Cn c vo hiu ng in t c th c so snh v gii thch tnh acid ca cc cht trong cc dy sau: a- n-C4H8ClCOOH, nguyn t clo cc v tr khc nhau . b- m-ClC6H4(CH2)nCOOHn = 0,1,2 . c- m-ClC6H4(CH2)nCOOHn = 0,1,2 4. Vit cng thc gii hn ca sn phm to thnh khi:

a-

NH2 C NH2

Guanidin bC CH2 C CH2 O O + HO -

NH

+ H+

30

Chng 3

CU TRC PHN T HP CHT HU C NG PHN V CU DNG

Mc tiu hc tp 1. Trnh by c cc loi ng phn gp trong Ha hu c. 2. c c tn cu hnh cc hp cht hu c dng Z, E v R,S. 3. Xc nh c cu dng gh ca dn cht cycloalkan.

Ni dung
Cc hp cht hu c c cu to theo mt trt t xc nh. Cng thc phn t cho bit thnh phn v s lng nguyn t c trong mt phn t. Cng thc cu to phn nh bn cht v th t sp xp cc lin kt trong phn t. Mt cng thc phn t c th c nhiu cng thc cu to khc nhau hoc nhng cht khc nhau. Hin tng mt cng thc phn t ng vi hai hoc nhiu cng thc cu to khc nhau c gi l hin tng ng phn (isomery). Thut ng isomery xut pht t ting Hy Lp "isos" c ngha l "cng" v "meros"c ngha l "phn". Da vo c im cu trc ngi ta chia thnh 2 loi ng phn: ng phn phng v ng phn lp th (ng phn khng gian) 1. ng phn phng Cc nguyn t v nhm nguyn t trong phn t cht hu c u cng nm trong mt mt phng. Cc ng phn ch khc nhau v v tr v th t lin kt gia cc nguyn t to thnh phn t. ng phn phng c cc loi sau: 1.1. ng phn mch carbon C mch carbon sp xp khc nhau. Mch thng hoc phn nhnh.
CH3 CH2 CH2 CH3 CH3 CH CH3 iso Butan CH3

n- Butan

CH3 CH3 CH2 CH2 CH2 CH3 CH3 CH CH3 CH2 CH3 CH3 C CH3 neo Pentan CH3

n- Pentan

iso Pentan

31

1.2. ng phn v tr nhm nh chc Nhm nh chc trn mch carbon cc v tr khc nhau. Dng cc ch s ch v tr nhm chc trn mch chnh ca mch carbon.
CH3 CH3 CH2 CH2 CH2 OH CH3 CH OH CH CH3 CH3 C OH CH3

1-Butanol CH3 CH2 CH CH2

2- Butanol CH3 CH

2-methyl-2-propanol CH CH3

1-Buten

2- Buten

1.3. ng phn nhm chc C nhm chc khc nhau.

CH3 COOH HO CH2 CHO H COOCH3 CH3 CH2 CHO CH3 C O CH3

Acid acetic

Aldehyd glycolic

Ester methyl formiat Aldehyd propionic

Aceton

1.4. ng phn lin kt Cc nguyn t trong phn t c cch lin kt khc nhau
CH3 CH2 CH
1- Buten

CH2

CH2 CH2 CH2 CH2

Cyclobutan

CH2=CH-CH=CH2
1,3-Butadien

CH3-CH-CCH
1-Butyn

CH3-CC-CH3
2-Butyn

S h bin C cc trng hp cc ng phn vi nhau nhng chng khng bn trong nhng iu kin xc nh v chng c th thay i cho nhau to thnh hn hp cn bng. Hin tng ny gi l s h bin (hin tng tautomer - mesomer) V d: Ester ethyl acetoacetat CH3COCH2COOC2H5 c 2 ng phn. Hai ng phn ny c th phn ring tng cht ch nhit -78C. Hai ng phn c dng ceton v dng enol. nhit cao hn khng th phn ring chng c. Chng tn ti nh l mt hn hp 2 cht trng thi cn bng. Dng ceton lun bin i thnh dng enol v ngc li. Khi nng cc cht trong hn hp c xc nh th chng t n trng thi cn bng. Chng l 2 ng phn h bin (mesomer). 32

CH3 C CH2 COOOC2H5 O Ester ethyl acetoacetat Dng ceton

CH3 C CH COOOC2H5 OH Ester ethyl acetoacetat Dng enol

2. ng phn lp th - ng phn khng gian ng phn lp th hay cn gi l ng phn khng gian c cng cng thc cu to nhng khc nhau v s phn b khng gian (phn b lp th) ca cc nguyn t hay nhm nguyn t trong phn t. Tnh cht v phn ng ca cc cht hu c lin quan cht ch vi s phn b khng gian ca cc nguyn t trong cu trc ca chng. C cc loi ng phn khng gian: ng phn hnh hc ng phn quang hc ng phn cu dng 2.1. ng phn hnh hc 2.1.1. Cu to v danh php ng phn hnh hc C th biu din cng thc ca ethylen theo dng khng gian:
H H
H H
H H H

S phn b ca cc nguyn t hydro nm v 2 pha ca mt phng cha lin kt (mt phng ). Cc nguyn t carbon khng th quay t do xung quanh lin kt c v s cn tr ca mt phng . Nu thay th cc nguyn t hydro ca etylen bng cc nguyn t hoc nhm nguyn t khc nhau th s phn b khng gian ca chng so vi mt phng s khc nhau. S phn b v 2 pha ca mt phng cng thng gp trong hp cht vng.
H H H H H H H H H HH H H H

S phn b khng gian ca cc nguyn t hay nhm nguyn t v 2 pha ca mt phng hay mt phng ca vng lm xut hin mt loi ng phn. l ng phn hnh hc. ng phn hnh hc l nhng hp cht c cng cng thc phn t nhng c v tr khng gian ca cc nguyn t hay nhm nguyn t khc nhau i vi mt phng hoc mt phng ca vng. 33

2.1.2. Phn loi ng phn hnh hc

C 2 loi ng phn hnh hc: ng phn cis v ng phn trans. + Dng cis ch ng phn c 2 nguyn t hoc nhm nguyn t ging nhau cng mt pha i vi mt phng hay mt phng vng. + Dng trans ch ng phn c 2 nguyn t hoc nhm nguyn t khc pha vi mt phng hay mt phng vng.
CH3 C H C H H CH3 CH3 C C CH3 H CH3 C H CH3 Mat phang CH3 C H H

Cis Cis 2-buten

Trans Trans 2-buten

C
H

C
CH3

Tng qut: Hp cht c lin kt c dng abC =Cab , acC=Cab lun tn ti ng phn hnh hc cis v trans.

abC=Cab a b
C C

acC=Cab a b
C C

a b

b a

a c

a b

a c

b a

Cau hnh cis

Cau hnh trans

Cau hnh cis

Cau hnh trans

V d:
H HOOC C C H H HOOC C C COOH H H H HOOC C C COOH C C HOOC cis CH3 Acid isocrotonic CH3 H

cis

trans

trans

Acid maleic

Acid fumaric

Acid crotonic

Trng hp hp cht c dng tng qut abC =Ccd cng c ng phn hnh hc vi a,b,c, d l nhng nguyn t hay nhm th hon ton khc nhau v " ln ".

S phn b khng gian cc nhm th ln v mt pha ta c ng phn Z v khc pha ta c ng phn E. Z v E l nhng ch u ca Zusammen (cng pha) v Eintgegen (khc pha).
Nu a > b, c > d.
a b C C c d abC=Ccd a a>b;c>d b C C d

Cau hnh Z (cis)

c Cau hnh E (trans) H

V d:
I Br C C Cl I C C

Br H Cl E Z 1-Brom-1-Iod-2-Cloethylen

I > Br > Cl > H 34

V th I > Br ; Cl > E

OHC H3C C Z C

COOH H

OHC H3C C E C

H COOH

COOH > CHO > CH3 > H

CHO > CH3; COOH > H

Nguyn tc xc nh ln ca nguyn t v nhm nguyn t: + Nguyn t c s th t trong bng tun hon cng ln th ln ca n cng ln
I > Br > Cl > S > P > F > O > N > C > H -CH2Cl > -CH2OH > -CH2CH3
CH OCH3 CH2 CH3

>

OH CH CH2 CH3

+ Nu trong mt nhm nguyn t c mt nguyn t lin kt vi ni i, ni ba th xem nh nguyn t c 2 ln, 3 ln lin kt vi nguyn t kia.
CH = CH2 CH C CH2 C
CH = O C O O

Cho nn:
CH CH3 CH2CH3

>

CH

CH2

>

CH

CH3 CH3

-COOCH3 > -COOH > -CONH2 > -COCH3 > -CHO -CN > -C6H5 > -CCH > -CH=CH2 S ng phn hnh hc tng ln nu phn t c nhiu lin kt i V d: Phn t 1,4-diphenyl-1, 3-butadien c 3 ng phn hnh hc
C6H5 C H C H C C H C6H5 C H C H C C C6H5 H C C6H5 C H H C C C6H5 H

C6H5 H Trans-trans

H H Trans-cis

Cis-cis

35

ng phn hnh hc trong cc hp cht vng

CH3 cis CH3 H H trans H 1,3-Dimethylcyclobutan CH3 H CH3 Cl Cl Cl
H

H trans Cl H H cis 1,3-Diclocyclohexan

Cc trng hp khc v ng phn hnh hc.

ng phn hnh hc trong h thng ethylen phc tp
CH3 O CH3 Cis O CH3 O Trans O CH3

ng phn hnh hc trong hp cht c ni i C=N v N =N

CH3CH2 CH3 C6H5 OH C N .. Butanoxim Z ( syn ) C6H5 Azobenzen CH3CH2 CH3 C6H5 C N OH

..

E (anti) N .. N

..

N ..

N ..

Z ( syn )

E (anti)

C6H5

Ch : Cc thut ng trans, cis, E, Z, anti v syn l cc h thng danh php gi tn cc ng phn hnh hc. 2.1.3. Tnh cht ca cc ng phn hnh hc Do s khc nhau v khong cch gia nhm th v mc n ng khng gian, hai ng phn hnh hc c nhiu tnh cht l -ha khc nhau.

Tnh cht vt l Nhit nng chy (tnc) : ng phn trans (E, anti ) c nhit nng chy cao hn ng phn cis (Z, syn). Nhit si (ts): ng phn trans (E, anti ) c nhit si thp hn nhit si ca ng phn cis (Z, syn) . Momen lng cc: Tu thuc vo bn cht ca cc nhm th phn b chung quanh lin kt i hoc vng, momen lng cc cc ng phn hnh hc c khc nhau. Nu hp cht c dng aCH =CHa th momen lng cc ca ng phn E (trans) bng khng E = 0 v momen lng cc ca ng phn Z (cis) ln hn khng Z > 0.
36

Hp cht c dng aCH =CHb : Nu a v b cng c bn cht in t (ngha l a v b u cng ht hoc cng y in t th Z > E Nu a v b khc nhau v bn cht in t (a ht in t cn b y in t hoc ngc li) th E > Z. Ch : Xc nh momen lng cc theo nguyn tc hnh bnh hnh c th minh ha nh sau:
H aCH=CHa a C C H b C a C H a H C C b a H C a C H

z a Z > 0
H

E = 0
H aHC=CHb a,b u ht electron

E < Z
b C a C H a H C C b H

H aCH=CHb a hut, b ay electron

E > Z

Bng 3.1. Tnh cht vt l ca mt s ng phn hnh hc

Hp chat
ClCH=CHCl PhCH=CHCOOH p-O2NC6H5CH=CHNO2 CH3CH=CHCl

Nhiet o nong chay Nhiet o soi Momen lng cc Trans (E ) Cis (Z) Trans(E) Cis (Z) Trans(E) Cis (Z)
-50oc -80,5oc 48,4oc 68,0oc 60,2oc 134,0oc 0D 0,5D 2,0D 2,95D 7,4D 1,7D

bn
ng phn trans bn hn ng phn cis v nhit . Di tc dng ca nhit ng phn cis c th chuyn thnh ng phn trans. S chuyn i cis trans
H a C C a H H a C H a Quay a C C H

H a

cis (Z , syn)

trans (E , anti)

Cc gi tr ph t ngoi, ph hng ngoi ca cc ng phn hnh hc cng khc nhau. 37

 Tnh cht ha hc ng phn cis d tham gia mt s phn ng loi nc, to vng.
H COOH COOH

to

H H

O C O C O + H2O

Acid cis butendioic

Anhydrid maleic

2.2. ng phn quang hc ng phn quang hc l nhng cht ha hc c tc dng quay mt phng nh sng phn cc. Cht c tc dng vi nh sng phn cc l cht quang hot.

nh sng t nhin
Theo l thuyt v nh sng th nh sng t nhin gm nhiu sng in t c vect in trng hng theo tt c cc hng trong khng gian v thng gc vi phng truyn sng.
Anh sang t nhien Phng truyen song Vect ien trng

nh sng phn cc, mt phng nh sng phn cc

Khi cho nh sng t nhin i qua lng knh Nicon hoc mt cht phn cc no (nh HgS, KClO3....) th cc vect in trng s hng theo mt phng dao ng xc nh v vung gc vi phng truyn sng. nh sng i ra khi cht phn cc gi l nh sng phn cc. Mt phng nh sng phn cc (mt phng phn cc) l mt phng vung gc vi phng dao ng ca nh sng phn cc.
Mat phang anh sang phan cc Phng truyen song

Anh sang phan cc Anh sang t nhien Lang knh Nicon

Cht quang hot (cht hot ng quang hc)

Khi cho nh sng phn cc qua dung dch cht hu c hoc mt cht no , nu cht ny lm quay mt phng nh sng phn cc mt gc c gi tr + hoc - th gi cht l cht quang hot (cht hot ng quang hc). 38

Chat quang hoat

Goc quay

Mat phang phan cc

Mat phat phang phan cc sau khi qua chat quang hoat

c trng kh nng quang hot ca mt hp cht quang hot ngi ta dng i lng quay cc ring hay cn gi l nng sut quay cc ring v k hiu l [].

Trong :

to

= 100 __

LC

l gc quay cc xc nh trn my phn cc k, c th c 2 gi tr .

Ga tr + ch mt phng phn cc quay phi. Ga tr - ch mt phng phn cc quay tri. L b dy lp cht quang hot m nh sng phn cc i qua n v tnh l dm. C l s gam cht ha tan trong 100ml dung mi.

l bc sng ca nh sng.
t l nhit o. Nh vy tnh quang hot ca mt cht l tnh cht ca phn t gn lin vi cu trc phn t. S phn b khng gian lm cho cu to phn t tr thnh khng i xng l nguyn nhn ch yu gy ra ng phn quang hc. 2.2.1. Phn t c nguyn t carbon khng i xng 2.2.1.1. Phn t c nguyn t carbon bt i xng Nu nguyn t carbon lin kt trc tip vi 4 nguyn t hoc 4 nhm nguyn t hon ton khc nhau th gi l carbon khng i xng (bt i xng, phi i xng).

b
*C

b c d hay
*C

c d

a,b,c, d l cc nguyn t hay nhm nguyn t khc nhau. Carbon khng i xng k hiu l C*. Phn t c carbon khng i xng th khng c cc yu t i xng (mt phng i xng, tm i xng v trc i xng) v phn t c ng phn quang hc. 39

V d: Acid lactic c mt carbon bt i xng CH3*CH(OH)COOH.

COOH COOH OH CH3 H COOH

CH3CHOHCOOH

C H

CH3 OH

hay
H

CH3 OH

Nu xem m hnh t din ca acid lactic l mt vt tht th nh ca n qua gng l mt vt th th hai. Vt v nh khng bao gi trng kht ln nhau khi quay vt hay nh chung quanh mt phng mt gc 180.
Gng phang Gng phng COOH HOOC

C CH3 H OH HO

H3C C H (- )

Vt Vat

(+ )

nh Anh

nh v gng l hai ng phn quang hc ca nhau, c cu to hon ton ging nhau, ch khc nhau l nu vt quay mt phng nh sng phn cc mt gc + th nh quay mt phng phn cc mt gc - . Quan h gia phn t (vt) v nh gng ca n nh bn tay phi v bn tay tri. Vt v nh khng trng ln nhau (chirality). Hai ng phn vt v nh l 2 i quang (2 cht nghch quang). 2.2.1.2. Phn t c mt nguyn t carbon bt i xng Cc ng phn i quang (enantiomer, gc t ting Hy Lp enantio l ngc chiu) c khong cch gia cc nguyn t trong phn t nh nhau. Chng ng nht v cc tnh cht vt l, ch khc nhau v s tng tc vi nh sng phn cc. Hp cht c mt nguyn t carbon khng i xng c 2 ng phn quang hc. Mt ng phn quay mt phng phn cc bn phi vi gc (+) gi l ng phn quay phi (+)hay l ng phn hu tuyn (cn gi l ng phn d = dextrogyre). Mt ng phn quay mt phng phn cc v bn tri (-)gi l ng phn quay tri (-) hay l ng phn t tuyn (trc y gi l ng phn l = levogyre). Nu trn nhng lng bng nhau ca 2 cht i quang (50% ng phn quay phi v 50% ng phn quay tri) s c mt hn hp khng c kh nng quay mt phng nh sng phn cc. Hn hp gi l bin th racemic k hiu l ( ).

40

 thun tin khi biu din cc ng phn quang hc, ngi ta biu din cng thc theo hnh chiu Fischer (xem mc ng phn cu dng) nh sau: Cc ng phn quang hc ca acid lactic
CH3 CHOH COOH COOH
C

COOH H OH CH3 (+ ) Cong thc chieu Fisher

COOH

COOH HO H CH3

H (+ )

CH3 OH

H3C HO

(- )

Cong thc t dien

Cong thc t dien Cong thc chieu Fisher

2.2.1.3. Phn t c nhiu nguyn t carbon bt i xng Hp cht c nhiu carbon bt i xng th s dng phn quang hc tng ln. Trong phn t, cc nguyn t carbon bt i xng c cu to khc nhau th s ng phn quang hc l 2n ; n l s nguyn t carbon bt i xng. V d: Monosachcarid C6H12O6 vi 4 nguyn t carbon bt i xng c 24 = 16 ng phn quang hc . D - Glucose l mt trong 16 i quang .
CH2OH CHOH CHOH CHOH CHOH CHO

Phn t acid ,-dihydroxybutyric c 2 nguyn t carbon bt i xng nn c 4 ng phn quang hc. C th minh ha cc ng phn nh sau: Cc ng phn quang hc ca , - dihydroxybutyric
CH3 CHOH CHOH COOH

COOH H H OH OH CH3 I HO HO

COOH H H CH3 II H HO

COOH OH H CH3 III HO H

COOH H OH CH3 IV

I v II l 2 i quang, III v IV l 2 i quang vi nhau. Cn I v III, I v IV, II v III, II v IV l cc cp ng phn quang hc khng i quang vi nhau (diastereoisomer). Trong phn t, nhng nguyn t carbon c cu to ging nhau (tng ng nhau) lm cho phn t c mt phng i xng trong phn t th s ng phn quang hc s t hn 2n v c thm ng phn meso. V d: Phn t acid tartaric c 2 nguyn t carbon bt i xng ging nhau nn ch c 2 ng phn quang hc v mt ng phn meso. C th minh ha nh sau: 41

Cc ng phn quang hc v ng phn meso ca acid tartaric

* * HOOC CHOH CHOH COOH

COOH OH H HO H COOH I Acid(+) tartaric

COOH HO H H OH COOH II Acid(-) tartaric

COOH OH H OH H COOH III

COOH H HO mp oi xng H HO COOH

IV Acid mesotartaric

Trong : I v II l 2 i quang (2 ng phn quang hc). III v IV c mt phng i xng trong phn t nn chng khng quay mt phng phn cc, chng khng c tnh quang hot. Ngi ta gi l ng phn meso. Ch : III v IV ch l mt cng thc. C th gii thch s ng phn trong cc trng hp s carbon bt i xng c cu to khc nhau v ging nhau nh sau: Carbon bt i xng c cu to khc nhau th gc quay mt phng phn cc khc nhau. Trong trng hp acid ,dihydroxybutyric, gi s gc quay ca mi carbon bt i l a v b, a>b. Acid tartaric c 2 carbon bt i vi cu to ging nhau, gc quay mt phng phn cc ca mi carbon bt i ging nhau (a= b). Gc quay mt phng phn cc l tng gi tr gc quay ca tt c carbon bt i trong phn t. C cc trng hp:
CH3CHOHCHOHCOOH

a>b 1 2 2 2 = ( +a ) + (+b ) = = ( -a ) + (-b ) = = ( +a ) + (-b ) = = ( -a ) + (+b ) =

(+) (-) 2 oi quang 2 oi quang

HOOCCHOHCHOHCOOH

a=b

( +) ( -)

1 2 3 4

= ( +a ) + (+b) = = ( -a ) + (-b ) = = ( +a ) + (-b) = = ( -a ) + (+b) =

(+) (+)

2 oi quang

(0) mot ong pham meso (0)

Kt qu: Acid , -dihydroxybutyric c 4 ng phn quang hc v acid tartaric ch c 2 ng phn quang hc v 1 ng phn meso. 2.2.2. Danh php ng phn quang hc Danh php ny dng k hiu cu hnh ca nguyn t carbon bt i. C 2 loi danh php: Danh php D, L v danh php R,S 2.2.2.1. Danh php D,L Ngi ta chia cc cht quang hot thnh hai dy: dy D v dy L. Loi danh php ny c tnh cht so snh, ngha l ngi ta ly cu hnh khng gian ca aldehyd glyceric CHOHCHOHCHO lm chun so snh. 42

Aldehyd glyceric c mt carbon bt i xng c 2 ng phn quang hc. Cu hnh ca chng c m t di y: Cu hnh chun ca aldehyd glyceric
CH2OH CHOH CHO CHO
C

CHO H OH CH2OH

CHO

CHO HOH2C
C

CH2OH OH

va HO

D ( + ) Aldehid glyceric

HO CH2OH L ( - ) Aldehid glyceric

II

Cong thc t dien

Cong thc chieu Fisher

Cong thc chieu Fisher

Cong thc t dien

Trong cng thc I nhm OH bn phi ngi ta quy c n c cu hnh D. Trong cng thc II nhm OH bn tri, quy c n c cu hnh L. Nhng hp cht quang hot c carbon bt i xng vi s th t cao nht c cu hnh ging cu hnh ca D - aldehyd glyceric th chng thuc dy D. Nhng hp cht quang hot c carbon bt i xng vi s th t cao nht c cu hnh ging cu hnh ca L - aldehyd glyceric th chng thuc dy L . V d: D- Glucose v L - Glucose c cu hnh nh sau: Trong phn t glucose carbon bt i xng s 5 (s th t cao nht ca C *) c cu hnh ging D - aldehyd glyceric c gi l D - Glucose v ging L -aldehyd glyceric l L -Glucose. Cu hnh ca D - Glucose v L - Glucose
CH2OH_CHOH_CHOH_CHOH_CHOH_CHO
6 5 4 3 2 1

H HO H 4 H 5

H OH OH 6 CH2OH D(+) - Glucose

1CHO 2 OH 3

HO H OH 4 HO H 5 HO H 6 CH2OH L(-) - Glucose

1CHO 2 H 3

Du (+) v du ( - ) ch chiu quay mt phng nh sng phn cc. Danh php D, L cng p dng cho cch gi tn ca cc acid amin. 2.2.2.2. Danh php R, S (danh php Cahn - Ingold-Prelog ). R t ch Rectus (phi), S t ch Sinister (tri). Danh php D, L c nhiu hn ch l khng ch r ht cu hnh ca cc nguyn t carbon trong phn t v c tnh cht so snh. Danh php R, S khc

43

phc iu . Theo h danh php ny th 4 nhm th chung quanh nguyn t carbon bt i xng c sp xp theo th t gim dn v ln" . V d: C*abcd a > b > c > d Xt s phn b cc nhm th a,b,d,c chung quanh carbon bt i xng ca vt v nh trn hnh t din sao cho nhm th nh nht d vo nh t din xa nht so vi mt ngi nhn v ba nhm th a,b,c cn li chim 3 gc ca y t din. Nu theo th t " ln " ca 3 nhm th a,b, c theo chiu quay kim ng h ta c cu hnh R, nu th t ngc chiu kim ng h ta c cu hnh S.

a c
*C

a b c
*C

a d b d *C b
Gng phang

a c b
*C

I
a,b,c theo chieu quay cung chieu kim ong ho Cau hnh R

II
a,b,c theo chieu quay ngc chieu kim ong ho Cau hnh S

V d: Phn t acid lactic c 2 ng phn: acid R- Lactic v acid S Lactic

CH3_CHOH_COOH o ln cac nhom the OH > COOH > CH3 > H OH *C H3C OH
C*

OH H COOH H HOOC *C CH3 HOOC acid S-Lactic

OH *C CH3

COOH

H3C

acid R Lactic

Gng phang

i vi cc hp cht c nhiu carbon bt i xng c danh php theo h thng R, S ngi ta ln lt xc nh cu hnh ca tng carbon bt i. V d: i vi acid tartaric HOOC _CHOH_CHOH_COOH ta c cc ng phn: acid (2R, 3R )-tartaric acid (2S, 3S )-tartaric acid (2R, 3S )-tartaric (aid mesotartaric ).

Phng php xc nh cu hnh R,S Chuyn cng thc dng t din v hnh chiu Fischer. Xt ln lt tng carbon bt i xng vi 4 nhm th c ln khc nhau.

44

Theo qui tc:

Nu thay i v tr nhm th 1 ln th cu hnh thay i. Nu thay i v tr nhm th 2 ln th khng thay i cu hnh.

(Ch thay i sao cho nhm th b nht v pha di).

Xt chiu theo th t gim dn ln ca cc nhm th.

V d: Xt cu hnh ca aldehyd D Glyceric HOCH2 _ C*HOH _ CHO. C mt carbon bt i v 4 nhm th chung quanh
C* l HO > CHO > CH2OH > H
HOCH2_CHOH_CHO Cong thc t dien CHO *C H CH2OH OH H CHO *C CH2OH OH H CHO * OH CH2OH CH2OH
I

Cong thc chieu Fisher CHO * OH CH2OH OH CHO

H oi v tr lan 1
II

H oi v tr lan 2
III

T cng th t din chuyn v cng thc chiu Fischer (I). Cu hnh I l cu hnh ca aldehyd D -glyceric. T (I) thay i v tr ln 1 thu c (II). i v tr tip tc ln 2 ta c (III). Cho H l nhm th b nht v pha di. Cu hnh ca (III) l cu hnh ca (I) Xt chiu quay ca 3 nhm th OH, CHO, CH2OH. Ta c OH CHO CH2OH theo chiu kim ng h. (III) c cu hnh R v suy ra (I) phi c cu hnh R. Vy D- aldehyd glyceric l R - aldehyd glyceric . 2.2.2.3. Danh php Erythro v Threo phn bit cc ng phn quang hc khng i quang ca cc hp cht quang hot c 2 nguyn t carbon bt i xng ngi ta gi tn theo danh php erythro v threo. Dng erythro l dng trong 2 i nhm th tng t nhau c th a v v tr che khut, cn dng threo ch c mt i nhm th tng t nhau c th v tr che khut V d: 2-Phenyl -2-butanol c dng ng phn erythro v threo nh sau:

45

CH3_CH(Ph)_CHOH_CH3 CH3 H H
S R

OH Ph

CH3 HO Ph
R S
25

CH3 HO H
R R
25

CH3 H Ph H Ph
S S
25

H H

OH H

CH3 [] = -0,69o
25

[] = +0,69o
D

CH3

[] = -30,2o
D

CH3

[] = +30,2o
D

CH3

2 ong phan erythro

2 ong phan threo

2.2.3. Cc ng phn quang hc khng c carbon bt i xng C mt s hp cht trong phn t khng c carbon bt i xng, nhng do s cn quay lm cho phn t tr thnh bt i xng nn phn t c tnh quang hot (c ng phn quang hc). Cc hp cht thuc dy allen, diphenyl, paracyclophan, thuc loi cht quang hot khng c carbon bt i xng.
a b Hp chat allen c
C C C d R' R''' R R"

O
(CH2)n

Hp chat diphenyl

Hp chat paracyclophan

2.3. ng phn cu dng Cu dng hay cn gi l hnh th (Conformation) ca mt phn t dng ch cc dng cu trc khng gian c th hnh thnh khi cc nhm th quay t do chung quanh lin kt n. Mt cht hu c c th c trnh by theo cc dng cng thc sau: Cng thc t din Cng thc chiu Fischer Cng thc phi cnh Cng thc Newman V d: Phn t etan c th c trnh by cc dng cng thc:
H H H H H H H H H H H H CT phoi canh H H H H H H H H H H

H CT t dien

H CT chieu Fisher

CT Newman

46

Cng thc phi cnh v cng thc Newman thng c dng bin din cu dng cc cht hu c. Cng thc phi cnh c m t trong khng gian 3 chiu, lin kt gia 2 nguyn t carbon hng theo ng cho t tri sang phi v xa dn ngi quan st. C 2 loi cng thc phi cnh l dng xen k v dng che khut.

a b
C

c c

b b

a
C

a c b
C

Dng xen k

Dng che khut

a,b,c l nhng nguyn t hoc nhm nguyn t phn b chung quanh nguyn t carbon. Cng c th m t theo ng m nt ( ),ng chm chm .....)v ng nht (__). ng m nt ch r lin kt hng v pha trc mt ( phng. ng chm chm hng v pha sau mt phng. ng nt nht nm trong mt phng.

a b
C

c c

b b

a
C

a c b
C

Dng xen k

Dng che khut

Cu dng xen k c nng lng thp hn (bn hn) cu dng che khut (km bn). T cng thc phi cnh c th m t theo cng thc Newman bng cch nhn phn t theo dc trc lin kt C1 C2. Ta biu din C2 b che khut bng vng trn, cn C1 tm vng trn. Ba lin kt xut pht t mi nguyn t carbon to nn nhng gc 120 trn mt phng giy.

a b
C
1

c c

c a b b
1 2

aa b b
1 2

a b
C
1

a
C2

CT phoi canh

CT Newman

cc

c b

CT Newman

CT phoi canh

Dang xen ke

Dang che khuat

Trong cc hp cht vng cc nguyn t khng phn b trn cng mt phng. Chng c cc cu dng khc nhau. Phn t cyclohexan c hai loi cu dng: cu dng gh v cu dng thuyn.

47

H H H H H H

H H H H

H H
H

H H
H

H H H

H H

Cau dang ghe

Cau dang thuyen

dng gh cc nguyn t hydro trn 2 carbon cnh nhau phn b theo cch xen k. Cn dng thuyn cc nguyn t hydro trn 2 carbon cnh nhau phn b theo cch che khut. V vy cu dng gh bn hn cu dng thuyn (xem phn cycloalkan). 2.4. Tc dng sinh hc ca cc ng phn quang hc Cc ng phn quang hc ng vai tr quan trng trong i sng t nhin ca con ngi v th gii sinh vt. Cc cht chuyn ha, cc cht men l nhng h thng hp cht quang hot. Thay i cc dng i quang dn n s thay i qu trnh v c ch ca s chuyn ha. Acid Lactic tn ti (+) Lactic, (-)Lactic v L () Lactic (racemic). Chng c cc tc dng sinh hc khc nhau. D -(+)-glucose l ng c tc dng sinh hc lm cht tim truyn. Ngc li L -(-)-glucose hon ton khng c tnh cht ...

Bi tp
1- Cng thc phn t mt hydrocarbon l C7H14. Bao nhiu ng phn c th c ? 2- Cng thc phn t C5H12. Bao nhiu ng phn c th c? 3- Vit cng thc cu to cc ng phn hnh hc ca cc cht sau: a- 2-Penten ; b-2-Phenyl-2-buten ; c- 1,2-Dimethylcyclopentan. d-1-Phenyl-1-clo-2,3,3-trimethyl-1-buten. Cho bit danh php cu hnh ca cc ng phn . Dng ng phn no bn hn. Gii thch. 4- C hp cht CH2Cl-CHOH-CHOH-CH2Cl. a- Hp cht ny c bao nhiu nguyn t carbon i xng, bt i xng . b- Hp cht c bao nhiu i quang v c loi ng phn no. c- V cng thc t din, cng thc chiu Fischer, cng thc phi cnh v cng thc Newman . d- Gi tn cc ng phn theo danh php D, L; danh php R, S v danh php Erythro -Threo . 5- V cc cu dng gh v thuyn ca cc cht sau y: a- cis-1,2-dimethylcyclohexan c- cis-1,3-dimethylcyclohexan e- cis-1,4-dimethylcyclohexan 48 b- trans-1,2-dimethylcyclohexan. d- trans-1,3-dimethylcyclohexan f-trans-1,4-dimethylcyclohexan

Chng 4

KHI NIM ACID -BASE TRONG HA HU C

Mc tiu hc tp 1. Trnh by c cc quan nim v acid v base trong ha hu c. 2. Gii thch v so snh c mnh tng i tnh acid hoc base ca mt s hp cht hu c. 3. Nm c khi nim acid -base lin quan n phn ng ca cc hp cht hu c. 4. S dng khi nim acid -base ca Bronsted - Lowry v Lewis trong ho hu c gii thch v tnh acid -base ca cc cht v c ch phn ng. Ni dung 1. Khi nim acid - base theo Bronsted -Lowry (1923) Acid l nhng tiu phn c khuynh hng cho proton. Base l nhng tiu phn c khuynh hng nhn proton. V d c cht HA cho proton H+.

HA

A- + H+

Theo phng trnh trn th s phn ly to H+ l mt qu trnh thun nghch. HA l acid v cho proton H+. A to thnh gi l base, v A nhn proton to thnh acid HA. V vy c th gi HA l acid lin hp ca base A v A l base lin hp ca acid HA. Trong bng 4-1 trnh by mt s acid -base lin hp.
Bng 4.1. S phn ly ca cp acid base lin hp
HA

+ H Proton
H+ H+

A Base lien hp
CH3COO CH3O
-

Acid lien hp
CH3COOH CH3OH NH +
4

+ CH3_O_CH3 H

H+ H+

NH3 .. CH _O_CH
3

..

49

Theo bng trn khi BH+ phn ly to thnh base khng c in tch ( - )

BH

H + B
+ -

Kt hp c 2 trng hp ta c

HA + B

BH + A

Vy phn ng gia mt acid HA v mt base B l s chuyn dch proton t acid sang base hay l phn ng proton ha. Tnh cht ca acid hoc base khng ph thuc in tch ca tiu phn. Nh vy c nhng phn t acid khng mang in (H2SO4, HCl, CH3COOH), c phn t acid tch in dng (NH4+, [CH3OCH3]H+), c phn t base mang in tch m (CH3COO-, CH3O-), c phn t base khng c in tch (NH3, CH3OCH3) . Acid ha tan vo nc c s tng tc acid base: Nc l dung mi c tnh base.

CH3COOH + H2O Acid Base

H3O+ + CH3COOAcid Base

Ho tan mui ca acid hu c vo nc, c s tng tc acid -base : Nc l dung mi c tnh acid.
H2O + CH3COO Base Acid CH3COOH + HO Acid Base

Nc l mt dung mi lng tnh ph thuc vo tnh cht ca cht ha tan.

Mt s phn ng ha hc c xc tc acid, thc cht l s tng tc acid - base. V d: Phn ng to ether t alcol c xc tc acid l s tng tc acid (H+) vi base (alcol) to cht trung gian khng bn trc khi hnh thnh ether.

H2SO4 + R_O_H Acid Base

+ R_O_H + HSO 4 H Base Acid

Phn ng cng hp nc vo olefin c xc tc acid cng l qu trnh tng tc acid -base, to carbocation trung gian trc lc to thnh alcol.
H3PO4 + CH3 CH=CH2 Acid Base + CH3CH_CH3 + Acid H2PO4 Base

Mt s phn ng c xc tc base cng c qu trnh tng tc acid base to carbanion trung gian.
CH3_CHO + HO Base Acid

H2O + CH2_CHO Base (carbanion) Acid

Ch : Mt acid rt mnh th base lin hp ca n l mt base rt yu. Mt acid rt yu th base lin hp ca n l mt base rt mnh. 50

CH3 + Acid rt yu
-

CH2 B BH
+

+
Base rt mnh

Base rt mnh
-

Acid rt yu

HO , CH3O l nhng base mnh H2O, CH3OH l nhng acid yu

2. Khi nim acid - base theo Lewis (1923) Base l phn t c kh nng cung cp cp in t (c cp in t khng lin kt). Acid l phn t c nguyn t m in t lp ngoi cng cha y (c kh nng kt hp vi cp in t ca base). Cc cht sau y l nhng base Lewis:
R_O_R

..

.. .. .. ; R_NH2 ; R_OH ; NH3 ; HO- ; RO -

Cc cht sau y l acid Lewis:

+ BF3 , AlCl3 , FeCl3 , ZnCl2 , SO3 ,NH4

Acid Lewis c kh nng to lin kt cng tr (lin kt phi tr cng l mt dng ca lin kt cng tr) vi cc base Lewis nh H2O, R2O, NH3 .
H .. N H : ..: H
Base Lewis

F Acid Lewis

F .. B ..: F

H F .. .. N :..: F H: .. B H F

3. Hng s cn bng acid - base Acid phn ly trong nc. Cc ion b hydrat ha (solvat ha)

HA

H+ + A- hay HA( nc )

H+(nc) + A- (nc)

S solvat ha H + (nc) v A - (nc) c th minh ha:

H2O H + O H + H3O (H2O)n OH2 H OH2 H O H H O H H O H H

A-

H O A- 2O)n (H

51

Bng 4.2. Gi tr pKa ca mt s cht hu c

Hp chat CH3CONH2 H2O CH3OH (CH3CH2)2 O CH3COOH CH3COOC2H5 CH3CHO CH3COCl CH3CN Acid lien hp + OH CH3 C NH2 + H3O + CH3OH2 + (CH3CH2)2 OH + OH CH3 C OH + OH CH3 C OC2H5 + OH CH3 C H + OH CH3 C Cl + CH3 C NH 00 -1.7 -2.2 -3.6 -6.0 -6.5 -8.0 -9.0 -10.7 pKa

Hng s cn bng ca phn ng:

HA( nc )
K

Ka =

H+(nc) + A-(nc) [H+][A-]

[HA]

Ka > 1 thuc nhng acid mnh Ka < 10-4 thuc nhng acid yu Gi tr Ka rt b thuc nhng acid rt yu S dng i lng pKa = -logKa nh gi mnh yu ca acid pKa cng b th acid cng mnh v ngc li pKa < -1 thuc acid mnh . pKa > 3 thuc acid yu. Tng t ta c hng s cn bng ca base.

B + H2O Kb =

Kb

BH + + HO-

[ BH +][HO-] v [H2O] = 55,5 M [B]

S dng i lng pKb = - logKb nh gi mnh ca base. Kb cng ln th tnh base cng yu pKb cng ln th tnh base cng mnh v ngc li 52

Bng 4.3. nh hng ca cc hiu ng n tnh acid

Acid Ka ,M pKa

CH3COOH FCH2COOH F3CCOOH ClCH2COOH Cl2CHCOOH Cl3CCOOH BrCH2COOH

1,8.10-5 2,6.10-3 0,59 1,4.10-3 5,5.10-2 1,3.10-3 6,7.10-4 1,5.10-4 2,9.10-4 4,5.10-5 4,8.10-4 1,3.10-5 3,4.10-3 4,9.10-5 0,23

4,74 2,59 0,23 2,86 1,26 0,64 2,90 3,18 3,83 3,54 4,35 3,32 4,87 2,46 4,31

ICH2COOH

HOCH2COOH CH3OCH2COOH CH2=CHCH2COOH CH3CH2COOH NCCH2COOH HC CCH2COOH

C6H5CH3COOH

Ch : Tnh acid v tnh base ca mt cht l mi quan h bin chng. Mt cht c tnh acid mnh th n l mt base yu. Mt cht c tnh base mnh th n l mt acid yu. Ether ethylic C2H5OC2H5 l mt base yu, v vy n ch tc dng vi mt s acid mnh .

.. CH3CH2OCH2CH3 + H+

CH3CH2OCH2CH3 H

4. Yu t nh hng n tnh acid -base ca cht hu c Cu trc in t ca phn t nh hng n tnh acid -base Cc nguyn t, nhm nguyn t gy nh hng cm ng, nh hng lin hp, nh hng siu lin hp c nh hng n tnh acid -base. Hiu ng - I, - C lm cho tnh acid ca mt cht tng (tnh base gim). Hiu ng + I, + C lm cho tnh acid ca mt cht gim (tnh base tng). Cc s liu ghi trong bng 4-3 chng t iu .

Bi tp
1- Vit cng thc ca cc base lin hp ca cc acid sau: C6H5COOH, C6H5CH2COOH, CH3CH2NO2, C6H5OH, (CH3)3NH+ 2- Vit cng thc cc acid lin hp ca cc base sau: NH3, C6H5NH2, CH3OCH3, CH3COCH3, HCC-, RO3- V sao AlCl3, ZnCl2, NH4+, BF3 l nhng acid. 53

Chng 5

CC LOI PHN NG TRONG HA HU C v KHI NIM V C CH PHN NG

Mc tiu hc tp 1. Trnh by c cc c ch phn ng thng gp trong ha hu c. 2. Vit v gii thch c cc c ch phn ng: th (S), cng hp (A), tch loi (E) Ni dung C nhiu phng php phn loi phn ng trong ha hu c. Trong gio trnh ny cc phn ng c phn loi theo hng phn ng. C cc loi phn ng nh sau: 1. Cc loi phn ng trong ha hu c 1.1. Phn ng th (Substitution) Phn ng th (k hiu S) l phn ng trong mt nguyn t hay nhm nguyn t trong phn t c thay th bng mt nguyn t hay nhm nguyn t khc.
R_I + CN- R_CN + IR_Li + H2O R_H Tng qut: R_A + Y + LiOH R_Y +A

A l nhm b th (nhm i ra) A = I-, Li+ , ... Y l nhm th ( nhm i vo) Y = CN-, H+ Trong ha hu c tn gi ca mt s phn ng c lit k trong bng 5-1.
Bng 5.1. Tn gi mt s phn ng th
RA+Y
Nhom the Y Halogen X NO2 SO3H R' Ar R'CO CHO N=N_Ar R'COO

RY+A San pham the R_Y Ten phan ng

R_X R_NO2 R_SO3H R_R' R_Ar Phan ng halogen hoa Phan ng nitro hoa Phan ng sulfonic hoa. Phan ng alkyl koa Phan ng aryl hoa Phan ng acyl hoa Phan ng formyl hoa Phan ng azo hoa Phan ng ester hoa

R'CO_R R_CHO R_N=N_Ar R'COO_R

54

Mt s phn ng th c km theo s loi nc, alcol, amoniac ...cn gi l phn ng ngng t. V d: R_CHO + CH3COC6H5

R_CH=NR' + H2O

RCOOC2H5 + CH3COC6H5 RCOCH2CO C6H5 + C2H5OH Tu theo c ch phn ng v tc nhn phn ng, phn ng th cn chia thnh cc loi phn ng th khc nhau:

Phn ng th i nhn. Phn ng th gc t do. Phn ng th i in t.

1.1.1. Phn ng th i nhn SN

R-A + Y

R-Y + A

Y- gi l tc nhn i nhn V d: CH3Cl + HO-

CH3OH + Cl-

1.1.2. Phn ng th gc t do SR

R-A + R .

R-R + A

R l gc t do (nhng gc c mt in t) V d: SO2Cl2 + C6H5 C6H5Cl + SO2Cl 1.1.3. Phn ng th i in t SE R _ A + E+

R_ E

+ A+

E+ l tc nhn i in t
+ V d: Ar _ H + NO2 Ar _ NO2 + H+

Trong phn c ch phn ng s cp v cc qu trnh xy ra phn ng th. 1.2. Phn ng cng hp (Addition) Phn ng cng hp (k hiu Ad) l phn ng trong hai phn t (hoc ion) kt hp vi nhau thnh mt phn t (hoc ion) cht mi. Phn ng thng xy ra trong cc hp cht c ni i, ni ba: C=C, CC, C=O, C=NH, CN. Phn ng cng hp xy ra c s thay i trng thi lai ha ca nguyn t carbon. HCCH + HCl R_CH=CH2 + Br2 H2C=CHCl: Carbon trng thi sp thnh sp2

R_CHBr_CH2Br: Carbon trng thi sp thnh sp3

55

Ty theo cu to cht phn ng, ngi ta chia phn ng cng hp thnh cc loi:

Phn ng cng hp i in t P (AdE , AE ) Phn ng cng hp i nhn P (AdN , AN) Phn ng cng hp gc P (AdR , AR )
1.2.1. Phn ng cng hp i in t (AdE , AE)
R_CH=CH2 + H2O R_CHOH_CH3

1.2.2. Phn ng cng hp i nhn (AdN , AN )

R_CH=O + HCN R_CH(CN)_OH

1.2.3. Phn ng cng hp gc (AdR , AR )

. + Cl

Cl

Cl

+ Cl2

Cl . + Cl Cl

Phn ng cng gc c nh sng lm xc tc l phn ng dy chuyn. Phn ng cng hp hydro vo lin kt i, ta cn c th gi l phn ng hydro ha hay phn ng kh. 1.3. Phn ng tch loi (Elimination) Phn ng tch loi (k hiu E) l phn ng m 2 nguyn t hay nhm nguyn t tch ra khi phn t v khng c nguyn t hay nhm nguyn t no thay th. Phn ng xy ra c s thay i trng thi lai ha ca nguyn t carbon. H_CH2_CH2_OH CH2=CH2 + H2O: Carbon trng thi sp thnh sp2. Br_CH2_CH2_Br + Zn CH2=CH2 + ZnBr2: Carbon trng thi sp thnh sp2 1.4. Phn ng chuyn v (Rearrangement) Trong cc loi phn ng k trn c lc c th xy ra s chuyn v lm chuyn ch mt nguyn t hay nhm nguyn t no trong phn t. Phn ng xy ra c s chuyn i v tr trong phn t gi l phn ng chuyn v.

R R C CH2 X -XR

Chuyen v tr R .. + + R C CH2 R C CH2 R R R

Mt s phn ng th, tch loi, cng hp c th xem l phn ng oxy ha kh. V trong qu trnh phn ng c s thay i s oxy ha ca mt hay nhiu nguyn t trong phn t. Cc phn ng c s tng v gim s oxy ha (hay s nhng v thu in t) gi l phn ng oxy -ha kh.

56

2. Khi nim v c ch phn ng Phng trnh ha hc thng thng ch trnh by cc cht u v cui ca h phn ng m khng cho bit qu trnh ha hc c thc hin bng cch no v tin trnh din bin ca phn ng. C ch phn ng ha hc l con ng chi tit m h cc cht phn ng phi i qua to ra sn phm. Cc qu trnh phn nh cc bc c bn ca phn ng, s ct t lin kt, s hnh thnh lin kt mi, hnh thnh cht trung gian v phc hot ng (trng thi chuyn tip); tin trnh lp th, s solvat ha ... 2.1. Ct t lin kt v hnh thnh cc tiu phn phn ng Mt lin kt c th b ct t theo kiu d ly hoc ng ly. V d c lin kt cng ha tr gia hai nguyn t hoc hai nhm nguyn t A v B: 2.1.1. S ct t d ly Khi lin kt b ct t, cp in t lin kt thuc A hoc B

. A__B .
A+ v B- l cc ion.

A+ + B-

hoac

. A__B .

A- + B +

Nu tiu phn to thnh A+ hoc B+ l R+ th tiu phn gi l carbocation. Nu tiu phn B - hoc A - l R - th tiu phn gi l carbanion. Carbocation v carbanion l nhng tiu phn ng vai tr quan trng trong cc phn ng th, cng hp v tch loi.
2.1.2. S ct t ng ly Khi lin kt b ct t, cp in t c phn i. Trn mi tiu phn mang mt in t t do. Cc tiu phn gi l gc t do.

. A__B .
. CH3-CH2 ,

. . A + B
la cac goc t do

. CH2=CH-CH2

Cc gc t do tham gia cc phn ng theo c ch gc.

2.1.3. Cu to v tnh cht tiu phn to thnh khi ct t lin kt

Carbocation Carbocation (k hiu R+) l nhng cation m trung tm in tch dng nguyn t carbon (trn orbital p khng c electron - orbital trng). Carbocation c to thnh khi ct t d ly lin kt cng tr hoc khi cng hp proton H+ vo ni i, ni ba.
57

CH3CH=CH2

CH3CH_CH
+

Carbocation c cu trc phng. Ba lin kt ca carbon C+ nm trong mt mt phng. Orbital trng (khng c in t) c trc i xng thng gc vi mt phng .
Carbanion

Carbanion (k hiu R) l nhng anion m in tch m (2 in t) tp trung ch yu nguyn t carbon (trn orbital p c 2 in t). Carbanion c to thnh khi ct t d ly lin kt cng ha tr . H_CH2CHO + HO- -CH2CHO + H2O

Carbanion c cu trc hnh thp, tm l nguyn t carbon v 4 nh l 3 nhm th v cp in t.

Gc t do

Gc t do (k hiu R) l nhng tiu phn c cha 1 in t t do (khng cp i) nguyn t carbon (trn orbital p c 1 in t). Gc t do c to thnh do s ct t ng ly lin kt cng tr di tc dng ca nh sng hoc nhit. Gc t do c cu trc phng. Ba lin kt ca carbon C . nm trong mt mt phng. Orbital p cha mt in t thng gc vi mt phng . Hnh 5.1 minh ho trng thi khng gian ca carbocation, carbanion v gc t do.
+

CH3CHCH3
CH3

CH3CHCH3
CH3

CH3CHCH3
CH3

CH3

C
CH3 H H CH3

:
H CH3

CH3

Cau truc phang cua carbocation orbital p khong co eletron

Cau truc hnh thap cua carbanion

orbital p vi 2 electron

Cau truc phang cua goc t do orbital p vi 1 elctron

Hnh 5.1. Cu trc khng gian ca carbocation, carbanion v gc t do.

Carben

Carben k hiu RR'C: l tiu phn c 2 in t khng lin kt lp ngoi cng ca nguyn t carbon .
V d: H2C: , Cl2C: , CH2=CHCH:

Nu 2 in t phn phi trn 2 orbital p, carben dng lng gc. Nu 2 in t cng phn phi trn mt orbital p, trn carbon c mt orbital p trng khng c in t. Carben c dng mt ion dng ng vai tr mt tc nhn i in t .

58

Ion dng

Lng goc

H H

orbital trong orbital sp2 H H

Hnh 5.2. Cu trc ca carben H2+C: v lng gc CH2

bn ca cc tiu phn

bn ca cc tiu phn ph thuc vo cu trc in t. Mt in tch trn carbocation v carbanion cng gim th nng lng ca chng cng thp v chng cng bn (d tn ti trong cc qu trnh phn ng). Cc hiu ng electron I, C v H lm gim mt in tch c nh hng quyt nh n bn vng ca cc tiu phn.
+

Carbocation bn vng kh in tch dng c gii ta. Cc hiu ng +I v C c tc dng lm cho carbocation bn vng hn.
V d: CH3+ < CH3CH2+ < (CH3)2CH+ < (CH3)3C+ do hiu ng +I ca CH3.

CH3+ < C6H5CH2+< (C6H5)2CH+ < (C6H5)3C+ do hiu ng +C ca C6H5 Carbanion bn vng khi c cc nhm ht in t . Hiu ng -I v -C lm tng bn ca carbanion.
V d: CH3 < (CF3)2CH- < (C6H5)2CH

CH3 CH2CH2- < CH2 = CH CH2 < (CH2=CH)2CH Cc gc t do km bn v c kh nng phn ng cao. Cc nhm alkyl, aryl lm tng bn. Gc phenyl C6H5 - c kh nng c hiu ng +C hoc -C
V d: CH3. < CH3CH2. < (CH3)2CH. < (CH3)3C

CH3. < C6H5CH2. < (C6H5)2CH. < (C6H5)3C. Cc nhm th c hiu ng I , C v H v tr para trong gc p-X-C6H4CH2. lm cho bn ca gc tng ln.
2.2. Tc phn ng

Tc v ca phn ng A + B C c th c th hin qua phng trnh .

v = k [A].[B] = k c

Trong : c = [A].[B]
k l hng s tc phn ng .

[A],[B] l nng ca cc cht A v B . Theo phng trnh Arrhenius ta c .

k = P.Z .e

EA RT

59

Theo th k t l thun vi s va chm Z. Nhng khng phi tt c cc va chm u dn n phn ng ha hc. V vy cn c mt nng lng ti thiu EA gi l nng lng hot ha a cc phn t n " trng thi kch thch " lm cho cc phn t thnh cc tiu phn giu nng lng (carbocation, carbanion, gc t do). xy ra phn ng, s cc tiu phn c nng lng ti thiu bng nng lng hot ha EA c xc nh bi nh lut phn b nng lng Boltzmann. Kt qu l tc phn ng ph thuc mnh vo nhit T. Theo phng trnh trn, khi nhit tng ln khong 10oC th tc cc phn ng ha hc tng ln gp 2 n 3 ln. Khi cc tiu phn nng lng cn thit th ch c nhng va chm ca cc tiu phn nhng v tr khng gian thch hp mi lm cho phn ng xy ra. Tr s k thc nghim thng nh hn rt nhiu so vi gi tr tnh ton c t EA, T v Z. Gi tr k l thuyt v k thc nghim khc nhau bi mt i lng P. i lng P c gi l h s khng gian hay l h s xc sut . Khi nghin cu v c ch phn ng, tc phn ng cn c tnh ton theo l thuyt phc cht hot ng (hay cn gi l trng thi chuyn tip) gii thch cc trng thi ng hc ca phn ng. L thuyt ny gi thit rng trn bc ng n sn phm cui cng, cc phn t tham gia phn ng hp li vi nhau thnh mt phc cht hot ng (hay l trng thi chuyn tip). Trng thi chuyn tip c c trng bng mt cc i nng lng (im A trong hnh 5-3a) ca cc phn t tham gia phn ng. Phc cht hot ng khng phi l mt cht trung gian v n khng c cc tiu nng lng. Cc tiu nng lng ca cht trung gian trnh by trn hnh 5-3b (im B).

A
Nang lng hoat hoaEA

E
EA1

A1 Phc chat hoat ong A1 A2 Phc chat hoat ong A2 EA1

Chat trung gian B

Chat ban au

AH Chat cuoi (b)

Tin trnh phn ng

Tin trnh phn ng

(a)

Hnh 5.3. Gin nng lng v tin trnh phn ng

C th xem nng lng hot ha EA tng ng vi entanpi hot ha H. Mc trt t khng gian trng thi chuyn tip c c trng bi i lng Entropi S hot ha. Gi tr S hot ho ca trng thi chuyn tip cng m s phn nh mc cc cht phn ng tng tc a phn t hay n phn t. Bit gi tr S v H tc l bit c tin trnh v c ch phn ng xy ra.

60

Thc t khng phi nng lng hot ha EA m l nng lng t do F hot ha mi l yu t quyt nh chuyn phn t t trng thi u ln trng thi chuyn tip . F = H - T S
2.3. C ch phn ng th 2.3.1. C ch phn ng th i nhn

Phn ng th i nhn xy ra theo 2 c ch chnh. C ch lng phn t SN2 v c ch n phn t SN1.

C ch SN2

C ch lng phn t SN2 th hin trong phng trnh tc phn ng c nng ca 2 cht phn ng. Phn ng xy ra mt giai on v c trng thi chuyn tip gia cht phn ng v tc nhn i nhn Y -.
V d: CH3Cl + HO- CH3OH + Cl-

Phng trnh tc phn ng: v = k [CH3Cl] [HO-] Trng thi chuyn tip:
H HO + H H Tac nhan ai nhan Chat phan ng C Cl

HO

H H

Cl

HO

H C H San pham cuoi

H + Cl

Trang thai chuyen tiep

trng thi chuyn tip lin kt c sp b ct t v lin kt mi sp to thnh. Tc nhn i nhn HO - (tng qut Y -) tn cng vo carbon t pha sau ca Cl (nhm i ra X) Sn phm ca phn ng c thay i cu hnh. Nu cht phn ng ban u c cu hnh R th sn phm phn ng s c cu hnh S v ngc li.

C ch SN1

Xy ra theo 2 giai on. Giai on chm l giai on quyt nh tc phn ng. Trong phng trnh tc phn ng ch c nng ca cht phn ng. Giai on chm quyt nh tc phn ng l giai on to ra carbocation trung gian R+.
V d: HO- + (CH3)3C_Br

(CH3)3C_OH + Brv = k [(CH3)3C_Br]

Phng trnh tc phn ng: Giai on chm: (CH3)3C_Br

(CH3)3C+

Br -

Giai on nhanh: (CH3)3C+ + HO - (CH3)3C_OH

61

Phn ng xy ra theo c ch SN1 c s racemic ha. C s racemic ha v carbocation R+ to ra giai on chm c cu trc phng v tc nhn i nhn HO tn cng vo carbon v 2 pha ca mt phng vi kh nng nh nhau. V vy c 2 sn phm vi cu hnh ngc nhau c to thnh v c s racemic ha. C th minh ha qu trnh lp th nh sau:
HO CH3 HO C CH3 CH3
CH3 CH3 CH3

HO -

C+

CH3 CH3 CH3

OH

San pham cuoi

Carbocation
+

San pham cuoi

Phn ng xy ra theo c ch SN1, c carbocation R hnh thnh nn kh nng c s chuyn v v to thnh sn ph l th hoc tch loi (xem thm phn alcol). Cc tc nhn i nhn Y trong phn th i nhn c th l anion (HO-, Cl-, Br -, I-), carbanion (-CH2CHO ...), cc tiu phn c cp in t lin kt (anion CH3O- ..), hoc cc phn t c cp in t khng lin kt (NH3...)
Ch : Tnh base ca Y- cng mnh th tnh i nhn ca Y- cng mnh.

Ngc li tnh i nhn ca Y- mnh khng nht thit n l mt base mnh.

V d: HO l mt base mnh ng thi HO cng l mt tc nhn i nhn mnh.

Ngc li ion I l mt base rt yu nhng n l mt tc nhn i nhn mnh. C ch phn ng th SN1 xy ra c tnh cht ion gia tc nhn i nhn Y- v carbocation R+ (hnh thnh giai on chm). Phn ng th nhm X trong phn t R _X v tc nhn i nhn Y-, nu X gn trc tip vi carbon bc nht RCH2 _ X phn ng ch yu xy ra theo c ch SN2 RCH2_X + HO- RCH2_OH + X-: c ch SN2. Phn ng th nhm X trong phn t R X v tc nhn i nhn Y-, nu X gn trc tip vi carbon bc ba (R)3C X phn ng ch yu xy ra theo c ch SN1 (R)3C_X + HO- (R)3C_OH + X- c ch SN1 Phn ng th nhm X trong phn t R _X v tc nhn i nhn Y-, nu X gn trc tip vi carbon bc hai (R)2CH_X phn ng xy ra theo c ch SN1 hoc SN1 ph thuc vo cc yu t cu trc hoc dung mi. (R)2CH _ X + HO- (R)2CH_OH + X- c ch SN1 hoc SN2

Dung mi c nh hng n c ch phn ng. Dung mi phn cc lm cho phn ng u tin xy ra theo c ch SN1. Dung mi khng hoc t phn cc lm cho phn ng u tin xy ra theo c ch SN2.

62

2.3.2. C ch phn ng th i in t SE

Phn ng th i in t ch yu xy ra cc hp cht ca hydrocarbon thm v d vng thm (xem thm phn hydrocarbon thm v d vng). Tc nhn i in t Y + l nhng tc nhn mang in tch dng (+NO2, Br+) hoc phn t thiu in t (SO3, CO2...). Cht phn ng l nhng hp cht vng c cu trc thm Ar -H (ph hp vi cng thc Huckel) .
Phc
H E+

Phc + E Chat trung gian Chat phan ng

H H

H E

San pham

Tien trnh phan ng

HnhHnh 5.4: c qua trnh cua phaphngng th in t t 5-4. CaCc qu trnh ca n n the ai ie in

Phn ng th i in t xy ra qua nhiu giai on.

Giai on tng tc gia E+ v Ar -H to phc . Giai on chuyn phc hnh thnh phc . Giai on to sn phm cui cng.

Thc t trong phn ng th i in t thng c vai tr ca xc tc (xem phn hydrocarbon thm).

H E+ Phc H + E Phc + H E E + H+ San pham

+ E+

T cht phn ng ban u n sn phm cui tri qua s hnh thnh cc phc hot ng (trng thi chuyn tip ng vi cc cc i nng lng trn gin nng lng (hnh 5-4).
2.3.3. C ch phn ng th gc t do SR

Phn ng th theo c ch gc l phn ng dy chuyn c ba giai on:

Giai on khi mo. Giai on pht trin mch v to sn phm. Giai on tt mch v kt thc phn ng .

63

V d: Phn ng clor ha alkan xy ra nh sau .

Giai on khi mo: Giai on pht trin mch:

Cl_Cl

Cl. + Cl.

R_H + Cl. R. + HCl tip tc...............................

Giai on tt mch v kt thc phn ng: R. + R. R _ R Cl. + Cl. CL - CL Giai on quyt nh tc phn ng l giai on pht trin mch . Gc t do c cu trc phng, phn t Cl2 tn cng t 2 pha ca mt phng (tng t c ch th SN1) v vy sn phm phn ng dn n s racemic ha.
2.4. C ch phn ng cng hp (k hiu Ad) 2.4.1. C ch phn ng cng hp i in t AdE

Phn ng cng hp xy ra gi phn t E _Y v cht phn ng c lin kt i C =C v lin kt ba C C l phn ng cng hp i in t c cc giai on:
Giai on to tc nhn i in t E+ v anion Y - t phn t E Y Tng tc ca E+ vi cht phn ng c ni i, ba to thnh carbocation R+ Tng tc gia carbocation R+ v Y- v to thnh sn phm cng hp.

