Giáo trình Hóa học hữu cơ - Đinh Văn Hùng

B gio dc v o to Trng i hc nng nghip I - H Ni --------------------------
inh vn hng - trn vn chin Pgs.ts. inh vn hng (Ch bin)
Gio trnh Ho hc hu c
Nm 2007
1 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..1
Li ni u
Gio trnh ho hu c ny c bin son theo cng mn hc chnh thc dng cho khi ngnh Nng- Lm- Ng nghip do b mn ho trng i hc Nng nghip I ch tr v c hi ng khi ngnh thng qua. Gio trnh nhm cung cp cho sinh vin nhng kin thc c bn v Ho hu c. Trng tm ca gio trnh l cu to v tnh cht ca cc hp cht hu c, cu to v tnh cht ca mt s loi hp cht t nhin c lin quan nhiu n cc mn hc c s v chuyn mn ca khi ngnh. Tuy nhin, do thi lng mn hc rt t (2 VH), nn chng ti ci tin chng mc sao cho gn nht. Cng chnh v vy khng trnh khi sai st khi bin son. chng ti rt mong nhn c nhng kin ng gp ca bn c v ng nghip gio trnh c hon thin hn cho ln ti bn sau. H Ni, 2007 Cc tc gi
Chng I. i cng Xa kia, ngi ta khng phn bit cht v c v cht hu c, mc d t thi c i ngi ta bit dng v sn xut mt s cht hu c nh ngi n bit ly ng t ma, bit ly chm t cy chm; ngi Ai Cp bit ly tinh du thm, cho ln men nc ngt thnh ru. Cng chnh v vy, khi ngi ta cha phn bit ha hc v c v ha hc hu c. S pht trin ca ha hc hu c bt u t th k XVII, khi cc hp cht ly t cy ci v ng vt c a vo nghin cu. n gia th k XVIII, trn c s phn ng t chy ngi ta xc nh c cacbon, hiro, nit, oxi c trong cc hp cht tch t ng vt v thc vt, t ha hc hu c thc s bt u pht trin. Khi nim ha hc hu c do Beczeliuyt (Bezelius) xut nm 1807. ng cho rng c th sinh vt l xng ha hc, c b phn ring bit sn xut cc sn phm quan trng cho s sng. Nm 1824 Vuele (Wohler) tng hp c axit oxalic (H2C2O4) t xianogen (C2N2) v nm 1828 ng cng tng hp c ur (H2N-CO-NH2) t amoni xianat (H4NOCN). Tip sau hng lot cc cng trnh mi c cng b, k c cc cng trnh tng hp cc hp cht hu c khng tch c t t nhin. n u th k XIX ngi ta khng nh rng cacbon l thnh phn c bn khng th thiu c trong cc hp cht hu c. Ngi ta a ra nh ngha: Ho hc hu c l hc thuyt v ho hc ca cc hp cht ca cacbon. Trn c s nghin cu cc c im cu to chung ca cc hp cht hu c, Soolemme (Soorlemmer) v mt s tc gi nh ngha: Ho hc hu c l ngnh ho hc ca hirocacbon v cc dn xut ca chng. Cho n nay c hai nh ngha trn vn c cng nhn. S pht trin ca ho hc hu c khng nhng c tc dng trc tip n cc ngnh kinh t quc dn c lin quan n ho hc hu c, m cn nh hng su sc n cc ngnh khoa hc khc nh sinh hc, ho sinh, y hc, dc hc, nng nghip ...lm cho con ngi ngy cng lm ch thin nhin v bt thin nhin, iu khin thin nhin phc v i sng con ngi. Ho hc hu c l ho hc v nhng hp cht ca cacbon. i tng nghin cu ca mn hc ny l cc hirocacbon v cc dn xut ca chng. i tng ny c kho st ring l do mt s nguyn nhn sau y: - S lng cc hp cht hu c rt ln v tng rt nhanh. Khong trn 10 triu hp cht hu c c bit. Trong c nhng hp cht ng vai tr v cng quan trng i vi cc qu trnh hot ng sng ca c th sinh vt nh cc hp cht gluxit, cc hp cht protein, cc axit nucleic, cc vitamin, cc hocmon - Vai tr to ln v ng dng phong ph ca ho hc hu c trong i sng hng ngy v trong cc ngnh kinh t quc dn: Nhin liu v du nhn, cc loi nng dc, thuc cha bnh, cc cht hot ng b mt, cc cht mu v phm nhum
- i vi cc ngnh sinh hc ni chung v cc ngnh Nng-Lm-Ng ni ring, ho hc hu c c coi nh l mn hc c s nghin cu cc quy lut v c ch ca cc qu trnh chuyn ho cc cht trong c th, t c th ra nhng bin php k thut thch hp tc ng lm tng nng sut, cht lng ca cy trng v vt nui. 1. Cu to v c im ca Cacbon Nh trn ni, ho hc hu c l ngnh ho hc dnh ring cho nguyn t cacbon. S lng cc hp cht hu c rt nhiu v ngy cng c tng ln rt nhanh bi nhng hp cht mi tm c trong th gii t nhin v bng con ng tng hp trong cc phng th nghim. Vn t ra l ti sao nguyn t cacbon li c kh nng hnh thnh nhiu hp cht n nh vy? Mun gii quyt vn ny trc ht chng ta nghin cu cu to v c im ca nguyn t cacbon. Cacbon l nguyn t thuc chu k hai, phn nhm chnh nhm bn ca bng h thng tun hon. Lp v in t ca n c 6 in t c chia thnh 2 lp : lp trong c 2 in t ( 1s2); lp ngoi c 4 in t ( 2s22p2).
2p2 1s2 2s2 Cc lp in t s v p s to nn nhng m my in t (obitan) khc nhau. Obitan s c dng hnh cu. Cc obitan p c dng s 8 ni. Cc obitan p phn chia trong khng gian theo 3 chiu px, py v pz. y + z x z y y z + x z y + x z + x y + x
S phn b in t trn cc obitan nh vy chnh l cu to ca nguyn t cacbon trng thi c bn hay trng thi tnh. trng thi ny, cacbon c 2 in t c thn (2p2), do vy ta c th ngh rng cacbon c ho tr 2.
Thc t th trong cc hp cht hu c, cacbon bao gi cng c ho tr 4. iu ny c th gii thch c trn c s thuyt lng t. Theo quan nim ca thuyt ny, trc khi to thnh cc lin kt, di tc dng ca nng lng, mt in t phn lp 2s s c kch thch chuyn ln phn lp 2p : 1s2 2s2 2p2 1s2 2s1 2p3 Nng lng cn thit dng cho qu trnh ny gi l nng lng kch thch v n s c b li sau khi hnh thnh lin kt. trng thi kch thch, nguyn t cacbon c 4 in t c thn, v th cacbon c ho tr 4. Bn in t c thn ca cacbon c phn b hai trng thi khc nhau v mt nng lng. Mt in t 2s trng thi nng lng thp hn, kh nng i vo lin kt kh hn. Ba in t 2p tn ti trng thi nng lng cao hn, kh nng i vo lin kt d dng hn. Do vy, mt trong bn lin kt ca cacbon to bi in t 2s phi khc vi ba lin kt cn li to bi cc in t 2p. Tuy nhin, trong thc t ho hc hu c li khc. Ngi ta gp cc hp cht hu c, trong bn lin kt ca nguyn t cacbon hon ton ging nhau. gii thch vn ny ngi ta cho rng, obitan 2s trn ln vi cc obitan 2p to thnh cc obitan mi c nng lng v hnh dng khng gian ging nhau. l s lai ho (hay cn gi l s lai to) ca cc obitan. y x z Hnh dng ca obitan lai ho
Trong cc hp cht hu c, nguyn t cacbon c th tham gia vo ba trng thi lai ho khc nhau. Lai ho sp3 hay lai ho t din : trng thi ny, mt obitan 2s trn ln vi ba obitan 2p c bn obitan lai ho ging ht nhau hng v bn nh ca mt hnh t din u. Trc ca cc obitan lai ho to vi nhau nhng gc bng nhau v bng 109028 (gc ho tr). y chnh l gc ho tr bn vng nht ca nguyn t cacbon. Trng thi lai ho sp3 l c s gii thch khi nim ca L Ben v Van Hp (1874) v thuyt t din ca nguyn t cacbon. Trng thi lai ho sp3 gp trong cc hp cht no, trong mi lin kt gia nguyn t cacbon vi nguyn t ca nguyn t khc hoc vi chnh nguyn t cacbon l nhng mi lin kt n (ni n).
Lai ho sp2 hay lai ho tam gic: trng thi ny, obitan 2s trn ln vi hai obitan 2p to thnh ba obitan lai ho. Ba obitan lai ho ny nm trn cng mt mt phng v trc ca chng to vi nhau nhng gc 1200. trng thi lai ho sp2 nguyn t cacbon cn li mt in t 2p khng tham gia vo s lai ho, trc ca n vung gc vi mt phng cha ba obitan lai ho. n t p ny s tham gia vo s hnh thnh lin kt cng vi cc in t p ca cc nguyn t cacbon bn cnh. Trng thi lai ho sp2 thng gp trong cc hp cht cha lin kt i (ni i). Lai ho sp hay lai ho ng thng : trng thi ny, obitan 2s trn ln vi mt obitan 2p c hai obitan lai ho ging ht nhau. Hai obitan ny cng nm trn mt mt phng v trc ca chng to vi nhau gc 1800. trng thi lai ho sp, nguyn t cacbon cn hai obitan p khng tham gia vo s lai ho. Cng ging nh in t p trng thi lai ho sp2, cc in t p ny s tham gia vo s hnh thnh cc lin kt . Trng thi lai ho sp thng gp trong cc hp cht cha lin kt ba (ni ba). Di y m t hnh dng v s phn b m my in t cc trng thi lai ho khc nhau.
+ + + +
+ + + + + + + +
Lai ho sp3
Lai ho sp2
Lai ho sp
Nh vy nguyn t cacbon ho tr bn l vin gch xy dng nn ton b ho hu c cu to. Tr mt vi ngoi l, ta c th biu din nhng hp cht ca cacbon bng nhng cng thc trong cacbon c bn lin kt cng ho tr (bt k l nguyn t cacbon lin kt vi nguyn t cacbon hay nguyn t ca nguyn t khc). biu din cng thc ca cc hp cht hu c, ngy nay ngi ta thng dng cng thc cu to, trong quy c rng mt vch ni lin cc k hiu nguyn t tng trng cho mt lin kt n, hai vch cho mt lin kt i v ba vch cho mt lin kt ba. Cch hay c dng nht l biu din di dng cng thc na cu to. Cch ny cho php tit kim ch v thi gian, nhng ng thi cng kh r rng: CH4 CH3-CH3 CH2=CH2 CHCH metan etan etylen axetylen
H2C H2C CH2 CH2
HC HC
CH
CH CH
CH3 -CH2 -OH
CH2 CH2 xiclohexan
CH benzen
ancol etylic
CH3 -O -CH3 imetyl ete
CH3 CH3 -C =O axeton
OH CH3 -C =O axit axetic
Khc vi cc nguyn t khc, ngoi kh nng c th tham gia vo c ba trng thi lai ho sau hnh thnh nn cc lin kt khc nhau, nguyn t cacbon cn c nhng c im m cc nguyn t khc khng c c lm tng kh nng hnh thnh cc hp cht khc nhau, lm cho s lng cc hp cht hu c rt ln. Nhng c im l cc nguyn t cacbon c kh nng kt hp vi nhau to thnh mch, trong lin kt cacbon- cacbon rt bn. Mch cacbon c th l mch khng phn nhnh (mch thng), mch phn nhnh hoc mch vng. Nhng mch c th rt ngn ch gm vi nguyn t cacbon ni vi nhau, nhng cng c th rt di, bao gm hng trm, hng ngn nguyn t:
C -C-C-C-C-C-C-C-CC C C
mch khng phn nhnh
mch phn nhnh
mch vng
Khi to thnh mch, cc nguyn t cacbon lin kt vi nhau. Cc nguyn t cacbon u mch ch lin kt trc tip vi mt nguyn t cacbon khc, cc nguyn t cacbon gia mch c th lin kt vi hai, ba hoc bn nguyn t cacbon khc. Tu thuc s lin kt m mt nguyn t cacbonn lin kt trc tip vi cc nguyn t cacbon khc, ngi ta phn bit thnh cacbon bc 1, cacbon bc 2, cacbon bc 3 hoc cacbon bc 4. Th d, trong phn t etan: CH3- CH3 hai nguyn t cacbon u l bc 1, bi v mi nguyn t cacbon trong ch c lin kt trc tip vi mt nguyn t cacbon khc. Trong phn t propan:
1 2 3
CH3- CH2- CH3 cc nguyn t cacbon s 1 v s 3 l cacbon bc 1 do chng ch lin kt trc tip vi mt nguyn t cacbon khc. Nguyn t cacbon s 2 l cacbon bc 2 v n lin kt trc tip vi hai nguyn t cacbon s 1 v s 3. Trong phn t isobutan:
1 2 3
CH3- CH- CH3 CH3 nguyn t cacbon s 2 l cacbon bc 3 v n lin kt trc tip vi ba nguyn t cacbon khc. Tng t nh vy chng ta c th d dng nhn thy, trong phn t neopentan: CH3 CH3- C- CH3 CH3 nguyn t cacbon s 2 l cacbon bc 4.
Kh nng phn ng ca cc nguyn t lin kt vi cc nguyn t cacbon c bc khc nhau s khc nhau. V vy, vic nhn bit bc ca cc nguyn t cacbon cho php phn on c kh nng phn ng ca cc phn t hp cht hu c. iu ny s c chng ta cp ti cc chng sau. 2. lin kt ho hc trong cc hp cht hu c Nguyn t ca cc nguyn t, tr cc kh tr, u c th phn ng vi nhau to nn phn t, tc l lin kt vi nhau to nn cc hp cht. Ni mt cch khc, cc nguyn t u c khuynh hng bo ho lp v in t ngoi cng tr thnh lp v in t bn vng (lp v ca kh tr). C nhiu kiu lin kt ho hc vi nhng c im khc nhau: lin kt ion, lin kt cng ho tr, lin kt phi tr, lin kt hiro, lin kt kim loi...cc loi lin kt ny u c nghin cu trong mn c s l thuyt ho hc. Trong cc loi lin kt trn, lin kt cng ho tr l ph bin v quan trng nht i vi cc hp cht hu c. V vy chng ta nhc li mt s im c bn v loi lin kt ny. 2.1. lin kt cng ho tr Lin kt ho hc thc hin bng nhng cp in t dng chung gi l lin kt cng ho tr. Cp in t dng chung ny tt nhin phi c spin ngc chiu nhau v khi n thuc v c hai nguyn t. Theo quan im hin i th lin kt ho hc c hnh thnh khi c s xen ph ti a ca hai obitan nguyn t. Obitan xen ph nhau nhn c khi y gi l obitan phn t. Tu theo kiu xen ph ca cc obitan nguyn t, ngi ta phn bit lin kt cng ho tr thnh lin kt xicma () v lin kt pi (). a. Lin kt Lin kt l lin kt m cc obitan nguyn t xen ph nhau theo kiu ni ui. Obitan phn t bao quanh trc ni hai nhn nguyn t. Lin kt c th to bi cc obitan nguyn t s vi s, s vi p, p vi p hoc sp3, sp2, sp vi nhau. Di y gii thiu s phn b mt in t khi to thnh lin kt gia hiro-hiro, gia cacbon-hiro v gia cacbon-cacbon.
C C C
H H
Lin kt gia H-H, H-C, C-C
Vng xen ph ca cc obitan nguyn t l cc i, do vy lin kt l loi lin kt bn vng. Lin kt c i xng trc, do vy hai nguyn t hoc nhm nguyn t c th quay tng i t do quanh trc i xng lm xut hin cc cu dng khc nhau trong mt s hp cht hu c. b. Lin kt Lin kt l lin kt m cc obitan nguyn t xen ph nhau theo kiu cnh sn. Obitan phn t i xng nhau qua mt phng nt (mt phng cha trc ni hai nhn nguyn t v vung gc vi trc ca obitan nguyn t). Lin kt ch to thnh gia hai obitan p vi nhau, p vi d hoc d vi d. Hnh di dy l s phn b mt in t ca lin kt to bi cc obitan nguyn t p.
+ + C C -
+ C C -
S phn b mt in t ca lin kt Cc obitan nguyn t xen ph nhau t, do vy cc lin kt thng km bn, d b ph v tham gia trong cc phn ng ho hc. Lin kt khng c i xng trc, do vy cc nhm th khng c kh nng quay t do xung quanh trc i xng. y chnh l nguyn nhn lm xut hin ng phn hnh hc cis- trans trong cc hp cht c ni i C=C. Trong cc hp cht hu c, lin kt c thc hin gia hai nguyn t cacbon vi nhau nh trong cc hp cht hu c cha no cha lin kt i v lin kt ba:
C=C C=C
gia cacbon v nguyn t ca nguyn t khc nh oxi, nit...

C=O C = NH C=N
Trng hp cc lin kt hnh thnh gia hai nguyn t ca hai nguyn t c m in chnh lch nhau th n s b phn cc.
Th d:
C=O
+
nhng hp cht c lin kt i lin hp, chng hn nh trong phn t butaien (CH2=CHCH=CH2), cc in t linh ng, chng thng c gii to trn ton b mch lin hp lm cho cc hp cht thuc loi ny thng c nhng tnh cht c bit so vi cc hp cht cha ni i bnh thng. c. Mt s c im ca lin kt cng ho tr Lin kt cng ho tr c mt s c tnh khc vi nhng loi lin kt khc: - di lin kt Bng thc nghim ngi ta xc nh c rng, khong cch gia hai ht nhn nguyn t trong lin kt cng ho tr l mt i lng khng i. Khong cch c gi l di lin kt. di lin kt thng c k hiu l d, n v tnh bng angxtron (A0) hay nanomet (nm) (1nm = 10A0; 1A0 = 10-8cm). di lin kt khng phi l tng bn knh ca hai nguyn t, m l tng bn knh cng ho tr ca hai nguyn t lin kt vi nhau. Bit bn knh cng ho tr ca nguyn t ta c th tnh c mt cch gn ng di lin kt. Th d, bn knh ca nguyn t hiro l 0,54A0, bn knh cng ho tr ca n l 0,37A0, th di lin kt H-H l 0,37A0 +0,37A0 = 0,74A0, ch khng phi l 0,54A0 + 0,54A0 = 1,08A0. Nh vy khi to thnh phn t hiro c s xen ph nhau gia hai obitan 1s ca hai nguyn t hiro. Cc cng trnh nghin cu chng t rng, s xen ph gia hai nguyn t cng nhiu, di lin kt cng ngn, lin kt cng bn, cng kh b ph v. Song, di lin kt khng phi l i lng c bn nh gi s bn vng ca mt lin kt ho hc. - phn cc ca lin kt Trong lin kt cng ho tr, nu obitan phn t c cu to cn i, ngha l mt in t ca obitan phn t phn b u gia hai ht nhn, trng tm in tch dng v m trng nhau th lin kt l khng phn cc. Lin kt cng ho tr khng phn cc ch to thnh gia hai nguyn t ca cng mt nguyn t. Th d, lin kt H- H trong phn t H2, lin kt Cl- Cl trong phn t Cl2, lin kt C- C trong phn t CH3- CH3 v CCl3- CCl3...l nhng lin kt cng ho tr khng phn cc. Trong trng hp nu obitan phn t c cu to khng cn i, ngha l mt in t ca obitan phn t lch v pha mt trong hai nguyn t th lin kt cng ho tr l phn cc.
Lin kt cng ho tr phn cc to thnh do cc nguyn t c m in khc nhau lin kt vi nhau. Khi y, mt in t ca obitan phn t s lch v pha nguyn t no c m in ln hn, lm cho nguyn t giu in t hn, tc n mang mt phn in tch m (k hiu -). Ngc li, nguyn t kia ngho in t hn, mang mt phn in tch dng (k hiu +). Nh vy, trng tm in tch dng v m khng trng nhau, m cch nhau mt khong l no . Th d, trong lin kt C- F, flo c m in l 4, cn ca cacbon l 2,5, ngha l flo c m in ln hn, lin kt C- F b phn cc v pha nguyn t flo, flo mang mt phn in tch m, cn cacbon mang mt phn in tch dng: c trng cho lin kt cng ho tr phn cc ngi ta dng i lng mmen lng cc, k hiu l muy (). Mmen c tnh bng cng thc: = e.l e l in tch in t l l di lng cc (khong cch gi cc trng tm in tch dng v m) n v ca mmen lng cc l bai (D) hay culong.met (C.m), 1C.m = 3.1029 D. Th d, mmen lng cc ca mt vi lin kt nh sau: C- C = 0, C- H = 0,4D, C- N=1,2D, C- O =1,6D, C- Cl =2,3D. Mmen lng cc c trng cho phn cc ca lin kt cng ho tr. Lin kt khng phn cc c = 0, lin kt phn cc c 0. Mmen lng cc cng ln lin kt cng phn cc v ngc li. Ni chung, lin kt cng phn cc, cng km bn, cng d b ph v trong qu trnh tham gia phn ng. Song, cng c kh nhiu trng hp ngoi l. Trong nhng trng hp , ngi ta phi xt ti kh phn cc ca lin kt hay ng hn l xt ti nng lng lin kt. phn cc ca lin kt quyt nh trc ht bi m in ca cc nguyn t lin kt vi nhau. Hai nguyn t c m in chnh lch nhau cng ln lin kt vi nhau th lin kt y cng phn cc v ngc li. Cn ch thm rng, i lng mmen lng cc khng phi l i lng c nh m n thay i do nh hng ca cc nguyn t hoc nhm nguyn t trong phn t, nh hng ca mi trng. phn cc ca lin kt C- H cn ph thuc vo trng thi lai ho ca nguyn t cacbon. Th du, Csp3-H =0,307D (metan), Csp2-H =0,629D (etylen), Csp-H =0,754D (axetilen) 2.2. Nng lng lin kt Trong qu trnh hnh thnh phn t cc cht t cc nguyn t t do c s gii phng nng lng. Nng lng gi l nng lng nguyn t v c tnh bng Kcal/mol. Vy nng lng nguyn t hnh thnh phn t l nng lng gii phng ra khi hnh thnh mt phn t gam cht t cc nguyn t t do iu kin tiu chun.
Th d, khi to thnh mt phn t gam HCl t cc nguyn t t do H v Cl gii phng ra mt nng lng 102 Kcal/mol, nn nng lng nguyn t hnh thnh phn t bng 102 Kcal/mol. i vi phn t hai nguyn t th nng lng nguyn t hnh thnh phn t cng chnh l nng lng lin kt. Vy nng lng lin kt chnh l nng lng cn thit ph v lin kt . Nng lng lin kt cng nh, lin kt cng km bn, cng d b ph v v ngc li. i vi phn t nhiu nguyn t nh CH4, C2H6... ngi ta dng khi nim nng lng lin kt trung bnh bi v trong phn t nhiu nguyn t d rng gm nhng lin kt ging nhau, cc lin kt vn c nng lng lin kt khc nhau tu theo th t hnh thnh trc hoc sau. Th d, trong phn t metan (CH4) c 4 lin kt C-H. Lin kt th nht c nng lng 102 Kcal/mol, lin kt th hai l 83 Kcal/mol, lin kt th ba l 128 Kcal/mol, lin kt th t l 80 Kcal/mol. Do vy nng lng nguyn t hnh thnh phn t CH4 l 102 + 83 + 128 + 80 = 393 Kcal/mol. Nng lng lin kt trung bnh ca lin kt C- H l 393:4 = 98,25 Kcal/mol. 3. Phn loi cc hp cht hu c v phn ng hu c 3.1.Phn loi cc hp cht hu c Theo cch phn loi ph bin nht, cc hp cht hu c c phn thnh dy cc hp cht khng vng v dy cc hp cht vng. Mi dy li c phn chia thnh nhng nhm v nhng phn nhm nh hn, m ta c th hnh dung bng s tm tt sau y: Cc hp cht hu c
Cc hp cht khng vng
Cc hp cht vng
No
Khng no
Cc hp cht ng vng
Cc hp cht d vng
Cc hp cht Cc hp cht vng khng thm vng thm
D vng khng thm
D vng thm
No
Khng no
No
Khng no
H thng phn loi trn y ly hirocacbon hoc hp cht d vng n gin nht lm hp cht c s. Nu ta thay th nguyn t hiro ca hp cht c s bng mt nguyn t hoc nhm
nguyn t khc ta s c cc hp cht c nhm nh chc. Mi nhm nh chc ny li c chia thnh cc phn nhm theo mch khng vng, mch vng... 3.2. Phn loi cc phn ng hu c Cc phn ng hu c c phn loi theo nhiu cch khc nhau: Theo c im ca s bin i lin kt, theo c im ca tc nhn phn ng, theo s lng cc tiu phn tham gia vo giai on quyt nh tc phn ng, theo hng ca phn ng hoc phi hp tt c cc cch phn loi ni trn. a. Phn loi theo c im ca s bin i lin kt Cc phn ng hu c thng thng xy ra bng cch lm t lin kt cng ho tr c v to thnh lin kt cng ho tr mi. Mt lin kt cng ho tr c th b t theo hai cch khc nhau. Theo cch th nht, sau khi lin kt cng ho tr b t mi nguyn t em theo n mt electron ca i electron lin kt. Khi trong mi trng phn ng xut hin nhng gc t do hay nguyn t hot ng. R:X Hay R X R. + X. R. + X.
Cch t nh vy c gi l t i xng hay ng li v phn ng tng ng c gi l phn ng ng li hay phn ng gc t do. Theo cch th hai, sau khi lin kt cng ho tr b t th i electron lin kt li mt nguyn t, cn nguyn t kia khng em theo electron lin kt no.
R : X R + X
Hay
R X
chnh l cch t khng i xng hay d li v phn ng xy ra trong trng hp ny l phn ng d li hay phn ng ion. b. Phn loi theo c im ca tc nhn phn ng Nhng tc nhn phn ng (Y-) l cc anion, cc phn t trung ho trong c nguyn t cn cp electron t do c th cho i mt cch d dng, mt s phn t c cha electron c i lc mnh i vi trung tm mang in tch dng.
Nhng tc nhn nh vy c gi l cc tc nhn nucleophin (tc nhn i nhn). Phn ng xy ra vi s tham gia ca cc tc nhn nucleophin gi l phn ng nucleophin. Cc tc nhn l nhng ion dng, nhng phn t c cha nguyn t khng c bt t y (axit liuyt), cc lng cc hoc phn t b phn cc di nh hng ca mi trng phn ng thng c i lc i vi trung tm mang in tch m.
l cc tc nhn electrophin (tc nhn i in t). Phn ng xy ra vi s tham gia ca tc nhn electrphin c gi l phn ng electrophin. c. Phn loi theo hng ca phn ng Theo cch ny ngi ta chia cc phn ng hu c thnh phn ng th, phn ng cng hp v phn ng tch. Phn ng th (k hiu l S) l phn ng trong mt nguyn t hay mt nhm nguyn t trong phn t ny c thay th bng mt nguyn t hay mt nhm nguyn t khc. Th d, phn ng: askt CH4 + Cl2 CH3Cl + HCl
y mt nguyn t hiro trong phn t metan c thay th bng nguyn t clo. Phn ng cng hp (k hiu l A) l phn ng trong hai hay nhiu phn t kt hp vi nhau to thnh phn t mi. Th d, phn ng cng hp phn t hiro vo phn t etylen to thnh etan. Ni H2C = CH2 + H2 CH3-CH3 Phn ng tch (k hiu l E) l phn ng trong mt phn t b loi i mt s nguyn t hoc nhm nguyn t to thnh hp cht mi c ni kp. Th d, phn ng loi nc ca ancol etylic to thnh etylen. H2SO4 CH3-CH2-OH CH2=CH2 + H2O Trong cc loi phn ng ni trn, ty thuc vo c im ca tc nhn phn ng chng cn c th c phn chia chi tit v c th hn. Chng hn, phn ng th c th gm phn ng th gc (SR), phn ng th electrophin (SE), phn ng th nucleophin (SN).
Cn ch thm rng, trong qu trnh phn ng ca c ba loi phn ng trn u c th xy ra s i ch mt nguyn t hay mt nhm nguyn t trong phn t c gi l s chuyn v. S chuyn v cng c th c coi l loi phn ng th t. d. Phn loi theo s lng tiu phn tham gia vo giai on quyt nh vn tc ca phn ng Theo cch phn loi ny ta phn bit thnh phn ng n phn t, phn ng lng phn t, phn ng tam phn t v phn ng a phn t. 4. C ch phn ng C ch phn ng l con ng chi tit m phn ng din ra t cht u n cht cui qua cc hp cht trung gian v trng thi chuyn tip. Hp cht trung gian (hay sn phm trung gian) l cc gc t do hay cc ion ng vi cc cc tiu nng lng, cn trng thi chuyn tip (hay phc hot ng) l trng thi c nng lng cc i ca h phn t trc khi phn ng. Th d: HO- + CH3B r Cht u TTCT1 TTCT2 HO- ... CH3 ... Brtrng thi chuyn tip HO- CH3 + Brcht cui TTCT E
E2
HCTG
E1
Cht u
H Cht cui
Cht u
H Cht cui
Tin trnh phn ng
Tin trnh phn ng
E l nng lng hot ha, H l hiu ng nhit ca phn ng trong iu kin ng p. Phn ng xy ra khi H< 0. 5. Cu trc phn t hp cht hu c Trong ho hc hu c ta thng gp nhiu hp cht khc nhau v tnh cht, song li c cng mt cng thc phn t. Hin tng mt cng thc phn t ng vi hai hoc nhiu hp cht khc nhau c gi l hin tng ng phn. Hin tng ng phn c gii thch trn c s thuyt cu to ho hc ca nh bc hc Nga A. M. Butlrp. Do c hin tng ng phn m s lng cc cc hp cht hu c c tm thy tng ln gp bi. C hin tng ng phn l do cc cht c cu trc khc nhau.
Ngi ta bit rt nhiu loi ng phn khc nhau, nhng chung quy li da vo cc c im v cu trc ta c th phn chng thnh hai loi chnh, l ng phn cu to (ng phn mt phng) v ng phn khng gian (ng phn lp th). 5.1. ng phn cu to Cc ng phn cu to phn bit nhau v trt t sp xp ca cc nguyn t trong phn t hoc v loi lin kt gia cc nguyn t, tc l phn bit nhau v mt cu to. Sau y l mt s ng phn cu to ch yu. a. ng phn mch cacbon Cc ng phn loi ny phn bit nhau v cch sp xp cc nguyn t cacbon trong mch. Th d, n-pentan; isopentan v neopentan u c cng thc phn t l C5H12, nhng c cu to mch cacbon khc nhau: CH3-CH2-CH2-CH2-CH3 n-pentan CH3 CH3-CH-CH2-CH3 isopentan CH3 CH3-C-CH3 CH3 neopentan
S ng phn mch cacbon tng ln rt nhanh theo s nguyn t cacbon c trong phn t. Th d, butan C4H10 c 2 ng phn, heptan C7H16 c 9 ng phn, ecan C10H22 c 159 ng phn, triecan C13H28 c 803 ng phn, tricontan C30H62 c 411846763 ng phn ... b. ng phn nhm nh chc Cc ng phn nhm nh chc c cng thnh phn phn t, nhng khc nhau v nhm nh chc. Th d: CH3-CH2-C-H v O anehit propionic CH3-C-CH3 O axeton
Hai cht ny cng c thnh phn phn t C3H6O, nhng c nhm nh chc khc nhau. Nhm nh chc ca anehit propionic l -CH=O, cn ca axeton l >C=O. Anehit propionic c im si 500C, tham gia c phn ng trng bc v phn ng vi thuc th Phlinh. Axeton si 400C, khng tham gia c phn ng trng bc cng nh phn ng vi thuc th Phlinh. c. ng phn v tr nhm nh chc Cc ng phn loi ny c cng thnh phn phn t, cng nhm nh chc, nhng phn bit nhau v v tr ca nhm nh chc trong mch cacbon. Th d: CH3-CH2-CH2-OH CH3-CH-CH3 OH
propan-1-ol
propan-2-ol
Hai ng phn ny c cng thnh phn phn t C3H8O, cng nhm nh chc ru (nhm OH), nhng v tr ca nhm -OH trong mch cacbon khc nhau. d. ng phn lin kt Cc ng phn ny phn bit nhau v loi lin kt gia cc nguyn t cacbon. Th d, buten-2 v xiclbutan. H2C CH3-CH=CH-CH3 But-2-en nhau. Ngoi bn loi ng phn cu to chnh trn y, hin tng h bin hay hin tng tautome l hin tng t chuyn ho qua li gia hai dng ng phn khng bn cng c xp vo mt loi ca ng phn cu to. Th d, hai dng cu to tn ti trong dung dch ca axetamit: CH3-C-NH2 CH3-C=NH O OH (dng amit) (dng imit) 5.2. ng phn khng gian Cc ng phn khng gian c cng thnh phn phn t, cng mt cu to, nhng khc nhau v s phn b khng gian ca cc nguyn t hoc cc nhm nguyn t trong phn t. Hai loi ng phn khng gian chnh l ng phn hnh hc v ng phn quang hc. hai loi ny cc cht ng phn phn bit nhau v cu hnh, tc l s phn bit trong khng gian ca cc nguyn t hay cc nhm nguyn t xung quanh phn cng nhc hoc phn khng trng vi nh ca phn t. Ngoi ra, cc ng phn cu dng cng c th c coi l loi ng phn khng gian th ba. Tt c cc loi ng phn khng gian ny nhiu khi xut hin xen k nhau. a. ng phn hnh hc Nu c hai nguyn t ni vi nhau bng mt lin kt cng ho tr cng nhc, ngha l khng c s quay ca hai phn phn t quanh trc ni ca hai nguyn t ny th hai nhm th ni vi chng c th c nhng cch phn b khng gian khc nhau: Nu chng cng pha i vi nhau ta gi l ng phn cis, khc pha l ng phn trans. Da trn c s , ng phn hnh hc thng c cc hp cht c ni i cacbon-cacbon, ni i gia cacbon v mt s d t no hoc gia cc d t vi nhau v cc hp cht mch vng. l nhng phn cng nhc, lm cho cc nhm th ni vi chng khng c kh nng quay t do. Sau y l mt s th d:
CH2 CH2
H2C
xiclobutan
Trong phn t hai ng phn ny cc nguyn t cacbon lin kt vi nhau theo cc cch khc
h c hooc C
h c C
cooh
cooh
hooc
axit maleic (cis)

h c hooc
r1
h axit fumaric (trans) ch3 c C
h C ch3
r2
hooc
C6H5 N
axit iso crotonic (cis) r2 r1