Tng tc ca E+ vi cht phn ng c ni i, ba to thnh carbocation R+ xy ra chm nn n l giai on quyt nh tc phn ng.
V d: Phn ng cng hp ca HBr vo propylen CH3CH=CH2 xy ra nh sau:

H_Br

H+

+ Br+ H+

H+ l tc nhn i in t E +; Br l Y -.
CH3 CH3 + CH + CH2 CH3 CH2 H +

CH3

CH

CH2

Cham

hoac CH3

CH

CH2

CH3 CH3

+ CH CH2

CH3 + Br + CH2 + Br -

CH3 CH3

CHBr CH2

CH3 CH2Br

Nhanh

Carbocation to thnh l vng tam gic cu to phng. Mt in tch dng trn hai nguyn t carbon l nh nhau. Y - (Br-) tn cng v hai pha ca mt phng vi xc sut nh nhau. V vy cng lc hai sn phm cng hp c to thnh. Gii thch iu theo s di y:
H

CH3

CH Br

CH2

CH3

CH Br -

H +

Br Br

CH2

CH3

CH H

CH2

64

Dung mi v cu to phn t E _Y c nh hng quyt nh n s hnh thnh tc nhn i in t E+.

2.4.2. C ch phn ng cng hp i nhn

Phn ng cng hp i nhn thng xy ra gia tc nhn i nhn Y - vi cc hp cht c ni i C =O, C=N_ .... Phn ng c cc giai on nh sau:
S tng tc gia tc nhn i nhn Y - vo trung tm mang in tch dng ca carbon trong nhm carbonyl ( C=O +C O) to thnh ion mang in tch m trn oxy.

RCH=O + Y-
+

RCHY_O-

Ion m to thnh s kt hp ion dng (H ) to thnh sn phm cui cng.

RCHY_O- + H+ RCHY_OH Nhiu hp cht c cha nhm chc carbonyl tham gia phn ng cng hp i nhn v ng thi km theo s tch loi. C th xem loi phn ng ny nh l mt loi phn ng th hoc phn ng cng v tch''
O R C X + YO R C Y + X-

in tch dng trn nguyn t carbon ca C =O cng ln th kh nng phn ng cng cao. Thay X bng nhm th c nh hng in t th kh nng phn ng thay i.
O R C Cl > O R C O O C R' .. O

> R C O H > R C O R' > R C O .. .. -

2.5. C ch phn ng tch loi (k hiu E)

Phn ng tch loi to lin kt i xy ra theo 2 c ch: c ch lng phn t E2 v c ch n phn t E1.
2.5.1. C ch tch loi E2

Phn ng xy ra theo cc giai on.

Tng tc gia mt base mnh vi cht phn ng hnh thnh trng thi chuyn tip. S tch loi xy ra v to sn phm c lin kt i.
Tng qut:
Y- + Base manh H C C X Y H C C X

YH + C

C + X-

Chat phan ng

Trang thai chuyen tiep

San pham

65

V d: Phn ng tch loi HBr t ethylbromid di tc dng ca C2H5O l mt base mnh to thnh ethylen c c ch nh sau:
H CH3 C2H5O + H Br H H H CH3 C C
Br

H H C2H5O Trang thai chuyen tiep

CH3 + C2H5OH

+ Br H

iu kin v ha lp th cho c ch E2 xy ra khi 4 trung tm phn ng (H C C Br) trn mt mt phng. H v Br v tr trans vi nhau (v tr anti). Minh ha c ch theo cch biu din hnh chiu Newman:
CH3 H
H

Br

H H

+ C2H5O -

CH3 H

Br

H H

- Br - C2H5OH

CH3 H

C H

2.5.2. C ch tch loi E1

Phn ng xy ra theo 2 giai on.

Cht phn ng to carbocation R+ l giai on chm. Tch H+ v to ni i l giai on nhanh.
Tng qut:
H C C X H C C+ + XCham

Chat phan ng H C C+

Carbocation C C San pham + H+ Nhanh

Carbocation

V d: Tch HBr khi 2-Brom-2,3-dimethylbutan .

CH3CH3 H C C Br CH3 CH3

- Br -

CH3 CH3 H C C+ - H+ CH3 CH3 Carbocation

CH3 CH3

CH3 CH3

Cc phn ng c s cnh tranh ln nhau. Khi tin hnh phn ng th thng km theo phn ng tch loi. Cc iu kin nh dung mi, nng , nhit c nh hng ng k n c ch phn ng.

66

Chng 6

CC PHNG PHP HA HC V VT L XC NH CU TO CHT HU C

Mc tiu hc tp 1. Hiu v bit cch s dng cc phng php ha hc v vt l xc nh cu trc ca phn t 2. ng dng ca quang ph t ngoi, hng ngoi v cng hng t ht nhn trong vic xc nh cu trc phn t.

Ni dung
Mt cht hu c c ng dng trong thc t phi bo m tinh khit, phi tha mn v thnh phn cc nguyn t ha hc v cng thc cu to. Xc nh cng thc cu to ca mt cht hu c tch/chit c t ngun gc thin nhin hay tng hp c l cng vic rt cn thit v quan trng trong ha hu c. C th xc nh cu to cht hu c bng phng php ha hc hay vt l.
1. Phng php ha hc ng dng phng php php ha hc xc nh cng thc phn t v nhm chc ha hc bng cc phn ng c trng. 1.1. nh tnh v nh lng nguyn t

nh tnh v nh lng cc cht hu c l xc nh s hin din cc nguyn t v thnh phn nh lng ca cc nguyn t trong mt cht hu c.
1.1.1. nh tnh cc nguyn t v nhm chc

xc nh s c mt cc nguyn t c trong cht hu c, thng tin hnh v c ha, ngha l chuyn cc nguyn t v dng ion v dng cc phn ng nh tnh xc nh cc ion . V d: V c ha hp cht hu c th carbon s chuyn thnh CO2 hoc CO32-, nguyn t halogen (X ) chuyn thnh X -, nguyn t N chuyn thnh CN - ... Dng cc phn ng nh tnh c trng xc nh cc ion CO32-, ion X-, ion CN-. nh tnh cc nhm chc bng cc phn ng c trng. V d: Chc OH alcol tc dng vi natri c hydro thot ra. Chc aldehyd cho phn ng trng gng vi thuc th Tollens... Ngy nay c cc phng php vt l xc nh cc nhm chc mt cch nhanh chng v chnh xc. 67

1.1.2. nh lng cc nguyn t

Xc nh thnh phn phn trm v khi lng cc nguyn t trong cht hu c theo 2 phng php ch yu sau:
Phng php Dumas

nh lng cc nguyn t C, H, N, S v halogen c trong cc cht hu c.

Nguyn tc: t chy cht hu c bng mt lung kh oxy. Cc nguyn t chuyn thnh CO2, H2O, N2, SO2, X2. Hp thu cc kh sinh ra vo cc cht thch hp. Xc nh khi lng cc kh v suy ra thnh phn phn trm cc nguyn t c trong hp cht hu c. Ngy nay c cc my mc tinh vi nh lng chnh xc cc nguyn t.

Phng php Kjendall

ng dng phng php Kjendall nh lng nguyn t nit c trong cc cht hu c. Phng php ny rt ph bin xc nh nit trong cc cht amin v acid amin. Nguyn tc ca phng php Kjendall l chuyn nit v dng NH3 hay NH4+ sau dng phng php chun xc nh hm lng NH3 hay NH4+ v suy ra thnh phn phn trm ca nit c trong cht hu c. 2. Phng php vt l ng dng cc phng php vt l xc nh cc tiu chun v tinh khit v xc nh cc nhm chc, cc lin kt c trong hp cht hu c. 2.1. Cc tiu chun vt l 2.1.1. Nhit nng chy v nhit si

Nhit nng chy

Cc cht hu c dng rn tinh khit c nhit nng chy xc nh. Nhit nng chy ca mt cht l nhit m tng rn v tng lng nng chy ca cht trng thi cn bng vi nhau. Nhit m tt c cc tinh th u nng chy c coi l im kt thc ca khong nhit nng chy.
Nhit si

Cht hu c lng tinh khit c c trng bng nhit si. Nhit si ca mt cht l nhit m ti cht lng bin thnh hi. Tng lng v tng hi trng thi cn bng. Nhit si ca cht lng ph thuc vo p sut. Cht lng tinh khit lun c nhit si xc nh. Nhit nng chy, nhit si l nhng tiu chun xc nh tinh khit ca cht rn hoc cht lng.
2.1.2. Ch s khc x

Ch s khc x l mt tiu chun nh gi tinh khit ca cht lng. Theo nh lut Snellius, nu nh sng n sc b khc x ti b mt ranh gii gia hai mi trng ta c: 68

Moi trng 1 Moi trng 2

n=

sin sin

= C1
C2

C1 va C2 la toc o ang sang trong moi trng 1 va 2

Thng ngi ta ly khng kh lm mi trng so snh. Ch s khc x ph thuc vo nng , nhit v bc sng ca nh sng.
2.2. Cc phng php sc k

S dng cc phng php sc k tch ring cc cht trong hn hp v cn dng phng php sc k xc nh tinh khit ca mt cht. Sc k l mt phng php vt l dng tch cc thnh phn ra khi hn hp bng cch phn b chng thnh 2 pha: mt pha c b mt rng gi l pha c nh v pha kia l mt cht lng hoc cht kh gi l pha di ng, di chuyn i qua pha c nh. C 2 loi sc k: sc k lng v sc k kh.
2.2.1. Sc k lng

Sc k lng l phng php sc k dng cht lng lm pha di ng. Trong sc k lng c cc k thut:
Sc k giy: Pha tnh (pha c nh) l giy. Sc k lp mng: Pha tnh l mt lp mng cht hp ph c trng bng phng v u n trn mt tm knh hoc kim loi. Sc k ct: Pha tnh l cht rn c nhi thnh ct. Trong k thut sc k ct, ty theo bn cht ca cht rn lm ct cn c chia thnh: + Ct c in: Ct n gin vi cht hp ph thng thng v c hoc hu c.

Ct trao i ion: Ct l cht trao i ion m (anion) hoc dng (cation).

+ Ct gel hoc lc gel (gel filtration) : Pha c nh l mt loi gel tng hp c l xp xc nh dng lc cc cht c kch thc phn t khc nhau. Sc k lng cao p (high pressure liquid chromatography) cn gi l sc k lng hiu nng cao HPLC (high performance liquid chromatography).
2.2.1. Sc k kh

Sc k kh l phng php sc k dng cht kh lm pha di ng. Da vo pha c nh, cn chia ra:
Sc k kh -rn: Pha c nh l cht rn. Sc k kh -lng: Pha c nh l cht lng.

69

2.3. Cc phng php ph

Khi mt cht hu c hp th nng lng bc x in t th phn t c th tri qua nhiu dng kch thch. Cc kch thch c th l kch thch chuyn dch in t, kch thch quay, kch thch lm thay i spin ht nhn nguyn t, kch thch lm bin dng lin kt, nu nng lng cao c th gy ion ha phn t.
Bng 6.1: Vng bc x in t
Vng ph in t Bc x gama, tia X di sng Nng lng kch thch Dng kch thch

< 100 nm

> 286 Kcal

V tia v tr
- Tia t ngoi

Xa (vng chn khng) Gn (vng thch anh)

- Kh kin - Hng ngoi

100-200 nm 200-300 nm 350-800nm 0,8-2,0 m 2-16,0 m 16,0-300 m cm mt

286 - 143 Kcal 143 - 82 Kcal 82 - 86 Kcal 36 - 14,3 Kcal 14,3 - 1,8 Kcal 1,8 - 0,1 Kcal 10-4 Kcal 10-6 Kcal

in t in t in t Bin dng lin kt -nt-ntQuay Thay i spin ht nhn

Hng ngoi gn Hng ngoi Hng ngoi xa

- Vi sng - Tn s radio

Mi dng kch thch u cn n mt nng lng nht nh v s hp th tng ng vi mi mc nng lng s xy ra mi vng khc nhau trn ph in t . Bng 6-1 lit k vng ph electron, di sng, nng lng kch thch v dng kch thch khi chiu bc x vo cht hu c. Nu chng ta v th ph thuc ca nng lng bc x c truyn qua vi tn s (), s sng (), bc sng (),chng ta nhn c mt ph hp th. Cc phn t hu c c cu to khc nhau th c ph hp th khc nhau. V vy quang ph hp th l phng php xc nh cu trc phn t rt chnh xc v hiu qu. Ghi nhng ph hp th c tin hnh bng nhng thit b (my quang ph) gm c nhng b phn ch yu l ngun bc x A, mt cuvet o B ng cht kho st, mt my n sc C (cch t hay lng knh) v mt thit b pht hin bc x D vi my ghi cc tn hiu c phng i E.
A B C D E

Hnh 6.1: S mt quang ph k

Ty thuc vo v tr tn s hp th trong di tn s ca bc x in t m ta gi chng l quang ph Rnghen, quang ph electron, quang ph hng ngoi hay quang ph vi sng. Ngy nay quang ph t ngoi (UV), quang ph hng ngoi (IR), quang ph cng hng t ht nhn (NMR) v khi ph l nhng phng tin quan trng v chnh xc xc nh cu to cc cht hu c. 70

2.3.1. Quang ph t ngoi (UV)

S hp th trong vng t ngoi v kh kin ph thuc vo cu trc in t ca phn t. S hp th y gy ra s chuyn dch cc in t t orbital c bn ln orbital c nng lng cao hn trng thi kch thch. Ph t ngoi ch p dng xc nh cu trc ca phn t c h thng lin kt - v p -. Trn ph t ngoi cc v tr bng (hay cn gi l di) hp th c o bng di sng (lam- a). n v di sng trong vng t ngoi thng c biu th bng nanomet (1nm = 10-7cm). Cng hp th c biu th bng hp th phn t max hoc logmax . S hp th c nhiu ng dng trong quang ph t ngoi l trong vng t 200 - 380 nm, gi l vng t ngoi gn. Nng lng ca mt phn t l tng cc nng lng electron, nng lng dao ng v nng lng quay ca chng. ln cc nng lng ny gim theo th t: Nng lng in t > Nng lng dao ng > Nng lng quay Nng lng hp th trong vng t ngoi gy ra s bin i nng lng electron, do s chuyn dch in t ha tr trong phn t t orbital trong trng thi c bn (thng l orbital p khng lin kt hoc orbital lin kt) ln orbital c nng lng cao hn (orbital phn lin kt * hoc *).
Bng 6.2: Trnh by cu trc in t v s chuyn dch ca chng trong mt s hp cht hu c.
Cu trc electron Hp cht Chuyn dch electron * max (nm) max Bng hp th -

Etan H2O Methanol Ethylen Acetylen

135 167 183 165 173 150 188 279 217 210 180 200 255 208 262 210 270

7.000 500 10.000 6.000 1.860 15 21.000 11.500 60.000 8.000 215 2.460 174 6.200 1.450

n n

* * * * * * * * * *thm *thm *thm *thm *thm *thm *thm

R K K E1 E2 B E2 B E2 B

v n

Aceton

n n

- v n thm

1,3-Butadien Acrolein

Benzen

Toluen

-n thm

Phenol

71

Mt s thut ng thng dng trong quang ph t ngoi:

Nhm mang mu (Chromophore): l nhng nhm khng no gy ra hp th in t. Cc nhm nhm mang mu c: C=C, C=O, NO2. Nhm tng mu (Auxochrome): l nhng nhm chc no hoc c in t p khng lin kt. Cc nhm chc ny c tc dng ko di h thng lin hp. Khi gn cc nhm ny vi nhm mang mu th nh hng n di sng hp th v cng hp th.

Cc nhm tng mu thng gp:

-OH, -NH2, - Cl

Hypecromic (Hypechromic): l s tng cng hp th. Hypocromic (Hypochromic): l s gim cng hp th. Chuyn v hng hng hay chuyn v bathocromic (Bathocromic shift): l s chuyn dch bng hp th sang bc sng di hn do c cc nhm th hoc nh hng ca dung mi. Chuyn v hng lam hay chuyn v hypsocromic (Hypsochromic shift): l s chuyn dch bng hp th sang bc sng ngn hn do cc nhm th hoc dung mi. C th trnh by s chuyn dch in t trong mt s hp cht nh sau: + S chuyn dch in t ca phn t butadien v hexatrien c m t theo m hnh di y:

4 3 2 1
Trang thai c ban cua butadien
217 nm

6 5 4
h

3 2 1

258 nm

Trang thai kch thch cua butadien

Trang thai c ban cua hexatrien

Trang thai kch thch cua hexatrien

+ S chuyn dch in t ca phn t aceton v methylvinylceton:

4
h

1
Aceton

3 2 1

h (n-) n

Methyl vinyl ceton

72

 Hp th c trng ca mt s nhm chc hu c. + Cc hp cht no ch c lin kt hoc electron khng lin kt (n hoc p) khng cho cc bng hp th trong vng t ngoi gn. V vy alcol thng c dng lm dung mi trong vic o quang ph t ngoi. + Cc hp cht hu c cha nhm chc c lin kt (C=C, C=N-, C=O, N=O, S=O) thng c cc bng hp th c trng trn ph t ngoi. Cc nhm chc ny gi l nhm mang mu.
Bng 6.3: di sng v chuyn dch in t cc nhm mang mu
Nhm mang mu Cu to V d

max
(nm)

max
15.00 10.00 6.000 900 15 16 60 5.000 4.500 100 12 1.120 18.60 -

Chuyn dch electron - * - * - * - *

Ethylenic Acethylenic Carbonyl

RCH=CHR RCCR RR1C=O RCH=O

CH2=CH2 CHCH CH3COCH3 CH3CHO CH3COOH CH3CONH2 (CH3)2C=N-OH CH3CN CH2-N=N C4H9-N=O C2H5ONO2 C5H11NO CH3NO2 (CH3)2SO2

165 193 173 188 279 290 204 208 190 160 347 300 270 218 271 180

n - * n - * n - * n - *
- * - *

Carboxyl Amid Azometin Nitril Azo Nitroso Nitrat Nitrit Nitro Sulfon

RCOOH RCONH2 C=N-CN -N=N-N=O -ONO2 -ONO -NO2 - SO2 -

n - * n - *
- *

n - *

+ Nu trong phn t c nhm tng mu hoc c h thng lin hp th bc sng s tng ln. V d:
Bng 6.4: nh hng cc nhm tng mu n bc sng
Hp cht 1 2 3

CH3COOH CH3(CH=CH)2COOH C6H6 C6H5Cl C6H5OH C6H5NO2

204 254 204 210 210 252

256 265 270 280

330

73

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1.1 1.2 1,3 1,4 1,5 200 250 300 350 400

(nm)

Hnh 6.2: Ph t ngoi ca ceton oxyd mesityl (CH3)2C=CHCOCH3

2.3.2. Quang ph hng ngoi (IR)

Cc cht hu c hp th bc x hng ngoi nhng tn s trong vng t 10.000 -100cm-1(1-100m) v bin thnh nng lng dao ng ca phn t. Trong nhng dao ng ca phn t, cc nguyn t c th chuyn ng theo chiu ca lin kt gi l dao ng ha tr hoc chuyn ng ca nguyn t lm bin dng (quay) lin kt gi l dao ng bin dng. Nng lng dao ng bin dng thp hn nng lng dao ng ha tr. Phn t H2O c cc dao ng nh sau:

3756cm-1

3655cm-1

1595cm-1

Dao ong hoa tr khong oi xng

Dao ong hoa tr oi xng

Dao ong bien dang goc len ket

Hnh 6.3: Cc dao ng ca phn t nc

Tn s hay di sng hp th ca mi cht ph thuc vo khi lng tng i ca cc nguyn t, vo hng s lc lin kt, vo cu trc hnh hc ca phn t.

d =
74

1 2

m1.m2 m1+m2

 l tn s dao ng ca lin kt. l khi lng rt gn m1 v m2 l khi lng ca 2 nguyn t lin kt vi nhau K l hng s lc lin kt. V tr di hp th c o bng di sng hoc bng s sng . n v di sng s dng trong vng hng ngoi l micromet - m (m = 10-6 m). n v s sng c dng l cm -1.

cm-1 =

1 104 m

Cng hp th c biu th bng truyn nh sng (Transmittance) vit tt l T, hoc bng hp th (Absorbance) vit tt l A.

A = log ( 1 ) T
Xut hin mt s di hp th nht nh trong ph hng ngoi l c trng s c mt ca mt s nhm chc xc nh trong phn t. V vy ph hng ngoi c ngha phn tch cu trc phn t cc cht hu c. Cc cht hu c thng hp th trong vng hng ngoi t 4.000 - 400cm-1 (2,5-25m).
Bng 6.5: Tn s c trng cc chc hu c
Hp cht Tn s cm -1 Cng Dao ng lin kt

Alkan

2850-3000 1450-1470 1370-1380 720 - 725

s s s m m m m s s m m m f f m f tf

C-H dao ng ho tr CH2 v CH3 bin dng

Alken RCH=CH2 3080-3140 1800-1860 1645 990 910 R2C=CH2 3080-3140 1750-1800 1650 890 Alkyn RCCH 3300 2100-2140 600-700 RCCR 2190-2260
C-H

=C-H

C=C C-H =C-H C=C C-H

CC
C-H

CC

75

Bng 6.5 (tip)

Hp cht Tn s cm -1 Cng Dao ng lin kt

Alkyl halogenid R-F R-Cl R-Br R-I Alcol RCH2OH

1000-1350 700-850 500-600 200-500 3600 3400 1050 3600 3400 1150 3600 3400 1200 1070-1150 2500-3300 1760 1725 2720, 2820

tf f f f v f f v f f v f f f v f f m

C-F C-Cl C-Br C-I O-H O-H C-O O-H O-H C-O O-H O-H C-O C-O O-H C=O C=O C-H

R2CHOH

R3COH

Ether Acid R-COOH Aldehyd R - CHO

Hnh 6.4 l ph hng ngoi IR ca phn t 2-methylprophanol

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400

3360

1200

Hnh 6.4: Ph hng ngoi (IR) ca phn t 2-methylpropanol.

2.3.3. Quang ph cng hng t ht nhn (RMN)

Cc ht nhn nguyn t c proton v ntron. Nhng ht nhn c s l proton hoc s l ntron u c momen t . 76

Bng 6.6: T tnh ca mt vi ht nhn nguyn t

Ht nhn
1

S proton 1 6 6 7 8 9 15 16

S ntron 0 6 7 7 8 10 16 16

Spin 1/2 0 1/2 1 0 1/2 1/2 0

Momen t 2,79267 0.00 0,70216 0,40357 0,00 2,6275 1,1306 0,00

H C C N F

12 13 14 16

O P S

19 31 32

Nu mt ht nhn nh vy nm trong mt t trng ng dng Ho (t trng tnh, t trng c nh, t trng bn ngoi) th momen t ca ht nhn c hai kh nng nh hng khc nhau. Kh nng nh hng ca ph thuc vo s lng t spin ca ht nhn. nh hng th nht song song vi hng ca t trng ng dng Ho k hiu l spin . nh hng th hai i song vi t trng ng dng k hiu spin .

Ho

Momen t hat nhan

Momen t hat nhan trong t trng

Hnh 6.5: S nh hng ca momen t ht nhn

Spin trng thi nh hng song song - spin c mc nng lng thp. Nu tc dng mt tn s bc x thch hp ln phn t hu c ang t trong t trng Ho, proton c spin hp th nng lng, b kch thch v chuyn dch ln mc nng lng cao hn lm thay i nh hng thnh spin . Hin tng gi l s cng hng t ht nhn. Ghi li nhng tn hiu cng hng, thu c ph cng hng t ht nhn (NMR).

Ho

Hnh 6.6: S thay i nh hng spin do hp th nng lng

o trng hp cng hng, ngi ta a mu hp cht kho st (cht lng hay rn) vo t trng khng i Ho (trng ng dng). Hp cht c bao quanh bi mt bobin cm ng to ra mt trng xoay chiu cao tn c tn s . 77

Cng Ho ca trng c thay i cho n khi thu c trng hp cng hng. Mu tip nhn nng lng ca trng xoay chiu v nhn bit bi s bin thin ca ngun pht sng cao tn. S bin thin dng in c o v ghi li bi my ghi. S my cng hng t ht nhn c trnh by trn hnh 6-7

Ong ng mau
... ... ... ... ... ...

H o Cc t trng N

S Cc t trng H o

May ghi Nguon phat song cao tan

Hnh 6.7: S my cng hng t ht nhn

Hnh 6.8 l ph cng hng t ht nhn ca ethanol vi phn gii thp

CH3

CH2 HO

Hnh 6.8: Ph RMN ca ethanol vi phn gii thp.

Cc thng s phn tch ph RMN: Hng s chn v chuyn dch ha hc Nu ht nhn b che chn bi mt v in t th v in t lm yu t trng chung quanh ht nhn. Ta c biu thc: Hhiu dng = Ho - Ho l hng s che t (hng s chn) Tn hiu cng hng ch xut hin mt cng t trng bn ngoi Ho ln hn so vi mt ht nhn khng b che chn. Hiu ng ny c gi l chuyn dch ha hc (Chemical shift), bi v n ph thuc vo thuc tnh in t bao quanh ht nhn (cu trc ha hc). chuyn dch ha hc k hiu l . 78

 xc nh v tr ca mi dng proton trn ph NMR ngi ta dng mt cht lm chun. Cht chun thng dng l TMS (tetramethyl silan (CH3)4Si). Mc chnh lch v v tr hp th gia proton cht th v proton cht chun l chuyn dch ha hc ca cht th. n v dng biu th chuyn dch ha hc l (delta) hoc ppm (phn triu). Nu pic ca TMS ti v tr hp th 60 Hz ( 60) trong tn s bc x in t 60MHz th s l 1, 00 hoc 1, 00 ppm.

( hoac ppm ) =

60 60.106

.106 = 1,00

Trong h thng n v (hoc ppm) ngi ta qui c v tr hp th ca TMS l 0 Hz ( = 0 ppm). chuyn dch ha hc ca proton cht th s c so snh vi tr s ny. Cn c h thng n v khc gi l (tao) cng c s dng o chuyn dch ha hc. Theo h thng n v ny th tr s hp th ca TMS l 10.

= 10,00 -
Ph NMR ca ethanol (hnh 6-8) c 3 tn hiu cng hng tng ng vi nhn hydro ca nhm OH, CH2 v nhm CH3, v proton ca cc nhm trn c min ph cn khc nhau v mt ha hc. Cc proton ca nhm methyl b che chn mnh nht, proton ca nhm OH b che chn yu nht. S tng tc spin - spin v hng s tng tc spin -spin J Khng phi lc no mi dng proton ng lng cng cho mt nh ring bit. Nhiu trng hp, mt dng proton li th hin s hp th ca n bng mt vch hp th nhiu nh. C hin tng l do cc proton ng cnh nhau tng tc spin - spin vi nhau. Hin tng tng tc spin -spin xy ra l v cc in t lin kt c xu hng ghp i spin ca n vi spin ca proton gn nht bn cnh. Spin ghp i ny li nh hng n proton bn cnh tip theo v gy nn cc t trng ca cc ht nhn bn cnh. T trng ny tc ng ln proton v xut hin s cng hng ng thi cho cc tn hiu. Cc tn hiu ny chnh l cc nh i (doublet), nh ba (triplet), nh t (quartet)..., nh a (multiplet) trn ph NMR. Khong cch gia 2 nh tch ra c o bng Hz gi l hng s tng tc spin -spin k hiu J (cn gi l hng s ghp spin). Cn c vo cc gi tr v J thu c trn ph NMR ngi ta bin lun v tm cng thc cu to ph hp ca cht hu c.
V d: o ethanol trn my c phn gii cao, ph NMR ca ethanol c cc nh 3, nh 4.., (hnh 6-9).

79

-CH3 -CH2TMS

-OH

ppm

Hnh 6.9: Ph RMN ca C2H5OH vi phn gii cao

2.3.4. Ph khi (MS)

Ph khi l phng php phn tch s dng mt chm in t c nng lng cao (70 von electron) bn vo cht cn xc nh cu trc, ph chng thnh tng mnh (fragmentation) ion mang in tch dng. My pht hin cc ion ny v ghi thnh pic vi cng khc nhau tng ng vi khi lng ca chng. l khi ph.
V d: Cc mnh ion to thnh khi bn chm in t vo phn t 2-methylpentan. Trc tin phn t mt mt in t v b ion ha. Phn t ion ny b phn chia thnh cc mnh mang in tch dng c khi lng tng ng:
CH3

CH3CH2CH2CHCH3

+ e-

2e- +
CH3CH2CH2

CH3

CH3CH2CH2CHCH3
CH3

+ .

+ +

+ CHCH

m/e 43
CH3

CH3CH2CH2CHCH3 m/e 86

CH3

+ .

CH .
3

CH3CH2CH2CH+ m/e 71 CH3CHCH3 +

CH3

CH3CH2

m/e 57

Cc tn hiu v khi lng v cng ca cc mnh c ghi li trn ph khi. Hnh 6-10 l khi ph ca phn t 2-metylpentan. Ngy nay cc my quang ph c thm cc b phn my tnh, cho nn cc qu trnh tnh ton v v ph u c t ng v kt qu phn tch ngy cng c hon thin hn.

80

Cng o
100 80 60 40 20

43

71 57 10 30 40 50 60 70 80 86 M+ 90 100

20

m/e

Hnh 6.10: Ph khi ca 2-methylphentan

Trn y ch trnh by khi qut cc phng php ha hc v phng php vt l xc nh cu trc cht hu c. C nhiu ti liu chuyn su v lnh vc ny. C th tm tt cc giai on xc nh cu to cht hu c theo s sau:
S o cac giai oan xac nh cau tao chat hu c
Chat hu c tach chiet hoac tong hp
Tinh che (ket tinh, chng cat, sac ky)

Chat hu c tinh khiet

Xac nh cac hang so vat ly

toc

tos

nh tnh, nh lng cac nguyen to

nh tnh nhom chc

UV

IR

RMN

MS

Ket luan ve cau truc cua chat hu c

81

Chng 7

ALKAN - HYDROCARBON NO (CnH2n+2)

Mc tiu hc tp 1. c c tn cc alkan thng dng 2. Nu c ha tnh ca alkan v ng dng ca chng trong cuc sng. Ni dung 1. Ngun gc thin nhin - Cu to, ng phn, cu dng 1.1. Ngun gc thin nhin Alkan l nguyn liu t nhin c t du m, kh thin nhin. Kh thin nhin cha cc kh vi thnh phn khng c nh, thng cha 75% metan, 15% etan, 5% propan, phn cn li l cc alkan cao hn v nhiu cht khc. Kh thin nhin c dng lm nhin liu v trong qu trnh k ngh. Ngun alkan ch yu l du m, thng thu c cc cht sau:
Bng 7.1: Cc alkan trong du m
Cc cht Kh Ether du ha Xng Ligroin Gazolin Keroxin Du mazut Du bi trn Thnh phn C 1 C4 C 5 C6 C 6 C8 C7 C6 C12 C12 C15 C16 C23 C18 C22 t si < 20 20-60 60-200 60-90 85-200 200-300 200-400 300

Atphan dng phng php hydro ha than nu bng cch nghin nh than vi du nng c xc tc st v H2 nhit 450C, p sut 200-300 atm, thu c sn phm th, sau khi chng ct thu c kh, xng v sn phm du nng. 1.2. Cu to Alkan l hydrocarbon no (hydrocarbon bo ha, parafin) c cng thc chung CnH2n+2. Cht n gin nht l metan CH4. Cu to mch thng hay phn nhnh. 82

H H H H H H

H H H H

H H H H

H H H H

H H H

H H

metan

n-pentan

H H H H iso- pentan

1.3. ng phn Alkan c ng phn mch thng v phn nhnh. S ng phn tng khi s carbon tng.
Bng 7.2: S ng phn ca mt s alkan
S carbon 1 2 3 4 5 6 Tn cht Metan Etan Propan Butan Pentan Hexan S ng phn 1 1 1 2 3 5 S carbon 7 8 9 10 20 30 Tn cht Heptan Octan Nonan Decan Eicozan Tricozan S ng phn 9 18 35 75 366319 4,11.109

1.4. Cu dng Do tnh cht i xng trc ca lin kt , hai nguyn t carbon lin kt vi nhau c th quay t do quanh trc lin kt. S quay t do km theo s tiu hao nng lng. Chnh v c s quay t do quanh trc lin kt C C nn cc alkan c cc ng phn cu dng (ng phn hnh th - conformer). Etan tn ti di nhiu cu dng khc nhau. Hai dng cu dng thng thng nht l dng che khut (t bn) v dng lch (bn), hnh 7-1
H H H H H H H H H H H H H H H H H H H H Lech H H H H H HH H H H H H H

Cong thc lap the thong thng

Khuat

H Khuat

Cong thc phoi canh

H Lech Cong thc Newman

Hnh 7.1: Cch biu din cc cu dng ca etan

Che khut

Lch

M hnh phn t etan

83

Khi gc nh din bng Khi gc nh din bng

HH H H H H H H H H H H H

0; 120 ; 240 ; 360 c cc dng che khut. 60; 180 ; 300

HH H H H H H H H H H H

c cc dng lch.
HH H H H H H H H H H HH H

E
Kj/mol

11,7

goc quay

60

120

180

240

300

360

Hnh 7.2: Gin ph thuc nng lng v gc quay ca cc cu dng ca etan

H H H HH H H H HH

E H (Kj/mol)

H HH

H H H

H
H H H H

H H

25,5 14,2 3,4

60

(goc quay)

120

180

240

300

360

Hnh 7.3: Gin ph thuc nng lng v gc quay cc cu dng ca n-butan

CH3 k hiu l

Dng che khut c nng lng cao hn dng lch. S ph thuc nng lng c biu din trn hnh 7-2. Etan c mt cc i v mt cc tiu nng lng. S chnh lch c gi tr 11,7 kj / mol Phn t butan tn ti nhiu cu dng v gin nng lng cng phc tp hn. Gin nng lng ca phn t butan CH3CH2CH2CH3 trnh by trn hnh 7-3

84

2. Danh php Cc hydrocarbon no u c tip v ng l an 2.1. Tn gi cc gc hydrocarbon thng gp CnH2n+2 CnH2n+1_ an Nguyn tc: Thay v ng ''an'' trong tn gi ca hydrocarbon no bng tip v ng ''yl" Cc gc bc 1
CH3 methyl CH3CH2 ethyl CH3CH2CH2 n-propyl

yl

CH3CH2CH2CH2n-butyl

CH3 CH CH2 CH3 isobutyl

CH3 CH3CCH2CH3 neopentyl

CH3CH2CH2CH2CH2n-pentyl

CH3CHCH2CH2CH3 isopentyl

CH3CH2CH2CH2CH2CH2n-hexyl

CH3CHCH2CH2CH2CH3 isohexyl

CH3 CH3CCH2CH2CH3 neohexyl

Cc gc bc hai
CH3CHCH3 isopropyl CH3 CH3CH2CHsec-butyl

Cc gc bc ba
CH3 CH3CCH3 tert-butyl CH3 CH3CH2CCH3 tert-pentyl

2.2. Danh php quc t

Chn mch chnh l mch thng di nht. nh s carbon trn mch chnh sao cho tng cc ch s ch v tr ca nhm th l mt s nh nht (theo IUPAC). Nu mch nhnh khc nhau khong cch nh nhau so vi hai carbon u mch chnh th phi nh s t u no c mch nhnh vi s carbon t nht (theo danh php Genve). 85

Nu mch nhnh c s phn nhnh th phi nh s mch nhnh bt u t v tr gn vi mch chnh.

CH3_ CH2_ CH_ CH2_ CH_ CH2_ CH2_ CH3 7' 6' 5' 4' 3' 1' 8' 2' CH2CH3 CH3 CH3_ CH2_ CH_ CH2_ CH2_ CH_ CH2_ CH3 CH2CH3
5 8 7 6 5 4 3 2 1 1 2 3 4 5 6 7 8

anh so theo nguyen tac tong so nho nhat 3+5 < 4'+6' 3-etyl-5-methyl octan Nhom methyl quyet nh v tr anh so 3-methyl ,6-ethyl octan anh so theo nguyen tac tong so nho nhat 2+3+7 < 2'+6'+7' 2,3,7-trimethyl octan Chon mach chnh la mach dai mhat

CH3

CH3_ CH_ CH2_ CH2_ CH2_ CH_ CH_ CH3 4' 1' 2' 3' 5' 6' 7' 8' CH3 CH3 CH3 CH3

va anh so theo quy tac tong so nho nhat 2+3+6+7 < 3+4+5+7 CH3 CH CH CH CH2 CH CH3 6 4 5 3 7 Mach nhanh co phan nhanh va anh so CH 3 CH3 CH CH3 1 2 mach nhanh tai v tr gan vao mach chnh CH3 2,3,6,7-tetramethyl -5-(1',1'-dimethylpropyl) nonan CH3 C CH2 CH 3 1',1'-dimethylpropyl
1' 2' 3'

CH3 CH2 CH3 C CH2 CH3

1'

2'

3'

Cch gi tn:

Tn cc gc (mch nhnh) v ch s ch v tr cc gc gn vo mch chnh. Tn gc (mch nhnh) ln lt t n gin n phc tp.

Dng cc t Hylp (di, tri, tetra, penta, hexa, hepta, octa) ch s lng cc nhm th ging nhau v gi tn ca hydrocarbon no c s carbon tng ng vi s carbon trong mch chnh. 3. Phng php iu ch alkan 3.1. Phng php gi nguyn mch carbon 3.1.1. Kh ha hydrocarbon cha no Tc nhn kh l hydro phn t vi xc tc c hot tnh cao nh kim loi Pt, Pd, Ni. Phn ng c th xy ra nhit thng.
R R CH CH CH CH R' R' + H2 + 2H2 Ni Ni R R CH2 CH2 CH2 CH2 R' R'

86

3.1.2. Kh ha dn xut halogen Tc nhn kh c th l Zn /H+ hoc acid hydroiodic c (HI)

R-X + Zn +H+ R-H + Zn2+ + XR-I + HI R-H + I2

3.1.3. Kh ho alcol Tc nhn kh l HI c (80%), nhit 180-200C v c mt phosphos Khi un nng: 2HI 2H + I2 Ban u alcol chuyn thnh sn phm trung gian l dn xut iod v cht ny li b kh nhit cao hn thnh alkan R-OH + HI R-I + HI V d: CH3-CH2-CH2-CH2-OH + 2HI CH3-CH2-CH2-CH3 + H2O + I2
Alcol n-butylic butan

R-I + HOH R-H + I2

S c mt ca phosphor lm tng cng kh nng kh ha ca HI. Phosphor tc dng iod to phosphor triiodid PI3 v cht ny khi tc dng vi nc li ti to HI. 3.1.4. Kh ha acid v dn xut acid R-CH3 + 2H2O + 3I2 R-COOH + 6HI Phn ng dng iu ch alkan c mch carbon ln. Kh ester d hn acid. 3.1.5. Thy phn hp cht c kim CnH2n+1Br + Mg / ether khan CnH2n+1MgBr CnH2n+1MgBr

CnH2n+2 + MgBrOH

3.2. Phng php lm tng mch carbon 3.2.1. Phn ng Wurtz Dn xut halogen tc dng natri kim loi s to hydrocarbon no do hai gc ca dn xut halogen kt hp li nn mch carbon s tng gp i. 2 R-X + 2Na V d: 2CH3-CH2-I + 2Na CH3-CH2-CH2-CH3 + 2NaI Phn ng dng hn ch trong tng hp cc dn xut i xng. Nu dng hai dn xut khc nhau s thu c hn hp sn phm: 3R-X + 6Na + 3X-R R-R + R-R + R-R + 6 NaX R-R + 2NaX (hiu sut 80%)

87

3.2.2. Phn ng in phn dung dch mui acid (phn ng Kolbe)

CH3CH2COONa

anod CH3CH2COO -e . CH3CH2COO - CO2 CH3CH2 .

-

catod Na+ +e Na H2O NaOH + H2

CH3CH2CH2CH3 chnh

CH3CH3 + CH2 ph

CH2

3.3. Phng php lm gim mch carbon Ct khan mui kim, kim th ca acid carboxylic vi vi ti, xt s thu c hydrocarbon c mch gim 1 carbon so vi acid carboxylic.
R-COONa + NaOH R-H + Na2CO3 CH3COONa + NaOH CH4 + Na2CO3

4. Tnh cht l hc Nhit si v nhit nng chy tng dn khi s carbon tng. Cc alkan phn nhnh c nhit si thp. Alkan khng tan trong nc. D tan trong ether, trong cc hydrocarbon khc v trong cc dn xut halogen. Ph hng ngoi: Cc tn s dao ng ha tr : Lin kt CH c dao ng ha tr trong khong 2850-3000 cm-1; lin kt C_C c dao ng yu v thay i. Cc tn s dao ng bin dng Gc methyl CH3 v methylen CH2 c dao ng bin dng c trng ca CH t 1400-1700 cm-1

88

Bng 7.3: Tnh cht vt l ca mt s alkan

Hydrocarbon Metan CH4 Etan C2 H 6 Propan C3H8 Butan C4H10 Pentan C5H12 HexanC6H14 Heptan C7H16 Octan C8H18 Nonan C9H20 Decan C10H22 Undecan C11H24 Dodecan C12H26 Tridecan C13H28 Tetradecan C14H30 Pentadecan C15H32 Eicosan C20H42 Triacontan C30H62 Nhit si -161,7 - 88,6 42,6 - 0,5 6,1 68,7 98,4 125,7 150,8 170,4 195,8 216,3 235,4 253,7 270,6 343,0 449,7 Nhit chy -182,0 -183.3 -187,7 -138,3 -129,8 - 95,3 - 90,6 - 56,8 - 53,5 - 29,7 - 25,6 - 9,6 - 5,5 5,9 10,0 36,8 65,8 T khi 0,5005 0,5787 0,5572 0,6603 0,6837 0,7026 0,7177 0,7299 0,7402 0,7487 0,7564 0,7628 0,7685 0,7886 0,8097

5. Tnh cht ha hc Trong phn t alkan ch c 2 loi lin kt: C_H v C_C. Chng l nhng lin kt hu nh khng phn cc. 5.1. Phn ng th - Tnh cht ca lin kt C - H 5.1.1. Phn ng halogen ha -Tc dng vi halogen CnH2n+2 + X2 CnH2n+1X + HX F2 > Cl2 > Br2 > I2.

Phn ng xy ra theo c ch gc t do, c xc tc nh sng hoc nhit cao. Kh nng phn ng ca halogen sp xp theo

Kh nng phn ng ca C _H bc 3 > C_H bc 2 > C_H bc 1 CH4 + 2F2 C + 4HF Phn ng clor ha metan xy ra qua cc giai on sau:
Cl2
h

CH3 + Cl2 CH4 + Cl2

CH4 + Cl

. 2Cl

CH3 + HCl

H = +270kcal H = -1kcal

CH3Cl + Cl CH3Cl + HCl

. H = -23kcal

89

Thc t phn ng to thnh hn hp sn phm CH3Cl, CH2Cl2, CHCl3, CCl4 Phn ng s ngng hn khi cc gc t do kt hp vi nhau.
Cl + Cl

Cl2

. . ; Cl + CH3

CH3Cl

. . ; CH3+ CH3

CH3CH3

Phn ng clor ha phn t propan to ra nhiu cht:

CH3 CH2 CH3 h + Cl2 CH3 CH2 CH2Cl + Cl2

CH3 CHCl CH3 + Cl2

CH2Cl CH2 CH2Cl + CH3 CHCl CH2Cl

+ Cl2

+ CH3 CCl2 CH3 + Cl2

CH2Cl CHCl CH2Cl

+ CH3 CCl2 CH2Cl

Brom ha c tnh chn lc cao hn qu trnh clor ha. Khi clor ha isopentan thu c hn hp sn phm. Cn khi brom ha isopentan sn phm th brom ch yu xy ra lin kt C _H bc 3. Theo nh lut Hess, hiu ng nhit H0 l hiu s nng lng lin kt mi c to thnh trong phn ng v nng lng phn ly ca lin kt b phn ct.
. Cl + H_CH2CH3 Lien ket phan ly Cl_H+

CH2CH3

o H = 98 - 103 = - 5 kcal. mol-1 Lien ket tao thanh Lien ket phan ly

Lien ket tao thanh

Lin kt HCl bn vng hn lin kt CH. Phn ng ca gc F vi mt lin kt CH c hiu ng nhit ln, ngha l phn ng xy ra mnh lit. Phn ng gia gc brom Br vi lin kt CH xy ra chm hn. Nh vy chng t rng hot tnh halogen cng ln th chn lc cng nh v ngc li. Clor ha:
CH3 C CH2 CH3 H h CH3

CH2Cl C CH2 CH3 + CH C CH CH Cl 3 2 2 H 30% H 15%

CH3

CH3

+ Cl2

+ CH3 C CHCl CH3 + CH3 C CH2 CH3

H 33% Cl 22%

CH3

CH3

90

 Brom ha:
CH3 C CH2 CH3 H CH3

Br2

CH3 C CH2 CH3 Br

CH3

HBr

Phn ng iod ha alkan l qu trnh thun nghch:

RH + I2 RI + H

Trong iu kin thng, phn ng c khuynh hng chuyn v pha tri ti to alkan. Ngi ta thm mt cht oxy ha nh acid iodic HIO3 tch HI v phn ng chuyn v pha to iodoalkan. 5.1.2. Phn ng nitro ha - Tc dng vi HNO3 Phn ng nitro ha l phn ng th nguyn t hydro ca alkan bng gc NO2. nhit thng alkan khng phn ng vi acid nitric. nhit cao (150450C) alkan tc dng vi acid nitric long hoc kh NO2 to thnh dn xut nitro. Nu dng acid nitric c th alkan b oxy ha.
RH + HO_NO2 ( long ) 450o RNO2 + H2O

Trong phn ng nitro ha ngoi sn phm th, c th xy ra s ct mch carbon. V d khi nitro ha propan to thnh hn hp sn phm sau:
CH3_CH2_CH3 + HNO3 CH3_CH2_CH2_NO2 + CH3_CH_CH3 + CH3_CH2_NO2+ CH3_NO2 25% NO2 40% 10% 25% 1-Nitropropan Nitroetan Nitrometan 2-Nitropropan

Phn ng nitro ha xy ra u tin th vo hydro carbon bc cao. Gc NO2 sinh ra do tc dng ca nhit :
HNO3 + HNO3 to

. H2O + 2 NO2

Vai tr ca gc NO2 trong phn ng nitro ha ging vai tr X trong phn ng halogen ho. 5.1.3. Phn ng sulfon ha Tc dng vi acid sulfuric Acid H2SO4 m c nhit thng khng tc dng vi alkan. Acid sulfuric bc khi (c ho tan SO3 - oleum) tc dng vi nhng alkan c mch 6- 8 carbon v to thnh alkansulfoacid.
C6H14 H2SO4 SO3 C6H13SO3H

91

 Tc dng vi SO2 v Cl2 - Phn ng sulfoclor ha Alkan tc dng trc tip vi hn hp SO2 v Cl2 nhit 20 - 30C c chiu sng bng n t ngoi hoc c peroxyd lm cht khi mo th thu c alkansulfoclorid.
RH + SO2 + Cl2 RSO2Cl + HCl hoc peroxyd h

Khi thy phn hp cht alkansulfoclorid c mch carbon ln (> 10 carbon) bng NaOH s thu c cc mui sulfonat l nhng cht c tc dng ty ra tt.
RSO2Cl + 2NaOH RSO3Na + H2O + NaCl

Sulfo oxy ha Khi cho hn hp SO2 v O2 vi t l ng phn t tc dng vi alkan c mch 6- 8 carbon nhit 20-30C, c chiu sng s thu c hp cht alkansulfoacid.
RH + SO2 + 1 O 2 2 h RSO 3H

5.2. Cc phn ng thuc lin kt CC 5.2.1. Nhit phn v cracking nhit cao khng c oxy khng kh, cc phn t alkan b phn hy hoc b gy mch carbon to thnh alkan v hydrocarbon cha no c mch carbon ngn hn. Qu trnh gi l qu trnh cracking. CnH2n+2 CxH2x+2 + CyH2y (n = x +y )
. . CH3 + CH3CH2CH2CH2 . . + CH3CH2CH2 CH3CH2

Khi cracking n-pentan, phn ng xy ra theo c ch gc.

CH3CH2CH2CH2CH3

. . CH3 + CH3

CH3CH3

. . CH3 + CH3CH2
. . CH3CH2 + CH3CH2CH2CH2
. CH3CH2 + . CH3CH2CH2

CH3CH2CH3
CH3CH2CH2CH2CH2CH3
CH3CH3 + CH3CH=CH2

92

5.2.2. Oxy ha v t chy iu kin bnh thng, alkan khng tc dng vi oxy khng kh v cc cht oxy ha mnh nh H2SO4 c, KMnO4. Nhng nhit cao, alkan b oxy ho to thnh cc sn phm cha oxy. Khi un nng c xc tc, cc alkan b oxy ha bi oxy khng kh to thnh acid hu c tng ng.
RCH3 + xuc tac 3 O2 2 to RCOOH + H2O

Nu oxy ha mnh hn c th xy ra s ct t lin kt CC v sau oxy ha tip to thnh cc acid c s nguyn t carbon t hn.
CH3_(CH2)nCH3 oxy ho CH3(CH2)xCOOH + CH3(CH2)yCOOH

n=x+y+2

Khi t chy alkan to CO2 v hi nc ng thi gii phng nng lng.

CnH2n+2 + 3n + 1 2 O2 CO2 n CO2 + (n+1) H2O + Q + 2 H2O + 885 kj

CH4 + 2 O2

Chnh v vy cc alkan nh metan, butan, octan ... c dng lm nhin liu. 6. Cht in hnh Metan CH4 Tng hp metan: Be2C + 4H2O CH4 + 2Be(OH)2 Al4C3 + 12H2O 3CH4 + 3Al(OH)3 CH4 + 4Cu2S CS2 + 2H2S + 8Cu

Trong phng th nghim, iu ch metan bng cch nhit phn mui acetat kim loi kim CH3COONa + NaOH Tnh cht v ng dng: Metan l kh khng mu, khng mi, t tan trong nc, chy cho ngn la xanh nht v to nhiu nhit (8560 kcal/m3) v vy lng ln metan c dng lm nhin liu. t metan trong iu kin thiu khng kh v trong thit b c bit to ra carbon dng bt mn dng lm cht n trong sn xut cao su. CH4 + O2 C + H2 O CH4 + Na2CO3

93

Cho metan qua hi nc xc tc Ni 850C thu c hn hp hydro v carbon monooxyd dng lm nguyn liu trong tng hp. CH4 + H2O CO + 3H2

Metan cn dng lm nguyn liu tng hp acetylen, cc dn xut clorometan, acid cyanhydric. . . Bi tp 1. Nhng tn gi sau y c ng khng : a- 2-Ethylhexan b- 2,2,5-Trimethylheptan c- 3-Ethylheptan d- 2-Methyl,3-isopropylpentan e- 1-Methyl,3- ethylnonan Hy vit li nhng tn gi ng. 2- Etan phn ng vi clor theo t l th tch v trng lng no khi iu ch ethylclorid ? 3- Khi nitro ha v clor ha cc hydrocarbon sau: Butan, isobutan, n-pentan, 3-methylbutan th c bao nhiu dn xut mt ln th c th c to thnh ? .

94

Chng 8

CYCLOALKAN

Mc tiu 1. Gi c tn cc loi cycloalkan: 1 vng, 2 vng. 2. Vit v trnh by c cu dng ca cyclohexan.

Ni dung
Cycloalkan l nhng hydrocarbon no mch vng. Nguyn t carbon trng thi lai ha sp3. C nhiu loi hp cht vng no. Hp cht n vng: Monocycloalkan Hp cht a vng: Polycycloalkan. Phn chia hp cht a vng thnh cc loi sau: Hp cht a vng ngng t, Hp cht a vng c mch cu carbon, Hp cht a vng spiran. 1. Monocycloalkan 1.1. Danh php Gi tn alkan tng ng v thm tip u ng ''cyclo'' Nu trong phn t c mch nhnh th gi tn mch nhnh t n gin n phc tp. nh s cc nguyn t carbon trn mch vng xut pht t mch nhnh n gin v nh s theo chiu sao cho tng s cc ch s ch mch nhnh l nh nht.
CH3 CH3 CH3
1 2 3

CH3
1 2 3

Methylcyclopropan Methylcyclobutan

CH2CH2CH3 CH2CH3 1-Methyl 3-ethylcyclopentan 1-Methyl, 3-(n-propyl) cyclohexan

1.2. ng phn Monocycloalkan c s ng phn nhiu hn s ng phn ca alkan c s carbon tng ng. V d: C8H16 c cc ng phn vng 3, 4, 6, 7, 8 cnh. 95

Trn mi loi ng phn vng c cc mch nhnh nn s ng phn tng ln.

CH2CH3 CH3
1 2

CH3 CH3
1 3

CH3
1 4 2

CH3

CH3 Ethylcyclohexan 1,2-dimethylcyclohexan 1,3-dimethycyclohexan 1,4-dimethycyclohexan

Khc vi cc alkan, cycloalkan c ng phn hnh hc cis - trans

CH3 CH3 CH3 CH3 trans 1,2-dimethylcyclohexan

cis 1,2-dimethylcyclohexan

1.3. bn vng ca vng Cc hp cht c vng 3, 4 cnh km bn hn so vi vng 5, 6 cnh. gii thch hin tng , Bayer a ra gi thuyt rng: Tt c cc vng u c cu to phng. Gc lin kt b bin dng (c ln khc 10928' - gc t din) v xut hin sc cng ca vng (Sc cng Bayer). bin dng ca gc lin kt cng ln th sc cng Bayer cng ln. V vy vng c nng lng cao nn km bn. Gc bin dng c tnh nh sau:

1 [109o28' 2

(goc lien ket trong vong phang) ]

Bng 8.1: Sc cng Bayer ca mt s cycloalkan

Hp cht Cyclopropan Cyclobutan Cyclopentan Cyclohexan Cycloheptan Cyclooctan 60 90 108 120 12834 135 +2464' +964' +064' -536' -953' -1286' Ho (*) +12,7 +6,8 -18,4 -29,5 -28,2 -29,7

(*) kcal.mol-1 Theo thuyt sc cng Bayer th cyclopentan l hp cht bn nht, t cyclohexan tnh bn gim dn. iu ny khng ph hp v thc t cyclohexan l hp cht rt bn vng. Cyclohexan khng c cu to phng, chng t rng thuyt sc cng Bayer ch ng vi nhng cht c cu to phng . bn ca hp cht vng cn ph thuc nhiu yu t khc c bit l cu hnh v nhit to thnh. Nhit to thnh cng thp th vng cng bn. 96

Cc hp cht cu hnh lch c nng lng thp. Do nu cc nhm CH2 k nhau ca vng khng cu hnh lch m cu hnh che khut th phi c s tng tc ln nhau. S tng tc gi l Sc cng Pitzer . gim bt sc cng Bayer, sc cng Pitzer, hp cht vng c xu hng phn b khng ng phng sao cho thun li v nng lng (nng lng thp nht). 1.4. Cu dng ca cycloalkan 1.4.1. Cyclopropan Ba nguyn t carbon cng nm trn mt mt phng. Bayer gii thch tnh khng bn ca vng bng s bin dng ca lin kt. Trong cyclopropan cc lin kt H _C_H to thnh gc 120. Do ngi ta cho rng cc lin kt C -C b un cong v s xen ph cc i b vi phm mt phn (hnh 8-1).
Hnh 8.1
H H

C C
H

C
H

S xen ph cc i

S xen ph cc i b vi phm v lin kt C-C b un cong

S xen ph ca cc orbital sp2 to thnh cyclopropan

1.4.2. Cyclobutan Cyclobutan c cu dng gy gp - cu dng xp (hnh 8-2)

H H H H H H H H H H H H H H H H

S tng tac gay ra sc cangPitzer

Hnh 8.2: Cu to khng ng phng ca phn t cyclobutan

1.4.3. Cyclopentan Cyclopentan c cu to khng phng. Bn nguyn t carbon ca cyclopentan nm trn mt mt phng. Nguyn t carbon th 5 nm ngoi mt phng ny. Vng cyclopentan c hin tng " gi quay " (pseudorotation) (hnh 8-3).

97

H 1 H H H
2 5 4 3

H 2 H5 4 H 1 H 3 H H

5 1

H 3 H H
H 4 2

M hnh phn t cyclopentan

H S tng tc gy ra sc cng Pitzer

Hnh 8.3: S bin i ca phn t cyclopentan

1.4.4. Cyclohexan Cyclohexan c 2 cu dng: dng gh v dng thuyn (hnh 8- 4) .

S tng tac gay ra sc cang Pitzer H H H H H
HH H

H H H H H

H H H H H

H H
H

H H

Dang ghe

Dang thuyen

Hnh 8.4

Trong cu dng gh ca cyclohexan khng c sc cng Bayer v sc cng Pitzer, v vy dng gh c nng lng thp v bn vng hn cyclohexan cu dng thuyn. Cc lin kt C H trong cu dng gh c chia thnh 2 loi. Su lin kt C H song song vi trc i xng gi l lin kt axial (a, lin kt trc). Su lin kt C H sp xp gn song song vi mt phng trung bnh gi l lin kt equatorial (e, lin kt xch o, lin kt vnh) (hnh 8-5).
Truc oi xng H H H H H H H Lien ket equatorial H H H

H H Lien ket axial

Hnh 8.5. Lin kt axial v lin kt equatorial

Lin kt equatorial c nng lng thp v bn vng hn lin kt axial (hnh 8-6).
CH3 a Axial (a)-Methylcyclohexan Equaterial (e)-Methylcyclohexan CH3 e

Hnh 8.6: S chuyn i lin kt axial thnh lin kt equatorial

98

Cc nhm th c th tch ln v cu to phc tp thng tn ti dng equatorial. Hp cht th 2 ln ca cyclohexan tn ti cc ng phn hnh hc.
CH3 CH3 CH3 Cis 1,2 CH3 CH3 CH3 CH3 Cis1,3 Trans1,4 Cis1,2 CH3 CH3 CH3

CH3 Trans1,2

CH3 Trans1,3

Hnh 8.7: Cc ng phn hnh hc ca dimethylcyclohexan

T cc ng phn hnh hc (hnh 8-7) li c cc cu dng khc nhau.

CH3 a H CH3 e Cis a,e H H e CH3 H CH3 a Cis a,a CH3 a CH3 e Cis e,e e CH3 CH3 CH3 a e a CH3 e CH3

Cis e,a CH3

Cis a,e

Cis e,a

Hnh 8.8: Cc ng phn cu dng ca cis - dimethylcyclohexan

Trn hnh 8-8 l cc cu dng ca cis-dimethylcyclohexan cc v tr khc nhau. Tng t cng c cc cu dng trans-dimethylcyclohexan (hnh 8-9)
CH a 3 H a CH3 Trans a,a H e CH3 CH3 CH3 a CH3 CH3 a Trans e,a e CH3 H a CH3 CH3 Trans a,a e H H e CH3 Trans e,e

e H Trans e,e

CH3 e Trans a,e

Hnh 8.9: Cc ng phn cu dng ca trans - dimethylcyclohexan

1.5. Tnh cht ha hc ca cycloalkan Cc vng 3, 4 cnh th hin tnh cht cha no. Phn ng cng hp v vng b ph v. Cc cyclopropan khng tc dng vi kali permanganat v ozon.
2H CH3-CH2-CH3 ; HBr CH3-CH2-CH2Br; Br2 CH2Br-CH2-CH2Br

Cc cyclohexan th hin tnh cht ca hydrocarbon no. C phn ng th halogen khi c xc tc l nh sng. Khi c mt xc tc thch hp, cyclohexan c th b oxy ha to thnh cyclohexanol, cyclohexanon hoc vng b ph v to acid adipic. Cyclohexan b dehydro ha khi c xc tc l Pt hoc Pd.
H H H H H H Cl Cl Cl Cl Cl + 6HCl Cl

6Cl2

99

Xuc tac

OH Cyclohexanol O Cyclohexanon HOOC (CH2)4 COOH Acid adipic

O2

Xuc tac

Pt

+ 3 H2

Xuc tac

Tnh cht c bit ca cc hp cht cycloalkan l c th tham gia phn ng chuyn v tng hay gim ln ca vng.
CH2CH3 AlCl3 AlCl3 CH3

CH3 Methylcyclopentan

;
Cycloheptan

Methylcyclohexan

Ethylcyclobutan

2. Hp cht a vng 2.1. Hp cht a vng c lp Hp cht c 2 vng c lp lin kt vi nhau trc tip hoc bi mt mch carbon.

_CH2CH2_
Bicyclohexyl 1,2-Bicyclohexyletan

2.2. Danh php hp cht vng ngng t Hp cht vng ngng t l nhng hp cht m cc vng c cnh chung vi nhau.
10 9 8 7 1 6 2 3 4 5 2 3 4 5 1 6 9 7 8

Bicyclo[4.4.0] decan

Bicyclo[4.3.0] nonan

2.3. Hp cht a vng c mch cu carbon Hp cht vng c cu l hp cht khng c cnh chung nhng c cc nguyn t carbon chung cho cc vng. Nguyn t carbon chung l nguyn t u cu.
1 6 5 4 7 2 3 7 6 5 4 3 1 1 6 2 5 8 7 4 2 3 5 6 7 4 8 1 2 3

Bicyclo[2.2.1] heptan

Bicyclo[2.2.2] octan

100

C th c hp cht 3, 4 vng
1 8 7 6 5 10 4 9 2 3 9 8 6 7

3 1

4 5

1 6 5 4

Tricyclo[3.3.1. 3,7] decan

Tricyclo[3.3.1.0 2,9] decan

Tetracyclo [2.1.1.0 2,6. 0 3,5] hexan

Ch : 13,7 ch r mch c 1 carbon v 2 carbon u cu l carbon s 3 v s 7; 0 ch r mch khng c carbon v 2 carbon u cu l carbon s 2 v s 6.
2,6

H thng hp cht a vng c danh php phc tp. Theo danh php IUPAC, gi tn hp cht a vng phi xc nh s mch carbon. S mch carbon tng ng vi s vng (bicyclo, tricyclo, tetracyclo). Tm vng chnh c s carbon nhiu nht. Chn mch cu l mch di nht to bicyclo chnh. nh s trn vng bicyclo chnh xut pht t carbon u cu v n u cu kia t mch cu di nht n ngn nht (ch nguyn tc tng s nh nht). Sau xc nh tip cc mch cu cn li v ch r s nguyn t carbon c trn mch cu . S nguyn t carbon trn mi mch cu (khng k carbon u cu) c t trong ngoc vung theo th t t ln n nh. Tn ca hp cht a vng l tn ca hydrocarbon c tng s carbon to vng. 2.4. Hp cht vng spiran T ''spiro'' c ngha l xon. Hydrocarbon no loi ny ch r cc vng lin kt vi nhau bng nguyn t carbon chung. Nguyn t carbon ny gi l carbon spiro. C hp cht spiro, dispiro, trispiro .. . nh s carbon xut pht t vng b v bt u carbon gn carbon spiro v theo chiu sao cho carbon spiro (carbon chung) c s b nht. S carbon trn mi mch t trong du mc v theo chiu nh s.
7 6 8 4 5 1 2 3 5 4 6 7 3 1 2 9 8 7 6 10 5 4 1 2 3 8 7 9 5 10 4 3 1 8 2 7 6 9 10 11 5 12 3 1 2

Spiro[3.4] octan Spiro[2.4] heptan Spiro[4.5] decan Dispiro[2.1.4.1] decan

Dispiro[2.1.5.2] dodecan

Bi tp
1. V cc ng phn hnh hc c th c ca cc ng phn ca cyclohexan c CTPT C9H18. Gi tn cc ng phn . 2. V cc cu dng c th c ca diclocyclohexan. 3. Vit CTCT ca cc cht c tn gi sau: a. Bicyclo[4.1.0] heptan; b-Bicyclo[3.2.0]heptan ; c-Tricyclo[5.1.0.03,5]octan d. Spiro [3.3] heptan; e-Spiro [4.4] nonan; f- Dispiro [5.1.6.2] hexadecan 4. Gi tn theo danh php IUPAC ca cc cht c cng thc sau:
CH3 CH3

101

Chng 9

ALKEN - HYDROCARBON ETYLENIC (CnH2n)

Mc tiu hc tp 1. Trnh by c cu to alken, xc nh ng phn hnh hc v danh php Z -E ca chng. 2. Nu c cc tnh cht ha hc ca alken. Alken cn gi l olefin. Chng l nhng hydrocarbon cha no, khng vng, trong phn t c mt ni i. Alken c cng thc tng qut CnH2n. i vi hp cht vng c mt ni i c cng thc tng qut CnH2n-2 v gi l cycloalken, cycloolefin, hydrocarbon vng cha no. 1. Cu to ca alken Su nguyn t ca phn t ethylen nm trong mt mt phng. Lin kt ca C _C to thnh do xen ph ca orbital sp2. Lin kt c to thnh do 2 orbital p t do xen ph vi nhau. Mt phng cha lin kt thng gc vi mt phng cha cc nguyn t carbon v hydro ca ethylen. Orbital s ca hydro v orbital sp2 ca carbon xen ph vi nhau to thnh lin kt ca HC (hnh 9-1).

Csp2

C 2 sp
Lien ket tao thanh do 2 orbital p t do
o

Hnh 9.1:

Cac nguyen t H ,C cua ethylen nam tren mot mat phang

Lien ket tao thanh do 2 carbon lai hoa sp2

o

di lin kt ca HC l 1,076 A , ca C =C l 1,330 A Gc lin kt HCH l 116, 6o . Gc lin kt H_C=C l 121,7o . 2. ng phn 2.1. ng phn cu to Ngoi ng phn v mch carbon, alken cn c cc ng phn do v tr ca ni i. Do alken c s ng phn cu to nhiu hn alkan c cng s carbon tng ng. 102

Alken

S ng phn

Alkan

S ng phn

Buten

C 4 H8

3 5 12

Butan C4H10 Pentan C5H12 Hexan C6H14

2 3 5

Penten C5H10 Hexen C6H12

2.2. ng phn hnh hc - ng phn cis-trans Cc nhm th khng th quay t do chung quanh lin kt i m tn ti mt cch tng i v hai pha ca lin kt i. Do alken c ng phn hnh hc. Hai nhm th cng pha so vi mt phng th gi l ng phn cis. Hai nhm th khc pha so vi mt phng th gi l ng phn trans.
a b C C b a a b C C d c CH3 H CH3 H CH3 C C H CH3 Trans -2-buten H

C C

Co ong phan cis-trans

Co ong phan Z-E

Cis -2-buten

C th hnh dung m hnh phn t 2-buten nh sau.

Dng trans bn hn dng cis v dng trans c nng lng thp. Trong dng cis cc nhm th cng pha c tc dng y nhau.
CH3 H H C C CH3 CH3 H CH3 H CH3CH2CH=CH2 1-buten (3%)

C C

Trans -2-buten (74%)

Cis-2-buten (23% )

ng phn cis-trans tn ti khi cc nhm th chung quanh lin kt i c a b Cc nhm th chung quanh lin kt i c a b c d th c ng phn Z - E.
CH3 H CH2CH2CH3 CH2CH3 CH3 H C C CH2CH3 CH2CH2CH3 E -3-ethyl-2-hexen

C C

Z -3-ethyl-2-hexen

Ch : Cc t cis - trans hoc Z (zusammen - cng pha) - E (eintgegen khc pha) l cc danh php ch ng phn hnh hc trong cc trng hp khc nhau.

103

3. Danh php 3.1. Danh php thng thng Gi tn alken bng cch ly tn alkan c s carbon tng ng thay tip v ng ''an'' thnh ''ylen''. CH2=CH2 Ethylen CH3CH=CH2 Propylen CH3CH2CH=CH2 Butylen

Danh php ny ch gi tn nhng alken n gin 3.2. Danh php ethylen C th xem cc alken n gin nh l dn xut ca ethylen. Nguyn t hydro ca ethylen ln lt c thay th bi cc gc alkyl. S thay th ny c th i xng hoc khng i xng hai u lin kt i.
CH3CH=CH2 Methylethylen CH3_CH=CH_CH3 CH3 Dimethylethylen khong oi xng CH3_C=CH2

Dimethylethylen oi xng

3.3. Danh php IUPAC Gi tn nh hydrocarbon no v thay v ng ''an'' bng v ng ''en'' Chn mch chnh l mch di nht cha lin kt i . nh s carbon trn mch chnh sao cho ni i c s b nht.
V tr nhnh + Tn nhnh + S ch v tr ni i + Tn mch chnh + en
1 CH
3

CH3CH=CH2 Propen

CH3 4 1 4 3 3 2 _CH=CH_CH ; CH _C=CH_CH CH3 3 3 3 2-Buten 2-Methyl-2-buten

2 CH CH3 _CH_CH _CH _C_CH _CH ;CH3 2 2 2 3 7 6

6-Methyl-3-ethyl-3-hepten

3.4. Danh php Z - E Danh php Z- E dng gi tn cc ng phn hnh hc m cc nhm th chung quanh lin kt i hon ton khc nhau. Theo quy c 2 nhm th trn 2 carbon ca lin kt i c ln nht sp xp v mt pha ca mt phng th gi l ng phn Z v ngc li gi l ng phn E.
Khi a > b va c > d

a b

C C

c d

a b

C C

d c

ong phan Z

ong phan E

Xc nh ln nhm th theo quy c Cahn -Ingold-Prelog, danh php R,S

104

R- Rectus - bn phi, S - Sinister - bn tri

CH3CH2 CH3 CH2CH3 H ClCH2CH2 CH3CH Cl CH2Cl CH3

C C

C C

Z -3-methyl-3-hexen

E -1,4-diclo,2-methyl-3-(2-clorethyl) -2-penten

4. Phng php iu ch 4.1. Tch hydro halogenid t cc dn xut monohalogen Cc dn xut monohalogen no, c bit l dn xut bc ba, khi tng tc vi cc dung dch base mnh nh KOH, NaOH, EtONa trong alcol v un nng s b tch mt phn t hydrohalogenid to ra alken tng ng. Ty cu to ca dn xut halogen no, alken thu c c th l mt hn hp ng phn v mt lng nh sn phm ca phn ng th i nhn l ether. S tch loi HX theo kh nng: R-I > R-Br > R-Cl > R-F . V nng lng lin kt: C-I 51 kcal.mol-1; C-Br 58 ; C-Cl 81 ; C-F 116
R CH H C CH3 X CH3 Dung dch KOH / alcol CH3 _CH=C_CH + HX R 3

Dung dch KOH/alcol khi un nng xy ra s cn bng sau:

ROH + OH RO- + H2O

S tch loi HX tun theo qui tc Zaixep. Khi tch HX khi dn xut halogen, X s b tch cng vi nguyn t hydro gn ti nguyn t carbon lin bn cnh c bc cao nht. Qui tc Zaixep ng c trong hai trng hp tch loi E1 v E2. 4.1.1. Phn ng tch loi E1 alkylhalogenid
R_CH2_CH_CH3 X + R_CH2_CH_CH3 Cham + R_CH2_CH_CH3 + X R_CH=CH_CH3 + + H (I)

Nhanh

+ R_CH2_CH=CH2 + H ( II )

Nu X cng tch loi vi H bc cao hn s hnh thnh olefin (I). Olefin (I) c nng lng thp hn so vi olefin (II) v hiu ng siu lin hp ca CH3 vi lin kt i C =C c s lin kt C -H nhiu hn.

105

+ R_CH2_CH_CH3

H + R CH2 CH C H H Co 3 lien ket C-H sieu lien hp

H Co 2 lien ket C-H sieu lien hp Ch co 2 lien ket C-H

H + R C CH CH3

H _CH=CH_C_H R
(I)

Co 3 lien ket C-H

H _C_CH=CH R 2 H (II)

4.1.2. Phn ng tch loi E2 alkylhalogenid Phn ng E2 xy ra trong iu kin c base mnh v dung mi km phn cc.
CH3CH2CH2CHBrCH3 EtOK EtOH + CH3CH2CH=CHCH3+ CH3CH2CH2CH=CH2 CH3CH2CH2CH(OEt)CH3 41% 25% 20%

Trong c ch E2 c th hnh thnh trng thi chuyn tip sau:

CH3CH2CH_CHCH3 . . Br

HO ..... H

H ..... OH CH3CH2CH2_CH_CH2 .

Br

Trong trng hp tch loi theo c ch E2 (cng nh E1) sn phm to thnh tun theo quy tc: Khi tch HX khi dn xut halogen s thu c olefin c s nguyn t H i vi lin kt i l ln nht
CH3 CH3_CH_CH2_CH_CH2_CH3 X CH3 _CH_CH _CH=CH_CH Co 5 H CH3 2 3 CH3 CH3_CH_CH=CH_CH2_CH3 Co 3 H

Hiu sut olefin thu c ph thuc vo iu kin phn ng .

CH3CH2CBr(CH3)2 EtOK EtOH
(CH3)3COK (CH3)3COH (C2H5)3COK (C2H5)3COH

CH3CH=C(CH3)2 + 71%
28%

CH3 CH3CH2C=CH2 29%

72%

11%

89%

Tc phn ng E2 ph thuc vo nng ca alkylhalogenid, nng base v ph thuc vo bn cht ca nhm X.

106

Phn ng c nh hng bi cc lin kt: Lin kt CX d b ct t hn lin kt CH. Phn ng c tnh lp th: Nguyn t hydro v nguyn t X b tch phi lun lun trn cng mt mt phng.
H C6H5 Br H C 6 H5 Br

H C C6H 5 Br

H C C6H 5 Br
Base

C6H 5
HBr + Br

H C C C6H 5

H C6H5

C6H5 Br

(R,R) 1,2 -dibromo-1,2-diphenyl etan H

(Z) 1-bromo-1,2-diphenyl ethylen

H H

C6H5 C6H5

H C Br

H C C6H 5 Br
Base HBr +

Br C C6H 5 C

H C6H 5

H Br

C6H5 C6H5

C6H 5 Meso-1,2 -dibromo-1,2- diphenyl etan

Br

(E) 1-bromo 1,2-diphenyl ethylen

4.2. Tch loi nc t alcol C th tin hnh tch loi nc khi alcol no theo 2 phng php: 4.2.1. pha lng un nng alcol vi acid mnh (H2SO4, H3PO4) hoc vi KHSO4 s to alken.
RCH2CH2OH H2SO4 180oC RCH=CH2 + H2O

Phn ng xy ra qua giai on to ester v c sau s hnh thnh alken hoc sn phm ph l ether .
RCH2CH2OH H2SO4 140oC RCH2CH2OSO3H + H2 O

RCH2CH2OSO3H RCH2CH2OSO3H RCH2CH2OH

RCH=CH2 + H2SO4 RCH2CH2OCH2CH2R + H2SO4

i vi nhng alcol bc 1 c s carbon n 4 th to hn hp cc alken. V d khi loi nc khi 1- octanol c th to thnh hn hp cc alken:
CH3(CH2)6CH2OH H3PO4 , CH3(CH2)5CH=CH2 + CH3(CH2)4CH=CHCH3

C hin tng trn l do s chuyn v ca hydro trong carbocation to thnh.

H H+ CH (CH ) CH_+ CH2 CH3(CH2)6CH2OH 3 26 - H 2O + CH3(CH2)5CH_CH_CH3 H H + CH3(CH2)4CH_CH_CH2_CH3

..

107

Phng php ny c dng thay i v tr ca chc alcol. Alcol bc 2, bc 3 d loi nc trong mi trng acid. Phn ng theo c ch E1.
OH CH3CH2CH2CHCH3 H2SO4 62% CH3CH2CH=CHCH3 + H2O 95o

C ch E1
+OH 2 + + + CH3CH2CH2CHCH3 H CH3CH2CH2CHCH3- H2O CH CH CH CHCH -H CH CH CH=CHCH 3 2 2 3 3 2 3 OH

C trng hp xy ra s chuyn v:
CH3-C__CH-CH3 CH3 CH3 + CH3_C_CH_CH3 CH3 CH3 OH H+ to + CH3-C__CH-CH3 CH3 CH3 _CH_CH CH2=C 3 CH3 CH3 CH3 + CH3-C__CH-CH3 CH3 CH3 CH3_C=C_CH3 CH3

-H+

4.2.2. pha hi Alcol di tc dng ca Al2O3 350 - 400C cng to alken theo c ch:
CH3CH2OH R Al + O H OH + Al Al2O3 300-400oC R+ CH2=CH2 + H2O + OH Al

Al

+ alken

Al

+ H2O

4.3. T dn xut dihalogen S tng tc gia dihalogen trn 2 carbon lin nhau vi bt kim loi (Zn,Cu) s thu c alken.
Cl Cl
RCH_CHR' + Zn RCH=CHR' + ZnCl2

4.4. Phng php dehydro ho, cracking hydrocarbon no Trong cng nghip cc alken thng c iu ch bng cch dehydro ha cc alkan di tc dng ca xc tc thch hp (V d crom trioxyd 450C). T butan, isobutan iu ch c buten v isobutylen. 108

CH3CH2CH2CH3

CrO3 450oC

CH3CH2CH=CH2 + H2

Cc alken cng c to thnh khi nhit phnC, cracking cc hydrocarbon no.

n- C6H14 700-800oC CH + CH =CH + CH CH=CH + San pham khac 4 2 2 3 2 25% 15% 20% 40%

Propen l nguyn liu sn xut polypropylen. Alken quan trng trong cng nghip l buten v ethylen c iu ch bng phng php dehydro ha hoc cracking nguyn liu thu c t du m. 5. Tnh cht l hc Ba thnh phn u tin ca dy ng ng iu kin thng l cc cht kh. Cc thnh phn trung bnh l nhng cht lng. Cc thnh phn cao hn l cht rn. Tnh cht vt l c trng ca mt vi cht hu c c trnh by trong bng 9-1.
Bng 9: Tnh cht l hc ca cc alken
Cong thc CH2=CH2 CH3CH=CH2 CH3CH2CH=CH2 CH3CH=CHCH3 CH3C=CH2 CH3 CH3CH2CH2CH=CH2 CH3CH2CH=CHCH3 CH3CHCH=CH2 CH3 CH3C=CHCH3 CH3 Ten goi Ethylen Propylen 1-Buten cis 2-Buten isoButylen 1-Penten 2-Penten 3-Methyl-1-buten 2-Methyl -2-buten tochay -169,4 -185,2 -130,0 -139,0 -140,0 -138,0 -139,0 -135,0 -124,0 tosoi -103,9 - 47,0 -5,0 -3,5 -6,0 +29,9 +36,4 +25,0 +38,4 Ty khoi 0,566 0,609 0,668 0,635 0,566 0,640 0,651 0,648 0,668

Ph hng ngoi: Lin kt -C=C- alken c vch hp th gn 1650 cm -1. Tuy nhin cng v tr s ca vch ny cn ph thuc vo cu to phn t ca alken (lin hp vi C=C- hoc -C=O). Cc vch hp th do dao ng ca lin kt C -H ca nhm -CH=CH2 c tn s khong 3100, 1420 v 915 cm -1

Lin kt i d b phn cc. Phn t alken c momen lng cc thay i ty thuc vo cu to ca alken.

109

Cl R CH=CH2 C H =0 C

H Cl

Cl C H C

Cl H

Cl C H C

H CH3

Cl C H C

CH3 H

= 2,95D

= 1,97D

= 1,71D

6. Tnh cht ha hc Trong lin kt i, nng lng lin kt ln hn nng lng lin kt . chnh lch vo khong 20 kcal.mol1. iu ny gii thch tnh km bn ca lin kt v kh nng phn ng cao ca lin kt i. Lin kt i l trung tm phn ng ca alken. Cc phn ng quan trng nht i vi alken l phn ng cng, phn ng oxy ha v phn ng trng hp. 6.1. Phn ng cng hp Lin kt b b gy v kt hp vi hai nguyn t hoc 2 nhm nguyn t mi to hp cht no. Lin kt i -C=C- c tnh i nhn. S chung ca phn ng cng hp vo ni i nh sau:
C=C

+ X_Y

C_ C X Y

6.1.1. Phn ng hydro ho c xc tc Cng hp hydro vo alken to alkan. Phn ng ch xy ra khi c xc tc. Xc tc thng dng l Pt, Pd hoc Ni. Phn ng ta nhit ( = - 32,7 kcal.mol-1) .
C=C

H2

xuc tac

C_ C H H

Dng nickel hot ng mnh l ''nickel Raney''. Nickel Raney c iu ch t hp kim nickel -nhm. Khi ch ha hp kim ny vi dung dch NaOH, nhm b ha tan. Nickel thu c trng thi bt rt mn v d bc chy. Nickel Raney hnh thnh theo phn ng.
2Ni-Al + 2HO + 2H2O 2Ni + 2AlO2 + 3H2

Cc hp cht ca lu hunh, phosphor, arsen lm mt tc dng hot ha ca cc xc tc. Phn ng hydro ha alken xy ra trn b mt ca xc tc v theo c ch cng hp cis.
H2 Be mat xuc tac H H C2H4 H H CH2=CH2 H_CH2_CH2_H

S cng hp cis vo lin kt i c th trnh by trong phn ng sau:

H 3C

C
C

C O OH

H2 Pd

H OO C H3C C H

C OO H C H3 H

HO OC H3 C H

H C C C O OH C H3

H 3C

C OO H

Phn ng hydro ha c xc tc do Sabachie v Sendoren pht minh nm 1899 v tr thnh phng php quan trng v ph bin ca ha hu c. 110

6.1.2. Phn ng cng hp i in t (AE) Phn ng xy ra gia alken v tc nhn i in t (electrophile). C 2 giai on sau: Giai on I Tc nhn i in t kt hp vi carbon ca lin kt i giu in t hn hnh thnh ion carboni. y l giai on chm quyt nh tc phn ng.
Y

- +
X

- +
C== C

Cham

+ X C__C

+ Y-

Giai on II Ion carboni kt hp vi phn cn li ca tc nhn tch in m.

+ X C__C

+ Y-

Nhanh

X C__C

Cc tc nhn phn ng halogen X2 (Cl2, Br2, I2), cc hydrohalogenid HX (HCl, HBr), cc acid hypohalogen HOX (HOCl, HOBr), nc, acid sulfuric u cng hp vo lin kt i ca alken theo c ch i in t v to thnh hp cht no tng ng.
+ Br2 + HOCl C__ C Br Br C__ C Cl OH

Hp chat dibromo

Hp chat clorhydrin

- +
C== C

+ H2SO4 + HCl + H2O , H+

C__ C Ester cua acid sulfuric H OSO3H C__ C H Cl C__ C OH

Hp chat monoclor Alcol n chc

Cng hp HX 2-Methylpropen cng hp vi HCl. Trc tin lin kt i tc dng vi proton H + to thnh carbocation trung gian. Sau carbocation kt hp vi ion clorid Cl - v to thnh tert butylcloid.
CH3 CH3 H H H Cl CH3 CH3 + C H H H CH3 Cl CH3 C C H H H

+ Cl

111

Alken khng i xng tc dng vi proton to thnh carbocation bn vng.

CH3 CH3C=CH2 + HCl CH3 CH3 + _C_CH khong tao thanh CH3_C_CH2 CH3 3 + H

Phn ng xy ra theo qui tc Markonikov Cc hydrohalogenid cng vo lin kt i theo kh nng HI > HBr > HCl Tc dng ca dung dch nc clor hoc brom vi alken to sn phm halogenohydrin. Trong trng hp ny tc nhn phn ng l acid hypoclor HOCl hoc hypobrom HOBr CH3CH2CH=CH2 + HOCl CH3CH2CHOH-CH2Cl (Butylen clorohydrin) Carbocation trung gian c th b chuyn v hydro cho nn khi alken tc dng vi HX c th to ra hn hp cc alkylhalogenid.
+ CH3CH2CH -CH2CH3 Br + CH3CH2CH2 -CHCH3 Br CH3CH2CHBr -CH2CH3 3-Bromopentan CH3CH2CH2 -CHBrCH3 2-Bromopentan

CH3CH2CH = CHCH3 + HBr 2-Penten

Cng hp vi nc H2O Hydrat ha alken l phng php quan trng iu ch alcol trong cng nghip. Phn ng cng hp nc thng xy ra trong mi trng acid. Phn ng qua giai on to carbocation trung gian. Carbocation tc dng vi nc to thnh alcol.
CH3 + CH3C = CH2 + H Isobuten CH3 CH3C_ CH3 + Carbocation + H2O CH3 CH3C_ CH3 +OH 2 CH3 CH3C_ CH3 + H+ OH t-Butanol

Cc quy tc nh hng trong phn ng cng hp vo alken Quy tc Markonikov Trong phn ng cng hp, tc nhn khng i xng (HX...) tc dng vi mt alken khng i xng th nguyn t hydro ca HX s tn cng vo nguyn t carbon ca ni i c nhiu hydro hn, cn X s tn cng vo nguyn t carbon cn li ca ni i.
CH3CH = CH2 + HCl Propylen CH3CH _ CH3 Cl isopropylclorid

C th gii thch theo cc trng thi ca phn ng. Trng thi tnh Trong phn t propylen do tc dng y in t ca nhm metyl v pha lin kt i (hiu ng +I v hiu ng siu lin hp) lm cho lin kt ny phn cc. 112

Mt in t dch chuyn v pha nhm CH2 (carbon bc thp) v nhm ny mang mt phn in tch m -, cn nhm methyl CH mang mt phn in tch dng +. Do s phn b mt in t trong phn t propylen c th trnh by nh sau.
H _C H H

CH = CH2 -

Khi cho H+Cl tc dng vi propylen, phn cation H+ (tc nhn i in t) s tn cng vo carbon mang in tch m v phn anion Cl tn cng vo carbon c in tch dng +. Trng thi ng V phn ng xy ra theo c ch cng hp i in t (AE), giai on quyt nh tc phn ng l giai on ca H+ tn cng vo phn t propylen. Gi thit c 2 carbocation to thnh:
+ CH3_CH _ CH3 ( I )
H H + + _C_CH _ C_H ( I ) va CH _CH _ CH ( II ) H 3 2 2 H H H _C _ CH+ ( II ) CH3 2 H

Phn ng xy ra theo qu trnh no l ph thuc vo nng lng v bn ca carbocation trung gian. Carbocation c nng lng cng thp v bn cng ln khi in tch dng trn nguyn t carbon ca carbocation cng c gii ta. iu xy ra khi in tch dng ca carbon lin hp vi cng nhiu in t ca cc lin kt C -H. Carbocation c bn cng ln th thi gian tn ti cng lu v d hnh thnh. Carbocation (I ) lin hp vi 6 lin kt C_H . Carbocation (II) ch lin hp vi 2 lin kt C_H. Do ion (I) bn v d hnh thnh hn ion (II). iu gii thch v sao khi cng hp HCl vo propylen th isopropylclorid l sn phm ch yu. Trn c s gii thch s cng hp vo alken theo quan im trng thi ng, c th pht biu quy tc Markonikov nh sau: Phn ng cng hp i in t vo alken xy ra ch yu qua dng ion carboni trung gian c bn ln nht Phn ng cng tri qui tc Markonikov - Hiu ng Kharasch Khi cng hp HBr vo hp cht c ni i vi s c mt ca mt t peroxyd th sn phm to thnh tri quy tc Markonikov
CH3CH=CH2 + HBr
peroxyd peroxyd

CH3CH2_CH2Br BrCH2_CH2CH2B

CH2=CHCH2Br + HBr

Cc peroxyd nh dibenzoylperoxyd (C6H5CO)2O2, Peracetic CH3COOOH. 113

nh hng ca peroxyd i vi phn ng cng hp gi l hiu ng peroxyd hoc hiu ng Kharasch. Phn ng xy ra theo c ch cng hp gc qua cc giai on sau:
R-O-O-R R-O . + HBr
. ROH + Br

2R-O .

H = +35 kcal

Br + CH3CH=CH2 CH3CH_CH2Br + HBr

H = -23 kcal _CH Br CH3CH H = -5 kcal 2 _CH Br + Br. CH3CH2 H = -11 kc 2

Phn ng kt thc khi cc gc t do kt hp vi nhau

Br. + Br. Br2

C th gii thch s to ra sn phm tri vi sn phm Markonikov bng bn ca gc t do to thnh. Khi nguyn t brom Br. tc dng vi alken c kh nng to ra 2 gc t do (I) v (II). Gc t do (I ) bn v d hnh thnh hn ( II). Gc t do (I) chu nh hng ca 2 gc y in t v pha carbon mang in t n c .
Br + CH3CH=CH2
.

CH3CH_CH2Br (I ) CH3CHBr_CH2 (II)

CH3

CH

CH3CHBr

CH2Br

CH2

Kh nng to thnh v bn ca gc t do gim dn theo th t: Gc bc 3 > Gc bc 2 > Gc bc 1 Qui tc Wagner Tc nhn khng i xng tc dng vi alken, trong hai nguyn t carbon mang ni i l ng bc lin kt vi 2 gc alkyl khc nhau l methyl th phn anion Xca tc nhn s kt hp vi carbon ca ni i mang nhm methyl.
CH3CH2_CH=CH_CH3 + HBr CH3CH2_CH2_CHBr_CH3

C th gii thch quy tc trn theo quan nim: To carbocation trung gian bn vng. Gii thch theo hiu ng cm ng v hiu ng siu lin hp. Cng hp Halogen L phn ng quan trng ca lin kt i
C==C + X2 X__C__C__X (X2 = Cl2 , Br2 ..)

Phn ng xy ra nhanh. C th xem phn ng ny nh l mt phn ng th i nhn vo nguyn t halogen. Alken l tc nhn i nhn. Phn t alken tn cng vo phn t halogen theo s sau:

114

C C

Br

Br

C C +

Br + Br -

+ Br__C__C + Br

Br__C__C_ Br

Trn carbocation c nguyn t carbon thiu in t v nguyn t halogen c 3 cp in t khng lin kt. Chng c kh nng to thnh ion halonium vng.
X C + C

.. :X :
C C

.. . :X .
C C

.. :X
C + C

S tao thanh ion halonium vong

V vy s cng hp halogen c tnh lp th. Anion halogen X - tng tc vi vng halonium t pha ngc vi halogen trong vng. S cng hp halogen thng to thnh sn phm trans. iu thng thy trong cc hp cht vng cha no.

.. : X
X C + C X C C

Br2 CCl4 - 5o Cyclopenten

Br +

Br H Br H

.. :Br..

Trans 1,2-dibromocyclopentan

Sn phm cng hp halogen vi alken l cht trung gian trong tng hp hu c. 6.2. Hydroboran ha Phn ng ca lin kt i vi diboran B2H6 l mt phn ng quan trng ca alken. Lin kt BH cng vo lin kt i vi hiu sut cao v nhanh to thnh trialkylboran 6RCH=CH2 + B2H6 2(RCH2CH2)3B 6.3. Phn ng oxy ha Alken b oxy ha bi cc cht oxy ha khc nhau. 6.3.1. Vi KMnO4 Alken tc dng nhanh vi kali permanganat KMnO4. Sn phm to thnh ph thuc vo nng ca cc cht phn ng. Vi dung dch kali permanganat long th to thnh diol cnh nhau (glycol)
3 C C + 2KMnO4 + 4H2O loang 3 C OH OH C + 2MnO2 + 2KOH

Phn ng xy ra theo c ch cng hp cis

H + KMnO4 loang to O O Mn O O H H 2O OH OH

115

Vi dung dch kali permanganat m c, lin kt i b ct v to hn hp ceton v acid carboxylic.

R' R'' C==C R H KMnO4 R' R'' O C==O + HO_C R

; RCH=CH2

KMnO4

RCOOH + CO 2

6.3.2. Vi ozon (O3 ) Phn ng oxy ha alken bng ozon to thnh aldehyd, ceton hoc acid ty thuc cu to ca alken. Phn ng tri qua giai on to cht trung gian l ozonid. Ozonid kh phn ring c v b thu phn to thnh sn phm.
O3 O C O O C C O O C O

C
O O

Molozonid
C O + H2O C O+ O C

Ozonid
+ H2O2

C th dng phn ng ny xc nh cu trc ca alken.

CH3 CH3 C C CH2CH3 H
O3

CH3 C CH3

O O O

CH2CH3 H
H2O

CH3_C_CH3 + CH3CH2CHO + H2O2

Ozonid

6.3.3. Vi cc peroxyd Alken b oxy ha bng cc peracid. Sn phm to thnh l cc oxiran (epoxyd)
C6H5 H
O

+ CH3COOOH C C H C6H5 Trans-Stilben

C6H5

H Trans-2,3-diphenyl oxiran

H + CH3COOH C6H5

O COOH COOH CH3(CH2)3CH__CH2 + 1-butyl oxiran CH3(CH2)3CH=CH2 + 1-2-epoxyhexan Cl Cl 1-Hexen Acid 3-cloro benzoic Acid 3-cloro peroxybenzoic 1-oxydhexen
O

6.4. Phn ng trng hp (phn ng polymer ha) Phn ng trng hp cc alken hoc cc hp cht cha no khc c tm quan trng c bit trong cng nghip ha hc. C th c s chung nA (A)n. A l cc monomer, (A) n l cht cao phn t (polymer), n l h s trng hp. 116

Ty theo bn cht v iu kin phn ng, s trng hp xy ra theo cc c ch khc nhau. Polymer to thnh c cu to khc nhau v h s trng hp khc nhau. C ch phn ng trng hp c th l c ch gc, c ch ion (anion hoc cation) 6.4.1. Phn ng polymer ha theo c ch gc t do Xy ra qua cc giai on.

S to gc t do:
Y + CH2=CH2

Y-CH2CH2

S pht trin mch:

Y-CH2CH2 + CH2=CH2

Y-CH2CH2-CH2CH2

Y-(CH2CH2)n-CH2CH2

S kt thc phn ng:

Y-(CH2CH2)n-CH2CH2 Y-(CH2CH2)n-CH2CH2

. .

Y-(CH2CH2)n-CH2CH3 + Y-(CH2CH2)n-CH=CH2 -CH Y-(CH2CH2)n-CH2CH2 2CH2-(CH2CH2)n-Y

6.4.2. Phn ng polymer ho theo c ch cation C cc qu trnh

Qu trnh to cation: (CH3)2C=CH2 + H+ (CH3)3C+ Qu trnh pht trin mch polymer. Qu trnh kt thc Trong qu trnh trng hp c cc dimer, trimer c to thnh
cham + (CH3)3C-CH2-C(CH3)2 CH3 (CH3)3C-CH=C(CH3)2+ (CH3)3C-CH2-C=CH2 20% 80%

(CH3)2C=CH2

6.4.3. Phn ng theo c ch anion Xc tc to anion thng l cc hp cht c kim.

(CH3)3- Li+ + CH2=CH2 (CH3)3C-CH2-CH2- Li+

Hn hp gm R3Al + TiCl4 gi l xc tc Zigler -Natta c s dng trong phn ng polymer ha theo c ch anion. Cc polymer thng gp: Polyethylen (PE), Polypropylen (PP), Teflon X-(CF_Y, Polystyren. CF)n 6.5. Phn ng th 6.5.1. Th v tr allyl Tu theo cu to s th vo v tr allyl xy ra cc iu kin khc nhau 117

CH3_CH=CH2 + Cl2
CH3C=CH2 + Cl2 CH3

500-600o

ClCH2_CH=CH2 + HCl
ClCH2C=CH2 + HCl CH3

Nhiet o phong

Phn ng xy ra theo c ch nh sau:

CH3_C=CH2 + Cl_Cl CH3
+ CH3_C_CH2Cl CH3 -H +

+ CH3_C_CH2Cl + Cl CH3
CH2=C_CH2Cl CH3 Cl _C_CH Cl CH3 2 CH3 San pham chnh

+ Cl

San pham phu

6.5.2. Th vo v tr vinyl Xy ra iu kin kh hn s th vo v tr allyl. Nguyn t hydro lin kt vi carbon c ni i (gi l hydro vinyl) bng lin kt C_H. Lin kt C_H c nng lng lin kt ln hn nhiu so vi cc lin kt C _ H khc. Phn ng theo c ch gc.
CH2=CH2 + Cl2 200-600 o CH2= CH_Cl + HCl

S th v tr allyl cn th hin qua phn ng t oxy ha Cc alken d xy ra phn ng oxy ha ti v tr allyl v to thnh cc peroxyd. S oxy ha xy ra nhit thng v bng oxy khng kh. Phn ng ny l nguyn nhn cc du, m b oxy ha.
CH3CH2CH2_CH=CH2 + O2 CH3CH2CH_CH = CH2 O_O_H

7. Cht in hnh Ethylen CH2=CH2 Cht kh khng mu, khng mi, hu nh khng tan trong nc, ha lng -105C. Ethylen chy cho ngn la sng hn metan, to thnh CO2 v hi nc Hn hp ethylen v oxy n mnh v phn ng t chy ta nhiu nhit, c th dng hn hp ny ct hn kim loi nh acetylen. Ethylen kt hp vi nc to alcol ethylic. Ethylen tc dng vi dung dch clor trong nc to ethylen clorhydrin v t clorhydrin c th iu ch ethylen oxyd 118

Cl2 CH2 CH2 H2O

CH2 Cl

CH2 OH

KOH

CH2 O

CH2

ethylen clorhydrin

ethylen oxyd

Ethylen tc dng vi benzen xc tc AlCl3 to ethylbenzen, t ethylbenzen to styren dng sn xut polystyren v cao su tng hp BuNa -S.
+ CH2 CH2 AlCl3 CH2CH3 ethylbenzen styren H2 CH = CH2

Trng hp ethylen to polyethylen l hp cht cao phn t c nhiu ng dng trong k thut v i sng Ethylen c tc dng kch thch s hot ng ca cc enzym lm qu mau chn, c dng dm chn qu xanh nh c chua, chui . . . nng rt long.

Bi tp
1. Vit cng thc cu to ca cc cht sau: a. 3-Methyl-1-penten; b. 2,4-dimethyl-1-penten; c. 2,2-Dimethyl-3-ethyl-1-octen. d. Dipropylethylen khng i xng.

e. Diisopropylethylen i xng. Gi tn theo IUPAC ca cc cht c CTCT di y:

Cl CH2CH2Br CH2CH2CH(CH3)2

a-

CH3 H

C C

CH3

CH2CH3

b-

BrCH2 CH3

C C

CH2C(CH3)3 CH3

; c-

CH3CH2CHCH2 H

H C C

; d-

CH2 C

CH2CH3

2. Khi un nng 3- bromo-2-methyl pentan vi kim ru thu c mt hydrocarbon cha no. Vit phng trnh phn ng. Trong cc iu kin y s nhn c hydrocarbon no, nu i t: a. Isobutyl iodid. b. 2-bromopentan. c. 3-cloropentan. 3. Nhng hp cht no c to thnh khi oxy ha cc cht di y bng dung dch KMnO4 long nhit thp: a. 2-Hepten. b. Metyl isopropyl ethylen i xng. c. Trimethylethylen. 4. Hy vit CTCT ca cc hydrocarbon ethylenic bit rng ozonid ca chng b thy phn trong mi trng acid th to thnh cc cht: a. Formaldehyd HCHO v aldehyd methylacetic CH3CH2CHO b. Aceton v aldehyd propionic CH3CH2CHO c. Methylisopropylceton CH3COCH(CH3)2 v formaldehyd. 119 d. 4- Bromo-2,2 -dimethyl pentan. e. 2- Bromo-2-methyl butan.

Chng 10

ALKYN - HYDROCARBON ACETYLENIC (CnH2n-2)

Mc tiu hc tp 1. Trnh by c cu to v gi tn cc alkyn. 2. Nu c cc tnh cht ha hc ca alkyn. 3. Vit c s cc phn ng chuyn ha to thnh sn phm. Alkyn hoc hydrocarbon acetylenic l hp cht khng vng cha no c cha mt lin kt ba ng vi cng thc chung CnH2n-2 1. Cu trc in t Alkyn l nhng cht cha lin kt ba -CC-. Nguyn t carbon ca ni ba trng thi lai ha sp. Lin kt ba gm mt lin kt v 2 lin kt . Lin kt C_C c to thnh do s xen ph vi nhau ca 2 orbital lai ha sp ca carbon. S xen ph ca orbital lai ha sp ca carbon vi orbital s ca hydro to thnh lin kt C_H. Lin kt ca alkyn c to thnh do s xen ph tng i mt ca cc orbital p t do ca nguyn t carbon lai ha sp. Hai lin kt ca alkyn nm trong 2 mt phng thng gc vi nhau.

_C _

C_

. . _ C C_ _. .
Cac electron p t do cua carbon 2 orbital p t do cua carbon
o

Carbon lai hoa sp

orbital s cua hydro

Acetylen c cu to thng. di lin kt C C (1,2A ) ngn hn lin kt C -C. Lin kt C -H (1,06A ) ngn hn lin kt C -H trong ethylen (1,08A ) v trong o etan (1,10A ). Hnh di y m t s to thnh lin kt ba:
o 1,06 A H C o 1,20 A C H
H C C H H1s Csp
o o

Csp Csp

H1s Csp

180 o o dai va goc lien ket

S tao lien ket trong phan t acetylen

S xen phu cua cac orbital p

Nng lng kin kt: i vi lin kt ba l 199,6 kcal.mol1, ca lin kt i l 145,8 kcal.mol1 v ca lin kt n l 82,6 kcal.mol1. Mt in t tp trung ch yu khong 120

gia hai ht nhn ca 2 nguyn t carbon. m in ca carbon lai ha Csp > Csp2 > Csp3. iu gii thch kh nng phn ng cng hp i in t ca lin kt ba km hn so vi lin kt i. 2. Danh php v ng phn 2.1. Danh php IUPAC Cc alkyn u c tn cng l yn. Mch chnh l mch di nht c lin kt ba. nh s mch chnh sao cho lin kt ba c s nh nht.
V tr nhnh + Tn nhnh + V tr lin kt ba + Tn mch chnh + yn
CH 4 3 3 2 1 CH3_CH_C CH CH 1 5 6 3 7 2 3 4 3-Methyl-1-butyn; CH _C C_CH _CH _CH_CH 3 2 2 3

6-Methyl-2-heptyn

2.2. Danh php hp l - Danh php acetylen Cc alkyn n gin c xem nh dn xut ca acetylen CH3CCH (CH3)2CHCCCH3 F3C_CCH 2.3. Tn cc gc -CCH
C CH

Methyl acetylen Methylisopropylacetylen Trifluoromethyl acetylen

Etynyl

CH3-CCH

Propynyl
C CCH3

CH3_CC-CH2- 2-Butynyl

Etynylcyclopentan ; Cyclopentylacetylen

Propynylcyclohexan Methylcyclohexylacetylen

2.4. ng phn Cc alkyn c ng phn cu to v mch carbon v ng phn c v tr ca ni ba . Khc vi alken, cc alkyn khng c ng phn lp th. 3. Phng php iu ch 3.1. Tch loi 2 phn t HX t hp cht gem v vic -dihalogen Nguyn tc: T gem dihalogen T vic -dihalogen -CB r 2 -CH 2 -

-C C- + 2HX CHX-CHX- -C C- + 2HX

Phn ng xy ra qua 2 giai on:

Nhanh

-C H Br-CH Br-

-C X =C H -

Cham

_ -C _ C -

121

S tch loi xy ra khi c mt ca KOH hoc NaOH trong alcol v nhit .

CH3CH2CHBr2 Br2 ete KOH alcol to Br Br CH3_C CH + 2 HBr

C6H5CH=CHC6H5 Stilben

KOH alcol C6H5CH-CHC6H5 to (77-81%) 1,2-Dibrom-1,2-diphenyletan Br Br CH3CH_CH2

C6H5_C C_C6H5 + 2 HBr (66-69%) Diphenylacetylen

CH3CH=CH2 + Br2 Propen

KOH alcol to

1,2-dibromopropan

CH3_C CH + 2 HBr Methylacetylen

Natri amidid NaNH2 l mt base mnh c th s dng tch HX trong phn ng iu ch cc 1-alkyn.
RCX2-CH3 RCHX-CH2X RCH2-CHX2 + 2NaNH2 - NaX - NH3 R_C C_H NaNH2
+ R_C C _Na + NH3

+ R_C C _Na + H2O

R_ C C_ H +

NaOH

Phn ng tch HX trong iu kin c mt base mnh v nhit thng c th xy ra s chuyn v ca ni ba.
CH3CH2_C C_H 1-Butyn KOH alcol t o CH3_C C_CH3 2-Butyn

3.2. Phng php alkyl ha acetylen Anion acetylid l mt tc nhn i nhn mnh (mt base mnh) d dng tc dng vi alkylhalogenid to thnh alkyn c mch carbon di hn.
H_C C_H + Na CH3_C C_H + Na Propyn + RX H_C C_Na CH3_C C_Na H_C C_R + NaX CH3_C C_CH2CH3 + NaI 2-Pentyn

+ CH3CH2I

C th s dng natri amidid to acetylid trong phn ng alkyl ha acetylen.

H_C C_H + NaNH2
NH3 (lng)

-33oC

H_C C_Na Natri acetylid

n-C4H9Br

CH3(CH2)3_C C_H Hexyn-1 (89%)

3.3. T hp cht tetrahalogen Cc hp cht c 4 halogen gn trn 2 carbon cnh nhau tc dng vi bt Zn kim loi trong iu kin thch hp cng to c lin kt ba. 122

X X _C C_R' R X X

+ 2 Zn

R_C C_R' +

2 ZnX2

4. Tnh cht l hc S to thnh lin kt C_C c to thnh do xen ph ca orbital lai ha Csp ca metyl v orbital lai ha ca carbon acetylenic . Mt orbital sp c tnh cht ca orbital S nhiu hn orbital sp3. Kt qu l lin kt c chnh lch v m in. Mt in t trn lin kt C_C l khng i xng v xut hin momen lng cc.
3

CH3CH2CCH (sp3v sp) CH3CH2CH=CH2 (sp3 v sp2) CH3CCCH3 = 0,80 D = 0,30 D = 0 Hp cht alkyn khng c ng phn hnh hc nh hp cht alken v acetylen c cu trc thng. Mt vi tnh cht vt l ca alkyn c trnh by bng 10-1.
Bng 10: Tnh cht vt l ca cc hp cht alkyn
Hp cht to si to nng chy T khi

Etyn Propyn Butyn-1 Butyn-2 Pentyn-1 Pentyn-2 Hexyn-1 Hexyn-2 Hexyn-3 Phenylacetylen Diphenylacetylen

- 84,0 - 23,2 8,1 27,0 39,3 55,5 71,0 84,0 81,0 143,0 300,0

- 8,9 - 102,7 - 122,5 - 32,3 - 90.0 - 10,0 -132,0 - 88,0 -105,0 - 43,0 - 63,5 0,7152 0,7317 0,7231

5. Tnh cht ha hc 5.1. Tnh acid ca alkyn Lin kt C -H phn cc mnh v pha carbon ca lin kt ba CC-H+ lm tng momen lng cc ca lin kt v tng kh nng tch hydro di dng proton. Do tnh acid ca acetylen ln hn so vi etylen v etan. Gi tr pKa ca mt s cht sau y:
Hp cht pKa H2O 15,7 Alcol 16-19 Acetylen 25 NH3 35 Ethylen 44 Metan 50

123

Lc base

CH3CH2=CH HC C-

CH4 CH2=CH2 HC CH

Lc acid

Tnh base ca cc anion khc nhau v nguyn t carbon mang in tch m cc trng thi lai ha khc nhau.
H H C

H sp3 H C C

..
sp2

H_C C

H Anion methyl

H Anion vinyl

sp

Anion acetylid

Cc alkyn c ni ba u mch (cc 1- alkyn) cng rt d to carbanion khi tc dng vi anion amidid trong amoniac lng.
R_C C_H + NH2R_C C+ NH3

Cc carbanion RC C-, CH2=CH- v H3C- c bn khc nhau. Nguyn t hydro trong lin kt C H cn th hin cc phn ng sau y: Acetylen v 1-alkyn tc dng vi kim loi kim, CuCl trong amoniac, AgNO3 trong amoniac u to thnh acetylid hoc alkynylid kim loi.
R_C C_H + AgNO3 + NH3 R_C C_H + CuCl + NH3 R_C C_Ag

+ NH4NO3

R_C C_Cu + NH4Cl

Acetylen cng hp vi aldehyd formic nh l mt tc nhn i nhn.

H_C C_H + 2HCHO Aldehyd formic HOCH2_C C_CH2OH 1,4-Butyndiol

Alkyl lithium tch proton khi alkyn. CH3(CH3)2CCH + n-C4H9Li CH3(CH3)2CCLi + n-C4H10 5.2. Phn ng cng hp 5.2.1. Cng hp vi hydro Alkyn tc dng vi hydro c xc tc to thnh alkan
R_C C_R' + 2H2 Pt ,( Pd , Ni) R-CH2CH2-R'

Phn ng thng xy ra 2 giai on. Giai on mt to nhit hn giai on hai. HCCH + H2 CH2=CH2 CH3_CH3 H = -41.9 kcal mol-1 H = -32,7 kcal mol-1

H2C=CH2 + H2 124

S hydro ha c th dng li giai on to alken khi dng xc tc c lm gim kh nng hot ha mt phn. Hn hp xc tc l PdCaCO3, PdBaSO4-Quinolin.
CH3CH2_C C_CH2CH5 3-Hexyn

H2

Pd- BaSO4 Quinolin

C2H5

H H cis-3-Hexen

C C

C2H5

S cng hydro cng c th xy ra khi s dng natri kim loi trong amoniac lng.
C4H5C CC4H9 5-Dekyn Na/NH3(lng) NH4OH H9C4 H C C

H C4H9 Trans- 5-deken

5.2.2. Phn ng cng hp i in t Phn ng cng hp i in t xy ra ti lin kt ba theo 2 giai on v tun theo qui tc Markonikov. Cc tc nhn cng i in t c th l X2 (halogen), HX, H2O.
RC CR' RC CH + X2 + HX RCX CXR' RCX CH2 + X2 + HX RCX2 CX2R' RCX2 CH3

Khi cng hp vo ni ba, carbocation dng vinylic R -C+=CH2 c to thnh v d dng tc dng vi cc tc cht i nhn c trong mi trng phn ng. V d s to thnh vinyl clorid: CHCH + H+ CH2=CH+ ;
HC C CH=CH2 + H+

CH2=CH+ + Cl- CH2=CHCl

+ ClH2C CCl CH=CH2

+ H2C C CH=CH2

Phn ng cng hp vi nc c xc tc xy ra qua giai on to cht trung gian enol. Enol khng bn d b chuyn v to thnh aldehyd hoc ceton .
HgSO4-H2SO4

R C C H + 1- Alkyn

H2O

OH R C CH2 Dang enol

O R C CH3 Ceton

C4H9 C C H 1- Hexyn

H2O

HgSO4-H2SO4

O C4H9 C CH3 Methylbutylceton

5.2.3. Cng hp i nhn Khc vi alken, cc alkyn tham gia phn ng cng hp vi cc cht i nhn nh alcol, amin, acid carboxylic, amid, HCN to thnh cc hp cht tng ng.

125

ROH R2NH H C C H RCOOH RCONH2 HCN

H2C CH OR H2C CH NR2 H2C CH OCOR

Ether vinylic Vinyl amin Ester vinylic

H2C CH NHCOR Amid H2C CH CN Acrylonitril

5.2.4. Phn ng carbonyl ho vo lin kt ba Khi c xc tc l cc carbonyl kim loi v p sut, acetylen tng tc vi hn hp gm carbon oxyd (CO) v cc cht c hydro linh ng (nc, alcol, amin bc mt v hai) th to cc cht nh acid, ester, amid...
CO + H2O H C C H CO + ROH CO + R2NH H2C H2C H2C CH CH CH COOH COOR Acid acrylic Ester acrylat

CONR2 Amid cua acid acrylic

5.2.5. Phn ng vi diboran B2H6 Alkyn tc dng diboran 0C to cc cht trung gian trivinylboran. Khi c mt ca acid acetic th to thnh alken dng cis.
3 R C C R' + 1B H 2 2 6 1B H 2 2 6 R H R H C C C C R' 3 H 3 B 3 CH3COOH R H R H C C C C R' H H H

3R C C H +

B 3 CH3COOH

Phn ng cng c th xy ra vi bor dialkyl v theo c ch cng cis

CH3CH2 C C CH2CH3 + R B H R CH3CH2 CH2CH3 CH2CH3 CH3CH2 C C C C CH3COOH R H H H B 0oC cis 3-Hexen (90%) R

Lin kt CB trong hp cht vinylboran d b oxy ha bi nc oxy gi (H2O2) to thnh enol v sau chuyn v thnh aldehyd hoc ceton.
C4H9C CH 1-Hexyn B2H6 H2O2 OHC4H9 H C C H OH C4H9CH2CHO Hexanal

126

5.3. Phn ng trng hp cc iu kin thch hp v xc tc, nhit v p sut, cc alkyn c th b nh hp, tam hp to thnh cc cht tng ng.
2 HC CH Cu(NH3)2Cl HC C CH=CH2 Vinylacetylen Benzen

3HC CH

Carbon ,600oC

200 - 300C khi c bt ng lm xc tc, acetylen b trng hp to polyacetylen cn gi l cht cao phn t Cupren.
n HC CH 200-300oC Cu

-CH=CH- Cupren n

hay viet (CH)n

6. Cht in hnh Acetylen C2H2 iu ch Thy phn carbur calci (t n) CaC2 + 2H2O HCCH + Ca(OH)2 T kh thin nhin: Phn ng quan trng trong cng nghip iu ch acetylen l in cracking v cracking oxy ha nhit metan. + in cracking: Cho CH4 i qua cc in cc, in th mt chiu 8000V, nhit phn ng 1600C, tc dng kh 1000 m /s. Hn hp kh thot ra c lm lnh ngay. 2CH4 HCCH + 3H2 H0298 = 91 kcal/mol

Hn hp kh cha 13% acetylen + Cracking oxy ha nhit 6CH4 + 4O2 HCCH + 8H2 + 3CO + CO2 +3H2O

T l CH4 : O2 = 1 : 0.65. Nhit l phn ng 1500C, tc kh i qua l rt ln. Lm nhanh s thu c hn hp kh vi khong 8% acetylen. Tnh cht v ng dng. Acetylen l cht kh khng mu, nguyn cht khng mi, nh hn khng kh, t tan trong nc, tan nhiu trong cc dung mi hu c nh alcol, ether, tan rt nhiu trong aceton. Acetylen khng bn v mt nhit ng, n c th b phn hy to C v H2 km theo hin tng n. Phn ng n to nhiu nhit, H0298 = -54.9 kcal/mol, nhit kh lc ln ti hng ngn . 127

Acetylen chy trong khng kh cho ngn la sng, to CO2 v nc, nhit lng ta ra rt ln. Khi dng hn hp C2H2-O2 lm kh hn, ct kim loi mu, mun hn tt phi dng kh tr (Argon) oxy khng tip xc trc tip ln b mt kim loi hn.

Bi tp
1. Vit cng thc cu to ca hydrocarbon sau: a- 2- butyn; b- 2- methyl-3-hexyn; c- 2,2,5-trimethyl-4-hexyn; d- isopropylacetylen. 2. Gi tn nhng hp cht sau:
CH3 CH3 a- CH3_C_CH2_CH2_CH HC C CH3

b-

CH3 CH3 _C_C C_C_CH CH3 3 _CH CH3 CH3 2

c-

C CH

3. Vit phng trnh phn ng gia dung dch kim - ru d vi cc cht di y: a- 1,1- dibromobutan; b- 2,2- dibromo-3,3- dimethylbutan; c- 2,2- diclopentan 4. Vit phng trnh phn ng gia B2H6-H2O2 - OH- vi cc cht sau: a- 1-butyn; b- 2-butyn; c- 2- pentyn; d- methylisopropylacetylen. 5. Vit s phn ng ca acetylen vi nhng cht sau: a- alcol ethylic; b- acid cyanhydric; c- aldehyd formic; d- aldehyd acetic; e - aceton .

128

Chng 11

AREN - HYDROCARBON THM

Mc tiu hc tp 1. Gii thch cu to ca nhn thm. 2. Gi tn c cc hydrocarbon thm. 3. Trnh by cc tnh cht ha hc ca benzen: c ch SE. Aren hay l hydrocarbon m trong phn t c mt ca mt hay nhiu nhn benzen. Aren cn gi l hydrocarbon thm - hydrocarbon hng phng 1. Benzen v nhn thm 1.1. Cu to benzen Benzen c cng thc phn t C6H6. Nm 1825 ln u tin Faraday M. pht hin benzen trong kh t. Nm 1834 Mitscherlich E. A. iu ch benzen t acid benzoic thu c t cy Styrax benzoin. Nm 1845 Hofmann tm thy benzen trong nha than . Benzen c mt s tnh cht c trng gi l " tnh thm ". gii thch tnh cht c trng cc nh ha hc a ra cc dng cng thc cu to ca benzen. 1.1.1. Cc dng cng thc c in

Kekule

Closs

Ladenburg

Amstrong

Dewar

Thiele

Cc cng thc trn khng gii thch y tnh cht ha hc c trng ca benzen. Cng thc benzen theo Kekule c 3 lin kt i suy ra benzen d tham gia phn ng cng hp hn phn ng th v benzen khng bn vi tc nhn oxy ha. Trn thc t benzen d tham gia phn ng th, kh cng hp v rt bn vi cc cht oxy ha. Cc cng thc Closs, Ladenburg, Amstrong, Dewar v Thiele u cha tha mn y cc tnh cht ha -l ca benzen nh di lin kt v kh nng phn ng.

129

1.1.2. Khi nim hin i v cu to benzen Bng cc phng php vt hin i: phng php Rnghen, quang ph v nhiu x in t, cu to ca ben zen c xc nh nh sau:

Benzen c cu to vng phng, 6 nguyn t carbon v 6 nguyn t hydro u nm trong mt mt phng. Vng benzen hon ton i xng. Khong cch gia cc nguyn t carbon trong vng u bng nhau 1,398 A l i lng trung gian gia di lin kt n thun ty v (1,54) v lin kt i (1,35A ). Gc gia cc lin kt CCC v CCH u bng nhau v c gi tr 120 (hnh11-1 a )
o o

Hnh 11.1:

H H

. .

H 120o . . H o 1,398A

H H

Lien ket H

C 2 sp
H

a c b d Goc va o dai S xen phu cac orbital Xen phu cac orbital p t do Cac orbital p t do lien ket va tao lien ket tao lien ket C-C va C-H tren cac nguyen t carbon

H1s Csp2 H 2 sp C

Mi nguyn t carbon to 3 lin kt . Trong c 2 lin kt do s xen ph ca 2 orbital lai ha sp2 gia carboncarbon bn cnh nhau. Cn mt lin kt gia CH do xen ph ca orbital lai ha sp2 ca carbon v ca orbital s ca hydro (hnh11.1b).

Trn mi nguyn t carbo cn mt orbital p cha lai ha. Trc cc orbital ny thng gc vi mt phng ca vng benzen (hnh 11.1c).

Tt c cc orbital ny xen ph ln nhau to thnh mt orbital phn t chung duy nht (hnh 11.1d). Nh vy cc orbital p trong vng benzen lin hp vi nhau thnh mt h thng lin hp hon chnh. Do h thng lin hp ny m khong cch gia cc nguyn t carbon trong vng benzen hon ton ng nht. Benzen tr nn bn vng, kh tham gia phn ng cng hp, kh b oxy ha v d tham gia phn ng th. Tnh cht c trng ny ca benzen gi l "tnh thm". Vy: "Tnh thm " l kh nng ca mt hp cht: D cho phn ng th, kh cho phn ng cng hp v phn ng oxy ha C th tng trng cng thc cu to ca benzen nh sau:

130

1.2. Nng lng cng hng ca benzen Nu dehydro ha cyclohexan to thnh cyclohexatrien phi cn nng lng 81,4 kcal.mol1. Nu chuyn ha cyclohexan thnh benzen th ch cn mt nng lng l 49,3 kcal.mol1. iu khng nh rng benzen khng phi l cyclohexatrien. H thng lin hp hon chnh ca benzen l nguyn nhn gim nng lng trn. Hiu s nng lng ca 2 trng hp trn gi l nng lng cng hng ca benzen (hay cn gi nng lng thm ha, nng lng lin hp) = 81,4-49,3 = 32,1 kcal.mol1 (hnh 11-2).

Nng lng cng hng -1 -30 kcal mol

o H = -24,5

kcal mol -1

o H = -26,5 o 1 H = -49,3 kcal mol o H = -28,4

kcal mol -1

kcal mol -1

Hnh 11.2: Gin nng lng cng hng ca benzen

1.3. Nhn thm Benzen l hp cht c tnh thm c bn nht . Nhng hp cht khc c cu to vng phng, cha no v lin hp c s electron p to h thng lin hp tha mn v cng thc Huckel 4n+2 u c tnh thm tng t benzen. Trong cng thc Huckel, n l s t nhin n = 0,1,2, 3... Nhng phn t hoc ion tha mn cng thc trn gi l nhn thm. Cc ion c th l carbocation hoc carbanion. V d: V cc nhn thm vi cc gi tr n khc nhau.

+ n= 0
2 electron
CH3

Cation cyclopropenyl
+

6 electron Toluen

n=1

_
Cation Anion cyclopentadienyl cycloheptatrienyl

.N . Pyridin

.. N H Pyrrol

131

n=2
10 electron Naphthalen

_
Anion cyclononatetraenyl

Dianion cyclooctatetraen

Cyclooctatetraen khng c tnh thm; khng phi l nhn thm v cyclooctatetraen ch c 8 electron v khng c cu trc phng (khng lin hp). 2. Danh php v ng phn Nu thay th mt hay mt s nguyn t hydro trong phn t benzen bng mt hay mt s gc alkyl th thu c cc ng ng ca benzen. Cc ng ng benzen c gi tn bng cch gi tn gc alkyl theo th t t n gin n phc tp c km theo v tr trn nhn thm v cui cng thm ch benzen.
V tr nhnh + tn nhnh + benzen
CH2_CH3 CH3 CH_CH CH3 CH2CHCH3 Iso-butylbenzen CH3

CH3 Toluen

CH2CH2CH3

Ethylbenzen n-Propylbenzen

Iso-Propylbenzen

CH3 Tert-butylbenzen

C CH3

Nu cc ng ng c 2 gc alkyl gn vo nhn benzen th 2 nhm ny c th cc v tr khc nhau. Chng l nhng ng phn ca nhau.
CH3 CH3 1,2-Dimethylbenzen o-Xylen CH3 CH3 1,4-Dimethylbenzen p-Xylen CH3 CH3 CH CH3 CH3

CH3 1,3-Dimethylbenzen m-Xylen

1-Methyl-4-isopropylbenzen p-Xymen

Cc tip u ng ortho (o), meta (m), para (p) c dng gi tn cc ng phn c hai nhm th. Ortho ch 2 v tr cnh nhau. Meta ch 2 v tr trn vng cch nhau mt nguyn t carbon. Para ch 2 v tr i din nhau.
X Y X Y Meta ( m-) 1, 3 Y Para (p- ) 1, 4 X

Orto ( o-) V tr : 1, 2

Hp cht c 3 nhm th trn vng: Vicinal (vic-) ch 3 nhm th hon ton cnh nhau. Asymmetrical ( as-) ch 3 v tr khng i xng. Symmetrical ( s-) ch 3 v tr i xng.