C n C n
h axit crotonic (trans)

C 6H 5 N C6H5 N N C 6H5
ho
oh
oxim
ch3 ch3
azobenzen
ch3 ch3 trans-1,2-imetyl xiclopropan
cis-1,2-imetylxiclopropan
Cc ng phn hnh hc khc nhau r rt v tnh cht vt l v ho hc. phn bit cc ng phn dng cis v dng trans ngi ta c th cn c vo: Mmen lng cc: mmen lng cc ca ng phn dng cis lun lun ln hn mmen lng cc ca dng trans.
Th d, phn t 1,2-icloeten:
H C C Cl H H Cl H C C Cl Cl
trans-1,2-icloeten =0
cis-1,2-icloeten = 1,89D
Nhit si, nhit nng chy, t khi khc nhau. Chng hn, cis-1,2-icloeten si 60,80C, t trng l 1,283, cn trans- 1,2-icloeten si 47,90C v t trng l 1,256. Kh nng tham gia phn ng ho hc ca ng phn dng cis thng mnh hn ng phn dng trans.
Th d, axit maleic (dng cis) d dng tham gia phn ng loi nc to thnh anhirit maleic.
H O C C OH C C OH = O
H C C C C = H
O = O O + H 2O
trong khi dng trans (axit fumaric) khng th tham gia phn ng ny. b. ng phn quang hc iu kin cn v xut hin ng phn quang hc cc hp cht hu c l phn t ca chng phi c cc trung tm bt i xng. Trung tm bt i xng ph bin nht i vi cc hp cht hu c l nguyn t cacbon bt i, tc l nguyn t cacbon m bn ho tr ca n c lin kt vi bn nguyn t hoc nhm nguyn t hon ton khc nhau. Th d: Trong phn t axit lactic:
H CH3 C COOH OH
Nguyn t C2 c lin kt vi cc nguyn t v nhm nguyn t -H, -OH, -CH3, hon ton khc nhau, do vy C2 l nguyn t cacbon bt i. Ngi ta k hiu nguyn t cacbon bt i l C*.
-COOH
Nhng phn t hp cht hu c c cha nguyn t cacbon bt i c th tn ti nhng cu hnh khng gian khc nhau v biu din chng ngi ta c th dng cc kiu m hnh hoc cng thc khc nhau, ph bin nht l cc m hnh t din, m hnh qu cu v c bit l cng thc chiu Fis (Fisher).. Phn t axit lactic trn y c hai cu hnh khng gian i xng nhau qua mt phng gng.
cooh
cooh
ho ch3 cooh
h (a)
h ch3 cooh
oh
C ho h ch3 ho cooh (b) h
C oh ch3 cooh
ho
oh
ch3
(c)
ch3
Cu hnh khng gian ca axit lactic a) M hnh t din b) M hnh khi cu v thanh ni c) Cng thc chiu Fis Hai cu hnh ny trng chng rt ging nhau, song khng bao gi c th trng kht ln nhau c, m chng lun lun i xng nhau nh vt v nh trong gng, nh bn tay tri v bn tay phi, nh hai chic giy ca mt iKhi trng thi lng, kh hoc trong dung dch chng u c kh nng lm quay mt phng nh sng phn cc. Gc quay i vi c hai dng u bng nhau v gi tr tuyt i, nhng hng quay th i lp nhau. Ngi ta gi l nhng ng phn quang hc. Vy, ng phn quang hc l nhng cht c cng thnh phn phn t, c cng cu to, nhng c cu hnh khng gian khc nhau do c kh nng lm quay mt phng nh sng phn cc khc nhau.
Ngoi nguyn t cacbon, cn mt s nguyn t khc nh nit, photpho, silic cng c th ng vai tr trung tm bt i xng. Chng hn, ngi ta phn lp c cc mui amoni, cc hp cht silic v cc photphin quang hot ca cc hp cht sau y:
(ch3)2ch (ch3)2chch2 ch3 n ch2ch3.cl ; h si c6h5
ch3 ch3 ; c6h5 p n-c3h7
Tnh quang hot cn c tm thy c mt s trng hp phn t khng trng vi nh m khng c cc trung tm bt i xng. Th d: axit 6,6- initro iphenic
NO2 COOH
COOH NO 2
COOH NO2
NO2 COOH
Hai ng phn quang hc c tr s tuyt i ca gc quay cc bng nhau nhng khc du c gi l hai cht nghch quang v chng to thnh mt cp nghch quang. Trong t nhin v trong cc phn ng tng hp nhiu khi ngi ta nhn c cc ng phn i quang cng vi nhau. Mt tp hp gm cc lng bng nhau ca cc ng phn quay phi v ng phn quay tri gi l bin th raxemic. trng thi rn ta cn phn bit hn hp raxemic v hp cht raxemic. Hn hp raxemic l mt hn hp vi lng bng nhau cc tinh th ca dng quay phi v dng quay tri, khi hnh thnh tinh th t mt dung dch bin th raxemic th cc dng ny kt tinh ring r. Tri li, khi hnh thnh hp cht raxemic th cc phn t nghch quang kt hp tng i mt thnh t bo c bn ca tinh th, trong t bo ny lun c mt lng bng nhau ca cc ng phn quay phi v quay tri. Trong trng hp phn t c nhiu trung tm bt i xng th s ng phn quang hc tng ln rt nhanh. Chng hn, vi phn t c n nguyn t cacbon bt i khc nhau th s ng phn quang hc l 2n, s cp nghch quang v s bin th raxemic s l 2n-1. Tuy nhin, nu c nhng trung tm bt i xng ging nhau trong phn t th s ng phn quang hc, cng nh s cp nghch quang v s bin th raxemic s t hn so vi cch tnh trn. Th d, phn t , -ihiroxibutyric.
* * ch3-choh-choh-cooh
Trong phn t ca n c hai nguyn t cacbon bt i, do vy s c 4 ng phn quang hc, to thnh hai cp nghch quang v hai bin th raxemic. Cng thc chiu Fis ca cc ng phn quang hc nh sau:
cooh h h ch3 oh oh ho ho cooh h h ch3 h ho cooh oh h ch3 ho h cooh h oh ch3
Cn c vo cu hnh, cc cht hot quang c th c chia thnh hai dy ln: Dy D v dy L. l nhng k hiu dng ch cu hnh ca phn t cht hot quang. Cn c xp mt cht hot quang no vo dy D hay dy L l cc cu hnh chun ca phn t glixeranehit. Phn t glixeranehit c mt C*, do c hai cu hnh khng gian khc nhau, ng vi hai ng phn quang hc.
cho h oh ho cho h ch2-OH L(-)glixeranehit
ch2-OH D(+)glixeranehit
Nhng cht hot quang c 1 C*, nu s sp xp H v OH quanh nguyn t C* ging s sp xp ca D-glixeranehit th cht thuc dy D, nu s sp xp ging L-glixeranehit th thuc dy L. Th d:
cooh h oh ch3 axit d(-)lactic ho
cooh h ch3 axit l(+)lactic
i vi nhng cht c nhiu nguyn t C* ngi ta cng xp tng t, nhng phi cn c vo cu hnh ca nguyn t C* xa nhm chc, trong nguyn t cacbon c ch s oxi ho cao nht.
Th d:
cho oh h ho h h h oh oh cho h oh h h ch2oh L(-) glucoz
ho h ho ho
ch2oh D(+) glucoz
Du (+), (-) trong cc cng thc chiu l dng ch chiu quay ca mt phng nh sng phn cc. Trong cc hp cht khc, nhm chun c th l SH, NH2, X, CH3. Hin tng quang hot rt ph bin trong cc hp cht hu c, c bit trong cc hp cht t nhin v c ngha sinh hc rt ln. Trong t nhin, c nhiu cht (gluxit, axit amin, protein, ankaloit) l nhng cht quang hot.
c. Cu dng
Khi nim cc cu dng hay cn gi l cc hnh th ca mt phn t dng ch cc dng cu trc khng gian ca n ch phn bit nhau do quay quanh mt lin kt n v khng th a v trng kht ln nhau. Chng hn, phn t etan, hai nhm metyl c th quay quanh trc lin kt cacbon-cacbon v do phn t c th c v s cu dng khc nhau, trong hai cu dng in hnh l cu dng che khut v cu dng xen k. biu din cc cu dng ngi ta dng cng thc phi cnh hoc thun tin hn l cng thc Niumen. Cu dng che khut:
h h h h h h h h h h h h h h h h h h h h h h h h
Cu dng xen k:
cng thc phi cnh cng thc Niumen
cng thc phi cnh
cng thc Niumen
cu dng che khut, cc nguyn t hiro ca hai nhm metyl che khut nhau. cu dng xen k, cc nguyn t hiro ca hai nhm metyl vo ch trng ca nhau. Cu dng xen k bn hn cu dng che khut, hiu s nng lng gia hai dng ny l 2,8 kcal/mol.
cc dn xut th 1,2 ca etan ta cng xt tng t. Tuy nhin, s cu dng in hnh y khng phi l hai, m l su, trong c ba l dng xen k v ba l dng che khut. Th d, n-butan ta c ba cu dng xen k v ba cu dng che khut nh sau:
h h ch3 h h ch3 ch3 h ch3 h h h h h ch3 ch3 h h ch3ch3 h h h h h h ch3 ch3 h ch3 ch3 h
h h hh
dng i (anti)
cc dng lch
dng khut
cc dng na khut
Cc dng lch v na khut mc nng lng nh nhau. Cu dng u tin l cu dng i. Cu dng ny bn hn cu dng lch 0,8 kcal/mol, bn hn cu dng na khut 3,4 kcal/mol v cu dng khut khong 4,4 - 6,1 kcal/mol. Ta gi cc cu dng c th tn ti bn vng l cc ng phn cu dng. Cc ng phn cu dng thc t c tn ti v c th nhn bit c thng qua vic kho st cc tnh cht vt l v ho hc, song khng th phn lp c chng ring bit bi v chng rt d dng chuyn ho ln nhau qua vic quay quanh trc lin kt n.
6. nh hng tng h gia cc nguyn t v nhm nguyn t trong phn t hp cht hu c
Vn nh hng tng h gia cc nguyn t v nhm nguyn t trong phn t hp cht hu c c nh bc hc Nga A. M. Butlrp trnh by trong thuyt cu to ho hc nm 1861. Sau , Maccpnhicp pht trin thnh hc thuyt gi l thuyt nh hng tng h gia cc nguyn t v nhm nguyn t trong phn t hp cht hu c. Ni dung ca hc thuyt ny c trnh by di dng mt s hiu ng in t sau y. 6.1. Hiu ng cm ng hiu th no l hiu ng cm ng, trc ht chng ta xt mt s th d sau y. Th d 1, so snh mc linh ng ca nguyn t hiro trong nhm hiroxyl ca axit axetic v axit cloaxetic. CH3-C-O-H O axit axetic Ka= 1,8. 10-5 Cl-CH2-C-O-H O axit cloaxetic Ka= 155. 10-5
c hai axit trn u c nhm cacboxyl (-COOH). Trong nhm ny lin kt O-H vn l lin kt phn cc v pha nguyn t oxi do n c m in ln hn. Mt khc, nhm cacbonyl (>C=O) cng ht electron dng chung trong lin kt C-O v pha mnh, khin cho nguyn t oxi
cng ht cp electron dng chung ca lin kt O-H v pha n mnh hn. Kt qu l lin kt O-H cng phn cc mnh v nguyn t H trong nhm -OH tr nn linh ng. Ta c th biu din qu trnh nh sau:
c o o h
Qua hng s Ka ta thy tnh axit ca axit cloaxetic mnh hn rt nhiu so vi axit axetic. Ni mt cch khc, nguyn t H trong nhm OH ca axit cloaxetic linh ng hn ca axit axetic. Nguyn nhn ca iu c gii thch nh sau: Trong phn t axit cloaxetic, nhm cacboxyl c lin kt trc tip vi nhm -CH2Cl, do nh hng ca nguyn t clo c m in ln m lin kt C-Cl b phn cc v pha nguyn t clo. Nh s phn cc ny m nguyn t clo mang phn in tch m (k hiu -), nguyn t cacbon trong nhm CH2 mang phn in tch dng (k hiu +), nguyn t cacbon ny li ht cp electron dng chung gia n v nguyn t cacbon trong nhm cacboxyl v pha n, t gy nh hng tip theo v cui cng dn n lin kt O-H tr nn rt phn cc.
cl + ch2 + c o o h
Ngc li, trong phn t axit axetic, nhm cacboxyl lin kt vi nhm metyl (-CH3). Ngi ta chng minh c rng nhm metyl c kh nng y li cp electron ra xa mnh. Trong trng hp nhm metyl trung ho bt phn in tch dng ca nguyn t cacbon trong nhm cacboxyl, t gy nh hng tip theo lm gim bt s phn cc ca lin kt O-H.
ch3 + c o o h
nh hng ca nguyn t clo v nhm metyl theo kiu nh vy c gi l hiu ng cm ng. Nguyn t clo v nhm metyl l nhng trung tm gy nn hiu ng cm ng. Th d 2, xt hai phn t propan v n-propyl clorua ta thy rng, khc vi propan, phn t npropyl clorua c lin kt C1-Cl b phn cc mnh v pha nguyn t clo l nguyn t c m in ln hn.
h h c h h c h h c h h h h " + c 3 h h h ' + + c c 1 2 h h cl
Do nguyn t clo mang mt phn in tch m, cn nguyn t C1 mang mt phn in tch dng. V nguyn t C1 mang mt phn in tch dng nn lin kt C1-C2 cng b phn cc v pha C1, ri n lin kt C2-C3 cng b phn cc v pha C2, mc d s phn cc yu hn
nhiu. S phn cc cng xy ra c cc lin kt C-H trong phn t. Kt qu chung l phn t n-propyl clorua l phn t phn cc. T nhng th d trn ta c th hiu v hiu ng cm ng nh sau: Hiu ng cm ng l s di chuyn my electron dc theo mch cacbon di tc dng ht hoc y ca cc nguyn t th hay nhm th; hay hiu ng cm ng l s phn cc lan truyn cc lin kt lin tip theo mch lin kt do s phn cc ca mt lin kt no . Ngi ta thng dng mi tn thng ( ) ch hng lan truyn ca hiu ng cm ng.
Hiu ng cm ng c k hiu bng ch I (Inductive effect). Nu quy c rng trong lin kt (C-H), nguyn t H c I=0 th nhng nhm th c kh nng ht electron mnh hn H c coi l nhng nhm c hiu ng cm ng m (-I), cn nhng nhm c kh nng y electron mnh hn H l nhng nhm c hiu ng cm ng dng (+I).
+ y +i c h i=0 c x -i + c
Hiu ng +I thng thy cc nhm ankyl v cc nhm mang in tch m. Nhm ankyl cng ln, cng phn nhnh hiu ng +I cng ln. Trong cc nhm mang in tch m, m in cng nh hiu ng +I cng ln.
ch3 -ch3 < -ch2-ch3 < -ch < ch3 ch3 ch3 -c ch3
-o < -s < -se Hiu ng -I thng thy cc nhm khng no, cc nhm mang in tch dng v cc nhm ng vi nhng nguyn t c m in ln. Ni chung, cc nhm cng khng no, c m in cng ln th hiu ng -I cng ln. -c cr > -cr=cr2 > -cr2-cr3
-f > -cl > -Br > -I -or2 > -or ; -NR3 > -NR2 -or2 > -sr2 > SeR2 , ... c tnh quan trng nht ca hiu ng cm ng l n gim rt nhanh khi mch cc lin kt ko di. Th d, phn t axit butyric: ch3 - ch2 - ch2 - c - o - h o
=
Nu thay th mt nguyn t H cc v tr , , bng nguyn t clo th lm cho lc axit tng ln. Nu nguyn t clo v tr lc axit tng 92 ln, nu v tr lc axit tng 6 ln, cn nu v tr lc axit ch tng c 2 ln so vi lc axit ca axit butyric. 6.2. Hiu ng lin hp Hiu ng lin hp ch c trng cho cc phn t c cha h lin hp. Phn t c cha h lin hp l nhng phn t t.rong c cc lin kt bi lun phin lin kt n -) hoc nhng phn t trong cn nguyn t hay nhm nguyn t c cp electron khng phn chia (cp electron t do, cha tham gia lin kt) cch lin kt bng mt lin kt n. Th d: Cc phn t sau y c cha h lin hp:
ch2 = ch - ch = ch2 ch3 - c - nh2 o
=
; ch2 = ch - ch = ch - ch =O ; ch2 = ch -cl oh ;
cc h lin hp nh vy c mt c ch chuyn dch electron c trng cho obitan phn t ca h lin hp, khc hn c ch chuyn dch cm ng trn. biu din chiu chuyn dch in t trong h lin hp ngi ta dng mi tn cong. Th d: Phn t lin hp but-1,3-ien trng thi bnh thng khng phn cc, 4 electron p ca 4 nguyn t cacbon xen ph ln nhau, pha ho chung vo nhau to thnh mt obitan phn t duy nht gii ta u trn c 4 nguyn t cacbon.
+ CH2 CH CH CH2
CH2
CH
CH
CH2
Nu thay th mt nguyn t H nhm -CH2 bng nhm -CHO chng hn th nhm ny s tham gia lin hp vi obitan phn t ca butaien. Nh c tnh phn cc sn c ca nhm -CHO, ton b obitan phn t mi hnh thnh ca phn t b dch chuyn mt phn v pha nguyn t xi. Ta ni y c hiu ng lin hp -.
+ +
CH2 CH CH CH CH O
CH2
CH
CH
CH
CH
Mt th d khc, trong phn t vinyl clorua:

ch2 = ch - cl
Nguyn t clo cn ba cp electron p t do cha tham gia lin kt. Mt trong ba cp ny c trc song song vi trc ca cc electron ti vng ni i, v vy chng s tham gia lin hp vi nhau to thnh obitan phn t mi. Ton b obitan phn t mi ny b y lch v pha nguyn t C2.
ch2 = ch cl
Hiu ng lin hp trong trng hp ny l hiu ng lin hp p-. Vy, hiu ng lin hp l hiu ng dch chuyn my electron trong h lin hp di nh hng ht hoc y electron ca cc nhm th. Hiu ng lin hp c k hiu bng ch C (conjugate effect). Ngi ta cng phn bit hiu ng lin hp thnh hai loi: Hiu ng lin hp m (-C) v hiu ng lin hp dng (+C). Nhng nhm th c kh nng ht electron gy ra hiu ng lin hp m, thng l nhng nhm th khng no nh cc nhm -NO2, -CN, -CHO, -COOH, >C=O, >C=NH ...Hng chuyn dch electron trong h lin hp c cha nhm vi hiu ng -C c m t nh sau:
c
Dy nhm th sau y gy ra hiu ng -C gim dn:

-no2 > -cho > -c-r > -c-oh o o
Cc nhm th c kh nng y electron gy ra hiu ng lin hp dng, l cc nhm th c cp electron p t do nh cc halgen (-X), -NH2, -OCH3, ...Hng chuyn dch electron theo hng i v pha lin kt .
Dy nhm th sau y gy ra hiu ng +C gim dn: - F > - Cl > - Br > -I > -OH > - NH2 Ngoi nhng nhm th lun lun biu hin hiu ng -C hoc +C, cn c mt s nhm c hiu ng lin hp vi chiu thay i tu thuc vo bn cht ca nhm th lin kt vi chng. l cc nhm nh vinyl (CH2=CH-), phenyl (C6H5-), etinyl (CH C-) ... Th d:
o n o +c -c -c nh2 +C
Mt s nhm th nh cc halogen, -NH2, -OH, vvng thi gy hai hiu ng +C v -I ngc chiu nhau. Trong nhng trng hp nh vy, ni chung +C > -I v hiu ng +C quyt nh c kh nng ln chiu hng phn ng. Ring trng hp cc halogen, do c m in ln nn -I > +C, hiu ng -I quyt nh kh nng phn ng, nhng hiu ng +C quyt nh chiu hng ca phn ng. Xt v c tnh ca hiu ng lin hp ngi ta thy rng khc vi hiu ng cm ng, hiu ng lin hp ch thay i rt t nu tng chiu di mch lin hp. c tnh na l hiu ng lin hp ch xut hin trn h lin hp phng hay gn phng, tc l h lin hp trong trc ca cc ocbitan v p song song hay gn nh song song vi nhau.
H phng xen ph
H khng phng khng xen ph
6.3. Hiu ng siu lin hp Trong h thng nhng phn t c cha nhng lin kt C-H ng cch lin kt kp bi lin kt n C-C nh:
H -C-C=C ;
H -C-C N ;
H -C-C=O
nhng h thng nh vy c s lin hp gia cp electron ca lin kt kp vi cp electron ca lin kt C-H (dng mi tn cong i t lin kt C-H n lin kt C- C ch s lin hp ). S lin hp nh vy c gi l hiu ng siu lin hp hay hiu ng lin hp -.
H C c c ; H C c N ; H C c O
Hiu ng siu lin hp c k hiu bng ch H (hyperconjugate effect). Hiu ng siu lin hp tng theo s lng lin kt C-H v tr ca nhm ankyl. - CH3 > - CH2- CH3 > -CH(CH3)2 > - C(CH3)3 Trn y chng ta cp n ba loi hiu ng chnh thng c biu hin trong cc hp cht hu c. Vic xem xt cc hiu ng ny cho php ta tin on c kh nng phn ng v nhng chiu hng chnh s xy ra ca cc phn ng hu c, ng thi cn cho php gii thch cnhiu tnh cht ca cc hp cht hu c. V vy hiu c chng l rt cn thit nghin cu v cc hp cht hu c v cc phn ng hu c.
Cu hi v bi tp 1. Cc loi ng phn? Biu din cc ng phn bng cng thc cu to hoc cu hnh khng gian thch hp. 2. Cc loi hiu ng in t trong phn t hp cht hu c. ng dng ca vic xt cc hiu ng in t trong ho hc hu c. 3. Vit cng thc cu to cc ng phn c th c ca cc hp cht c cng thc phn t C6H12; C4H8; C2H4O2; C3H6O. 4. Cu hnh khng gian v gi tn cc ng phn hnh hc ca cc hp cht sau: But-2-en 2-metylbut-2-enoic 1,2- iclo xiclopropan But-2-enioic 5. Cng thc chiu Fis v gi tn cc ng phn quang hc ca cc hp cht sau: Axit lactic Alanin Anehit glixeric Serin Glucoz Fructoz 6. So snh tnh linh ng ca nguyn t H trong nhm -OH ca cc hp cht sau v gii thch bng cc hiu ng in t: HOH; C2H5OH; HCOOH 7. So snh tnh axit ca cc axit sau v gii thch: HCOOH; CH3- CH2- COOH; CH3- CH2-CH2- COOH v CH3- CH- COOH CH3 CH3- CH2- CH2- COOH; CH2= CH- CH2- COOH v CH3- CH= CH- COOH CH3- CH2- COOH; CH3- CH- COOH v CH2- CH2 - COOH Cl Cl 8. So snh s phn cc ca lin kt C- Cl gia cc hp cht sau v gii thch. CH3 CH3- CH2- CH2- Cl; CH3- CH- Cl v CH3- C- Cl CH3 CH3 CH3- CH2- Cl v C6H5- Cl 9. Xt chiu phn cc ca cc lin kt trong cc hp cht sau y v gii thch. Pent- 2-en 2- metylbut-2-en Vinyl clorua Allyl clorua
Chng II Hirocacbon
Hirocacbon l hp cht hu c trong phn t ch gm cc nguyn t cacbon v hiro. Cc nguyn t cacbon lin kt vi nhau thnh mch cacbon. Tu theo cu to mch cacbon ngi ta chia hirocacbon thnh: Hirocacbon dy khng vng (hirocacbon axiclic) v hirocacbon dy vng (hirocacbon xiclic). Trong mi dy, tu thuc bn cht ca lin kt gia cacbon v cacbon c th chia hirocacbon thnh ankan, anken, ankaien, ankin, xiclo anken, xiclo anken, hirocacbon thm. Trong chng ny chng ta ch cp n mt s hirocacbon chnh, l hirocacbon no, hirocacbon khng vng cha no v hirocacbon thm.
1. Hirocacbon no (ankan, xicloankan)
Hirocacbon no bao gm ankan v xicloankan. Trong phn t hirocacbon no, cc nguyn t cacbon lin kt trc tip vi nhau bng lin kt xch ma (). An kan l hirocacbon mch khng vng c cng thc chung l CnH2n+2 ( n 1). Xicloankan l hirocacbon mch vng c cng thc chung l CnH2n ( n 3). 1.1. Cch gi tn v ng phn
a. Tn gi thng thng
Cc ankan c tn cng l ui an (ngha l no). Bn cht u ca dy ng ng c tn gi khng h thng: CH4 metan C2H6 etan C3H8 propan C4H8 butan
Nhng ankan tip theo gi tn theo th t: Ch s Hilp ch s nguyn t cacbon + an Th d: C5H12 pentan C8H18 octan C6H14 hexan C9H20 nonan C7H16 heptan C10H22 ecan
ch hircacbon khng phn nhnh thng thm tip u ng n (normal) hoc khng c. Tip u ng iso gi nhng hp cht c hai nhm metyl u mch khng phn nhnh, cn tip u ng neo ch hp cht c 3 nhm metyl u mch khng phn nhnh. Th d: CH3- CH2 -CH2- CH2- CH3 n-pentan
b. Tn gc v bc ca gc
CH3 - CH- CH2- CH3 CH3 isopentan
CH3 CH3- C- CH3 CH3 neopentan
Trong hp cht hu c thng gp nhng nhm nguyn t c xem nh mt n v cu trc c thnh phn, s lng tng t ankan, ch t hn mt nguyn t hiro c gi l gc ankyl (cng thc chung CnH2n+1-). Tn gc ankyl ging ankan tng ng ch thay ui an bng ui yl. Th d: CH3metyl C2H5etyl C3H7propyl
Da vo bc ca nguyn t cacbon mang ho tr t do, cc gc ankyl li c chia thnh: gc ankyl bc I, gc ankyl bc II, gc ankyl bc III. Th d: CH3- CH2 - CHCH3-CH2-CH2-CH2CH3 n- butyl (gc bc I) sec- butyl (gc bc II) CH3 CH3 - CH - CH2CH3 CH3- CCH3 iso- butyl (gc bc I) tert- butyl (gc bc III)
c. Tn gi IUPAC
Danh php h thng ho y nht l danh php IUPAC ca hip hi ho hc quc t v ng dng (International Union of Pure and Applied Chemistry). Nguyn tc gi tn ankan theo IUPAC bao gm cc im sau: - Tn ca ankan c kt thc bng an. - Mch chnh c chn l mch cacbon di nht khng phn nhnh. Nhng nhm ankyl kt hp vi mch chnh c xem nh nhm th. - Vic nh s mch chnh c tin hnh t pha no sao cho tng cc ch s ca nhm th l b nht. Mi nhm th c ch s tng ng vi v tr ca n trong mch. - Trng hp c cc nhm th ging nhau cng mt nguyn t cacbon hoc cc nguyn t cacbon khc nhau th phi ghi s ch ca mi mt nhm th trong chng. - Gi tn theo th t: V tr nhnh + tn nhnh + tn mch chnh Khi c mt nhiu nhm th khc nhau th th t gi tn c th theo th t tng dn tnh phc tp ca nhm th hoc theo a, b, c.
Th d: CH3 - CH - CH - CH2 - CH2 - CH3 CH3 CH3 2,3 -imetyl hexan CH3 CH3 -C - CH - CH2 - CH2 - CH3 CH3 CH2-CH3 2,2-imetyl-3-etyl-hexan
Cc xicloankan c gi tn theo cch gi IUPAC. Mch chnh lun phi l mch vng. Vic nh s ch c tin hnh i vi cc xicloankan c hai nhnh tr ln. Bt u nh s t nguyn t cacbon lin kt vi nhnh n gin nht v theo chiu sao cho tng s s ch v tr mch nhnh l nh nht, sau gi tn theo th t: V tr nhnh + tn nhnh + xiclo + tn ankan tng ng Th d:
CH3
CH3 CH2 -CH3 1-mtyl-2-tylxiclpentan
mtylxiclhexan
d. ng phn
Cc ankan c ba loi ng phn chnh l ng phn mch cacbon, ng phn quang hc v ng phn hnh th. Th d 1: Cc ng phn v cu to mch cacbon ca pentan. CH3 CH3- CH2 -CH2- CH2- CH3 CH3 -CH- CH2- CH3 CH3- C- CH3 CH3 CH3 n- pentan isopentan neopentan Th d 2: C7H16 c hai cng thc cu to cha nguyn t cacbon bt i, do c cc ng phn quang hc. * CH -CH -CH -CH -CH -CH
3 2 2 2 3
CH3 CH3 * CH3 -CH -CH -CH2 -CH3 CH3 Th d 3: ng phn cu dng ca n-butan CH3 CH3CH3 H H
H CH3
H H
dng khut ca butan dng i ca butan Xicloankan c s ng phn nhiu hn s ng phn ca ankan. Xicloankan c cc loi ng phn sau:
- ng phn v cu to mch cacbon phn nhnh Th d: CH2 -CH2 -CH3 n propylxiclopentan - ng phn v cu to mch vng Th d:
CH3
CH3 CH -CH3 isopropylxiclopentan
metylxiclopentan - ng phn v v tr nhnh Th d: CH3 CH2 -CH3
xiclohexan
CH3
CH2 -CH3 1-metyl-2-etyl xiclohexan - ng phn hnh hc Th d: CH3

CH3 CH3 cis -1,2-imetyl xiclopropan trans -1,2-imetyl xiclopropan
1-metyl-4-etyl xiclohexan
CH3
1.2. Phng php iu ch

a. Phn ng Vuyc- Fittic
Nguyn tc ca phng php ny l cho dn xut halgen tc dng vi kim loi Na. 0 CH3 - CH -Cl + 2 Na + Cl - CH -CH3 t CH3 - CH2 - CH -CH3 + 2NaCl
2
CH2 -CH2 - CH2 + 2 Na Br Br
CH3 t0
CH3 + 2NaBr
b. Phn ng cacboxyl ho
iu kin nhit cao v c xc tc, axit cacboxylic b loi CO2 to thnh ankan.
Th d:
CH3 - CH2-COOH CH2 - CH2-C CH2 - CH2-C O t0 xt CH3 - CH3 + CO2 CH2 - CH2 [H] CH2 Zn + HCl CH2 - CH2 - H 2O
O OH MnO , t0 CH2 - CH2 2 C =O OH - H2O, -CO2 CH2 - CH 2
Thng thng ngi ta tin hnh cacboxyl ho mui cacboxylat. Th d:

CH3COONa + NaOH rn CH2 - CH2-C CH2 - CH2-C O O O O Ca CaO CH + Na CO 4 2 3 t0 CH2 - CH2 [H] CH2 Zn + HCl CH2 - CH2 - H2O
CH2 - CH2 t0 C =O -CaCO3 CH2 - CH 2
c. in phn dung dch mui natri ca axit monocacboxylic

2 RCOONa + 2 H2O p R -R + 2 NaOH + 2 CO + H 2 2
1.3. Tnh cht vt l

Ankan l nhng cht khng mu, khng mi, t tan trong nc, tan nhiu trong dung mi hu c, c khi lng ring nh hn 1,0. Bn cht u ca dy ng ng l cht kh, nhng ankan c t 5-17 nguyn t cacbon trong phn t l cht lng, t C18H28 tr ln l nhng cht rn. Nhit si, nhit nng chy tng dn theo chiu tng mch cacbon. Cc ng phn mch nhnh c nhit si thp hn ng phn mch thng. nhit si cng thp nu s nhnh cng nhiu v cng gn u mch chnh. Xicloankan cng l nhng cht khng mu, khng mi c nhit si cao hn nhit si ca ankan tng ng. Xiclopentan v xiclohexan l nhng cht lng, cn cc xicloankan cao hn l nhng cht rn.
1.4. Cu to
Trong phn t ankan v xiclankan cc nguyn t cacbon u trng thi lai ho sp3. Bn obitan lai ho sp3 ca nguyn t cacbon c hnh dng, mc nng lng nh nhau hng v bn nh ca mt t din u. Gc ho tr l 109028. Bn obitan lai ho sp3ca nguyn t cacbon ny to vi obitan sp3 ca nguyn t cacbon khc hoc vi obitan s ca nguyn t hir bn lin kt
. Do trong phn t ankan ch gm cc lin kt bn vng nn ankan kh tham gia cc phn ng ho hc.
Hnh 2.1. Cc lin kt trong phn t metan v etan
Trong phn t xicloankan cng ch gm cc lin kt bn vng, nhng do mch cacbon ng vng lm cho gc lin kt b thay i so vi gc ho tr 109028, dn n bn ca cc xicloankan thay i. Cc xicloankan c s cnh ca vng khc nhau, gc lin kt khc nhau, bn s khc nhau. gii thch bn khc nhau ca cc xicloankan, nm 1885 Annph Bayer a ra thuyt sc cng Bayer. Ni dung ca thuyt sc cng Bayer nh sau: - Mi nguyn t cacbon to vng cng nm trn mt mt phng, ngha l vng c cu to phng. - Gc ho tr bn l gc 109028. Cc gc ho tr ca vng ln hn hay nh hn 109028 u lm cho lin kt cacbon-cacbon km bn v n phi chu mt lc cng ra hay p li. Gc cng hay gc p cng ln vng cng km bn v kh nng phn ng ca vng cng ln. Gc cng hay p c tnh bng biu thc:
= 109028' - 2
Trong : l gc cng hay gc p

l gc ca vng
Kt qu tnh chnh lch gc ho tr ca mt s xicloankan nh sau: n 3 +24044 4 +9044 5 +0044 6 -5016 7 -9033 8 -12051
Nh vy sc cng ln nht l xiclopropan, nhng sc cng ny gim bt mt cht do nhng obitan lai ho ca nguyn t cacbon b xen ph theo dng lin kt hnh qu chui.
1600 600
Hnh 2.2. Lin kt hnh qu chui
Lin kt ny km hiu qu, l trung gian gia lin kt v lin kt . iu cho php gii thch xiclopropan c khuynh hng tham gia phn ng cng hp m vng. Khi tng kch thc ca vng chnh lch ca gc ho tr so vi gc l tng gim. Nhng xiclohexan c gc ca vng l 1200, vy n phi c sc cng ln hn xiclopentan. Kt lun ny mu thun vi tnh cht. S d nh vy l v thuyt sc cng Bayer da vo gi thuyt cu to phng ca mi h thng xicloankan. Thc t chng c s sp xp khng gian khng phng ca cc nguyn t cacbon trong vng, do sc cng gim.
1.5. Tnh cht ho hc iu kin thng cc ankan km hot ng ho hc, chng khng phn ng vi kim c, axit c v cc cht oxi ho nh kali pecmanganat, kali bicromat. nhit cao hoc trong nhng iu kin c bit ankan tham gia mt s phn ng, trong phn ng th, phn ng hu l nhng phn ng quan trng nht.
a. Phn ng th
Quan trng hn c l phn ng halogen ho, l phn ng thay th nguyn t hiro ca ankan bng nguyn t halogen. Phn ng ch thc hin c khi c nh sng khuch tn hoc nhit cao. Phng trnh phn ng tng qut:
RH + X2 h (t0) RX + HX
thy r trung tm phn ng, ta c th biu din di dng sau:

C - H + X2 h (t0) C -X + HX
y, X2 l F2, Cl2, Br2, I2.