132

X
1 5 2 3 4

Y Z
5

X
1 4 2 3

X
1

V tr :

Vicinal (vic-) 1, 2 , 3

Z Asymmetrical (as-) 1, 3 , 4

Z 5 4

2 3

Symmetrical (s-) 1, 3 , 5

Danh php cc gc: Nu ly bt mt nguyn t hydro ca benzen hoc ng ng s thu c gc ha tr mt v c tn gi nh sau:

CH3 CH3 m-Tolyl p-Tolyl CH3

Phenyl

o-Tolyl

Nu ly 2 nguyn t hydro trn vng benzen ta c gc ha tr 2 v c tn gi:

CH o-Phenylen 1,2-Phenylen p-Phenylen 1,4-Phenylen Benzylyden Benza C

m-Phenylen 1,3-Phenylen

Benzo

Theo danh php IUPAC cc hydrocarbon thm n gin thng c quy c gi theo tn thng thng v nh s theo nhng quy tc nht nh.
CH3
8 7 6 5 1 8 7 6 5 9 1 2 10 4 3 3 2 1 10 9 4 5 6 7 8 10 9 8 7 6 1 2 3 4 5

1 2

CH3 CH3

2 3

Toluen

o-Xylen

Naphthalen

Antracen

Phenantren

Pyren

3. Phng php iu ch Nha than l ngun nguyn liu ch yu v quan trng cung cp cc hydrocarbon thm. ng dng mt s phng php ha hc iu ch cc hydrocarbon thm. 3.1. Phng php dehydro ha cc cycloalkan Cc cycloalkan n vng v a vng nh cyclohexan, decalin (perhydronaphtalen) khi c xc tc v nhit thch hp c th b dehydro ha v to thnh hydrocarbon thm tng ng.
Xuc tac , to + 3 H2

Xuc tac , to

+ H2

133

3.2. Phng php trimer ha Benzen, mesitylen (1,3,5- trimetylbenzen) c th c iu ch t acetylen, propyn hoc aceton khi c cc xc tc ph hp .
CH3 3 CH CH Carbon . 600oC.
CH3 CH3 O CH3 O CH3 H2SO4 (16%) CH3

CH3 Mesityllen CH3

3 CH3 C CH Propyn

Carbon . 600oC.

CH3 + CH3 3 H2O

CH3 O

CH3

3.3. Phng php Wurtz -Fittig Phng php ny tng t vi phng php iu ch alkan. Cho kim loi hot ng tc dng vi dn xut halogen thm v alkyl halogenid.
X + R_ X + 2Na ete R + 2 NaX

BrH2C

CH2Br + 2Na ete

CH2 CH2 + 2 NaBr

3.4. Phng php alkyl ha theo phn ng Friedel - Crafts y l phng php iu ch cc ng ng ca benzen (Xem tnh cht ha hc ca hydrocarbon thm).
+ RX AlCl3 R + HX

4. Tnh cht l hc Cc ng ng ca benzen l nhng cht lng, mt s l cht rn. Chng u c mi c trng.

134

Bng 11: Tnh cht l hc ca mt s hydrocarbon thm

Cong thc C6H6 C6H5CH3 Ten goi Benzen Toluen o-Xylen m-Xylen p-Xylen Ethylbenzen Propylbenzen iso-Propylbenzen V tr 1 1,2 1,3 1,4 1 1 1 1,4 to nong chay + 5,51 -95,0 -29,0 - 53,6 + 13,2 -94,0 -101,6 -96,9 -73,5, to soi 80,10 110,6 144,4 139,1 138,4 136,2 159,2 152,4 176,0

T khi
0,8790 0,8669 0,8802 0,8641 0,8610 0,8669 0,8620 0,8618 0,8570

C6H4(CH3)2

C6H5C2H5 C6H5C3H7 C6H5CH(CH3)2

CH3C6H4CH(CH3)2 p-Methylisopropyl benzen

5. Tnh cht ha hc T cu to lin hp ca vng benzen, hydrocarbon thm c cc loi phn ng: Phn ng th i in t vo nhn benzen. Phn ng cng vo vng benzen. Phn ng oxy ho. 5.1. Phn ng th i in t trn vng benzen C ch chung cc phn ng th i in t xy ra qua 2 giai on ch yu: Giai on mt l s hnh thnh tc nhn i in t Y+. Giai on hai l s tng tc gia tc nhn i in t vi vng benzen to phc phc v sn phm ca phn ng th. Phn ng th tin hnh trong mi trng acid mnh hoc c mt mt cht xc tc. Acid mnh hoc xc tc c tc dng chuyn ha tc nhn phn ng thnh dng i in t Y+ (electrophile). Y_X + FeBr3 Y+ + FeBr3XTc nhn Y + s tng tc vi nhn benzen ti v tr c mt electron cao nht
Y + Y+ Phc Y+ H + Y hoac Phc H FeBr3X + HX + FeBr3

Phc

(Cation pentadienic)

C cc loi phn ng th i in t vo vng benzen nh sau:

135

5.1.1. Phn ng halogen ha Tng tc ca halogen nh clor, brom vi benzen khan nhit thng, c mt xc tc bt st hoc cc acid Lewis nh FeCl3, FeBr3, AlCl3, SbCl3 hoc cc iod, s xy ra phn ng mnh lit v to sn phm l cc dn xut halogen ca hydrocarbon thm nh clorobenzen, bromobenzen. Phn ng brom ha nh sau:
H + Br-Br + FeBr3 + Br + FeBr4 -

Carbocation trung gian c h lin hp, c mt carbon trng thi lai ha sp3
H + Br + H Br + H Br H Br

Trang thai chuyen tiep xac nh ong hoc

H Br. . . Br. . .FeBr3 Br H. . . Br. . .FeBr3

Hnh 11.3. Gin thay i nng lng ng vi cc trng thi trong phn ng brom ho

Phn ng brom ha c s chung:

H Br

C th trnh by gin thay i nng lng ng vi cc trng thi hnh thnh trong phn ng brom ho nh hnh 11-3.

Nng lng phn ng

+ Br-Br + FeBr3

Trng thi chuyn tip to sn phm

H Br

+ FeBr4-

Chat trung gian + Br2 + FeBr3 Chat phan ng

Br + HBr + FeBr3 San pham

Tien trnh phan ng

Br + FeBr4 + HBr + FeBr3

136

Clor ha toluen c xc tc FeCl3 to ra hn hp o -clorotoluen v p - clorotoluen

CH3 CH3 + Cl2 FeCl3 FeCl3 CH3 + Cl HCl Cl + HCl

Phn ng halogen ha vo mch nhnh ca hydrocarbon thm khi c xc tc l nh sng khng phi l phn ng th i in t m l phn ng halogen ha xy ra theo c ch th gc. Clor ha toluen khi c xc tc nh sng to ra cc sn phm benzylclorid, benzylyden clorid (benzalclorid) v benzotriclorid.
CH3 Cl2 , h - HCl Toluen CH2Cl Cl2 , h - HCl Benzylclorid CHCl2 Cl2 , h - HCl Benzylydenclorid Benzotriclorid CCl3

S to gc t do benzyl cn nng lng thp. Gc benzyl bn nh s lin hp.

CH3
. + Cl

CH2 . + HCl H = - 16 kcal.mol-1 ; Goc t do benzyl

CH2

CH2

CH2

CH2

S to thnh hp cht halogen nhn benzen v mch nhnh l nhng hp cht hu c c nhiu lnh vc ng dng. 5.1.2. Phn ng nitro ha Phn ng nitro ha l phn ng thay th nguyn t hydro ca hydrocarbon bng nhm NO2. Tc nhn to ra +NO2 thng l hn hp sulfonitric (HNO3+H2SO4 ). Ty trng hp, tc nhn nitro ha c th l acid nitric c hay long hoc hn hp acid nitric vi anhydrid acetic. Nitro ha benzen, toluen bng hn hp acid nitric v acid sulfuric xy ra d dng. Sn phm to thnh ty theo nhit , nng acid.
H2SO4 + HNO3 NO2 + H2O

NO2 NO2
+ HNO3 H2SO4

NO2 NO2
+ HNO3 H2SO4

NO2 NO2

Tip tc nitro ha mononitrobenzen phi s dng hn hp acid nitric c nng v nhit cao hn. Sn phm to thnh l meta - dinitrobenzen. a thm nhm nitro th ba vo phi tin hnh trong iu kin khc nghit hn. L do l nhm nitro lm gim hot ha, mt electron trn cc v tr ca vng benzen gim i, s th i in t tip tc vo nitrobenzen s kh khn hn. 137

Toluen b nitro ha s to thnh hn hp sn phm gm o -nitrotoluen v p - nitrotoluen.

CH3 CH3 + HNO3 H2SO4 CH3 + HNO3 H2SO4 NO2 + H2O p-Nitrotoluen NO2 + H2O

o-Nitrotoluen

Nhm methyl trong toluen c tc dng y electron (do siu lin hp v cm ng) lm cho mt electron trong vng benzen tng ln, c bit cc v tr ortho v para, v vy s th xy ra u tin ti cc v tr ny. nh hng c th c minh ha bng cc trng thi cng hng ca toluen nh di y:
H H C H CH3 CH3 CH3 CH3

Cc sn phm nitro ha hydrocarbon thm lm phong ph thm ngun nguyn liu sn xut nhiu loi thuc nhum, thuc n ... C ch phn ng nitro ha NO2+ l tc nhn i in t rt mnh, c cu trc thng. S hnh thnh tc nhn ny l do s tng tc gia acid nitric v acid sulfuric.
2 H2SO4 + HONO2
O

NO2+ + HSO4 + H3O+

H

N+
O

O + N + O

- H+

NO2 +

+ H

5.1.3. Phn ng sulfonic ha Sulfonic ha l phn ng gn nhm sulfonic -SO3H vo phn t cht hu c. Cc tc nhn sulfonic ha thng l H2SO4 m c, hn hp H2SO4 + SO3 (oleum). Phn ng sulfonic ha c tnh cht thun nghch.
Ar_H + H2SO4 Ar_SO3H + H2O

Lng nc sinh ra khng nhng lm long nng ca acid m cn gy nn tnh cht thun nghch ca phn ng.

138

Cc ng ng ca benzen d xy ra phn ng sulfonic ha.

SO3H + H2O Acid benzensulfonic CH3 + H2SO4 - H2O CH3 CH3 SO3H + SO3H

+ H2SO4

Acid o-toluensulfonic

Hp cht a nhn thm nh naphthalen: s sulfonic ha ph thuc nhiu n nhit v nng ca acid.
< 100o + H2SO4 SO3H + H2O 160o 160o SO3H + H2O

Acid -naphthalensulfonic

Acid -naphthalensulfonic

Acid arenosulfonic l nhng acid mnh v nhit nng chy khng xc nh. Cc cht hu c dng mui sulfonat d tan trong nc . 5.1.4. Alkyl ho hydrocarbon thm Thay th nguyn t hydro ca nhn thm bng gc alkyl. Tc nhn phn ng l alkyl halogenid RX vi xc tc l cc acid Lewis nh AlCl3 khan (phn ng Friedel -Crafts) hoc FeBr3, FeCl3.
+ Cl HC CH3 AlCl3 khan CH CH3 CH3 + HCl

CH3

C che :

CH3 CH3

CH Cl + AlCl3

CH3 + CH. . . .Cl. . . .AlCl3 CH3

CH3 + AlCl4 CH CH3 phc H CH3 + AlCl3+ HCl CH3

CH + 3 + CH. . . . . . . .AlCl Cl 3 CH3

CH + 3 . . . . . CH. Cl AlCl3 CH3 phc

CH

Tc nhn alkyl ha cng c th l alken, alcol khi c H2SO4 hoc H3PO4 lm xc tc:
+ CH3CH=CH2 H2SO4 CH CH3 CH3 ; CH3CH_CH3 + OH H2SO4 CH CH3 CH3 + H 2O

Trong nhng phn ng ny tc nhn i in t dng carbocation c hnh thnh do alken, alcol tc dng vi proton H+ theo cc phn ng nh sau: 139

CH3CH=CH2+ H+

+ CH3CH_CH3 ; CH3CH_CH3 + H+ OH

CH3CH_CH3 + OH2

+ CH3CH_CH3 H2O +

Phn ng alkyl ha kh dng li giai on to monoalkyl. Tip tc phn ng to di, trialkyl. S c mt ca gc alkyl s hot ha nhn thm v lm thun li cho phn ng th i in t tip theo. Sn phm phn ng alkyl ha c th l mch thng hoc mch nhnh v cc tc nhn i in t hnh thnh c th b chuyn v c carbocation bn vng.
CH2 CH2 CH3
+ CH3CH2CH2Cl

+ HCl

AlCl3 CH CH3 CH3 CH3CHCH2+ H + HCl

S chuyn v xy ra

+ CH3CHCH3

5.1.5. Phn ng acyl ha Thay th nguyn t hydro ca hydrocarbon thm bng nhm acyl RCO gi l phn ng acyl ha. Tc nhn acyl ha l halogenid acid RCOX, anhydrid acid (RCO)2O. Xc tc cho phn ng acyl ha thng l AlCl3 khan (phn ng Friedelp -Crafts) hoc c th dng cc loi xc tc i in t khc nh AlBr3, GaCl3, FeCl3, SbCl3, SnCl4, BCl2 Sn phm acyl ha l cc ceton:
O C-R + RCOOH O C-R + HX

+ (RCO)2O

AlCl3

+ RCOX

AlCl3

Alk ylphenylceton
+ O AlCl3 O AlCl3 R-C-X R-C-X + + O AlCl3 R-C

Alk ylphenylcet on

RCOX + AlCl3

; R-C-X

+ O ..

+ .. R-C O. .

+ AlXCl3

140

V d: S Acetyl ha benzen bng acetylclorid hoc anhydrid acetic xy ra theo phn ng

AlCl3 O C-CH3 +

CH3COCl Acetylclorid

HCl

+ (CH3CO)2O Anhydrid acetic

Acetophenon ( methyl phenylceton) O C-CH3 AlCl3 + CH3COOH

Phn ng acyl ha thng tin hnh trong dung mi carbondisulfid (CS2) hoc nitrobenzen. Lng xc tc AlCl3 phi dng nhiu hn v gia sn phm v xc tc c th to phc cht.
O C-CH3 + AlCl3 O .....AlCl3 C-CH3

5.1.6. Mt s phn ng th i in t khc Phn ng th hydro ca hydrocarbon thm bng nhm chc aldehyd - CHO. Phn ng Gatterman Tc nhn phn ng l hn hp HCl + HCN + AlCl3
HCl , HCN , AlCl3 CHO CH3 ; HCl , HCN , AlCl3 CH3

CHO

C th gii thch c ch qua cc giai on trung gian:

HC N + HCl ClCH=NH HC N - HCl + H2O ClCH=N_CH=NH.AlCl3 Ar-CH=N_CH=NH.AlCl3 Ar-CHO + 2NH3 + HCOOH

ArH + ClCH=N_CH=NH.AlCl3 Ar-CH=N_CH=NH.AlCl3

Phn ng Gatterman - Koch Tc nhn phn ng l hn hp CO + HCl + AlCl3 .

CO + HCl , AlCl3 CHO + HCl ; CH3 CO + HCl , AlCl3 CH3 + HCl CHO

141

C che : CO + HCl

Cl_C_H O

Ar-H (- HCl)

Ar-CHO

Phn ng th hydro ca hydrocarbon thm bng nhm _ CH2Cl Tc nhn phn ng l hn hp HCHO + HCl c ZnCl2 lm xc tc.
+ HCHO + HCl ZnCl2 60o CH2Cl + H2O

5.2. Phn ng cng hp ca hydrocarbon thm Phn ng cng hp ca hydrocarbon xy ra kh khn hn s cng hp vo alken v alkyn v nhn benzen l mt h thng lin hp. 5.2.1. Cng hp vi hydro Khi c xc tc nh Ni, Pt, Pd v nhit , hydrocarbon thm c kh nng cng hp vi hydro to thnh hp cht vng no (cycloalkan).
Ni , 10at 130o Cyclohexan CH3 CH3 + 3 H2 Ni , to Methylcyclohexan

+ 3 H2

i vi cc cht c 2 nhm th nh dialkylbenzen, s cng hp ch yu to sn phm cis. Ha lp th ca phn ng ty iu kin v xc tc.

CH3 CH3 o-Xylen 5% Rh/ C , 100o
p sut

CH3 CH3

CH3 +

CH3 cis- 1,2-Dimethylcyclohexan (90%) Trans- Dimethylcyclohexan (10%)

Nu trn nhn benzen c cc chc nh aldehyd, ceton hoc ni i th nhm chc hoc ni i b cng hp trc tin.
Br CHO H2-PtO2 2-Bromo-5-metoxybenzaldehyd OCH3 C2H5OH Br CH2OH

OCH3 Alcol 2-bromo-5-metoxybenzylic

C6H5 H

C C

H C6H5

H2-Pt C2H5OH

C6H5 CH2 CH2

C6H5

Trans-stilben

1,2-Diphenyletan

142

5.2.2. Phn ng cng halogen Khi cho clor hoc brom i qua benzen c nhit , nh sng t ngoi, phn ng cng xy ra.
+ 3 Cl2 h
Cl Cl Cl Cl Cl

Cl

Hexaclocyclohexan thu c l mt hn hp cc ng phn lp th. Phn ng xy ra theo c ch cng hp gc nh sau .

Cl
. Cl Cl:Cl . Cl Cl

. . Cl

2 Cl
Cl Cl Cl

Cl

Cl

.
Cl

Cl Cl:Cl Cl Cl

Cl

. Cl Cl

.
Cl

Cl Cl Cl:Cl Cl Cl

Cl

Cl

Cl . + Cl Cl

5.3. Phn ng oxy ha Nhn benzen bn vng vi cc tc nhn oxy ha. Cc tc nhn oxy ha nh HNO3, KMnO4, CrO3 u khng oxy ha c vng benzen. Ch nhit cao v c xc tc V2O5 vng benzen b oxy ha thnh anhydrid maleic.
+ O2 V2 O5 400-450o O C C V2 O5 400-450o O C C

+ O2

O Anhydrid maleic

O Anhydrid phtalic

Cc ng ng ca benzen ch b oxy ha mch nhnh. Sn phm to thnh c th l acid, aldehyd hoc ceton ph thuc vo cht oxy ha.
CH3 + 3 O COOH + H2O
COOH + CH3COOH + 2 H2O

CH3 CH3 + 6 O

COOH + 2 H2O COOH

COOH + 2HCOOH+ 2 H2O

CH2 CH2 CH3 + 6 O

CH CH3 CH3 + 8 O

Oxy ha o - xylen bng acid nitric long 155C thu c acid o -toluic.
CH3 CH3 HNO3 loang 155o COOH CH3

143

5.4. S nh hng trong phn ng th i in t Khi nghin cu phn ng th i in t vo hydrocarbon thm, ngi ta nhn thy khi trn nhn thm c sn mt hay nhiu nhm th th nhng nhm th ny c nh hng n kh nng v v tr th tip theo vo nhn thm. nh hng biu hin nh sau:

Nhm th lm cho phn ng th tip theo d dng hn (nhm th tng hot) hoc lm cho phn ng tip theo kh khn hn (nhm th h hot). Nhm th s nh hng cc nhm th mi v nhn thm cc v tr ortho, meta hoc para ty thuc vo bn cht cu to ca nhm th gy nh hng.

5.4.1. Nhm th nh hng n kh nng phn ng ca nhn thm Bn cht ca phn ng th i in t l s tng tc gia h thng electron lin hp ca nhn thm vi tc nhn i in t mang in tch dng.

Mt electron ca nhn thm tng, kh nng phn ng th i in t d dng. Mt electron gim th kh nng phn ng th i in t ngc li.

Nhm th y electron gy nh hng cm ng dng (+I), nh hng lin hp dng (+C) v nh hng siu lin hp lm tng mt electron ca nhnthm.
X l nhng nhm th tng hot Do hiu ng electron

X CH3, C2H5 ,C3H7 + I , sieu lien hp NH2 , NR2 , NHCOR , _O -, OH , OCH3 ,OR , OCOR - I ,+ C - I ,+ C F , Cl , Br , I

Cc nhm th trn l nhm th loi I Nhm th lm gim mt electron ca nhn thm l nhng nhm th ht electron c hiu ng - I , - C.
X
X l nhng nhm th gim hot Do hiu ng electron
+

NO2 ,SO3H , COOH CN , CHO , COOR , COR COCl , CONH2 , CN , CCl3, CF3 , NH3 , NHR2
+

- I ,- C - I ,- C

Cc nhm th trn l nhm th loi II 5.4.2. S nh hng v quy tc th vo nhn thm Cc nhm th X tng hot lm cho mt electron cc v tr ortho v para tng ln. S th i in t tip theo u tin ch yu vo 2 v tr ny. Cc nhm th X h hot lm cho mt electron ca nhn thm gim nhiu nht cc v tr ortho v para. Phn ng th i in t tip tc xy ra kh khn v u tin ch ti v tr meta. 144

Quy tc nh hng - Quy tc Holleman (Holleman Arnold Frederich 1859-1953)

Nu trn nhn benzen c mt nhm th loi I (nhm tng hot) th nhm th ny nh hng cc nhm th mi vo v tr ortho v para ca vng benzen.
OCH3 OH OH + HNO3 + H2O NO2 OH para NO2 + H2O

OCH3 + Br2 FeBr3

+ HBr para ( 96%) Br OCH3 Br + HBr o-Bromoanisol ( 4% )

H2SO4

o-Nitrophenol

Nu trong nhn benzen c sn mt nhm th loi II (nhm h hot) th nhm ny s nh hng nhm th mi vo v tr meta trn nhn benzen.
COOH + Br2 COOH + HBr Br acid m-Bromobenzoic CHO H2SO4 CHO + H2O NO2 m-Nitrobenzaldehyd

+ HNO3

5.4.3. L thuyt v s nh hng Mt electron t nhm th chuyn dch v pha benzen to ra mt h lin hp mi. Trong h lin hp ny mt electron ti cc v tr ortho v para cao hn cc v tr khc. iu hon ton ph hp vi cc cu trc gii hn c nng lng thp. Trng thi nng lng thp dn n cu trc trung gian pentadienyl v sn phm th m t trn gin hnh 11-4.
Trang thai chuyen tiep H + ...Y + + H. . Y +

Trang thai chuyen tiep

Nng lng phn ng

+ Y+ Chat phan ng

H Y + Chat trung gian Y + H+ San pham Tien trnh phan ng

145

Hnh 11.4. Gin nng lng ng vi cc trng thi th i in t vng benzen

Nu trn vng benzen c nhm th loi I th mt electron tng ln. S phn b li mt electron trn nhn c minh ha qua cc cng thc gii hn nh sau:

:OH

..

+OH

..

+OH

..

+OH

..

:OH

..

cc v tr ortho, para c mt electron cao hn v phn ng th i in t ch yu xy ra y. Cng c th gii thch s th vo v tr ortho, para bng s n nh bng trng thi nng lng thp. Gi thit tc nhn i in t Y tn cng vo c 3 v tr ortho, para v meta ca toluen v cc cu trc trng thi phc nh sau:
CH3 H + CH3 H Y CH3 + H Y CH3
+

+ Y

CH3 + Y H Y

CH3 + H

+ Y

Th vo v tr ortho v para th cc cu trc trung gian c carbocation bc ba bn vng. Nu th vo v tr meta th ch c cc cu trc carbocation bc hai km bn.
CH3 H + Y + CH3 H Y CH3 +

H Y

Cc phc c n nh nh nhm methyl y electron. S th i in t xy ra nhanh hn v ch yu u tin v tr ortho v para. Khi trn vng benzen c nhm th loi II. Mt electron trn nhn thm gim. Cc cng thc gii hn chng t s gim nhiu nht v tr ortho v para.
O N O O + ON O + + N O O N O O + N O O N O

Khi tc nhn i in t Y+ tc dng vo nitrobenzen, cc phc to thnh c cu trc trung gian. Trong phc , nhm nitro lm gim mt electron cc v tr ortho v para.

146

O + O N + Y

O + O N +

O + O N + H

O + O N H + Y

O + O N H + Y

O + O N H + Y

Y O + O N

Trng thi nng lng phc v tr meta thp hn 2 trng thi ortho v para.
O + O N + H Y O + O N + H Y

H Y

5.4.4. S nh hng vo hp cht nhiu nhm th Hp cht c 2 nhm th Nhng quy tc sau y c p dng nh hng nhm th th ba vo nhn thm. Nhng nhm th tng hot v nh hng ortho, para c nh hng mnh hn nhng nhm h hot v nh hng meta, ngha l nhm tng hot ng vai tr quyt nh s nh hng. Hiu ng lp th cng ng vai tr quan trng trong vic xc nh v tr th ca nhm th ba.
Cl Cl CH3 Cl CH3 COOH Br OCH3 NO2

NO2

Nu c hai nhm th cng tng hot v nh hng ortho, para th nhm no tng hot mnh s ng vai tr ch ng . Cc nhm y electron tng dn theo th t:
(CH3)2CH < CH3 < CH3CONH- < OCH3 < NH2 < NHR < NR2

Cc nhm ht electron gim dn theo th t

NO2>SO3H>COOH>CN>COCl>CHO>COOR>COR>CONH2>CCl3>NH3>NR2

V d:
CH3 HNO3 CH3 NO2 CH3 HNO3 H2SO4 NHCOCH3 CH3 NO2 NHCOCH3 CH3 CH3 NO2

CH3

CH

H2SO4 ; CH CH3 CH3 CH3

NO HNO3 2 NO H2SO4
2

Khi tin hnh phn ng th i in t vo nhn thm thng thu c hn hp sn phm c t l khc nhau.

147

CH3 HNO3 H2SO4 NO2 COOH NO2 Na2Cr2O7 H2SO4 NO2 HNO3 H2SO4 NO2 COOH NO2 + NO2 Na2Cr2O7 H2SO4

COOH NO2

CH3

NO2 COOH

NO2 Hon hp

NO2

Br
Br2 FeBr3

Br

Br Br

Br

+
Orto (13%)

Br
Meta (0,1%)

Br Para ( 86,9%)

S nh hng trong phn ng th i in t vo nhn thm c tc dng gip cc nh nghin cu trong lnh vc tng hp hu c iu ch c cc cht theo mong mun.

Bi tp
1. Hy vit cng thc cu to ca cc hp cht sau: a- p-xylen; b- o- etyltoluen; c- p-diisopropylbenzen; d- 1,2,3-trimethylbenzen; e- mesitylen; f- cumen; g- p-xymen; h-p-clorotoluen; i - 1,3,4-tribromobenzen. 2. Hy gi tn cc gc sau y:
CH3 aCH2 C2H5 CH3

; bCH(CH3)2

; cCH3 hCH3

dCH

CH3 i-

;
CH=CH

e-

; g- CH 3 ;
l-

k-

CH=CH2

; m-

n-

148

3. Hy gi tn cc cht sau y:
aCl

; bCl Cl

CH2Cl

c-

CHCl2

d-

CCl3

e-

CH3 Br F

gCH3

CH3

hCl

Cl

; i-

CH2Cl

;
Cl

kNO2

NO2

CH3

CH2 NO2

CH2 n-

lNO2

; m-

4. Nhng cht no c to thnh khi un nng hn hp sau y vi AlCl3 khan: a. Butylclorid vi toluen; b-Benzylclorid vi benzen; c-Alcol propylic vi benzen. d. Propylen vi toluen; e- 1- Buten vi ethylbenzen; g- Cloroform vi benzen. h. Toluen vi anhydrid acetic; i- Toluen vi carbon oxyd v HCl. 5. Hy ch r v tr th ca nhm th th ba vo cc cht sau:
OH aBr OH eCH3 Cl NO2 Cl OH NO2 CH3

; b-

; c-

; dOH

NO2

CN

gNO2

; hCl

i-

CH3

6. Hy xc nh cng thc cu to ca cht C7H7SO3Cl bit rng khi oxy ha n to ra acid benzensulfonic, cn khi halogen ha to ra dn xut monohalogen.

149

Chng 12

HYDROCARBON A NHN THM

Mc tiu hc tp 1. Gi c tn cc hydrocarbon a vng ngng t thm. 2. Trnh by c cc tnh cht ha hc chnh ca hydrocarbon a vng thm naphtalen, anthracen v phenanthren. Ni dung 1. Cu to v danh php C hai loi hp cht a nhn thm. Hp cht a vng to thnh do cc vng lin kt vi nhau bng lin kt n.
, 3 2 , , 1 1 , 3 2 6 3 4 5 4 , 5 , 6 ,

NO2 Cl 2 ,
2 , 1 , 1

3 4

, 4 , 5

Biphenyl

P-terphenyl

, Acid 2,6-dicloro- 2 nitro -5'-biphenylcarboxylic

10

HOOC

Cl 6 5

Hp cht a vng to thnh do cc vng ngng t vi nhau.

8 7 6 5 4 1 8 2 3 7 6 5 9 1 2 10 4 3 7 6 5 4 3 12 1 2 3 4 8 7 6 5 9 8 1 2

Naphtalen
10 10 9 8 7 6 5 4 11 12 1 2 3 8 7 6 9

Antracen
1 2 3 4 5 9 8 7 6 5 10 11 12 1

Phenantren
11 2 4 3 10 9

Naphthacen (Tetracen)

Pyren

Srysen

Coronen

Nguyn tc nh s nh trn chu vi ca hp cht a nhn ngng t theo nguyn tc: Tng s nhn ln nht phi nm theo mt trc ngang

150

Hng un g

H n g sai

S ti a cc nhn khc phi nm cao hn ht v bn phi, trn trc ngang.

Hng ng

Hng sai

Cch nh s vi nhn cao nht v bn phi v tip tc theo chiu kim ng h nhng b cnh tip hp cc nhn (khng nh s nhng carbon chung ca cc vng).
2 10 9 8 7 6 5 1 3 4 9 8 7 6 5 10 11 12 1 2 4 3

Hng nh s ng theo chiu kim ng h

i vi cc hp cht a vng ngng t phc tp. Ngi ta xem chng nh l dn xut ca cc hp cht ngng t n gin c tn gi theo quy c. gi tn nhng hp cht ny ngi ta nh du cc cnh bng cc ch a, b, c ...v gi tn nh cc v d sau y:

Naphthalen

1 2 3

10 9

11

12

13

14

1 2 3

hoac Naphto[ 1,2-a] pyren benzen

11 10 12

4 7 6 5

Pyren Benzen j i

Naphto[ 1,2-a] pyren

13 14 9 2 1 3 4 6 5

a b

h gf ed c Antracen

Dibenz [a , j] antracen

2. Biphenyl 2.1. Tng hp biphenyl

151

Tng hp biphenyl theo cc phng php sau: Nhit phn benzen nhit cao trong ng st (phng php Berthelot,M, 1867)
2 600-800 o + 2H

Nung iodobenzen vi bt ng (phng php Ullman. Fp, 1903)

2 I + 2 Cu + 2Cu I

C th iu ch cc biphenyl th bng phn ng th i in t hoc phn ng chuyn v benzidin.

NH NH
Hydrazobenzen H+

H 2N

NH 2

Benzidin ; (4,4'-diaminobiphenyl)

2.2. Cu to ca biphenyl trng thi hi hoc dung dch, hai nhn benzen ca biphenyl trn 2 mt phng to mt gc 45. S bin dng ny l do 2 cp nguyn t hydro cc v tr 2-2' v 6-6' tng tc vi nhau (hnh 12-1).
45o

Hnh 12.1. Hai mt phng to gc 45o

S c mt cc nhm th cc v tr 2-2' v 6-6' s cn tr s quay ca 2 vng chung quanh lin kt n v dn n cc ng phn quang hc. V d hp cht acid 6,6'- dinitro 2,2'- biphenyldicarboxylic c tnh quang hot (hnh 12-2).

152

Mat phang gng HOOC O2N O2N COOH

NO2 COOH COOH HOOC NO2 NO2

HOOC HOOC O2N O 2N

NO2

COOH

Hnh 12.2. Cc i gng ca acid 6,6-dinitro-2,2-biphenyldicarboxylic

Biphenyl c nhng tnh cht ha hc ging benzen. Phn ng th i in t u tin xy ra v tr ortho v para. Nitro ha xy ra v tr para mt cch d dng. Brom ha thu c 4- bromo biphenyl hoc 4,4'-dibromo biphenyl. Phn ng th xy ra v tr 4 d hn vo v tr 2. Phn ng acyl ha bng acetyl clorid xy ra v tr 4 v 4'. 3. Biphenylmetan v triphenylmetan Cc hp cht ny c iu ch bng phn ng Friedel -Crafts
CH2Cl + CH2Cl2 +2 - HCl AlCl3 - 2HCl CH2 Biphenylmetan
CH CHCl 3 + 3

AlCl 3

+ 3HCl Triphenylmetan

Cc lin kt C _ H ca di id triphenyl rt linh ng. D b th v d b oxy ha.

Br2 CH2 2O [CrO3] C O Br CH + HBr + H2O

153

KNH2 CH Br2 [O ]

.. + ( C6H5 )3 C K + NH3

( C6H5 )3 C_ Br + HBr ( C6H5 )3 C_ OH

Triphenylclorid trong benzen khi c mt ca khng kh v bc to ra dung dch mu vng. Khi thm vo dung dch ny mt lng aceton hoc bc hi ht benzen th thu c mt hydrocarbon khng mu. Gomberg, M xc nh dung dch mu vng cha gc t do triphenyl. Gc t do ny s to ra mt dimer khng mu.

C Cl

2 Ag - AgCl

C.

Triphenylmethylclorid

Triphenylmethyl (mau vang)

3-Biphenylmethylyden-6-triphenylmethyl1,4-cyclohexadien (khong mau)

Gc t do triphenylmethyl bn hn cc gc t do alkyl v gc triphenylmethyl tn ti cc cng thc gii hn do s lin hp ca nhn benzen vi electron n c.

C.

C .

C
.

4. Naphthalen Naphthalen c nhiu trong nha than hoc trong phn cn li khi nhit phn du m. Naphthalen c dng kt tinh hnh bn mng. Cng thc cu to ca naphtalen c xc nh bng tia X. di lin kt c trnh by trn hnh 12-3.
8

'7 '6

'

1 2 3

1,424 A

1,365 A 1,424 A
o

'

1,393 A

Hnh 12.3. K hiu cc v tr ca naphthalen

di lin kt ca naphthalen

Naphthalen l mt h thng lin hp vi 10 electron . Nng lng cng hng ca naphthalen (60 kcal. mol-1) thp hn nng lng cng hng ca 2 vng 154

benzen. Do naphthalen c kh nng phn ng cao hn benzen. Cc dng cng thc gii hn ca naphthalen nh sau:

Cc v tr 1, 4 c k hiu l ; v tr 2, 3 k hiu l . V tr 5, 8 l ' v cc v tr 6, 7 l '. 4.1. Cc phn ng ha hc ca naphthalen 4.1.1. Phn ng th i in t Naphthalen tham gia cc phn ng halogen ha, nitro ha, sulfonic ha, alkyl ha v acyl ha theo Friedel -Crafts. Nitro ha naphthalen to hn hp sn phm 1- v 2-nitronaphthalen.
NO2 CH3COOH + 50-70o - Nitronapthalen - Nitronapthalen HNO3 NO2

4.1.2. Phn ng cng hp Hydro cng hp vi naphthalen c xc tc nhit cao to thnh tetralin (1,2,3,4-tetrahydronaphthalen) v decalin (Bicyclo[ 4,4,0]decan).
4 H ( Ni) 150o 6 H ( Ni) 200o

Tetralin Decalin ( 1,2,3,4-Tetrahydronaphthalen ) ( Bicyclo [4,4,0 ] decan)

4.1.3. Phn ng oxy ha Oxy ha naphthalen bng oxy khng kh c xc tc V2O5 to thnh anhydrid phtalic. Crom oxyd oxy ha naphthalen trong mi trng acid acetic to ra 1,4naphtoquinon (1,4-dihydro-1,4-naphthalendion).
O

O2 , V2 O5

C O C O

CrO3 ,CH3 COOH

155

5. Anthracen Nm1867 Dumas tch c anthracen t nha than . C th tng hp anthracen t 2-methylbenzophenon theo phn ng:
O C CH3 + H2O

hoc tng hp theo phng php Friedel - Crafts qua cc giai on hnh thnh acid 2-benzoylbenzoic, ng vng di tc dng ca acid polyphosphoric (PPA) v kh ha:
O +O C AlCl3 O C HOOC PPA - H 2O O Antraquinon O [ H]

C O Anhydrid ftalic

Acid-2-benzoylbenzoic

Tnh thm ca antracen (E =351,5 kj.mol1) km hn naphthalen. V tr 9, 10 ca anthracen c kh nng phn ng cao: cc phn ng oxy ha, kh ha, halogen ha v phn ng Diels -Alder xy ra v tr 9, 10. Phn ng sulfon ha xy ra v tr 1 v 2.
O

3O [HNO3] - H2O

2 H [Na ,ROH] 9,10-dihydro antracen Cl2

Cl

Cl

Cl

- HCl

9,10-diclo-9,10-dihydro antracen
O O O O O O

Anhydrid cua acid 2,3; 5,6- dibenzodicyclo[2,2,2]octa2,5-dien-7,8-dicarboxylic

156

6. Phenanthren Nm 1872 Greabe tch phenanthren t nha than . C th tng hp phenanthren qua cc giai on sau:
NO2 CHO - H2O COOH O2N 6H - 2H2O COOH O2N 6H - 2H2O COOH

o- Nitrobenzaldehyd Acid phenyl acetic

Acid phenyl-2-nitro crotonic Acid phenyl-2-nitro crotonic

+ N2

X[Cu] COOH - N2 COOH

+ CO2

Phenanthren l tinh th hnh kim, khng mu. Nhit nng chy 99,2C. Phenanthren trong dung mi benzen c mu xanh hunh quang. Phenanthren c tnh thm. Nng lng cng hng 387,0 kj.mol1. Lin kt v tr 9, 10 th hin tnh cht ca lin kt i -C=C- . Phenanthren tham gia phn ng th i in t. Phn ng cng hp th hin qua cc phn ng sau:

2H CuO/Cr2O3 9,10-Dihydrophenantren

Br2

- HBr Br 9-Bromo phenantren

Br Br 9,10-Dibromo-9,10-dihydrophenantren

3O (CrO3) - H2O O O 9,10-Phenantrequinon

Phenanthren v cc dn xut ca n l nguyn liu quan trng sn xut thuc nhum. Khung phenanthren c trong cu trc ca nhiu hp cht t nhin quan trng nh steroid, alcaloid dy morphin.

Bi tp

157

1- Vit cng thc cu to ca cc cht sau: a- Benzo[c]phenanthren; b- naphto[2,3-a]pyren; c- Perhydrophenanthren. 2- Vit phn ng iu ch cc cht th mt ln ca naphthalen. a- -Benzoylnaphthalen; b- - Iodonaphthalen; c- -Isopropylnaphthalen.

158

Chng 13

H THNG LIN HP V ALKADIEN

Mc tiu 1. Gii thch c s lin hp ca cc h thng dien. 2. Nu c c ch v ha tnh ca cc dien lin hp

Ni dung
H lin hp l mt h thng lin kt (i, ba) lun phin vi lin kt n, hay l h cha nguyn t c cp electron p t do lin kt vi nguyn t carbon c lin kt i. 1. H thng allylic 1.1. Cation allylic: CH2 = CH-CH2+

Khi cho 2-butenol-1 tc dng vi acid bromhydric 0C th to thnh mt hn hp gm 75% 1-brom-2-buten v 25% 3-brom-1-buten. Mt hn hp nh vy cng thu c khi cho 3-buten-2-ol tc dng vi HBr trong cng iu kin.
CH3CH = CHCH2OH CH3CHOHCH = CH2

+ HBr + HBr

0 oC CH3CH = CH CH2Br 0 oC

+
3:1

CH3CHBrCH = CH2

iu c th gii thch l do s to thnh cation trung gian. in tch dng trn cation ny khng nh v (delocalise) trn 2 nguyn t carbon.
CH3CH = CHCH2OH2 + OH2 CH3CHCH = CH2
+

-H2O CH3CH = CH CH2 Cation +Br CH3CH = CH CH2Br

+

-H2O

CH3CHCH = CH2 Cation +Br

CH3CHBrCH = CH2

Carbocation trung gian t phn ng trn l s cng hng ca 2 cu trc quan trng. Kiu carbocation n gin thuc loi ny l 2-propenyl hay gi l cation allylic.
+ + 1 + 2 1 + 2 +

CH2=CHCH2

CH2CH=CH2

Cation allylic

CH2 CH CH2 Cation allylic

CH2

CH

CH2

Cation allylic

159

K hiu tng qut trn c dng m t cu to in t ca cation allylic Hai cu trc cng hng trong du mc biu hin in tch dng phn b ng u trn 2 v tr hon ton ging nhau. Gc: CH2=CH-CH2gi l gc allyl

CH2=CH-CH2-Cl CH2=CHCH2OCOCH3

clorid allyl acetat allyl

c trng quan trng v cu to ca cation allylic l tt c cc nguyn t u cng trong mt mt phng. Orbital p trng ca carbocation xen ph vi orbital ca lin kt i. Mt in tch ca lin kt i nh c phn chia u trn 3 nguyn t carbon. S phn b mt electron nh vy lm cho cation allyl c nng lng thp hn cation c in tch dng tp trung trn mt carbon. Trong cation allylic c s phn b li mt elecron thnh mt orbital phn t bao trm ln c 3 nguyn t carbon.
+ CH2=CHCH2 + CH2CH=CH2 ( CH2 CH CH2 )+ +

... ..CH .. . CH CH..

2

bn vng ca cation allylic tng t vi bn ca gc alkyl bc 2. Khi cation tng tc vi mt tc nhn i nhn, phn ng xy ra ti trung tm mang in tch dng, do mt hn hp sn phm c to thnh. C phn ng xy ra theo kiu chuyn v allylic.
Cp Cp H H

C HS 2

sp
H H

C
H

sp2 C C sp2

Hnh 13.1. Biu din cation allylic di dng orbital

1.2. Phn ng SN2 - S chuyn v allylic Cc halogenid v alcol allylic u c kh nng to carbocation mt cch d dng theo c ch SN2 v c s chuyn v ni i. S chuyn v gi l chuyn v allylic.

CH3CH=CHCH2OH + HBr

CH3CHBrCH=CH2

iu chng t rng lin kt i c tc dng n nh trng thi chuyn tip v lm gim mc nng lng hot ha (hnh 13-2).

160

Nu

..............
H2C CH CH2

..............
Br

Hnh 13.2. Trng thi chuyn tip ca phn ng gia bromid allyl vi tc nhn i nhn Nucleophyl theo c ch SN2

H thng allylic cng d xy ra phn ng theo c ch SN1.

CH3CH=CHCH2OH +

HBr

CH3CH=CHCH2Br

V carbocation CH3CH=CHCH2+ cng d hnh thnh trong iu kin khng xy ra s chuyn v allylic theo c ch SN2
C6H5SO2Cl CH3CH = CHCH2OSO2C6H5 CH3CH = CHCH2OH Pyridin 2-Buten-1- ol Cl CH3CH = CHCH2Cl 1-Clor-2- buten

Phn ng nh vy cng xy ra khi hp cht allylic tc dng vi thuc th Grignard.

CH2=CH-CH2Br

MgBr

CH2CH=CH2 70%

+ MgBr

Phn ng theo kiu trn l phng php tt iu ch 1-alken. Phn ng nh th khng xy ra i vi halogenid alkyl no. 1.3. Anion allylic CH2=CH-CH2Thuc th Grignard allylic c iu ch theo phng php thng thng sau:
CH2=CH-CH2-X + Mg
eter

CH2=CH-CH2-Mg

Thuc th ny b ng phn ha rt nhanh

CH3-CH= CH-CH2-MgX
4 3 2 1

Nhanh

CH3-CH-CH = CH2 MgX

C th hiu rng in tch m ca anion allylic phn b trn cc nguyn t carbon lin hp.
CH2 = CH_CH2
CH2 CH CH2 MgX

CH2 _ CH = CH2

CH2

.... .... CH CH2

+ CH2 CH CH2 MgX

CH2

.... CH....CH

2 MgX

161

Anion allylic bn vng hn anion khng lin hp. Nhng anion bn vng loi khc c n nh nh s cng hng hoc lin hp c bn cht ngc nhau. V d:
O = C OR
-

C= O R

R2C

C= O R

R2C= C R

O-

Ion carboxylat

Ion enolat

1.4. Gc t do allylic:

CH2 = CH = CH2

Gc allylic c n nh nh cng hng

. CH2 = CH_CH2

. CH2 _ CH = CH2

. .... .... CH2 CH CH2

Electron t do (n) c phn chia trn 2 carbon lin hp. Gc t do loi ny bn hn gc t do no tng t (CH3CH2CH2). Khi brom ha phn t c cha allylic bng N -bromosuccinimid s c qu trnh phn ng xy ra theo c ch gc t do (Phn ng c xc tc nh sng)
O H 2C C N Br H 2C C O

Br CCl4 83%
H 2C

O C NH H 2C C O

N-Bromosuccinimid

Succinimid

C ch
O H 2C H 2C C N Br C O O

Anh sang

H 2C H 2C

C C O

. . N + Br . ; + . Br + HBr

. +

O H 2C H 2C C N Br C O H 2C H 2C C C O

Br

. ; .

. N

Ch : C th minh ha s phn b li mt electron trong gc allyl

CH2 = CH _ CH2

CH2 _ CH = CH2 CH = CH _ CH2

Cation allylic

CH2 _ CH = CH2 CH2 = CH _ CH2 CH2 _ CH = CH2 Goc t do allylic Anion allylic

2. Dien 2.1. Cu to v s bn vng Dien c ni i cch bit C =C_C_C=C Dien c ni i tip cn C =C=C_C_C Dien c ni i lin hp 162 C =C_C=C_C

Dien lin hp c 2 lin kt i cch nhau mt lin kt n (cn gi l dien lun phin, tip cch). Dien lin hp bn vng hn dien khng lin hp v mt electron phn b u trn cc nguyn t carbon ca h lin hp. Cu trc nh vy c nng lng thp. Phn t 1,3-butadien c 4 nguyn t carbon trng thi lai ha sp2. Cc lin kt C_C v C _H c to thnh do s xen ph ca cc orbital lai ha sp2 ca carbon vi nhau hoc vi orbital s ca hydro. Lin kt c to thnh do cc orbital p t do trn cc nguyn t carbon xen ph vi nhau (trn hnh 13.3 v s xen ph c minh ha bng ng thng khng lin tc).

............ ............ ...................................

Lien ket
Csp 2

Lien ket
Cp Cp

H2C

CH

CH

CH2

Csp 2

................................... ............ ............ Cp H s

Hnh 13.3: Cu to ca 1,3-butadien

di lin kt trong 1,3-butadien Lin kt i C1=C2 v C3=C4 c di l 1,37 ln hn lin kt i bnh thng (1,34 ). Lin kt n C2_C3 c di 1,46 ngn hn lin kt n bnh thng (1,54 ). iu gii thch rng trong 1,3-butadien cc electron ca cc ni i lin hp tng tc vi nhau. S tng tc nh hng n di lin kt, nh hng n bn cng nh kh nng phn ng ca phn t c h lin hp. V lin kt C2_C3 trong butadien c mt phn electron nn kh nng quay t do xung quanh lin kt ny b hn ch. 1,3- butadien c th tn ti 2 dng cu dng S -trans v S -cis . Dng trans c nng lng thp nn n bn vng hn dng cis.
H H C H C H
S-trans

C C H

H H

H C C H
S-cis

H C
CH

2.2. Phn ng cng hp

Quan st phn ng gia phn t brom vi 1,3-butadien

CH2 = CH_CH = CH2 + Br2 Hexan -15o CH2 = CH_ CH _CH2Br
+ +

Br-

CH2 _ CH = CH _ CH2Br BrCH2_ CH = CH_ CH2Br + CH2 = CH_CHBr_ CH2Br 46% 54%

163

un hn hp thu c 60C th to thnh 90% (E)-1,4-dibromo-2-buten

BrCH2_ CH = CH_ CH2Br (54%) CH2 = CH_CHBr_ CH2Br

60o

BrCH2 H

(46%)

C C 90%

H CH2Br

S d cc dien lin hp to c hn hp sn phm cng hp -1, 4 v sn phm cng hp -1, 2 v cation trung gian c cu trc carbocation allyl
CH2=CH_CH=CH 2 + H+ CH2=CH_CH_CH3 Cau truc carbocation allyl

CH2_CH=CH _CH3 Cau truc carbocation allyl

CH2 _ CH _ CH_CH3 Cau truc carbocation allyl

Cc dien lin hp cng c th cng hp theo c ch i nhn hoc c ch gc.

C=C_ C=C + N N C_ C_ C=C N C_ C=C_ C Cau truc carbo anion allyl

N ..C .. _ C .. ..C _ _ C

2.3. Dien -1,2 allen Propadien-1, 2 c gi l allen CH2=C=CH2. Hai lin kt i tip cn nhau v di lin kt i b ngn i (1,31 ). y l g tr trung gian gia lin kt i1,34 (C=C) v lin kt ba 1,20 (CC). Cu trc electron (hnh 13-4) biu hin 2 h thng lin kt i thng gc vi nhau.
H H

.............
C

...............
C C

H2C=C=CH2
H
Csp 2 Csp 2 Csp 2 Csp 2

................ ...............

Hnh 13.4: Cu to orbital ca allen

Tnh cht c trng ca allen l phn t khng ng phng. Hai lin kt nm trong 2 mt phng thng gc vi nhau. V vy phn t allen th c tnh cht bt i xng (c tnh quang hot). 2.4. Tng hp cc dien Phn ln cc dien c iu ch t hp cht c 2 nhm chc.
OH (CH3)2C OH C(CH3)2

Al2O3
420-470o 575o

CH2 = C C = CH2

+ 2H2O

CH3 CH3 79-89% 2,3-dimethyl-1,3- butadien 2 CH3COOH + CH2=CHCH2CH=CH2 1,4-pentadien 63-71%

CH3COOCH2CH2CH2CH2CH2OOCCH3

164

Thay th halogen trn phn t halogenid allyl bng gc vinyl t halogenidvinylmagnesi

CH2=CHCH2Cl + CH2=CHMgBr ether CH2=CHCH2CH=CH2 + BrMg

Phn ng Wittig:
CH2=CHCH2Cl + P(C6H5)3 CH2=CHCH2P(C6H5)3Cl Allytriphenylphosphin clorid
C6H5CHO

CH2=CHCH2P(C6H5)3

C2H5OLi

CH2=CHCHP(C6H5) 3

1-Phenyl-1-3- butadien

CH2=CHCH =CHC6H5 + (C6H5)3P

2.5. Polymer ha Cc dien b polymer ha. Polymer ha butadien c xc tc Ziegler -Natta (Alkyl nhm v titan clorid).
nCH2=CH-CH=CH2
n CH2=CH-CH=CH2

Xuc tac

(-CH2-CH=CH-CH2-)n
CH2-CH=CH-CH2 n CH2-C=CH-CH2 n CH3 Polyisopren CH2-CH=CH-CH2CH-CH2 n Cao su Buna S C6H5

CH3 2-Methyl-1,3- butadien (isopren )

n CH2=C-CH=CH2

Xuc tac

n CH2=CH-CH=CH2
1,3-Butadien

n CH=CH2 Xuc tac

Styren C6H5

Cao su lu ha
S S S

3. H thng lin hp bc cao H thng trans 1,3,5-Hexatrien Hp cht c nhiu ni i lin hp bn vng hn cc hp cht no c s carbon tng ng. S bn vng l do s lin hp , gia cc ni i. Cc ion, gc t do hoc cc trng thi trung gian c nhiu ni i c n nh nh c s lin hp v s phn b u mt electron trn cc nguyn t carbon.

165

CH2 = CH _ CH = CH_CH=CH2 CH2 = CH _ CH = CH_CH_CH3

H+

+ CH2 = CH _ CH _CH=CH_CH2
CH2 _CH =CH _ CH=CH_CH3

CH2 _ CH _ CH _ CH _ CH _ CH3

4. Phn ng Diels - Alder H thng dien lin hp cng hp vi mt lin kt kp (ni i hoc ni ba gi l dienophyl) to hp cht vng 6 cnh c ni i v tr 2, 3 ca hp cht dien lin hp ban u. Phn ng nh vy l phn ng Diels-Alder. Cc dien lin hp cu dng cis d xy ra phn ng tng hp Diels -Alder. Phn ng n gin gia1,3- butadien v ethylen:
CH2 CH2

+
CH2

CH2 CH2

CH2 CH2

CH2

Cc dienophyl thng c hot ha bng cc nhm ht electron (COOH, COOR, CHO, COR, CN, NO2)
COOCH3 COOCH3

+
Dien Dienophyl 4-Methyl cyclohexencarboxylat

+
H O Acrolein

CHO

CHO

COOC2H5

C C COOC2H5

COOC2H5 COOC2H5 Diethyl 1,4-cyclohexa 1,2-Dien dicarboxylat

Diethylacetylendicarboxylat

C ch phn ng c trnh by trn hnh v 13-5. Bn electron ca h thng dien lin hp xen ph vi 2 electron ca alken (dienophyl).

166

H HC

CH2

CH2

H C H C H

Hnh 13.5. Trng thi chuyn tip ca phn ng Diels-Alder

Phn ng xy ra theo c ch lp th cis .

COOCH3 H H COOCH3 COOCH3

+
COOCH3
COOCH3 H H

C C COOCH3

H H
7 5

CH3 COOCH3 COOCH3 CH3

4 3 1 2

+
COOCH3

75 - 80oC

(79-91%)

COOCH3 Ester methyl bicyclo[2,2,1]hepten-5 endo carboxylat

Cyclopentadien

Ester methylacrilat

Bi tp
1. Vit cng thc cc sn phm khc nhau ca phn ng gia (R)-2-hydroxy (E)-3-hexen v HBr 2. T halogenid allyl hy trnh by phn ng iu ch: 4,4- dimethyl-1- penten v 4-methyl-1-hexen 3. C sn phm no c to thnh khi cho 3-cloro-1-penten tc dng vi Mg trong dung mi ether. Sau tc dng vi CO2 v thy phn trong mi trng H2SO4 long.

167

4. Hy vit phn ng gia N -bromosuccinimid vi cc alken sau: a- 2-Methyl propen ; b- Cyclopenten ; c- 2-Penten 5. a- Vit cng thc cu to ca cc sn phm to thnh khi cho cc ceton sau tc dng vi D2O trong mi trng base:
O O CH3 CH3 O O

; CH

b. Vit phng trnh phn ng ca 4-methyl-3-penten-2-on vi cc cht sau: n-C4H9Li; n-C4H9HgBr , CuBr; H2/ Pt ; HCN , (C2H5)3N; Br2 , CCl4 6. Vit cc phng trnh phn ng Diels -Alder ca cyclopentadien vi cc cht sau: Vinylacetat; Acid acrylic; Ester dimethyl acetylendicarboxylat CH3OOCC CCOOCH3 (Gi tn cc sn phm to thnh)

168

Chng 14

DN XUT HALOGEN

mc tiu 1. Gi c tn cc alkylhalogenid v arylhalogenid 2. Trnh by v so snh c tnh cht ha hc ca RX v ArX

Ni dung
Nu thay th mt hay nhiu nguyn t hydro ca hydrocarbon bng mt hay nhiu nguyn t halogen th thu c dn xut halogen.

CnH2n+2-2k

CnH2n+2-m-2k Xm

C cc loi hp cht halogen sau: Halogenoalkan, Halogenocycloalkan. Halogenoalken, Halogenocycloalken. Halogenoalkyn Halogenoaren. Tu thuc s lng nguyn t halogen c trong phn t c th c hp cht monohalogen v polyhalogen. Cc halogen hydrocarbon c nhiu ng dng quan trng. Chng c kh nng phn ng cao v vy hp cht halogen l nguyn liu u trong tng hp hu c. 1. Danh php 1.1. Danh php IUPAC Gi tn hydrocarbon tng ng v thm tn halogen nh mt tip u ng. Chn mch chnh l mch di nht cha halogen. nh s sao cho v tr halogen l b nht. Gi tn theo th t:
S ch v tr v tn halogen + S ch v tr v tn mch chnh + Tn hydrocarbon ng vi mch chnh
Br CH2=C_CH3 2-Bromopropen

CH3_CH2_Cl Cloroetan

2-Fluor-1-cloroetan

Cl_CH2_CH2_F

Cl C C Cl dicloroacetylen

168

3 2 1

Br Br

Cl

Br

2,3-dibromocyclohexen

Clorobenzen

F 6-fluoro-2-bromo-1-iodonaphtalen

Nu phn t c nhiu halogen cng loi th dng cc ch di, tri, tetra... ch s lng nguyn t halogen. Nu phn t c nhiu halogen khc loi th gi tn halogen theo th t a, b, c.. hoc theo th t " ln ".
Cl_CH2_CH2_CH2_CH_CH2_CH2_Cl CH3 Cl CH3 _CH_CH_CH _CH_CH _CH _CH CH2 CH2 3 4 2 5 2 6 7 2 8 2 9 3 CH2 Cl Br 1,6-dicloro-3-(2-cloroethyl) hexan
6 5 4 3 2 1 1

CH2=C_CH=CH2 CF3

4-cloro-3-bromo-6-methylnonan 2-(trifluoromethyl) -1,3-butadien

1.2. Danh php thng thng Ngi ta xem dn xut halogen l sn phm thay th ca HX (HX RX). V vy c tn gi: Tn gc hydrocarbon + tn halogenid.
CH3Cl
Methylclorid

CH2Br2
Methylendibromid

CH2=CH_F
Vinylfluorid

CH2=CH_CH2I
Allyliodid

Vn thng gi tn mt s hp cht halogen theo tn quen dng nh cc haloform.

CHCl3 Cloroform CHBr3 Bromoform CHI3 Iodoform

2. ng phn S ng phn ty thuc cu to ca mch carbon v v tr ca halogen.

CH3CH2CHCl2 1,1-dicloropropan 1,1-propylydenclorid CH3CCl2CH3 2,2-dicloropropan 2,2-propylydenclorid CH2ClCH2CH2Cl 1,3-dicloropropan 1,3-propylendiclorid

3. Phng php iu ch C th iu ch cc hp cht halogen nh alkylhalogenid, vinylhalogenid, allylhalogenid, halogenoaren, benzylhalogenid theo cc phn ng ha hc c phn hydrocarbon. Cn ch rng cc hp cht fluor kh iu ch theo cc phng php nh iu ch cc hp cht clor, brom v iod. 3.1. Halogen ha alkan (xem phn alkan). 3.2. Cng hp HX vo alken (xem phn alken).

169

3.3. Phn ng gia HX vi alcol 3.3.1. T alcol Khi alcol tc dng vi HX to thnh dn xut halogen theo s : ROH + HX RX + H2O
CH3 CH3 C Cl + H2O CH3 ZnCl2 CH3 CH2 CH2 Cl + H2O

CH3 CH3 C OH + HCl CH3 CH3 CH2 CH2 OH + HCl

Tc phn ng ph thuc vo cu to ca alcol v bn cht ca halogen. i vi alcol kh nng phn ng gim theo th t sau: Alcol bc 3 > Alcol bc 2 > Alcol bc 1 i vi cc HX th kh nng phn ng gim theo th t HI > HBr > HCl. Phn ng gia HCl vi alcol thng c xc tc l ZnCl2. Phn ng to dn xut halogen t alcol v HX xy ra theo 2 giai on: Giai on 1 to acid lin hp ca alcol.
ROH + H+ ROH2
+

acid lin hp ca alcol

Giai on 2 l giai on chm, giai on xc nh tc phn ng. C hai kh nng xy ra phn ng:
(1) + ROH2 R+ + X R+ + H2O RX

Phn ng xy ra theo c ch ny s to thnh hn hp racemic. Nu phn ng xy ra qua giai on to thnh carbocation R+ th c kh nng to alken v mt sn phm ph do s chuyn v. iu c th minh ha theo phn ng:

170

CH3 CH3 __C__C__H CH3 CH3 Br +Br -

CH3 CH3 __C__C__H CH3 Br CH3 + Br -

CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 + CH3__C__C__H H CH3__C__C__H -H2O CH __C__C__H CH3__C__C__H 3 + + chuyen v CH3 OH CH3 OH2 CH3 CH3 + -H+ -H+ -H+ CH3 CH3 CH3 CH3 CH3 CH3__C__CH=CH2 CH __C C_CH CH2 C__C__H 3 3 CH3 CH3

(2)

+ + R__OH2

+ # [X....R...OH2 ]

X_R

+ H2O

Phn ng xy ra theo c ch th i nhn lng phn t. Sn phm to thnh c hin tng nghch quay Walden (hin tng thay i cu hnh) Phn ng xy ra gia alcol bc 1 hoc bc 2 vi HCl c xc tc ZnCl2 theo c ch:
Cl + CH2 R + ZnCl2 O H RCH2Cl + HOZnCl + Cl -

3.3.2. Phn ng gia phosphor halogenid hoc thionylclorid vi alcol. Alcol tc dng vi phosphotriclorid hoc phosphopentaclorid u to thnh dn xut monohalogen. 3 ROH + PCl3 ROH + PCl5 3RCl + H3PO3 RCl + POCl3 + HCl

Alcol phn ng vi thionylclorid SOCl2 xy ra theo c ch sau:

O ..

..

R_OH + SOCl2

-HCl

R .. : Cl ..

S O ..

..

R .. : Cl ..

:O ..

..

S O ..

..

R_Cl + SO2

3.3.3. iu ch dn xut monofluor Cho dn xut monoclor tc dng vi bc fluorid: RCl + AgF RF + AgCl

171

3.3.4. iu ch cc hp cht monohalogenoaren Thc hin phn ng th i in t gia halogen v aren hoc un nng mui diazoni (phn ng Sandmeyer).
+ N N: X

X + N2

3.3.5. iu ch cc dn xut polyhalogen Cc dihalogen c iu ch bng cch cho aldehyd hoc ceton tc dng vi phosphopentahalogenid PX5.
R_C_R'(H) + PCl5 O Cl _C_R'(H) + POCl R 3 Cl

Cc phn ng cng hp halogen vo alken, alkyn u c kh nng to thnh cc cht di hoc tetrahalogen. S clor ha toluen c xc tc nh sng thng thu c hn hp mono v polyclorid
CH3 Cl2 , h -HCl CH2Cl Cl2 , h -HCl CHCl2 Benzalclorid Cl2 , h -HCl CCl3 Benzotriclorid

Benzylclorid

Cc haloform c iu ch t ethanol v clor theo s phn ng sau:

Cl2 + H2O HCl + HClO ; HClO H+ + ClO +HOCHCl3 + HCOOCloroform

O + 3ClOO CH3CH2OH + ClO CH3 C CCl3 C - , -H O -Cl 2 H - 3OHH Ethanol Cloral

Hp cht hexaclocyclohexan iu ch t benzen v clor c xc tc tia t ngoi xy ra theo c ch gc.

+Cl. Cl +Cl. Cl Cl +Cl.

.....

Cl Cl

Cl

Cl Cl

Cl

Hexaclocyclohexan tn ti 8 ng phn lp th. Trong ch c ng phn c tc dng tr su b.

Cl H H Cl Cl H Cl H H H Cl Cl 1,2,3,4,5,6-hexaclocyclohexan e,e,e,a,a,a-hexaclocyclohexan

172

1,1,1-Tricloro-2,2-bis(4'-clophenyl) etan l hp cht halogen c tc dng dit cn trng thng gi l DDT. DDT c iu ch t clorobenzen v cloral.
2 Cl + CHO CCl3 H2SO4 Cl CH Cl + H2O

CCl3 1,1,1-tricloro-2,2-bis (4,4'-clorophenyl) etan

4. Tnh cht l hc Ngoi mt vi cht trng thi hi nh fluoroetan, clorometan, bromometan... phn ln cc dn xut halogen l cc cht lng khng mu hoc cc cht rn. Hp cht halogen khng tan trong nc nhng tan nhiu trong cc dung mi hu c. Mt s tnh cht vt l ca dn xut halogen c trnh by trong bng 14-1. Lin kt C _X l lin kt phn cc v vy hp cht halogen c momen lng cc ()
Bng 14.1: Momen lng cc v di lin kt C-X ca mt vi hp cht halogen
CH3X CH3F CH3Cl CH3Br CH3I C---X di lin kt d (A ) 1,385 1,784 1,929 2,139
o

Momen lng cc (D) 1,82 1,94 1,79 1,64

= q.d l mt i lng vect q l lc tng tc gia 2 ht nhn e1, e2 l in tch ca 2 ht nhn. d l di lin kt

q=

e 1e 2 r2

r l khong cch gia hai nhn nguyn t 5. Tnh cht ha hc 5.1. Cu to v kh nng phn ng Trung tm phn ng ca cc dn xut halogen l lin kt C _X. m in ca halogen ln hn ca carbon. Lin kt C _X l lin kt cng ha tr phn cc. u m ca lin kt lch v pha halogen. Kh nng phn ng ca cc dn xut halogen ph thuc vo bn cht ca halogen. Kh nng phn ng tng theo th t RI > RBr > RCl > RF. Dn xut iod c kh nng phn ng cao v phn cc ca lin kt C _I ln nht so vi cc lin kt C _X khc. phn cc ca cc lin kt C _X ph thuc vo m in v kch thc ca nguyn t X. m in ca X cng nh v kch thc nguyn t X cng ln th lin kt C _X cng d phn cc. 173

Bng 14.2: Tnh cht vt l ca mt vi hp cht halogen

Hp chat Fluorometan Clorometan Bromometan Iodometan Cloroetan 1-Cloropropan 2-Cloropropan Vinylclorid Allylclorid Methylenclorid Cloroform Carbontetraclorid Fluorobenzen Clorobenzen Bromobenzen Iodobenzen Benzylclorid Benzalclorid Benzotriclorid

Cong thc cau tao

CH3F CH3Cl CH3Br CH3I CH3CH2Cl CH3CH2CH2Cl CH3CHClCH3 CH2= CHCl CH2=CHCH2Cl CH2Cl2 CHCl3 CCl4

Nhiet o chay Nhiet o soi

-141,8 -97,7 -93,7 -66,5 -138,7 -122,8 -117,0 -159,7 -136,4 -96,8 -63,5 -22,9 -41,9 -45,2 -30,6 -31,3 -41,1 -16,4 -4,8 -78,5 -23,7 3,6 42,5 12,3 47,2 35,4 -13,8 44,6 40,2 61,2 76,7 84,7 131,7 156,5 188,5 179,3 205,2 220,8

C6H5_F C6H5_Cl C6H5_Br C6H5_I C6H5_CH2Cl C6H5_CHCl2 C6H5_CCl3

Kh nng phn ng ca dn xut halogen cn ph thuc vo c im ca gc hydrocarbon lin kt vi halogen. C th chia thnh 3 loi dn xut halogen theo kh nng phn ng: Kh nng phn ng bnh thng l cc dn xut alkyl v cycloalkyl halogenid.
CH3CH2CH2Cl Cl

Kh nng phn ng thp l cc dn xut cha cc gc hydrocarbon cha no v gc hydrocarbon thm, trong nguyn t halogen X lin kt trc tip vi carbon c lin kt i hoc nhn thm. Nguyn nhn kh nng phn ng thp l do cp in t p trn halogen lin hp vi gc hydrocarbon.
CH3_C = CH2 : Cl 2-Cloropropen CH2 = CH Br Bromobenzen

..

Cl: vinyl clorid

174

 Kh nng phn ng cao l hp cht c cu to allylic.

CH2 = CH_CH2_Cl Allylclorid CH2Cl Benzylclorid

S khc nhau ca 3 loi hp cht trn c cn c vo phn ng thy phn: RX + HOH

CH3 CH2CH2_Cl + HOH
Cl + HOH

ROH + HX

CH3 CH2CH2_OH + HCl un nong vi dung dch kiem

OH + HCl Kh, un nng 380 v p sut
o

CH2 = CH_CH2_Cl + HOH

CH2Cl + HOH

CH2 = CH_CH2_OH + HCl Rt d b thy phn

CH2OH + HCl Rt d b thy phn

Kh nng phn ng gim dn theo cu trc ca gc R nh sau: RCH=CH-CH2_X > ArCH2_X > R_X > Ar_X > RCH=CH_X > RCC_X 5.2. Phn ng th i nhn Cc dn xut halogen tham gia nhiu loi phn ng th khc nhau nh phn ng thy phn, th amin, to ether.... 5.2.1. Phn ng th i nhn ca hp cht alkyl halogenid Phn ng th xy ra gia alkyl halogenid RX v tc nhn i nhn Y - theo s : RX + Y- RY + X-

Ty thuc vo cu to ca dn xut halogen, tc nhn i nhn, dung mi phn ng c th xy ra theo c ch lng phn t SN2 hoc n phn t SN1.

SN2 SN1

Y + R _X

[ Y .....R.....X ] R +

Y_R + X

V k

d[Y-][RX] dt

Cham + R + X ; R_X

-Nhanh _ + Y R Y

d[RX] dt

Bng phn ng th i nhn, t hp cht halogen to ra nhiu hp cht c cc nhm chc khc nhau.

175

Phn ng th ca hp cht alkylhalogenid

Amin bac 1 Amin bac 2 Amin bac 3 Nitril Alkyn Alkan Nitroalkan RNH2 + HX RNHR' + HX RNHR'2 + HX RCN + X R'C CR + XR_R' + MX RNO2 + X NH3 R'NH2 R'2NH CN R'C CR'M NO2R_X HO R'O R'COO HS R'S HOO R'OO SCN X - + ROH X - + ROR' X - + R'COOR X - + RSH X - + RSR' X - + ROOH X - + ROOR' X - + R_SCN Thiocianat Alcol Ether Ester Thioalcol Thioether Hydroperocyd Perocyd + R_NCS Isothiocianat

RCH(COOR')2 + X (R'OOC)2 CH Esteralkyl malonat

..

Dn xut halogen tc dng vi cc alcolat hay phenol trong mi trng kim to thnh ether ROR' hoc ArOR' (phn ng Williamson).
CH3_Br + OH NaOH Anisol OCH3 + NaBr + H2O

Ha lp th ca phn ng th i nhn Nu hp cht halogen c carbon bt i xng th tu thuc hng tn cng ca tc nhn i nhn m carbon bt i xng c thay i cu hnh hay khng. Nu hng tn cng ca Y - cng hng i ra ca X - th khng c s thay i cu hnh
CH3 CH3CH2 ( R) C H I + YCH3 CH3CH2 C H Y + I-

( R)

Nu hng tn cng ca Y - i vo t pha sau hng i ra ca X - th c s thay i cu hnh xy ra.

H13C6 Y- + H C CH3 ( S) I Y C C6H13 H + CH3 ( R) I-

S thay i ca cu hnh carbon qua giai on trng thi chuyn tip (phc hot ng).

176

H13C6 Y- + H C CH3 ( S) I

C6H13 Y...... C ...... I H CH3

C6H13 + C H CH3 ( R)

I-

Minh ha cc trng thi c th c trong qu trnh phn ng SN2 qua hnh 14.1
E Trang thai chuyen tiep
Y
-

C
C

X B

Y C

Thay oi cau hnh

Y + C

X A E Y C + X

Chat phan ng Tien trnh phan ng

San pham

Hnh 14.1: Cc trng thi nng lng ng vi c ch phn ng SN2

V vy cc hp cht to thnh t dn xut halogen quang hot c th l quang hot vi s thay i cu hnh (th SN2) hoc mt hn hp racemic (th SN1). Phn ng gia tert - butylbromid vi alcol ethylic to ether tert - butylethyl (CH3)3COC2H5 l phn ng th i nhn theo c ch SN1. Phn ng qua giai on to carbocation (hnh 14-2).
E

+ (CH3)3C + Br - + HOC2H5

(CH3)3CBr + C2H5OH

+ (CH3)3CO

H + BrC2H5 (CH3)3COC2H5 + HBr

Tien trnh phan ng the SN1

Hnh 14.2: Cc trng thi nng lng ng vi c ch phn ng SN1

177

(CH3)3C_ Br (CH3)3C+ + C2H5OH

Cham

+ (CH3)3C_OCH2CH3 H

(CH3)3C+ + Br(CH3)3COCH2CH3 + H+

Gin minh ha tin trnh phn ng th SN1 ng vi cc trng thi nng lng v s hnh thnh carbocation. Carbocation (CH3)3C+c cu to phng. Nu dn xut halogen bc 3 c tnh quang hot th carbocation to thnh b alcol tn cng vo t 2 pha ca mt phng vi xc sut nh nhau, kt qu l thu uc mt racemic khng quang hot. 5.2.2. Phn ng th i nhn ca hp cht allylhalogenid Ngoi sn phm th i nhn cn c sn phm th do chuyn v allylic.
R_CH=CH_CH2_Cl - X+ R_CH=CH_CH2 +Y R_CH=CH_CH2_Y
Sn phm th S N1

+ R_CH_CH=CH2 +Y R_CH_CH=CH2 Y
Sn phm th c chuyn v

5.2.3. Phn ng th i nhn ca hp cht halogenoaren S th xy ra kh khn, i hi nhit cao v p sut.

NaOH , 300oC Cl NH3,200oC Cu2O NH2 + HCl OH + NaCl

Nu trn nhn thm c nhm ht in t th phn ng xy ra d dng hn. Phn ng th gia clorobenzen v NH3 xy ra theo c ch "tch -cng" hoc ''c ch aryn"
Cl

NH2 +NH3 -NH3, - Cl 1,2-dehydrobenzen (aryn)

NH2 48%

+H+H-

52%

NH2

Phn ng th loi ny cng xy ra i vi cc tc nhn i nhn l cyanid CN-

ArCl + CuCN

ArCN + CuCl

178

5.2.4. nh hng ca c cht v dung mi ln phn ng i nhn. Cu to gc alkyl v dung mi c nh hng n tc v c ch ca phn ng th i nhn. nh hng s phn nhnh ca mch carbon ln tc phn ng SN2 trnh by trong bng 14.3:
Alkyl halogenid CH3CH3CH2(CH3)2CH(CH3) 3CTc tng i 30,00 1,00 0,02 0

Tc SN2 Methyl > gc bc nht > gc bc 2 >> gc bc 3 Tc SN1 Methyl < gc bc nht < gc bc 2 < gc bc 3 Dung mi phn cc thun li cho phn ng th i nhn theo c ch SN1 Dung mi t phn cc thun li cho phn ng th i nhn theo c ch SN2. Phn ng th i nhn ca hp cht halogen b cnh tranh bi phn ng tch loi. 5.3. Phn ng tch loi (Xem phn iu ch alken) 5.4. Phn ng vi kim loi 5.4.1. Tc dng vi natri Cc dn xut halogen mch thng cng nh vng thm u tc dng vi natri kim loi to thnh hydrocarbon (phn ng Wurtz v Wurtz - Fittig).
R_X + 2Na + X_R
Ether

R_R + 2NaX

Phan ng Wurtz.
Phan ng Wurtz - Fittig

Ether Ar_X + 2Na + X_R Ar_R + 2NaX

Phn ng ny cho php iu ch nhng hydrocarbon c s lng carbon ty . 5.4.2. Dn xut halogen tc dng vi nhiu kim loi hot ng khc Dn xut halogen tc dng vi kim loi to thnh hp cht c kim c nhiu ng dng v thc t cng nh l thuyt. c bit l phn ng ca hp cht halogen vi magnesi to thuc th Grignard (xem phn hp cht c kim). RX + Mg RMgX

Bi tp
1. Vit cng thc cu to cc cht c tn gi sau y: a. 1,2- Diclobutan; c. 3-Cloro-4,4-dimethylpentyn b- 1-Cloro- 2-bromo-3-methylpenten; d- Propylbromid;

179

e. Isohexylclorid; g. Allylbromid; i. Tetracloroethylen; k. Benzylidenbromid;

f- Vinylfluorid; h- Ethylidenclorid j- Trimethylenclobromid; l- Methylenbromid

2. Trnh by phng php iu ch cc cht sau: a. 2,2-Diclorobutan t 2,3-diclorobutan; b- sec- Butylbromid t butylbromid. c. 2,2-Diclopropan t aceton; d- Benzalclorid t aldehyd benzoic. e. Acid 4-cloro-3-nitrobenzensulfonic t benzen; g- Acid 4-nitrobenzoic t toluen. 3. Trong cc hp cht sau y: ethylclorid, vinylclorid, allylclorid th lin kt C _Cl ca cht no bn vng hn trong phn ng thu phn? Sp xp theo th t tng dn v gii thch. Phn ng xy ra theo c ch no ? 4. Hy vit phn ng ca cc hp cht di y vi methylat natri: a. 2-Bromopentan; b- 1-Bromo-4-methylbutan; c- 3-Bromo-2-methyl-2-penten; d. 1-Bromo-3-methyl-2-buten; e- Isopropyliodid. 5. Vit cc phn ng to cc cht trung gian v cht cui trong cc s phn ng
a- Isobutylen b- Allyliodid HBr A ddNaOH B Na A 2HBr B HI C C

ddKOH

6. Vit phn ng ca cis-1-iodo-4-methylcyclohexan vi ion iodid. Gii thch c ch.

180

Chng 15

HP CHT C KIM

Mc tiu hc tp 1. c c tn theo danh php cc loi hp cht c kim. 2. Trnh by c ha tnh ca hp cht c Magnesi (thuc thou Grignard. 3. Nu c ng dng ca cc hp cht c kim trong tng hp hu c.

Ni dung
Hp cht c kim l nhng cht hu c c nguyn t kim loi lin kt trc tip vi nguyn t carbon trong gc hydrocarbon. Khc vi cc cht v c, hp cht c kim dng kh, dng lng hoc dng rn c nhit nng chy thp. Hp cht c kim tan c trong dung mi t phn cc nh hydrocarbon v ether. 1. Cu to Lin kt C - M c tnh cht ion. M l kim loi Cc kim loi (trong trng hp ny) thiu in t.
R - + R M + R M

Ty thuc ha tr ca kim lai hp cht c kim c cc lai: RM ; R2M ; RMX (X l halogen) ; R3M. Hp cht Grignard (thuc th Grignard): RMgX (X = Cl, Br).

Trong dung mi ether hp cht dialkyl magnesi to lin kt phi tr vi 2 nguyn t oxy ca ether. Trong dung dch ether long (0,1M), thuc th Grignard tn ti dng monomer. Magnesi phi tr vi 2 phn t dung mi ether. Trong dung dch m c hn (0,5-1M) thuc th Grignard tn ti dng dimmer.
R R Mg O(C2H5) 2 O(C2H5) 2 Br

O(C2H5) 2 Mg O(C2H5) 2

R Mg

Br Mg R Br

2. Danh php 2.1. Tn gc hu c + Tn kim loi CH3) 3CLi t-Butyllithi (CH3)4Si Tetramethylsilan (CH3CH2)2Mg Diethylmagnesi (CH3CH2)4Pb Tetraethyl ch 181

(CH3CH2) 3B CH3Cu

Triethylboran Methylng

(CH3) 3Al (CH3)2Hg

Trimethyl nhm Dimethyl thy ngn

Ch : Cc hp cht ca bo, thic, silic gi tn theo dn xut hydrid ca chng BH3 boran ; SnH4 Stannan ; SiH4 Silan 2.2. c tn nh mui v c Ha tr ca kim loi khng s dng ht lin kt vi gc hu c m lin kt vi cc nguyn t khc. Hp cht loi ny xem nh mui v c c gc hu c. CH3CH2MgBr CH3HgCl CH3CH2AlCl2 3. Tnh cht l hc
Bng 15.1: Tnh cht l hc ca mt s hp cht c kim
Hp cht CH3CH2Li (CH3)2Mg (CH3)3 Al CH3AlCl2 (CH3)4Si (CH3CH2)4Si (CH3)2Zn (CH3)2Cd (CH3)2Hg tc 95 240 0 73 - 42 - 4,5 ts 95,0 130,0 97-100* 26,5 153,0 46,0 106,0 96,0 Hp cht (CH3CH2)2Hg CH3CH2HgI CH3CH2HgCl (CH3)3Ga (CH3)3In (CH3)3Te (CH3)4Ge (CH3)4Sn (CH3)4Pb tc 186,0 193,0 -19,0 89,0 38,5 - 88,0 - 55,0 -27,5 ts 159 40** 56 89** 147 43 78 110

Ethyl magnesi bromid Methyl thu ngn clorid Ethyl nhm diclorid

tc = nhit nng chy; ts = nhit si; * mmHg ; ** thng hoa 4. Phng php iu ch cc hp cht c kim 4.1. Phn ng gia alkyl halogenid vi kim loi Trong phng th nghim s dng iu ch hp cht c lithi v c magnesi. Dung mi l ether hoc hydrocarbon

RMgX
C che :

R'X'

RR' + XMgX'
. R + X Mg

R-X
. R +

+ Mg X Mg

R-Mg-X

182

Trong phng th nghim, thng s dng alkylbromid. iu ch hp cht c lithi. Hp cht c Na, K khng iu ch theo phng php ny v c phn ng Wurtz:
2CH3CH2CH2Br + 2Na
ether

CH3CH2CH2CH2CH2CH3 + 2NaBr

C ch:
CH3CH2CH2Br + 2 Na CH3CH2CH2-Na+ + NaBr CH3CH2CH2CH2CH2CH3 + Br-

CH3CH2CH2- + CH3CH2CH2Br

Phn ng ca hp cht alkyldihalogenid vi Zn hoc Mg thng to hp cht cha no hoc hp cht vng

BrCH2CH2Br

+ Mg

MgBr2 + CH2=CH2
ZnBr2 +
(80%)

BrCH2CH2CH2Br + Zn
4.2. Phn ng ca hp cht c kim vi mui To hp cht c kim mi v mui mi

RM + M'X

RM' + MX

Phn ng xy ra theo chiu ty thuc th kh ca 2 ion kim loi

Bng 15.2: Th kh tiu chun
Phn ng Li+ Al Si
3+ 4+

Eo, vol - 3,045 - 2,370 - 1,660 - 0,840 - 0,763 - 0,402 0,000 0,014 0,522 0,854

+ e+ 3e+ 4e+ 2e+ e-

= Li = Mg = Al = Si = Zn = 1/2H2 = Cu = Hg

Mg2+ + 2e-

Zn2+ Cd H+ Sn
4+ + 2+

+ 2e- = Cd + 4e- = Sn + e+ 2e-

Cu

Hg2+

183

2CH3CH2MgCl + CdCl2 o E = -0,402 4CH3MgCl + SiCl4 o E = -0,840 CH3Li + CuI o E = -0,522

Ether

(CH3CH2)2Cd + MgCl2 o E = -2,370 (CH3)4Si + 4MgCl2

o E = -2,370 CH3Cu + LiI

o E = -3,045

4.3. Thay kim loi vo lin kt C -H

CH3CH2CH2CCH + n C4H9Li CH3CH2CH2CCLi + nC4H10 1 - Pentynyl liti

Phn ng acid -base : Pentyn l acid; n-Butyl lithi l base phn ng chuyn dch v pha phi. Chng t 1-pentyn c tnh acid mnh hn n -butan. y l phng php chung thay i lin kt C -H thnh C -M (M l kim loi). Thuc th Grignard c s dng thay kim loi vo alkyn.
HC CH + CH3CH2MgBr
ether

Ethyl magnesi bromid

HC

CMgBr + C2H6

Ethyl magnesi bromid

4.4. Phng php iu ch c th Hp cht c kim c th iu ch bng cch cng hp vo alken hoc alkyn. Hydrurboran ha
6CH2=CH2 + B2H6 2(CH3CH2)3B

Cng hp mt lin kt Al -H vi alkyn.

CH3 CH3CHCH3 2AlH + CH3CH2C CH
Diisobytyl nhm hydrid (DIBAl)

CH3 CH3CHCH3 2Al H

C=C

H CH2CH3

(E) 1-Butenyl diisobutyl nhm

Hp cht c kim tc dng vi kim loi t do c th to thnh 2 hp cht c kim.

6CH2=CH2 + B2H6 2(CH3CH2)3B

(CH3)2Hg + 2CH3CH2Li

(CH3CH2)2Hg + 2CH3Li

5. Cc phn ng ca hp cht c kim 5.1. Tc dng vi hp cht c hydro linh ng Hp cht c kim tc dng vi nhng hp cht c hydro linh ng to hydrocarbon. 184

Trong hp cht c kim, kim loi c in tch dng Rt d tc dng vi hp cht c hydro linh ng Thy phn
(CH3)3Al + 3H2O 3CH4 + Al(OH)3

Phn ng vi alcol v acid carboxylic

CH3 H3C C Li + CH3OH H3C CH3 CH3 C H CH3 + CH3O Li +

CH3 H3C C Li + CH3COOH H3C CH3

CH3 C H CH3

+ CH3COO Li +

Phn ng vi thiol v amin

RSH, RNH2

Khng th to c thuc th Grignard t hp cht alkyl halogenid c cha chc hydroxy hoc chc acid (v c hydro linh ng) 5.2. Phn ng vi halogen Hp cht c kim tc dng rt mnh vi clor v brom Cl2 + 2e- = 2Cl- Eo = +1,358 vol RM + Cl2 RCl + M+Cl-. Phn ng t dng tng hp alkylhalogenid RX. (V iu ch RM t RX). 5.3. Phn ng vi oxy Hp cht c kim rt nhy cm vi oxy. C th bc chy trong khng kh. Cc phn ng ca hp chy c kim thng tin hnh trong mi trng tr (kh nit, kh argon). Oxy ha thuc th Grignard l phng php iu ch alcol. RMgX + O2 ROOMgX ROOMgX + RMgX 2ROMgX ROMgX + HCl ROH + XMgCl

Phn ng oxy ha cnh tranh vi phn ng to thuc th Grignard. Vic iu ch thuc th Grignard thng tin hnh trong mi trng kh tr.

185

5.4. Phn ng vi hp cht carbonyl, dioxydcarbon v epoxyd Lin kt C -M phn cc c dng C -_ M+ nn c kh nng phn ng cao vi carbon tch in dng ca nhm carbonyl trong aldehyd v ceton.
Cl Mg
ether

HCHO

CH OH
2

H2O
ether

(CH3)2CHMgBr + CH3CHO

+ H H2O +

(CH3)2CHCHOHCH3 3-Methyl-2- butanol (53-54%) OH (CH3)2CHCH2CCH2CH3

C2H5MgBr + (CH3)2CHCH2COCH3

ether

H2O

CH3 3,5-Dimethyl-3-hexanol

ng dng iu ch alcol bc 1, bc 2, bc 3. Phn ng ca thuc th Grignard vi aldehyd formic to alcol bc 1; vi aldehyd to alcol bc 2 v vi ceton to alcol bc 3.
CH3MgBr CH3CH2MgBr + + O CH3CH2CCH2CH3 O CH3CCH2CH3CH3 O

OH CH3CH2CCH2CH2CH3 CH3

CH3CH2CH2MgBr + CH3CCH2CH3

Cc phn ng ph:
O (CH3)2CHMgBr + (CH3)2CHCCH(CH3)2 OH (CH3)2CHCHCH(CH3)2 + CH3CH=CH2

Hp cht c lithi c s dng nhiu hn thuc th Grignard v n hot ng hn v phn ng xy ra nhit thp. Phn ng kh v s enol ha xy ra c tm quan trng.
O (CH3)3CLi t-butyl liti + (CH3)3C-C-C(CH3)3 -70o di-t-butylceton
ether

H2O

(CH3)3C 3C-OH

S cng hp cc mui natri hoc lithi ca alkyn vi aldehyd hoc ceton.

CH3C CH + NaNH2 CH3C CNa CH3COCH3 H2O CH3C OH CC(CH3)

186

Thuc th Grignard tc dng d dng vi carbondioxyd. Sn phm trung gian ca phn ng l mui magnesi ca acid carboxylic. Mui ny tc dng vi acid v c long to thnh acid carboxylic. y l phng php iu ch acid carboxylic t cc alkyl halogenur.
Cl CH3CHCH2 CH3 + Mg MgCl CH3 CHCH2CH3
CO2

COOMgCl CH3CHCH2 CH3

H2O H2SO4

COOH CH3CHCH2CH3

Phn ng xy ra gia carbon dioxyd v hp cht c lithi.

Li
CO2

CO2 Li
H3O+

COOH

Phenyl liti

Acid benzoic

Thuc th Grignard tc dng vi ethyl ortoformiat to acetal. Thy phn acetal to aldehyd.
C H3
Mg

C H3
C H(OC 2 H 5 )3

C H3
H+

C H3

Br

M gB r

CH( OC 2H 5 )2

C HO

C ch:

CH(OC2H5)3 + MgBr2

- + Br2MgOC2H5 CH(OC2H5) 2

+ Br 2MgOC2H 5 + C2H 5O-CH-OC2H 5

+ C2H 5O=CH-OC2H 5

RMgBr

RCH(OC2H 5) 2

Phn ng gia hp cht c lithi v epoxyd xy ra theo c ch SN2

O C6H5CH -O Li+ CH2 + C6H5Li C6H5CH CH2C6H5 H 2O OH C6H5CH CH2C6H5 1,2-diphenyletanol (70-72%)

ng dng tng 2 nguyn t carbon trn mch carbon:

RCl Mg
Ether
O

R-MgCl

H2C

CH2

H+

R-CH2-CH2OH

187

5.5. Phn ng vi cc hp cht c kim khc Phn ng vi hp cht c kim to ra mt hp phc c kim khc c nhiu ng dng trong tng hp hu c
CH3Li + CH3Cu (CH3)2CuLi

C th to hp phc c kim bng phn ng

2CH3CH2CH2Li + CuI (CH3CH2CH2)2CuLi + LiI

ng dng: S cng hp 1 4 vo cc nguyn t - ethylenic

1O

O a
4

+ (CH3)2CuLi R

C CH3 R

Bi tp
1. Trnh by cu to ca hp cht c kim. 2. Hp cht c kim c cc loi phn ng no? Cho v d.

188

Chng 16

ALCOL

Mc tiu hc tp 1. c c tn cc alcol theo danh php IUPAC v tn thng thng. 2. Trnh by c ha tnh ca alcol v polyalcol. 3. Vit c s chuyn ha tng hp cc alcol.

Ni dung
Alcol l nhng hp cht c nhm hydroxyl - OH gn trc tip vi nguyn t carbon trng thi lai ha sp3 ca gc hydrocarbon. C nhiu loi alcol khc nhau: Alcol no, alcol cha no, alcol vng, alcol thm. Monoalcol v polyalcol. Cng thc tng qut ca alcol: CnH2n +2-2k-m(OH)m ; 1. Monoalcol 1.1. Danh php 1.1.1. Danh php IUPAC Alcol c tip v ng l ol. Chn mch chnh l mch carbon di nht cha nhm chc OH. nh s sao cho chc alcol c s b nht.
V tr v tn nhm th + V tr ca OH + tn hydrocarbon tng ng + ol
CH3 CH CH2OH CH3 2-Methylpropanol CH3 CH CH CH2OH CH3 Cl 2-cloro-3-methylbutanol CH3 OH CH2=CH_CH2OH Propenol CH C CH CH2OH CH3 2-Methyl-3-butyn-1-ol C6H5_CH2OH Phenylmethanol

n 1; k 0; m 1

CH3 CH CH CH2OH CH3 CH2 CH2F 2-isopropyl-4-fluorobutanol OH

CH3 CH CH CH CH3 CH3 CH2 CH2 Br OH 3-bromo-4-methyl-2-heptanol

CH2OH

1-methylcyclopentanol

CH2OH cis-4-(hydroxymethyl) cyclohexanol

cyclopropyl methanol

189

1.1.2. Danh php thng thng Gi tn gc hydrocarbon tng ng v thm tip v ng ic

CH3OH CH3CH2OH

Alcol methylic CH2=CHCH2OH Alcol allylic Alcol ethylic

C6H5CH2OH (CH3)3C_OH

Alcol benzylic Alcol tert-butylic

CH3CH2CH2CH2OH Alcol butylic

1.1.3. Danh php carbinol Alcol methylic c gi l carbinol. Cc alcol n gin khc c xem l dn xut th hydro ca carbinol.
CH3 CH2OH Methylcarbinol CH3 CH2 CH CH3 OH Ethylmethylcarbinol CH3 CH2=CH_CH2OH CH3 C OH CH3 Vinylcarbinol Trimethylcarbinol CH3 CH CH2OH CH3 isopropylcarbinol

Danh php ny ch gi cc alcol n gin.

1.1.4. Bc alcol Chc alcol OH lin kt vi carbon c bc khc nhau ta c alcol bc 1, alcol bc 2, alcol bc 3.
CH3CH2CH2CH2OH Alcol bac 1 CH3CH2CHCH3 OH Alcol bac 2 CH3 CH3 C OH CH3 Alcol bac 3

1.2. ng phn ng phn do mch carbon v do v tr nhm OH Phn t alcol C4H9OH c cc ng phn.
CH3 CH3 CH2 CH2 CH2OH n-Butanol CH3 CH CH3 CH2OH CH3 C OH CH3 CH2 CH CH3 OH Sec-butanol CH3 Tert-butanol

Isobutanol

Ph thuc cu to ca alcol c th c ng phn quang hc. 1.3. Phng php iu ch alcol C nhiu phng php iu ch alcol xut pht t tnh cht ha hc ca cc hp cht tng ng. 1.3.1. T alken Hydrat ha alken (xem phn alken). 190

Trong cng nghip alcol ethylic c sn xut theo phng php hydrat ha ethylen.
CH2=CH2 + H2O 300o ,H3PO4 C2H5OH

Cc alcol isopropylic, alcol tert-butylic cng c iu ch bng phng php hydrat ha cc alken tng ng. 1.3.2. Thy phn dn xut halogen (xem phn dn xut halogen).
RX + H2O HO ROH + HX

1.3.3. Kh ha cc hp cht aldehyd, ceton Kh ha hp cht carbonyl to thnh alcol bng cc phng php khc nhau. Hydro ha hp cht carbonyl c xc tc
H2 [Ni] R CHO R CH2OH ; H2 [Ni] R C O
Aldehyd Alcol bc 1 Ceton

R'

R CH R' OH
Alcol bc 2

Nu hp cht carbonyl cha no th ni i cng b hydro ha.

R CH=CH CHO 4H [Ni] R CH2 CH2 CH2OH

Kh ha bng natri trong alcol Aldehyd, ceton b kh thnh alcol bc 1 v bc 2.

R C R' O 2H [Na-C2H5OH] R CH R' OH

Kh ha bng cc hydrid kim loi AlLiH4, NaBH4

Aldehyd Acid Ester Clorid acid R_CHO R_COOH 2 H [H4LiAl]

2 H [H4LiAl] - H2O 2 H [H4LiAl] R_COOR' - ROH R_COCl 2 H [H4LiAl] -HCl

R_CH2OH Alcol

Kh ha bng lithi nhm hydrid tin hnh trong dung mi ether. Cc aldehyd, ceton, acid, ester v clorid acid u b kh ho to alcol. Trong trng hp ny nu hp cht cha no th ni i C =C khng b kh ha. 191

R CH=CH CHO

2H [H4LiAl]

R CH=CH CH2OH

Natri bo hydrid NaBH4 l tc nhn kh ha c tnh cht chn lc. Ch c aldehyd, ceton v halogenid acid b kh bng natri bo hydrid. Natri bo hydrid khng tan trong ether, tan trong alcol methylic v ethylic. 1.3.4. Kh ha ester ca acid carboxylic Kh ha theo Buve - Blanc Cht kh l natri v alcol ethylic.
RCOOR' 4 H [ Na + C2H5OH ] RCH2OH + R'OH

Hydro ha ester c xc tc C th kh ha ester bng hydro c xc tc l hn hp ng oxyd (CuO) v crom oxyd (Cr2O3).
RCOOC4H9 2H2 [CuO+Cr2O3 ] RCH2OH + C4H9OH

1.3.5. T hp cht c magnesi RMgX (xem phn hp cht c kim). Hp cht c magnesi tc dng vi aldehyd, ceton v ester th to thnh cc alcol bc 1, bc 2 hoc bc 3. Vi aldehyd, ceton
HCHO + RMgX Aldehyd formic OMgX + H 2O H C R RCH2OH + HOMgX H Alcol bc 1 OMgX + H 2O R' C R H

R'CHO + RMgX

Aldehyd

R' CH R + HOMgX OH Alcol bc 2

R' C R" + RMgX O Ceton

OH OMgX + H 2O R' C R + HOMgX R' C R R" R" Alcol bc 3

Vi ester Ester ca acid formic tc dng vi thuc th Grignard to alcol bc 1. Ester ca nhng acid khc tc dng vi thuc th Grignard to ceton. Ceton to thnh li tip tc tc dng vi phn t thuc th Grignard thu c alcol bc ba.

192

HCOOR' + RMgX Ester alkyl formiat

OMgX OH + RMgX OMgX H O + H2O + 2 H C R RCHO R C R R C R + HOMgX OR' -ROMgX H H Alcol bac 2 OMgX R R + RMgX + H2O + H2O R" C R R" C R R" C R R" C R + HOMgX OR' -ROMgX O OMg OH

R"COOR' RMgX + Ester

1.3.6. Oxy ha hp cht c magnesi Oxy ha hp cht c magnesi (thuc th Grignard) v sau thy phn.
RMgX + O2 ROOMgX + H2O ROH + HOMgX

1.3.7. Thy phn ester Ester b thy phn trong mi trng kim hoc acid to alcol
RCOOR' + H2O H+hoac HORCOOH + R'OH

Alcol ethylic, alcol butylic c th iu ch theo phng php ln men. Trong cng nghip, sn xut alcol methylic bng phn ng hydrat ha carbon monooxyd vi xc tc thch hp v p sut.
CO + H2O 400oC , 200atm ZnO - Cr2O3 CH3OH H = - 28,4 kcal

1.4. Tnh cht l hc 1.4.1. Nhit si v nhit nng chy Cc alcol c s carbon thp dng lng, c mi v v c trng. Cc alcol c s carbon cao dng rn, khng mi. Nhit si tng dn theo phn t lng. Lin kt hydro nh hng ln n nhit si ca alcol. S lin quan gia nhit si ca alcol bc 1 v phn t lng trnh by trn hnh 16-1

193

t osoi 300
200

alcol bac 1

100

n-alcan
0

-100 -200

20

40

Khoi lng phan t

60

80 100 120 140 160 180 200

Hnh 16.1. Quan h gia nhit si v phn t lng ca alcol bc 1

1.4.2. tan ca alcol Methanol, ethanol,1-propanol, 2-propanol, 2-methyl-2-propanol tan rt nhiu trong nc v chng to lin kt hydro vi nc. Cc alcol khc c tan trong nc gim.

... O_H ... O_H ... O_H ... O_H ... O_H ... O_H ... O_H ... O_H ...
H R H R H R H R

Bng 16.1. Tnh cht vt l ca mt s alcol

Cong thc CH3OH CH3CH2OH CH3CH2CH2OH CH3CHOHCH3 CH3CH2CH2CH2OH CH3CH2CHOHCH3 (CH3)2CHCH2OH (CH3)3C_OH CH2=CHCH2OH C6H5CH2OH C6H11OH Ten thong thng Alcol methylic Alcol ethylic Alcol propylic Alcol isopropylic Alcol butylic Alcol sec-butylic Alcol isobutylic Alcol tert-butylic Alcol allylic Alcol benzylic Alcol cyclohexylic Ten theo IUPAC Methanol Ethanol 1-Propanol 2-Propanol 1-Butanol 2-Butanol 3-Methyl-1-propanol 2-Methyl-2-propanol 1-Propenol Phenylmethanol Cyclohexanol

tochay
-97,1 -114,5 -126,1 -89,5 -89,8 -114,7

tosoi
64,7 78,3 97,2 82,3 117,2 99,5 107,9 82,5 97,0 205,4 161,5

25,5 -129,0

-15,3 23,9

194

1.4.3. Cc c trng v quang ph hng ngoi trng thi hi cc alcol khng c lin kt hydro, nhm chc OH t do c vch c trng trn quang ph hng ngoi 3700 cm -1. trng thi dung dch, vch c trng ca nhm OH trn quang ph hng ngoi c gi tr 3640- 3350 cm-1. Di hp th c trng ca nhm OH m rng ra l do cc alcol trng thi dung dch c lin kt hydro. Lin kt hydro t to thnh khi dung dch alcol cng long trong cc dung mi khng phn cc. Dung dch alcol cng m c, lin kt hydro gia cc phn t alcol cng d hnh thnh. 1.5. Tnh cht ha hc 1.5.1. Tnh acid -base ca alcol Tnh cht quan trng ca nc l tnh t phn ly.
H2O + H2O Ke + H3O + HO

+ Ke = [H3O][HO-] = 10 -14

Ke l hng s t phn ly ca nc Ke = [H3O+][ HO -]. Nng ca [H3O+] v [HO-] rt thp v bng 10-7mol/lt. Hng s t phn ly ca alcol methylic cn thp hn ca nc.
2 CH3OH Ke + CH3OH2 + CH3O -

+ KCH OH = [CH3OH2][CH3O -] = 1,2.10-17 3

Cc ng ng ca alcol methylic gi tr Ke cn thp hn. Tnh acid ca alcol gim dn khi s carbon ca alcol tng ln. Tnh acid ca alcol trong nc c xc nh theo phng trnh:
ROH + H2O Ka + RO - + H3O + [H3O][RO ] [ROH]

Ka =

Alcol c tnh acid yu hn nc. Tnh acid: alcol bc 1 > alcol bc 2 > alcol bc 3. Alcol c tnh base mnh hn tnh base ca nc. Cc phn ng th hin tnh acid ca alcol:
2ROH + 2Na 2RONa + H2

C2H5OH

+ + Na_NH2 Natriamidid + + Na_H Natri hydrid

+ C2H5O_Na + NH3 Natri etoxyd + C2H5O_Na + H2 Natri etoxyd

C2H5OH

195

 Cc phn ng th hin tnh base ca alcol:

R _O _ H + BF3 ..

..

+ .. R _O _ H

-BF

CH3: O : H + HBr ..

..

Methyloxoni

H+ .. CH3: O : H + Br ..

Tnh base ca alcol cn th hin qua phn ng vi acid Lewis nh Bo triflo

BF3 hoc km clorid (ZnCl2).
R _O _ H + ZnCl2 ..

..

+ .. R _O _ H -ZnCl2

Ion RO c tn gi l alkoxy. Cc alkoxy l nhng base mnh.

RO-+H2O ROH + HOCH3OC 2 H5O (CH3)2CHO(CH3)3C_O-

Metoxy Ion methylat

Etoxy Ion ethylat

Isopropoxy Ion isopropylat

t-Butoxy. Ion t-butylat.

Gi tr pKa ca mt s alcol v ca acid c trnh by trong bng 16-2

Bng 16.2. Gi tr pKa ca mt s alcol v acid
Hp chat H2 O CH3OH C2H5OH (CH3)C_OH ClCH2CH2OH CF3CH2OH C6H5OH CH3COOH pKa 14,0 15,5 15,9 18,0 14,3 12,4 10,0 4 ,8 Hp chat HCl H2SO4 H3PO4 HF H2 S HOCl H2 O2 pKa -2,2 -5,0 2,15 3,18 6,97 7,53 11,64

1.5.2. Phn ng loi nc to ether hoc alken Hai phn t alcol tc dng vi nhau khi c acid mnh nh H2SO4 to ether.
2 R _O _ H to= 140oC H2SO4 R _O _R + H2O

Cc alcolat RO - (alkoxy) l nhng tc nhn i nhn mnh tc dng vi alkyl halogenid to ether. Alcol tc dng vi alkyl halogenid xy ra rt chm.
R _O - + R'_ I Ion alcolat R _O _R' + I- Nhanh ; Ether ROH + R'I ROR' + HI Rat cham

196

 Cc alcol di tc dng ca acid sulfuric m c v nhit (>140oC) to alken.

CnH2n+1OH CnH2n + H2O

1.5.3. Phn ng to ester Alcol tc dng vi acid hu c, anhydrid acid, halogenid acid to thnh ester hu c.
RCOOH + R'OH (RCO)2 O + R'OH Anhydrid acid RCOCl + R'OH Clorid acid H+ H+ Pyridin RCOOR' RCOOR' Ester + H2O + RCOOH

RCOOR' + HCl.Pyridin Ester

Phn ng ester ha l phn ng thun nghch. cho phn ng chuyn dch v pha to ester ngi ta thng s dng cc cht lm gim nng ca nc, acid to thnh trong phn ng. Cc cht thng s dng l acid v c (H2SO4, H3PO4, acid 4-toluensulfonic), cc base hu c (pyridin). Hng s cn bng ca phn ng ester ha c tnh theo cng thc:
Kcb = [RCOOR'][ H2O] [RCOOH][ R'OH]

Acid sulfuric m c trong phn ng ester ha ng vai tr cung cp proton lm xc tc ng thi ng vai tr ht nc lm gim nng ca nc sinh ra trong qu trnh phn ng. Phn ng c tc nhanh hn v chuyn dch cn bng v pha to ester. C ch phn ng ester ha l c ch "cng - tch" c trnh by theo 2 cch:
C ch AAc 2
H + OH +R'OH HO O + H+ R C R C O R' + OH -H OH -R'OH HO +

R C

.. H2O+ -H2O + OH -H+ O R C R C O R' R C +H2O OR' + H+ OR' HO

Theo s trn th H2O sinh ra trong phn ng do tch hydro H ca alcol R'OH v nhm OH ca acid. Phn ng xy ra theo cch nh trn ph hp vi cc alcol bc 1 Theo c ch ny, nu acid c nh th tc phn ng ph thuc vo cu to ca alcol. Kh nng phn ng ester ha ca alcol gim dn theo th t sau: Alcol bc 1 > Alcol bc 2 > Alcol bc 3

197

 C ch AAlk 1

Cc alcol bc 3 xy ra theo c ch nh sau:

R'OH + H+ O OH + R' + R'OH2 + OR' R C OH + R' + H2O -H+ +H+ OR' O
+

R C

R C

Giai on to carbocation R + t acid lin hp ca alcol ROH2 l giai on xc nh tc phn ng. Cc alcol tc dng vi cc hp cht c cng thc chung RCOX to ester l qu trnh acyl ha alcol theo c ch:
O X

R C

HOR'

..

O H R C OR' + X

:OH R C OR' X R C

+ HX OR'

X = Cl , Br , R''COO -

Alcol tc dng vi acid v c to ester v c.

HONO (H+) acid nitr HONO2(H+) acid nitric R_OH R_ONO + H2O R_ONO2 + H2O Alkylnitrit Alkyl nitrat

POCl3triclor oxyd phosphor PO(OR) + 3HCl Trialkyl phosphat 3 H2SO4 acid sulfuric SO3 tri oxyd lu huynh R_OSO3H + H2O Alkyl hydrosulfat R_OSO3H R_OH SO2(OR)2 + H2O Dialkyl sulfat

Nhiu ester ca acid v c nh acid phosphoric, acid thiophosphoric c s dng lm thuc tr su.
O CH2 CH3 S P O CH2 CH3 O NO2 Parathion ( thiophos) O CH2 CH3 S P O CH2 CH3 O CH2 CH2 S CH2 CH3 Sistoc (mercaptophos) O CH3 S P O CH3 S CH2 C NHCH3 O Dimetoat ( phosphamid)

Mui natri alkylsulfat ca cc alcol t C10 _C20 nh natri lauryl sulfat C12H25OSO3Na c s dng lm cc cht nh ha trong dc phm, trong thuc nh rng v trong mt s cht c tc dng ty ra khc. Alcol cetylic n-C16H33OH c trong sp ong. 198

1.5.4. Phn ng oxy ha

Ty thuc vo v tr ca nhm OH, alcol b oxy ha to ra cc sn phm khc nhau. Alcol bc 1 b oxy ha thnh aldehyd v sau thnh acid:
R_CH2_OH [O] - H2O R_CHO [O] - H2O R_COOH

Alcol bc 2 b oxy ha to ceton:

R' CH OH R" + [O] R' C O R" + H2O

V mt l thuyt, trong mi trng kim v trung tnh cc alcol bc ba khng b oxy ha. Trong mi trng acid mnh alcol bc ba b oxy ha to ceton v acid c s carbon b hn ru ban u.
R' C OH R" CH2R'" + + 3[O] H R' C O R" + R'''COOH + H2O

Cc cht oxy ho thng s dng oxy ha alcol l mt s oxyd kim loi nh ng oxyd (CuO), crom oxyd (CrO3). Trong phng th nghim CrO3 c iu ch t kali bicromat (K2Cr2O7) v acid sulfuric m c trong dung mi acid acetic. C th trnh by c ch oxy ha alcol bng crom oxyd theo cc qu trnh sau:
3 CH3 CH3 CH OH + 2CrO3 + 6 H+ CH3 CH3 H 3 CH3 CH3 C O + 2Cr3+ + 6H2O

C che

CH OH + CrO3 H H

CH3 CH3 CH3 CH3

CH O CrO3H

CH3 CH3

:O

O CrO3H

C O

+ H3O+ + HCrO3

H3O+ + HCrO3
6H+ + 3H2CrO3

H2O + H2CrO3 CrO3 + Cr3+ + 6H2O

Cc alcol cha no b oxy ha bi CrO3 to hp cht carbonyl m lin kt i khng b oxy ha, nhng oxy ha bng KMnO4 th ni i b oxy ha thnh alcol a chc.
K2Cr2O7 + H2SO4 R_CH=CH_CHO R_CH=CH_CH2OH KMnO4 R_CHOHCHOH_CHOH

199

2. Alcol cha no

Trong phn t c lin kt i hoc lin kt ba. Nhm chc OH lin kt trc tip vi carbon c ni i thng khng bn v d chuyn thnh aldehyd hoc ceton.
H C C OH H H C C O H OH C H C CH3 H O

H H Alcol vinylic

H H Aldehyd acetic

2-Propenol

H C C CH3 H Aceton

Alcol vinylic khng bn nhng ester v ether ca n th bn vng v c iu ch bng phn ng cng hp gia acetylen v acid hoc alcol tng ng.
H C C H

+ CH3COOH
+ CH3CH2OH

H2C CH OOCCH3 Ester vinylacetat

H C C H

H2C CH OC2H5 Eter ethyl vinyl

Alcol cha no c nhm OH lin kt vi carbon lai ha sp3 th bn vng.

H2C CH CH2OH Alcol allylic
Propenol

CH3CH CH CH2OH Alcol crotonic 2-Butenol

H C C CH2OH Alcol propagylic Propynnol

HOCH2 C C CH2OH 1,4-Butyndiol

Alcol cha no propagylic v 1,4-butyndiol c th iu ch t acetylen v aldehyd formic

H C C H

+ HCHO

Cu C C Cu

H C C CH2OH

H C C H

Cu C C Cu

+ 2HCHO

HOCH2 C C CH2OH

Trong thin nhin tn ti nhiu loi alcol cha no c s carbon cao nh citronellol, geraniol, linalol, pharnezol, phytol c nhiu ng dng trong cng nghip hng liu v dc phm.
CH3_C=CH_CH2_CH2_CH_CH2_CH2OH
CH3 CH3

CH3C=CHCH2CH2C=CHCH2OH
CH3 CH3

Citronelol ( 3,7-dimethyl-6-octenol)
OH CH3C=CHCH2CH2CCH=CH2

Geraniol ( 3,7-dimethyl-2,6-octadienol)

CH3_C=CH_CH2_CH2_C=CH_CH2_CH2_C=CH_CH2 OH

CH3

CH3

CH3

CH3

CH3

Linalol ( 3,7-dimethyl-1,6-octadien-3-ol)

Pharnezol ( 3,7,1-trimethyl-2,6,9--dodecatrienol)
2

CH3_CH_CH2_CH2_CH2_CH_CH2_CH2_CH2_C=CH_CH2 OH
CH3 CH3 CH3 Phitol ( 3,7,11,15-teramethyl-2--hexadekenol)

200

3. Alcol vng

Alcol vng c th l no hoc cha no. C cc loi alcol vng thng gp sau y.
CH3 OH CH(CH3)2 (Menthol) 2-Isopropyl-5-methylcyclohexanol CH2OH OH 2-Cyclohexenol CH3 O CH(CH3)2 Menthon Cyclohexylcarbinol

OH Cyclohexanol

Cc alcol vng b oxy ha thnh ceton vng.

CH3 OH CH(CH3)2 Menthol CrO3, H+

Oxy ha cyclohexenol bng dung dch KMnO4 trong mi trng trung tnh to polyalcol vng.
OH KMnO4, OH pH 7 OH OH
1,2,3-Cyclohexatriol

2-Cyclohexenol

Mt s alcol vng c nhiu ng dng. Menthol c trong tinh du bc h c ng dng nhiu trong y dc. Cyclohexanol l dung mi cn thit ho tan cc polymer ng dng lm keo dn. Hp cht 1,2,3,4,5,6-cyclohexahexanol c nhiu ng phn trong ch c ng phn Inositol c ng phn quang hc v c ng dng trong dc phm.
HO HO OH 1,2,3,4,5,6-Cyclohexahexanol OH OH OH
OH OH OH OH OH OH OH OH OH OH OH OH

(+) - Inositol

(-) - Inositol

4. Polyalcol - alcol a chc

Polyalcol l loi hp cht trong phn t c hai hay nhiu nhm chc alcol OH.
4.1. Phn loi polyalcol

C cc loi polyalcol sau: Cc nhm hydroxyl trn cng mt nguyn t carbon.

R_CH2C(OH)2CH3 ; R_CH(OH)2 ; R_C(OH)3

201

Nhng polyalcol ny khng bn. Chng ch tn ti trong dung dch nc.

Nhng polyalcol c cc nhm alcol lin kt vi cc nguyn t carbon cnh nhau
CH2OHCH2OH ; CH2OHCHOHCHOHCH2OH

Cc polyalcol ny c tnh cht c bit hn so vi monoalcol.

Nhng polyalcol c cc nhm hydroxyl xa nhau
CH2OHCH2CHOH ; CH2OHCH2CH2CHOHCH3.

Loi polyalcol ny c tnh cht ging monoalcol.

4.2. Danh php polyalcol

Cc polyalcol c gi tn theo danh php thng thng hoc danh php IUPAC. Theo danh php IUPAC tn gi cc polyalcol xut pht t tn gi ca hydrocarbon tng ng thm cc tip v ng diol, triol, tetraol... ch s lng nhm OH v cc ch s ch v tr cc nhm OH.
Bng 16.3: Tn gi mt s polyalcol
Cong thc cau tao HOCH2_CH2OH CH3 CHOH CH2OH HOCH2 CH2 CH2OH HOCH2 CH2 CH2 CH3CH3 CH3 C C CH3 OH OH CH2 CH OH OH CH2 CH OH OH CH2 CH OH OH CH2 CH OH OH CH2 OH CH CH2 OH OH CH CH CH2 OH OH OH CH CH CH CH2 OH OH OH OH Tetramethylethylenglycol Glycerin 2,3-Dimethyl-2,3butandiol 1,2,3-Propantriol CH2OH Danh phap thong thng Ethylenglycol Propylenglycol Trimethylenglycol Tetramethylenglycol Danh phap quoc te 1,2-Etandiol 1,2-Propandiol 1,3-Propandiol 1,4-Butandiol

Erytrit Pentit

1,2,3,4-Butantetraol 1,2,3,4,5-Pentahydroxy petan 1,2,3,4,5,6-Hexahydroxy hexan

Hexit Pentaerytrit

CH2OH HOH2C C CH2OH CH2OH

Tetrahydroxyneopentan

202

4.3. iu ch polyalcol Thy phn cc dn xut polyhalogen:

CH2Cl CH2Cl CH2Cl CHCl CH2Cl

+ 2H2O

CH2OH CH2OH

+ 2 HCl + 3 HCl

+ 3H2O

CH2OH CHOH CH2OH

Oxy ha olefin bng dung dch KMnO4:

3 CH2=CH2 + 4 H2O + KMnO4

3 CH2OH_CH2OH + MnO2 + 2KOH

T clohydrin iu ch glycol:
CH2Cl CH2OH + H2O CH2OH CH2OH + HCl

Clohydrin tc dng vi Ca (OH)2 v sau thy phn trong mi trng acid.

2 CH2Cl CH2OH + Ca(OH)2 O CH2 CH2 O 2 CH2 CH2 + CaCl2 + 2H2O

+ H2O

H+

CH2OH CH2OH

Kh ha aceton bng in ha hoc tc dng vi magnesi v iod:

2 CH3 + 2 Mg + I2 CH3 C O CH3 2H O CH3 2 C C CH3 CH3 OMgI OMgI CH3 CH3 C C CH3 CH3 OH HO

iu ch glycerin t propylen:

Trc tin ngi ta clo ha propylen 500oC thu c allylclorid. Sau cho allylclorid tc dng vi dung dch clor vi nc th thu c glycerin.
CH3CH=CH2 + Cl2 CH2ClCH=CH2 + HCl CH2ClCHOH_CH2Cl+ HCl CH2OH-CHOH-CH2OH + 2HCl

CH2ClCH=CH2 + Cl2 + H2O CH2ClCHOH_CH2Cl +2H2O

Cng c th iu ch glycerin t aldehyd formic v aldehyd acetic bng phn ng kh theo Oppenauer -Meerwein-Ponndorf to thnh aldehyd allylic. Sau hydroxyl ha aldehyd ny bng hydro peroxyd.
HCHO + CH3_CHO HOCH2_CH2_CHO - H2 O CH2=CH _CHO Acrolein

CH2=CH_CHO + C2H5OH Al( OR)3 CH _CHO +CH2=CH_CH2OH Alcol allylic 3 CH2=CH_CH2OH + H2O2 CH2OH_CHOH_CH2OH Glycerin

203

4.4. Tnh cht l hc v ha hc ca polyalcol

Phn ln cc polyalcol tan c trong nc v c v ngt. Glycerin rt ho nc, c nht cao. Glycerin c dng lm cht ht m v s dng rng ri trong hng liu, thc phm v dc phm.
Cc polyalcol c mt s tnh cht ha hc c bn nh sau: Cc glycol tc dng vi HCl, HBr to thnh clohydrin v bromhydrin. Chc OH kh tc dng vi HCl v HBr.
CH2OH_CH2OH + HCl HOCH2_CH2_OCOR
[O] CH2OH_CH2OH - H2O Ethylenglycol R CH OH R' C R'' OH

CH2Cl_CH2OH + H2O RCOOCH2 _CH2_OCOR

[O] - H2 O OHC_CHO Glyoxal ( aldehyd oxalic) R C H O + R' C R'' O

Cc glycol tc dng vi acid hu c c kh nng to 2 loi ester.

v

Oxy ha glycol to aldehyd hoc ceton.

CH2OH_CHO

HIO4 hoac (CH3COO)4Pb

Phn ng dehydrat ha glycol (loi nc): Di tc dng ca acid v c hoc km clorid ZnCl2 ethylenglycol b loi nc to aldehyd acetic. Phn ng xy ra c s chuyn v anion hydro (H-).
H .. H OH OH Loai nc

.. +

CH2

CH2

CH + 2

C H

CH3

C H

H+

O H Chuyn v H-

O Aldehyd acetic

Phn t pinacol (tetra methylethylenglycol - 2,3-dimetyl-2,3-butadiol) di tc dng ca acid v c b dehydrat to thnh ceton l pinacolon. Trong phn ng ny xy ra s chuyn v nhm methyl. S chuyn v ny gi l s chuyn v pinacol.
CH3 CH3 C C CH3 CH3 - H2O CH3 + C CH3 CH3 C

..

OH OH H+

CH3

CH3 CH3

CH3 C C O CH3 +

H+

O H

Pinacol
OH CH2 CH2 OH OH OH CH2 CH2

Chuyen v CH3-

Pinacolon

Glycol b mt nc to ether vng.

H2SO4 CH2 CH2 O CH2 CH2

2H2O

Ethylenglycol

O Dioxan

204

 nh hng ca cc nhm OH lm cho polyalcol c tnh acid mnh hn monoalcol. Cc polyalcol ha tan c ng hydroxyd (Cu(OH)2) to dung dch mu xanh.
CH2OH CH2OH + Cu( OH) 2 CH2 O CH O CH2 H OH H Cu O CH2 O CH + 2H2O

2 CHOH

HO CH2

Bi tp
Monoalcol

1. Vit cng thc cu to ca nhng cht sau: a. Alcol tert- butylic ; b- Alcol isoamylic ; c- sec-Butylethylmethylcarbinol; d. 2-Propanol: e- 2,2-Dimethyl-2-pentanol; f- Alcol cetylic. g- Alcol lauric. 2. Vit cng thc cu to tt c cc ng phn ca alcol c cng thc phn t l C7H16O. Gi tn nhng ng phn theo danh php thng thng, danh php IUPAC v danh php carbinol. ng phn no c tnh quang hot. 3. Nhng alcol no c to thnh khi thy phn bng dung dch kim t cc hp cht halogen sau: a. Isobutylbromid; b- sec-butylbromid; c- Ethylenclohydrin; d- 1-Brom2-buten ; 4. Vit phn ng xy ra trong cc trng hp di y: a. Hydrat ha propylen, trimethylethylen, isobutylen, 2,2-dimethyl-3-hexen. b. Phn ng loi nc ca hp cht (CH3)2C(OH)CH2CH2CH2OH. c. Oxy ha cc alcol n -butylic, sec-butylic bng hn hp kali bicromat v H2SO4. d. Cho alcol octylic tc dng ln lt vi cc cht POCl3, HNO2, HNO3, SO3. 5. Gii thch c ch phn ng xy ra khi cho acid acetic tc dng vi alcol n-butylic c xc tc l H2SO4 6. Hon thnh v cn bng cc phn ng oxy ha - kh di y:
a. (CH3CH2CH2)CHOH + CrO3 = (CH3CH2CH2)C=O + Cr3+

b. CH3CH2CH2CH2CH2OH + H2CrO4 = CH3CH2CH2CH2COOH + Cr3+ c. CH3OH + CuO = HCHO + Cu

Alcol cha no

7. Vit cng thc cu to cc cht sau: a- 2,2-Dimethyl-4-hepten-3-ol; b-Alcol allylic; c-Alcol 11-dodekenol; d-Alcol propagylic

205

8. Vit cc phn ng xy ra trong cc trng hp sau: a. Alcol allylic tc dng vi dung dch brom, dung dch KMnO4, dung dch HCl. b. 2-Cyclohexenol tc dng vi dung dch KMnO4 v hn hp kalibicromat v H2SO4. c. Cho linalol tc dng vi acid acetic c H2SO4 lm xc tc.
Alcol vng

9. Vit cng thc cu to ca cc cht sau: a. 2,3- Dimethylcyclohexanol; b- 2,6,6-Trimethylbicyclo[3,1,0]heptanol-3. 10. Vit phn ng oxy ha cyclohexanol bng CrO3.
Polyalcol

11. Vit cng thc cu to ca cc cht sau: a-2,3-Dimethyl-2,3-butadiol; b-1,4- Butyndiol; c- 1,2,3-Cyclohexantriol; d- (+)Inositol. 12. Vit phn ng loi nc trong mi trng acid km theo s chuyn v pinacol ca hp cht tetraphenylethylenglycol. 13. Gii thch v sao polyalcol c tnh acid mnh hn monoalcol. Cho phn ng chng minh iu . 14. V sao polyalcol d tan trong nuc hn monoalcol.