Phn ng xy ra theo c ch th gc (SR)qua cc giai on: - Giai on u tin l giai on khi mo phn ng. Do tc dng ca nh sng t ngoi hoc nhit cao, lin kt gia hai nguyn t halogen b ct t theo kiu ng li to thnh hai nguyn t halogen hot ng, mi nguyn t halogen mang mt in t t do:
X X
2X
- Giai on tip theo, nguyn t halogen hot ng tc dng vi ankan ct t ng li lin kt C-H to ra mt gc cacb t do, gc ny phn ng tip vi phn t halogen khc to ra dn xut halogen v nguyn t halogen hot ng. Phn ng tip tc xy ra lp i lp li theo kiu phn ng dy chuyn. Giai on ny thng c gi l giai on pht trin mch.
C-H +X C + X2 C + HX CX + X
- Phn ng dng li khi xy ra mt trong s cc phn ng sau:

X C C + + + X C X X2 C C C -X
Giai on ny c gi l giai on tt mch. Kh nng tham gia phn ng halogen ho gim dn t flo n it. Flo phn ng cc k mnh lit vi ankan cho sn phm ca phn ng hu do tt c cc lin kt C-C v C-H u b ct t. Cc ankan c cc nguyn t cacbon bc khc nhau trong phn t khi tham gia phn ng s cho nhiu sn phm, nhng sn phm th nguyn t hiro ca nguyn t cacbon bc cao l sn phm chnh. Th d: Cl h CH3 -C -CH3 + CH3 -CH -CH2Cl + 2 HCl 2 CH3 -CH -CH3 + 2Cl2 CH3 CH3 CH3 sn phm chnh sn phm ph
b. Phn ng cng hp ca xicloankan
Cc vng 3, 4 cnh km bn, c tnh cht ging anken, chng d dng tham gia cc phn ng cng hp m vng. Th d: CH2
H2C CH2 + Br2 Br -CH2 -CH2 -CH2 -Br
c. Phn ng oxi ho
iu kin bnh thng cc ankan khng b oxi ho bi oxi khng kh, cc cht oxi ho mnh nh H2SO4 c, KMnO4Nhng nhit cao, cc ankan b oxi ho to thnh sn phm cha oxi. Khi un nng t 100 - 1600C vi s c mt ca cc cht xc tc (KMnO4, Na2CO3) cc ankan b oxi ho bi oxi khng kh to thnh cc axit.
Th d:
100 -1600C CH3 -(CH2)16 -CH3 + 3 O2 2CH3 -(CH2)16 -COOH + 2 H2O
Trong mt s trng hp c th gy nn s t mch cacbon.

CH3 -(CH2)n -CH3 O2,xt CH3 -(CH2)x -COOH CH3 -(CH2)y -COOH
Khi c mt oxi d, cc ankan b chy to thnh kh CO2 v H2O, ng thi gii phng mt lng nhit ln. Th d:
CH4 + 2 O2 CO2 + 2 H2O +885Kj
Chnh v th m mt s ankan c dng lm nhin liu t.

d. Phn ng hu
nhit cao, khng c oxi khng kh, cc ankan b phn hu gy mch to thnh cc ankan v cc hirocacbon khng no (anken) c mch ngn hn. Qu trnh ny c gi l qu trnh crckinh. crckinh CnH 2n+2 CxH 2x+2 + CyH 2y ankan anken
2 CH3-CH2-CH2-CH3 CH3-CH=CH2 + CH4 + CH2=CH2 + CH3-CH3
Phn ng ny c dng nhiu trong cng nghip du m iu ch xng.

2. Hirocacbon khng vng cha no (anken, ankaien, ankin)
Hirocacbon cha no l nhng hirocacbon m trong phn t c mt hay nhiu lin kt pi (). Nhng hirocacbon thuc loi ny ch yu gm c: anken, ankaien, ankin. Anken l hirocacbon cha no, mch h c mt lin kt i trong phn t. Cng thc chung l CnH2n (n2). Cc anken lp thnh mt dy ng ng, ng u dy ng ng l tylen (C2H4). Ankaien l hirocacbon cha no, mch h c hai lin kt i trong phn t. Cng thc chung l CnH2n -2 (n3). Tu theo v tr ca hai lin kt i ngi ta phn ankaien thnh ba loi: - Ankaien c hai lin kt i cch xa nhau
Th d: CH2=CH - CH2 - CH2 - CH=CH2 hex-1,5-ien - Ankaien c hai lin kt i lin nhau Th d: CH2=C = CH2 prop-1,2-ien CH3- CH = C = CH2 but-1,2-ien
- Ankaien c hai lin kt i xen k mt lin kt n (ankaien lin hp) Th d: CH2=CH - CH = CH2 but-1,3 -ien CH2=C - CH = CH2 CH3 2-metylbut-1,3-ien (iso pren)
- Ankin l hirocacbon cha no, mch h c mt lin kt ba trong phn t. Cng thc chung l CnH2n -2 (n2). Chng lp thnh mt dy ng ng, ng u dy ng ng l axetylen (C2H2).
2.1. Cch gi tn v ng phn

a. Tn gi thng thng
Cch gi tn ny ch p dng cho cc hircacbon khng vng, cha no n gin, c mt lin kt i. Ngi ta gi tn ankan tng ng ri thay ui an bng ui ylen. Th d: CH2=CH2 etylen CH3-CH=CH2 propylen CH3-C=CH2 CH3 isobutylen
Mt s ankaien c tn gi h thng nh sau: CH2=C-CH=CH2 CH3 allen ivinyl iallyl isopren i vi cc ankin, ngi ta ly axetilen lm cht gc, cn cc ng ng ca axetilen c coi l dn xut th ca axetilen khi th nguyn t hir trong axetilen bng gc ankyl v gi tn nh sau: Tn gc ankyl + axetilen Th d: CH3-C C-CH3 CH3-C CH metyl axetilen imetyl axetilen CH2=C=CH2 CH2=CH-CH=CH2 CH2=CH-CH2-CH2-CH=CH2
b. Tn gi IUPAC
gi tn cc hirocacbon khng vng cha no theo tn gi IUPAC, th t cc bc tng t nh gi tn ankan, nhng ch khc: - Chn mch chnh l mch cacbon di nht cha lin kt kp. - nh s th t cacbon trn mch chnh bt u t pha gn lin kt kp nht. - Mch chnh c tn gi ca ankan tng ng b ui an, s ch v tr lin kt kp v ui en, ien hoc in. Th d: CH3-CH=CH-CH3 but-2-en CH2=C-CH=CH2 CH3 2-metylbut-1,3-ien CH3 C C-CH-CH3 CH3 4-metyl pent-2-in
Cc gc cha lin kt i c tn gi chung l ankenyl. Cn ch tn gi thng dng ca mt s ankenyl sau y: CH2=CCH2=CH- CH2=CH-CH2CH3 vinyl allyl iso- propenyl CH3-CH= CH2= metylen etylien Gc ho tr mt ca ankin gi l ankinyl. CH=C CH=C -CH2 etinyl prop-2-inyl
c. ng phn
Cc hirocacbon cha no c cc loi ng phn: - ng phn v cu to mch cacbon Th d: CH3-CH-CH=CH2 CH3 3-metyl but-1-en (isopentylen) - ng phn v v tr lin kt kp
CH3 -CH2 -C=CH
CH3 -C=C -CH3
CH3-CH2-CH2-CH=CH2 pent-1-en (pentylen)
but-1-in
but-2-in
- ng phn hnh hc
CH3 H C =C CH2 -CH3 H trans-pent-2-en CH3 CH2 -CH3 C =C H H cis-pent-2-en
2.2. Phng php iu ch

a. i t dn xut halogen
Cc hirocacbon cha no c th iu ch bng cch loi HX ca dn xut halogen trong mi trng kim/ru:
CH3 -CH -CH -CH3 Br CH3
CH3 -CH2 -CHCl2
KOH CH - CH =C -CH + HBr 3 3 ru CH3

KOH CH - C =C + 2 HCl 3 ru
CH2 -CH2 -CH2 -CH2 Br Br
KOH CH = CH -CH =CH + 2 HBr 2 2 ru
b. i t ancol
Cc hirocacbon cha no c th iu ch bng cch loi nc ca ancol trong iu kin c H2SO4 c lm cht ht nc nhit trn 1700C.
CH3 -CH2 -OH H2SO4 CH2 = CH2 + H2O >1700C
H SO CH3 -CH -CH2 -OH 2 04 CH3 - C = CH + 2H2O >170 C OH H SO CH2 -CH2 -CH2 -CH2 2 04 CH2 = CH - CH =CH2 + 2H2O >170 C OH OH
Khi c mt Al2O3 v nhit thch hp c th tng hp c but-1,3-ien t ancol etylic.

2 CH3 -CH2 -OH Al2O3 CH2 = CH - CH =CH2 + 2H2O + H2 t0
c. Cc phng php ring iu ch axetilen
CaC2 + 2 H2O
Ca(OH)2 + C2H2
2 CH4
15000C
CH =CH + 3 H2
2.3. Tnh cht vt l

Cc anken t C2H4 n C4H8 l cht kh, t C5H10 n C16H32 l cht lng, cn li t C17H34 tr ln l nhng cht rn. Cc anken c nhit si v nhit nng chy thp hn so vi ankan tng ng. Nhit si ca ng phn cis cao hn ng phn trans, cn nhit nng chy th ngc li. Cc ankin tnh cht vt l cng tng t nh anken. Khi trng lng phn t ca cc ankin tng ln th nhit si v nhit nng chy, t trng cng tng.
2.4. Cu to
a. Cu to ca cc anken Hai nguyn t cacbon lin kt i trng thi lai ho sp2. Ba obitan lai ho sp2 ca nguyn t cacbon ni i hnh thnh ba lin kt , trong c mt lin kt (C-C) hnh thnh do s xen ph ca obitan sp2- sp2 v hai lin kt khc c th l lin kt (C-H) do s xen ph ca obitan sp2- s hoc lin kt (C-C) do s xen ph ca obitan sp2 ca cabon ni i v sp3 ca cacbon. Mi nguyn t cacbon lin kt i cn li mt obitan 2pz cha tham gia lai ho, chng c trc vung gc vi mt phng cha lin kt , song song vi nhau, c spin ngc chiu nhau, chng xen ph vi nhau hnh thnh lin kt . Do lin kt i gm mt lin kt v mt lin kt . V trong phn t c cha lin kt km bn, d dng b ph v tham gia cc phn ng cng hp, oxi ho v trng hp.
H C C H H H
Hnh 2-3. Lin kt trong phn t etylen Hnh 2-4. Lin kt trong phn t etylen b. Cu to ca ankaien Cc ankaien c cu to tng t nh anken. Ring cc ankaien lin hp cc in t lin hp vi nhau to thnh mt obitan phn t duy nht gii to trn ton b h lin hp.
H H H
H H H
Hnh 2-5: Lin kt trong phn t but-1,3-ien

c. Cu to ca ankin
Hai nguyn t cacbon lin kt ba trng thi lai ho sp. Hai obitan lai ho sp to thnh hai lin kt , trong c mt lin kt (C-C) hnh thnh do s xen ph ca hai obitan lai ho sp, v mt lin kt , do s xen ph ca obitan lai ho sp ca cacbon ni ba vi obitan s ca nguyn t hir hoc hnh thnh do s xen ph ca hai obitan lai ho sp vi sp3. Mi nguyn t cacbon ni ba cn li hai obitan p cha tham gia lai ho, chng c trc vung gc vi mt phng cha lin kt , song song vi nhau v c spin ngc chiu nhau. Cc obitan p ny xen ph vi nhau tng i mt hnh thnh nn hai lin kt . Cc lin kt km bn nn cc ankin l hp cht hot ng ho hc mnh, d dng tham gia cc phn ng cng hp, xi ho, phn ng trng hp.
Hnh 2-6: Cc lin kt trong phn t axetilen
Hnh 2-7: Cc lin kt trong phn t axetilen
2.5. Tnh cht ho hc

Trong phn t ca tt c cc hirocacbon cha no u c lin kt km bn, lin kt ny b phn cc ho mnh bi cc hiu ng in t c trong ni b phn t, bi tc nhn phn ng v iu kin phn ng, do vy cc hirocacbon cha no d dng tham gia phn ng cng hp, phn ng oxi ho, phn ng trng hp.
a. Phn ng cng hp vo lin kt kp
Phn ng cng hp xy ra lin kt , chng hn phn ng cng hp ca anken xy ra theo s tng qut sau:
+ C
C + A+B-
A C B C
y AB c th l X2, HOH, HX, HOX, H2SO4

Phn ng xy ra theo c ch cng hp i in t qua hai gia on: - giai on u, tc nhn i in t (cation A+) cng hp vo nguyn t cacbon mang phn in tch m ni i to thnh cacbocation trung gian. y l giai on chm, thun nghch, quyt nh tc phn ng. AB A+ + B-
+ C
A + A+ chm + C C
- giai on sau, cacbocation trung gian tc dng vi anion B- cho sn phm. Giai on ny phn ng xy ra nhanh, mt chiu. A A + nhanh C C + BC C
B
Sau y ta xt mt s phn ng cng hp c th:

- Phn ng cng hp halogen
C C + X2 C X C X
y X2 l F2, Cl2, Br2, I2.

Th d:
CH3 -CH =CH2 + Br2 2 CH2 =CH -CH =CH2 +2Br2 CH3 -CH -CH2 Br Br CH2 -CH -CH =CH2 + CH2 -CH =CH -CH2 Br
CH3 -C =CH Br2 CH3 -C =CH Br Br Br2
Br Br Br CH -C -CH
Br Br
Br
Br
Phn ng cng hp Br2 c dng nhn bit lin kt kp.

- Phn ng cng hp hiro halogenua (HX)
Tt c cc hirocacbon cha no u d dng cng hp vi HX. + C C + HX C C
X
Th d:
+ CH3 -C = CH -CH3 CH3
H
Br
+ HBr
CH3 -C -CH2 -CH3 CH3
C ch cng hp i in t: HBr H+ + Br+ CH3 -C = CH -CH3 + H CH3
CH3 -C -CH2 -CH3 CH3 Br
CH3 -C -CH2 -CH3 + Br CH3 -C -CH2 -CH3 CH3 CH3 Cc ankaien lin hp cng hp vi hirohalogenua bao gi cng cho hai loi sn phm cng hp 1,2 v cng hp 1,4.
Th d:
Br CH3 -C -CH =CH2 + CH3 -C =CH -CH2 2 CH2 =C - CH =CH2 +2 HBr Br CH3 CH3 CH3 C ch phn ng: HBr H+ + Br+ CH2 C - CH CH2 + H+ CH3 - C CH CH2 CH3 CH3
Trong cacbocation lin hp in tch dng gii to trn c ba nguyn t cacbon, nhng tp trung hn l C2, C4. Br + + CH3 - C CH CH2 CH3 - C CH CH2 CH2 + 2Br 2 CH3 C CH CH3 Br CH3 CH3
Hirohalogenua cng hp vo ankin s cho sn phm l gem ihalogen ankan. Th d: Cl + HCl + HCl CH3 -C=C -CH3 CH3 -C =CH -CH3 CH3 -C -CH2 -CH3 Cl Cl - Cng hp nc Trong mi trng axit cc anken v ankaien cng hp nc to ra cc ancol.
C C + HOH H H C C OH
Th d:
CH3 -CH =CH2 + H2O
CH2 =CH -CH =CH2 + H2O
H
H
CH3 -CH - CH3 OH

CH3 -CH = CH -CH2 -OH
Khi c mt ca xc tc Hg2+ v axit mnh (H2SO4), cc ankin phn ng vi nc to thnh enol, cht ny khng bn chu s ng phn ho to thnh hp cht cacbonyl. Nu ankin l axetilen s thu c anehit axetic, cn ankin l ng ng ca axetilen thu c xeton. Th d: 2+ Hg chuyn v CH = CH + H2O CH2=CH - OH CH3 -CHO H2SO4
CH3 -C = CH + H2O
Hg2+ chuyn v CH3-C= CH2 CH3 -C -CH3 H2SO4 O OH

=
b. Phn ng oxi ho
Ph thuc vo iu kin ca phn ng cc hirocacbon cha no c th b oxi ho to thnh cc sn phm khc nhau: poli ancol, anehit, xeton, axit,
nhit bnh thng cc hirocacbon cha no b oxi ho bi dung dch KMnO4 hoc dung dch H2O2 trong mi trng axit yu to thnh poli ancol.
Th d:
CH3 - Ch = CH2 +KMnO4 +H2O CH2 =Ch - CH = CH2 +KMnO4 +H2O CH3 - CH -CH2 + KOH + MnO2 oh oh
CH2 - CH -CH-CH2 + KOH + MnO2 oh oh oh oh Vi tc nhn oxi ho mnh nh hn hp KMnO4 + H2SO4 hoc K2Cr2O7, cc hirocacbon cha no b oxi ho cho sn phm l axit cacboxylic, xeton v cacbon ioxit. Th d: K Cr O +H2SO4 CH3 - Ch =CH - CH3 2 2 7 2 CH3 - COOH + H2O
CH2 =Ch - CH = CH2 Ch3 - C = CH2 CH3
K2Cr2O7 +H2SO4
HOOC -COOH + 2CO2 + H2O
CH3 - C -CH3 + CO2 + H2O O Nhng phn ng ny c dng xc nh v tr ca lin kt i trong phn t anken hoc ankaien. Khi b oxi ho bi ozon (O3), lin kt i trong phn t anken b t ra to thnh nhng hp cht cacbonyl. Th d: O HO CH3 - CH CH -CH3 2 2 CH3CHO + H2O2 CH3 - Ch =CH - CH3 + O3
O O
K2Cr2O7 +H2SO4
O CH2 =Ch - CH = CH2 + O3 H2O

O Ch3 - C = CH -CH3 + O3 CH3 CH3 - C CH -CH3 CH3 O O
O CH - CH O O CH2
CH2 O O
2HCHO + OHC -CHo + H2O2

H2 O
CH3 - C -CH3 + CH3CHO + H2O2 O

=
Khi c mt cht xc tc Ag kim loi 150 -3500C hirocacbon cha no b oxi ho bi oxi khng kh to thnh ete oxit. Th d: O Ag CH2 =CH2 + O2 CH2 CH2 1500-3500C O O Ag CH2 =C - CH =CH2 +O2 C - CH CH2 0 0 CH2 150 -350 C CH3 CH3 Phn ng oxi ho ng vai tr quan trng trong vic xc nh cu to ca nhng hp cht t nhin phc tp v xc dnh cu to ca nhng hp cht cha lin kt i.
c. Phn ng trng hp
Phn ng trng hp l phn ng to thnh hp cht cao phn t t nhng phn t n gin. Th d: 1900-2100C n ( - CH - CH -) n CH2 =CH2 (-CH2 -CH2 -)n 2 2 1500-2000at pli tylen tylen n ( -CH2 -CH =CH -CH2 -) (-CH2 -CH =CH -CH2 -)n n CH2 =Ch - CH = CH2 cao su buna d. Phn ng th Nhng ankin c cha nguyn t hiro lin kt vi cacbon trng thi lai ho sp c th tham gia phn ng th. Nguyn t hiro c thay th bi nguyn t kim loi to thnh mui. Trong phn ng ny ankin th hin tnh axit. iu ny c gii thch do nguyn t cacbon trng thi lai ho sp c m in ln, lin kt Csp-H b phn cc mnh. Kali hiroxit khan c th chuyn ankin-1 thnh kali axetilua, tuy nhin phn ng ny xy ra thun li hn nu ta dng kali amiua trong amniac lng.
R -C =CH + KNH2 NH3 lng R -C =C -K + NH3
Cc ankin -1 v axetilen d dng phn ng vi phc bc amoniacat cho kt ta bc axetilua.

R -C =CH + 2[Ag(NH3)2]OH
R -C =C Ag + 2NH3 + H2O
HC =CH +2[Ag(NH3)2]OH
AgC =C Ag + 4 NH3 +2 H2O
3. hirocacbon thm
Hirocacbon thm l nhng hirocacbon c cha nhn benzen trong phn t. Da vo cu to ngi ta chia hirocacbon thm thnh hai loi: - Hirocacbon thm mt nhn - Hirocacbon thm nhiu nhn 3.1. Hirocacbon thm mt nhn benzen Hirocacbon thm mt nhn benzen c cng thc chung CnH2n-6 (n6), k hiu Ar-H. Gc hirocacbon thm ho tr mt c tn gi l gc aryl, k hiu ArTh d: C6H5-CH2C6H5phenyl benzyl
a. Cch gi tn v ng phn
Ngi ta thng dng tn gi hp l gi tn ng ng ca benzen. Theo tn gi ny ngi ta ly cht gc l benzen, cn cc ng ng khc ca benzen c coi l dn xut th ca benzen khi th nguyn t hir trong nhn benzen bng gc ankyl v gi tn theo nguyn tc: Tn gc ankyl +benzen Ngoi ra mt s ng ng khc ca benzen cn c gi tn theo tn gi h thng. Th d:
CH3 CH -CH3 CH3 isopropylbenzen (cumen) CH3
metylbenzen (toluen) CH3

CH3
CH3 CH3
o-xilen
CH3 p-xilen
m-xilen
Nhn thm c hai nhm th ankyl tr ln th hnh thnh ng phn v v tr nhm th. gi tn cc ng phn ngi ta tin hnh nh s cc nguyn t cacbon ca vng benzen. Bt u nh s t nguyn t cacbon trong vng benzen lin kt vi nhm th n gin nht. nh s theo chiu sao cho tng cc con s ch v tr nhm th l nh nht. Gi tn theo nguyn tc: V tr nhm th + tn nhm th + benzen Th d:
CH3 CH2 -CH3 CH2 -CH3 CH2 -CH3 1-metyl-4-etylbenzen CH3 CH3
1-metyl-2-etylbenzen
1-metyl-3-etylbenzen
Ngi ta qui c v tr s 2 v s 6 c gi l v tr octo (vit tt l o-), v tr s 3 v s 5 c gi l v tr meta (vit tt l m-), v tr s 4 gi l v tr para (vit tt l p-). Theo qui c cc ng phn trn c gi tn tng ng l o-etyl toluen, m-tyl toluen, p-etyl toluen. Vi cc dn xut ca benzen nhng nguyn tc c bn trn y vn c p dng. Th d:
NO2 Cl
nitrobenzen Br Br
clobenzen NO2
Br Cl
1,2-ibrom benzen
3-clo-5-brom nitrobenzen
Tuy nhin nhiu benzen th mt ln mang tn h thng v chng ph bin rt rng ri i hi chng ta phi nh. Th d:
NH2 OH
OCH3
CHO
COOH
anilin
phenol
anisol
benzanehit
axit benzoic
Cc ng ng ca benzen c hai loi ng phn: - ng phn v cu to mch nhnh.

CH2 - CH2 -CH3 CH -CH3 CH3 isopropylbenzen
CH3 CH3 CH3
n- propylbenzen - ng phn v v tr nhm th CH3

CH3
1,2-imetylbenzen
b. Phng php iu ch
1,3-imetylbenzen
CH3 1,4-imetylbenzen
Benzen c iu ch bng phn ng trng hp ba phn t axetilen 6000C.

6000C C Cc ng ng ca benzen c iu ch bng hai phng php chnh sau y: - Phn ng Vuyc-Fittic
3 CH =CH
Ar -X + 2Na + X -R Th d: Cl Ar -R + 2NaX
CH3 + 2NaCl
+ 2Na + Cl -CH3
- Phn ng Frien-Crap
R + RX AlCl3 HX
CH2 -CH3 +CH3 -CH2 -Cl AlCl3 HCl
Th d:
c. Tnh cht vt l
Phn ln cc hirocacbon thm l nhng cht c mi c trng. Cc ng phn khc nhau v v tr ca gc ankyl trong nhn benzen c nhit si gn ging nhau, nhng nhit nng chy li khc nhau rt nhiu. Cc ng phn para c im nng chy cao nht.
d. Cu to ca benzen
Tt c cc hirocacbon thm u c cha nhn benzen. V vy vic nghin cu cu to ca benzen cho php hiu v cu to ca cc hirocacbon thm. - Cu to phn t benzen theo Kkul: Ben zen c cng thc C6H6. Theo Kkul cu to ca benzen l nh sau:
Cu to ny th hin s khng no rt ln, ngha l n d dng tham gia phn ng cng hp v kh i vi phn ng th. Ngc li, benzen tng i tr vi cc tc nhn oxi ho, d tham gia phn ng th, kh tham gia phn ng cng hp. - Cu to phn t benzen theo quan im hin i: Benzen c cu to vng 6 cnh phng, tt c 6 nguyn t cacbon v 6 nguyn t hiro u nm trn mt phng . Cc nguyn t cacbon u trng thi lai ho sp2, l kiu lai ho tam gic, gc lai ho 1200. Mi nguyn t cacbon to thnh ba lin kt , trong c hai lin kt C-C (sp2-sp2) v mt lin kt C-H (sp2-s). Mi nguyn t cacbon cn li mt obitan 2pz cha tham gia lai ho. Cc obitan ny vung gc vi mt phng cha lin kt (mt phng vng benzen), c spin ngc chiu nhau. Tt c 6 obitan 2pz ny xen ph, pha ho ln vo nhau, lin hp vi nhau to thnh mt obitan phn t khp kn. Do s lin hp nh vy lm cho khong cch gia cc nguyn t cacbon trong phn t u bng nhau (1,40A0), vng tr nn bn vng kh tham gia phn ng cng hp, bn vi tc nhn oxi ho v d tham gia phn ng th. c tnh ny ca benzen c gi l tnh thm.
h C h C C h C C
h C h h
Cc lin kt trong phn t benzen
biu din cng thc cu to ca benzen ta c th dng mt trong ba cng thc sau:
c. Tnh cht ho hc - Phn ng th
Benzen v ng ng ca benzen d dng tham gia phn ng th nguyn t hiro trong nhn thm bng nguyn t hoc nhm nguyn t khc. Phng trnh phn ng tng qut:
Ar -H + AB xt Ar -A + HB
Phn ng xy ra theo c ch th i in t (electrophin) hai giai on. Giai on u, tc nhn i in t ( cation A+) tn cng vo h thng in t trong nhn, mt cp in t c A nhn to thnh lin kt vi mt nguyn t C, trong nhn cn li hai cp in t c gii to ng u trn nm nguyn t cacbon cn li. Sn phm trung gian khng bn ny c gi l phc .
chm H Ar - A
Ar -H + A
Giai on sau, phc loi proton cacbon b th to thnh sn phm.

H A Ar
Ar
A + H
Sau y ta xt mt s phn ng c th.

- Phn ng halogen ho
L phn ng thay th nguyn t hiro trong nhn benzen bng nguyn t halogen. Tc nhn ca phn ng l halogen v xc tc thng dng l cc axit liuyt nh AlCl3, FeX3. Trong thc t phn ng ny thng dng xc tc l bt st. Bt st tc dng vi cc halogen to thnh cc axit liuyt l FeX3. S phn ng tng qut nh sau:
X + X2 Fe bt + HX
Cl2 v Br2 halogen ho benzen mt cch bnh thng, I2 phn ng thun nghch, F2 khng phn ng trc tip vi benzen.
Th d:
Br
+ Br2
CH3
Fe bt
+ HBr
CH3 Br
CH3 +
+ 2Br2 Fe bt
+ 2HBr
Br
Tc nhn i in t c to thnh nh sau: 2 Fe + 3 X 2 2FeX3 FeX3 + X2 X. ..... X. ....FeX3 Sau phn ng xy ra. H + + X +X
FeX4 + X
+ + H
iu kin nhit cao hoc chiu nh sng t ngoi, cc ng ng ca benzen thc hin phn ng halogen ho phn nhnh theo c ch th gc tng t cc ankan.
Th d:
Cl C -CH3 + HCl CH3
CH -CH3 + Cl2 CH3
h t0
- Phn ng nitro ho
Tc nhn phn ng thng dng l hn hp nitro ho ( HNO3 c + H2SO4 c). Th d:

H2SO4
+HNO3
NO2 +
H2O
Tc nhn i in t NO2+ c to ra do phn ng:

HNO3 + 2H2SO4 + NO2 NO2 + 2HSO4 + H3O + H NO2 NO2 + H
H + 2HSO4 + H3O
H2SO4 + H2O
- Phn ng ankyl ho
C th ankyl ho hirocacbon thm bng cc tc nhn ankyl halogenua, anken, vvKhi dng tc nhn ankyl halogenua cn c xc tc l AlCl3 khan hoc FeCl3 lm xc tc.
AlCl3 R + HX
+ AlCl3X + R H R +
+R -X
Tc nhn i in t R+ c to thnh do:

AlCl3 + RX
+ AlCl3 ....X....R
+ R+
H+ + AlCl3X - Phn ng axyl ho
R+
HX + AlCl3
+ + H
Tc nhn axyl ho thng dng l axyl halogenua R-CO-X, xc tc l AlCl3.

C -R O + HX
=
+ R -C -X O
=
Tc nhn i in t c hnh thnh v c ch phn ng xy ra nh sau:

+ R -C ...Cl ....AlCl3 O
=
R -C -Cl O
=
+ AlCl3
+ R -C + AlCl4 O
=
+ + + R -C O + H + AlCl4 HCl + AlCl3

=
H C -R O
C -R + O +H
+ Quy tc th i in t trong nhn thm
Khi trong nhn thm c sn nhm th th cc nhm th ny s nh hng n s th tip tc v hai phng din: - Lm tng hay gim tc phn ng th - Hng tc nhn th vo v tr nht nh i vi nhm th c sn.
iu c quyt nh ch yu l do bn cht in t ca nhm th. C th phn chia cc nhm th thnh hai loi nh sau: - Nhng nhm th nh hng octo v para gm c: -R, -X, -OH, -NH2, -NHR, -NR2, -NH-CO-R Nhng nhm th ny u hot ho nhn thm (tr nhng nguyn t halgen X), do chng c ng thi hiu ng cm ng dng (+I) v hiu ng siu lin hp (-) hoc hiu ng lin hp dng (+C) ln hn hiu ng cm ng m (-I) lm cho mt in t trong nhn benzen tng ln v tng ch yu cc v tr octo v para. Do vy phn ng xy ra d dng hn v cho sn phm th v tr octo v para. Th d:
H H C H +I
+C NH2 -I
+C OH -I
Khi nhn benzen c mt nguyn t halogen, mt in t trong nhn gim i bi nguyn t halogen gy hiu ng cm ng m (-I) mnh hn hiu ng lin hp dng (+C). Tc phn ng th i in t chm hn so vi benzen, nhng nguyn t halogen vn thuc nhm th nh hng octo v para, v hiu ng lin hp dng (+C) quyt nh chiu phn cc ca lin kt kp lm cho mt in t cc v tr octo v para ln hn v tr meta. +C Cl -I
- Nhng nhm th nh hng meta: Gm c -CN, -NO2, -CH=O, -COR, -COOH, -COOR Nhng nhm ny c ng thi hai hiu ng ht in t (-I, -C) lm mt in t trong nhn gim i, phn hot ho nhn thm v gim ch yu cc v tr octo v para. Phn ng th xy ra kh khn hn so vi benzen v cho sn phm th v tr meta. Th d:
-C -I C O H -I -C C O OH -I -C N O O
S tn ti hai nhm th trong vng benzen lm phc tp ho tc dng nh hng. C th tin on hng ca phn ng da theo nguyn tc sau: Nu trong vng benzen tn ti hai nhm th cng hot ho vng hoc c tc dng nh hng khc nhau th nhm hot ho mnh s khng ch hng ca nhm th th ba.
- Phn ng cng hp
Phn ng cng hp ph v h lin hp ca nhn thm xy ra tng i kh khn so vi cng hp vo anken. - Cng hp hiro: Phn ng xy ra khi c xc tc Ni, Pt, Pdta thu c xiclo ankan tng ng. Th d:
+ 3 H2
benzen CH3
+3H2
xiclohexan CH3
toluen metyl xiclohexan - Cng hp halogen: Quan trng hn c l phn ng cng hp clo. Khi cho clo i qua benzen c chiu nh sng khuch tn, phn ng xy ra ta thu c hexaclo xiclohexan. Cl Cl 0 Cl 50 C + 3 Cl2 h Cl Cl Cl Hexaclo xiclohexan c nhiu ng phn lp th, trong ng phn gamma () c hot tnh c i vi cn trng, v vy ng phn ny c dng lm thuc tr su (c tn gi l thuc tr su 6.6.6). Hin nay thuc tr su ny c cm s dng do s tn lu lu di v gy c hi i vi mi trng.
Phn ng oxi ho
Benzen ch b oxi ho khi cho oxi khng kh tc dng nhit cao, c V2O5 xc tc to thnh anhirit maleic.
4000C-4500C V2O5 O C= O + CO2 C = O
+ O2
anhirit maleic Benzen cng tham gia phn ng ozon ho to thnh glioxal.
+ O3 H 2O CHO CHO + H2 O 2
Vi cc cht oxi ho mnh: KMnO4 +H2SO4, K2Cr2O7 +H2SO4cc ng ng ca benzen b oxi ho mch nhnh, ct t lin kt C - C v oxi ho chng thnh nhm chc axit. Th d:
CH2 -CH2 -CH3 0 + KMnO4 + H2SO4 t
COOH + CH3COOH + K2SO4 + MnSO4 + H2O
n- propyl clorua
axit benzoic
CH3 t0 + KMnO4 + H2SO4 CH3
o-xilen
COOH + CH3COOH + K2SO4 + MnSO4 + H2O COOH axit o- phtalic
3.2. Hirocacbon thm nhiu nhn Hirocacbon thm nhiu nhn cn gi l hirocacbon thm a vng. Chng c chia lm hai loi: - Hirocacbon thm a vng ri rc Th d:
- CH2 -
iphenyl - Hirocacbon thm a vng ngng t Th d:
iphenylmetan
naphtalen
a. Hirocacbon thm a vng ri rc
anthraxen
- i phenyl i phenyl c th c iu ch t dn xut monohalogen thm bng phn ng Fittic.

Th d:
Br +2Na + Br + 2NaBr
iphenyl l nhng tinh th rn, khng mu, nng chy 710C, tan tt trong etanol v ete. iphenyl cng tham gia cc phn ng th i in t nh nitro ho, halogen ho u tin phn ng v tr 4, sau l v tr 4. Th d:
HNO3 H2SO4
NO2
O 2N
NO2
b. Hirocacbon thm a vng ngng t
- Naphtalen (bng phin)

8 7 6 5 9 10 1 2 3 4
Naphtalen nguyn cht l cht kt tinh thnh nhng l mng ng nh, nng chy 80,30C v si 2180C, c mi thm c trng, d bay hi v d thng hoa. Naphtalen ging benzen nhiu phn ng, nhng kh nng phn ng ca naphtalen mnh hn benzen. Nhng phn ng th c th xy ra v tr (v tr 1, 4, 5 hoc 8) Th d:
NO2 + HNO3 + H2O
Khi b oxi ho, naphtalen bin thnh anhirit phtalic.

O2 V2O5, 4500C C O = O +2 H2O C O
=
- Phenanthren
Phenanthren l cht rn kt tinh di dng tinh th khng mu, nng chy 1010C v si 3400C. Phenanthren c tnh cht ho hc tng t nh naphtalen. Phenanthren rt gn vi nhiu hp cht t nhin c hot tnh sinh l quan trng nh vitamin D, cc kch thch t sinh dc.
Cu hi v bi tp
1. C ch th gc t do v hng ca phn ng halogen ho ankan? Gii thch bn ca cc xicloankan. 2. Cu to v tnh cht ca cc hirocacbon khng no. C ch cng hp i in t v hng ca phn ng cng hp vo lin kt i C=C; lin kt ba CC. 3. Cu to ca benzen. Tnh thm v tnh cht ho hc ca cac hirocacbon thm. C ch th i in t v quy lut th trong nhn thm. 4. Gi tn cc hp cht sau y theo tn gi thng thng v tn gi IUPAC. 4.1. CH3- CH2- CH2- CH2- CH3 4.2. CH3- CH- CH2- CH2- CH3 CH3 CH3 4.3. CH3- C- CH2- CH2- CH3 CH3 4.4. CH3- C=CH2 CH3 CH3- CH2- CCH 5. Vit cng thc cu to ca cc hp cht sau: 5.1. 2,5-imetyl octan 5.2. neoheptan 5.3. 2,5,5-trimetyl hept-3-en 5.4. isopropylbenzen 6. Vit cng thc cu to cc ng phn ca cc hirocacbon c cng thc phn t C6H14; C5H10 v gi tn chng theo tn gi IUPAC. 7. Vit phng trnh v c ch cc phn ng sau: 7.1. 2-metyl propan + Cl2 askt 7.2. 2-metyl butan + Cl2 askt 7.3. 7.4. 7.5. 7.6. 7.7. 7.8. isopropyl benzen + Cl2 t 2-metyl buta-1,3-ien + HCl Pent- 2-en + HCl Vinyl clorua + HCl Bezen + HNO3 Fe Toluen + Br2
)
8. Hon thnh cc phng trnh phn ng ho hc sau: 8.1. 2-metylpropen + KMnO4 + H2O ) 8.2. Axetilen + KMnO4 + H2O t 8.3. isopropyl benzen + KMnO4 + H2SO4 8.4. Buta-1,3-ien + O3 9. Cho bit cng thc cu to v gi tn cc hp cht c cng thc phn t: 9.1. C5H12; c mt nguyn t cacbon bc 3.
9.2. C4H8; khi cho tc dng vi dung dch KMnO4 thu c ru hai chc, trong c mt nhm chc ru bc mt v mt nhm chc ru bc 3. 9.3. C9H12; khi halogen ho nhit cao thu c dn xut halogen bc 3. 9.4. C5H10; oxi ho bng ozon, sau thu phn thu c anehit axetic v axeton. 10. T benzen v cc hp cht khc, hy vit phng trnh phn ng ho hc dng iu ch: 10.1. Axit o v m nitro benzoic. 10.2. Metyl phenyl xeton. 10.3. 2-clo- 2- phenylpropan. 10.4. p v m clo nitrobenzen.
Chng III
Dn xut ca hirocacbon
Dn xut ca hirocacbon l nhng hp cht m trong phn t ca chng cha mt hay mt s nhm chc lin kt vi gc hirocacbon. Da vo bn cht ca nhm chc m dn xut ca hirocacbon c chia thnh nhng loi khc nhau. Th d dn xut halogen, ancol, ete, axit cacboxylic vv Trong ni dung chng ny chng ta ch xt mt s dn xut quan trng, l dn xut halogen, ancol- phenol, anehit-xeton, axit cacboxylic v amin.
1. Dn xut halogen
1.1. Phn loi

Dn xut halogen l loi hp cht hu c c cha nguyn t halogen (X) lin kt vi gc hirocacbon. phn loi, ta da vo nhng c s sau y: - Cu to ca gc hirocacbon: Da vo cu to ca gc ta c dn xut halogen khng vng no, khng vng cha no; dn xut halogen vng no, vng cha no v dn xut halogen thm. Th d: CH3- CH2- Cl dn xut halogen khng vng no CH2=CH-Br, CH2=CH-CH2-Cl dn xut halogen khng vng cha no
Cl Cl dn xut halogen vng no dn xut halogen vng cha no dn xut halogen thm
Cl
- Bn cht ca nguyn t halogen: Da vo bn cht ca nguyn t halogen ta c dn xut flo, dn xut clo, dn xut brom v dn xut iot. - S lng halogen c mt trong phn t: Da vo s lng ca halogen ta c dn xut monohalogen, i, polihalogen. Th d: CH3Cl CCl4
dn xut monohalogen
dn xut polihalogen
- Da vo bc ca nguyn t cacbon lin kt trc tip vi nguyn t halogen ta c dn xut halogen bc mt, bc hai v dn xut halogen bc ba. Th d: CH3- CH2-Cl dn xut bc 1 CH3 CH3-CH-Cl dn xut bc 2 CH3 CH3-C-CH3 Cl dn xut bc 3

a. Tn gi thng thng
Theo cch gi tn thng thng, ta gi tn gc hirocacbon ri n tn anion halogen (halogenua). Th d: CH3- CH-Br CH2=CH-Cl CH2=CH-CH2-Cl CH3 V tr halogen + tn halogen + tn hirocacbon tng ng theo IUPAC isopropyl bromua vinyl clorua
Br
allyl clorua
CH2 -Cl benzylclorua
phenylbrmua
b. Tn gi IUPAC
gi tn cc dn xut halgen theo tn gi IUPAC cn tin hnh cc bc ging nh gi tn cc hircacbon. Mch cacbon c nh s sao cho cacbon lin kt vi halogen c s th t thp. Sau vic gi tn c tin hnh theo quy tc sau y: V tr halogen + tn halogen + tn hirocacbon tng ng theo IUPAC Nu phn t c cha hai, banguyn t halogen ging nhau, th trc tn halogen c thm cc t i, tri, Th d: CH3-CH-CH-CH3 CH2=CH-CH2-Cl ClCH2-CH2Cl Br CH3 2-brom-3-metylbutan 1-clo prop-2-en 1,2-iclo etan
CH C -Cl clo etin
Cl clo benzen
CH2 -Cl clo phenylmetan
c. ng phn
Dn xut halogen khng vng no c ng phn mch cacbon v ng phn v tr nhm chc. Dn xut halogen khng vng cha no c thm ng phn v tr ca lin kt i v ng phn hnh hc. Th d 1: C4H9Cl c cc ng phn mch cacbon: CH3-CH-CH2-Cl CH3 1- clo butan 1- clo- 2- metylpropan ng vi mi ng phn mch cacbon trn li c mt ng phn v tr nhm chc: Cl CH3 CH3-CH-CH2CH3 CH3-C-Cl CH3-CH2-CH2-CH2-Cl CH3 2- clobutan 2- clo-2- metylpropan 1-clobutan th d 2: C3H5Cl c cc ng phn v tr ca lin kt i v ng phn v tr nhm chc: CH2=CH-CH2-Cl CH3-CH=CH-Cl CH2=C-CH3 Cl 1-cloprop-2-en 1-cloprop-1-en 2-cloprop-1-en Th d 3: C2H2Cl2 c cc ng phn hnh hc:
h c= C Cl cl Cl cis iclo ten h h c= C cl h
CH3-CH2-CH2-CH2-Cl
trans iclo ten
1.3. Phng php iu ch

a. Halogen ho hirocacbon
Ty thuc vo iu kin phn ng (chiu sng hoc nhit thch hp), ngi ta c th iu ch dn xut halogen bng phn ng thay th nguyn t hiro trong hirocacbon bng nguyn t halogen. Th d: askt CH3 - CH3 + Cl2 CH3 - CH2 - Cl + HCl
CH2 = CH2 + Cl2 5000C CH2 = CH - Cl + HCl vinyl clorua
450 -5000C CH2 = CH - CH3 + Cl2 CH2 = CH -CH2 -Cl + HCl allyl clorua
+Br2
Fe
Br
+ HBr
b. Cng hp HX vo hirocacbon cha no
Th d: CH2 = CH - CH3 + HBr
CH3 - CH - CH3 Br 2-brom propan
1.4. Tnh cht vt l

Ankyl halogenua l nhng cht khng mu, khng tan trong nc, d ho tan trong ancol, ete v cc dung mi hu c khc. Allyl clorua l cht lng, c nhit si 450C. Vinyl clorua l cht kh khng mu, nhit si l 13,80C.
1.5. Cu to ca dn xut halogen

Tnh cht ho hc ca dn xut halogen c quyt nh bi s c mt ca nguyn t halogen trong phn t. Do vy xt cu to ca dn xut halogen thc cht l xt lin kt cacbonhalogen v nh hng ca gc hirocacbon n lin kt ny. Lin kt C-X l lin kt cng ho tr phn cc v pha nguyn t halogen (X) do nguyn t halogen c m in ln hn m in ca nguyn t cacbon. S phn cc ca lin kt C-X c m t nh sau:
C X
Gc hirocacbon c nh hng quyt nh n s phn cc ca lin kt C-X v kh nng hot ng ca nguyn t halogen. - Gc ankyl gy hiu ng cm ng dng +I lm tng s phn cc ca lin kt C-X, s lng cc gc ankyl tng, trng lng ca gc v bc ca gc tng th hiu ng cm ng dng tng, dn n s phn cc ca lin kt C-X tng.
R R CH2 X R CH X R R C X
R Gc vinyl v gc phenyl gy hiu ng lin hp C lm gim s phn cc ca lin kt C-X. Th d: +C X -C +C

CH2 CH X -C
Do kh nng phn ng ca nguyn t halogen trong dn xut thm ( kiu clo benzen) v trong dn xut cha no (kiu vinyl clorua) kh khn hn so vi dn xut khng vng no. Lin kt C-H cng l mt trung tm phn ng ca dn xut halogen. Do nh hng ca hiu ng cm ng m -I ca nguyn t halogen m lin kt C-H phn cc mnh, nguyn t H hot ng. S phn cc c m t nh sau:
+ C H + C X
1.6. Tnh cht ho hc

a. Phn ng th nguyn t halogen * C ch tng qut
Phn ng xy ra theo c ch th i nhn (SN). Tc nhn i nhn thng l mt anion tn cng vo nguyn t cacbon mang mt phn gi tr in tch dng ca lin kt C-X.
+ C X +Y
C Y +X
Phn ng xy ra theo hai loi c ch + C ch th i nhn n phn t (SN1) theo c ch ny, phn ng qua hai giai on: Giai on 1 to ra cabocation trung gian bn vng. Giai on ny chm, thun nghch v quyt nh tc phn ng; giai on 2 to ra sn phm phn ng.
+ C
Chm
C +
C +
nhanh
Tc phn ng ch ph thuc nng dn xut halogen v = k.[RX]. + C ch th i nhn lng phn t (SN2). Theo c ch ny, phn ng xy ra 1 giai on qua bc to thnh phc trung gian hot ng hay trng thi chuyn tip:
Y + + C X Y C X
C +X
phc trung gian
Tc phn ng ph thuc nng dn xut halogen v kim: v =k.[RX].[OH-]

* Nhng phn ng c th
+ Phn ng thu phn Phn ng thu phn cc dn xut halogen cho sn phm l cc ancol hoc phenol tng ng. Tc nhn i nhn l HO-.
RX + H2O ROH + HX
R : gc hirocacbon. cho phn ng ch xy ra theo chiu thun, ngi ta tin hnh trong mi trng kim:
RX + H2O OHROH + HX
Phn ng thu phn ankyl halogenua d dng xy ra khi un nng vi kim trong dung dch nc hay etanol-nc. Th d:
to CH3Cl +KOH CH3OH + KCl Cc dn xut kiu vinyl v phenyl halogenua ch b thu phn trong nhng iu kin rt khc nghit.
Th d:
Cl OH
0
400 C +NaOH (rn)200at clo benzen
+ NaCl phenol
Dn xut polihalogen thng l nhng hp cht hot ng ho hc mnh hn cc dn xut monohalogen no. Th d, clorofoc rt d dng b thu phn trong mi trng kim.
Cl C Cl + 3 HOH OH -3 HCl OH H C OH - H2O
Cl clorofoc
OH gem triol (khng bn)
H -C -OH O axit fomic

=
+ Phn ng vi amoniac Phn ng ny c dng iu ch cc amin

R -X + NH3 to R -NH2 + HX
Th d:
Cl + 2 NH3 clo benzen 200 C 60-100 at xt anilin
0
NH2 + NH4Cl
+ Phn ng vi kali xianua ( KCN). Sn phm ca phn ng ny l hp cht nitrin. Tc nhn i nhn l CN-.
R -X + KCN R -CN + KX
b. Phn ng loi hiro halogenua
Phn ng loi HX c thc hin trong mi trng kim-ancol:
C X
kim-ancol
+ HX
Hoc:
H C
X
C
kim-ancol
+ HX
OH- + HX Th d:
CH3 -CH2 -Cl
HOH + X-
KOH CH2 =CH2 + HCl C2H5OH
Phn ng loi HX c th xy ra theo c ch loi E1 hoc c ch loi E2. - C ch tch loi i nhn n phn t ( E1) Theo c ch E1, phn ng xy ra qua hai giai on. Giai on u to ra cacbocation, tng t c ch SN1. Giai on sau cacbocation loi H+ to thnh sn phm cha no:
chm C C X
C H C H
C X C
H cacbocation nhanh C =C H
- C ch tch loi i nhn lng phn t (E2) C ch E2 xy ra mt giai on qua phc trung gian hot ng hay trng thi chuyn tip. C ch E2 tng t c ch SN2.
C C Y
+ HY + X
trng thi chuyn tip Cc dn xut bc mt ch c mt nguyn t cacbon v tr nn phn ng loi ch to ra mt hirocacbon cha no.
Th d:
CH3 -CH2 -CH2 -Br KOH CH3 - CH =CH2 + HBr C2H5OH
Cc dn xut bc hai v bc ba khi tham gia phn ng loi s to ra mt hn hp cc hirocacbon cha no. Phn ng xy ra theo hng u tin loi H lin kt vi C c bc cao hn.
Th d:
2 CH3 -CH -CH2 -CH3 KOH CH3 - CH =CH -CH3 + CH2 =CH -CH2 -CH3 + 2 HBr C2H5OH (chnh) (ph) Br
c. Phn ng vi kim loi
Trong mi trng ete khan, dn xut halogen tc dng vi magi to hp cht c magi, cn gi l hp cht Grinha. 0 t R -X + Mg R -Mg -X ete khan Th d: t0 CH -CH2 -Mg -Br CH3 -CH2 -Br + Mg ete khan 3 etylmagi bromua
d. Phn ng ca gc hirocacbon
Nhng gc cha no v gc thm ca ankenyl v aryl halogenua c nhng tnh cht tng t anken v tng t hirocacbon thm. Cc dn xut cha no d dng tham gia cc phn ng cng hp theo c ch i in t. Th d:
CH2 CH Cl + HBr CH3 - CH - Cl
Br
CH2
CH
CH2
Cl + HBr
CH3
CH Br
CH2Cl
Ngoi ra chng cn tham gia phn ng trng hp to ra cc hp cht cao phn t. Th d:

n CH2 =CH -Cl vinyl clorua CH2 -CH Cl P.V.C
Nhng dn xut halogen thm tham gia cc phn ng th nguyn t H nhn thm theo c ch th i in t.
Th d:
CH2Br 2 Fe +2 Br2 Br CH2Br + Br CH2Br + 2 HBr
2. Ancol v phenol
Khi thay th nguyn t hiro trong phn t hirocacbon bng nhm OH (nhm hiroxyl) ta c cc dn xut hyroxyl. Tu theo bn cht ca gc hirocacbon lin kt vi nhm hyroxyl m ta phn bit ancol (ru) v phenol. Phenol khc ancol l nhm hyroxyl lin kt trc tip vi nhn thm, cn ancol nhm hyroxyl lin kt vi gc hirocacbon mch h hay mch nhnh ca nhn thm. Th d:
OH CH3 -CH2 -OH phenol ancol no CH2 =CH -CH2 - OH ancol cha no ancol thm CH2OH
2.1. Phn loi
Tu theo s lng nhm hyroxyl c trong phn t, ta phn bit thnh dn xut mono, polihyroxyl. Th d:
OH OH OH
OH mono phenol CH3 -CH2 -OH mono ancol i phenol HO -CH2 -CH2 -OH i ancol
HO tri phenol
OH
HO -CH2 -CHOH -CH2 -OH tri ancol
i vi cc ancol, ngi ta cn phn bit ancol bc mt, ancol bc hai v ancol bc ba tng ng vi nhm hyroxyl lin kt vi cacbon bc mt, cacbon bc hai, cacbon bc ba.
R R -CH2 -OH ancol bc 1 R -CH -OH R ancol bc 2 R -CH -OH R ancol bc 3
Cc ancol khng vng cha no c mt lin kt i c phn bit vi nhau bi v tr ca lin kt i v nhm hyroxyl. Nu nhm hyroxyl lin kt trc tip vi cacbon sp2 ta c enol. Cc enol khng bn, ng phn ho thnh hp cht cacbonyl tng ng. Th d:
CH2 =CH - OH CH3 -CH =O
Nhng ancol cha no khc c nhm hyroxyl lin kt khng trc tip vi nguyn t cacbon sp2, i din tiu biu l ancol allylic CH2=CH-CH2-OH.
a. Tn gi thng thng
Tn gi thng thng ch c p dng gi tn cho cc monoancol n gin v theo quy tc chung nh sau: Ancol + tn gc hirocacbon + ic Th d: CH3-CH2- OH ancol etylic CH3CH2CH2-OH ancol n propylic
CH2 -OH ancol benzylic
CH3 -CH-OH CH3 ancol isopropylic
CH3-CH-CH2-OH CH3 ancol isobutylic
b. Tn gi IUPAC
Tn gi ca cc ancol c da theo nguyn tc: Tn hirocacbon tng ng theo IUPAC + s ch v tr nhm OH+Ol Mch cacbon c nh s sao cho cacbon chc c s th t thp nht. Nu trong mch c 2, 3, 4, nhm OH th ta thm cc t i, tri, ttravo trc m ol.
Th d: CH3CH2CH2-OH propan-1-ol
CH3-CH-CH3 OH propan-2-ol
CH3-CH-CH2-OH CH3 2-metyl propan-1-ol
CH2=CH-CH2-OH prop-2-en-1-ol
CH2-OH CH2-OH etan -1,2-iol (etylen glicol)
CH2OH-CHOH-CH2OH propan-1,2,3-triol (glixrin)
Hiroxyl benzen (C6H5OH) l i din u tin ca cc phenol, cn c gi l axit phenic. Sau ny th hin mi quan h vi ancol, ngi ta gi l phenol. OH
c. ng phn
Tng t dn xut halogen, ancol c ng phn mch cacbon, ng phn v tr nhm chc v ng phn lin kt. Th d 1: C4H9OH c cc ng phn: CH3 CH3-CH2-CH2-CH2-OH CH3-CH -CH2-OH CH3-CH-CH2-CH3 OH CH3 butan-1-ol 2-metylpropan-1-ol butan-2-ol Th d 2: C3H5OH c cc ng phn lin kt: CH2=CH-CH2-OH prop-2-en-1-ol
OH
xicl prpanol
CH3 CH3-C-CH3 OH 2-metylpropan-2-ol
2.3. Phng php iu ch
Ta c th iu ch cc ancol v phenol bng nhiu phng php khc nhau. Di y xin gii thiu mt s phng php thng c dng trong cng nghip v trong phng th nghim.
a. Tng hp t hp cht c magi
T hp cht c magi c th tng hp cc ancol c bc khc nhau: Anehit fomic hoc etylen oxit tc dng vi hp cht c magi cho ancol bc mt:
Cc anehit khc hoc dn xut ankyl th ca etylen oxit tc dng vi hp cht c magi cho ancol bc hai:
R'
R MgX
R -CH=O
R -CH -O -MgX
HOH
R' R -CH-OH
X Mg OH
Xeton, este hoc clorua axit tc dng vi hp cht c magi cho ancol bc ba:
R -C -R R MgX O
=
R R -C -O -MgX R
HOH
R R -C-OH R
X Mg OH
b. Tng hp t hp cht cha no

R- CH CH2 + H2O H+ R -CH OH CH3
Th d:
CH3 - CH CH2 + H2O H+ CH3 -CH CH3 OH
c. Thu phn dn xut halogen
Th d:
CH2 -Cl + HOH OH-
CH2 -OH
+ HCl
benzyl clorua Cl
ancol benzylic
+NaOH rn clo benzen
4000C 200at phenol
OH + NaCl
2.4. Tnh cht vt l

Ancol l nhng cht lng hoc rn. Nhit si, nhit nng chy ca ancol tng dn khi trng lng phn t tng v cao hn so vi nhit si, nhit nng chy ca nhng hirocacbon tng ng. iu ny c gii thch bi s hnh thnh nhng lin kt hiro gia cc phn t ancol:
R O H H O R H
R O H O R
nhit thng, phenol l cht rn kt tinh khng mu. Phenol t tan vo nc, tan nhiu trong nhng dung mi hu c. 2.5. Cu to ca ancol v phenol
xt cu to ca ancol v phenol ta xt bn cht ca lin kt oxi-hiro, nhng yu t nh hng n s phn cc ca lin kt ny v nh hng ca nhm hiroxyl n gc hirocacbon. Lin kt oxi-hiro l lin kt phn cc v pha nguyn t oxi, do oxi c m in ln hn m in ca hiro. Gc hirocacbon gy nhng hiu ng quyt nh s phn cc mnh hay yu ca lin kt ny: - Cc gc ankyl gy hiu ng cm ng dng +I lm gim s phn cc ca lin kt oxihiro. Khi s lng ca gc R tng, hiu ng +I tng, do vy s phn cc ca lin kt O-H gim dn t ancol bc mt, ancol bc hai, ancol bc ba.
R" R CH2 O H R CH R' O H R C R' O H
- Nhng gc cha no gy hiu ng ht in t I v - lm tng s phn cc ca lin kt O-H, lm tng kh nng hot ng ca hiro trong nhm OH. Th d:
H
CH2 =CH
H - Gc phenyl c hiu ng lin hp -C vi cp in t p ca oxi trong nhm OH, ng thi cn c hiu ng -I. Nhng hiu ng ny u lm tng s phn cc ca lin kt O-H, quyt nh tnh axit ca phenol.
-C O -I H
Cc nhm hiroxyl trong poliancol no gy hiu ng -I v nh hng tng h ln nhau, lm tng s phn c ca lin kt O-H, lm cho kh nng hot ng ca nguyn t hiro trong nhm OH mnh hn cc ancol no tng ng. Th d:
-I CH2 OH CH O H CH2-I OH CH2 O -I CH OH CH -I OH
2
CH2 CH2 -I
O OH
tylenglicol
glixrin
Ngoi lin kt oxi-hiro, lin kt cacbon-oxi cng l mt trung tm phn ng ca loi hp cht ny. Lin kt cacbon-oxi phn cc v pha nguyn t oxi, v oxi c m in ln hn. Mi hiu ng cng phng, cng chiu vi chiu phn cc ca lin kt C-O u lm tng s phn cc ca lin kt ny, v ngc li nhng hiu ng cng phng nhng ngc chiu vi chiu phn cc ca lin kt C-O u lm gim s phn cc. i vi cc monoancol khng vng no s phn cc ca lin kt C-O tng dn t ancol bc mt n ancol bc ba, do hiu ng +I ca gc ankyl tng dn.
R R CH2 OH R CH R OH R C OH R
Ngc li, trong phn t phenol th s phn cc ca lin kt C-O b gim i do hiu ng +C ca nhm OH.
+C OH
Bn cnh nhng trung tm phn ng c xt trn, chng ta thy nhm hyroxyl cng gy nh hng ng k n hot ng ca gc hirocacbon. i vi cc gc no, nhm OH gy hiu ng -I lm tng kh nng hot ng ca nhng nguyn t H.
C OH
C H
i vi cc gc cha no, nhm OH gy hiu ng -I lm gim mt in t ca lin kt i cacbon-cacbon. Th d:

CH2 =CH CH2 OH
Trong phn t phenol, nhm OH gy hiu ng +C lm tng mt in t trong nhn thm v tng ch yu v tr o. v p.
+C OH
2.6. Tnh cht ho hc

a. Phn ng ca nguyn t hiro trong nhm OH - Phn ng vi kim loi v hiroxit kim loi
Ancol no tc dng vi kim loi kim v mt vi kim loi khc to thnh ancolat. Th d: 2C2H5-OH +2 Na 2 C2H5-ONa + H2
Ancolat kim loi kim l nhng cht rn, d b thu phn: C2H5-ONa + H2O C2H5-OH + NaOH
Poliancol v phenol c tnh axit yu nn chng khng ch phn ng vi kim loi kim m cn phn ng vi hiroxit kim loi. Th d: Glixerin tc dng vi Cu(OH)2 to ra phc mu xanh.
CH2 - OH 2 CH -OH CH2 - OH Cu(OH)2
CH2 - O CH -O H CH2 - OH Cu H
O -CH2 O -CH HO -CH2 2 H2 O
Phenol c tnh axit yu hn so vi axit cacbonic, nn phnolat phn ng vi axit cacbonic gii phng phenol.
OH + NaOH phenol O Na + CO2 + H2O O Na + H2O natri phenolat OH + NaHCO3
- Phn ng este ho Ancol phn ng vi axit cacboxylic, anhirit axit, axyl halogenua v axit v c khc to ra cc este. Phn ng ny c gi l phn ng este ho.
R -OH + R' -C -OH O H+ t0 R' -C -OR + H2O O
= =
OH + (R -C -O)2
=
H+ t0
O C R
=
+RCOOH
Th d:
CH3 -CH -CH2 -CH2 -OH + CH3-C -OH O CH3
=
H2SO4 t0
CH3-C -OCH2 -CH2 -CH -CH3 + H2O O CH3