206

Chng 17

PHENOL

Mc tiu hc tp 1. Gi c tn cc phenol v polyphenol. 2. Trnh by c cc tnh cht ha hc ca phenol.

Ni dung
Phenol l hp cht c nhm hydroxyl - OH gn trc tip vi nhn benzen. i din n gin nht ca loi hp cht ny l hydroxybenzen. Phn loi phenol thng da vo bn cht ca gc hydrocarbon thm v s nhm OH c trong phn t. Cng thc tng qut ca cc phenol thng gp:
Monophenol Polyphenol

Ar-OH hoc CnH2n-7OH Ar'(OH)m CnH2n-6-m(OH)m m >

2

1. Monophenol 1.1. Danh php v ng phn

Tn gi phenol thng dng gi theo danh php thng thng. Xem phenol l dn xut ca hydrocarbon m hydro c thay th bi nhm OH Gi tn cc phenol khc nh l dn xut ca phenol n gin nht.
OH OH CH3 OH CH3 OH

Phenol
Hydroxybenzen Acid Phenic OH CH3

o-Cresol
o-Hydroxytoluen 2-Methylphenol

m-Cresol

m-Hydroxytoluen 3-Methylphenol

CH3 p-Cresol p-Hydroxytoluen 4-Methylphenol

CH (CH3 )2

OH

OH

Thimol
3-Hydroxy-p-cymen 5-Methyl-2-Isopropylphenol
1-Hydroxynaphthalen 2-Hydroxynaphthalen

-Naphtol

-Naphtol

207

OH
1-Phenantrol

OH OH
10-Phenantrol

p-Hydroxydiphenyl (1,4)

ng phn ca phenol ph thuc vo v tr ca nhm OH trn nhn benzen v ph thuc vo v tr hoc s phn nhnh ca gc hydrocarbon.
1.2. iu ch phenol 1.2.1. Thy phn cc halogeno aren

Halogeno aren b thy phn bng dung dch kim c p sut v nhit cao.
Ar_Cl + NaOH 300oC Ap suat Ar_OH + NaCl

1.2.2. Nung nng chy acid aren sulfonic vi NaOH

2Ar_SO3H + 2NaOH 300oC 2Ar_OH + Na2SO3 + H2O

1.2.3. Thu phn mui aren diazoni

+ Nhiet o + Ar_OH + H3O Ar_N2 + 2H2O + N2

1.2.4. Oxy ho hp cht aryl magnesi halogenid ArMgX

Ar_MgCl+ O2

Ar_OOMgCl

Ar_MgCl

2Ar_OMgCl

2H2O

2Ar_OH+2Mg(OH)Cl

hoc cho hp cht c magnesi tc dng vi ester ca acid boric v sau oxy ha bng hydro peroxyd H2O2.

Ar_MgCl

- Mg(OR)Cl

+ B ( OR)3

Ar ( OR )2

2H2O - 2ROH

Ar _B( OH )2

+ H2O2 - H3BO3

Ar _ OH

1.2.5. Oxy ha cumen

Trong cng nghip phenol c iu ch bng cch oxy ha cumen. Sau tc dng vi acid sulfuric thu c phenol v aceton. Phn ng oxy ha xy ra theo c ch gc.
CH(CH3)2 + O2 Cumen HOOC(CH3)2 H2SO4 Cumen hydroperoxyd OH + CH3 C CH3 O Aceton

208

1.3. Tnh cht l hc

S c mt nhm hydroxyl gn trc tip vo nhn benzen quyt nh tnh cht vt l ca phenol. Do tng tc vi nhn benzen, lin kt O-H b phn cc mnh hn OH ca alcol. Lin kt hydro trong phenol bn hn lin kt hydro ca alcol. Phn ln cc phenol u dng rn, kh tan trong nc v t bay hi. Tnh cht vt l mt s phenol c trnh by trong bng 17-1 :
Bng 17.1: Hng s l hc mt s hp cht phenol
Ten chat Phenol o-Cresol m-Cresol p-Cresol Thymol -Naphtol -Naphtol o-Clorophenol m-Clorophenol p-Clorophenol o-Nitrophenol m-Nitrophenol p-Nitrophenol 2,4-Dinitrophenol 2,4,6- Tribromophenol Cong thc C6H5OH o-CH3C6H4OH (1,2) m-CH3C6H4OH (1,3) p-CH3C6H4OH (1,4) (CH3) CH(CH3)2C6H3OH (1,5,2) C10H7OH C10H7OH ClC6H4OH (1,2) ClC6H4OH (1,3) ClC6H4OH (1,4) O2NC6H4OH (1,2) O2NC6H4OH (1,3) O2NC6H4OH (1,4) (O2N)2C6H3OH (1,2,,4) Br3C6H3OH (1,2,,4,6)

to c
43 30 12 35,5 51 96 122 8 29 37 44,5 96 114 113 95

tos
181 191 201 201 233 288 291,8 176 214 217 214

pKa 10. 10,2 10,01 10,17 8 9,11 9,39 7,21 8,0 7,16 4,

1.4. Tnh cht ha hc ca phenol

Nhm OH gn trc tip vo h thng lin hp ca nhn benzen. Phenol c cu to nh mt enol CH =C_OH bn vng. Tnh cht ca phenol do nhm OH quyt nh. Phenol c tnh acid. Nhm chc OH phenol l nhm th loi I, phn ng th xy ra trn nhn benzen to hn hp ng phn ortho v para.
1.4.1. Tnh acid - base

Phenol c tnh acid mnh hn alcol do cp in t trn oxy ca nhm OH lin hp vi nhn benzen khin hydro ca nhm O _ H tr nn linh ng. Phenol c cc trng thi cng thc trung gian sau:
:OH

+ OH

+ OH

+ OH

209

Phn ng th hin tnh acid ca phenol:

OH ONa OH ONa

+ Na

+ [ H] ;

+ NaOH

+ H2O

Phenol c tnh acid yu hn acid carbonic. Phenolat tc dng vi acid carbonic:

ONa + CO2 + H2O OH + NaHCO3

Phenolat c tnh base: Tnh base v tnh i nhn ca phenolat yu hn tnh base v tnh i nhn ca alcolat RO - v cp in t trn oxy ca phenolat lin hp vi nhn benzen lm gim mt in t trn oxy. Phenolat natri tan trong nc, phn ly thnh ion:
C6H5ONa C6H5O- + Na+
O O

Ion phenolat tn ti cc trng thi trung gian do s cng hng:

-O

Tnh acid ca phenol tng khi trn nhn benzen c cc nhm ht electron nh Cl, NO2, COOH... (c hiu ng -I,-C). Cc nhm y electron nh CH3 lm gim tnh acid ca phenol.
1.4.2. Phn ng ester ha ca phenol

Phenol tc dng trc tip vi acid hu c to ester vi hiu sut thp. Phn ng xy ra kh khn hn s ester ha ca alcol. Phn ng ester ha ca phenol l phn ng thu nhit:
CH3COOH + C6H5OH CH3COOH + C2H5OH CH3COOC6H5 + H2O Ho = + 1,5 kcal.mol-1 CH3COOC2H5 + H2O Ho = - 4.6 kcal.mol-1

Phn ng to ester ca phenol d xy ra hn khi phenol tc dng vi cc clorid acid hoc anhydrid acid c xc tc base hoc acid:
OH + RCOCl Base OCOR + HCl

210

COOH OH + ( CH 3 CO ) 2 O
Acid salicylic

H 3 PO 4

COOH OCOCH 3 + CH 3 COOH

Aspirin

Ester ca phenol tham gia phn ng chuyn v Fries to ceton thm khi c xc tc AlCl3:
OH OCOR AlCl3 t = 60o t = 160o OH
p- Oxyphenylceton

C R O

o- Oxyphenylceton

O C CH3

1.4.3. Phn ng to ether ca phenol

Cc phenolat tc dng vi alkyl halogenid to ether (Phn ng Williamson): ArO- + RX

ArOR + X-

Di tc dng ca nhit , ether cha no allylphenylether tham gia chuyn v Claisen

OCH2CH=CH2 200oC Chuyen v Claisen Eter allylphenyl o- Allylphenol OH CH2CH=CH2

C ch chuyn v Claisen:
O CH2 CH CH2 O. CH . . . ... .. ...CH2 CH2 ..

CH2

CH CH2 H

CH2 OH CH CH2

1.4.4. Phn ng thay th nhm OH

Nhm OH phenol c th b thay th bi Cl hoc NH2 khi tc dng vi PCl5 hoc NH3 vi xc tc AlCl3:
OH Cl O2N OH NO2 O2N Cl NO2

PCl5 -POCl3,-HCl

;
NO2 Acid picric

PCl5

Phenol

Clorobenzen

-POCl3,-HCl

NO2 Picrylclorid

211

OH NH3 ( AlCl3) , - Naphtol

NH2 + H2O - Naphtylamin

1.4.5. Phn ng vi aldehyd

Phenol tc dng vi aldehyd formic trong mi trng base to hn hp alcol ortho v parahydroxybenzylic:
OCH2OH OH + HO O+ H2O O+ HCHO O-

CH2OH

Phn ng xy ra kh iu khin v tc . Cc alcol to thnh tng tc vi nhau tng t phn ng trng ngng v to thnh polymer gi l bakelit. Phn ng cng c th xy ra trong mi trng acid. Alcol o-hydroxy benzylic c to thnh (alcol salicylic). Phenol tc dng vi formaldehyd v amin bc 2 to hp cht o -aminomethylphenol.
OH HCHO + H+ + CH2OH
OH HCHO + R2NH - H2O

+ CH2OH

+ OH

OH H CH2OH - H+ CH2OH

OH

CH2NR2

1.4.6. Phn ng tng hp Kolbe. Tng hp acid salicylic.

Phenolat natri tc dng vi CO2 c p sut v nhit , to natri salicylat.

ONa + CO2 p, to OH COONa ;
OH COONa + H+ OH COOH

C ch phn ng:
.. : O: + C O O O C H O O OH COO + H+ OH COOH

Thng p dng phn ng ny sn xut acid salicylic trn quy m cng nghip. 212

1.4.7. Phn ng Reimer -Tieman

Phenol tc dng vi cloroform trong mi trng kim mnh to thnh hydroxybenzaldehyd. Sn phm phn ng c th l hn hp ng phn ortho v para.
OH OH CHO + CHCl3 + 3KOH + 3KCl + 2H2O Aldehyd salicylic

Phn ng xy ra theo c ch to diclorocarben do cloroform tc dng vi KOH.

Cl .. HO H :C Cl Cl

+ KCl + H2O + :CCl2

Diclorocarben (CCl2) nh l mt tc nhn i in t tn cng vo phenol v tr ortho hoc para v sau xy ra s thy phn.
.. : O:
+ + :CCl2 O H CCl2

CHCl2 + 2KOH -2KCl,-H2O

CHO + H 2O -HO -

OH

CHO

Ty theo cu to, diclorocarben c th l tc nhn i in t (c 2 electron u sp xp trong mt orbital v c mt orbital khng c electron. C in tch dng (+) trn carbon) hoc cng c th l mt lng gc (trn mi orbital ch c mt electron):

..

Cl Cl

+ : CCl2

. .

Cl Cl

Tc nhn i in t

Lng gc

1.4.8. Phn ng ghp i vi hp cht diazoni

Phenol tc dng vi mui diazoni trong mi trng kim to hp cht arylazophenol. y l mt phn ng th i in t vo nhn thm hot ng vi mt tc nhn i in t km bn l mui diazoni:
HO + + N N Muoi diazoni Base HO N N Phenylazophenol

1.4.9. Cc loi phn ng th i in t khc

Phenol tham gia cc phn ng th i in t khc nh nitro ho to cc hp cht nitrophenol; phn ng halogen ha to hp cht halogenophenol; phn ng sulfon ha to acid hydroxybenzensulfonic: 213

Nitro hoa

OH HNO3
H2SO4

O2N

OH

O2N HNO3
H2SO4

OH HNO3 NO2
H2SO4

O2N

OH

NO2

2-Nitrophenol OH + Br2 CS2

NO2 2,4,6-Trinitrophenol

2,4 Dinitrophenol OH + HBr Br

Halogen hoa

OH + 3Br2 H2O Br

OH

Br + 3HBr

Br

Sulfon ha
OH HO3S + H2SO4 + 2H2O OH

o-Nitrophenol c lin kt hydro ni phn t. p -Nitrophenol ch c lin kt hydro gia cc phn t vi nhau
1.4.10. Phn ng to mu bi dung dch FeCl3.

Vi dung dch FeCl3 phenol to hp cht C6H5OFeCl2 c dung dch mu tm ; Cresol to dung dch mu xanh v cc phenol khc to dung dch mu vng.
1.4.11. Phn ng oxy ha phenol

Phenol d b ha nu bi oxy khng kh. Nhiu phn ng oxy ha ca phenol xy ra rt phc tp. Tnh cht ca sn phm ph thuc vo bn cht ca nhm th. Trong qu trnh oxy ha, hydro ca nhm OH b phn ct v to thnh gc phenoxyArO.
OH [O] - H. O. O

. .

Cromoxyd CrO3 oxy ha phenol to p -benzoquinon. Phn ng xy ra qua giai on to acid phenylcromic. 214

OH

O CrO3H

+ CrO3 H

O_CrO3H - H2CrO3 H O H H H

OH

O H2CrO4 O p- Benzoquinon

OH OH p- Hydroquinon

-Naphtol b oxy ha to sn phm 4,4'-dihydroxy-1,1'-dinaphtyl. Phn ng xy ra theo c ch:

OH O. O OH O

-H

H 2 OH 4,4'-Dihydroxy-1,1'-dinaphtyl

Trong trng hp 2,4,6-tri-tert-butylphenol, gc t do 2,4,6-tri-tertbutylphenoxy c mu xanh sinh ra c bn cao. Chng tc dng vi oxy to hp cht mu vng:
(CH3)3C OH C(CH3)3 (CH3)3C -e -H+ C(CH3)3
(CH3)3C O (CH3)3C

C(CH3)3 (CH3)3C

C(CH3)3 (CH3)3C

C(CH3)3

C(CH3)3
C(CH3)3 O C(CH3)3

C(CH3)3

C(CH3)3

O2

Bu Bu O O

Bu

(CH3)3C

Mau vang

2. Polyphenol

Polyphenol l hp cht c hai hay nhiu nhm OH gn trc tip trn vng benzen. Cc polyphenol l cc cht rn.
OH OH OH OH

Catechol (tc = 104o) 1,2 -Dihydroxybenzen

OH Resorcinol (tc = 114o) 1,3 -Dihydroxybenzen

OH Hydroquinon (tc = 169o) 1,4 -Dihydroxybenzen

215

HO

OH

OH

OH

OH
OH Phloroglucinol (tc = 218o) 1,3,5 -Trihydroxybenzen HO OH OH Hydroxyhydroquinon (tc = 140o) 1,2,4 -Trihydroxybenzen

Pyrogalol (tc = 132o) 1,2,3 -Trihydroxybenzen

Polyphenol c iu ch theo cc phng php c bn trong iu ch monophenol:

Cl Cl OH OH

NaOH , H2O CuII, 200oC

H+

SO3H SO3H

NaOH

H+,H2O

OH

OH

Nong chay NH2 Na2Cr2O7 H2SO4 O 2[H] O OH

OH

OH

HO

OH

OH

un nong - CO2

HO

OH

COOH Acid Galic

O2N

COOH NO2 Sn,HCl NO2

H2N

COOH NH2 H2O , 100oC

HO OH

OH

NH2

Polyphenol t do khng tn ti trong thin nhin. Chng ch tn ti dng ether hoc ester. C th chng ct polyphenol. Chng d thng hoa v d tan trong nc, alcol ; khng tan trong hydrocarbon. Cc phn ng ca polyphenol cng ging phn ng ca monophenol. Kh nng phn ng ca polyphenol cao hn monophenol. Cc cht catechol, hydroquinon, pyrogallol d b oxy ha trong mi trng kim. Kh phn ring cc sn phm oxy ha. Hydroquinon c s dng lm cht hin hnh trong k ngh nh: 216

OH

OH

Ag2O

OH

O Na2Cr2O7 H2SO4

MgSO4,ether Catechol o-Benzoquinon

;
OH Hydroquinon

O p-Benzoquinon

Resorcinol kh b oxy ha hn. Khi b oxy ha khng to thnh m -quinon. Sn phm oxy ho resorcinol l mt hn hp phc tp. Resorcinol c kh nng h bin do s di chuyn hydro ca nhm OH do resorcinol d b hydro ha bi hn hng natri to thnh 1,3-cyclohexandion:
OH O +2 H OH Resorcinol O O 1,3 -Cyclohexandion O

Phloroglucinol cng c kh nng h bin to ceton:

OH HO O O

OH

Phloroglucinol

O 1,3,5 -Cyclohexantrion

Polyphenol to dung dch c mu vi FeCl3. Catechol cho mu xanh. Resorcinol cho mu tm. Pyrogallol cho mu .

Bi tp
1. Hy vit cng thc cu to cc cht sau y: a. m-Cresol; d. o-Nitrophenol; g. Pyrogalol; b. p-Ethylphenol; e. Acid picric; h. Phloroglucinol; c. 2,4- Dinitrophenol; f. Acid 2,4-Phenoldisulfonic i. Acid galic.

2. Hy gi tn cc cht sau y:
a- CH3 OH

; bH5C2

OH

c- Cl

OH

; dCl

OH

OH e- CH3 OH

HO

HO OH

; fH5C2

g - Cl

OH

; h - HO
Cl

OH

217

3. Vit phng trnh iu ch cc phenol: a. p-Bromophenol, Tribromophenol t benzen. b. Acid picric t clorobenzen; t acid 2,4-phenoldisulfonic. c. o-Cresol t o -clotoluen. 4. Hy sp xp cc cht sau y theo th t tng dn tnh acid:
OH NO2 OH NO2 OH OH OH CH2OH

;
NO2 NO2

;
Cl

;
OCH3

5. Vit cc phng trnh phn ng trong cc trng hp sau: a. Cc cht methyliodid, isoamylbromid, allylbromid tc dng vi kaliphenolat. b. o-Cresol tc dng vi hn hp KOH v CHCl3. c. p-Cresol tc dng vi aldehyd formic trong mi trng acid. d. Thc hin s chuyn v Fries ca cc cht ester p -hydroxyphenylacetat, m-metoxyphenylacetat. 6. B tc v hon thnh cc phn ng theo s :

Benzen

H2SO4

NaOH Nung chay

H2 O H+

(CH3)2SO4 NaOH

HNO3

218

Chng 18

ETHER

Mc tiu hc tp 1. c c tn cc loi ether. 2. Trnh by c tnh cht ha hc ca ether mch thng, ether vng.

Ni dung
Khi th H ca OH trong ROH, ArOH bng gc R, Ar, ta s c ether. R O_H R O_R' Phn loi ether:
Ether mch h Ether mch vng. 1. Ether mch h 1.1. Cu to

R O_H R_O_Ar

Ar_O_H Ar_O_Ar

Oxy ca ether lin kt trc tip vi 2 gc R, Ar ging nhau hoc khc nhau.
CH3_CH2_O_CH2_CH3 Diethyl ether Diethyl oxyd CH3_CH2_O_CH3 Ethylmethyl ether Ethylmethyl oxyd O CH3 Methylphenyl ether Methylphenyl oxyd CH2=CH_O_CH3 Methylvinyl ether Methylvinyl oxyd O_CH3 Methyl , naphtyl ether Methyl , naphtyl oxyd O CH2CH3 Cyclohexylethyl ether Cyclohexylethyl oxyd

CH2 O CH3 Benzylmethyl ether Benzylmethyl oxyd

O Diphenyl ether Diphenyl oxyd

1.2. Danh php

Gi tn cc gc alkyl v thm t ether hoc oxyd.

Tn gc hydrocarbon tng ng + ether (hoc oxyd)

219

Cng c th xem ether l dn xut ca hydrocarbon m hydro c thay th bng nhm alkoxy RO , aroxy ArO:
(CH3)2O CH3OCH2CH2CH3 CH3OCH(CH3)2 C6H5OCH3 p-CH3C5H4OC2H5 Dimethyl ether Methylpropyl ether Methylisopropyl ether Methylphenyl ether Ethyl,p-tolyl ether Dimethyl oxyd Methylpropyl oxyd Methylisopropyl oxyd Methylphenyl oxyd Ethyl,p-tolyl oxyd, Metoxymetan Metoxypropan 2-Metoxypropan Metoxybenzen p- Etoxytoluen

1.3. Phng php iu ch ether 1.3.1. iu ch ether theo phn ng Williamson

Phng php ph bin hay dng iu ch ether c gc hydrocarbon khc nhau l cho natri alkoxyd tc dng vi dn xut halogen (Williamson,1850):
C2H5ONa + ICH3 CH2=CHCH2ONa + IC2H5 C2H5OCH3 + NaI CH2=CHCH2OC2H5 + NaI

Phng php Williamson rt thun li iu ch cc ether c gc aryl. Cc tc nhn alkyl ha l dn xut halogen, alkylsulfat, ester alkyl-p-toluensulfonat (alkyl tosylat):
C6H5ONa + ICH3 C6H5ONa + SO2 (OCH3)2
C6H5ONa + p-CH3C6H4_O_SO2_OCH3 Ester Methyl-p- toluensulfonat

C6H5OCH3 + NaI. C6H5OCH3 + CH3OSO2ONa

C6H5OCH3 + p-CH3C6H4_O_SO2_ONa Anisol Natri p- toluensulfonat

C6H5ONa + BrC6H5

C6H5OC6H5 + NaBr.

1.3.2. iu ch ether t alcol

2ROH ROR + H2O

Phn ng xy ra c xc tc H2SO4 m c (140C) hoc Al2O3 nhit 200-300C. Phng php ny c hiu sut cao i vi cc alcol kh to alken.
1.4. Tnh cht l hc

Ether khng c kh nng to lin kt hydro nn nhit si ca ether thp hn nhit si ca cc alcol tng ng v khng tan trong nc, tan trong dung mi hu c. Cc ether thng c mi thm - ''Mi ether''

220

Bng 18: So snh nhit si ca ether vi alcol v phenol

Ether (CH3)2O (C2H5)2O C4H9OCH3 C6H5OCH3 to s -24oC +35oC 70oC 155oC CH3OH C2H5OH C4H9OH C6H5OH Alcol, phenol to s

66 oC 78oC 118oC 183oC

Cn c vo ph hng ngoi c th phn bit cc loi ether:

Dialkylether c vch c trng trn quang ph hng ngoi IR ca lin kt ether vng 1060 - 1150 cm-1. Vch c trng IR ca lin kt ether trong alkylarylether vng 12301270cm-1.
1.5. Tnh cht ha hc

Ether c kh nng phn ng km hn alcol v lin kt C _O_C l lin kt km phn cc v kh b tch ra. Ether thng c dng lm dung mi trong tng hp hu c. Khc vi alcol, ether khng c tnh acid v khng c phn ng vi base.
1.5.1. Phn ng to mui oxoni

Ether c tnh base yu. Khi tc dng vi acid mnh (H2SO4, HClO4, HBr) ether to thnh mui oxoni khng bn:

.. C2H5_O_C2H5 + HBr ..

H+ .. _O_C H + Br C2H5 .. 2 5 Diethyloxoni

Ether tc dng vi acid Lewis (BF3, RMgX) to phc phi tr tng i bn:
F B .. C 2 H5 _ O_ C 2 H5 .. Botriflorid etherat F F

C2H5_O_C2H5 + BF3 ..

..

Ion dialkyloxoni nhy cm vi phn ng th i nhn v phn ng tch loi hn phn t ether trung ha. V vy trong mi trng acid mnh ether c th xy ra phn ng th cho sn phm th v phn ng tch loi to olefin:
C2H5_O_C2H5 + H+

..

H C2H5_O_C2H5 +

+Br C2H5_O_H + BrC2H5 SN2

221

(CH3)3C_O_C(CH3)3 + H+ Di-tert-butyl ether

..

H _O_C(CH ) HSO4 (CH3)3C 33 + E1 Di-tert-butyloxoni

+ (CH3)2C=CH2 + HO_C(CH3)3 H2SO4 (CH3)2C=CH2 + H2O

1.5.2. Phn ng oxy ha ether

Ether mch h l cht t oxy ha. Ether ethylic tip xc lu ngy vi khng kh (c bit khi c nh sng) s to hydroperoxyd v peroxyd:
CH3_CH2_O_CH2_CH3 + O2 CH3_CH_O_CH2_CH3 OOH Hydroperoxyd

Hydroperoxyd s b loi mt phn t alcol etylic v chuyn thnh hp cht peroxyd polymer, ethyliden peroxyd (-CH(CH3)_O_O_)n vi n = 4_8 v mt s hp cht cha oxy khc. Peroxyd polymer l cht lng snh nh du, d gy n khi c va chm v chng ct. Khi s dng ether phi kim tra peroxyd bng phn ng vi mui st (II), titan sulfat (IV). Peroxyd b ph v khi tinh ch ether vi natri kim loi, mui st (II), mui mangan (II). Ether rt nhy cm vi s tn cng ca gc t do. V vy ether khng phi l dung mi tt cho cc phn ng c c ch gc t do. Cc ether thng dng nh ether ethylic, dioxan, tetrahydrofuran thng b nhim peroxyd.
Cc ether cha no c gc aryl d tham gia chuyn v Claisen:

Trong thin nhin tn ti nhiu hp cht ether c ng dng trong y dc.

OCH3 OCH3 OCH3 OH OCH3 OH OCH3

OH

Gaiacol

Veratrol

CH2 CH CH2 Eugenol

CH CH CH3 Isoeugenol

2-Metoxyphenol 1,2-Dimetoxyphenol 4-Allyl-2-metoxyphenol 4-Propenyl-2-metoxyphenol

OCH3 CH2=CHCH2 O CH2 O CH2

CH3CH=CH

O O CH=CHCH3 Safrol Isosafrol Anetol 4-Propenylmetoxybenzen 4-Allyl-1,2-methylendioxybenzen 1,2-Methylendioxy-4-propenylbenzen

222

2. Ether vng
O O Tetrahydrofuran O Tetrahydropyran

O O
1,4-Dioxan

Epoxy Ethylen oxyd

Tetramethylen oxyd Pentamethylen oxyd

Ethylen oxyd l ether vng n gin nht. Vng ethylen oxyd d b ph v. Ethylen oxyd l nguyn liu to nhiu cht hu c c nhiu ng dng quan trng nh ethylen glycol, diethylen glycol, clohydrin, xelozol v cht cao phn t carbowax:
H2O HCl H2C CH2 CH3OH Base HOCH2CH2OH Ethylen glycol
H2 C O CH2

(HOCH2CH2)2O Diethylen glycol

ClCH2CH2OH Ethylen clohydrin

H2 C O

CH2

O Ethylen oxyd

HOCH2CH2OCH3 Methyl xelozol HO_(CH2CH2O)n_H Carbovac

CH3O(CH2O)CH2OH Methylen carbitol

Phn ng trng ngng ca ethylen oxyd to thnh cht cao phn t l polyethylenglycol (PEG) dng lm cht nh ha trong dc phm v k ngh dt:
PEG
HO_CH2_CH2_O_(_CH2_CH2_O_)n_CH2_CH2_OH

Cc ether ca monoalcol bc cao nh octadecylic C18H37OH hoc alcol thm c mch nhnh di c ng dng lm cht nh ha. Cng thc chung c dng:
C18H37O(CH2CH2O)xCH2CH2OH ; RC6H4O(CH2CH2O)mCH2CH2OH

Bi tp
1. c tn v vit cng thc cu to ca cht to thnh khi cho cc cht di y tc dng vi acid HBr.

a- CH=CHCH2OCH3 ;
O e-

b- CH3CH2OCH=CH2 O O

; c- ( CH3)3CCH2OCH3 ; d- C6H5OCH3
O O

f-

; g-

; h-

; i-

2. Vit cng thc cu to ca cc cht: Gaiacol, cineol, eugenol, anetol, safrol, PEG

223

Chng 19

ALDEHYD, CETON V QUINON

Mc tiu hc tp 1. Gi c tn cc hp cht carbonyl. 2. Gii thch c c ch AN v hot i nhn ca hp cht carbonyl. 3. Nu c cc ha tnh ca aldehyd v ceton ng thi cho bit phng php ha hc nhn bit chng. Ni dung 1. Cu to Aldehyd, ceton, quinon l nhng hp cht cha nhm carbonyl C = O. Tng qut:
O H C H R O C H R1 O C R2 O Quinon O

Aldehyd formic

Aldehyd

Ceton

Ty thuc cu to ca cc gc R, R1, R2 m aldehyd, ceton l nhng hp cht no, cha no, thm hoc aldehyd vng ceton vng. Nhm chc CHO trong aldehyd gi l chc aldehyd hay nhm formyl Nhm carbonyl C = O trong ceton gi l chc ceton hay nhm oxo Quinon l sn phm oxy ha cc diphenol. Quinon phi l mt h thng lin hp. C th xem quinon l diceton vng cha no. Chc ceton lin hp vi lin kt i ca vng. Tn ti 1,2 -hay orto-quinon v 1,4- hay para-quinon. Khng c 1,3-quinon.
O O O O

1,2-hay orto-Quinon

1,4- hay para- Quinon

Aldehyd, ceton, quinon thuc loi hp cht carbonyl - cha nhm carbonyl 1. Aldehyd v ceton 1.1. Danh php 1.1.1. Danh php ca aldehyd 224

 Theo danh php IUPAC: Gi tn hydrocarbon tng ng v thm tip v ng al

Tn hydrocarbon tng ng + al
O
3

O
5

CH3
5 4 3 2

O
1

CH3CH2 C H
2 1

CH3CH2CH=CH C H
4 3 2 1

CH3CHCH=CH C H

Propanal

2-Pentenal

4-Methyl-2-pentenal

nh s 1 t carbon ca chc aldehyd. Tn thng thng: Gi theo tn thng thng theo acid tng ng.
Aldehyd + Tn acid tng ng hay Tn gc Acyl RCO- + aldehyd
O H C H CH3 O C H C6H5 O C H CH2 CH O C H

Aldehyd formic Formaldehyd

Aldehyd acetic Acetaldehyd

Aldehyd benzoic Benzaldehyd

Aldehyd acrylic Acrolein

1.1.2. Danh php ca ceton Theo danh php IUPAC Gi tn hydrocarbon tng ng v thm tip v ng on
Tn hydrocarbon tng ng + ON Bng 19.1: Tn gi v tnh cht l hc ca mt s aldehyd v ceton
Cng thc cu to H_CHO CH3_CHO CH3_CH2_CHO CH3_CH2_CH2_CHO Tn thng thng Formaldehyd Acetaldehyd Aldehyd propionic Aldehyd butyric Aldehyd isobutyric Tn quc t Metanal Etanal Propanal Butanal 2-Methylpropanal tco - 92,0 -123,0 - 81,0 - 99,0 - 66,9 tso -21,0 20,8 48,8 74,7 61,0

CH3 CH CHO CH3

CH2=CH_CHO CHC_CHO

Acrolein Aldehyd propagylic

Propenal Propinal

- 87,7 -

52,5 60,0

225

Bng 19.1 (tip)

Cng thc cu to CH3_CH=CH_CHO Tn thng thng Aldehyd crotonic Benzaldehyd Tn quc t 2-Butenal Benzaldehyd tco -74,0 - 56,0 tso 104,0 179.5

CHO

CH2CHO CH=CHCHO
CH3COCH3 CH3_CH2_CO_CH3 C2H5COC2H5

Aldehydphenylacetic

2-Phenyletanal

-10,0

190.4

Aldehyd cinnamic

3-Phenylpropenal

252.0

Aceton Methylethylceton Diethylceton Pinacolin Methyl,tert- Butylceton

Propanon Butanon Pentanon-3 3.3-Dimethyl-butanon-2

- 95,0 - 86,4 - 42,0

56,1 79,6 101.7

CH3 CH3 C COCH3 CH3

- 52,5

106,2

CH3_CO_CH=CH2

Methylvinylceton -

Butenon-3 Cyclopentanon

- 51,3

79,1 130,6

O O

Cyclohexanon

- 31,2

156,7

Cycloheptanon

179,0

COCH3

Methylphenylceton

Acetophenon

19,6

202,3

CO

Diphenylceton

Benzophenon

49,0

305,4

Mch chnh l mch di nht cha chc ceton. nh s ch v tr ca chc ceton. S 1 bt u ti carbon ca mch chnh v gn chc ceton nht.
O CH3 CH2 CH2 C CH3
5 4 3 2 1

O CH2
1

O
5

CH CH2 C CH2
2 3 4

CH3 CH CH3
6 7

2-Pentanon

6-Methyl-1-hepten-4-on

Cyclohexanon

226

 Gi theo danh php ceton Gi tn 2 gc hydrocarbon lin kt vi nhm carbonyl v thm tn ceton.
Tn cc gc hydrocarbon + Ceton
O CH3 CH2 C CH3 CH2

O CH C CH CH2 CH2

O CH3 CH C CH CH3

Methylethylceton
1.2. iu ch aldehyd v ceton

Divinylceton

Vinylisopropylceton

Aldehyd v ceton u c nhm chc carbonyl C =O, v vy phng php iu ch aldehyd v ceton gn ging nhau. Tuy vy vn c mt s phng php c th iu ch aldehyd v ceton. 1.2.1. Oxy ha (hay dehydro ha) alcol. (Xem phn tnh cht ca alcol).
CH3 Na2Cr2O7 OH CH3 CH3 + H2O H2SO4 -H2O CH3 O CH3 CH3

iu ch aldehyd v ceton bng phn ng oxy ha alcol theo phng php Oppenhauer. Oxy ha alcol bc 2 bng aceton c xc tc nhm isopropylat - [(CH3)2CHO]3Al.
R CH OH + R' CH3 CH3 C O [(CH3)2CHO]3Al R C O + R' CH3 CH3 CH OH

Nu oxy ha alcol bc nht RCH2OH s to thnh aldehyd RCHO. 1.2.2. Ozon ha alken Thy phn hp cht ozonid s thu c aldehyd hoc ceton. Tin hnh phn ng ozon ha trong dung mi diclometan nhit thp.Sau ph vng ozonid bng acid acetic v km kim loi thu c aldehyd.
CH2Cl2

H O O

H H

AcOH Zn

+ O3

- 78o

CHO + HCHO

(xem li phn tnh cht ha hc ca alken) 1.2.3. Tng hp oxo (hay gi l hydroformyl ha - Phn ng Rouelle).

227

Di tc dng ca xc tc dicobanoctacarbonyl CO2 (CO)8 v p sut, olefin tc dng vi hn hp H2 v CO s to thnh aldehyd.

CO2 (CO)8 R CH CH2 + CO + H2 R CH2 CH2 CHO

to, p

R CH CHO CH3

1.2.4. Hydrat ha acetylen v alkyn (xem phn hydrocarbon alkyn). 1.2.5. Nhit phn mui ca acid carboxylic (RCOO)nM Khi nhit phn cc mui calci, bari...ca acid carboxylic nhit khong 300oC s to thnh ceton.
2RCOO
-

to

R R

C O

CO3

2-

Phn ng Perrier
to

Nn s dng hn hp 2 mui trong c mui ca acid formic s to aldehyd.

RCOONa + HCOONa RCHO + Na2CO3

1.2.6. Tng hp aldehyd theo phn ng Rosenmund (1918) Hydro ha hp cht acylclorid vi xc tc l palladi trn cht mang BaSO4.
O R C Cl Acylclorid Aldehyd + H2 Pd - H2SO4 O R C H + HCl

1.2.7. Tng hp aldehyd theo phn ng Stephen (1925) Kh ha hp cht nitril RC N bng thic clorid SnCl2 trong mi trng acid thng to thnh aldehyd. Phn ng qua giai on to cht trung gian l aldimin.
R C Nitril N SnCl2 2HCl - SnCl4 R CH NH Aldimin H2 O H+ O R C H + NH3

1.2.8. Phn ng ca ester vi thuc th Grignard Ty theo cu to ca ester, khi tc dng vi thuc th Grignard to thnh aldehyd hoc ceton (xem phn hp cht c kim)
O RO C H Ester alkylformiat - Mg(OR)X Aldehyd + R'MgX O R' C H

228

OR + R'MgX RO C H OR - Mg(OR)X R'

OR C H Acetal OR

+ H2O (H+) - 2 ROH

O R' C H Aldehyd

Ester alkyl orthoformiat

O R C OR' Ester

+ R''MgX - Mg(OR')X

R R'' C O Ceton

Thuc th Grignard tc dng vi nitril cng to thnh ceton.

R C N R'MgX R R' C NMgX + H2O R R' C NH Cetimin + H2O ( H+) - NH3 R R' C O

Nitril

- Mg(OH)X

1.2.9. Acyl ha vo nhn thm theo phn ng Friedel -Craft Xem li phn hydrocarbon thm. Phn ng acyl ha theo Friedel - Crafts c th xy ra trong ni phn t to ceton vng.
C AlCl3 O
4 5 6 7 1 3 2

Cl

+ HCl

3-Phenylpropanoylclorid

O Indanon-1

1.2.10. Phn ng Vilsmeier (1927) Cc alkylformamid tc dng vi aren, phenol, ether...khi c mt ca tricloroxydphosphor POCl3 xy ra phn ng formyl ha v to thnh aldehyd.
O + H C + POCl3 + 3H2O N(CH3)2 C O H + 3HCl + (CH3)2NH + H3PO4

Dimethylformamid

Aldehyd benzoic

1.3. Tnh cht l hc ca aldehyd v ceton Aldehyd v ceton l nhng cht lng hoc rn. Ch c aldehyd formic l cht kh. Aldehyd formic, aldehyd acetic, aceton tan v hn trong nc. Aldehyd v ceton thng c nhit si thp hn alcol tng ng. Vch c trng trn quang ph hng ngoi ca nhm carbonyl C = O trong aldehyd v ceton trong khong 1660-1740cm-1. Gi tr gim khi c h thng lin hp. 229

Bng 19.2: Dao ng ha tr ca nhm carbonyl trong aldehyd v ceton

Aldehyd R_CHO Ar_CHO R_CH=CH_CHO c=o, cm-1 1720......1740 1695......1715. 1680......1705 R_CO_R Ar_CO_R Ar_CO_Ar R_CO_CH=CH_R Ceton c=o, cm-1 1700......1725 1680......1700 1660......1670 1665......1685

1.4. Tnh cht ha hc ca aldehyd v ceton 1.4.1. Cu to v kh nng phn ng ca nhm carbonyl C =O Nguyn t carbon ca nhm carbonyl trng thi lai ha sp2. Nguyn t carbon v oxy to 1 lin kt v 1 lin kt (Hnh 13-1). di lin kt C =O l 1,22 A
o

+ 1,22 A
o

C
120o

+ C -

Hnh 19.1: Cu to nhm carbonyl C = O

Nhm carbonyl c tnh cht khng no v phn cc tr thnh trung tm tn cng ca nhng tc nhn i nhn. Nhm carbonyl hot ha cc nguyn t hydro v tr ca gc hydrocarbon. V vy xy ra kh nng enol ha trong cc hp cht carbonyl c nguyn t hydro linh ng. Ngc li nhm carbonyl s lm gim kh nng phn ng ca nguyn t hydro trong nhn thm. Phn ng ca hp cht carbonyl rt phong ph. C 3 loi phn ng chnh: Phn ng cng hp vo nhm carbonyl. Phn ng th vo gc hydrocarbon. Phn ng oxy -ho kh. 1.4.2. Phn ng cng hp i nhn vo nhm carbonyl Tc nhn i nhn tn cng vo nhm carbonyl theo cc giai on:
Y- + C O: .. Y C .. : O

.. -

H+

Y C OH

Mi trng acid thch hp thun li cho phn ng cng hp vo nhm carbonyl.

230

Kh nng cng i nhn vo nhm carbonyl ca aldehyd d hn ceton. Ceton c hai gc hydrocarbon lm gim mt in tch dng trn nguyn t carbon v c cn tr khng gian s tng tc ca tc nhn i nhn vo nhm carbonyl.
H H

1+
O

>

C H

2+
O

>

C R'

3+
O

1+> 2+ >3+

Gemdiol Aldehyd v ceton tc dng vi nc to thnh gem-diol.

R C O R' + H2O R' R C OH OH

Gem-diol l nhng cht khng bn. Phn ng cng nc l phn ng thun nghch. Nu c nhm ht in t ti gc R ca aldehyd v ceton th gem-diol l cht bn vng.
Cl O Cl C C H Cl Cl OH Cl C C OH Cl H

+ H2O

Cl3C CHO. H2O

Cloral

Cloral hydrat

Formaldehyd b hydrat ho gn nh hon ton, trong dung dch nc n tn ti di dng gem-diol CH2(OH)2. Mc hydrat ha ca hp cht carbonyl ty thuc vo cu to.
Bng 19.3: Mc hydrat ha ca mt s hp cht carbonyl
Hp cht carbonyl HCHO CH3CHO CH3COCH3 C6H5 CHO Cl3CCHO F3CCHO Mc hydrat 99,99% 58% 0% vt. 100% 100%

Acetal v cetal Cng hp mt mol alcol vi aldehyd hoc ceton s to thnh bn acetal (hemiacetal, Semiacetal) hoc bn cetal (hemicetal, semicetal).

231

Aldehyd tc dng vi mt mol alcol

O R C H Aldehyd + R'OH Alcol R OH C OR' ; CH3 C H OH O + CH3OH Methanol CH3 C OCH3 H Hemiacetal

H Hemiacetal

Acetaldehyd

Ceton tc dng vi alcol theo t l 1: 1 v s mol:

OH O R C R' Ceton Alcol + R''OH R C R' ; O CH3 C CH3 + CH3OH Methanol CH3 OH C CH3

OR'' Hemicetal

OCH3

Aceton

Cng hp 2 mol alcol vi aldehyd hoc ceton s to thnh acetal v cetal.

O R C H + 2R'OH Aldehyd Alcol H+ OR' OR' Acetal O R C H ; CH3 C H + 2C2H5OH Aldehyd Alcol H+ OC2H5 R C H OC2H5 Acetal

Kh nng to acetal ph thuc vo cu to ca aldehyd v alcol.

Bng 19.4: Mc acetal ha aldehyd vi cc alcol
Aldehyd CH3_CHO (CH3)2CH_CHO (CH3)3C_CHO C6H5_CHO Ethanol 78 71 56 39 Mc Cyclohexanol 56 26 23 2-Propanol 43 23 11 13

Ceton khng tc dng trc tip vi alcol to cetal. C th iu ch cetal bng cch cho ceton tc dng trc tip vi ester ca acid orthoformic H -C(OR)3
O CH3 C CH3 + HC(OC2H5)3 Ester ethyl ortoformiat CH3 OC2H5 C CH3 OC2H5 Cetal + HCOOC2H5 Ester Ethylformiat

Ceton

Ceton v aldehyd tc dng vi diol to cetal v acetal vng:

R R R C R' O + HO HO C C R
+ H H

R C R'

H + H2O

Ceton

1,2-diol

R' Cetal vng

232

Acetal v cetal l mt loi hp cht quan trng. Cc acetal v cetal vng c ng dng iu ch nhng aldehyd v ceton cha no khc.
R R' C O + R HO C H HO C H R 1,2-Diol R H+ R R' O C C H R Cetal vng O C H + H2O

Ceton

O BrCH2CH2 CH3CH2C CLi +

O H

O CH2CH2 CH3CH2C C

O H

+ LiBr

O CH3CH2C C CH2CH2

O + H + H 3O

CH3CH2C C CH2CH2CHO + HOCH 2CH2CH2OH

Khi tng hp cc cht hu c, mun bo v nhm carbonyl ngi ta thng chuyn n v dng acetal hoc cetal. Cng hp vi acid cyanhydric HCN to -cyanoalcol hay cyanohydrin.
O CH3 C H Acetaldehyd Acid cyanhydric + HCN CH3 CN C OH Cyanohydrin acetaldehyd H

O CH3 C Aceton CH3

CN + HCN HO Cyanohydrin aceton CH3 C CH3

Acid cyanhydric

Phn ng cng hp HCN vi aldehyd hoc ceton phi c xc tc base. Base lm tng nng tc nhn i nhn -CN. Hp cht cyanohydrin c dng iu ch acid hydroxycarboxylic (hydroxyacid) RCH(OH)CN RCH(OH)COOH. Cng hp vi natrihydrosulfit (NaHSO3) Aldehyd v ceton (methylceton) tc dng vi dung dch m c natrihydrosulfit to thnh sn phm cng trng thi tinh th gi l hp cht hydrosulfitic.
O H Benzaldehyd C6H5 C + NaHSO3 Natri hydrosulfit OH C6H5 SO3Na Hydrosulfitic benzaldehyd CH

233

O CH3 C Aceton CH3

OH + NaHSO3 Natri hydrosulfit CH3 C CH3 SO3Na

Hydrosulfitic Aceton

Hp cht hydrosulfitic thc cht l mui ca acid -hydroxysulfonic RCH(OH) SO3H. V nguyn t lu hunh c tnh i nhn mnh tc dng vi nguyn t carbon ca nhm carbonyl theo c ch :
O - + : S O Na + R C OH R' Ceton Natri hydrosulfit O - + O Na R C R' SO3H R OH C R' SO3Na

Hydrosulfitic Ceton

Hp cht hydrosulfitic d b thy phn trong mi trng acid to thnh hp cht carbonyl ban u v SO2. V vy phn ng cng hydrosulfitic c dng tch aldehyd hoc ceton ra khi hn hp. Aldehyd tc dng vi thuc th Schiff (acid fucsinsulfur) to dung dch c mu hng. Phn ng vi thuc th Schiff ch c trng cho aldehyd. Cng hp vi hp cht c kim. (Xem phn hp cht c kim). Hp cht carbonyl cng hp vi ion acetylid to hp cht etynyl carbinol c ng dng iu ch alcol loi allylic.
O H C Cyclohexanon O R C Ceton + + : Na C R' NH3 C H - 33o O Na R C R' C C H

- + C Na

NH3 -33o

ONa C C H

+ H 3O

OH C C H

Etynyl pentamethylen carbinol + H3O O H R C R' C C H Etynyl dialkyl carbinol

Phn ng cng hp vi cc hp cht c nhm methylen linh ng. Phn ng aldol ho: Cc nguyn t hydro v tr trong gc hydrocarbon ca aldehyd v ceton rt linh ng. Hai phn t aldehyd trong mi trng base long ngng t vi nhau to hp cht aldol (hp cht c chc aldehyd v chc alcol)
2 R CH2 CHO Aldehyd HOR CH2 CH CH CHO OH R Aldol

234

C ch aldol ha: Lin kt C _ H v tr so vi nhm carbonyl c hydro linh ng tc dng vi HO- to carbanion RC HCHO. Carbanion ny l tc nhn i nhn cng hp vo nhm carbonyl ca phn t aldehyd th 2 v to thnh hp cht aldol.
O R CH2 C H + CH CHO R

R CH2 CH CH CHO O- R

+H2O R CH2 CH CH CHO OH R

HO-

Trong hp cht aldol cn hydro linh ng v tr , di tc dng ca nhit , aldol b loi mt phn t nc to aldehyd cha no.
R CH2 CH OH
CH

CHO

CH2

CH

C R

CHO + H2O

Phn ng loi nc t aldol theo c ch trn gi l phn ng croton ha. Phn ng aldol ha cng xy ra gia 2 phn t aldehyd khc nhau.Trong mt aldehyd c hydro v phn t kia khng c hydro .
C6H5CHO Benzaldehyd + CH3CHO Acetaldehyd HOC6H5 CH CH2CHO OH Aldol to C6H5 CH CHCHO

Aldehyd cinnamic

Phn ng ngng t aldol xy ra gia acetaldehyd v formaldehyd to thnh pentaerythrid (c phn ng Cannizaro cho).
O 3H C H O + CH3 C H Ca(OH)2 HO CH2 CH2OH C C O H HCHO,H2O - HCOOH CH2OH HO CH2 C CH2OH

Phn ng aldol

CH2OH

CH2OH

Formaldehyd Acetaldehyd

Phn ng Cannizaro cho

Pentaerythrid

Hai phn t ceton cng xy ra phn ng kiu ngng t aldol nh aldehyd.

2 CH3 O C CH3 HO O OH CH3 C CH2 C CH3 CH3 4-Hydroxy-4-methylpentanon-2

Aceton

Phn ng ngng t aldol cng xy ra gia aldehyd v ceton.

OH O CHO H O + Benzaldehyd 25o 4 gi 25o 10 ngay O + H2O

- OH

Cyclohexanon

235

O C H + CH3 C O Aceton CH3

HO-H2O

CH

CH

C O

CH3

Benzaldehyd

4-Phenyl-3-butenon-2 (Benzalaceton)

Phn ng ngng t aldol cng xy ra khi c xc tc acid. C ch xy ra qua giai on to enol. Khi aldehyd tc dng vi ceton, ceton thng ng vai tr c hydro linh ng v tr (thnh phn metylen) to carbanion - tc nhn cng i nhn. Cc aldehyd - ceton tc dng vi cc dn xut ca acid carboxylic. Phn ng Perkin: Phn ng ca aldehyd thm vi anhydrid acetic v natri acetat.
CHO

CH3COONa

CH = CHCOOH + CH3COOH Acid cinnamic

+ (CH3CO)2O Benzaldehyd

C ch: Natri acetat ng vai tr xc tc base to cabanion - tc nhn i nhn.

CH3COO - + H CH2CO O COCH3
CH O CH 2 CO O CO CH 3

CH2CO O COCH3
CH OCH 2 CO O CO CH 3
+ CH 3 COOH
CHCO O C OC H3

+ CH3COOH
CH OH CH 2 CO O CO CH 3 + CH 3 COO C HC OOH

CH OH

C H 2C O

COCH3

CH

CH

- H2O

+ H2O

C H 3C O O H

Phn ng Perkin ch xy ra i vi aldehyd thm. Phn ng Knoevenagel: Cc aldehyd tc dng theo kiu ngng t croton vi acid malonic, cc hp cht c hydro linh ng nh CH3 _CN, CH3_NO2
CHO + H2C COOH COOH Amin CH CH COOH - H2O COOH Acid Cinnamic CH CH COOH + CO2

Acid malonic

Phn ng ngng t benzoin Khi c mt KCN lm xc tc, cc aldehyd thm tham gia phn ng c trng to hp cht mang chc -CH(OH)-CO- gi l phn ng ngng t benzoin. 236

H C O +

O C H

H O CN C C OH H Benzoin

Benzaldehyd

C ch phn ng: Anion -CN cng vo nhm carbonyl ca aldehyd to thnh cyanhydrin. Cyanhydrin cng vo nhm carbonyl ca phn t aldehyd th hai.

-CN

+ C H O

CN C H O-

C N + COH

H C O

Cc aldehyd khng thm RCHO khi c mt ca KCN ch tham gia phn ng aldol ha. Ring i vi aldehyd formic khi c mt Ca (OH)2 hoc TiOH c th Acyloin ha, nhng sn phm ny li aldol ha to thnh hexose. Acyloin ha A
H CHO + H CHO Ca(OH)2
HO CH2 CH O + HO CH2 Aldehyd glycolic CH O + HO CH2

HO

CH2

CH

CH

Aldol hoa

C 6 H1 2 O6 Hexose

Phn ng cng hp vi cc cht c chc amin - NH2 Hp cht c dng tng qut Z -NH2 trong mi trng acid hoc base thch hp cng hp i nhn vo nhm carbonyl ca aldehyd v ceton. Sn phm cng hp thng khng bn, d b loi mt phn t nc v to thnh cc loi hp cht khc nhau.
R C (H) R ' O + NH 2 _ Z
H+

R C (H) R '

NH OH

H+

R C (H) R '

NH + OH 2

- H2 O

R (H) R'

+ C

NH Z

R C (H) R'

+ NH Z

- H+

R C NH Z

(H) R'

Trong bng 19-5 trnh by cc loi hp cht ca phn ng dng ny. Ch in m l tn ca nhm chc to thnh. Trong phn t hydrazon RCH=N-NH2 c nhm -NH2 t do c th tc dng vi phn t c nhm carbonyl v to thnh hp cht azin RCH=NN=CHR'. RCH=N_NH2 + O=CHR' RCH=N_N=CHR' + H2O 237

Bng 19-5: Sn phm cng - tch ca Aldehyd -Ceton vi hp cht Z- NH2

RCHO hay RCOR' C6H5CHO Benzaldehyd Z-NH2 NH2OH Hydroxylamin Sn phm phn ng C6H5CH=N_OH Oxim. Benzaldoxim CH3COCH3 Aceton C6H5COCH3 Acetophenon NH2NH2 Hydrazin NH2OH (CH3)2C=N-OH Cetoxim Acetoxim

C N NH2 Hydrazon CH3 Acetophenon hydrazon

NH2NH2 Hydrazin C6H5CH=N_NH2 Hydrazon Benzaldehyd hydrazon C6H5CH=N_NHCONH2 Carbazon Benzaldehyd semicarbazon

C6H5

C6H5CHO Benzaldehyd

C6H5CHO Benzaldehyd

NH2NHCONH2 Semicarbazid

O
Cyclohexanon
C6H5CHO Benzaldehyd

NH2NHCONH2 Semicarbazid

C N NH C NH2 O
Cyclohexanon semicarbazon C6H5CH=N_R Benzadehyd imin

NH2R Amin bc nht

Imin

C6H5CHO Benzaldehyd

NH2NHC6H5 Phenylhydrazin

C6H5CH=N_NHC6H5 Phenylhydrazon Benzaldehyd phenylhydrazon

NH N CHC6H5

C6H5CHO Benzaldehyd

NH NH2 N O2 N O2 2,4-Dinitrophenylhydrazin

NO2

2,4-dinitrophenylhydrazon Benzaldehyd

NO2

Hp cht aldoxim v cetoxim c ng phn hnh hc syn v anti. Khi c xc tc thch hp cc cetoxim b chuyn v Beckmann to thnh amid th. C6H5(CH3)C=NOH Acetophenon oxim CH3CONHC6H5 Acetanilid

Aldehyd formic tc dng vi amoniac to hexamethylen tetramin. Hexamethylen tetramin (urotropin) l cht rn c cng thc (CH2)6N4.
6 HCHO + 4 NH3 (CH2)6N4 + 6 H2O

238

N CH2 N CH2 CH2 N N N CH2 CH2 N CH2

Hexamethylen tetramin

( Urotropin )

Phn ng trng hp Phn ng trng hp ch xy ra mt s aldehyd khng vng u dy ng ng. Aldehyd formic trng thi kh b trng hp to thnh trimer dng vng.
CH2 + O O+ CH2 CH2 O O CH2

O CH2+ Aldehyd formic

O CH2 Trioxymethylen

trng thi dung dch 40% trong nc (dd formalin), aldehyd formic b trng hp thnh polymer khng vng kt ta trng gi l polyoxymethylen hay paraformaldehyd.
n CH2=O (CH2O)n n = 10 - 100

Acetaldehyd cng b trng hp nhit thp khi c mt ca acid to paraldehyd v metaldehyd.

CH3 O H3C CH O CH CH3 Paraldehyd Metaldehyd CH O CH3 H3C O CH O CH CH3 CH O CH O CH3

C th thu acetaldehyd bng cch un nng paraldehyd v metaldehyd vi acid. Phn ng Wittig Aldehyd tc dng vi alkylhalogenid c xc tc l hn hp triphenylphosphin v lithi butyl to thnh alken c cu trc lp th xc nh.
CH2CH3 CH (C6H5)3P , C4H9Li 6 5 C C C6H5CHO + CH3CH2CH2Br + H Ether H Z Benzaldehyd Propylbromid C6H5 H H C C

E CH2CH3 1-Phenyl-1-propen

239

C ch phn ng:
(C6H5)3P+ CH3CH2CH2Br C H Li + - 4 9 (C6H5)3PCH2CH2CH2Br (C6H5)3P=CHCH2CH3 + LiBr + C4H10 Ether C6H5 H CH2CH3 H

(C6H5)3P=CHCH2CH3 + C6H5CHO

+ (C6H5)3P

Phn ng Mannich (1917) L phn ng aminometyl ho. Gn thm nhm (R)2NCH2- vo ceton. Ceton c nguyn t hydro linh ng tc dng vi hn hp aldehyd formic v amin (bc mt, bc hai) trong mi trng acid to thnh alkylaminoalkylceton.
R_CO_CH3 + HCHO + HN(R)2 H+ R_CO_CH2CH2N(R)2 + H2O

C ch phn ng:
H C + HN(R)2 H Amin O OH CH2 NR2 H+ - H2O + .. CH2 NR2 + CH2 NR2

O R C CH3 Methylceton

OH R C CH2

+ + CH2 NR2

..

+ OH O - H+ R C CH2 CH2 NR2 R C CH2 CH2 NR2 Alkylaminoalkylceton

1.4.3. Phn ng kh Aldehyd hay ceton b kh ha to thnh alcol bc nht v alcol bc hai.
R C O [H] R CH2OH

H Aldehyd

; R C O
Ceton

[H]

Alcol bac nhat

R'

CHOH

R'

Alcol bac hai

Cc tc nhn kh l: Cc hydrid kim loi (LiAlH4, NaBH4), H2 / xc tc. Kh ha aldehyd v ceton bng hydrid kim loi: Hydro trong hp cht hydrid kim loi c in tch m H -. C th xem ion hydrid l tc nhn i nhn tc dng vo nguyn t carbon ca nhm carbonyl to lin kt C _H.
CH2 CH CHO Aldehyd Acrylic + LiAlH4 H+ Ether CH2 CH CH2OH + H2 + Li+ + Al3+ Alcol Allylic

240

O 1) LiAlH 4 2) H+ 2- Cyclohexenon CH3 C CH2CH2COOC2H5 O Ester ethyl-4-oxopentanoat

OH

2- Cyclohexenol 1) NaBH4 CH3 CH CH2CH2COOC2H5 2) H+ OH Ester ethyl-4-hydroxypentanoat

N C CH2CH2CHO 3-Cyanpropionaldehyd

1) NaBH4 2) H+

N C CH2CH2CH2OH 4-Hydroxybutyronitril

Cc lithi nhm hydrid, natri bo hydrid l nhng cht kh c tnh chn lc cao. Cc hydrid kim loi ny ch kh ha chc carbonyl m khng kh ha cc nhm chc c ni i, ni ba khc nh -HC=CH-, -CC-, -CN, -COOR. LiAlH4 phn ng rt mnh v gii phng hydro, thng tin hnh phn ng trong dung mi ether. NaBH4 tc dng nh nhng v tin hnh phn ng trong mi trng nc -alcol. C th s dng cht kh l diboran B2H6 kh nhm carbonyl. Nhng diboran khng ch kh chc carbonyl m cn kh c lin kt i C =C. Kh ha bng hydro phn t c xc tc Aldehyd v Ceton c th b kh ha bng hydro phn t c xc tc kim loi (Pt, Ni, Pd) to alcol tng ng.
CH2 CH CHO Aldehyd acrylic O Xuc tac + 2H2 CH3 CH2 CH2OH Alcol propylic OH

+ 2H2 Xuc tac

2- Cyclohexenon

Cyclohexenol

Cc lin kt i C =C cng ng thi b kh ha Kh ha bng kim loi Kh ha pinacon Kh ha aldehyd hoc ceton bng kim loi (Na, Mg) to thnh hp cht 1,2diol. y l phng php in ha. Cht kh l in cc kim loi.
2 C CH3 Aceton CH3 O Na + 2H+ CH3 C C CH3 OH OH Pinacon CH3 CH3

241

2 C6H5

O H

Na + 2H+

H C6H5

Benzaldehyd

C C C6H5 OH OH Hydrobenzoin

C ch kh ha pinacon:
2 CH3 CH3 C O 2 Na-2e -2 Na+ CH3 CH3

.. C O: ..

CH3

C - : O: ..

CH3 CH3

C CH3 :O : ..

+ 2H+

CH3

C HO

CH3 CH3

C CH3 OH

Kh ha Clemmensen (1913) Hn hng km trong mi trng acid HCl m c kh ha aldehyd -ceton to hydrocarbon tng ng.
R' R C O + 2Zn + 4H+ CH2 + 2 Zn2+ + H2O R Hydrocarbon + 2 Zn2+ + H2O R CH3 Hydrocarbon R'

Ceton O H + 2Zn + 4H+

Aldehid

Khi kh ha Clemmensen lin kt i C =C cng b kh theo. 1.4.4. Phn ng oxy ha Oxy ha bng cc tc nhn oxy ha v c Cc aldehyd b oxy ha to thnh acid carboxylic.
R C O H [O] R C O OH

Aldehyd

Acid

Cc cht oxy ha l Ag2O, H2O2, KmnO4, CrO3, Cu(OH)2.

CHO + Ag2O THF H2O COOH + 2 Ag

Phn ng ca aldehyd vi dung dch AgNO3 trong amoniac to Ag kim loi v acid hu c (phn ng Tollens). Phn ng ca aldehyd vi thuc th Fehling to oxyd ng Cu2O c mu gch. Nhng phn ng ny c dng nh tnh hp cht c chc aldehyd. Cc ceton ch b oxy ha bng cc cht oxy ha mnh, mch carbon b ct t to thnh acid.

242

O Cyclohexanon

HNO3 V2O5

HOOC(CH2)4COOH Acid Adipic

Phn ng Cannizaro Aldehyd khng c nguyn t hydro v tr , c bit l aldehyd thm, di tc dng ca hydroxyd kim, kim th m c to thnh alcol v acid (aldehyd c nguyn t hydro ch tham gia phn ng aldol ha).
Ar C O H + Ar C O H Ar C O OH + Ar CH2OH

Aldehyd thm

Acid

Alcol thm

Nu hai aldehyd khc nhau u khng c nguyn t hydro v tr , tham gia phn ng loi ny gi l phn ng Cannizaro cho.
Ar C O + H C O H HO H C O + Ar CH2OH

H Aldehyd thm

OH Acid formic

Alcol thm

C th xem phn ng Cannizaro l phn ng oxy ha -kh hay l phn ng chuyn hydrid H - t nguyn t carbon ca nhm aldehyd ny n nguyn t carbon ca chc aldehyd kia. C ch xy ra nh sau:
O H

Ar

+ - OH

.. :O : Ar

:OH ..

C H

.. : O :Ar I :OH .. C H +

O H

C II

Ar

.. Ar C + Ar CH2O : .. I : OH II ..

O Ar I :O : .. C + Ar II

CH2OH ..

..

Trong phn ng Cannizaro cho, aldehyd formic ng vai tr chuyn hydrid H-. Phn ng Meerwein -Pondorf-Oppenauer un nng aldehyd hay ceton trong dung dch isopropanol c xc tc l isopropylat nhm th to thnh alcol bc nht hoc alcol bc hai.
R' R C O + CH3 CH3 CH OH [(CH3)2CH_O]3Al R' R CH OH + CH3 CH3 C O

Ceton

Alcol bac hai

y l phn ng oxy ha - kh c nhiu ng dng trong cc phn ng ca hp cht t nhin chuyn ha chc aldehyd, ceton thnh alcol. 243

Nu cho aldehyd tc dng vi nhm alcolat th to ester (phn ng Claisen Tishenco).

2R C O H (RCH2O)3Al R C Ester O OCH2R

Aldehyd

Nhng phn ng ny c th xem l phn ng chuyn dch hydrid H- t isopropylat nhm [(CH3)2CHO]3Al, alcolat nhm (RCH2O) 3Al sang carbon ca nhm carbonyl trong aldehyd-ceton. 1.4.5. Phn ng th. Phn ng halogen ha Tc dng vi HCl Acid HCl cng vi Aldehyd - Ceton to hp cht 1,1-clorhydrin kh tch ring trng thi tinh khit. y l phn ng thun nghch.
O CH3 C CH3 + HCl CH3 Aceton + OH C CH3 + ClCH3 OH C CH3 Cl 2-Cloropropanol

Trong dung dch alcol, t 1,1-halogenhydrin to thnh -halogeno ether. halogeno ether tch ring c khi hn hp phn ng.
+ H2CCl + CH3OH H + OCH Cl
3

H2C

+ H+ Cl Clomethylmethylether H2C

OCH3

Tc dng vi PCl5 v PBr3 Aldehyd v Ceton tc dng vi phosphor pentaclorid hoc phosphos tribromid to gem -dihalogen.
O CH3CH2 C CH3 + PCl5 Butanon-2 CH3CH2 Cl C CH3 + POCl3 Cl 2,2-Diclobutan

3-Methylbutyraldehyd

(CH3)2CHCH2CHO+ PCl5

(CH3)2CHCH2CHCl2+ POCl3 1,1-Diclo-3-methylbutan

Phn ng Haloform Acetaldehyd v metyl ceton tc dng vi Natri hypohalogen NaOX to haloform.

244

+ 3NaOI CH3CHO Acetaldehyd O R C CH3

+ 3NaOI CI3CHO

CHI3

HCOONa

Iodoform + 3NaOBr R O C CBr3 + 3NaOBr CHBr3 + RCOONa Bromoform

Methylceton

ng dng phn ng ny nh tnh acetaldehyd v methylceton. Ngi ta thng tin hnh phn ng vi hn hp halogen, KOH v KI. Tc dng vi halogen Ceton tc dng vi halogen c xc tc nh sng, phn ng th halogen xy ra i vi hydro v tr .
O R C CH3 + Br2 h O R C CH2Br + HBr

2. Aldehyd - ceton cha no Aldehyd - ceton cha no c hai loi: Aldehyd - ceton cha no lin hp:
RCH=CHCH=O, RCH=CHCOR' Aldehyd - ceton cha no khng lin hp: RCH=CH(CH2)nCH=O, RCH=CH(CH2)nCOR'.

Aldehyd hoc ceton cha no lin hp hoc khng lin hp c cng s nguyn t carbon l ng phn ca nhau.
CH2=CH-CH2-CH=O CH3-CH=CH-CH=O

Vinylacetaldehyd (ng phn khng lin hp)

C C

Crotonaldehyd

H = -6 kcal.mol-1

(ng phn lin hp)

C C CH C OH H H C C

CH2

O C H

CH

O C

ong phan cha no , (Kem ben)

ong phan dang enol

ong phan cha no , (Rat ben)

Nguyn t hydro ca nhm methylen (-CH2-) trong phn t vinylacetaldehyd rt linh ng, v n trn carbon v tr so vi nhm carbonyl. Vinylacetaldehyd c s enol ha. Ion enolat c n nh v c hin tng cng hng. (S enol ha d xy ra trong mi trng kim).

245

Anion tip nhn proton ca H2O. Proton ca nc tng tc trn oxy thu c dng enol; tng tc vo carbon th to butenal -3, nu xy ra carbon v tr thu c crotonaldehyd. Trong mi trng base s cn bng chuyn v pha to crotonaldehyd l ch yu (99,99%). S ngng t aldol ca aldehyd hoc ceton trong mi trng base hoc acid thng to thnh hp cht aldehyd, ceton cha no ,.
CH3 CH3C=CHCOCH3+ H2O 4-methyl-3- penten-2- on (mesytyl oxyd)

2 CH3COCH3

H2SO4

C ch phn ng:
OH+ CH3COCH3 + H+
OH _C CH3 CH3

OH CH3 CH2 C CH3 + H+

CH3

. OH .
+
CH2= C_CH3

OH OH _ C_CH _C_CH3 CH3 2 CH3

O OH _C_CH CH3_ C_CH2 3 CH3

+ H+

+ OH OH Hoac: CH _ C_CH _C_CH3 3 2 CH3

+ H+

- H+

OH OH + H+ CH3_ C_CH = C_CH3 CH3

+ OH OH2 CH3_ C_CH = C_CH3 CH3

OH OH2 CH3_ C_CH = C_CH3 CH3

H2O +

OH CH3 C CH = C_CH3 CH3

+ _ _

OH _ C= CH _ C_CH3 CH3 + CH3

OH _ C= CH _C_CH CH3 3 CH3

246

+ OH
CH3_ C= CH _C_CH3 CH3

O _ C= CH _C_CH CH3 3 CH3

+ H+

Aldehyd v ceton cha no , cng c th c iu ch bng cch oxy ha cc alcol cha no tng ng (trong iu kin lin kt i khng b oxy ha). Cc alcol cha no c iu ch theo phng php Grignard.
CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 (80%) Retinal CH3 CH3 CHO

CH2OH MnO2 Ether dau hoa

Retinol (Vitamin A1)

2.1. Tnh cht ca aldehyd - ceton cha no Aldehyd - ceton cha no lin hp th hin cc phn ng: 2.1.1. Phn ng cng hp Aldehyd - ceton cha no , th hin tnh cht ca mt alken (tnh cht ca lin kt C =C) cng nh tnh cht ca nhm carbonyl.
C6H5CH=CH_CO_CH3 + Br2 CCl4 (10-20o) C6H5CHBr_CHBr_CO_CH3 (52-57%)

CH2 = CH_CHO + Ag2O

CH2 = CH_COOH + 2 Ag

Phn ng cng hp xy ra trn 1 lin kt i (Cng hp 1, 2 thng thng) hoc 2 u ca h lin hp (Cng hp 1, 4 do lin hp). Cng hp 1,2
X Y C C C O + X Y C C C O hay X Y C C C O

Cng hp 1,4
X C C C O + X Y Y

C C C O

V d: Cng hp 1,2
O C6H5CH = CH _ C _ C6H5 CH3COOH CN O C6H5CH _ CH2 _ C _ C6H5 (93-96%)

+ KCN

247

H O

+ HCN

(C2H5)3Al

(85%) CN

V d: Cng hp 1,4:
+ CH2=CH_CH=O CH2=CH_CH_O Acrolein (aldehyd acrylic)
CH2=CH_CH=O + CH3SH CH3S_CH2_CH=CH_OH Acrolein Methylmercaptan (Metanthiol)

+ CH2_CH=CH_O
CH3S_CH2_CH2_CHO -Methylthiolpropionaldehyd

Cng hp Diels -Alder:

CH2 O CH2 CHO CHO O 2-Formyl-2,3-dihydropyran

Aldehyd acrylic

Ty thuc iu kin, cc hp cht c kim s c cng hp 1, 2 hoc 1, 4 vi thuc th Grignard. Yu t lp th l quyt nh chiu hng ca phn ng. Cng hp1,2
CH3 H C=C H CH3 H C=C H

C_CH 3

+ CH3MgBr

+ H 3O

C(CH 3)2 (80%) OH 2-Methyl trans 3- penten-2- ol

Cng hp1,4
O _ C_ C H C6H5CH = CH 6 5 H3O+ C6H5 C6H5 O _ CH _C_C H CH 6 5 2

+ C6H5MgBr

1,3,3-triphenyl-1- propanon

Hp cht c lithi c khuynh hng cng hp 1,2:

O C6H5CH = CH_C_C6H5 H3O+ C6H5CH = CH_C(C6H5)2 75% OH

+ C6H5Li

Hp cht lithi dialkyl ng (hp phc) thng to ra sn phm cng hp 1,4:

O _C_CH CH3C = CH 3 CH3 H3O+ CH3 O _C_CH _C_CH CH2 = CH 2 3 72% CH3

+ (CH2 = CH)2CuLi

248

2.1.2. Phn ng kh ha Kh ha hp cht carbonyl cha no , c th xy ra lin kt i (C=C) hoc vo nhm carbonyl (C=O). Cht kh l LiAlH4 cng vo nhm carbonyl.
O Ether + LiAlH4
O

H2O

OH (97%)

+ NaBH4

C2H5OH

OH

OH

+
(59%) (41%)

Kh ho bng hydro c xc tc xy ra ch lin kt i (C=C)

O O CH3 Pd-C

+ H2

CH3 H

(100%)

2.2. ng dng ca cc hp cht aldehyd -ceton cha no Citral: L mt aldehyd cha no c 2 lin kt i. Gi tn theo danh php IUPAC l 3,7-dimethyl-2,6-octadienal. Citral ngng t vi aceton to -ionon l sn phm trung gian trong cng nghip tng hp vitamin A.
CH3 CH3 CHO CH3 CH3 CH3 O CH3 BF3 CH3 CH3 O CH3 CH3 -Ionon

Citral

+ CH3COCH3 HO CH3

Aldehyd cinnamic: L thnh phn ch yu ca tinh du qu.

CH CH CHO

Aldehyd cinnamic

Metylvinylceton: L mt ceton lin hp; th hin tnh cht cha no:

HCl + CH2=CH_CO_CH3 Methylvinylceton ClCH2_CH2_CO_CH3 -Cloroetylmethylceton

249

Cc ceton lin hp b hydro ha rt chn lc. Vi H2 c xc tc, nhm carbonyl khng b hydro ha. Khi tc dng vi NaBH4 ch c nhm carbonyl b kh ha:
CH3_CH2_CO_CH3 H2 Pt CH2=CH_CO_CH3 Methylvinylceton NaBH4 CH2=CH2_CHOH_CH3

Cc ceton lin hp c th tham gia phn ng ng vng vi mt s ceton khc:

R + R O O Base O R O R O HO Aldol O R R O

3. Aldehyd - ceton a chc Trong phn ny ch cp nhng hp cht c 2 nhm carbonyl. l nhng hp cht dialdehyd, diceton v hp cht ceton aldehyd. 3.1. Hp cht 1,2-Dicarbonyl (-1,2-Dicarbonyl) Glyoxal (Aldehyd oxalic: CHO-CHO) iu ch glyoxal bng phng php oxy ha paraaldehyd bng selen dioxyd SeO2 hoc oxy ha 1,2-etadiol bng oxy ca khng kh c Cu l xc tc nhit 250-300oC. Diacetyl (Butadion-2,3: CH3_CO_CO_CH3) Diacetyl ngng t vi hydroxylamin to diacetyldioxim (dimetylglyoxim). Dimetylglyoxim tc dng vi ion niken to phc, kh tan, mu .
H:O: C C N N

..

CH3 CH3

:O :
N N C C

CH3 CH3

CH3 CH3

- .. H :O: :O :
C C N + N + Ni + N N C C

CH3 CH3

+ Ni+ +

:O :

H Dimetylglyoxim

:O : H ..

:O : .. H Phc niken ( mau o )

:O :

Dibenzoyl (1,2-Diphenyletandion - Benzyl: C6H5_CO_CO_C6H5) Oxy ha benzoin thu c dibenzoyl. Dibenzoyl l tinh th mu vng, nhit nng chy 95oC. Kh ha dibenzoyl trong cc iu kin khc nhau th thu c cc sn phm khc nhau.

250

4H [ Sn/HCl]

- H 2O
C6H5 C C C6H5 O O Dibenzoyl 6H [Zn/Hg. HCl] - 2H 2O 4H2 /Ni - 2H2O

C6H5 C6H H C6H5

CH2 C C

CO H

C6H5 Desoxybenzoin Trans-Stylben

C6H5 CH2

CH2

C6H5 1,2-Diphenyletan

Methylglyoxal (2-oxopropanal: CH3-CO-CHO) Methylglyoxal c iu ch bng cch oxy ha 2-oxopropanol (1hydroxypropanon, hydroxyaceton) bng selen dioxyd.
CH3 C CH2OH O 2-Oxopropanol SeO2 CH3 C CHO O Methylglyoxal

Methylglyoxal l sn phm trung gian trong chuyn ha carbohydrat. 3.2. Hp cht 1,3-dicarbonyl (-dicarbonyl: R-CO-CH2-CO-R) 3.2.1. iu ch Phng php quan trng iu ch hp cht 1,3-dicarbonyl l phn ng ngng t Claisen. Ceton tc dng vi ester ca acid carboxylic trong iu kin c mt base hu c nh alcolat natri RO-, natri amidid NaNH2...
CH3 C CH3 O Aceton + CH3 R'O C OR CH3 C CH2 C CH3 + ROH O O O Ester alkylacetat Acetoaceton (petandion,2,4)

C ch phn ng:
CH3 C CH3 :O : Aceton
CH2

R'O -

-R'OH

CH3

C CH2 :O : Carbanion

CH3

:O : ..

CH2

.. :OR
CH3

:O :

:O :

CH3

.. :OR
CH3 C CH2 :O : .. C CH3 :O : -RO CH3 C CH2 C CH3 :O : :O :

3.2.2. Tnh cht ha hc Tnh cht h bin Hp cht 1,3-dicarbonyl c dng h bin (tautomer, mesomer) ceton-enol. Dng enol c h thng lin hp v c kh nng hnh thnh lin kt hydro ni phn t. V vy hp cht acetoaceton tn ti ch yu dng enol. 251

R' R CH R" R

R' C

R" O..: .

CH3

CH2

CH3

CH3

CH

CH3

: O:

: O:

:O ..

Dng ceton

H ..

: O:

Dng enol

1,3-dicarbonyl

.O : H . . .. Dng ceton Dng enol Acetoaceton :O: :O ..

Cc phn ng ch yu ca hp cht 1,3-dicarbonyl Tnh acid: Hp cht 1,3-dicarbonyl c tnh acid mnh hn cc hp cht 1,2-dicarbonyl v cc aldehyd, ceton n chc. Nguyn nhn l nguyn t hydro ca lin kt C - H linh ng hn. Acetoaceton c pKa = 9, 0 ha tan c trong dung dch kim v tc dng vi natri kim loi gii phng kh hydro v to mt carbanion bn vng nh s lin hp.
CH3 C O CH2 C O CH3 + Na CH3 C O Na CH C O CH3 + 1/2 H2

CH3

C O - : .. :

CH

C :O:

CH3

CH3

C :O:

CH

C :O:

CH3

CH3

C :O:

CH

Carbanion

CH3 C :O : ..

To phc vi ion kim loi: Hp cht 1,3-dicarbonyl tc dng vi cc mui ca kim loi nng to phc bn, tan trong cc dung mi hu c nh ether, benzen, cloroform. Acetoaceton to phc vi Cu2+ thnh acetoacetonat ng c cng thc sau:
CH3 CH3 CH2 C C : O: + : O : Cu2+ CH3 C :O CH
Cu

C : O: O: C

CH3 + 2H+

: O: +
CH3 C

: O:
C

: O:
CH3 CH3 C CH

CH2

CH3

Acetoaceton

Acetoacetonat ng

Phn ng th C th alkyl ha hp cht 1,3-dicarbonyl. Hp cht 1,3-dicarbonyl tc dng vi dn xut halogen trong mi trng kim. Phn ng xy ra oxy to ether. Phn ng xy ra carbon to mch nhnh.

252

CH3

C - : O: ..

CH

C :O :

CH3
RX

CH3

C :O :
R

CH

C :O :

CH3 Th vo O

CH3

C :O:

CH

-X C : O: CH3 CH3

C :O :

CH

C :O :

CH3 Th vo C

Ct mch carbon un nng hp cht 1,3-dicarbonyl vi cc kim mnh, mch carbon b ct t to thnh mui ca acid v ceton.
CH3 O C CH2 O C HO CH3

to

CH3

O C

O-

CH3

O C

CH3

4. QUINON 4.1. Danh php Quinon c cu to nh l cyclohexadiendion. Theo qui c, gi tn hp cht quinon theo dn xut ca benzen l benzoquinon, dn xut ca toluen l toluquinon... V vy thut ng quinon c xem l t gc gi tn nhng hp cht thuc loi ny.
O O O O CH3 O O CH3 OH

O Toluquinon

o-Benzoquinon; p-Benzoquinon; 2-Methylbenzoquinon-1,4.

O Antraquinon-9,10

O Phthiocol

2-Hydroxy-3-methylnaphthoquinon-1,4

4.2. iu ch Phng php iu ch quinon l oxy ha cc phenol v amin thm.

OH Na2Cr2O7 H2SO4 30o OH O Hydroquinon p-Benzoquinon OH O NH2 Cl O Na2Cr2O7 H2SO4 < 30o O Cl

2-Clorobenzoquinon-1,4

4.3. Tnh cht ha hc 4.3.1. Cn bng oxy ha -kh. Cc hp cht 1, 2 v 1,4-dihydroxybenzen b oxy ha to thnh quinon. Ngc li, kh ha quinon th to thnh hp cht dihydroxybenzen. 253

CH3 Na2S2O4 , H2O Ether

OH

CH3

OH

Tnh cht quan trng c minh ha bng phng trnh in ha nh sau:

O p-Quinon O + 2H+ + 2e OH OH Hydroquinon

Hydroquinon c s dng lm in cc. in th ca in cc xc nh theo phng trnh Nernst:

E = Eo+ [Quinon][H+]2 2,303.RT log nF [Hydroquinon]

Qu trnh oxy ha -kh quinon -hydroquinon c nhiu ng dng. 4.3.2. Phc chuyn in tch Phc chuyn dch in tch c to thnh l s kt hp hai phn t. Mt phn t cho electron v phn t th hai nhn electron. Phn t cho in t l phn t c cc nhm -OH, -OCH3, -N(CH3)2, -CH3 gn trn nhn benzen. Phn t nhn in t c cc nhm ht electron nh nhm nitro trong acid picric, quinon. S thay i mu t cc phn t ban u xc nhn s to phc chuyn in tch. Phc chuyn in tch quinhydron c mu xanh lc l mt v d.
O + O Quinon OH Hydroquinon OH O Quinhydron OH O OH

4.3.3. Cc phn ng ca quinon Phn ng cng hp Quinon l hp cht carbonyl cha no, c phn ng c trng ca lin kt i
O + HCl O OH OH Cl

254

C ch phn ng cng HCl vo quinon.

O + H+ O O O + OH OH + OH OH Cl O H OH Cl

-Cl

Quinon cng hp vi cc dienophyl - Phn ng Diels -Alder.

O + O Quinon Butadien CH3COOH 25o OH OH OH HCl CH3COOH OH

Phn ng acyl ha Quinon tc dng vi anhydrid acetic to triacetat hydroxyhydroquinon.

O H+ (CH3CO)2O - CH3COOH O H OCOCH3 OH OCOCH3 (CH3CO)2O , H+ OCOCH3 OCOCH3 OCOCH3

OCOCH3

- CH3COOH OCOCH3

Cc cht c cu trc quinon thng c mu. Quinon l thnh phn cu to c bn trong cc cht mu.
HOOC O HO COOH O Lauson O Antraquinon

HO

O COOH Muscaruphyn

Vitamin K1 c thnh phn quinon.

O Vitamin K1

255

Bi tp
1. Vit cng thc cu to ca cc hp cht c tn gi sau: a. 5-Methylhexanal; b. 4-Hydroxy-3-metoxybenzaldehyd; c. Butyroaldehyd; d. Methylethylceton; e. Methylbenzylceton; f. Acetophenon; g. Benzophenon. 2. T C6H5CH2CH2Cl hy tm phng php iu ch phenylacetaldehyd. 3. Chn cc phng php thch hp hy iu ch cc cht sau t cc nguyn liu cho: a. iu ch methylethyl ceton t sec -butanol. b. iu ch methyl n -hexylceton t alcol caprylic. c. iu ch methyl allylceton t acetaldehyd v allylbromid. d. iu ch aldehyd cinnamic t acetylen v benzaldehyd. 4. So snh kh nng phn ng ca nhm carbonyl trong cc hp cht sau: Aceton, diethylceton, acetaldehyd, cloral, diisopropylceton, benzaldehyd, benzophenon 5. Vit phn ng ca benzaldehyd vi cc cht sau: a. Aceton; b- Hydroxylamin; c- Phenylhydrazin; d- Nitrometan; e-Anilin. 6. Vit phn ng ca citral vi cc cht sau: a. H2/ Ni; a. PCl5; b. Zn/HCl; c. NaBH4; d. LiAlH4.

7. Vit phn ng ca Acetophenon vi cc cht sau: b-Cl2/ nh sng; c- Hn hp Br2, KOH, d-Semicarbazid.
HO- ac HO - loang
KCN HO-

8. Trnh by cc c ch ca cc phn ng sau:

a- Benzaldehyd

b- Acetaldehyd

c- p-Tolualdehyd

d- Benzaldehyd + Formaldehyd

e- Benzaldehyd + Anilin
9. Vit cng thc cu to ca cc cht sau: a. o-Benzoquinon; c. Naphtoquinon-1,4; b. p-Benzoquinon; d. Antraquinon-9,10

10. Trnh by cc phn ng c trng ca aldehyd v ceton lin hp. 11. Ngi ta thng s dng nhng loi hp cht c nhm carbonyl loi no to phc vi cc ion kim loi Ni2+, Cu2+ 256

Chng 20

ACID CARBOXYLIC

Mc tiu hc tp 1. Gi c tn cc hp cht acid n chc v a chc. 2. Trnh by v so snh c tnh cht ha hc ca acid carboxylic mch thng v acid carboxylic thm. Ni dung 1. Cu to Acid carboxylic l nhng hp cht hu c c nhm chc carboxyl -COOH C th vit cng thc nhm carboxyl dng cu to khai trin, cu to rt gn hay dng phn t.

:O: .. R C O H ..

R_COOH

R_CO2H

R c th l hydro, gc hydrocarbon aliphatic R hay gc aryl Ar Trong 4 orbital ca nguyn t carbon ca nhm carboxyl th 3 orbital trng thi lai ha sp2 trong cng mt phng v to lin kt vi gc R, nhm OH v oxy. Orbital p cn li lin kt vi orbital p ca oxy trong nhm carboxyl to lin kt . di v gc lin kt ca acid formic c trnh by trong bng 20-1.
Bng 20.1: Cu to ca acid formic (HCOOH)
H O H Acid formic

Lin kt
C O

di 1,202 1,343 1,097 0,972

Gc lin kt HC=O OC=O HC-O HO-C

gc 124,1o 124,9o 111,0o 106,3o

C=O CO CH OH

trng thi rn, lng v trng thi hi, acid carboxylic tn ti dng dimer.
O ... H O R C O H ... O C R

257

2. Danh php C 2 loi danh php quan trng. Danh php thng thng v danh php IUPAC. Danh php thng thng phn nh ngun gc ca acid. Danh php IUPAC:
Tn Hydrocarbon tng ng + tip v ng OIC

nh s: nh s trn mch chnh di nht cha chc acid. S 1 bt u t chc acid. Nu acid c phn nhnh th c tn nhm th v v tr gn vo mch chnh. Dng cc ch ci , , , xc nh v tr cc nguyn t carbon ca mch chnh. Ch ci bt u t nguyn t carbon sau nhm acid. Cng c th xem acid hu c l dn xut ca hydrocarbon. Hydro c thay th chc acid. Chc acid c tn gi l carboxylic.
Tn hydrocarbon tng ng vi gc R + carboxylic.

Danh php mt s acid trnh by trong bng 20-2.

Bng 20.2: Danh php v tnh cht vt l ca mt s acid.
Cng thc Danh php thng thng Danh php IUPAC t oc t os pKa

HCOOH CH3COOH CH3CH2COOH CH3(CH2)2COOH CH3(CH2)3COOH CH3(CH2)4COOH CH3(CH2)5COOH CH3(CH2)6COOH CH3(CH2)7COOH CH3(CH2)8COOH CH3(CH2)10COOH CH3(CH2)12COOH CH3(CH2)14COOH CH3(CH2)16COOH CH=CHCOOH

Acid formic Acid acetic Acid propionic Acid butyric Acid valeric Acid caproic Acid nantic Acid caprylic Acid pelagonic Acid capric Acid lauric Acid myristic Acid palmitic Acid stearic Acid acrylic Acid metacrylic

Acid metanoic Acid etanoic Acid propanoic Acid butanoic Acid pentanoic Acid hexanoic Acid heptanoic Acid octanoic Acid nonanoic Acid decanoic Acid dodecanoic Acid tetradecanoic Acid hexadecanoic Acid octadecanoic Acid propenoic Acid 2-methylpropenoic

8.4 16,6 -21, -5 -34 -3 -8 17 15 32 44 54 63 72 12,3 16

101 118 141 164 186 205 223 239 255 270 299 251 267 142 163

3,75 4,76 4,87 4,82 4,86 4,88 4,89 4,90 -

CH2 C COOH CH3

258

Cng thc

Danh php thng thng

Danh php IUPAC

t oc

t os

pKa

CH3 H

C C

H COOH
(CH2)7COOH

Acid crotonic

Acid E-2-butenoic

71,6

189

4,69

CH3(CH2)7 H
CH 3(C H 2) 7 H

Acid oleic

Acid Z -9-octadekenoic

16.3

C C

C C

H (CH 2) 7 COO H

Acid elaidic

Acid E - 9-octadekenoic

45

HCCOOH

Acid propiolic Acid cyclopentan carboxylic Acid carboxylic benzen

Acid propinoic Acid cyclopentan carboxylic Acid benzoic

9.0 -

144 -

COOH

121

249

4,17

COOH

Acid phenylacetic

Acid 2-phenyletanoic.

76,7

265

4,26

CH2 COOH H C6H5 COOH C C H

5 4

Acid cinnamic

Acid-E-3phenylpropenoic

135

300

4,44

CH3 CH2 CH CH CH COOH CH3 CH3 CH3

Acid 3-ethyl-4-methyl-hexanoic Acid -ethyl - -methylcaproic Acid 2-ethyl-3-methylpetancarboxylic

Khng phi tt c cc loi acid u c th gi tn theo phng php c tip v ng oic. V vy c th gi tn theo phng php carboxylic. c bit vi hp cht vng thng gi theo danh php carboxylic.
COOH Acid cyclohexan carboxylic CH3 COOH Acid 1-methylcyclohexan carboxylic

3. Phng php iu ch C mt s phng php ch yu sau. 3.1. Thy phn hp cht nitril R_CN Thy phn hp cht nitril to acid v amoniac.
R_CN + 2H2O R_COOH + NH3

259

Phn ng xy ra khi c xc tc acid hoc base.

CH2CN + 2H2O H2SO4 100o, 3 gi + CH2COOH + NH4 HSO4-

CH3 CH2 CH2 CH2CN + 2H2O

KOH

CH3 CH2 CH2 CH2COOK + NH4OH

3.2. Carboxyl ha hp cht hu c 3.2.1. Hp cht c kim tc dng vi kh CO2 to mui carboxylat
R MgX + CO2 R Li + CO2 R COOMgX R COOLi H2O H2O R COOH + R COOH + HOMgX LiOH

3.2.2. Hydrocarbon thm tc dng vi phosgen COCl2 Thy phn acylclorid hnh thnh v thu c acid .
Ar H + Cl Cl C O ACl3 Ar C O Cl + H2O - HCl Ar COOH

- HCl

3.2.3. Natri alcolat tc dng vi carbon oxyd CO

RONa + CO RCOONa RCOOH

3.2.4. Carboxyl ho alken

CH2 CH2 + CO 1- Ni(CO)4 2- H2O CH3 CH2 COOH

3.3. Oxy ha alcol bc nht v aldehyd (xem alcol, aldehyd-ceton) 3.4. Tng hp acid t ester malonat - Tng hp malonic Ester malonic ROOCCH2COOR v dn xut R'X l nguyn liu c bn iu ch acid carboxylic. Ester malonic ROOCCH2COOR l nguyn liu ph tr c bn chuyn dn xut halogen R'X thnh R'CH2COOH.

R'X
Phn ng xy ra nh sau:

R'CH2COOH

Khi c xc tc base, ester malonic chuyn thnh tc nhn i nhn ROOCCHCOOR v sau tc dng vi dn xut halogen. Tip theo l qu trnh thy phn ester v decarboxyl ha to thnh acid carboxylic.

260

ROOCCH 2 COOR + C 2H5 O -

ROOCCHCOOR

+ C 2 H 5 OH

ROOCCHCOOR + R'X H+

ROOCCHCOOR R'

+X-

ROOCCHCOOR + 2H2O R' HOOCCHCOOH R'

HOOCCHCOOH + 2ROH R' R'CH2COOH + CO2

Decarboxyl hoa

Vi phng php ny c th iu ch cc acid carboxylic c mch carbon thng hoc phn nhnh v s carbon ty thuc vo s la chn dn xut halogen. 3.5. Thy phn ester Thy phn ester trong mi trng acid thu c acid v alcol.
RCOOR' + HOH H+ RCOOH + R'OH

Thy phn ester trong mi trng kim (phn ng x phng ha) thu c mui ca acid v alcol.
RCOOR' + NaOH RCOONa + R'OH

Trong thc t ng dng phng php ny sn xut x phng t ngun nguyn liu du thc vt v m ng vt (xem thm phn ester). 3.6. S dng cc phn ng Thy phn hp cht trihalogen, phn ng Perkin u thu c acid (xem phn hp cht halogen v phn ng Perkin) 4. Tnh cht l hc Tnh cht l hc ca acid carboxylic ph thuc rt nhiu vo s cng kt cc phn t do lin kt hydro gy nn. Lin kt hydro acid carboxylic bn hn lin kt hydro ca alcol v nhm OH ca acid phn cc mnh hn. Acid carboxylic tn ti nhng dimer vng ngay c trng thi hi v tn ti dng polymer mch thng.
O ... H O R C O H ... O Dang dimer C R

. ; .. H

R C

H ...

C R

O ... H O

R C

...H

C R

O ... H O

R C

O.

..

Polymer dang thang

261

Tt c cc acid carboxylic l cht lng hoc rn (bng 20-2). Acid thm u l cht rn. Nhit si ca acid no mch thng khng phn nhnh tng dn theo trng lng phn t. Cc acid c s carbon chn c nhit nng chy cao hn acid c s carbon l trc v sau . Acid c s carbon < 4 tan v hn trong nc. Gc R l gc thn du (lipophile). Nhm COOH l nhm thn nc (hydrophile).Khi gc R cng tng th lin kt hydro ca nhm carboxyl vi nc khng lc gi ton b phn t acid trong nc. Cc acid c s carbon >11 hon ton khng tan trong nc. Trn quang ph IR dao ng ha tr ca nhm OH trong vng 3000-2500cm-1 (trong acid khng c lin kt hydro l OH =3550cm-1). Vch c trng ca nhm C =O cng tng t ph ca aldehyd nhng m rng hn. Trong vng t ngai, nhm carboxyl hp th bc sng ngn hn nhiu so vi nhm carbonyl. V d: Hp cht H CH3COOH CH3CHO 5. Tnh cht ha hc Nhm carboxyl l t hp ca 2 nhm carbonyl C =O v nhm hydroxyl (carboxy) do c tn gi l carboxyl. Hai nhm ny c nh hng ln nhau rt mnh do s lin hp ca orbital v cp in t khng lin kt ca oxy trong nhm OH. Kt qu l lin kt OH ca acid yu hn so vi alcol v in tch dng +ca carbon trong nhm carboxyl t hn so vi aldehyd.
O R C O .. H Acid R C O OH

197 nm 293 nm

max 60 12

..

O R C H Aldehyd

Nhm carboxyl v gc R c nh hng qua li ln nhau. C 4 loi phn ng c bn ca acid carboxylic nh sau:
O

1-

R C O H O

Phn ng lm t lin kt OH l cc phn ng: Phn ly acid, to mui vi kim loi v.v...

2-

R C YO H

Phn ng vo nhm carboxyl: a s l nhng phn ng vi tc nhn i nhn Y, lm t lin kt COH

262

3-

O R C O H O R C O H

Phn ng decarboxyl (tch nhm carboxyl)

4-

Phn ng gc hydrocarbon bao gm nhng phn ng th v tr v phn ng th vo gc thm v phn ng cng.

5.1. Phn ng lm t lin kt OH 5.1.1. S phn ly acid carboxylic trong dung dch Xy ra theo cn bng:
CH3COOH + H2O + CHCOO - + H3O Ka =
- + [CHCOO ][H] = 1,8.10-5M [CH3COOH]

Gi tr pKa ca mt s acid trnh by trong bng 20.3. Hng s phn ly ca acid benzoic bin i theo bn cht v v tr cc nhm th trong vng benzen.
Bng 20.3: Gi tr pKa ca mt s acid benzoic c nhm th
V tr Nhom the CH3 4,37 4,27 3,91 OCH3 4,47 4,09 4,09 OH 4,54 4,08 2,98 Cl 3,98 3,83 2,94 NO2 3,43 3,49 2,17

Para Meta Orto

Ion RCOO- gi l ion carboxylat. S phn b mt in t trong ion o carboxylat ng u trn 2 nguyn t oxy v di C _O u bng 1,27A 5.1.2. Tc dng vi kim loi, oxyd, hydroxyd kim loi, mui acid yu. Nguyn t hydro ca acid c thay th bng kim loi. 2 RCOOH + Na 2 RCOOH + MgO RCOOH + NaOH 2RCOONa + H2 (RCOO)2Mg + H2O RCOONa 2RCOONa + H2 O + H2O + CO2

2 RCOOH + Na2CO3

Mui ca acid gi l x phng. X phng natri, kali d tan trong nc. Tc dng ty ra ca x phng l do gc R c s carbon ln l gc thn du, nhm

263

COO - l gc thn nc. Cc phn t nc bao quanh nhm COO -. Cc gc R c tc dng bao bc cc cht bn, du m khng tan trong nc. Do cc cht bn b nc li cun theo x phng.
H2O -

H2O -

- 2 - H2O - H2O -- H2O + - H O - 2

Du m khng tan trong nc
H2O -

H O

H O H2O - 2 - H2O - H2O

- -

H2O

H O 2

H2O -

H2O -

- H2O - H O - 2

Xa phong tan trong nc

Du m b tan theo x phng

5.1.3. Tc dng vi diazometan to metylcarboxylat (RCOOCH3)

RCOOH + CH2N2 RCOOCH3 + N2

C ch phn ng:
O R C O H O .. R C O :..

+ CH2 N N :

O .. R C O :.. O R C OCH3

+ +

+ CH3 N N :

CH3 N N: +

:N N :

5.2. Phn ng vo nhm carboxyl -Phn ng cng v tch Nhm carboxyl phn cc. Mt in t tp trung trn nguyn t oxy. in tch dng trn nguyn t carbon.
O R C O H O R C O H +

Phn ng cng hp i nhn vo nguyn t carbon sau xy ra s tch. 5.2.1. Phn ng cng i nhn c xc tc base. Tc dng vi amoniac.
CH3CH2CH2COOH + NH3 Acid butanoic

+ CH3CH2CH2CO2 NH4 Amoni butanoat

Di tc dng ca nhit , amoni butanoat b tch mt phn t nc to butanamid.

+ CH3CH2CH2CO2 NH4 Amoni butanoat

185o

CH3CH2CH2CONH2 + H2O Butanamid

264

C ch chung:
O R C O H OR C O H + NH3 .. + Cong ai nhan OR C OH NH3+ O O + R C OH2 R C NH2 + H2O NH2 Tach nc

5.2.2. Tc dng vi LiAlH4 to alcol bc nht.

RCOOH + LiAlH4 RCOOLi + H2 + AlH3
R COOLi LiAlH4 H H H + H LiAlH4 LiAlH4 H3O R C OLi R C O R C OH R C OLi H H OLi H4LiAl Ether CH3O CH2OH CH3O

CH3O COOH CH3O

H2O H2SO4

5.2.3. Phn ng cng hp i nhn c xc tc acid - Phn ng ester ha Acid tc dng vi alcol to ester. Acid v c l xc tc. Alcol l tc nhn i nhn.

R COOH + R' OH

H+

R COOR' +

H2O

Phn ng ester ha l mt phn ng thun nghch. Hn hp trng thi cn bng c khong 65% ester v nc sinh ra, 35% acid v alcol cha phn ng. Hiu sut phn ng ester ha ph thuc nng ca cht phn ng hoc phng php tch ester hay nc ra khi mi trng phn ng (nh lut Le Chtelier). C ch phn ng nh sau:
H+ R C OH + Xuc tac acid OH + R C OH + R' OH .. O OH + R C OH OH R C OH HOR' + + H+ OH R C OH OR' + H+

..

Cong ai nhan OH R C OH OR' + OH R C OR'

+ OH + Tach nc R C OH2 R C OR' OR' O R C OR' Esther +

.. : OH

+ H2O

H+ Xuc tac

265

Alcol l tc nhn i nhn c chng minh bng phng php s dng alcol c oxy ng v 18. Ester to thnh c oxy 18, nc c oxy 16 chng t nhm OH ca acid b tch ra.
+ OH
16 18

CH3 C OH +

CH3 OH ..

Cong ai nhan

CH3 C OCH3 Ester co oxy 18

18

+ H2O

16

Phn ng th nhm OH ca acid bng cc halogen Acid tc dng vi thionylclorid SOCl2, phosphorpentaclorid PCl5, phosphor tribromid PBr3 to ra sn phm acylhalogenid RCOX (X= Cl, Br).
O CH3 O C OH + Cl S Cl Thionyl clorid O C OH + PCl5 Phosphor pentaclorid O 3 C OH + PBr3 3 Phosphos tribromid O CH3 C Cl + HCl + SO2 Acetyl clorid O C Cl + HCl + POCl3 Benzoyl clorid O C Br + H3PO3 Benzoyl bromid

5.3. Phn ng decarboxyl ha (loi nhm carboxyl) Kh nng decarboxyl ha ph thuc vo cu to ca acid. Acid c nhm ht in t d b decarboxyl hn. Acid formic b decarboxyl to H2 v CO2 hoc H2O v CO ty iu kin phn ng.
HCOOH Tia t ngoai

Os

H2 + CO2 H2O + CO

HCOOH

H2SO4 ac

Acid acetic kh b decarboxyl. Mui acetat b decarboxyl ha nhit cao:

CH3COONa + NaOH CH4 + Na2CO3

Dn xut th ca acid acetic c nhm ht in t d b decarboxyl ha nh:

Cl3CCOOH; O2NCH2COOH; NCCH2COOH; CH3COCH2COOH CH3COCH2COOH CH3COCH3 + CO2

V d:

266

Mui bc ca acid carboxylic d b decarboxyl ha khi c mt ca brom to dn xut halogen tng ng (Phn ng Hunsdiecker). Phn ng xy ra theo c ch gc t do.
C6H5CH2COOAg + Br2 CCl4 76oC C6H5CH2Br + CO2 + AgBr

C th thay i Ag bng thy ngn.

2 H COOH + HgO + 2 Br2 2 H Br + CO2 + HgBr2 + H2O

5.4. Phn ng ca gc hydrocarbon 5.4.1. Phn ng oxy ha Gc alkyl c th b oxy ha to hp cht acid oxocarboxylic. Phn ng oxy ha nh xc tc men to acid -oxocarboxylic ng vai tr quan trng trong chuyn ha cht bo.
R_CH2_CH2_COOH

Enzym

R_CO_CH2_COOH Acid oxo carboxylic

Cht oxy ha l SeO2 to acid -oxocarboxylic

R_CH2_CH2_COOH + SeO2

R_CH2_CO_COOH + H2O + Se Acid oxo carboxylic

5.4.2. Phn ng halogen ha gc alkyl Phn ng th xy ra gc hydrocarbon c cc trng hp sau: Brom ha c mt ca phosphor. Phn ng th xy ra v tr .
R CH2 COOH + Br2 P R CHBr COOH Br2 P R CBr2 COOH

Phn ng clor ha xy ra theo c ch gc. Phn ng xy ra ch yu v tr v v mt lng nh sn phm th v tr .

CH3_CH2_CHCl_COOH 5% CH3_CHCl_CH2_COOH 64% CH2Cl_CH2_CH2_COOH 31%

CH3_CH2_CH2_COOH

Cl2

267

5.4.3. Phn ng th vo gc thm Phn ng th i in t vo nhn thm ca acid carboxylic xy ra v tr meta.

COOH HNO3, H2SO4 to COOH NO2

Nhm carboxyl lm cho gc thm c hot tnh thp. V vy acid benzoic khng tham gia phn ng Friedel -Craft. 5.4.4. Cc acid cha no th hin cc phn ng ca lin kt
CH2

CH

COOH + Br2

CH2Br

CHBr

COOH

6. Acid carboxylic cha no Acid khng no l nhng acid cha ni i hoc ni ba. Mt s acid cha no trnh by trong bng 20-2. Acid carboxylic cha no c th lin hp hoc khng lin hp. Acid carboxylic cha no khng lin hp bn hn acid cha no lin hp.
CH3C = CH_CH2_COOH acid 4-methyl-3- pentenoic CH3 CH3 CH3CH _ CH = CH_COOH acid 4-methyl-2- pentenoic

6.1. iu ch Cc phng php iu ch acid cha no cng ging phng php iu ch alken v iu ch acid no. Acid carboxylic cha no v cc dn xut ca n c iu ch t cc hp cht cha no tng t. 6.1.1. T dn xut halogen cha no RX RCOOH
CH2 = CH_CH2_Cl Allylclorid CuCN CH2 = CH_CH2_CN dd HCl CH2 = CH_CH2_COOH Acid vinyl acetic (52-62%) (Acid 3-butenoic)

6.1.2. Tch loi HX khi ester hoc -halogenoacid Cc ester hoc acid c halogen v tr c th b tch loi to thnh acid cha no. Cc tc nhn base c vai tr quan trng trong qu trnh tch loi to ra cc acid cha no c v tr ni i xc nh. V d di y chng t iu :

268

PBr3 CH3(CH2)9CH _COOH Br2

CH3

CH3(CH2)9CBr _COBr

CH3

CH3OH

(CH3)3COK (CH3)3COH

CH3 CH3(CH2)9C _COOCH3 Br Quinolin 160-170o

CH2 CH3 CH3(CH2)9C _COOC(CH3)3 CH3(CH2)8CH = C _COOCH3 ddKOH ddKOH H+ CH2 CH3(CH2)9C _COOH Acid 2- decyl propenoic H+ CH3 CH3(CH2)8CH = C _COOH (68-83%) Acid 2-methyl-2- dodekenoic

Nhn xt: Cc base (CH3OK; Quinolin) c tc dng tch loi trc tip to lin kt i. Acid cha no n gin nht l propenoic (acid acrylic). Nitril tng ng l CH2 =CH_CN (acrylonitril). Chng l nguyn liu quan trng trong cng nghip cht polymer. iu ch acrylonitril bng cch oxy ha propen c xc tc vi amoniac.
CH3CH=CH2 + 3 O2 + 2NH3 450o Xuc tac 2 CH2=CH_CN + 6 H2O

Cc ester cha no c nhiu trong thin nhin. Cc acid cha no thng gp:
Acid Oleic Acid Ricinoleic Acid Linoleic Acid Linolenic CH3(CH2)7CH=CH(CH 2)7COOH CH3(CH2)5CHOHCH 2CH=CH(CH 2)7COOH CH3(CH2)4CH=CHCH 2CH=CH(CH 2)7COOH CH3CH2CH=CHCH 2CH=CHCH 2CH=CH(CH 2)7COOH

6.2. Tnh cht ha hc Th hin tnh cht cha no ca lin kt v tnh cht ca nhm carboxyl. Acid cha no c mt s tnh cht c trng nh: Tnh acid mnh hn acid no tng ng.
CH3CH2CH2COOH pKa= 4,82 CH3CH=CHCOOH pKa= 4,6

269

 Phn ng to lacton l phn ng ng vng to ester ni phn t.

CH2 CH CH2

CH2 C

+ H+ OH

CH2

CH2

CH2 CH3 CH

CH2 C O

+ CH3 CH .. C O HO

Acid allylacetic

O Valerolacton

Acid , cha no kh to lacton. Vng lacton bn vng khi c vng 5, 6 cnh. 7. Acid a chc - polyacid Cc diacid c trnh by trong bng 20-4.
Bng 20.4. Cng thc, tn gi v gi tr pKa ca mt s diacid
Cng thc Tn gi tco pKa1 pKa2

HOOC_COOH HOOC_CH2_COOH HOOC_(CH2)2_COOH HOOC_(CH2)3_COOH HOOC_(CH2)4_COOH HOOC_(CH2)5_COOH HOOC_(CH2)6_COOH HOOC_(CH2)7_COOH HOOC_(CH2)8_COOH

Acid Oxalic, Etandioic Acid Malonic, Propandioic Acid Succinic, Butandioic Acid Glutaric, Pentandioic Acid Adipic, Hexandioic Acid Pimelic, Heptandioic Acid Suberic, Octandioic Acid Azelaic, Nonandioic Acid Sebacic, Decandioic Acid Maleic z-2-Butendioic

189,5 135,6 185. 97,5 153 104 142 106 134 137

1,27 2,86 4,21 4,34 4,41 1,92

4,27 5,70 5,64 5,27 5,28 6,23

HOOC H HOOC H

C C

COOH H H COOH

Acid Fumaric, E-2-Butendioic

287

3,02

4,38

C C COOH COOH COOH

Acid Phtalic, 1,2-Benzendicarboxylic

208

2,58

5,62

Acid Isophtalic, 1,3-Benzendicarboxylic

346

COOH COOH HOOC

Acid Terephtalic, 1,4-Benzendicarboxylic 300 -

270

Tnh cht ha hc Nhm acid nh hng qua li ln nhau. Tnh acid ca diacid mnh hn monoacid. Tnh acid ca diacid gim dn khi chc acid cng xa nhau. Diacid to 2 mui, 2 ester.
KOH - H2O C2H5OH, H+ - H2O COOH COOK KOH - H2O COOK COOK COOC2H5 COOC2H5 Diethyl ftalat

COOH COOH

COOC2H5 C2H5OH , H+ COOH - H2O

Acid oxalic v acid malonic d b decarboxyl to acid n chc.

HOOC_COOH

to to

HCOOH + CO2 CH3_COOH + CO2

HOOC_CH2_COOH

Diacid d to thnh anhydrid vng.

O CH2 CH2 COOH COOH

CH2 CH2

C O C + H2O

Acid Succinic
COOH COOH Acid Ftalic

O Anhydrid Succinic
C C O O O Anhydrid Ftalic + H2O

Bi tp
1. Gi tn cc cht sau theo danh php IUPAC:
a- ClCH2CH2CH2CH2COOH b- (CH3)3CCH2CH2CH2COOH c- CH3CH2CH(CH3)CH2CHCOOH d- CH2=CHCH=CHCOOH

2. Acid formic c hng s phn ly Ka = 1,77.10-4M. Tnh gi tr pKa. Tnh nng ca ion formiat trong dung dch acid formic 0,1M.

271

3. Hy thc hin cc chuyn ha sau:

a- (CH3CH2CH2)3CBr (CH3CH2CH2)3CCOOH HOCH2CH2CH2CH2CH2CH2COOH CH3CH2CH2CH2CH2COOH

b-HOCH2CH2CH2CH2CH2CH2Br c- CH3CH2CH2CH2CH=CH2

4. Vit phng trnh phn ng ca acid 3-methylpentanoic vi cc cht sau: a. Diazometan trong ether. b. Tc dng vi NaOH v tip theo vi metyl iodur trong dioxan. 5. Vit phng trnh phn ng ca acid hexanoic vi: a. Ethanol c mt H2SO4 m c. c. Phosphor pentaclorid. 6. Trnh by c ch phn ng ester ha.
CH3COOH + C2H5OH H2SO4 CH3COOC2H5 + H2O

b - Thionyl clorid. d- Phosphor tribromid.

272

Chng 21

CC DN XUT CA ACID CARBOXYLIC

Mc tiu 1. Trnh by c s hnh thnh cc loi dn cht acid carboxylic v nguyn tc chung gi tn chng. 2. Nu c tnh cht ha hc ca cc dn cht acid carboxylic.

Ni dung
Khi thay th nhm OH ca acid carboxylic bng nhng nhm th khc nhau thu c cc dn xut nhm chc ca acid carboxylic.
R C O R C O

OH Acid carboxylic

Y Dan xuat cua acid carboxylic

Trong bng 21-1 trnh by cc loi dn xut ch yu ca acid carboxylic.

Bng 21.1: Mt s dn xut ca acid carboxylic
Cng thc Loi dn xut acid Cng thc Loi dn xut acid

R C

O
Hal (F , Cl, Br , I) O C R

Halogenid acid

R C

O
OR'

Ester

O R C O O

Anhydrid acid

R C

O
NR2

Amid

R C

Acid Hydroxamic

NHOH

R C

O
NH NH2

Hydrazid

R C

O
N3

Azid

R_CN

Nitril

O R C O OH

Peroxyacid

R R

C C O

Ceten

273

Cng c th xem nitril l dn xut ca acid khi thay th nhm OH v C =O ca acid bng nguyn t nit -N. Ceten cng c th xem l dn xut ca acid carboxylic. Chng ta s nghin cu mt s dn xut quan trng: Ester, halogenid acid, anhydrid acid, amid, nitril v ceten. 1. Ester Ester l sn phm th nhm OH ca acid carboxylic -RCOOH bng nhm alkoxy R'O ca alcol (hay nhm aroxy ArO - ca phenol). Bng 21-3 trnh by cc ester.
RCOOH RCOOR'

1.1. Cu to di v gc lin kt ca ester methyl formiat trnh by trong bng 21-2.

Bng 21.2
di lin kt (A )
o

Gc lin kt ()

H C O CH3 Methyl formiat O

C=O.............1,200 C(=O)_O.......1,344 C(H3)_O.......1,437 C(=O)_H.......1,101

H_C=O.........124,95 O_C=O.........125,87 H_C_O.........109,78 CH3_O_C....114,78

1.2. Danh php C th xem ester nh l mt mui ca acid hu c. Cch gi tn ca ester l c tn gc alkyl ca alcol v c tn acid tng ng thay ''ic" ca acid bng " at"
Tn gc alkyl ca alcol + Tn ca carboxylat tng ng
O Goc alkyl cua alcol O CH3 C O CH2CH3 Ethyl acetat Ethyl etanoat CH3 O CH3 CH C O CH(CH3)2 Isopropyl isobutyrat Isopropyl-2-methylpropanoat

R C O R' Alkylcarboxylat

Danh php mt s ester trnh by trong bng 21-3

274

Bng 21.3. Danh php v tnh cht l hc ca mt s ester

Cng thc Tn gi tco tso

d20 4
0,975 0,917 0,924 0,901 0,887 0,882 0,871 0,898 0,832 1,094 1,051 1,235 1,148

HCOOCH3 HCOOC2H5 CH3COOCH3 CH3COOC2H5 CH3COOC3H7n CH3COOC4H9 CH3COOC5H11 CH3CH2CH2COOCH3 CH3(CH2)14COO(CH2)15CH3 C6H5COOCH3 C6H5COOC2H5 C6H5COOC6H5

Methylforniat Ethylformiat Methylacetat Ethylacetat n-Propyl acetat Butyl acetat Amylacetat Methylbutyrat Cetylpalmitat Methylbenzoat Ethylbenzoat Phenylbenzoat Dimethyl oxalat

- 99,9 - 80,5 - 98,1 - 83,6 - 92,5 -76,8 -78,5 -95,5 55,5 - 12,5 - 34,6 70,0 - 54,0

31,5 54,3 57,1 77,1 101,6 126,5 142,6 102,3 199,6 212,6 314,0 163,8

COOCH3 COOCH3 COOC2H5 COOC2H5

CH2(COOCH3)2

Diethyl oxalat

- 40,6

185,4

1,078

Dimethyl malonat

- 62,0

181,0

1,151

CH2COOCH3 CH2COOCH3
o-C6H4(COOCH3)2

Dimethyl succinat

19,5

192,8

1,120

Dimethyl ftalat

49,5

1.3. Phng php iu ch 1.3.1. Phng php ester ha. Xem phn alcol v acid.
RCOOH + R'OH CH3COOH H2SO4 RCOOR' + H2O H2SO4 CH3COOC2H5 + H2O

+ C2H5OH

Phn ng iu ch ester ethylacetat l phn ng thun nghch c hng s cn bng:

K= [CH3COOC2H5][H2O] = 4 [CH3COOH] [C2H5OH]

Nh vy c khong 66% c chuyn ha thnh ester. Mun tng hiu sut ester, tc l chuyn dch cn bng v pha bn phi, ta c th tng nng ca 275

mt trong 2 cht phn ng (alcol hoc acid) hoc tch sn phm (ester hoc nc) bng cch chng ct. Phn ng ester ha xy ra chm. Hn hp ng phn t ca CH3COOH v C2H5OH nhit phng cn khong 16 nm mi t ti cn bng. tng tc phn ng, ngoi vic un nng hn hp, ngi ta cn dng cc cht xc tc nh H2SO4 m c, HCl khan... 1.3.2. Acyl ha alcol bng anhydrid acid. Xem phn alcol
ROH + (R'CO)2O RCOOR' + R'COOH.

1.3.3. Acid carboxylic tc dng vi diazometan. Xem phn acid.

RCOOH + CH2N2 RCOOCH3 + N2

1.3.4. Phn ng Claisen - Tishenco. Xem phn acid 1.3.5. Phn ng gia mui ca acid carboxylic vi dn xut halogen RCOONa + R'Cl RCOOAg + R'Br 1.4. Tnh cht l hc Ester thng c mi thm. t tan trong nc. Ester c trong cc loi tinh du, cht bo v sp. Mt s tnh cht vt l ca ester trnh by trong bng 21-3. 1.5. Tnh cht ha hc 1.5.1. Phn ng thy phn Thy phn trong mi trng acid RCOOR' + NaCl RCOOR' + AgBr

RCOOR' +

H2O

RCOOH + R'OH

C ch phn ng thy phn Phn ng ester ha l phn ng thun nghch. i vi ester ca alcol bc nht v bc hai th c ch thy phn l phn ng ngc li ca phn ng ester ha c trnh by trong phn acid. i vi ester ca alcol bc ba th c ch thy phn c xc tc acid nh sau:

276

O CH3 C + OH

O C CH3 CH3 CH3 CH3

CH3

+OH + H+ CH3 C

O C CH3 CH3 CH3 +C CH 3 CH3

CH3

CH3 C O : C CH3

OH CH3 C O

H2 O

CH3 +C CH 3 CH3

HO C CH3 CH3

CH3

+ H+

Thy phn trong mi trng base Cn gi l phn ng x phng ha. Thy phn ester trong mi trng base to mui carboxylat l phn ng khng thun nghch. V alcol to thnh c tnh acid yu hn tnh acid ca acid carboxylic.
RCOOR' + HO- RCOO- + R'OH

C ch phn ng thy phn c xc tc base.

O R C OR'

+ HO -

O OR' OH

O
R C

R C

: OR'

R C OH

R'O -

OH

O R C OH +

R'O -

O R C O+ R'O H

1.5.2. Phn ng chuyn i ester Khi un ester vi alcol c xc tc acid hoc natri alcolat xy ra phn ng trao i ester.
O R C O R'

+ R"OH

H+

O R C

O R" + R'OH
CH2=CH_COOC4H9 + CH3OH

CH2=CH_COOCH3 + C4H9OH

CH3C6H4SO3H

277

1.5.3. Phn ng vi amoniac v mt s dn xut ca amoniac

RCOOR' Ester RCOOR' + + NH3 Amoniac HNR"2 Amin RCOOR' + H2N_NH2 Hydrazin RCOOR' + H2NOH Hydroxylamin RCO_NH2 Amid RCO_NR''2 Amid th RCO_NH_NH2 + Hydrazid RCO_NHOH + R'OH R'OH + R'OH + R'OH

Acid hydroxamic

1.5.4. Phn ng vi hp cht c kim to alcol bc ba (Xem cht c kim) 1.5.5. Phn ng kh Ester b kh bng LiAlH4, NaBH4 v hn hp Na + alcol (phn ng Buve Blanc) to ra alcol bc nht.
R COOR' 4[H] R CH2OH + R'OH Na+ C2H5OH CH3(CH2)7CH=CH(CH2)7COOC4H9 CH3(CH2)7CH=CH(CH2)7CH2OH + HOC4H9 Butyl oleat Alcol oleic

1.5.6. Phn ng ca nhm methylen linh ng Phn ng ngng t Claisen. Khi c tc dng ca natri kim loi hoc natri alcolat, hai phn t ester c th ngng t vi nhau to ester ca acid -cetocarboxylic.
O R C OC2H5 + R' H CH COOC2H5 NaOC2H5 O R C R' CH COOC2H5 + C2H5OH

Cc ester ca acid bo vi glycerin gi l cht bo (lipid).

R1CO OCH2 HOCH HOCH2 Monoacylglycerin Monoglycerid R1CO R2CO OCH2 OCH HOCH2 Diacylglycerin Diglycerid R1CO R2CO R3CO OCH2 OCH OCH2

Triacylglycerin Triglycerid

278

R1, R2, R3 l cc gc hydrocarbon no hoc cha no, khng phn nhnh c t 11-19 nguyn t carbon. Lipid cng c th l ester ca acid bo v acid phosphoric. Cc acid bo thng gp nh: Acid lauric Acid palmitic Acid stearic Acid oleic Acid linoleic CH2(CH2)10COOH, CH3(CH2)14COOH CH3(CH2)16COOH; CH3(CH2)7CH=CH(CH2)7COOH, CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH,

Acid linolenic CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH Acid stearolic CH3(CH2)7CC(CH2)7COOH,

CH2 O CO(CH2)14CH3 CH O CO(CH2)14CH3 CH2 O CO(CH2)14CH3 Lipid CH2 O COR1 CH O COR2 O + CH2 O P OCH2CH2N(CH3)3 OPhospholipid Lecitin

Tripalmitatglicerin

2. Anhydrid acid Hai phn t acid b loi nc to thnh anhydrid acid. Cng thc chung:

O R C OH OH R C O Acid R C

O O R C O Anhydrid acid

Anhydrid acid ht nc to thnh acid. ng dng iu ch anhydrid acid.

OH OH CH2 C O Acid succinic

CH2 C

O + (CH3CO)2O Anhydrid acetic CH2 C CH2 C

O O + 2 CH3COOH Acid acetic

O Anhydrid succinic

Trong bng 21-4 trnh by cng thc, tn gi v tnh cht vt l ca mt vi anhydrid.

279

Bng 21.4. Cng thc, tn gi v tnh cht l hc ca mt s anhydrid acid

Cng thc (CH3CO)2O (C2H5CO)2O (C3H7CO)2O (n-C4H9CO)2O (n-C17H35CO)2O
CH2 CH2 C C O O O

Tn gi Anhydrid acetic Anhydrid propionic Anhydrid n-butyric Anhydrid n-valeric Anhydrid stearic.

t co -73,0 -45,0 -75,0 72,0

t so 139,6 168,0 198,0 218,0

Anhydrid succinic

119,6

261,0

(C6H5CO)2O
O C O C O

Anhydrid benzoic

42,0

360,0

Anhydrid phtalic

132,0

284,0

CH CH

C C

O O O

Anhydrid maleic

53,0

Anhydrid acid l tc nhn acyl ha.