=
ancol isoamylic
b. Phn ng ca nhm hiroxyl
isoamyl axetat (du chui)
Nhm hiroxyl trong ancol d dng c thay th bng nhm NH2 hoc bng nguyn t halogen khi ancol phn ng vi amoniac, HX, PCl3, PCl5 hay SOCl2.
R -OH + NH3 R -OH + HX R -OH + PCl5
Al2O3
R -NH2 + H2O
R -X + H2O R -Cl + POCl3 + H2O
c. Phn ng loi nc (phn ng hirat ho)
Khi c mt cht ht nc (H2SO4 c) nhit cao (1700C), cc ancol tham gia phn ng hirat ho to thnh cc hirocabon khng no.
R- CH H CH2 OH H+ t0 R- CH CH2 + H2O
C ch:
R - CH2 - CH2 -OH + HOSO3H -H2O R - CH2 - CH2 -OSO3H t0 H2SO4 R -CH =CH2
i vi ancol bc hai, bc ba, phn ng ch yu xy ra theo hng loi hiro lin kt vi C c bc cao hn to thnh anken c cu to bn vng. i vi nhng ancol khng cn nguyn t H phn ng hirat ho xy ra cng vi s chuyn v ni phn t. Th d: CH3 -H2O CH3 -C -CH2 -OH CH3 -C =CH -CH3 H+ CH3 CH3 C ch: CH3 CH3 H CH3 H H+ CH -C - C -OH -H2O CH -C - C CH3 -C -CH2 -OH 3 2 3 CH3 H CH3 H CH3 CH3 CH3 H CH3 -C =CH -CH3 + H+ CH3 -C C CH3 -C C H CH3 CH3 H CH3 H 0 Khi c mt axit sunfuric c v nhit <140 C, hai phn t ancol b hirat ho to te. H2SO4 R -OH + HO -R 0 R -O -R + H2O t te Th d: H SO CH3 -CH2 -OH + HO -CH2 -CH3 0 2 4 CH3 -CH2 -O -CH2 -CH3 + H2O 140 C
ancol etylic ietyl ete
d. Phn ng oxi ho
Ancol d dng b oxi ho bi cc tc nhn khc nhau, trong nhng iu kin khc nhau to thnh hp cht cacbonyl, hoc axit cacboxylic. Trong phng th nghim ngi ta oxi ho ancol bng CuO v nhit , KMnO4 trong mi trng kim hay mi trng trung tnh, trong c th sng c s tham gia ca men hirogenaza. Trong nhng iu kin nh trn, oxi ho ancol bc mt cho anehit, ancol bc hai cho xeton. R-CHO + H2O anehit R- C R + H2O R-CH- OH R O axeton Phn ng oxi ho ancol bc mt v ancol bc hai xy ra qua giai on to thnh gem iol. H H [O] R C OH R C OH R -CH =O + H2O
H OH gem iol
R- CH2- OH
Ancol bc ba ch b oxi ho trong iu kin rt khc nghit to thnh hn hp axit cacboxylic. Chng hn, khi un nng vi hn hp K2Cr2O7 +H2SO4 c, phn ng xy ra theo phng trnh tng qut sau y:
R3 [O] R1 -CH2 -C -OH CH2 R2
R1 -COOH + R2 -COOH + R3 -COOH
Phn ng ny xy ra qua giai on to thnh cc hp cht khng no:

R3 R3 H2SO4 c, t0 [O] R1 -CH2 -C -OH R1 -CH =C -CH2 -R2 -H2O -R1COOH CH2 R2 R2 -COOH + R3 -COOH R2 -CH =C -R3 R2 -CH2 -C -R3 OH O
Phenol d b oxi ho ngay trong khng kh nhit thng to ra quinon c mu hng:
OH [O]
O +H2O
phenol
O quinon
= =
c. Phn ng ca gc hirocacbon
Ph thuc vo bn cht ca phn gc hirocacbon, ancol v phenol c tnh cht ca hirocacbon tng ng. Cc ancol cha no tham gia phn ng cng hp vo lin kt i theo c ch i in t.
Th d:
CH2 = CH - CH2 - OH + HBr CH3 - CH - CH2OH Br
Ancol thm v phenol d dng tham gia phn ng th i in t trong nhn thm: Th d:
CH2OH 2 + 2Br2 Br
p o- brom
CH2OH +
CH2OH Br +2HBr
op- brom
ancol benzylic
ancol benzylic
ancol benzylic
OH + 3Br2 phenol
Br
OH Br + 3HBr
Br 2, 4,6- tribrom phenol
3. Hp cht cacbonyl (anehit v xeton)
Hp cht hu c c cha nhm >C=O ( nhm cabonyl) lin kt trc tip vi gc hirocacbon c gi l hp cht cacbonyl.
Nu nhm >C=O lin kt vi mt gc hirocacbon v mt nguyn t hiro ta gi hp cht cacbonyl l anehit, nu nhm >C=O lin kt vi hai gc hirocacbon ta gi l xeton. R-C-H O anehit R-C-R O xeton
3.1. Phn loi

Anehit v xeton c chia thnh nhng loi khc nhau tu theo bn cht ca gc hirocacbon v s lng nhm cacbonyl. Theo bn cht ca gc hirocacbon ta c: - Hp cht cacbonyl no Th d: CH3- CH=O axetanehit
CH=O
CH3-C-CH3 O axeton
C O
xiclhexyl cacbxanhit
ixicl hexyl xtn
- Hp cht cacbonyl thm: Th d: CH=O
C CH3 O axeto phenon benzanehit - Hp cht cacbonyl cha no: Tiu biu l hp cht cacbonyl cha no c hai lin kt i lin
=
hp. Th d: CH2=CH-CH=O acrolein (anehit acrylic) CH2 =CH - C CH3 O mtyl vinyl xtn Theo s lng ca nhm cacbonyl ta c hp cht monocacbonyl, i,v policacbonyl.
Th d: O=CH-CH=O glioxan
= =
O=CH-C6H4-CH2-CH=O anehit phtalic
CH3 - C CH2 - C CH3 O O axtyl axtn

a. Tn gi thng thng
Tn ca anehit c gi theo tn ca axit cacboxylic tng ng, ch khc l thay t axit bng t anehit, hoc l b t axit v i ui oic trong tn gi ca axit bng t anehit. Th d: CH2=CH-CH=O H-CH=O CH3-CH=O anehit fomic anehit axetic anehit crotonic (fomanehit) (axetanehit) (acrolein) CH=O
anehit benzoic (benzanehit) Tn ca xeton c gi theo quy tc: Tn gc hirocacbon + xeton Th d: CH3-CO-CH3 imetyl xeton (axeton)
b. Tn gi IUPAC
CH3-CO-CH2-CH3 metyl etyl xeton
CH2=CH-CO-CH3 metyl vinyl xeton
Tn ca anehit c gi theo quy tc: Tn hirocacbon tng ng theo IUPAC + al Mch cacbon c nh s bt u t cacbon nhm chc anehit. Th d: (CH3)2CH-CH=O 2-metylpropanal CH2=CH-CH=O prop-2-enal CH3-CH=CH-CH=O but-2-enal
Tn ca xeton c gi theo quy tc:

Tn hirocacbon tng ng theo IUPAC + s ch v tr nhm cacbonyl + on Mch cacbon c nh s sao cho cacbon ca nhm cacbonyl c s th t thp nht. i vi cc hp cht policacbonyl c thm cc t i, tri, vvtrc m on ch s nhm >C=O trong phn t l hai, ba,vv Th d: CH3CH2-CO-CH3 butanon CH3- C -CH=CH2 O but-3-en-2-on
c. ng phn
CH3CH2-C-CH2- CH3 CH3- CH- C- CH3 O CH3 O pentan-3-on 3- metyl butan-2-on CH3CH2- C- C- CH3 O O pentan -2,3-ion
Mono anehit khng c ng phn v tr nhm chc, ch c ng phn mch cacbon, ng phn lin kt v ng phn hnh hc. Th d 1: C3H7-CH=O c hai ng phn mch cacbon. CH3-CH2-CH2-CH=O butanal (CH3)2CH-CH=O 2-metylpropanal
Th d 2: C3H5-CH=O c cc ng phn mch cacbon, ng phn v tr ca lin kt , ng phn lin kt v ng phn hnh hc. - ng phn mch cacbon: CH2=CH-CH2-CH=O But-3-enal - ng phn v tr lin kt : CH2=CH-CH2-CH=O But-3-enal - ng phn loi lin kt:
CH2=CH -CH2 -CH =O
buten -3 -al - ng phn hnh hc:
CH2=C-CH=O CH3 2-metylprop-2-enal
CH3-CH=CH-CH=O but-2-enal
CH=O fomyl xiclprpan
h c CH3 C
cHO h
h c CH3 C
h cHO
cis buten-2-al trans buten-2-al Mono xeton c y cc loi ng phn nh mono anehit v cn thm ng phn v tr nhm
chc. Th d 1: C4H10C=O c cc ng phn mch cacbon v ng phn v tr nhm chc.

CH3 -C -CH2 -CH2 -CH3 O pentanon-2
=
CH3 -C -CH -CH3 O CH3 3-mtyl butanon-2

=
CH3 -CH2 -C -CH2 -CH3 O pentanon-3

=
Th d 2: C3H6C=O c cc ng phn loi lin kt:

CH2 = CH -C -CH3 O mtyl vinyl xtn
=
H2C
CH2
H2C C=O xicl butanon
Th d 3: C4H8C=O c cc ng phn v tr ca lin kt , ng phn hnh hc v cc ng phn khc:

CH2 = CH -CH2 -C -CH3 O penten-4-on-2
=
CH3 - CH=CH -C -CH3 O penten-3-on-2

=
CH3 c h
CH3 C -CH3 C O h
=
h c C C -CH3 O
=
cis penten-3-on-2
trans penten-3-on-2
3.3. Phng php iu ch

a. oxi ho hirocacbon
Ngi ta c th oxi ho nhng hirocacbon khc nhau. Th d khi t chy chm n-ankan tng kh sinh ra mt lng nh anehit, hoc xeton.
Th d:
CH4 + O2 600-7000C H -CH=O + H2O xt metanal
O2 0 xt, t C - CH3+ H2O O
=
CH2 -CH3
axeto phenon xt 1 CH2 = CH2 + O2 0 2 50 C CH3 -CH=O axetanehit
b. oxi ho ancol
y l phng php quan trng iu ch cc anehit, xeton Th d: Cu, t0 2 CH3OH + O2 2H -CH=O + 2 H2O
CH3 -CH -CH3 OH [O] CH3 -C -CH3 + H2O O
=
c. Phn ng Frien- Crap
Th d:
2C6H6 +Cl -C -Cl O C6H6 + (CH3CO)2O C6H6 +C6H5 -C -Cl O = = AlCl3 AlCl3 AlCl3 C6H5 -C -C6H5 + 2HCl O C6H5 -C -CH3 + CH3COOH O C6H5 -C -C6H5 + HCl O = = =
d. Thu phn dn xut gem i halogen
Phn ng xy ra trong mi trng kim

R R C X X + H2O OH - HX R R C OH - H2O OH
R -C -R O
=
Th d:
C6H5 -CHCl2
+ 2 H2O
OH
C6H5 - CH=O + benzanehit
HCl
benzylien clorua
3.4. tnh cht vt l

Anehit fomic l cht kh, c mi xc, cay kh chu, tan nhiu vo nc. Cc anehit khc v cc xeton l nhng cht lng hoc cht rn. Axeton c mi xc nh. Benzanehit v nhiu anehit thm khc c mi c trng ca hnh nhn. Ni chung anehit v xeton c nhit si thp hn so vi ancol bc mt v bc hai tng ng.
3.5. cu to ca nhm cacbonyl

Trong phn t anehit v xeton, nguyn t cacbon ca nhm cacbonyl trng thi lai ho sp2, vi gc ho tr 1200. Hai nguyn t oxi v cacbon lin kt vi nhau bng mt lin kt v mt lin kt . 1,22A0
C
1200 Lin kt trong nhm C=O lun phn cc v pha oxi, v oxi c m in ln hn m in ca cacbon. Ta c th m t: C O
S phn cc ny to ra mt trung tm C+ cho phn ng i nhn. Gc hirocacbon khc nhau c nh hng khc nhau n gi tr in tch dng ca cacbon chc. - Gc ankyl gy hiu ng cm ng dng +I lm gim gi tr in tch dng ca cacbon trong nhm C=O. S lng ca gc ankyl tng, trng lng ca gc ankyl tng th hiu ng +I tng, do vy + ca cacbon trong nhm C=O gim. ' R R C R CH O
> '
O '
- Gc phenyl gy hiu ng +C lm gim gi tr in tch dng ca cacbon chc. Th d:

CH +C O
- Trong phn t anehit v xeton cha no lin hp, gc vinyl gy hiu ng lin hp dng +C. Hiu ng ny lm gim gi tr in tch dng ca cacbon chc. Th d: +C CH2 CH CH O Vi cc policacbonyl, c bit 1,2-icacbonyl, cc nhm C=O gy hiu ng I v nh hng tng h ln nhau. nh hng lm tng gi tr in tch dng ca cacbon chc. Th d:
CH
-I CH
Bn cnh nh hng ca gc hirocacbon n nhm cacbonyl, nhm cacbonyl cng gy nh hng nht nh n gc hirocacbon v lin kt Cchc-hiro. - Vi cc gc no, nhm C=O gy hiu ng cm ng m (-I). Hiu ng ny lm tng s phn cc ca lin kt C-H.
Th d:
H H C -I CH=O
H - Vi cc gc thm, nhm C=O gy cc hiu ng ht in t I v -C. Nhng hiu ng ny lm gim mt in t trong nhn thm, v ch yu gim v tr octo v para. Do vy to ra trung tm phn ng th i in t v tr meta. Th d: -C CH O -I
Nhng hp cht cacbonyl cha no lin hp, nhm C=O gy hiu ng lin hp m (-C). Hiu ng ny lm phn cc ho h lin hp. Th d:
CH2 -C
CH CH O
Cc lin kt trong nhm C=O lun phn cc v pha oxi, lm cho mt in t cacbon gim i, cacbon mang mt phn in tch dng, dn n lm tng s phn cc ca lin kt CchcH trong anehit v to ra trung tm ca phn ng oxi ho lin kt ny.
C
O H
3.6. tnh cht ho hc

a. Phn ng cng hp vo nhm C=O

+ C + O +H Y hoc X Y C OH Y
HY l H-OH, H-OR, H-SO3Na, XY l R-MgX, CHCNa, Phn ng cng hp vo nhm C=O xy ra theo c ch cng hp i nhn hai giai on. Giai on mt: Tc nhn i nhn Y- kt hp vi nguyn t cacbon mang in tch dng ca nhm C=O v to thnh sn phm trung gian l mt anion. Giai on hai: Giai on proton ho sn phm trung gian, xy ra nhanh.
+ C chm O +Y
O nhanh Y H
OH
Y
- Cc phn ng c th + Cng ancol: Phn ng ca anehit, xeton vi ancol to thnh sn phm gi l hp cht bn axetal.
R - CH - OH OR Khi un nng bn axetal vi lng d ancol s thu c axetal. R - CH - OH OH2 R - CH - OR' R OH OR OR axetal bn axetal + Cng hiro xianua (HCN) OH + C C O + HCN CN Phn ng xy ra khi c baz lm cht xc tc v to ra sn phm xianhirin. Th d: CH3 CH3 CH3 C OH CH3 C = O + HCN CN Khi thu phn hp cht xianhirin s to thnh - hiroxi axit. CH3 CH3 2 H 2O CH3 C OH CH3 C COOH NH3 CN OH + Cng natribisunfit (NaHSO3) OH + C C O + NaHSO3 SO3Na R CH = O + R OH
Sn phm ca phn ng trng thi tinh th v gi l hp cht cng bisunfit. Phn ng ny c dng tch cc anehit hoc xeton ra khi hn hp vi cc cht khc. Th d: OH C6H5CH =O + HSO3Na C6H5 -CH -SO3Na OH CH3 -C -CH3 + HSO3Na CH3 -C -SO3Na CH3 O C ch chung nh sau: O O + C H S - O Na C OH C=O + =O S OH SO3Na ONa OH
+ Cng hp cht c kim T hp cht c magi v cc anehit hoc xeton, c th tng hp c cc ancol c bc khc nhau. Trong cc phn ng ny th hp cht c magi tc dng nh l mt cht phn cc:
+ R MgX ( R: gc ankyl)
+ + C = O + R MgX C OMgX R HOH -MgXOH C OH R
Hp cht cacbonyl ban u l HCHO ta c ru bc mt, nu l ng ng ca anehit fomic c ru bc hai, cn nu l xeton c ru bc ba. + Phn ng vi amoniac v dn xut ca n ( NH3 v B-NH2. B c th l: Gc hirocacbon; -NH2; -OH, vv) V nguyn t nit cn mt cp in t sp3 t do, nn nit trong NH3 v B-NH2 ng vai tr l tc nhn i nhn. Phn ng din ra qua qu trnh cng i nhn vo nhm C=O v sau l qu trnh loi nc ca sn phm cng hp to sn phm ngng t hay sn phm th nguyn t oxi ca nhm >C=O. S tng qut ca phn ng:
+ C O N -B C O NH2 -B C OH NH -B H2 O C = N -B
Phenyl hirazin (C6H5NHNH2) phn ng vi anehit hay xeton to thnh sn phm kt ta mu vng.
C O
H2N -NH -C6H5
C = N -NH -C6H5 + H2O
Th d: CH =O H2N -NH -C6H5 CH =N -NH -C6H5 H2N -NH -C6H5 CH =N -NH -C6H5 CH =N -NH -C6H5 CH =O CH =O - H2O - H2O bis phenylhirazon
b. Phn ng oxi ho
Phn ng oxi ho to thnh axit cacboxylic. Anehit d dng b oxi ho bi cc cht oxi ho khc nhau, ngay c bi cc tc nhn oxi ho yu nh thuc th Tlens, thuc th Phlinh
Phng trnh tng qut:

R -CH=O + [O] anehit R -C =O OH axit cacboxylic
Phn ng vi thuc th Tlens v Phlinh c dng pht hin nhm chc anehit. Anehit phn ng vi thuc th Tlens to thnh bc kt ta. R-CH=O + 2[Ag(NH3)2]OH thuc th Tlens Thuc th Tlens c iu ch bng cch cho AgNO3 phn ng vi NH4OH d. AgNO3 + NH4OH AgOH + 2 NH4OH AgOH + NH4NO3 [Ag(NH3)2]OH + H2O RCOONH4 + 2Ag +3NH3 + H2O
Phn ng ny cn c gi l phn ng trng gng. Th d:

0 CH2=CH -CH=O +2[Ag(NH3)2]OH t
CH2=CH -COONH4 + 2Ag + 3NH3 + H2O
acrlin
Anehit khi phn ng vi thuc th Phlinh, ta thy xut hin kt ta mu gch ca Cu2O.
R CH =O
COOK CH O 2 Cu + 2H2O CH O COONa
t0
R -COOH
COOK CH OH 2 CH OH COONa
Cu2O
Thuc th Phlinh c iu ch nh sau: CuSO4 + 2NaOH Cu(OH)2 + Na2SO4

COOK CH O Cu CH O COONa
COOK CH O H Cu(OH)2 CH OH COONa kali natri tactrat
2 H2O
Thuc th Tlens oxi ho c c anehit bo v thm, cn thuc th Phlinh ch oxi ho c anehit bo. Khi tip xc vi oxi khng kh anehit ni chung d dng b oxi ho. Th d: 2C6H5CH=O + O2 anehit benzoic 2C6H5COOH axit benzoic
Khc vi anehit, xeton ch b oxi ho bi cc cht oxi ho mnh nh KMnO4 + H2SO4, K2Cr2O7 + H2SO4 khi un nng. Khi phn ng xy ra, lin kt gia nguyn t C vi cacbon cacbonyl b t ra to thnh hn hp cc axit cacboxylic.
R -CH2 -C -R' + [O] O
=
R -COOH + R' -COOH
Trc khi b oxi ho, dng xeton ng phn ho thnh dng enol.
R -CH2 -C -R' O dng xeton
=
R -CH =C -R' OH dng enol
[O]
R -COOH + R' -COOH
Nu trong phn t xeton c nhiu nguyn t C c bc khc nhau, th phn ng u tin ct dt lin kt pha nguyn t C c bc cao hn. Th d:
CH3 -CH2 -C -CH3 O
[O]
2CH3 -COOH
c. Phn ng ca gc hirocacbon
- Th H bng halogen Do nh hng ca nhm cacbonyl m nguyn t H linh ng v d dng c th bi clo, brom, thm ch c iot. Th d:
CH3 -CH =O + Cl2 hv xt CH2Cl -CH =O + HCl
clo axetanehit Nhng hp cht kiu R-CO-CH3 khi halogen ho trong mi trng kim cho dn xut trihalogen. R - C -CH3 + 3X2 + 3 NaOH R -C -CX3 + 3NaX + 3 H2O O O Dn xut trihalogen b phn ct to halofoc. CHX3 + R -COONa R -C -CX3 + NaOH O - Phn ng th nhn thm Th d: CHO Fe CH = O+ Br2 + HBr
= =
- Phn ng cng hp Hp cht cacbonyl cha no d dng tham gia phn ng cng hp theo c ch i in t vo lin kt ca gc hirocacbon cha no. Nhng hp cht cacbonyl cha no lin hp tham gia phn ng cho sn phm cng hp 3,4 l ch yu. Th d:
CH2 =CH -CH=O + HBr CH2 -CH2 -CH=O Br
Br m- brombenzanehit
C ch:
CH2
CH -CH
+H Br
CH2 CH CH2 -CH =CH OH Br
CH - OH CH2 -CH2 CH=O Br
CH2 CH
CH - OH
4. Axit cacboxylic
Axit cacboxylic l nhng hp cht hu c c nhm cacboxyl COOH lin kt vi gc hirocacbon.
4.1. Phn loi

Ngi ta phn loi axit cacboxylic da vo cu to ca gc hirocacbon v s lng nhm cacboxyl. Da vo cu to ca gc ta c: - Axit cacboxylic no, th d:
COOH
CH3 -CH2 -COOH axit prpinic - Axit cacboxylic thm, th d: COOH

axit xiclhexyl cacbxylic
axit benzoic - Axit cacboxylic cha no, th d: CH2=CH-COOH axit acrylic
CHC-COOH axit propinoic
Phn ln cc axit cha no quan trng u cha lin kt i lin hp v tr , i vi nhm cacboxyl. Da vo s lng nhm cacboxyl ta c: - Axit mono cacboxylic (c mt nhm cacboxyl) Th d:
CH3 -COOH axit axtic COOH axit xiclpentan cacbxylic
- Axit i cacboxylic (c hai nhm cacboxyl) HOOC-COOH HOOC-CH2-COOH axit oxalic axit malonic
4.2.cch gi tn, ng phn

a. Tn gi thng thng
Axit cacboxylic thng c tn gi lin quan n ngun gc tm ra chng. Th d: H-COOH axit fomic CH3- COOH axit axetic CH3- CH2- CH2- COOH axit butyric CH3-CH=CH-COOH axit crotonic HOOC-CH2-CH2-COOH axit sucxinic HOOC-CH2-CH2-CH2-COOH axit glutaric
Tn gi hp l coi axit cacboxylic l dn xut ca axit axetic khi th nguyn t H bng cc gc hirocacbon, v c gi tn theo qui tc: Axit + gc hirocacbon + axetic Th d:
CH3 -CH3 -COOH axit metylaxetic CH2COOH axit phenyl axetic CH2 =CH -CH2 -COOH axit vinylaxetic
b. Tn gi IUPAC
Theo danh php ny, tn ca axit cacboxylic c gi theo qui tc sau: Axit + tn hirocacbon tng ng theo IUPAC + oic Mch cacbon c nh s bt u t nhm cacboxyl. Nhng axit c hai, banhm cacboxyl c thm t i, trivo trc m oic. Th d: CH3- CH2- COOH CH3-CH=CH-COOH axit propanoic axit but-2-enoic
CH3 - C H-COOH CH3 axit 2-mtyl prpanic
CH2 = C-COOH CH3 axit 2-mtyl prpenic
c. ng phn
Axit cacboxylic khng vng no c cc loi ng phn tng t mono anehit khng vng no, cc axit mono cacboxylic cha no (c mt lin kt i) c thm ng phn hnh hc. Th d 1: C3H7-COOH c hai ng phn mch cacbon. axit butanoic CH3- CH2- CH2- COOH axit 2-metyl propanoic CH3 - C H-COOH CH3 Th d 2: C3H5-COOH c cc ng phn mch cacbon, ng phn loi lin kt v ng phn hnh hc. CH2=CH-CH2-COOH axit but-3-enoic
CH2 = C-COOH CH3 axit 2-mtyl prpenic
CH3 c h C cOOH axit trans buten-2-ic h h
CH3-CH=CH-COOH axit but-2-enoic

COOH
axit xiclprpan cacbxylic

CH3 c C h COOH
axit cis buten-2-ic
4.3. Phng php iu ch

a. Phng php thu phn
+ Thu phn dn xut ca axit cacboxylic Cc dn xut ca axit d dng b thu phn trong mi trng axit hay kim to ra axit tng ng theo phng trnh sau:
H R -C -Y + HOH R -C -OH + HY O O Y c th l halogen (halogenua axit), -OCOR (anhirit axit), -NH2 (amit), -OR ( este), v.v Th d:
= =
H CH3 -C -O -CH2 -CH3 + HOH CH3 -C -OH + CH3 -CH2 -OH O O + Cc hp cht nitrin khi b thu phn trong mi trng axit hay baz cng sinh ra axit cacboxylic.
R -C N + 2 HOH
R -COOH + NH3
Th d:
H2SO4 CH2=CH -CN + 2H2O CH2=CH -COOH + NH3 + Thu phn dn xut poli halogen Cl OH +3H2O -HOH R -C -Cl R - C - OH R -C -OH -3HCl Cl O OH
b. Phng php oxi ho
Bng cch s dng cc tc nhn oxi ho thch hp c th oxi ho hirocacbon, ancol, anehit v xeton thnh axit cacboxylic. Nhng phn ng ny c nghin cu nhng chng trc.
c. Cacboxyl ho hp cht c kim v anken
Th d:
CH3 -CH2 MgBr + CO2 CH2 =CH2 +CO CH3 -CH2 -COOMgBr H2O/H+ CH3CH2COOH + Mg(OH)Br
xt CH3 -CH2 -COOH + H2O
4.4. tnh cht vt l

Cc axit mono cacboxylic no l cht lng hoc rn, cc axit thm v axit icacboxylic u l cc cht rn. Nhiu axit cacboxylic tan tt vo trong nc. Gia nhng phn t axit c nhng lin kt hiro. lin kt ny bn hn ancol v nhm OH phn cc mnh. S c mt ca nhng lin kt hiro lm cho axit cacboxylic c nhit si cao hn so vi dn xut halogen v ancol tng ng. Nhit si ca axit mono cacboxylic no khng phn nhnh tng dn khi trng lng phn t tng. Nhit nng chy ca axit c s nguyn t cacbon chn cao hn so vi axit c s nguyn t cacbon l.
4.5. cu to ca nhm cacboxyl

Nhm cacboxyl l s t hp cht ch gia nhm cacbonyl v nhm hiroxyl. -C -O -H O
Nhm cacboxyl quyt nh tnh cht ho hc ca axit cacboxylic. Khi xt cu to ca nhm cacboxyl chng ta xt bn cht ca nhng lin kt trong nhm ny, v xt cc yu t nh hng n s phn cc ca chng. - Lin kt oxi-hiro: y l lin kt phn cc v pha oxi, v oxi c m in cao hn d m in ca hiro. Mt khc, cp in t p ca oxi trong nhm OH tham gia lin hp vi nhm cacbonyl, trong nhm C=O gy hiu ng -C, ng thi nhm C=O cn gy hiu ng -I. Nhng hiu ng ny (-C, -I) ng thi lm tng s phn cc ca lin kt oxi-hiro, lm cho nguyn t hiro trong nhm OH rt linh ng v quyt nh tnh axit ca axit cacboxylic.
C
O Nhng gc hirocacbon khc nhau c nh hng rt khc nhau n s phn cc ca lin kt
-C
-I
O-H. Gc ankyl y in t theo hiu ng cm ng dng +I, lm gim s phn cc ca lin kt O-H. Khi trng lng ca gc tng, cu to ca gc cng phn nhnh th hiu ng +I cng mnh, do vy s phn cc ca lin kt O-H cng gim. Th d: S phn cc ca lin kt O-H gim dn theo th t sau: C -O H CH3CH2 C -O H CH3 H - C -O H O O O axit propionic axit fomic axit axetic Gc phenyl gy hiu ng -I lm tng s phn cc ca lin kt O-H.
Th d:
-I
C O
axit benzoic V vy nguyn t hiro trong nhm OH ca axit thm hot ng nmnh hn so vi nhng axit khng vng no. Nhng gc cha no, tng t cc gc thm, gy hiu ng -I lm tng s phn cc ca lin kt O-H, do vy cc axit cha no u c tnh axit mnh hn axit no tng ng. Khi lin kt i C=C cng xa lin kt O-H, th nh hng -I ca gc cha no yu dn. Khi lin kt i C=C v tr , th ngoi hiu ng -I, n cn tham gia lin hp vi nhm C=O ca chc axit, hiu ng lin hp +C ny lm gim s phn cc ca lin kt O-H. Do vy trong dy ng ng ca cc axit cacboxylic cha no, axit cha no , c lin kt O-H phn cc yu nht v axit cha no , c lin kt O-H phn cc mnh nht. Th d: +C H CH2 =CH CH2 =CH -I CH2 - C O H C O -I -C O O
=
2
Trong phn t axit poli cacboxylic, nhm cacboxyl gy hiu ng -I v chng c nh hng tng h ln nhau lm tng s phn cc ca lin kt O-H. Th d: H HOOC -I CH - C O
=
O
Khi hai nhm cacboxyl nhng v tr cng xa nhau th nh hng tng h yu dn, s phn cc ca lin kt O-H gim dn. - Lin kt cacbon-oxi: Nhng lin kt C-O u l nhng lin kt phn cc v pha oxi, v nguyn t oxi c m in cao hn m in ca nguyn t cacbon. OH C
O Mi hiu ng cng phng, cng chiu vi chiu phn cc ca lin kt C-O u lm tng s phn cc ca lin kt ny. Gc ankyl gy hiu ng y in t +I cng phng, cng chiu lm tng s phn cc ca lin kt C-O. R C OH
O Nhng hiu ng cng phng nhng ngc chiu vi chiu phn cc ca lin kt C-O u lm gim s phn cc ca lin kt ny. Th d:
Do nhng nh hng m nhm OH hot ng. Ngoi nhng trung tm phn ng , chng ta thy nhm cacboxyl cn gy hiu ng cm ng m (-I), hiu ng ny hot ho nguyn t hiro v tr (H). Th d: H -I H C OH C
H O Trong phn t axit cacboxylic cha no hoc cha no lin hp (cha no , ), nhm cacboxyl cng gy hiu ng -I hoc -C. Nhng hiu ng ny c nh hng ng k n kh nng cng hp i in t vo lin kt i C=C. Th d: -C -I CH2 =CH CH2 =CH CH2 C O H C O -I OH O i vi axit thm, nhm cacboxyl gy hiu ng -C v -I to ra nhng trung tm phn ng th i in t v tr meta. Th d:
C
=
-I
C O
OH
O OH
4.6. Tnh cht ho hc

a. Tnh axit ca axit cacboxylic
S phn li axit cacboxylic trong dung dch nc xy ra theo mt cn bng:
RCOO + H3O ion cacboxylat Tt c mi yu t (hiu ng) lm tng s phn cc ca lin kt O-H v lm tng bn ca anion cacboxylat u lm tng s phn li axit. - Do c tnh axit nn axit cacboxylic phn ng c vi mt s kim loi, oxit kim loi v kim to mui.
2R-COOH + 2 Na 2R-COOH + MgO R-COOH + NaOH 2R-COONa + H2 (R-COO)2Mg + H2O R-COONa + H2O
RCOOH + H2O
V axit cacboxylic l axit yu nn mui ca n b thu phn trong dung dch nc. R-COOH + NaOH R-COONa + H2O
b. Phn ng ca nhm OH
- Phn ng vi ancol to este- phn ng este ho Phn ng ny c p dng rng ri iu ch este t axit cacboxylic v ancol.
R -COOH +H -OR' R -COOR' + H2O
xc tc: H2SO4 c hoc HCl khan vv C ch ca phn ng este ho nh sau:

+ R- C
H R C OH OH
+ R
OH
OH t0
OH H R C O R OH O R +H
- H 2O
R C O R OH
C O
Th d:
H CH3COOH + CH3CHCH2CH2 -OH 0 CH3C -O -CH2CH2CHCH3 H2O t CH3 CH3 O axit axetic ancol isoamylic iso amylaxetat (du chui) - Phn ng vi amoniac to amit Khi phn ng xy ra ta thu c mui amoni, khi un nng mui amoni tch nc to thnh amit. t0 R -C -NH2 + H2O R -COOH + NH3 R-COONH4
- Phn ng to thnh axyl halogenua ( R-C-X ) O Axit cacboxylic phn ng vi PCl5, SOCl2, COCl2 to ra axyl halogenua. R -C -OH + PCl5 R -C -Cl + HCl + POCl3 O O
R -C -OH O
= = = =
+ SOCl2
R -C -Cl O
=
+ HCl + SO2 + HCl + CO2
R -C -OH + COCl2 O - Phn ng to thnh anhirit axit
R -C -Cl O
=
T hai phn t axit cacboxylic, vi s c mt ca P2O5, POCl3vv... loi i mt phn t nc cho ta anhirit axit.
O 2 R -C -OH O
=
t0
R -C R -C O + H2 O O
Nhng axit i cacboxylic c 4, 5 nguyn t cacbon khi loi nc cho anhirit ni phn. Th d:
O CH2 -COOH CH2 -COOH 3000C CH2 -C CH2 -C O + H2O O
c. Phn ng cacboxyl ho (loi nhm cacboxyl)
C th thc hin phn ng cacboxyl ho bng cch nhit phn axit cacboxylic hoc nhit phn mt s mui ca axit. Th d:
xt CO2 + H2 tia t ngoi H2SO4 CO2 + H2 H -COOH Nhng axit i cacboxylic v tr 1,2 hoc 1,3 khi nhit phn to axit mono cacboxylic. Th d: HOOC -COOH H -COOH + CO2 axit oxalic axit fomic H -COOH
Nhng axit i cacboxylic 1,6; 1,7 hoc xa hn na khi b nhit phn to xeton vng. Th d:
CH2 -CH2 -COOH 3000C CH2 -CH2 C =O + CO2 + H2O CH2 -CH2 CH2 -CH2 -COOH axit aipic xiclo pentanon Axit axetic kh b cacboxyl ho hn axit fomic. Do vy cn phi nhit phn mui natri axetat vi vi ti xt. t0 CH3 -COONa + NaOH CH4 + Na2CO3 CaO
d. Phn ng ca gc hirocacbon
- oxi ho: Nhm cacboxyl ca axit cacboxylic rt tr vi tc dng ca cc cht oxi ho, v nguyn t cacbon-cacboxyl c s oxi ho cao nht. Ring axit fomic H-COOH, do cu to trong phn t cn nhm chc anehit, nn axit fomic d b oxi ho ngay bi cc tc nhn oxi ho yu nh thuc th Tlens v thuc th Phlinh. Th d: t0 H -C -OH + [Ag(NH3)]OH H2O + CO2 + Ag - NH3 O Trong cc qu trnh sinh hc s oxi ho xy ra nh cht xc tc enzim hirogenaza v xy ra v tr .
R -CH2 -CH2 -COOH R -C -CH2 -COOH O
=
Axit -xeto cacboxylic tip tc b oxi ho ct t mch cacbon to thnh axit axetic v axit cacboxylic c mch ngn hn so vi axit ban u hai nguyn t cacbon.
R -C -CH 2 -COOH O
=
axit -xeto cacboxylic
enzim + CH3 -COOH R -COOH H 2O
Axit cacboxylic mi to thnh li tip tc b oxi ho. Sn phm cui cng ca qu trnh oxi ho trong c th sng l axit axetic tn ti di dng axetyl coenzim-A (CH3-CCoA). O - Halogen ho gc ankyl Tu iu kin ca phn ng m qu trnh halogen ho gc ankyl ca axit cacboxylic c th xy ra theo nhng c ch khc nhau (c ch gc hay c ch ion). Nu dng clo, hoc brom v c mt P hoc FeCl3...th phn ng xy ra ch yu v tr . P, Br2 P, Br2 R -CH2 -COOH R-CHBr -COOH R -CBr2 -COOH -HBr -HBr Nu dng clo c nh sng khuch tn th phn ng ch yu cc v tr v ch mt lng rt nh v tr . - Phn ng th gc thm Nhm -COOH phn hot ho nhn thm, nn cc phn ng th i in t trong nhn thm ca axit cacboxylic thm thng xy ra kh khn hn so vi benzen, ng thi phn ng u tin th v tr meta. Th d: H2SO4 COOH + HNO3 COOH + H2O t0
NO2 axit benzoic axit m- nitro benzoic Do s phn hot ho nhn thm ca nhm cacboxyl m axit benzoic khng tham gia phn ng Frien-Crap.
- Phn ng cng hp Axit cha no tham gia phn ng cng hp i in t tng t cc anken. Th d:
CH2 -CH2 COOH Br C ch cng hp vo axit cha no lin hp tng t nh phn ng ca but-1,3-ien v acrolein. C ch nh sau: CH2 -CH2 C=O CH2 CH -C O + H CH2 CH C - OH Br CH2 -CH =C -OH OH OH OH Br OH Br CH2 =CH -COOH + HBr
4.7. hiro xi axit Hiroxi axit l nhng axit tp chc va c nhm hioxyl va c nhm cacboxyl trong phn t. Cng thc chung:
COOH R v
(COOH)n
R OH (OH)m Cc hiroxi axit thng c gi theo tn ring, tn thng thng hay tn IUPAC nh l axit th. V tr nhm hiroxyl c k hiu bng ch s Hilp hoc bng ch s. CH3 CH3 -CH -COOH CH3 -C -COOH OH OH axit lactic axit - hiroxi isobutyric axit - hiroxi propionic axit 2-hiroxi-2-metyl propanoic axit 2-hiroxi propionic Hiroxi axit c cc ng phn v mch cacbon, ng phn v tr tng i gia cc nhm chc v ng phn quang hc.
CH3 -CH2 -CH -COOH OH CH3 -CH -CH2 -COOH OH CH2 -CH2 -CH2 -COOH OH axit - hiroxi butyric
axit - hiroxi butyric

COOH H H C OH C OH HO HO
axit - hiroxi butyric

COOH C H C H HO H COOH C H C OH
COOH H HO C OH C H
COOH axit D-tactric
COOH axit L-tatric
COOH COOH axit meso tatric
iu ch cc hiroxi axit c th p dng cc phng php iu ch ancol v axit, nhng phng php ph bin nht l cng hp HCN vi anehit hoc xeton ri thu phn. Th d:
CH3CHO + HCN CH3 -CH -CN OH
CH3 -CH -CN + 2 H2O CH3 -CH -COOH + NH3 OH OH Hiroxi axit c tnh axit mnh hn axit tng ng do hiu ng -I ca nhm -OH.
- Hiroxi axit c cc tnh cht ring ca nhm hirxyl v nhm cacbxyl. - Hiroxi axit c cc phn ng ng thi ca c hai nhm chc. - - hiroxi axit khi un nng, tch nc to este vng gia hai phn t gi l lactit.
CH3 -CH -OH + COOH HO C=O HO -CH -CH3 t0 CH3 -CH -O -C=O + H2 O
O=C - O - CH -CH3 - - hiroxi axit tch nc ni phn t cho axit cha no.
O Axit - hiroxi butyric -butyro lacton Cc hiroxi axit tiu biu nht l axit lactic v axit xitric.
t0 CH3 -CH -CH2 -COOH OH - v - hiroxi axit to thnh lacton. CH2 -CH2 t0 C=O CH2 OH OH
CH3 -CH=CH -COOH + H2O
CH2
CH2 -CH2
C=O + H2O
Axit lactic to thnh trong sa, rau, hoa qu khi c tc dng ca enzim. Axit lactic c trong c bp, u khp xng, l sn phm phn tch ca glicogen. Khi lm vic c bp hm lng axit lactic tng mnh lm ngi mt mi. Khi c ngh ngi, mt phn chuyn li glicogen, mt phn b oxi ho thnh CO2 v nc. Axit xitric (cn gi l axit limonic) c cng thc: OH HOOC -CH2 -C -CH2 -COOH COOH Axit xitric c trong thc vt, c bit l trong qu chanh (7-10%). Axit xitric ng vai tr quan trng trong qu trnh trao i cht ca c th sng, trong chu trnh xitric.
4.8. amit
Cng thc chung ca cc amit: R - C NH2 O

R - C NH - C - R O O R C=O R - C N - C - R' O O
= = = = =
amit bc 1 amit bc 2
amit bc 3
Th d: H-CO-NH2 fomamit CH3-CO-NH2 axetamit C6H5-CO-NH2 benzamit CH2-CO NH CH2-CO

sucxinimit
Amit c th tn ti hai dng cu to sau y:

R - C - NH2 R - C = NH OH O Ging nh amin, amoniac, amit c tnh baz, nhng do cp in t t do ca nit lin hp vi nhm >C=O, nn tnh baz rt yu. Dung dch nc ca cc amit khng to ra mi trng kim.
R - C NH2 O dng cu to th hai, cp in t t do ca oxi trong nhm -OH lin hp vi nhm >C=N lm cho lin kt O-H phn cc mnh, nguyn t hiro linh ng quyt nh tnh axit ca amit.
R-C NH OH
Amit phn ng vi axit, baz to mui. Th d:

CH3 - C - NH2 + HCl O
CH3 - C - NH2 +NaOH O
CH3 - C - NH3 Cl O
CH3 - C = NH + H2O ONa
5. Amin
Amin l dn xut th ca amoniac, chng c cng thc chung: R - NH2 amin bc 1

R -NH - R1 R -N -R1 amin bc 2 amin bc 3
R3 Bc ca amin c xc nh bi s gc hirocacbon lin kt trc tip vi nguyn t nit.
Tu thuc vo bn cht ca gc hirocacbon (R), ta c cc amin khc nhau.

5.1. Cch gi tn
a. Tn gi thng thng Tn gi thng thng ca cc amin tun theo theo quy tc:
Tn gc hirocacbon + amin Cc amin thm c nguyn t nit lin kt trc tip vi vng thm cn c gi nh dn xut ca anilin. Th d: CH3 -NH -CH2 -CH3 CH3 -CH -NH2
CH3 isopropy lamin NH2 metyl etyl amin CH3 -N -CH3
phenyl amin (anilin)
N-N imetyl anilin
b. Tn gi IUPAC
Tn gi IUPAC ca amin c tm tt theo quy tc: S ch v tr ca cacbon lin kt vi nguyn t N + amino hoc amino c nhm th + tn ca hirocacbon theo IUPAC
Th d:
3 2 1 4 CH3 -CH - CH -CH3 CH3 NH2 2- amin 3-mtyl butan 3 4 5 CH3 -CH2 -CH -CH2 -CH3 2 CH -NH -CH3 1 CH3 2- mtylamin 3-tyl pentan 5 7 6 4 CH3 -CH2 -CH -CH2 -CH2 -CH3 3 CH - N -CH2 -CH3 2 CH2 CH3 1 CH3 3- mtyl tyl amin 4-tyl heptan
5.2. phng php iu ch

a. Ankyl ho trc tip
Ankyl ho amoniac bng akyl halogenua ta c amin c cc bc khc nhau v mui amoni bc bn.
R - X + NH3 R - X + R -NH2 R - X + R2NH
RNH3X R2NH2X R3NHX
NH3 NH3 NH3
R -NH2 + NH4X R2NH + NH4X R3N + NH4X
R - X + R3N R4NX Tu theo t l s mol ca cc cht tham gia phn ng, ta c th nhn c cc amin c bc
khc nhau. Nu i t dn xut halogen thm ankyl ho amoniac, thng phi thc hin phn ng nhit cao v p sut cao. Th d:
X 3400C 340at
+ 2 NH3
NH2
+ NH4Cl
b. Kh hp cht nitro
Phng php kh hp cht nitro cho php iu ch amin bc mt, c bit l amin thm. Ar-NO2 + 6 H Ar-NH2 + 2 H2O Cc cht kh c dng thng l hiro mi sinh do tc dng ca kim loi v axit.
Th d:
NO2
NH2
+ 3Fe + 6HCl
+ 3 FeCl2 + H2O
c. Phn ng Hpman (phn ng thoi bin)
Khi cho amit tc dng vi brom trong kim hay natri hipoclorit hoc natri hipobromit, ta thu c amin bc mt c s nguyn t cacbon t hn amit ban u mt nguyn t.
R -C -NH2 O = + Br2 + NaOH R -NH2 + CO2 + NaBr
Th d:
CH3(CH2)4 -C -NH2 O + NaOBrH CH3(CH2)4 -NH2 + CO2 + NaBr =
5.3. Tnh cht vt l

Cc amin thp l nhng cht kh, c mi gn ging mi amoniac, cc amin cao l nhng cht lng, mt s l cht rn.
5.4. Cu to ca amin
xt tnh cht ho hc ca amin, chng ta xt cu to ca nguyn t nit trong nhm amin v nh hng ca cc gc hirocacbon n nhm ny. Ging nh amoniac, nguyn t nit trong amin trng thi lai ho sp3. Trc ca bn obitan lai ho sp3 ny to thnh cu trc khng gian dng hnh thp. Nguyn t nit s dng ba obitan lai ho to thnh ba lin kt cng ho tr vi nhng nguyn t hir hoc nhng gc hirocacbon. Gc ho tr ca nhng lin kt l 10905. Nh vy, nguyn t nit cn mt cp in t sp3 t do, chim obitan ring. Chnh cp in t t do ny l nguyn nhn gy nn tnh baz ca cc amin.
N R R R Cp in t t do ca nit hot ng cng mnh, hay ni cch khc, mt in t nguyn t nit cng ln th tnh baz ca amin cng mnh. Mt in t nguyn t nit li ph thuc ch yu vo gc hirocacbon lin kt vi n. Gc ankyl gy hiu ng cm ng dng +I lm tng mt in t nit. S gc ankyl lin kt vi nguyn t nit tng ln th hiu ng +I tng ln v mt in t nit tng ln. iu c m t nh sau: R1 R1 R2 NH R NH2 R2 N R3 Tuy nhin, do nh hng hiu ng khng gian ba gc ankyl, amin bc ba c tnh baz yu nht. Trong cc amin thm, gc phnyl gy hiu ng -C v -I nhng hiu ng ny lm mt in t nit gim i. Tnh baz ca anilin yu hn tnh baz ca cc amin khng vng no. +C -C NH2 -I
5.5. tnh cht ho hc

a. Tnh baz
Trong dung dch nc, nit nhng cp in t t do cho proton H+ v to ra mi trng baz.
R -NH2 + HOH
R -NH3OH ankyl amoni hiroxit
R -NH3 + OH
V c tnh baz nn amin phn ng vi axit to mui.

R -NH2 + HCl
R -NH3Cl
Tuy nhin cc amin u c tnh baz yu hn kim, cc mui amoni b kim phn tch:
R -NH3Cl + NaOH
R -NH2 + NaCl + H2O
b. Tc dng vi axit nitr
Cc amin c bc khc nhau, khi phn ng vi axit nitr s to ra nhng sn phm khc nhau. Cc amin bc mt tc dng vi axit nitr to thnh ancol hoc phenol v gii phng nit. Th d: C2H5OH + N2 + H2O C2H5NH2 + HONO
NH2 +HONO HCl OH2 N N Cl t0 OH2 OH + HCl + N2
phenyl iazoniclorua Cc amin bc hai u d dng tc dng vi axit nitr to nitrozamin. Th d: (CH3 -CH2)2 N-N=O + H2O (CH3-CH2)2 NH + HONO ietylnitrozamin Khi un nng, nitrozamin thm d dng chuyn v thnh p- nitrozo amin. Th d: H H N CH3 CH3 N N=O N CH3 t0 HONO
N =O N -nitrozo N -meylanilin N -metylanilin p. nitrozo metylanilin Cc amin bc ba ni chung khng phn ng vi axit nitr, tr amin bc ba kiu Ar-NR2 tham gia phn ng nitrozo ho nhn thm. CH3 CH3 CH3 N CH3 N
HONO -H2O N, N -imetylanilin N =O P- nitrozo imetylanilin
c. Phn ng th nhn thm
Cc amin thm tham gia nhng phn ng th i in t tng t hirocacbon thm. Nhm amino trong amin thm gy hiu ng +C hot ho nhn thm v inh hng nhm th mi vo v tr octo v para. - Phn ng halogen ho Khi brom ho hoc clo ho anilin ta thu c sn phm th ba ln, cn it ho ch cho sn phm th mt ln v tr para. Th d: NH2 NH2 Br Br 3 Br2 3 HBr
Br trng
- Phn ng nitro ho Nhm amino d b oxi ho bi axit nitric, nn trc khi thc hin phn ng nitro ho cn phi kho nhm amino bng phn ng axyl ho. Th d iu ch p- nitro anilin: NH2 NH -COCH3 NH2 NH -COCH3
(CH3CO)2O - CH3COOH HNO3 -H2O NO2 -H2O - CH3COOH NO2
Cu hi v bi tp
1. Tnh cht ho hc ca dn xut halogen. C ch th i nhn SN1, SN2. 2. nh hng ca cc gc hirocacbon khc nhau v nh hng tng h ca cc nhm OH n s phn cc ca lin kt O- H trong ancol v phenol. Tnh cht ho hc ca ancol v phenol. 3. Tnh cht ho hc ca anehit v xeton. C ch cng hp i nhn (AN) vo nhm cabonyl. 4. Cu to ca nhm cacboxyl v tnh axit ca cc axit cacboxylic. Tnh cht ho hc ca axit cacboxylic. 5. Gii thch tnh baz ca cc amin. nh hng ca cc gc hirocacbon n tnh baz ca cc amin. 6. Gi tn cc hp cht sau y theo tn gi IUPAC. CH3- CH2- CH- Cl CH3 CH3 CH3- C- CH3 Br CH3 CH3- C- CH2- CHO
CH3 CH2= C- CHO CH3 CH3- CH- CH- C- CH3 CH3 CH3 O CH3- CH- COOH CH3 HOOC- CH2- CH2- CH3 7. Vit cng thc cu to cc ng phn ca cc cht c cng thc phn t sau y v gi tn chng: C4H10O; C2H4O2 v C3H9N. 8. Cho bit cng thc cu to v gi tn cc cht: 8.1. Dn xut halogen bc 3 thu c khi halogen ho hirocacbon C4H10. 8.2. Dn xut halogen bc 1 c cng thc phn t C3H5Cl. 8.3. Thu c khi cho ankin- 1 c 4 nguyn t cacbon tc dng vi nc trong iu kin thch hp. 8.4. Axit thm thu c khi oxi ho ankyl benzen. 8.5. C cng thc phn t C7H8O, khi tc dng vi FeCl3 cho mu xanh tm. 9. Gii thch bng cu to v chng minh bng cc phn ng ho hc: 9.1. Hot tnh ca nguyn t H trong nhm OH ca glixerin v phenol. 9.2. Tnh axit ca nguyn t H trong nhm cacboxyl. 9.3. Tnh baz ca cc amin. 10. Vit phng trnh v c ch cc phn ng sau: 10.1. 2- brombutan + KOH 10.2. 2- clo-2- metylpentan + NaOH 10.3. Axeto + C6H5- NH- NH2 10.4. Ancol allylic + HBr 10.5. Anehit acrylic + NaHSO3 10.6. Axit benzoic + Br2 Fe 11. Hon thnh cc s phn ng sau: OH-/ru 11.1. 2-clo-2-metylpentan A KOH/H2O 11.2. 2-brom-2-metylbutan CH3CHO E H2O F B A HBr B H2SO4/1800C HBr Mg/ete khan D B C
H2SO4/1800C H2O 11.3. Ancol bc 3 2-metylbut-2-en 11.4. CH3- CHO + B C H2O butan-2-ol
H2O
11.5. HCHO + A B
butan-1-ol H2O C
11.6. Anehit acrylic + HCN B 11.7. A + C2H5MgCl B 11.8. Axeton + B C H2O
pentan-3-ol H2O 2-metyl propan-2-ol
12. T benzen v cc cht khc, hy tng hp cc hp cht sau: 12.1. Ancol benzylic 12.2. Tribrom anilin 12.3. Axit pycric 13. T tan v cc ho cht khc, hy tng hp cc cht sau: 13.1. Butan-2-ol 13.2. 2- metyl butan-2-ol 13.3. Axit lactic 14. Bng cc phn ng ho hc, hy phn bit: 14.1. Glixerin v propan-1-ol 14.2. Propan-1-ol v propan-2-ol 14.3. Axit fomic v axit benzoic 15. So snh s phn cc ca lin kt C-X trong dn xut mono halogen khng vng no v dn xut mono halogen thm. Gii thch bng cu to v chng minh bng phn ng ho hc.
chng IV Cc hp cht thin nhin
Ho hc cc hp cht thin nhin l mt lnh vc khoa hc gn lin vi cuc sng con ngi. T nhng sinh vt phong ph v a dng xung quanh chng ta bao gm cc thc vt, ng vt v vi sinh vt, ngi nghin cu chit xut c nhiu hp cht c hot tnh sinh hc nhm s dng vo vic phng v cha bnh cho con ngi, gia sc, gia cm, bo v thc vt, nng cao sc kho v mc sng cho con ngi. Trn c s nm vng cu trc ho hc ca cc cht con ngi tng hp, phn tch, nhn c nhng hp cht c hot tnh tt hn, cao hn, t c hn v tin ti sn xut c nhiu hp cht bng nhiu phng php ho hc. Trong chng ny chng ta ch yu ch cp n cu trc ho hc v tnh cht ho hc ca mt s nhm hp cht thin nhin chnh, nhm tip cn nghin cu cc gio trnh c s v chuyn mn ca cc ngnh nng, lm, ng nghip. Nhng nhm hp cht sau y s c cp, nghin cu trong gio trnh: cc hp cht gluxit, lipit, axit amin v protein.
1. Gluxit (cacbo Hirat)
Trong cc b phn ca thc vt, ng vt, trong c th ca vi sinh vt, thm ch trong thnh phn cc cht hu c ca t c cha mt lng ln cc hp cht gluxit. Trong c th sinh vt cc hp cht ny tham gia vo cc qu trnh trao i cht, cung cp cc cht dinh dng v nng lng cho s pht trin ca c th. Trong t, khi phn hu cc di tch thc vt v phn hu c, cc cht ny chu nhng tc ng ca cc qu trnh sinh ho khc nhau v ng vai tr quan trng trong vic hnh thnh nhng tnh cht, xc nh ph ca t, chng tham gia vo qu trnh hnh thnh mn t v cc cht hot ng sinh hc khc ca t. Thc vt c kh nng quang hp tng hp nn phn t glucoz l mt gluxit n gin t kh cacbonic v nc. Qu trnh ny xy ra rt phc tp, nhng c th tm tt nh sau:
6 co2 + 6 h2o nh sng dip lc t c6h12o6 + 6 o2
T phn t glucoz bng nhng cch kt hp khc nhau s to nn nhng hp cht gluxit phc tp nh tinh bt, xenluloz, vv Cc hp cht gluxit n gin, trong phn t ca chng lun lun bao gm nhm cacbonyl ( ca anehit hoc xeton) v nhiu nhm hiroxyl. Cc hp cht gluxit phc tp khi thu phn n cng lun to thnh cc phn t gluxit n gin. Do vy, gluxit l nhng poli hiroxicacbonyl (poli hiroxi anehit hoc poli hiroxi xeton) cng cc sn phm ngng t ca chng. C nhiu cch phn loi cc hp cht gluxit. Cch ph bin nht l da vo mc phc tp ca phn t. Theo cch ny cc hp cht gluxit c chia thnh ba loi chnh: - Mono saccarit (monoz) - Oligo saccarit - Polisaccarit (polioz) Cc hp cht gluxit cn c phn chia thnh cc gluxit kh v gluxit khng kh tu thuc vo quan h tnh cht ca chng vi cc tc nhn oxi ho l thuc th Tlens v thuc th Phlinh.
1.1. Monosaccarit (monoz)

Monosaccarit hay cn gi l monoz thuc nhng gluxit n gin nht. Trong phn t cc monosaccarit thng cha t 3 n 9 nguyn t cacbon. Tu thuc vo s lng nguyn t cacbon c trong phn t m cc monosaccarit c phn bit thnh cc trioz, tetroz, pentoz, hexoz,vv V bn cht ho hc, cc monosaccarit l cc polihiroxi cacbonyl. Tu thuc vo nhm cacbonyl l anehit hay xeton m monosaccarit tng ng l anoz hay xetoz. Da vo nhng c s nh vy m mt monosaccarit c 6 nguyn t cacbon v nhm chc anehit (hay nhm chc xeton) chng hn s c gi l ano hexoz (hay xeto hexoz).
Thuc vo cc monosaccarit cn c c cc hp cht xut hin do s thay th mt trong cc nhm OH bng nguyn t H, nhm amin, hoc c nhng hp cht c cha nhm cacboxyl, chng hn:
CHO (CHOH)n CH2OH Anoz CH2OH C=O (CHOH)n CH2OH xetoz CHO CH2 (CHOH)n CH2OH ng oxi CHO CHO CHNH2 (CHOH)n (CHOH)n COOH CH2OH ng amin axit uronic
a. Cu to ca cc monosaccarit
Trn c s cc kt qu nghin cu thc nghim ngi ta thy rng, cc monosaccarit u song song tn ti hai dng cu to: Cu to dng khng vng v cu to dng vng. Trong dung dch nc hai dng cu to ny tn ti trng thi cn bng ng, h bin:
Dng khng vng dng vng
Dng cu to khng vng ca cc anoz c th biu din bng cng thc tng qut:
CH2OH (CHOH)n C -H = O
v cng thc tng qut ca cc xetoz l: CH2OH (CHOH)n C -CH2OH O Nhn vo cc cng thc tng qut trn ta c nhn xt rng: Cc anoz c mt u mch l nhm chc anehit, u mch kia l nhm chc ru bc mt (CH2OH), trong mch l nhng nhm ru bc hai (CHOH). Cc xetoz, hai u mch l hai nhm ru bc mt, nguyn t cacbon th hai l nhm chc xeton (C=O), cn li trong mch l nhng nhm ru bc hai. Trong phn t cc monosaccarit u c cc nguyn t cacbon bt i, do chng u c tnh quang hot v c cc ng phn quang hc. mi ng phn quang hc, v tr ca H v nhm OH xung quanh nguyn t cacbon bt i l hon ton xc nh v mi ng phn quang hc ng vi mt hp cht gluxit ring bit.
Th d 1. Anhexza : CH2OH * (CHOH)4 CHO
Trong phn t c 4 nguyn t cacbon bt i hon ton khc nhau, nn c 24 = 16 ng phn quang hc, to thnh 8 cp nghch quang. Cng thc chiu Fis ca 16 ng phn quang hc c biu din nh sau:
CHO H C OH H C OH H C OH H C OH CH2OH D (+) aloz

CHO O H C H O H C H H C OH H C OH CH2OH D (+) manoz
CHO HO C H H C H O HO C H H C H O CH2OH L (-) aloz

CHO H C OH H C OH HO C H H C H O CH2OH L (-) manoz
CHO HO C H H C OH H C OH H C OH CH2OH D (+) altroz

CHO HO C H HO C H HO C H H C OH CH2OH D (+) taloz
CHO H C OH HO C H HO C H HO C H CH2OH L (-) altroz

CHO H C OH H C OH H C OH H C H O CH2OH L (-) taloz
CHO H C OH HO C H H C OH H C OH CH2OH D (+) glucoz

CHO
CHO HO C H H C OH HO C H H C H O CH2OH L (-) glucoz

CHO
CHO H H C OH C OH
CHO HO C H HO C H H C OH H C H O CH2OH L (-) huloz

CHO
HO C H H C OH CH2OH D (+) huloz

CHO
H C OH HO C H
HO C H
HO C H
H C OH
HO C H H
C OH
H C OH HO C H H
C OH
C OH
HO C H
H C OH
H C OH
H C H O
CH2OH L (-) galactza
H C H O
CH2OH L (-) Iza
CH2OH D (+) galactza