NH2 + (CH3CO)2O Acetanilid NHCOCH3 + CH3COOH

3. Ceten (CH2 = C = O) C th xem ceten l anhydrid acid khi phn t acid b loi mt phn t nc.
CH2 C H OH Acid CH3 CH C Methylceten O CH3 C C O O CH2 C Ceten R CH C O R C C O O + H2O

CH3

R'

Dimethylceten

Alkylceten

Dialkylceten

280

Cc phn ng ca ceten Cc ceten nh l mt tc nhn acyl ha.

CH2 C
-

.. O ..

CH2

+ C

.. O: ..

H+

CH2

+ C

.. OH ..

B-

CH2 C

.. OH ..
B

CH3 C

O .. B

..

B l nhng cht i nhn nh H2O, alcol, acid, amoniac.

H2O ROH CH2 C O RCOOH CH3 C CH3 C O OH O OR O O O O NH2 Anhydrid acid Acid Ester

CH3 C R C

NH3

CH3 C

Amid

4. Halogenid acid acyl halogenid Thay nhm OH ca acid carboxylic bng halogen (X) thu c halogenid acid. RCOOH 4.1. Cu to Nguyn t halogen c cp in t khng lin kt lin hp vi lin kt ca nhm C=O v vy phn t acyl halogenid c cc trng thi nh sau: RCOX

.. :O
CH3 C Cl : ..

.. : O: ..
CH3 C + Cl : ..

Acetyl clorid

di lin kt v gc lin kt ca acetyl clorid trnh by trong bng 21-5.

Bng 21.5. di v gc lin kt ca acetyl clorid
Acetyl clorur di lin kt Gc lin kt

O CH3 C Cl

C=O........ 1,192 C_C..........1,499 C_Cl.........1,789 C_H..........1,083

C_C=O......127,08o C_C_Cl......112,66o O=C_Cl......120,26o

281

4.2. Danh php c tn acid nhng thay tip v ng ca acid " ic" thnh "yl" hoc "oic"thnh " oyl" v c tn ca halogen CH3COCl CH3CH2COF Acetyl clorid, Etanoyl clorid

Propionyl florid, Propanoyl fluorid

Bng 21.6 trnh by cng thc, tn gi v tnh cht l hc ca mt s acyl halogenid

Bng 21.6. Tn gi, cng thc v tnh cht l hc ca acyl halogenid
Tn gi Cng thc t oc t os

Acetylflorid, Etanoylflorid Acetylclorid, Etanoyl clorid Acetylbromid, Etanoyl bromid Cloroacetylclorid Propionylclorid n-Butyrylclorid Isobutyrylclorid n-Valerylclorid Isovalerylclorid n-Caproylclorid Caprylclorid Stearylclorid Benzoylclorid

CH3COF CH3COCl CH3COBr CH2ClCOCl CH3CH2COCl CH3CH2CH2COCl (CH3)2CHCOCl CH3CH2CH2CH2COCl (CH3)2CHCH2COCl n-C5H11COCl CH3(CH2)6COCl CH3(CH2)16COCl C6H5COCl

20,5 52,0 76,7 105,0 80,0 102,0 92,0 128,0 113,0 153,0 196,0 215,0 197,0

0,993 1,104 1,520 1,495 1,065 1,028 1,017 1,016 0,975 1.212

4.3. Mt s tnh cht ha hc thng ng dng 4.3.1. Hp cht halogenid acid rt d thy phn to acid
O R C Cl + H2O O R C OH + HCl

4.3.2. Tc dng vi hp cht c kim to ceton hoc alcol bc ba

O R C Cl R'MgX O R C R' R'MgX OMgX R C R' R' H2O OH R C R' R'

4.3.3. Hp cht halogenid acid l tc nhn acyl ha to ceton,ester

O + R C Cl O R'OH + R C Cl AlCl3 O R C OR' + HCl O C R + HCl

282

5. Amid Thay th nhm OH ca acid carboxylic bng nhm NH2 thu c amid.
O R C OH Acid O R C NH2 Amid O R C NHR' R' R C N R" Amid the O

5.1. Danh php c tn acid c s carbon tng ng nhng thay tip v ng " ic" hoc "oic" bng tip v ng "amid" Chc CONH2 cn c gi l carboxamid
O H C NH2 O CH3 C NH2 O CH3CH2 C NH2 O H C N(CH3)2 O CH3CH2CH2 C NHCH3

Formamid Acetamid Metanamid Etanamid Metan carboxamid

Propionamid N,N-Dimethylformamid N-Methylbutyramid Propanamid N,N-Dimethylmetanamid N-Methylbutanamid 1-Propan-N-methylcaboxamid Etancarboxamid

CONH2 Benzamid Benzencarboxamid

CONH2

CONH2

CH2 CH

CONH2

Acrylamid Cyclohexancarboxamid 3-Cyclopentencarboxamid Etencarboxamid

Trong bng 21-7 trnh by mt s amid.

Bng 21.7: Tn gi, cng thc ca mt s amid
Tn gi Cng thc t oc

n-Valeramid n-Caproamid Steramid Benzamid Cinnanamid Succinamid

n-C4H9CONH2 n-C6H11CONH2 C17H35CONH2 C6H5CONH2 C6H5CH=CHCONH2 H2NCOCH2CH2CONH2

106 101 109 130 260

Cc amid th lng c nhit si cao v c lin kt hydro gia cc phn t.

...

O C NH2 CH3

Cng thc

...

tso

C NH2 ... O CH3

CH3_CONH2 CH3_CONHCH3 CH3_CON(CH3)2

221 204 165

C NH2 ... O CH3

C NH2 ... CH3

Lien ket hydro cua amid

283

Cp in t trn nit lin hp vi lin kt ca nhm C = O nn tnh base ca nhm NH2 gim.
O R C NH2

..

+ R C NH2

-O

5.2. Cc phn ng ca amid 5.2.1. Phn ng acid -base Amid l mt base yu ch tc dng vi nhng acid mnh. S proton ha xy ra nguyn t oxy.
R C O .. NH2

..

..

+ H+

R C

+ OH NH2

..

R C

OH .. NH2 +

..

Amid l mt acid yu. Amid tc dng vi natri hoc natri amidid trong ether to mui.
R C O ..

..

NH2

..

+ Na

R C

O .. NHNa

.. ;
R C

..

NH ..

O ..

..

..

R C

O: ..

.. -

NH ..

5.2.2. Thy phn amid Trong mi trng acid hoc base amid thu phn to thnh acid hoc mui. RCONH2 + H2O 5.2.3. Phn ng loi nc Di tc dng ca cc cht ht nc nh P2O5 v nhit , amid b loi nc to thnh nitril (RC N)
O (CH3)2CH C NH2 Isobutyramid P2O5 200 _ 220oC (CH3)2CH C N + H2O Isobutyronitril

RCOOH + NH3

5.2.4. Khi c nhit cc amid ca diacid d to thnh imid

CH2 CONH2 CH2 CONH2 Succinamid Nhiet CH2 CH2 C C O NH O

Succinimid

284

CONH2 CONH2 Phtalamid

Nhiet

O NH

C Phtalimid O

5.2.5. Chuyn v Hofmann Amid tc dng vi hn hp Br2 + NaOH to thnh amin.

R C NH2 + OBr Amid O
2R NH2 + CO3 + Br Amin bac nhat

C ch phn ng:
O R C NH2 Amid O + OBr -

2NaOH + Br2
O R C N Br H O

NaOBr + NaBr + H2O

..

+ OH

R C N Br + OH
H

..

R C N Br + H2O .. O

..

.. R C N Br ..
R: C N + .. Chuyen v O

R C N+ ..

..

+ Br -

..

O=C=N_R Isocyanat

O=C=N_R + 2OH
Isocyanat

2R NH2 + CO3 Amin bac nhat

V d:
CH3CONH2 + 2NaOH + Br2 C6H5CONH2 + 2NaOH + Br2 C6H5CH2CONH2 +2NaOH+Br2 CH3NH2 + Na2CO3 + NaBr + H2O

C6H5NH2 + Na2CO3 + NaBr + H2O C6H5CH2NH2 + Na2CO3 + NaBr +H2O

5.2.6. Kh ha amid bng LiAlH4, NaBH4 to thnh amin

R C O NH2 4H [LiAlH4] R CH2 NH2

6. Nitril (R-C=N) Nitril c cu trc R_CN v Ar _CN

285

6.1. Danh php nitril Danh php IUPAC: c tn hydrocarbon tng ng v thm nitril. Danh php thng thng: Gi tn ca gc acyl c s carbon tng ng v thm nitril. Gi tn gc hydrocarbon tng ng v thm cyanid
CH3_CN CH3CH2_CN C6H5_CN CH2=CH_CN

C N
Cyclopentylcyanid

Etannitril Acetonitril Methylcyanid

Propannitril Propionitril Ethylcyanid

Benzonitril Phenylcyanid

Propennitril Acrylonitril Vinylcyanid

a s cc hp cht nitril c c cao. 6.2. iu ch nitril T dn xut halogen v natri cyanid

R_X + NaCN R_CN + NaX

T amid v cht ht nc P2O5

R_CONH2 R_CN + H2O

6.3. Cc phn ng ca nitril Thy phn nitril Trong mi trng acid hoc base thy phn nitril to acid hoc mui ca acid.
CH3 C N

+ H2O

O CH3 C NH2

+ H2O
- NH3

O CH3 C OH

Kh ha nitril Kh bng LiAlH4, NaBH4 hoc natri trong alcol to thnh amin bc nht
R C N 4H [LiAlHl4] R CH2 NH2

Tc dng vi hp cht c kim - RMgX (xem phn hp cht c kim). Cc arylcyanid - ArCN c th b trimer ho to hp cht d vng triazin.
Ar 3 Ar C N Arylcyanid N Ar N N 2,4,6-Triaryl-1,3,5-Triazin Ar

286

Bi tp
1. T cc acid sau:
a- CH3CH2CH2CH2CH2COOH c- CH2=CHCH2CH2COOH b- (CH3)2CHCH2CH2COOH d- BrCH2CH2COOH

Hy vit cng thc ester, amid, acylclorid, anhydrid v nitril ca acid tng ng. Gi tn nhng cht . 2. Gi tn cc hp cht sau: a. (CH3)2CHCH2CH2COOCH2CH(CH3)2 b. (CH3)3CCH2CH2CON(CH2CH3)2 c. (CH3CH2CH2CO)2O d C6H5CH2CN 3. Hy vit phn ng cc giai on thy phn acetamid trong mi trng acid 4. Thc hin s chuyn ha: Propionamid Ethylamin

Trnh by c ch phn ng .

287

Chng 22

HP CHT AMIN

Mc tiu 1. Gii thch c cu to ca cc amin v gi c tn chng theo danh php quc t. 2. Nu c ha tnh ca amin mch thng v amin thm ng thi nu c phng php phn bit cc bc ca amin thng cng nh amin thm. Ni dung 1. Cu to Amin l nhng hp cht c cc gc alkyl, gc aryl lin kt trc tip vi nguyn t nit. C th xem amin l dn xut ca amoniac (cng nh alcol, ether l dn xut ca nc). Amoniac Nc NH3 H2 O RNH2 ROH R2NH R2O R3 N R l gc alkyl hoc aryl - Ar

1.1. Phn loi amin Amin bc nht: C mt gc hydrocarbon lin kt vi nguyn t nit: RNH2 Amin bc hai: C hai gc hydrocarbon lin kt vi nguyn t nit: RR 'NH Amin bc ba: C ba gc hydrocarbon lin kt vi nguyn t nit: RR 'R''N Ion amoni bc 4: R4 N + 1.2. Cu trc khng gian ca amin Phn t amoniac c cu trc hnh thp. di lin kt N _H l 1.008 . Gc lin kt HNH l 1073. Nguyn t nit trng thi gn nh lai ha sp3 v to thnh 3 lin kt (sp3_s) gia 3 orbital sp3 ca nit vi orbital s ca 3 nguyn t hydro. Cp in t khng lin kt nm trn orbital sp3 th t. Cc amin cng c cu to nh th.
..
N H H H H

..
N H R H

..
N R' R R''

..
N R R'

Amoniac

Amin

288

Do cu trc kiu t din, amin vi cc gc R khc nhau c tnh i quang (chiral). Hai i quang d dng chuyn ha ln nhau. trng thi chuyn tip, nguyn t nit c trng thi lai ha sp2.

..
N C2H5 H CH3 C2H5

..
N

CH3 H

C2H5 N

CH3 H

..
Ethylmethylamin

Ethylmethylamin

Trng thi chuyn tip

Cp in t khng lin kt c vai tr quan trng trong tnh cht ha hc ca amin: tnh base v tnh i nhn. 2. Danh php C cc cch gi tn, ty thuc cch s dng thut ng amin. 2.1. Amin l tip v ng (suffixe). Gi tn cc gc hydrocarbon v thm amin
Tn gc hydrocarbon + amin
CH2CH3 CH2CH3 C6H4CH3 p

CH3NH2 Methylamin Metanamin

(CH3CH2)2NH Diethylamin N-Ethyletanamin

CH3 Diethylmethylamin N-Methyl,N-Ethyletanamin

CH2CH3

C6H5

Ethyl, phenyl,p-tolylamin N-Ethyl,N-p-Tolylbenzenamin

2.2. Theo danh php IUPAC Gi tn hydrocarbon tng ng v thm tip v ng amin
Tn hydrocarbon tng ng + amin
NH2 N(CH3)2 CH3 Benzenamin N,N-Dimethylbenzenamin 4-Methylbenzenamin NH2

2.3. Amin l tip u ng (prefixe) Theo danh php IUPAC. Gi tn hydrocarbon tng ng, thm tip u ng amino.
Amino + Tn hydrocarbon tng ng CH3NH2 CH2=CHCH2NH2 CH3CH2N(CH3)2 C6H5NHCH3

Aminometan

3-Amino-1-propen

Dimethylaminoetan Methylaminobenzen

289

Ch c tn cc gc:
C6H5NH_ CH3(C2H5)N_ p-CH3C6H4NH- C10H7NH-

Phenylamino Methylethylamino p-Toluylamino

NH2

-Naphtylamino

S dng tip u ng amino gi tn nhng hp cht c nhm chc amin.

NH2 NH2

COOH Acid p-Aminobenzoic

CH3 p-Toluidin p-Aminotoluen

Acid Sulfanilic Acid p-Aminobenzensulfonic

SO3H

2.4. Danh php cc amin thm Theo danh php IUPAC, quy c aminobenzen l anilin. Cc amin thm n gin c c tn theo anilin.
NH2 NH2 Br Anilin m-Bromoanilin N,N-dimethylanilin N(CH3)2

3. iu ch 3.1. Alkyl ha trc tip amoniac v cc amin khc Phn ng gia amoniac v alkylhalogenid bc nht to thnh amin bc nht. Phn ng xy ra theo c ch SN2.
CH3CH2Br + NH3 + CH3CHNH3Br + NaOH -NaBr -H2O CH3CH2NH2

Trong thc t thng thu c hn hp cc amin c bc khc nhau.

RX + NH3 -HX RNH2 RX -HX RNHR RX -HX (R)3N

Cc amin bc nht tc dng vi alkylhalogenid thu c amin bc hai. Tnh cht i nhn ca amin thm yu hn amin mch thng. Anilin tc dng vi alkyl halogenid ch yu thu c amin bc hai.
NH2 + C6H5CH2Cl Anilin Benzylclorid

-+ Cl NH2CH2C6H5
-NaCl -CO2 -H2O NaHCO3

NHCH2C6H5

Benzylphenylamoniclorid

Benzylphenylamin

290

3.2. Tng hp Gabriel. Alkyl ha khng trc tip Xut pht t phtalimid, alkylhalogenid s thu c alkylamin bc nht. Phn ng xy ra nh sau:
C C O N H + NaOH - H2O C C O N O

+ R_X -X-

C C

O NR O

H2O

HO -

R_NH2 +

COO COO Ion phtalat

O Phtalimid

Ion phtalimid

Alkylphtalimid

Alkylamin

Ion phtalimid l mt tc nhn i nhn, tc dng vi alkylhalogenid (RX) to alkylphtalimid. Alkylphtalimid b thy phn to alkyl amin bc nht. 3.3. Kh ha hp cht nitro Kh ha hp cht nitro to hp cht amin. Cht kh thng dng l kim loi trong mi trng acid, hoc hydro phn t c xc tc. ArNO2 + 3Fe + 6HCl
CH3 NO2

ArNH2 + 3FeCl2 +2H2O

CH3 + 3H2 / Ni Ap suat, to NH2

+ 2H2O

CH(CH3)2 2-Nitro-5-isopropyltoluen

CH(CH3)2

2-Methyl-5-isopropylanilin

y l phng php thng s dng iu ch cc amin thm. 3.4. Kh ha hp cht nitril (RC N) Kh ha hp cht nitril bng hydro phn t c xc tc hoc bng LiAlH4 trong mi trng ether to amin bc nht.
RC N H2 / xc tc hoc LiAlH4 RCH2 NH2

3.5. Kh ha hp cht imin (RCH =NH) Xut pht t aldehyd hoc ceton v amoniac thu c hp cht imin. Trong trng hp ny imin l hp cht khng bn d b kh ho v to thnh amin. Kh ha imin bng hydro phn t c xc tc.
RCHO + NH3
RCH=NH Aldimin + 2H2

RCH=NH + H2O
RCH2 NH2 Amin bc nht

xc tc

291

Xut pht t ceton v amoniac thu c cetimin (cetoimin). Kh ha cetimin thu c amin bc hai. 3.6. Kh ha hp cht amid (RCONH2) Kh ha hp cht amid bng LiAlH4 thu c amin.
RC O NH2 + LiAlH4 R CH2NH2 + H2O + Al3+ + Li+

+ ...

H O C N(CH3)2

+ LiAlH4

H CH2 N(CH3)2

+ ...

N,N-Dimethylcyclohexancarboxamid

N,N-Dimethylcyclohexylmetanamin

3.7. Phng php chuyn v Hofmann Cc amid tc dng vi halogen trong mi trng kim to amin. Phn ng qua giai on chuyn v Hofmann. CH3(CH2) 8CONH2 + Cl2 + HO- CH3 (CH2) 8NH2 + CO2 + HCl + Cl Decanamid Nonanamin C ch chuyn v Hofmann (xem phn amid). 4. Tnh cht l hc Cc amin aliphatic l nhng cht khng mu, tan trong nc. Cc amin c t 3 nguyn t carbon dng lng. tan trong nc gim khi phn t lng tng. Cc amin thm l cht lng hoc rn khng mu. B ha nu v en dn khi tip xc vi khng kh. Cc amin thm u c mi kh chu. Cc amin bc nht, bc hai c lin kt hydro gia cc phn t. V vy nhit si ca amin cao hn cc hydrocarbon tng ng. Tnh cht vt l ca amin c trnh by trong bng 22-1. Amin bc nht c nhit si cao hn amin bc hai v bc ba c cng trng lng phn t. Nguyn nhn l amin bc nht d to lin kt hydro gia cc phn t. 5. Tnh base ca amin Vi s hin din ca cp in t khng lin kt trn nguyn t nit, amin c xem l nhng base Lewis nh alcol, ether. Nhng m in ca nit nh hn oxy do amin c tnh base mnh hn alcol v ether.

292

Bng 22.1: Tnh cht l hc ca cc amin

Cng thc CH3NH2 (CH3)2NH (CH3) 3N CH3CH2NH2 (CH3CH2)2NH (CH3CH2)3N CH3CH2CH2NH2 C6H5NH2 C6H5NHCH3 C6H5N(CH3)2 o-CH3C6H4NH2 m-CH3 C6H4NH2 p-CH3C6H4NH2 C6H5CH2NH2 C6H5NH C6H5 Tn gi Methylamin Dimethylamin Trimethylamin Ethylamin Diethylamin Triethylamin Propylamin Anilin, aminobenzen N-Methylanilin N,N-Dimethylanilin o-Toluidin, 2-Aminotoluen m-Toluidin, 3-Aminotoluen p-Toluidin, 4-Aminotoluen Benzylamin
-Aminotoluen

tc - 92,5 - 96,0 - 124,0 - 80,6 - 50,0 - 11,5 - 83,0 6,2 - 5,7 2,5 - 27,7 - 43,6 43,7

ts - 6,5 7,4 3,5 16,6 55,8 89,5 48,7 184,4 196,3 192,5 199,7 203,2 200.4 185,0

pKa 10,62 10,77 9,80 10,63 10,93 10,87 10,58 4,58 4,85 5,06 4,39 4,69 5,12 -

Diphenylamin
-Naphtylamin

54,0 50,0

302,0 301,0

NH2

1-Aminonaphtalen

NH2

-Naphtylamin

2-Aminonaphtalen

50,0

306,0

Trong dung dch nc cc amin c cn bng nh sau:

RNH2 + H2O + Kb RNH3 + HO + [RNH3][HO -] [RNH2]

+ RNH3 + H2O

Ka RNH + H O + 2 3 + [RNH2][H3O ] + [RNH3]

Kb =

Ka =

C mi quan h Ka.Kb = 1O-14 v pKa + pKb = 14 Gi tr pKb ca mt s amin v gi tr pKa ca cc ion amoni tng ng (acid lin hp) c trnh by trong bng 22-2.

293

Bng 22.2: Tnh base ca mt s amin

Amin pKb, 25C Acid lin hp A pKa, 25C

NH3 CH3NH2 CH3CH2NH2 (CH3)3CNH2 (CH3) 2NH (CH3CH2)2NH (CH3)3N (CH3CH2)3N

4,76 3,38 3,36 3,32 3.27 3,06 4,21 3,25

NH4+ CH3NH3+ CH3CH2NH3+ (CH3)3CNH3+ (CH3)2NH2+ (CH3CH2)2NH+ (CH3)3NH+ (CH3CH2) 3NH+

9,24 10,62 10,64 10,68 10,73 10,94 9,79 10,75

Cc arylamin c tnh base yu hn tnh base ca alkylamin. Trong dung dch nc c cn bng:
+ NH3 + H2O NH2 + + H3O

Ka = 2,5 . 10-5 M.
+ (CH3)2CHNH3 + H2O

pKa= 4,6

+ (CH3)2CHNH2 + H3O

Ka = 2,5 . 10-12 M.

pKa= 11,60

Tnh base ca anilin gim so vi amin mch thng l do hiu ng ht in t ca nhm phenyl v hiu ng lin hp - C ca nhm amin. Cp in t khng lin kt trn nit phn b vo nhn benzen theo cc cng thc gii hn sau:
NH2

..

+ NH2

+ NH2

+ NH2

Tnh base ca amin ph thuc cc nhm th v hiu ng khng gian. Cc nhm th y in t lm tng tnh base. Cc nhm th ht in t lm gim tnh base. Hiu ng khng gian c nh hng ng k n tnh base.

294

Bng 22.3: Gi tr pKa ca cc ion anilinium X -C6H4NH3+

pKa, 25C Nhm th X Orto meta para

H Benzoyl Bromo Cloro Cyano Fluoro Iodo Methoxy Methyl Nitro Trifluoromethyl

4,60 2,53 2,65 0,95 3.20 2,60 4,52 4,44 -0,26 -

4,60 3,58 3,52 2,75 3,57 3,60 4,23 4,72 2,47 3,20

4,60 2,17 3,86 3,98 1,74 4,65 3,78 5,34 5,10 1,00 2,75

6. Cc phn ng ca amin Cp in t khng lin kt trn nit lm cho amin c tnh base v tnh i nhn. V vy amin c phn ng th i nhn vi mt s cc cht c trung tm i in t. 6.1. Phn ng to amid Amin phn ng vi acid hu c v cc dn xut ca acid nh acylhalogenur RCOX to amid RCONH2.
RNH2 + R'COX NH2 + CH3COOH Anilin O CH2 CH C Cl Acryloylclorid NH2 C2H5O p-Phenetidin p-Etoxyanilin to R'CONHR to + HX

; X = H , Halogen , RCOO NHCOCH3

+ H2 O Acetanilid (N-phenylacetamid)

2 CH3NH2

O + CH2 CH C NHCH3 + CH3NH3Cl N-Methylacryloamid Methylamin clorhydrat NHCOCH3 C2H5O Phenacetin p-Etoxyacetanilid

+ CH3COONa HCl

(CH3CO)2O

295

6.2. Phn ng vi acid nitr (HNO2) Acid nitr phn ng vi amin mch thng v amin thm c cc bc khc nhau thng to ra cc sn phm khc nhau. 6.2.1. Vi amin bc nht Acid nitr phn ng vi amin bc nht mch thng to mui diazoni khng bn, phn hy thnh alcol v N2. Tng qut nh sau:
- 2H2O + RN N Cl RNH2 + O=N_ONa + 2HCl - NaCl Mui diazoni Amin bc nht
+

H2O

ROH + N2 +HCl Alcol

y l phn ng c bn ng dng nh lng nit trong cc acid amin. Acid nitr kh tn ti iu kin bnh thng. c c acid nitr phi s dng hn hp mui nitrit v acid ( NaNO2 + HCl). Trong thc t, amin bc nht mch thng tc dng vi acid nitr to hp cht mui diazoni khng bn phn hy thnh hn hp cc sn phm alcol, N2, alken v alkyl halogen. V d phn ng sau:
CH3(CH2)3NH2 NaNO2 HCl CH3(CH2)3OH + CH3CH2CHOHCH3+ CH3(CH2)3Cl + CH3CH2CHClCH3 5% 3% 25% 13% CH3 CH3 CH3 H + C C + CH3CH2CH=CH2 + C C + N2 H H H CH3 26% 3% 7%

C th gii thch cc c ch phn ng to thnh cc cht nh sau: Hp cht mui diazoni to thnh khng bn, phn hy thnh N2 v carbocation
CH3(CH2)3NH2 + NaNO2 + 2HCl + CH3CH2CH2CH2N Muoi diazoni N Cl + CH3CH2CH2CH2N N Cl + 2H2O +NaCl Butandiazoniclorid + CH3CH2CH2CH2 + Cl- + N2 Carbocation
-

Carbocation CH3CH2CH2CH2+ tc dng vi Cl to CH3CH2CH2CH2Cl v tc dng vi H2O to CH3CH2CH2CH2OH hoc chuyn v to carbocation bc hai CH3CH2CH+CH3.
+ CH3CH2CH2CH2 + CH3CH2CHCH3

Carbocation tc dng vi Cl- to CH3CH2CHClCH3 hoc vi H2O to CH3CH2CHOHCH3 hoc tch loi H+ v to 2-buten dng cis v trans.

296

+ CH3CH2CHCH3

CH3CH2CHClCH3 H2O CH3CH2CHOHCH3 + H+ CH3 H C C CH3 CH3 H + H+ + C C H H CH3

Cl-

Amin thm bc nht tc dng vi acid nitr to mui diazoni t < 5C.
Ar_NH2 + NaNO2 + 2HCl Amin thm bac nhat + Ar_N N Cl + 2H2O + NaCl

Muoi arendiazoniclorid

Mui diazoni ca amin thm c nhiu ng dng (xem phn mui diazoni). 6.2.2. Amin bc hai Cc amin bc hai tc dng vi acid nitr to hp cht N-nitroso amin c mu vng
Ar R N H + O=N_ONa + HCl Ar R N N O + NaCl + H2O

Amin bc hai

Hp cht nitroso amin

N H + HO_N=O Piperidin

N N=O + H2O N-Nitrosopiperidin

6.2.3. Amin bc ba Amin bc ba kh xy ra phn ng vi acid nitr. Cc alkylamin bc ba hu nh khng phn ng. Vi cc arylamin bc ba phn ng xy ra khng phi ti nit ca amin m xy ra phn ng th nhm chc nitroso vo v tr para so vi chc amin.
(CH3)2N H + HO_N=O (CH3)2N N=O + H2O

N,N-Dimethylanilin

p-Nitroso-N,N-dimethylanilin

6.3. Phn ng vi arylsulfonylclorid to sulfonamid Amin c bc khc nhau tc dng vi arylsulfonylclorid ArSO2Cl to thnh sn phm c kh nng tan khc nhau trong dung dch kim. Amin bc nht to sn phm tan trong kim (NaOH, KOH). RNH2 Amin bc nht + ArSO2Cl Arylsulfonylclorid ArSO2NHR + HCl Arylsulfonamid 297

 Amin bc hai to sn phm khng tan trong kim.

Ar' R Ar' N H + Ar SO2Cl Ar SO2 N AR'' + HCl

Amin bc hai Arylsulfonamid I ha tan c vo dung dch NaOH v cn c mt hydro c tnh acid gn trn nit. Arylsulfonat II khng tan trong dung dch NaOH v khng c hydro ny. Amin bc ba khng tc dng vi arylsulfonylclorid S dng phn ng ny phn bit cc amin c bc khc nhau v to cc loi sulfamid khc nhau c nhiu ng dng trong dc phm. 6.4. Phn ng vi halogen. To N -Halogen amin Trong mi trng kim long, amin bc nht v amin bc hai tc dng vi halogen to N -halogen amin.
R NH2 Amin + X2 Na2CO3,H2O - HX + X2 - HX R N X

R NH X

N-Halogen alkylamin

X N,N-Dihalogen alkylamin

6.5. Phn ng oxy ha Qu trnh oxy ho ph thuc vo cu to ca amin v cht oxy ho. Amin mch thng bc nht b oxy ha to hn hp cc cht: oxim, nitrosoalkan, N-alkylhydroxylamin v nitroalkan.
RCH2_NH_OH RCH2 NH2 H2SO5 Amin [O] RCH=N_OH RCH2_N=O RCH2_NO2 N-Alkylhydroxyl amin Oxim Nitroso alkan Nitroalkan

Amin mch thng bc hai b oxy ho to N,N-dialkylhydroxylamin.

R R N H [O] R R N OH

Amin mch thng bc ba b oxy ha to N -oxyd amin

298

R R" N R'

[O]

R + R" N O R' N-oxyd amin bac 3

N Pyridin

H 2 O2 CH3COOH

+ N O N-Oxyd pyridin

Amin thm bc nht b oxy ha bng acid permonosulfuric (acid Caro HOOSO3H) to hp cht nitrosoaren Ar N = O. Anilin b oxy ha bng dung dch KMnO4 hoc bicromat kali K2Cr2O7 to hp cht 1,4-benzoquinon hoc cht mu "en anilin". 6.6. Phn ng th i in t vo nhn thm Chc amin l nhm th loi I. Amin thm c phn ng th vo nhn thm.
NH2 + 3 Br2 Anilin Br NH2 Br + 3HBr Br 2,4,6-Tribromanilin

Chc amin quyt nh s nh hng vo nhn thm.

NH2 COOH + 3 Br2 Br Br NH2 Br + 3HBr COOH

Acid m-aminobenzoic NH2 COOH + 3 Cl2 Acid antranilic

Acid 3-amino-2,4,6-tribromobenzoic Cl NH2 COOH + 3HCl

Cl Acid 2-amino-3,5-diclorobenzoic

Nitro ha amin thm bc ba cho hiu sut cao trong mi trng acid acetic.
N(CH3)2 N(CH3)2 NO2 N(CH3)2 + NO2 + 2,4-Dinitro-N,N-Dimethylanilin NO2 N(CH3)2 NO2

HNO3 CH3COOH

N,N-Dimethylanilin

2-Nitro-N,N-Dimethylanilin

p dng phn ng Vilsmeier a chc aldehyd vo amin thm bc ba.

299

N(CH3)2 + HCON(CH3)2 Dimethylformamid DMF

N(CH3)2
1-POCl3 2-H2O

CHO p-Dimethylaminobenzaldehyd

Khi thc hin phn ng th i in t vo amin thm, ngi ta thng phi bo v chc amin bng s acyl ha nhm amin.
NH2 CH3COOH CH3 CH3 NHCOCH3 Br2 CH3COOH NHCOCH3 Br HCl CH3 Alcol NH2 NaOH CH3 2-Brom-4-methylanilin Br

4-Methylanilin

6.7. Tch loi nhm amin - Phn ng tch loi Hofmann Amin n gin RNH2 khng b tch loi chc amin. Chuyn amin v dng hydroxy amoni bc 4 [(R)4N]+OH. Di tc dng ca nhit , hydroxy amoni bc 4 b nhit phn to amin bc 3 v alken.
+ HO- + H_CH2_CH2_NR3

... HO H CH2 CH2... NR3

+ N(CH3)3I Ag2O H2O

HOH

+ CH2=CH2 + NR3

Phn ng tch loi ny gi l phn ng tch loi Hofmann.

NH2 CH3I K2CO3 + N(CH3)3OH 120o + N(CH3)3 + H2O

Khi tch loi to alken phi theo quy tc Hofmann l tch hydro nhm CH3 d hn hydro nhm RCH2.
CH3

N(CH3)3 OH

CH2 + 99%

CH2 + N(CH3)3 + H2O 1%

6.8. Mt s phn ng khc ca amin Amin bc nht tc dng vi sulfur carbon to acid dithiocarbamid th nguyn t nit RNH -C(S)_SH, dn xut th ca thiour, th nguyn t nit RNH _C(S)_NHR. 7. Amin cha no c mt lin kt i - Enamin Chc amin gn trc tip vi carbon c lin kt i _C=C_NH2 gi l enamin. 300

Cc enamin thng khng bn v c dng h bin (mesomer) imin C =N

H N N

Enamin

Imin

Khi nguyn t nit ca enamin l amin bc ba th enamin bn (khng c s h bin). Enamin bc ba c th iu ch:
O N

+
Cyclohexanon

N H Pyrolidin N-(1-cyclohexenyl) pyrolidin

Enamin rt nhy cm trong mi trng acid v d phn hy thnh hp cht carbonyl v amin.
N + H3O O

+
H

Cc enamin c tc dng lm cho nguyn t carbon v tr C c tnh i nhn.

:NR2

NR2

V vy enamin tc dng vi alkylhalogenid xy ra v tr .

+
N + CH2=CHCH2Br

Br -

O N Br H2O H H 2-allylcyclohexanon

8. Amin a chc Polyamin Cc amin a chc c nhiu ng dng dng mch thng hay vng.
NH2_CH2_CH2_NH2

Ethylendiamin

NH2

NH2

p-Phenylendiamin

301

NH2 NH2 H2N NH2

o-Phenylendiamin

H N

N H

Piperazin

m-Phenylendiamin

NH2 NH2

1,8-Diaminonaphthalen

Cc polyamin th hin cc tnh cht c trng ca amin. o-Phenylendiamin tc dng vi acid nitr to hp cht vng benzotriazol.
NH2 NH2 N + HNO2 N + 2H2O N H Benzotriazol

o-Phenylendiamin

Bi tp
1. Amin c CTPT C5H13N , C6H13N a. Vit cng thc cu to ca cc amin. b. Gi tn cc amin theo danh php thng thng v IUPAC (amin l tip v ng, tip u ng). 2. Amin thm c CTPT C9H15N. a. Vit CTCT cc amin thm. b. Gi tn cc amin . 3. Hy iu ch cc amin theo phng php Gabriel. a. iu ch n -butylamin t n -butylbromid. b. iu ch benzylamin t toluen. 4. Vit phng trnh phn ng ca cc cht sau y vi acid nitr (NaNO2+ HCl). a. n-pentylamin, o-toluidin, -naphtylamin. b. ethylisopropylamin, N-ethylanilin. N-methylcyclohexylamin. c. N-methyl, N-ethyl-p-toluidin. 5. C cc cht sau: Anilin, p-aminophenol, 2-cyclohexenamin. Cho cc cht ln lt tc dng vi cc cht sau: a. Acid acetic b. Acroleylclorid c. Benzensulfonylclorid. d. Acetylbromid. 302

e. H2O2 6. Thc hin phn ng chuyn v Hofmann ca cc cht sau: a. CH3(CH2)7CH2CONH2. b. C6H5CH2CONH2 c. CH2=CHCH2CH2CONH2 7. Vit cc phn ng trong cc trng hp sau: a. N,N-dimethyl -2-pentanamin, CH3I, Ag2O, nhit b. N,N-dimethyl -1-octanamin, CH3I, Ag2O, nhit

303

Chng 23

CC HP CHT KHC CHA NIT

Mc tiu 1. Gii thch c s hnh thnh cc loi hp cht nitro, isocyanat, ur, diazo. 2. Nu c mt s ha tnh ch yu ca chng. 3. Nu c mt s ng dng ca dn cht nitro trong tng hp hu c.

Ni dung
Ngoi hp cht amin cn c mt s nhm chc khc cha nit c trnh by trong bng 23-1.
Bng 23. Cc nhm chc cha nit
Cu to Nhm chc V d

R_NO2 R_N=C=O R_NHCOOR R_NHCONH_R' R_N=NN R_N=N_R'

O

Nitro Isocyanat Uretan,carbamat Ure Azid Azo

C6H5NO2 C6H5NCO C6H5NHCOOCH3 H2NCONH2 CH3CH2N3 C6H5N=NC6H5

O

Nitrobenzen Phenylisocyanat Methyl,N-Phenylcarbamat Ure Etylazid Azobenzen

Azoxy

Azoxybenzen

+ R N N R'
R_NH_NH2 R[NN]+ R2C=N2 R_CONH2

+ C6H5 N N C6H5
C6H5NHNH2 [C6H5NN]+ClCH2=N2 CH3CONH2

Hydrazin Diazoni Diazo Amid

Phenylhydrazin BenzendiazoniClorid Diazometan Acetamid

1. Hp cht nitro Hp cht nitro aliphatic tng i t gp. Hp cht nitro ca hydrocarbon thm c nhiu ng dng lm nguyn liu iu ch amin.

304

1.1. Cu to chc nitro

+ N O

.. O :..

+ N

O O-

+ N

OO

Chc nitro l nhm ht in t, c hiu ng - C v - I 1.2. Nitroalkan (R_NO2) Nitroalkan c iu ch bng phng php nitro ha alkan theo c ch gc.
CH4 + HNO3
400oC

CH3NO2 + H2

Trong phng th nghim c th iu ch nitroalkan bng phn ng th gia hp cht alkylhalogen v mui nitrit.
I CH3(CH2)5CHCH3 + NaNO2 2-Iodooctan NO2 CH3(CH2)5CHCH3 + NaI 2-Nitrooctan

Hp cht nitroalkan c tnh acid.

CH3NO2

pKa = 10,2

CH3CHCH3 NO2

pKa = 7,8

Cng nh acid carboxylic v ceton, hp cht nitroalkan c tnh acid yu. Base lin hp ca nitroalkan l nhng cht bn v c cng thc gii hn nh sau:
CH3 + N O H+ + CH2

ONitrometan ( acid)

CH2 CH2 OO OCarbanion , anion nitrometan (Base lien hp)

+ N

+ N

+ N

Anion nitroalkan l tc nhn i nhn (c tnh a nhn), do cc nitro alkan tc dng vi aldehyd theo kiu aldol ha.
CH3(CH2)7CHO + CH3NO2 Nonanal HO OH CH3(CH2)7CHCH2NO2 80% 1-Nitro-2-decanol

Cc -hydroxynitro ca hydrocarbon thm b dehydrat (loi nc).

CHO + CH3NO2 HO OH CH CH2 NO2 - H2O -Hydroxy phenylnitroetan

CH CH NO2 Nitrostyren

305

1.3. Nitroaren (Ar_NO2) 1.3.1. iu ch nitroaren Phn ng th i in t l phng php c bn iu ch hp cht nitroaren. Trinitrobenzen c iu ch t trinitrotoluen (TNT).
NO2 CH3 NO2 NO2 COOH NO2 NO2 NO2

Na2Cr2O7

NO2 TNT

H2SO4 45-55oC

NO2 Acid Picric

- CO2

NO2 1,3,5-Trinitrobenzen

1.3.2. Cc phn ng ca nitroaren Nhm nitro bn vng vi cc acid, cc cht oxy ha v cc tc nhn i in t. Phn ng quan trng ca hp cht nitroaren l phn ng kh to amin.
Ar_NO2 6[H] Ar_NH2 + 2H2O

Phn ng kh ha nitroaren qua nhiu giai on, to nhiu sn phm trung gian v ph thuc mi trng phn ng. Trong mi trng acid
NO2
2e- + 2H+

NO

2e- +

2H+

NHOH

2e- +

2H+

NH2

Nitrobenzen

- H2O

- H2O Nitrosobenzen

- H2O Anilin

Phenylhydroxylamin

Trong mi trng trung tnh Kh ha trong mi trng trung tnh to thnh arylhydroxylamin l ch yu. Trong mi trng kim. Kh ha trong mi trng kim to thnh cc sn phm trung gian.
As2O3 NO2 NaOH Zn NaOH H2NNH2 KOH ON N + Azoxybenzen 85%

(C2H5O)3P , H2O2 ,CH3COOH , 65o

N N

Azobenzen

84-86%

Pd/C , H2NNH2, khong kh

NH NH

Hydrazobenzen 80%

Cc sn phm trung gian ny trong mi trng acid u to thnh anilin. 306

Dn xut nitroaren c ng dng trong dc phm l chloramphenicol. Chloramphenicol c 2 nguyn t carbon bt i xng cu hnh threo v erythro.
CH2OH HOCH HCNHCOCHCl2 CH2OH HCNHCOCHCl2 HCOH

NO2 Threo

Cloramphenicol

NO2 Erythro

2. Isocyanat, carbamat v ure 2.1. Isocyanat (R_N=C=O, Ar_N=C=O) Isocyanat l mui (ester) ca acid isocyanic H_N=C=O. ng phn ca acid isocyanic l acid cyanic H -O-CN.

H N=C=O Acid isocyanic

HO C N Acid cyanic

Thay th nguyn t oxy bng nguyn t lu hunh thu c acid thioisocyanic R_N=C=O Alkylisocyanat Ar_N=C=O Arylisocyanat RO_CN Alkylcyanat ArO_CN Arylcyanat

Isocyanat l sn phm trung gian trong phn ng iu ch amin (chuyn v Hofmann). Isocyanat tc dng vi amin to ure.
H O H NCO + CH3NH2 Cyclohexylisocianat N C N CH3 N-Metyl , N'-Cyclohexylure

Khi c mt ca nc, isocyanat to thnh acid carbamic. Acid carbamic khng bn v phn hy thnh amin tng ng.
R NCO + H2O N-Alkyl isocyanat R NCOOH Acid N-alkyl carbamic R NH2 + CO2 Alkylamin

2.2. Carbamat - Uretan (H2N_COOR, RNH_COOAr) Carbamat hay l uretan l ester ca acid carbamic. Acid carbamic c cng thc cu to H2N_COOH. Cc dn xut ca acid carbamic c cc dng:

307

 Thay hydro ca nhm NH2 bng cc gc hydrocarbon

R R NH COOH Acid alkylcarbamic N COOH R' Acid dialkylcarbamic Ar NH COOH Acid arylcarbamic Ar N COOH Ar' Acid diarylcarbamic

Thay hydro ca nhm acid bng gc hydrocarbon thu c ester carbamat hay uretan. C cc loi ester carbamat (uretan): H2N_COOR alkyl carbamat; H2N_COOAr arylcarbamat. Isocyanat tc dng vi alcol to ester carbamat
N C O + CH3OH Cyclohexyl isocyanat N-Methylcyclohexylcarbamat H O N C OCH3

Hp cht carbamat (uretan) c nhiu ng dng lm thuc tr su, iu ch cc polymer hay l polyuretan. 2.3. Ure (H2NCONH2) C th xem ure (H2NCONH2) nh l amid ca acid carbamic (H2NCOOH) Ure c cc dn xut alkyl, aryl ure.
R_NHCONH_R' Ar_NHCONH_Ar'

Thay th oxy ca ure bng S ta c thioure H2NCSNH2. Thay th oxy ca ure bng nhm NH ta c hp cht guanidin - H2NC (NH)NH2 Cng thc cu to ca guanidin:
H2N C H2N NH

Guanidin c tnh base. Kt hp vi proton to ion guanidin c cng thc gii hn:

H2N H2N

C NH Guanidin

+ H+

H2N H2N ..

..

+ C NH2

+ H2N H2N ..

C NH2

..

H2N H2N +

..

C NH2

..

Ion guanidin

C th xem cc acid isocyanic, acid carbamic, ure... l dn xut ca acid carbonic; Hydro hoc nhm OH ca acid carbonic c thay th bi cc nhm th tng ng.

308

3. Hp cht diazo v mui diazoni Hp cht diazo c cng thc tng qut: R2C=N2. 3.1. Diazometan (CH2=N2) Cu to in t ca diazometan chng t nguyn t carbon c tnh i nhn.

CH2=N2 Diazometan
CH3 C2H5O C

+ + CH2 N N : CH2 N N: .. Diazometan

CH3 C2H5O C

iu ch diazometan t ester ethyl N -methylcarbamat (N-methyluretan).

NH O + HNO2 - H2O N N=O O HOCH2 - HCO3 - C2H5OH

..

+ N

N:

Ester ethyl N-methylcarbamat

N-nitroso-N-methyluretan

Diazometan

Cng c th iu ch diazometan t aldoxim v cloramin. Mui natri ca formaldoxim tc dng vi cloramin to thnh diazometan.
CH2=N-ONa + NH2Cl CH2

..

+ N

N:

+ NaCl + H2O

Diazometan l tc nhn methyl ha.

O R C OH + CH2N2 O R C OCH3 + N2

Diazometan c dng tng mt nguyn t carbon trn mch nhnh.

+ O + CH2N2 Cyclohexanon O CH2 C Cl + CH2N2

O: ..

..

+ CH2 N N :

O: .. - N2

.. + CH2 O Cycloheptanon O CH2 C CH2Cl + N2 83-85%

O CH2 C CHN2 + HCl

3.2. -Diazoceton (RCOCH=NN)

O

+ C CH N

N: ..

O-

+ C CH N

N:

Diazoacetophenon

309

3.3. Hp cht mui diazoni [Ar_NN]+ Hp cht mui diazoni ca hydrcarbon thm bn vng nhit thp < 5C. Mui diazoni c nhiu ng dng trong iu ch cc nhm chc khc nhau. Cu to in t ca mui diazoni:
N
+ +

N:

..

N:

..

3.3.1. Danh php mui diazoni

Tn hydrocarbon (hay tn gc hydrocarbon)+ diazoni + halogenid (sulfat)

C6H5N2Cl:

Benzendiazoniclorid hay Phenyldiazoniclorid p-Toluendiazonibromid hay p-Tolyldiazonibromid

p-CH3C6H4N2Br:

3.3.2. Cc phn ng ca mui diazoni C th chia cc phn ng ca hp cht mui diazoni thnh hai loi: Phn ng gii phng phn t N2. Phn ng ngng t khng gii phng phn t N2. a. Phn ng gii phng phn t N2 Phn ng thy phn khi c nhit . Dung dch mui diazoni, kh c nhit , to thnh phenol v kh N2.
NH2 + N2 Br CH3 Br HSO 4 +H O 2 OH

Br + N2

CH3

CH3

Phn ng xy ra theo c ch th i nhn SN1. ArN2+ Ar+ + H2O Ar+ + N2

Ar_OH2+ + ArOH + H+

Cation aryl c kh nng tng tc vi cc cht i nhn v to thnh cc dn xut ca hydrocarbon thm. Phn ng Sandmeyer. iu ch ArCl, ArBr, ArCN Hp cht mui aryldiazoni tc dng vi cc cht CuCl, CuBr, CuCN to ra cc dn xut hydrocarbon thm tng ng gi l phn ng Sandmeyer.

310

NH2 NaNO 2 HCl CH3

+ N2

Cl -

Cl CuCl CH3 + N2

CH3

NH2

Cl

+ N2 NaNO2 HBr

Cl

Br -

Br CuBr

Cl + N2

NH2 NaNO2 CH3 p-Toluidin HCl 5o

+ N2

Cl -

CN CuCN 0-5o CH3 p-Tolunitril + N2

CH3

Qua cc phn ng trn chng t mui ng (I) c vai tr xc tc.

Br - , CuBr , - N2 NO2 , CuCl , + N N: - N2 CN - , CuCN , - N2 SCN - , Cu2(SCN)2 , - N2 Br NO2 Bromobenzen Nitrobenzen

CN

Benzonitril

SCN

Benzosulfocyanid

Hp cht nitril thu c l nguyn liu iu ch acid thm, amin thm. Phn ng th nhm diazoni bng nguyn t hydro. Acid hypophosphor H3PO2 kh ha mui aryldiazoni thnh aren.
+ N N: X H3PO2 , H2O ( Cu+) -N2 - HX -H3PO4

Phn ng trn c ngha trong tng hp cc cht hu c: Khng th brom ha trc tip acid benzoic thu c acid 2,4,6tribromobenzoic. V vy phi qua chc amin nh hng brom vo v tr thch hp sau loi chc amin qua mui diazoni.

311

Br

COOH Br Br NH2

NaNO2 H2SO4 - 5o c

Br

COOH Br Br

H3PO2 + o N2 HSO4 - 5 c

Br

COOH Br Br

b. Phn ng ngng t khng gii phng phn t N2 Ion aryldiazoni [ArNN]+ l tc nhn i in t, d tc dng vi cc cht c tnh i nhn nh phenol v amin thm. Ngng t vi amin thm
N N + ..

.. + N N ..

NH2

N N p-Aminoazobenzen

NH2

Trc tin ion phenyldiazoni tng tc vo nguyn t oxy ca phenol hoc nguyn t nit ca anilin, sau c s chuyn v v to sn phm. Phn ng ngng t ca aryldiazoni l c s iu ch cc cht mu.
N N + ..

.. + N N ..

N(CH3)2

N N

N(CH3)2+ H+

4-Dimethylaminoazobenzen

4-Dimetylaminoazobenzen chnh l heliantin cht ch th mu ng dng trong ha phn tch. Cc cht mu rt ph thuc vo pH. Ngng t vi cc phenol
N N + ..

.. + N N ..

OH

N N

OH

4-Hydroxyazobenzen HO NaO3S N N
+

HO NaO3S N N + H+

+
-naphtol

Pham vang -naphtol

c. S dng mui diazoni trong tng hp cc cht hu c. iu ch p -nitrobenzaldehyd t benzaldehyd qua nhiu giai on nh sau: Chc aldehyd (formyl) nh hng meta. Khng th nitro ha trc tip benzaldehyd c p -Nitrobenzaldehyd m ch thu c m -Nitrobenzaldehyd.

312

CHO HNO3 H2SO4 CHO NaOH H2O NO2 NHCOCH3

CHO Fe , HCl NO2 CHO NaNO2 HCl NO2 NH2 H 2O H 2O

CHO CH3COOH NH2 CHO + N2 H3PO2

CHO HNO3 H2SO4 NHCOCH3 CHO

NO2

NO2

Chc nitro chuyn ha thnh amin. Thay th chc amin bng cc chc khc qua giai on diazo ha. V d:
CHO 1-HNO3,H2SO4 2-Fe, HCl,H2O 3-NaNO2 ,H2SO4 , H2O CHO CHO + N2 CHO CN SH CHO I

CHO F CHO

Bi tp
1. Gi tn cc cht c CTCT sau:

abcd-

Cl NH2 NH2 NH2

NO2 NCO N N

; CH3 ; NH2
OH

NO2 NCO

; NH2 ; C2H5_NCO
N N

NO2

NH2

+ Cl-

NH NH

OCH3

; CH3

NHOH

2. T benzen hy thc hin cc phn ng c phn ng Sandmeyer iu ch cc cht: clorobenzen, bromobenzen, acid benzoic, benzylamin, o-aminophenol. 313

Chng 24

HP CHT C LU HUNH V PHOSPHOR

Mc tiu 1. c c tn cc hp cht c S v P. 2. Nu c mt s tnh cht ha hc v ng dng ca chng trong tng hp hu c. Ni dung 1. Hp cht hu c c lu hunh Cc loi hp cht cha lu hunh trnh by trong bng 24-1
Bng 24.1: Cc loi hp cht c lu hunh
Loi hp cht Cng thc Loi hp cht Cng thc

Thiol , Mercaptan Sulfid Sulfoxyd Acid sulfenic Acid sulfinic Acid sulfonic Sulfohalogenid Sulffonylhalogenid Sulfinylhalogenid

RSH , ArSH RSR , ArSR

Metanthiol, Methylmercaptan Diethylsulfid Dimethylsulfoxyd Acid1-propen sulfenic Metansulfinic Metansulfonic Benzensulfoclorid Benzensulfonylclorid Metansufinylclorid

CH3SH C2H5SC2H5

R S O
RSOH RSO2H RSO3H RSO2Hal RSOHal

CH3 S O

CH3

CH3_CH=CHSOH CH3SO2H CH3SO3H C6H5SO2Cl CH3SOCl

1.1 .Thiol v sulfid Thiol c Thioalcol R _SH v Thiophenol Ar _SH Nhm chc SH gi l chc Thiol hoc mercaptan Danh php Gi tn hydrocarbon tng ng v thm thiol. Gi tn gc hydrocarbon tng ng thm mercaptan i vi Thiophenol: C th gi Thio + tn ca phenol c s carbon tng ng hoc Mercaptoaren.

314

V d:
CH3CH2SH HSCH2CH2SH C6H5SH
CH3

Etanthiol 1,2-Etandithiol Thiophenol

Ethylmercaptan . 1,2- Ethylendimercaptan Mercaptobenzen

CH2 SH

2- Thiocresol .
SH

Phenylmetanthiol Benzylmercaptan

2-Mercaptotoluen

di lin kt v gc lin kt trong metanthiol c trnh by di y:

H H C H S H
di lin kt (Ao) Gc lin kt ()

C_H ................1,10. S_H .................1,33 C_S .................1,82.

H_S_H ...........110,2 H_S_S ...........108 C_S_H ...........100,3

Metanthiol

Sulfid c cng thc R _S_R'. C th xem hp cht sulfid nh l hp cht ether, trong nguyn t oxy c thay th bi nguyn t lu hunh. Danh php: Gi tn cc gc hydrocarbon tng ng v thm sulfur. CH3CH2_S_CH2CH3 C6H5CH2_S_CH2CH3 p-CH3C6H4_S_C6H5 Diethylsulfid . Ethylbenzylsulfid. Phenyl p-tolylsulfid

di lin kt v gc lin kt ca dimethylsulfid trnh by di y:

H H C H H S C H H
di lin kt (Ao) Gc lin kt ()

C_H................1,09. C_S ..............1,80

H_S_H ...........109,5 H_S_S ........... 106.7 C_S_H ........... 98,9

Dimethylsulfid

Cc hp cht thiol v sulfid c nhiu ng dng trong y dc, cng nghip v nng nghip. Trong ha hc cc hp cht thiol c nhiu ng dng trong tng hp hu c. 1.2. Acid sulfonic Acid sulfonic cha nhm chc -SO3H . C cc loi acid sulfonic R_SO3H , Ar_SO3H

315

1.2.1. Danh php c tn hydrocarbon tng ng v thm "sulfonic "

O S OH O O S OH O Acid Benzensulfonic

CH3CH2CH2

Acid 1- Propansulfonic

1.2.2. iu ch acid sulfonic Bng phng php sulfon ha hydrocarbon tng ng. iu ch cc dn xut ca acid sulfonic cng ging nh iu ch dn xut ca acid carborcylic. V d: Ar_SO3H Ar_SO2Cl Ar_SO2Cl + PCl5 + NH3 + ROH Ar_SO2Cl + POCl3 + HCl Ar_SO2_NH2 + HCl Ar_SO2_OR + HCl

1.2.3. Acid sulfonic v cc dn xut

Bng 24.2: Danh php, tnh cht vt l ca acid sulfonic v dn xut
Cng thc Tn gi tc ts

CH3-SO3H CH3CH2-SO3H

Acid Metansulfonic Acid Etansulfonic Acid Benzensulfonic

20,0 - 17,0 44,0

167 -

SO3H
Acid p-Toluensulfonic 106.5 -

CH3
CH3 SO3H
SO3H

SO3H

Acid o-Toluensulfonic

67,5

Acid -Naphthalensulfonic

91,0

SO3H

Acid -Naphthalensulfonic

102,0

CH3SO2Cl

Metansulfonylclorid

160

316

Bng 24.2 (tip)

Cng thc
SO2Cl

Tn gi

tc

ts

Benzensulfonylclorid

14,5

246

p-Toluensulfonylclorid
CH3 SO2Cl

69,0

SO2Cl

-Naphthalensulfonylclorid

68,0

SO2Cl

-Naphthalensulfonylclorid

76,0

Benzensulfonamid; Benzensulfamid
SO2 NH2
SO2 NH2

156,0

-Naphthalensulfonamid ; -Naphthalensulfamid

Ester methyl p-toluensulfonat

CH3 SO2 OCH3

28

SO2 OC2H5

Ester ethyl -naphthalensulfonat

Cc phn ng ca hp cht sulfonic c ng dng trong tng hp ha dc. Tng hp cc loi sulfamid trn c s phn ng:
Ar_SO2_Cl + H2N_R' Ar_SO2_NH_R' + HCl

S phong ph ca cc hp cht sulfamid l do gc Ar khc nhau. R'cng khc nhau v c nhiu loi khung hydrocarbon khc nhau. Trong sulfamid nguyn t hydro trong NH, NH2 c th thay th cc nguyn t khc lm tng kh nng ng dng ca sulfamid trong nhiu lnh vc khc nhau. Cloramin T v Dicloramin T c tc dng st trng:

317

CH3 CH3 + NH3 NaOCl ( HO-) - H2O Cloramin T SO2NCl Na CH3 2 NaOCl

CH3 + HOSO2Cl

CH3

- HCl
SO2Cl

- HCl

SO2NH2

- 2NaOH

Dicloramin T SO2NCl2

Acid o-Toluensulfonic l nguyn liu iu ch saccharin (ng ha hc) :

CH3 PCl 5 -POCl3 - HCl SO3H CH3 + NH3 CH3 3[O],KMnO4 -H O SO2NH2 2 COOH -H2O SO2NH2 CO NH SO2

-HCl SO2Cl

Saccharin

Saccharin l imid ca acid 2-carboxybenzensulfonic hoc imid ca acid o-sulfobenzoic. Saccharin c ngt gp 550 ln ngt ca ng saccharose. 2. Hp cht cha phosphor Cc hp cht hu c cha phosphor nh l dn xut ca cc hp cht sau: Phosphin Phosphoran Acid phosphinic Acid phosphonic Acid phosphor Acid phosphoric PH3 PH5. (H3PO2) (H3PO3) (H3PO3) (H3PO4) HOH2P=O (HO)2HP=O (HO)3P (HO)3P=O (HO)2P(O)_O_(O)P(OH)2

Acid pyrophosphoric (H4P2O7)

Ngi ta chia hp cht hu c cha phosphor thnh 2 nhm: Hp cht c nguyn t phosphor lin kt trc tip vi nguyn t carbon P _C . Cc hp cht nguyn t phosphor khng lin kt trc tip vi carbon P _O_C 2.1. Phosphin Ging hp cht amin, phosphin c 3 loi: Monoalkyl RPH2 CH3CH2PH2 Ethylphosphin 6C6H5MgBr + 2PCl3 318 Dialkyl R2PH (CH3CH2CH2CH2)2PH Di n-butylphosphin Trialkylphosphin R3P (C6H5)3P Triphenylphosphin .

C th iu ch triphenylphosphin t hp cht c magnesi. 2(C6H5)3P + 3MgCl2 + 3MgBr2

2.2. Cc alkyl ca acid cha phosphor 2.2.1. Acid dialkylphosphinic

OH R P O R' Acid Dialkylphosphinic H CH3CH2 P CH2CH3 Diethylphosphin 2[ O] OH CH3CH2 P O CH2CH3 Acid Diethylphosphinic

2.2.2. Acid Alkylphosphonic

OH R P O OH Acid Alkylphosphonic H CH3CH2 P H Ethylphosphin 3[ O] OH CH3CH2 P O OH Acid Ethylphosphonic

2.3. Cc ester ca acid cha phosphor 2.3.1. Ester ca acid phosphonic

OR' R P O OR'' Ester dialkyl cua acid alkylphosphonic Ester dialkyl alkylphosphonat CH3CH2 P O OCH2CH3 OCH2CH3

Ester diethyl cua acid ethylphosphonic Ester diethyl ethylphosphonat

2.3.2. Ester ca acid phosphor

OR' P OR OH Ester Dialkylphosphit OCH2CH3 OH OR' P OR OR'' Ester trialkylphosphit OCH2CH3 OCH2CH3 P OCH2CH3

P OCH2CH3

Ester diethylphosphit

Ester Triethylphosphit

2.3.3. Ester ca acid phosphoric

OR' RO P O OR'' Ester Trialkylphosphat CH3CH2O P O OCH2CH3 Ester Triethylphosphat OCH2CH3

2.3.4. Ester ca acid pyrophosphoric

OR' OR''' C2H5O P O P OC2H5 O O Ester Tetraethylpyrophosphat C2H5O OC2H5

RO P O P OR'' O O Ester Tetraalkylpyrophosphat

319

Ti liu tham kho

1. E.Angeletcu - Nhng vn l thuyt ca Ho hu c - Rumani Bucarest, 1969. 2. Clayden, Greeves, Warren, Wothers - Organic chemistry - Oxford, 2001 3. I.L.Finar - Organic chemistry, 1969 4. Boyd Harrisson - Organic chemystry, 1999 5. Jerry March - Advanced organic chemistry - Wiley, 1992 6. C.D. Neninetscu - Ho hc hu c - Nga - Matxcva, 1963 7. Trn Quc Sn - C s l thuyt Ho hu c - Nh xut bn Gio dc, 1974 8. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s Ho hc hu c H Ni, 1976 - 1978. 9. Streitwieser, Heathcock - Introduction la chimie organique, 1995 10. L Vn Thi - Ho hc lp th hu c - B Vn ho Gio dc v Thanh nin, 1974 11. http:// www.uis.edu - University off lllnois 12. http:// www.ouc.bc.ca/chem

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