Th d 2.
CH2OH D (+) Iza
Xthexza : CH2OH
* (CHOH) C -CH2OH 3 O
Trong phn t c ba nguyn t cacbon bt i, nn c 23= 8 ng phn quang hc, to thnh 4 cp nghch quang.
Sau y l cng thc chiu Fis ca 8 ng phn quang hc .
CH2OH C O H C OH H C OH H C OH CH2OH D (-) aluloz CH2OH C O H C OH HO C H H C OH CH2OH D (-) socboz
CH2OH C O HO C H HO C H HO C H CH2OH L (+) aluloz CH2OH C O HO C H H C OH HO C H CH2OH L (+) socboz
CH2OH C O HO C H H C OH H C OH CH2OH D (-) fructoz CH2OH C O HO C H HO C H H C OH CH2OH D (-)tagaloz
CH2OH C O H C OH HO C H HO C H CH2OH L (+) fructoz CH2OH C O H C OH H C OH HO C H CH2OH L (+) tagaloz
Cc monosaccarit t nhin phn ln u tn ti cu hnh D. dng cu to khng vng, cc monosaccarit c cc nhm cacbonyl (anehit hoc xeton) v cc nhm chc ru, do vy khi dng cu to ny chng biu hin cc tnh cht ca hp cht cacbonyl v tnh cht ca ru (poliancol). Tuy vy, khi nghin cu v tnh cht ngi ta cng nhn thy rng cng thc cu to dng mch h khng gii thch c mt s tnh cht, chng hn: - Cc anoz mc d c cha nhm chc anehit nhng li khng to mu vi thuc th Shiff, khng c phn ng cng hp vi natribisunfit (NaHSO3). - Khi ho tan nhng tinh th D (+) glucza vi nhit nng chy 1460C vo nc, dung dch c gc quay cc ring ban u l +10906, sau gc quay cc ca dung dch gim dn theo thi gian n khi t ti gi tr +5207. Hin tng ny c gi l s i quay. Nu glucoz ch c mt dng cu to th khng th c hin tng ny. - Khi ete ho mt phn t hexoz cn 5 phn t ancol, sn phm l mt pentaete. Khi thu phn pentaete ny ngi ta nhn thy ch mt nhm ete b thu phn gii phng mt nhm -OH t do. iu ny chng t trong nm nhm -OH ca cc hexoz c mt nhm -OH khc vi cc nhm -OH kia. - Cc monosaccarit c s ng phn quang hc tm c trong thc t ln hn s ng phn tnh theo l thuyt.
Nhng tnh cht khng bnh thng trn y gii thch c khi cc nh khoa hc cho rng, trong dung dch cc monosaccarit ngoi dng cu to khng vng cn tn ti dng cu to vng. Dng cu to vng c hnh thnh do kt qu ca phn ng cng hp i nhn gia nhm -OH vi nhm >C=O. Th d, qu trnh to thnh vng 6 cnh ca phn t D (+) glucoz v 5 cnh ca phn t D (-) fructoz c biu din nh sau:
OH H H HO H H C C OH C H O C OH C CH2OH CHO H C OH HO C H H C OH H C OH CH2OH D (+) glucoz HO H HO H H H C C OH C H O C OH C CH2OH
-D (+) glucopyranoz
-D (+) glucopyranoz
CH2OH OH C HO C H H C OH O H C CH2OH D (-) fructofuranoz
CH2OH C O HO C H H C OH H C OH CH2OH D (-) fructoz
CH2OH HO C HO C H H C OH O H C CH2OH D (-) fructofuranoz
Dng vng 5 cnh c cu to ca khung furan, do vy thng c gi l dng furanoz. Dng vng 6 cnh c cu to ca khung pyran, do vy thng c gi l dng pyranoz. Khi chuyn sang dng cu to vng, nguyn t cacbon vn l nguyn t cacbon cacbonyl (C1 ca anoz v C2 ca xetoz ) cng tr thnh nguyn t cacbon bt i, do vy tu theo s phn b khng gian ca nhm -OH lin kt vi n dng cu to vng li c phn bit thnh dng v dng . Hai dng ny u l nhng ng phn quang hc nhng khng phi l nghch quang ca nhau, bi v gia chng ch khc nhau v cu hnh ca nguyn t cacbon bt i mi (C1 ca anoz v C2 ca xetoz ) m thi. Cc ng phn c gi l ng phn ia. Nhm hiroxyl mi c hnh thnh C1 hoc C2 c gi l nhm hiroxyl smi axetal hay nhm hiroxyl glucozit. Nh vy, dng cu to vng cc monosaccarit trong phn t ch c cc nhm chc ru v nhm hiroxyl glucozit. Do vy dng cu to vng cc monosaccarit ch c tnh cht ca ru v tnh cht ca nhm hiroxyl glucozit. biu din cng thc cu to dng vng ca cc monosaccarit ta c th dng cch biu din n gin ca Fis nh trn. Song cch biu din ny khng cho bit s phn b thc ca cc nhm th trong khng gian, do vy ngi ta cn dng cc cch biu din khc nh cch biu din ca Havooc.
Trn c s nhng trnh by trn y ta c th biu din cc dng cu to ca mt monosaccarit c th no , chng hn ca D (+) glucoz v D (-) fructoz nh sau:
CH2OH O H H OH H OH HO C H OH H H C OH O H HO C H H C OH H C CH2OH CHO C OH HO C H H C OH H C OH CH2OH D (+) glucoz H C OH H C OH O H OH H OH HO C H H C OH H C CH2OH -D (+) glucopyranoz (Tnc: 1460C, []=+10906) CH2OH O H OH H
H OH
H OH
-D (+) glucopyranoz (Tnc: 1500C, []=+190)
CH2OH CH2OH H H OH H O OH CH2OH OH HO C HO H H C C C CH2OH H O OH HO H H
CH2OH C O C C C H OH OH HO H H
CH2OH C OH C C C H OHO H OH H CH2OH H O OH OH CH2OH
-D (-) fructofuranoz
CH2OH D (-) fructoz
CH2OH -D (-) fructofuranoz
b. Tnh cht ca cc monosaccarit
Monosaccarit l nhng cht rn, kt tinh, c v ngt. Tt c cc monosaccarit u l cc cht hot quang. Tu thuc vo bn cht ca tc nhn phn ng m cc monosaccarit tham gia cc phn ng ho hc dng cu to khng vng hoc dng cu to vng.
- Cc phn ng ca nhm cacbonyl
Cc monosaccarit tham gia phn ng xi ho, cc phn ng cng hp i nhn tng t cc anehit v xeton nhng vi mc mnh hn. i vi cc anoz, tu thuc vo iu kin v tc nhn oxi ho m phn ng oxi ho ch nhm chc anehit hoc c nhm chc anehit v nhm ru bc mt. Vi cc tc nhn oxi ho yu nh dung dch nc brom trong kim, thuc th Tlens, thuc th Phlinh, v vch nhm chc anehit b oxi ho to thnh axit polihiroxi monocacboxylic. Vi cc tc nhn oxi ho mnh nh hn hp KMnO4 + H2SO4, K2Cr2O7 + H2SO4, HNO3 vvc hai nhm chc anehit v ru bc mt u b oxi ho to thnh sn phm l cc axit polihiroxi icacboxylic tng ng. Th d. Phn ng oxi ho ca D (+) glucoz:
COOH HO C OH CHO HO C OH HO C H H C OH H C OH CH2OH [Ag(NH3)2]OH HO C H + Ag + NH3 + H2O H C OH H C OH CH2OH COOH KMnO4 + H2SO4 HO C OH HO C H + MnSO4 + K2SO4 + H2O H C OH H C OH COOH
Trong c th sinh vt cn xy ra s oxi ha la chn, ngha l ch oxi ho nhm ru bc mt, cn nhm chc anehit vn c bo ton. Trong phng th nghim ngi ta cng thc hin c phn ng ny bng cch to axetal trc khi tin hnh phn ng oxi ho.
CH2OH (CHOH)4 glucoz
CHO
[O]
HOOC (CHOH)4 CHO axit gluco uronic
Khc vi cc xeton, cc xetoz cng b oxi ho bi cc cht oxi ho yu trong mi trng kim nh thuc th Phlinh. iu ny c gii thch l do trong mi trng kim mt phn xetoz b ng phn ho thnh anoz . Th d:
fructoz glucoz
Vi cc cht oxi ho mnh cc xetoz b oxi ho theo cch tng t nh cc xeton, sn phm ch yu ca cc phn ng l hn hp cc axit icacboxylic.
CH2OH C=O (CHOH)3 CH2OH COOH [O] (CHOH)2 COOH COOH COOH
H2O
Cc phn ng oxi ho ca cc monosaccarit rt c ngha trong thc tin. Chng hn, phn ng oxi ho bng tc nhn oxi ho Tlens c s dng trong cng ngh trng gng, trng rut phch, vvphn ng oxi ho bi thuc th Phlinh c dng nh lng ng trong c th sinh vt. Cc monosaccarit tham gia phn ng cng hp i nhn tng t nh cc anehit v xeton. Ring phn ng cng hp natribisunfit (NaHSO3) khng xy ra bi v trong mi trng ca phn ng ny cc monosaccarit ch tn ti di dng cu to vng.
Phn ng cng hp vi phenylhirazin (C6H5-NH-NH2) c th to thnh phenyl hirazon hoc ozazon tu thuc vo lng tc nhn phn ng. Nu lng tc nhn phenylhirazin khng d sn phm to thnh l phenylhirazon, nu d tc nhn sn phm to thnh l ozazon.
CH=N -NH -C6H5 (CHOH)n CH2OH
CH2OH C=N -NH -C6H5 (CHOH)n CH2OH
CH=N -NH -C6H5 C=N -NH -C6H5 (CHOH)n CH2OH ozazon
phenylhirazon Th d.
Phn ng ca D (+) glucoz vi phenylhirazin to thnh phenylhirazon v ozazon xy ra nh sau:

CHO C OH +C6H5NHNH2 C H C OH -H2O C OH CH2OH C =N -NH -C6H5 C OH C H + C6H5NHNH2 C OH (C6H5 -NH2 + NH3) C OH CH2OH
H HO H H
H HO H H
phenyl hirazon
C =N -NH -C6H5 C= O HO C H +C6H5NHNH2 H C OH -H2O H C OH CH2OH
CH =N -NH -C6H5 C = N -NH -C6H5 HO C H H C OH H C OH CH2OH

ozazon
Phn ng u tin xy ra qu trnh to thnh phenylhirazon, sau l qu trnh oxi ho nhm ru bc hai, ri qu trnh to ozazon. Phn ng dng li bc to thnh ozazon. Ozazon l nhng hp cht n nh do vic to thnh 2 lin kt hiro -NHN v -NHOH cng nh h lin hp di gia hai vng benzen.
N C
C= N N Ch H O (CHOH)2 H CH2OH
Phn ng ca D(-) fructoz vi phenylhirazin cng xy ra theo cch tng t, nhng qu trnh oxi ho xy ra nhm ru bc mt. D(+) glucoz v D(-) fructoz cho cng mt ozazon. Ozazon l nhng cht rn kt tinh mu vng c trng, kh tan trong nc. Nhiu ozazon khng c nhit nng chy xc nh hoc b phn hu nhit nng chy v kh kt tinh li. Phn ng to ozazon c dng xc nh cu to, nhn dng cc monosaccarit.
- Cc phn ng ca nhm hiroxyl
i a s cc phn ng ca nhm hiroxyl u xy ra dng cu to vng. Ring phn ng vi Cu(OH)2 nhit phng xy ra vi dng cu to thng. Phn ng c th xy ra mt, mt vi hoc tt c cc nhm hiroxyl, do vy sn phm phn ng thng rt phc tp. Chng hn, khi un nng monosaccarit vi dung dch ru metylic c mt HCl th ch c nhm hiroxyl glucozit tham gia phn ng ete ho.
CH2OH O H OH H CH2OH O H H OH
H OH
H +CH3OH OH
HCl t
0
H OH
H + H2O OCH3
H OH -D (+) glucopyranoz
H OH -D (+) metylglucopyranozit
Nhng khi un nng vi metylitua c oxit bc lm xc tc phn ng ete ho li xy ra tt c cc nhm hiroxyl.

CH2OH O H OH H CH2OCH3 O H H Ag2O H + 5hi 0 OCH3 H t OCH3 CH3O H OCH3 -D (+) pentametylglucopyranozit
H OH
H +5CH3I OH
H OH -D (+) glucopyranoz
Trong cc phn ng este ho vi cc axit th quan trng nht l este ca monosaccarit vi axit photphoric. Cc este ny tham gia vo cc qu trnh ng ho trong sinh vt. Cc este thng
gp l glucozo-6-photphat, glucozo-1-photphat, glucozo-1,6-iphotphat v fructozo-1,6iphotphat.

CH2OPO3H2 O H H H OH H OH OH H OH -D (+) glucozo-6-photphat CH2OPO3H2 O H H H OH H OPO3H2 OH H OH -D (+) glucozo-1,6-iphotphat CH2OH O H OH H
H OH
H OPO3H2
H OH -D (+) glucozo-1photphat CH2OPO3H2 OH O H OH CH2OPO3H2 H OH -D (-) fructozo-1,6-iphotphat H
Nhm hiroxyl glucozit cn c th tham gia phn ng ngng t vi nhm hiroxyl ancol hoc nhm hiroxyl glucozit ca phn t monosaccarit khc to thnh cc hp cht glucozit khc nhau.
Th d, phn ng ngng t hai phn t D(+) glucopyranoz to thnh phn t mantoz xy ra nh sau:
CH2OH O H H H + OH H O-H OH H OH CH2OH O H H H OH H OH OH H OH CH2OH CH2OH O H O H H H H H +H2O OH H OH H O OH OH H H OH OH
Phn ng ny l c s quan trng ca cc qu trnh hnh thnh cc hp cht oligosaccarit v polisaccarit.

S chuyn ho ca cc monosaccarit
Di tc dng ca kim nhit phng cc monosaccarit xy ra s epime ho hoc ng phn ho. Th d, di tc dng ca kim, D (+) glucoz b epime ho hoc ng phn ho nh sau:
CHO H C OH HO C H H C OH H C OH CH2OH D(+)glucoz

ph ng
CHO HO C pime ho H HO C H H C OH H C OH CH2OH D(+)manoz CH -OH C OH H C OH H C OH CH2OH HO C H CH2 -OH C O HO C H H C OH H C OH CH2OH D(-)fructoz
Trong c th sinh vt cc qu trnh ny xy ra di tc dng ca enzim epimeraza v izomeraza.

- S ln men ca cc monosaccarit
S ln men ca cc monosaccarit l mt qu trnh quan trng xy ra di tc dng ca cc enzim khc nhau. Th d, cc qu trnh ln men thng gp ca cc hexoz nh sau: S ln men ru etylic:
C6H12O6 2 C2H5OH + 2 CO2
o nh
S ln men lactic:
C6H12O6 2 CH3 -CH -COOH OH
S ln men xitric:
C6H12O6 CH2-COOH HO C COOH CH2 -COOH 2 H2O
Phn ng ny c ng dng vi nhiu mc ch khc nhau trong sinh hot cng nh trong cng nghip.
1.2. oligosaccarit Oligosaccarit cn c gi l cc polisaccarit c tnh cht ng. Nhm ny c v ngt, tan trong nc. Oligosaccarit quan trng v ph bin nht trong t nhin l cc isaccarit. isaccarit l nhng gluxit phc tp khi thu phn to thnh hai phn t monosaccarit tng ng. Chng c cng thc chung l C12H22O11. Cn c vo cu to v tnh cht ngi ta chia cc isaccarit thnh hai loi: isaccarit khng c tnh kh v isaccarit c tnh kh.
a. Cu to ca cc isaccarit.
- isaccarit khng c tnh kh
Nt c trng ca cc isaccarit thuc loi ny l trong phn t ca chng khng cn nhm hiroxyl glucozit, do vy vng eteoxit khng c kh nng b t tr thnh dng cu to khng vng c nhm cacbonyl v cng v vy chng khng biu hin tnh kh. i din quan trng ca cc isaccarit khng c tnh kh l saccaroz (cn gi l ng ma, ng c ci). Khi thu phn bng dung dch axit long hoc enzim invertaza to thnh -D (+) glucopyranoz v -D(-) fructofuranoz, do vy c th kt lun rng saccaroz do hai phn t monosaccarit l -D (+) glucopyranoz v -D(-) fructo furanoz lin kt vi nhau bng lin kt , -1,2-glicozit.
CH2OH 5 O H H H 1 4 OH H OH 3 2 H OH
6 6
O
1
O OH H
3 4
CH2OH
5
HOCH2
OH
Dung dch saccaroz c gc quay cc ring []D=+6605. Khi thu phn gc quay cc thay i t []D=- 4005 th n nh. Hin tng ny c gi l s nghch o ng.
- isaccarit c tnh kh
Trong phn t ca cc isaccarit c tnh kh vn cn mt nhm hiroxyl glucozit, do vy vng ete oxit d b ph v tr v dng khng vng c nhm chc anehit. iu ny c ngha rng trong dung dch cc isaccarit ny lun tn ti di hai dng cu to vng v cu to khng vng tng t nh cc monosaccarit. Sau y l mt s isaccarit c tnh kh quan trng. Mantoz: C12H22O11 Khi thu phn bng dung dch axit hoc enzim mantaza to thnh hai phn t -D (+) glucopyranoz. Mantoz hai phn t -D(+) glucopyranoz lin kt vi nhau bng lin kt 1,4- glucozit.
CH2OH CH2OH H O O H H H H H OH H OH H O OH OH H H OH OH
Xenlobioz: C12H22O11 Xenlobioz ch khc mantoz ch l khi n thu phn di tc dng ca enzim emunxina ch khng phi l enzimmantaza. Enzim emunxina ch thu phn lin kt - glucozit, v vy, cu to ca xenlobioz khc cu to mantoz ch, cc gc -D (+) glucopyranoz lin kt vi nhau bng lin kt -1,4- glucozit.
CH2OH CH2OH H O O OH H H H O OH H OH H H H OH H H OH OH
Lactoz ( ng sa): C12H22O11 Khi thu phn bi axit hoc enzim emunxina, lactoz chuyn thnh -D (+) glucopyranoz v -D (+) galactopyranoz. Lactoz do hai monosaccarit -D (+) galactopyranoz v -D (+) gluco pyranoz lin kt vi nhau bng lin kt -1,4-galactozit.
CH2OH CH2OH HO O O H H H H OH H OH H O H OH H H H OH OH
b. Tnh cht ca cc isaccarit
Cc isaccarit c tnh cht tng t nh cc monosaccarit: C tnh cht hot quang, lm tan kt ta ca Cu(OH)2, khi cng hp vi phenylhirazin to thnh ozazon. Ngoi ra, cc isaccarit l do cc monosaccarit lin kt vi nhau bng lin kt glucozit, bn cht ca cc lin kt ny l lin kt cu ete, do vy isaccarit cn c phn ng thu phn. Khi b thu phn cc isaccarit to thnh cc monosaccarit tng ng. Th d, khi thu phn mantoz bng xc tc axit thu c hai phn t monosaccarit l -D (+) glucopyranoz.
CH2OH CH2OH O H O H H H H H +H2O OH H OH H O OH OH H H OH OH
H+
CH2OH O H H H 2 OH H OH OH H OH
Cc isaccarit c tnh kh tham gia phn ng oxi ho tng t cc anoz. Th d, phn ng oxi ho mantoz vi thuc th Tlens xy ra nh sau:
CH2OH CH2OH O H O H H H H H + [Ag(NH3)2]OH OH H OH H O OH OH H H OH OH CH2OH O H H H H OH H O OH H OH
t0
CH2OH OH + Ag + NH3 + H2O H H COOH OH H OH
1.3. Polisaccarit (polioza) Polisaccarit l nhng polime t nhin, sn phm ngng t ca mt s ln phn t monosaccarit. Phn t ca chng gm hng trm n hng ngn gc monosaccarit lin kt vi nhau bng lin kt glucozit. Cng thc chung ca cc polisaccarit l (C6H10O5)n. Quan trng nht trong s cc polisaccarit l tinh bt v xenluloz, c hai u c gi tr ln i vi i sng con ngi.
a. Tinh bt: (C6H10O5)n
Tinh bt l polisaccarit d tr quan trng v rt ph bin trong thin nhin. N l sn phm quang hp cy xanh. N c mi b phn ca thc vt, ch yu tp trung ht nh go, ng, mch v cc loi c nh khoai, sn Thng thng phn t tinh bt cha khong 20% phn ho tan trong nc gi l amyloz v 80% phn khng tan c trong nc gi l amylopectin. Hai thnh phn cu to ny c cu to t cc gc -D (+) glucopyranoz, nhng khc nhau v kch thc v hnh dng phn t.
Amyloz c cu to t khong 200-400 gc -D(+) glucopyranoz, c khi ti 1000 gc -D(+) glucopyranoz lin kt vi nhau bng lin kt -1,4- glucozit to thnh mch thng khng phn nhnh. Phn t lng ca amyloz thay i t 35000 -100000 vC.
CH2OH O H H OH H H OH CH2OH O H H OH H H OH CH2OH O H H OH H H OH
H O
H O
H O
Mt khc, bng tia Rnghen ngi ta chng minh c rng amyloz c cu trc xon c to ra cc ng t do, mi vng xon gm khong 6 gc -D(+) glucopyranoz.
Amylopectin c cu to t 600 - 6000 gc -D(+) glucopyranoz, vi phn t lng khong 100.000 - 1000.000 vC. Cc gc -D(+) glucopyranoz lin kt vi nhau ch yu bng lin kt -1,4-glucozit, ti cc im phn nhnh l lin kt -1,6-glucozit. Do vy amylopectin c cu to phn nhnh, cc nhnh cch nhau chng 18 -26 gc.
CH2OH H O H OH H O H OH CH2OH H O H OH H O H OH H O H O H CH2OH H OH H O H H
OH O CH2 H O H OH H H OH H O H
CH2OH O H OH H H OH H O
Tinh bt khng tan trong nc lnh, trong nc nng to thnh dung dch keo gi l h tinh bt. Dung dch h tinh bt c gc quay cc ring []D=+1500 -2200. H tinh bt phn ng vi it to thnh dung dch mu xanh. Phn ng ny do mch polime ca amyloz cun theo ng xon c to thnh ng, phn t it chui va lt vo ng to thnh phn t mu xanh c thnh phn (C6H10O5)n.I2, mu xanh ny mt i khi un nng v li xut hin tr li khi ngui. Tinh bt khng c tnh kh, khng tham gia phn ng oxi ho. Cc nhm hiroxyl C2, C3 v C6 trong mi mt xch ca phn t tinh bt c th tham gia cc phn ng ete ho v este ho. Khi tham gia phn ng thu phn cc lin kt glucozit b ph v dn dn to thnh cc phn t extrin (tinh bt tan), sau l mantoz v nu thu phn hon ton tinh bt s to thnh -D(+) glucopyranoz. H2O (H+) H2O (H+) H2O (H+) (c6h10o5)x C12H22O11 C6H12O6 (c6h10o5)n x <n -D(+)glucopyranoz tinh bt mantoz cc extrin Trong c th sinh vt tinh bt b thu phn bi hai h thng enzim l -amylaza v enzim mantaza, enzim -amylaza xc tc cho qu trnh thu phn tinh bt n to thnh mantoz, sau enzim mantaza xc tc cho qu trnh thu phn tip theo t mantoz thnh glucoz.
b. Glicozen : (C6H10O5)n
Glicozen cng l polime cu to t cc gc glucoz nhng vi s mt xch ln hn so vi tinh bt ( n t 6000 - 24000). Glicozen c cu to tng t nh amylopectin, nhng mch phn nhnh nhiu hn. Glicozen l cht bt mu trng, v nh hnh, tan trong nc, khng c phn ng mu vi it.
Glicozen c to thnh trong gan ng vt t glucoza ca mu v l cht polisaccarit d tr khi cn thit li thu phn thnh glucoz, do vy glicozen cn c gi l tinh bt ng vt.
c. Xenluloz: (C6H10O5)n
Xenluloz rt ph bin trong thc vt, n l thnh phn chnh ca mng t bo to nn b khung ca thc vt, gi cho thc vt c hnh dng c nh v c tnh bn c hc. Trong thc vt xenluloz thng lin kt vi cc cht khc nh linhin, hmixenluloz, pectin, nha, vv V mt cu to, xenlul l polime cu to t cc gc D(+) glucopyranoz, nhng khc vi tinh bt nhng im sau: - S mt xch n rt ln, t 6000 - 12000 - Chui polime ca xenluloz l mch thng khng phn nhnh, v vy xenluloz c th to thnh si ( si bng, si gai, vv) - Xenluloz cu to t cc gc -D(+) glucopyranoz lin kt vi nhau bng lin kt -1,4glucozit.
CH2OH H O H OH H O H H OH H O CH2OH O H OH H H H OH O CH2OH H H OH H O H H OH O
Xenluloz l cht rn, c dng si, c tnh thm nc, khng tan trong nc, ete v ru, ch tan c trong mt s dung mi c bit nh dung dch Svyze ( hn hp Cu(OH)2 v NH3 m c), dung dch H2SO4 c (trn 72%), dung dch HCl c c ho tan ZnCl2. Xenluloz kh b thu phn hn tinh bt, phi un nng lu vi axit v c long, i khi phi dng p sut cao. Xenluloz b thu phn dn dn thnh amyloit, xenlobioz v cui cng l -D(+) glucopyranoz. (c6h10o5)n H2O (H+) H2O (H+) H2O (H+) (c6h10o5)x C12H22O11 C6H12O6 x <n D(+)glucopyranoz xenlobioz xenluloz amyloit
Phn ng ny c ng dng chuyn g thnh ng, sau cho ln men ru trong cng nghip. Xenluloz khng b thu phn do cc h thng men c trong h thng tiu ho ca con ngi. Tuy nhin n c th b thu phn hoc b phn gii bi cc men c hiu c tit ra t cc vi khun c trong d c ca cc loi ng vt nhai li, cc vi khun trong t, vv Do c cu to dng si nn cc nhm -OH b l ra ngoi, do vy xenluloz biu hin cc tnh cht ging nh ancol, nh cc phn ng vi kim, phn ng este ho vi cc axit khc nhau. Nhng tnh cht ny c s dng nhiu trong cc ngnh cng nghip. Chng hn, khi cho
xenluloz tc dng vi hn hp HNO3 c v H2SO4 c, khi c th mt, hai hoc c ba nhm OH trong gc glucoz b este ho to thnh sn phm tng ng l mononitroxenluloz [C6H7O2(OH)2(ONO2)]n, initroxenluloz [C6H7O2(OH)(ONO2)2]n c dng ch sn, lm phim, lm keo dn, ch nha xenluloit v trinitroxenluloz [C6H7O2 (ONO2)3]n l cht n mnh c dng lm thuc sng khng khi.
2. Lipit ( cht bo)
Cng vi cc cht gluxit, protit, lipit l nhng cht rt quan trng trong i sng ca con ngi. Lipit l ngun nguyn liu cung cp nng lng cho cc qu trnh bin i sinh ho trong c th sinh vt. Lipit ca ng vt thng c gi l m (m ln, m b, m cu, vv), cn lipit thc vt c gi l du ( du lc, du da, du liu, vv). M v du c tnh cht ging nhau nhng li c vai tr khc nhau trong c th. Trong c th sinh vt c th bt gp nhiu loi lipit khc nhau, nhng ph bin nht l lipit n gin v phtpholipit. Do vy chng ta ch i su nghin cu v cu to v tnh cht ca hai loi lipit ny.
Lipit n gin hay cn gi l glixerit c th c cc loi sau y:
CH2 - O - C O CH - O - C O CH2 - O - C O triglixerit

= = =
R R' R"
CH2 - O - R CH - O - C
= =
CH2 - O - Gl R' CH - O - C
= =
R'
O CH2 - O - C R" O ankyliglixerit
O CH2 - O - C R" O glicozyliglixerit
Cc gc ru, axyl, glicozyl cng c th c phn b cc v tr khc nhau. Trong t nhin bt gp ch yu l cc triglixerit, cn cc loi glixerit khc bt gp vi lng nh. Cc triglixerit t nhin li bt gp ch yu l cc triglixerit hn tp. Th d:
CH2 - O - C C15H31 O CH - O - C C17H33 O CH2 - O - C C17H35 O panmito - oleo -stearin
=
Rt him c cc triglixerit ca cng mt axit.

Cc axit tham gia vo thnh phn cu to ca triglixerit c th l axit bo no hoc khng no, nhng u c cu to mch khng phn nhnh, s nguyn t cacbon trong phn t thng chn v trongkhong t 4- 26, ch yu l 16 v 18. Cc axit thng gp l axit panmitic C15H31COOH, axit stearic C17H35COOH, axit lic C17H33COOH, axit linoleic C17H31COOH, axit linolenoic C17H29COOH, vv Trong lipit thc vt th axit cha no chim thnh phn ch yu, cn trong lipit ng vt th phn ln li l cc axit bo no.
Photpholipit hay photphatit t nhin ch yu c cu to dng tng qut:
CH2 - O - C R O CH - O - C R' OH O CH2 - O - P X O (X l gc ancolat cha nit)
= = =
Th d. Cholinphotphatit
CH2 - O - C R O R' CH - O - C O OH CH2 - O - P O - CH2 - CH2 - CH2 -N (CH3)3 O
= = =
Serinphotphatit
CH2 - O - C R O R' CH - O - C O OH CH2 - O - P O - CH2 - CH - COOH O NH2
=
Cc lipit ni chung c tnh k nc, khng tan trong nc nhng tan nhiu trong ru, ete v cc dung mi hu c khc.
Tnh cht ho hc c bn ca lipit l tham gia phn ng thu phn. Phn ng thu phn xy ra di tc dng ca axit, kim hoc men, i khi c th un si n vi nc p sut cao, nhit cao ( 25 atm, 2200C). Sn phm thu phn rt khc nhau tu thuc vo chng loi v cu to ca lipit. Chng hn, khi thu phn cc triglixerit xy ra nh sau:
CH2 - O - C O CH - O - C O CH2 - O - C O
= =
R R' R" 3 HOH xt
CH2 - O H CH - OH CH2 - OH
RCOOH R'COOH R"COOH
Nu thu phn bng kim s thu c glixerin v cc mui. Cc mui ny c kh nng ty ra gi l x phng. Phn ng thu phn cn c gi l phn ng x phng ho. Trong c th phn ng thu phn c thc hin di tc dng ca enzim lipaza. Ngoi phn ng thu phn cc glixerit cha no cn tham gia phn ng cng hp (cng H2), lm mt mu nc brom, it, oxi ho (lm mt mu dung dch KMnO4, oxi ho bi oxi khng kh, vvM lu ngy trong khng kh to ra mi hi kht, v ng do tc dng ca nh sng, hi m v vi khun.
3. Axit amin ( amino axit)
Axit amin l loi hp cht hu c tp chc trong phn t va c nhm cacboxyl va c nhm chc amin. Cng thc chung ca cc axit amin c th biu din di dng tng qut:
(COOH)m R (NH2)n
Trong cc axit amin t nhin hay gp ch yu l cc - amino axit, ngha l trong phn t ca chng lun lun c mt nhm amino v tr C so vi nhm cacboxyl. 3.1. Gi tn v phn loi a s axit amin c gi theo tn ring hoc gi theo tn cc axit tng ng vi tip u ng amino v v tr ca nhm ny bng cc ch s , , , vv Th d:
CH2-COOH NH2 glixin, glicocol ( axit amino axetic) CH3 - CH-COOH NH2 alanin ( axit amino propionic) CH3 -CH2 - CH CH-COOH CH3 NH2 izolxin ( axit amino, -metylvaleric)
HO -CH2 - CH-COOH NH2 serin (axit -amino - hiroxipropionic)
HS -CH2 - CH-COOH NH2 xistein (axit -amino - thiopropionic)
H2N -CH2 -CH2 - CH-COOH NH2 lizin (axit -,-iamino caproic)

HO
CH2 - CH-COOH NH2 phenylalanin (axit -amino - phenylpropionic)

HOOC -CH2 -CH2 - CH-COOH NH2 axit glutamic (axit - amino glutaric)
CH2 - CH-COOH NH2 tyrozin (axit -amino - (p-hiroxiphenyl) propionic)
N N CH2 - CH-COOH NH2 histiin CH2 - CH-COOH NH2
NH
triptophan (axit - amino - -inolylpropionic)
Nh vy chng ta c th thy rng, trong phn t cc axit amin, phn gc hirocacbon c th thuc dy khng vng, vng thm, d vng, ng thi tng quan t l gia nhm cacboxyl v amin cng khc nhau. Hin nay ngi ta bit khong trn 100 axit amin khc nhau, trong s c 26 axit amin tham gia vo thnh phn cu to ca protein. Ngi ta cng bit trong s cc axit amin tm thy trong thnh phn ca protein th c khong 10 axit amin ch tng hp c trong thc vt cn ng vt khng tng hp c m phi ly t ngun thc n thc vt. Cc axit amin ny c gi l cc axit amin khng thay th c, l valin, izolxin, treonin, metionin, lizin, histiin, triptophan, phenylalanin, lxin v acginin. 3.2. Phng php iu ch iu ch cc axit amin ta c th thu phn protein thin nhin vi xc tc axit, kim hoc men. u tin thu c hn hp cc axit amin, sau tch cc axit amin ny di dng tinh khit bng cc phng php ho l v ho hc. Trong cc phng php tng hp, c ngha nht l cc phng php: Cho tc dng amoniac c, d vi cc - halogenaxit.
Th d:
CH3 - CH-COOH Cl NH3 CH3 - CH-COOH NH2 HCl
Tc dng kaliphtalimit vi cc - halogen este.

O C N -K C O
=
O C N - CH2 -COOC2H5 KCl C O COOH C2H5OH COOH
3.3. Tnh cht Axit amin thng l nhng cht rn kt tinh khng mu, c nhit nng chy cao, phn ln d tan trong nc.
a. Ion lng cc v im ng in
Trong dung dch nc, axit amin in li theo hai kiu: kiu axit v kiu baz.
(COOH)m R (NH2)n
(COOH)m R (NH2)n
+ nHOH
Thc ra hai qu trnh ny xy ra gn nh ng thi, nhm cacboxyl in li mnh hn nn in li trc, H+ c in li ra lp tc nhm amin nhn, do vy trong dung dch nc cc axit amin lun tn ti di dng ion lng cc.
(COO)m R (NH3)n
Cl -CH2 -COOC2H5 H2O

=
NH2 -CH2 -COOH
(COO)m R (NH2)n
(COOH)m + n OH R (NH3)n
+ mHOH
+m H3O
Nu s nhm -COOH bng s nhm -NH2 th pH ca dung dch 7, nu s nhm -COOH nhiu hn s nhm NH2 th pH < 7 v ngc li, nu s nhm COOH t hn s nhm NH2 th pH > 7. Mc d lun tn ti di dng ion lng cc, nhng ln in tch ca ion lng cc ny trc ht ph thuc vo s lng nhm cacboxyl v nhm amino, ngoi ra cn ph thuc rt ln vo pH ca mi trng. Trong mi trng axit, do nng H+ ln, nn cn tr qu trnh in li ca nhm cacboxyl, axit amin khi mang in tch dng.
(COO)m R (NH3)n + mH
+
(COOH)m R (NH3)n
Nu thit lp mt in trng ion ny s chy v cc m, ngc li, trong mi trng kim axit amin mang in tch m s chy v cc dng.
(COO)m R (NH3)n + nOHR (NH2)n (COO)m + nH2O
Nh vy, bng cch iu chnh pH ca mi trng ta c th lm cho dung dch axit amin trung ho in. Gi tr pH ti phn t axit amin trung ho in tch gi l im ng in ca axit amin. im ng in c k hiu l pI. Cc axit amin khc nhau c im ng in khc nhau. Ti im ng in axit amin khng bn, d b kt ta. Bit im ng in ta c th tch c cc axit amin trong hn hp ra khi nhau bng phng php kt ta hay phng php in di.
b. Tnh cht quang hot
Tt c cc axit amin t nhin (tr glixin), trong phn t ca chng u c nguyn t cacbon bt i, do chng u c tnh hot quang. Tuy nhin, trong c th ng vt v thc vt cc axit amin u tn ti dng ng phn c cu hnh L.
COOH H2N -C -H R L -axit amin
Nguyn nhn ca iu l do h thng men ca c th ch thch ng mt cch c hiu vi cc L- axit amin.

c. Tnh cht ho hc
V mt tnh cht ho hc, do s c mt ng thi ca c nhm cacboxyl v amin m cc axit amin c y cc tnh cht ca nhm chc axit nh phn ng to mui vi kim loi hoc baz, phn ng to este, to amit, vv,v tnh cht ca nhm chc amin nh to mui vi axit, phn ng vi axit nitr, vv
Tnh cht lng tnh
Trong phn t axit amin c nhm cacboxyl mang tnh axit v nhm amin mang tnh baz, do vy axit amin l hp cht c tnh lng tnh, khi phn ng vi axit hoc baz u to mui. Th d:
CH3 - CH-COOH NH2 CH3 - CH-COOH NH2 HCl NaOH CH3 - CH-COOH NH3Cl CH3 - CH-COONa NH2 H 2O
Phn ng ngng t
Cc axit amin ngng t vi nhau to thnh cc hp cht peptit. Trong phn ng ngng t, phn t nc c tch ra t nhm -OH trong nhm -COOH ca phn t axit amin ny vi nguyn t H trong nhm -NH2 ca phn t axit amin kia. - H2O .... H - NH - CH-CO OH H - NH - CH-CO OH .... r r .... - NH - CH-CO - NH - CH-CO - .... r r Lin kt -CO -NH- c gi l lin kt peptit. Khi hai phn t axit amin ngng t vi nhau s to thnh hp cht ipeptit, ba phn t axit amin ngng t to thnh hp cht tripeptit, v nu nhiu phn t axit amin ngng t vi nhau s c hp cht polipeptit. Theo nguyn tc ca phn ng ngng t, khi cc axit amin ging nhau ngng t ch thu c mt hp cht peptit duy nht, nhng khi ngng t cc axit amin khc nhau ta c th thu c nhiu hp cht peptit khc nhau. Trong c th sinh vt phn ng ngng t xy ra di tc dng ca men. Phn ng ny l c s ca cc qu trnh hnh thnh cc hp cht peptit v protein t cc axit amin.
To mui phc ni
Cc axit amin c th to mui phc ni vi kim loi nng. Cc mui ny thng rt bn, kh tan v c mu c trng. Th d, mui phc ca glixin vi ng v coban:
CH2 -NH2 CO-O Cu
O-CO nh2 CH2
Co
O - CO NH2 -CH2 3
Phn ng cacboxyl ho
Phn ng ny c bit quan trng i vi c th sinh vt chuyn ho cc axit amin thnh amin. Phn ng c thc hin nh tc dng ca enzim cacboxylaza.
CH3 - CH-COOH NH2 men CH3 - CH2 -NH2 CO2
Phn ng vi axit nitr
Phn ng xy ra tng t cc amin.

CH3 - CH-COOH NH2
HNO2
CH3 - CH-COOH OH
N2 + H 2 O
Phn ng ny c dng nh lng axit amin da trn c s o lng kh N2 thot ra.

Phn ng oxi ho
Di tc dng ca men s xy ra phn ng loi b nhm amino, gii phng NH3 to thnh xeto axit.
CH3 - CH-COOH NH2 [O] men CH3 - C-COOH O axit piruvic
=
NH3
Phn ng mu ca axit amin
Phn ng mu c trng nht dng nh tnh v nh lng axit amin l phn ng vi ninhirin. Khi un nng dung dch axit amin vi dung dch ninhirin ( trong axton) pH < 5 thu c hp cht c mu xanh tm. Phn ng ny xy ra qua mt s giai on, n c biu din tm tt nh sau:
O C C O O C C =N -C C O C OH
=
R -CH -COOH NH2
0 C =O t
O C RCHO +CO2
4. Protit
Protit l nhng hp cht hu c c phn t lng ln, thnh phn cu to ch yu ca chng l cc phn t axit amin. Cng vi cc cht gluxit, lipit, protit l loi hp cht quan trng cho s hnh thnh v pht trin ca c th, l thnh phn khng th thay th c ca c th sng. Khi lng protit kh ln, chim khong 0,01% khi lng ca v tri t. 4.1. Phn loi Cn c vo thnh phn cu to ho hc, protit c phn chia thnh protit n gin hay protein m phn t ca n c cu to ch t cc axit amin v protit phc tp hay proteit, cu to nn chng ngoi cc axit amin cn c cc thnh phn khc. Trong nhm protein bao gm: - Anbumin: Ho tan c trong nc, khi un nng chng b kt ta. Cht tiu biu ca anbumin l protit ca trng. Rt nhiu anbumin ca ng vt v thc vt c th thu c di dng tinh th. - Globulin: Khng tan trong nc nhng tan c trong cc dung dch mui khc nhau. Globulin c ph bin trong thc vt, chng l nhng thnh phn quan trng trong protit cc ht, c bit cc cy h u v cy c du. - Prolamin: Nhm protit ny c trng cho ht ca cc cy thuc h ho tho, chng c kh nng ho tan tt trong ancol etylic. Khi thu phn chng to thnh lng ln axit amin prolin. Proteit c phn bit nhau theo thnh phn phi protein v c chia thnh nhng proteit sau: lipoproteit, glucoproteit, cromoproteit v nucleoproteit. Lipoproteit cha nhiu trong thnh phn nguyn sinh cht ca t bo. Cht in hnh ca cromoproteit l hng cu ca mu. Nucleoproteit cha nhiu trong nhn t bo v ng vai tr quan trng trong hot ng sng ca c th, nht l vn di truyn. 4.2. Thnh phn v cu to ca protein Thnh phn nguyn t ca protein gm c: C (50-55%), H (6,5-7,3%), O (21,5-23,5%), N (15-18%), S (0,3-2,5%) v mt s nguyn t khc nh P, Fe, Cu, I. Protein l nhng polime thin nhin c cu trc phc tp, cu to t cc phn t axit amin. Trong s rt nhiu cc axit amin thin nhin ch c khong 26 axit amin l tham gia vo thnh phn cu to nn phn t protein, l: glixin, alanin, serin, treonin, valin, lxin, izolxin, axit apactic, axit glutamic, xisin, metionin, phenylalanin, tirozin, prolin, triptophan, lizin, acginin, histiin, asparagin, glutamin, oxilizin, oxiprolin, xistin, tirozin, 3,5-ibromtirozin v 3,5-iiotirozin. Theo E. Fis v nhiu nh khoa hc khc th phn t protein c cu to bi mt hoc mt s chui polipeptit khng l lin kt li vi nhau. cu to nn phn t protein cc phn t axit amin kt hp vi nhau bng nhng lin kt chnh sau y:
Lin kt peptit ( - C-NH- ) O Lin kt peptit c hnh thnh do phn ng ngng t gia cc axit amin to thnh mch poli peptit:
-NH - C - CH -NH - C - CH -NH - C - CH O R O R O R = = =
lin kt peptit cc nguyn t u nm trong mt mt phng. di lin kt C -N bng 1,32A0, ngn hn lin kt C-N bnh thng (1,47 A0), do lin kt C-N c mt phn c trng ca lin kt i (khong 40%). di lin kt C=O l 1,28 A0, di hn di lin kt bnh thng 0,04A0. ( C=O bnh thng l 1,24A0). Cc gc lin kt nguyn t nit gn bng cc gc ca cacbon lai ho tam gic sp2.
O =
125
121 0
H 1200 N H 7,2A0
0
H N
R C
1,3 2A
0
110 C
C 114
0
C 1,28A0 O
H N 1,4 7A 0 C H
Trong trng hp phn t protein c to thnh t mt s mch polipeptit, khi cn c c lin kt peptit nhnh gia cc mch vi nhau. Lin kt peptit l loi lin kt bn vng nht trong cc loi lin kt c trong phn t protein. Lin kt ny phn nh trt t sp xp ca cc phn t axit amin trong mch polipeptit (cu trc bc mt). Trt t sp xp ca cc axit amin trong mch polipeptit l nguyn nhn ch yu quyt nh tnh cht c th v a dng ca cc nhm protein.
I leu Gli
Val Glu
11
6 Xis
Xis
Ala Ser
28 Xis
Val Leu His Glu Asp Phe Ser His Leu Val Glu Ala Leu
Gli
Xis Val
Leu Tir
Ser
Glu Leu Gli
Asp
Tir
20 Xis
40 Xis
Val Leu
Tir
Asp
Gli Glu Arg Gli Ala 51 Met Pro
Phe
45 Phe Tir Tre
M hnh cu to ca phn t polipeptit- insulin Lin kt hiro (>C=OH-N<)
Lin kt hiro c hnh thnh gia nhm imino (>NH) ca lin kt peptit ny vi nhm cacbonyl ( >C=O) ca lin kt peptit khc. Lin kt ny c th c thc hin gia hai mch polipeptit hoc trn cng mt mch polipeptit. Nh lin kt ny m phn t protein thng c nhng hnh dng khng gian khc nhau: dui thng, un cong, cun trn, xon, vvCu trc khng gian ny c gi l cu trc bc hai ca phn t protein. Cu trc bc hai l cu dng ca phn t protein, trong mi axit amin chim mt v tr khng gian xc nh ca mch polipeptit. C hai cu dng: cu dng xon v cu dng gp .
C C H O H N C N C C O C HO N C C C O H O H N C N C H C O NC H C O N C C H H O N N C C O
= = = =
H N
C C O
O C N C H R R O HC H C N N C H C H O R
= = =
H N
H O C C R H H N R C C O R H H C C NC N H H O
=
H H C H R N N R C C H O H H O C N C C O C H
= =
Trong cu dng xon lin kt hiro hnh thnh gia hai mt xch ca cng mt chui polipeptit, cn trong dng gp , lin kt hiro xut hin gia hai hoc nhiu chui polipeptit trn tng mt phng khc nhau.
Lin kt i sunfua ( -S-S-)
Lin kt i sunfua c hnh thnh do s oxi ho nhm -SH ca nhng gc axit amin xistein c trong mch polipeptit. Cng nh lin kt hiro, lin kt i sunfua c th c thc hin trn hai mch polipeptit khc nhau hoc trn cng mt mch polipeptit.
O - NH - CH -C -NH =
CH2 - S CH2 - S
=
CH2 -S - S - CH2
- NH - CH -C -NH O Lin kt i sunfua l mt trong nhng nhn t quyt nh cu trc bc ba v cu trc bc bn ca phn t protein.
Cu trc bc ba ca phn t protein c dng ch s phn b chung trong khng gian ca mt hoc mt s mch polipeptit c kt hp vi nhau bng nhng lin kt ng ho tr (lin kt i sunfua, lin kt kiu mui gia nhm -COOH v nhm -NH2, lin kt kiu este gia nhm -COOH v nhm -OH).
Cu dng xon v gp
O O - NH - CH -C - NH -CH -C -
Cc phn t protein to nn t mt s mch polipeptit kt hp vi nhau bng nhng lin kt hiro, lin kt ion hoc bng nhng lin kt k nc gi l tiu n v. Mi phn t protein c to thnh t mt s tiu n v kt hp vi nhau c gi l cu trc bc bn ca phn t protein. Tm li, ta c th hnh dung s to thnh phn t protein t cc axit amin xy ra theo ba giai on chnh sau y: - Giai on 1: Hnh thnh cu trc bc mt nh lin kt peptit. - Giai on 2: Hnh thnh cu trc bc hai nh lin kt hiro. - Giai on 3: Hnh thnh cu trc bc ba, bn nh lin kt i sunfua v cc lin kt mui, lin kt este. Vi cch cu to nh vy th vi hn 20 axit amin to nn mun vn protein khc nhau v thnh phn v cu to trong mi c th sinh vt. Mi phn t protein mang nhng hot tnh sinh hc c th khc nhau v thc hin nhng chc nng khc nhau trong hot ng sng ca c th. 4.3. Tnh cht ca protein a s protein t nhin dng bt trng, khng tan trong ru v cc dung mi hu c. Mt s protein tan c trong nc to thnh dung dch keo. Mt s khc tan c trong dung dch mui long, dung dch axit hoc baz. Protein rt d dng b bin tnh di tc dng ca cc tc nhn vt l, ho hc. Khi un nng hoc do tc dng ca cc mui kim loi nng hay axit (HNO3, CH3COOH) protein b kt ta khng thun nghch (ng t) km theo hin tng bin tnh. Khi b bin tnh hu nh tt c cc loi lin kt hiro, lin kt i sunfua, lin kt mui, lin kt este b ph hu lm cho cu trc bc hai v ba b bin dng v mt hot tnh sinh hc c trng ca protein . Tng t nh cc axit amin, trong phn t protein cn c cc nhm -NH2 v nhm -COOH t do nn protein cng c tnh cht lng tnh, im ng in. Protein b thu phn hon ton s to thnh cc axit amin. Thc t thng thu phn protein trong dung dch HCl 6N hoc NaOH 5N. Trong c th sinh vt protein b thu phn di tc dng ca enzim proteinaza v peptiaza.
protein H2O pepton H2O polipeptit H2O ipeptit H2 O axit amin
phn tch nh tnh v nh lng protein ta c th s dng mt s phn ng mu c trng. Nhng phn ng ny c c l do s c mt ca cc nhm chc trong phn t protein. Phn ng mu biure cho mu tm, c trng cho s c mt ca lin kt peptit. Khi un nng dung dch protein vi dung dch HNO3 c th xut hin mu vng do cc gc hirocacbon thm trong protein tham gia phn ng nitro ho.
OH O2N HNO3c Ch2 -CH -C NH O
N=
O2N
N=
O ONH4
OH NH OH 4 CH2 -CH -C NH O
=
CH2 -CH -C
=
Khi un nng protein vi ch axetat trong mi trng kim to thnh kt ta mu en ca sunfua ch. Ngoi ra, cn nhiu phn ng mu khc cng c trng cho protein.
5. Axit nucleic
Trong t bo sng c cha nucleoproteit, l loi hp cht gm protein kt hp vi phn phi protein l axit nucleoproteinic. Axit nucleic v protein l hai nhn t quyt nh hin tng sng, nu khng c chng th khng c s sng. V mt cu to, axit nucleic l nhng polinucleotit. Nucleotit l este ca axit photphoric vi cc nucleozit v nucleozit l N-glucozit ca baz purin hoc baz pirimidin. Ta c th m t s tng qut cu to ca axit nucleic nh sau:
baz gluxit O O P OH O baz gluxit O O P OH O
C hai loi axit nucleic tu thuc vo bn cht ca cu t gluxit trong phn t. Thnh phn gluxit l D-riboz gi l axit ribonucleic (ARN), l D-2-eoxiriboz th gi l axit eoxiribonucleic (ADN). C hai loi gluxit ny u tn ti dng cu to furanoz lin kt vi gc photphat qua cc nhm hiroxyl C3 v C5.
5 CH2OH OH O 4 H H 1 2 H H 3 OH OH D- riboz 5 CH2OH OH O 4 H H 1 2 H H 3 OH H D- 2- eoxirib
NH O
O CH2 H H O H R O CH2 H H O O H H ADN H R
H O OH HO P=O OCH2 R O H H H H O OH HO P=O O CH2 R O H H H H O OH HO P=O ARN
R c th l gc baz d vng aenin, guanin, xitozin v timin.

NH2 N N N H aenin N N N H N guanin O NH NH2 NH2 N O N H xitozin H3C O NH N H timin O O NH N O H uraxin
Nguyn t C1 ca pentoz lin kt vi mt baz cha nit no v tr 9 i vi cc baz aenin v guanin hoc v tr 3 i vi cc baz xitozin v timin, uraxin. Mch baz- gluxit gi l mch nucleozit, cn mch baz- gluxit - axit photphoric gi l nucleotit. Th d:
NH2 N O CH2 H O HO P= O O H O H H OH N N A aenin aenozin axit aenilic
Cc nucleotit cng c th b photphoril ho tip tc to thnh cc i v tri photphonucleotit. Chng hn, khi photphoril ho axit aenilic ta s c axit aenozin iphotphat
(ADP) v axit aenozintriphotphat (ATP). Nhng hp cht ny c lin kt cao nng, khi phn gii chng s gii phng nng lng. Nhng hp cht ny c gi l cc hp cht cho nng lng. Thnh phn ca cc nucleotit trong cc axit nucleic lun lun tun theo mt quy lut cht ch. Da trn nhiu cng trnh nghin cu Chahaff a ra quy tc sau: i vi cc ADN, s gc aenin bng s gc timin v s gc guanin bng s gc xitozin: A = T; G = X. i vi cc ARN, s gc uraxin bng s gc guanin v s gc xitozin bng s gc aenin: U = G; X = A.
Nhng nghin cu bng phng php Rnghen chng minh rng, phn t ADN c to thnh bi hai mch polinucleotit kt hp vi nhau theo kiu xon c sao cho mch cacbon, photphat v gluxit ezoxiriboza pha ngoi, cn cc baz nit pha trong. Hai mch ny lin kt vi nhau bng lin kt hiro sinh ra gia cc baz pirimiin v purin ca cc nucleotit ring bit. S phn b ca cc nucleotit ring bit trong mch rt nghim ngt, ng thi cu trc ca mt mch s phn nh cu trc ca mch kia theo quy lut: timin tng ng vi aenin, xitozin tng ng vi guanin v ngc li. Lin kt hiro ni hai mch nucleotit phtphat to thnh mt h thng nht lm cho phn t ADN tr nn bn vng. Khc vi ADN, s xon c ca mch polinucleotit ca ARN c thc hin trong gii hn ca mt phn t. Axit nucleic l nhng cht mu trng, c cu to dng si. trng thi t do kh ho tan trong nc, nhng dng mui ca cc kim loi kim li rt d ho tan. D ho tan trong cc dung dch mui. Axit nucleic c tnh quang hot, dung dch ca chng c nht cao. Khi un nng n nhit 80-900C axit nucleic nng chy, ng thi km theo s thay i nht. Trong qu trnh nng chy cc lin kt hiro vn c gia cc baz pirimiin v purin b t, khi lm lnh cu trc ban u li c ti to. V mt ho hc, ni chung cc axit nucleic rt tr. Chng lin kt mt cch bn cht vi cc ion kim loi, c bit l ion Cu2+, Mg2+ to thnh nhng phc hp khng tan. Nhng phn ng quan trng nht ca axit nucleic l s ankyl ho nhm amin ca aenin, guanin v qu trnh kh amin ho cc baz .
6. tecpenoit
Tecpen l tn gi chung ca nhng hirocacbon t nhin c thnh phn c biu din bng cng thc chung (C5H8)n (n2). Cn c theo thnh phn v cu to, cc tecpen c chia thnh 3 loi:
Tecpen chnh thc c cng thc C10H16. Nhm ny bao gm cc tecpen khng vng vi ba lin kt i, tecpen mt vng vi hai lin kt i v tecpen hai vng vi mt lin kt i. Sesquitecpen c cng thc chung (C5H8)3 . Nu n= 4 ta c tecpen C20H32 gi l itecpen, n=6 ta c (C30H48 l cc tritecpen
Tt c cc loi tecpen ni trn cng cc dn xut cha oxi ca chng c gi chung l cc tecpenoit. Tecpenoit c nhiu trong thc vt, chng l thnh phn chnh ca cc loi tinh du t nhin. 6.1. tecpen khng vng v dn xut Tiu biu cho loi tecpen ny l myrxen vi cng thc cu to: CH3- C=CH-CH2-CH2-C-CH=CH2 CH3 CH2 Myrxen l cht lng si 1670C, c trong thnh phn ca cy htb (houblon). Trong cy hng di ngi ta tm thy oximen, l ng phn ca myrxen: CH3- C=CH-CH2-CH2=C-CH=CH2 CH3 CH3 Trong t nhin ph bin v quan trng hn l cc dn xut cha oxi ca chng. Cc dn xut ny ph bin di dng ancol v anehit. Th d:
OH CH2OH CH2OH
CH2
CH2OH
CHO
CHO
geranddiol linalool xitrtonelol roinol xitral xitronelal Geraniol c trong tinh du hoa hng, linalool c trong tinh du hoa linh lan, cn xitral v xitronelal c trong v chanh, v cam, l bi
6.2. tecpen vng v dn xut Hu ht cc tecpen vng v dn xut ca chng u c khung cu to t 4 hirocacbon vng no l mentan, caran, piran v camphan.
mentan
caran
piran
camphan
Tecpen quan trng nht ca nhm mentan l limonen. Limonen l cht lng, si 1760C. Limonen c mt nguyn t cacbon bt i (C4)
7. Ancaloit
Ancaloit l nhng hp cht c ngun gc thc vt, c tnh kim v phn ln c tc dng sinh l mnh. Theo A.P.Orkhp, cc ancaloit ch gm cc hp cht hu c t nhin hay tng hp c cc nhn d vng, c tnh kim. Vic phn loi cc ancaloit c da trn c s cu to ho hc. Chng bao gm: Cc dn xut ca:
N N H piroliin N N
piriin
N N
quinolin
N N H
isoquinolin
NH N
N H
inol Cc ancaloit steroit Cc ancaloit mch thng
quinoxalin
imiazol
purin
Vai tr ca cc ancaloit cho n nay cha c gii thch r rng. Theo A.P.Orkhp v mt s tc gi th ancaloit l nhng cht xc tc hot tnh c tc dng gii c v cc sn phn c ca s chuyn ho. Mt s ancaloit (nicotin, covolamin...) c kh nng chuyn ho cacs nhm metyl ca mnh cho cc cht khc. Mt s ancaloit khc di dng N-oxit (platifilin, senesefilin) c kh nng cho oxi v chng tham gia vo cc phn ng oxi ho kh ca t bo. Ngi ta cng cn
nhn thy c s ging nhau v cu to vi cc men hot tnh, vi cc vitamin... ca mt s ancaloit, nn lm cho chng c kh nng tham gia vo hot ng sng ca thc vt. Cc ancaloit thng c trong cy vi lng khng nhiu v hm lng ny ph thuc mt phn vo nhit , chiu sng, cc bin php k thut trng trt. Cc ancaloit l nhng hp cht c tnh kim, chng trong dch ca cy di dng dung dch mui ca cc axit hu c hay v c v v vy c kh nng lu chuyn trong cy. Thng ancaloit ch tp trung trong mt s c quan ca cy nh l, ht, r. a s cc ancaloit l nhng cht rn kt tinh, c chy nht nh, him c ancaloit lng. Khi dng baz t do chng thng t tan trong nc, nhng d tan trong cc dung moi hu c nh ancol, ete... Hu nh tt c cc ancaloit khng c mi. Nhiu ancaloit c tnh quang hot. Vi cc axit cc ancaloit to mui. Cc mui ny phn ln tan trong nc, d phn li, b phn hu bi kim mnh, amoniac. Mt s ancaloit ngoi tnh kim cn cho cc phn ng c trng khc tu thuc vo s c mt ca cc nhm chc c trong phn t, nh nhm phenol (trong mocphin v sansolin), xeton (trong lobelin), nhm vinyl (trong quinin)...Chng hn, morphin ho tan trong cc dung dch kim mnh, quinin cng hp c vi hiro, halogen... Cc ancaloit cn c c trng bi hng lot cc phn ng to kt ta chung. Cc phn ng ny c dng pht hin v xc nh chng. Chng hn, thuc th Vacne (dung dch I2/KI) cho kt ta mu nu xm vi cc ancaloit hoc cc mui ca chng, thuc th Maver (dung dch HgCl2/KI) cho kt ta vng hoc trng, thuc th Macme (CdI2/KI) cng to kt ta trng hoc vng nht... Ngoi cc phn ng to kt ta chng cn c kh nng cho cc phn ng mu vi cc axit m c (H2SO4, HCl, HNO3), vi FeCl3 v cc cht khc. Th d, H2SO4 m c lm cho papaverin c mu tm xanh, veratrin c mu vng da cam chuyn thnh , coein c mu vng... Sau y chng ta xem xt s b mt s nhm ancaloit tiu biu.
7.1. Nicotin v anabaxin
N CH3
N H
nicotin
anabaxin
Nicotin c cu to t cc d vng piriin v piroliddin. Nicotin c nhiu trong l thuc l, thuc lo. trng thi t do, nicotin l cht lng khng mu, si 2470C, tan c trong nc v dung mi hu c.
Nicotin thuc loi hp cht c, tc dng n h thn kinh trung ng v ngoi bin. N c dng lm cht phng tr su bnh cho cy trng, thuc cha bnh ngoi da cho gia sc. Anabaxin cu to t d vng piriin v piperiin. Ch yu n c dng lm cht st trng, c tc dng c i vi cn trng.
7.2. cc ancaloit nhm quinin
Quinin l ancaloit chnh ca cc cy thuc loi Chinchona v Renmija thuc h Rubiaceae. Tn quinin c ngun gc t ch kina, ngha l v. V cy k ninh c dng iu tr bnh st rt. Trong v cy ny c khong 10% cc ancaloit. Ngoi quinin trong v cy k ninh cn c khong trn 25 ancaloit khc. Cc ancaloit ny c th tch ring bng phng php sc k. Cu to ca quinin bao gm 6-metoxiquinolin ni vi nhn quinucliin qua nhm ancol bc hai.
4 7 9
HO-CH
5' 4'
CH2 6 CH 2 8 N1
5
3 2
CH3O
6'
3' 2' 8'
7'
N 1'
Cc ancaloit khc ca nhm quinin ch khc quinin c tnh ca cc nhm th v tr 6 v 3. Trong phn t ca cc ancaloit nhm ny c 4 C*, do c 16 ng phn quang hc. Quinin l cht bt kt tinh nh, ngm 1,2,3,8 v 9 phn t nc. Nhit nng chy ca quinin khan l 1770C. Quinin t tan trong nc, d tan trong ancol v ete. Dung dch quinin trong nc c tnh kim, to mui c vi axit. Dung dch mui ca cc axit c oxi c hunh quang xanh, ngay c khi pha long n 1:50000. Quinin v cc mui ca n c v ng. Cc ch phm quinin c dng l quinin sunfat (C20H24O2N2).H2SO4.2H2O, quinin clohirat (C20H24O2N2). 2HCl 7.3. Cc ancaloit ca thuc phin Thuc phin l nha kh ly t qu thuc phin papaversomniferum, h papaveraceae. Thnh phn chnh ca thuc phin l mocphin, papaverrin, coein v thebain. a. Mocphin : C17H19O3N
HO O HO
N-CH3
Dung dch mocphin trong nc khng mu, trung tnh. Vi FeCl3 hoc axit fomalin sunfuric cho mu xanh nc bin. Vi hn hp HNO3 + H2SO4 cho mu mu, khi mocphin chuyn thnh apomocphin. -H2O C17H19O3N 4C17H19O3N + 4K3[Fe(CN)6] C17H19O2N C17H18O3N C17H18O3N + 3 K3[Fe(CN)6] + H4[Fe(CN)6] Mocphin kh kali ferixianua thnh hp cht c mu vng:
Mocphin b kt ta bi amoniac to thnh mocphin baz, cht ny ho tan trong cc kim mnh. Ngoi khng kh khi c kim, mocphin b oxi ho thnh pseumcphin hay oximocphin: Mocphin c tc dng gim au, gy ng, nhng c nhc im quen thuc v gy nghin.
b. Coein : C18H21O3N
CH3O O HO
N-CH3
Coein l nhng tinh th khng mu hoc bt kt tinh trng, v ng, tan t t trong nc, d tan trong ancol, ete, clorofocm, benzen v cacbon isunfua. Gn nh khng tan trong kim. Khng b kt ta bi amoniac, b kt ta bi kim mnh, []15D =-138,50. Vi FeCl3 khi c mt H2SO4 m c cho mu xanh, cho thm HNO3 chuyn thnh mu mu. Coein c tc dng tng t nh mocphin. Ch yu c dng cha ho v gim au khi vim phi.
c. Papaverin : C20H20O3N
CH2 CH3O CH3O N OCH3 OCH3
Papaverin l cht kt tinh nng chy 1470C.
7.4. ancaloit nhm purin
Cc ancaloit nhm ny c nhiu trong t nhin nh trong cc loi ch (Thea chinensis. L), qu ca cao ( Thea brome cacao L),...Trong l ch v ht c ph c t 1-3% cafein, trong qu ca cao c 3% theobromin.
a. Cafein (1,3,7-trimetyl xanthin mono hirat) : C8H10O2N4.H2O

O CH3 N O CH3 N H2O
N CH N 3
Cafein l nhng si hnh kim di, v ng, khng mi, nng chy 234-2370C. Tan nhiu trong CHCl3, CCl4, t tan trong ete, benzen, CS2...Kt tinh vi mt phn t nc, nc bay hi mt phn trong khng kh v hon ton mt nc 1000C, qu 1000C bt u thng hoa. Cafein l mt kim yu. T phn li trong dung dch nc. Cafein b kt ta bi cc thuc th ca ancaloit v c vi tanin (kt ta b tan trong thuc th d).
b. Theobromin (3,7-imetyl xanthin) : C7H8O2N4 O N-CH3 HN
Theobromin l cht bt kt tinh mu trng, nng chy 342-3430C, thng hoa 3900C, rt t tan trong nc, ancol, khng tan trong ete v clorofoc. Tan trong cc dung dch kim mnh to thnh cc dn xut kim loi. Vi axit to mui d phn li. Khi oxi ho phn hu thnh 3-metyl alloxan v metyl ure.
O O
HN O
=
[O]
HN O
=
N CH3
CH3
Dung dch theobromin vi bc nitrat trong amoniac cho kt ta trng bc theobrominat.
N CH3
N-CH3
O O + CH3-NH-C-NH2 O =
O N-CH3 N CH3
= AgN O
=
7.5. Ancaloit mch thng
Nhm ny gm cc ancaloit c nguyn t nit ngoi nhn. Cht tiu biu ca nhm ny l colchamin v colchixin. Colchamin (C21H25O5N):
CH3O CH3O CH3O =O OCH3 NH-CH3
Colchamin c trong cy ti c v cy ngt ngho. Colchamin l cht bt kt tinh mu trng hay hi vng nng chy 181- 1820C, []D = 1250. Tan trong nc khong 1%, tan trong clorofoc, kh tan trong ancol v axeton, khng tan trong ete. Dung dch ca nc clorofoc c phn ng kim. Khi tan trong cc axit v c long to thnh cc dung dch mu vng. Khi un si vi axit HCl long to thnh colchamein, cht ny cho mu xanh vi FeCl3. Colchixin (C22H25O6N) :
CH3O CH3O CH3O =O OCH3 NH-C-CH3 O
Colchixin t tan trong nc, tan nhiu trong ru, benzen, clorofocm. Colchixin c tc dng kch thch gy t bin ging cy trng.
8. STEROIT
Steroit l nhng hp cht ph bin trong ng vt. Ch mt lng nh l chng c tc ng mnh n c th, do my nm gn y ngi ta ch nhiu n vic nghin cu steroit
V vic cu to, steroit chnh l dn xut ca hirocacbon nhiu vng ngng t xyclo pentan pehirophenantren:
C A B D
Cc steroit khc nhau v mc khng bo ho ca b khung cacbon 4 vng v v c tnh ca mch nhnh gn vo h thng vng. Cc nhnh gn vo cc v tr 10, 13 thng l nhng gc metyl. Cc steroit c cha nhiu cacbon bt i nn chng tn ti nhiu di dng ng phn khng gian khc nhau. Bn thn h thng vng ca n cng c s phn b khng gian phc tp.
8.1 Nhm cc Sterol
Sterol l nhng cht c ngun gc thc vt. Este ca n vi axit l cc sterit. Sterol v sterit u l cu t ca cht bo thc vt. Cht quan trng nht trong nhm ny l colesterol c cng thc cu to nh sau:
CH3 CH3 A HO B CH3 C D CH3 CH3
Colesterol l ancol bc 2, l cht rn kt tinh, nng chy 1480C, c tnh cht hot quang [] = -360 ( trong clorofocm ). Khi oxi ho colesterol thu c colesteron c cng thc nh sau:
Trong phn t colesterol c 8 nguyn t cacbon bt i nn c tt c 512 ng phn quang hc v 256 hn hp raxemic. Esgosterol cng l mt steroit quan trng thuc nhm ny. Cht ny c nhiu trong nm, l, qu v r ca nhiu loi cy.
Cng thc ca esgosterol nh sau:
OH
8.2. Nhm cc Sapogenin
Sapogenin c bn cht steroit rt ph bin trong thc vt thng ng. Trong thc vt, sapogenin tn ti dng glucozit-saponin. Saponin l nhng cht c, ng thi l nhng cht to bt rt tt nn c dng trong nhng dng c dp tt la. Th d, igosgenin l sapogenin ca glucozit saponin , c cng thc nh sau:
O O
OH
Khi kh ho thu c tigogenin vi cng thc:

O O
OH
Ni chung, vi nng thp, cc steroit nhm saponin tc ng kch thch s ny mm ca chi v r cy, ng vai tr xc tc cho qu trnh tng hp dip lc t v.v... nng cao th ngc li, n km hm s ny mm.
8.3. Cc Steroit nhm Ancaloit
Cc ancaloit c bn cht steroit chi gp trong mt s loi thc vt.
Sau y l mt s cht in hnh:

O CH3 O O OH N CH3
solasoin
solaniiza
Ni chung, cac ancaloit u lm cho cy c v ng, nn ngi ta cho rng, chc nng ch yu ca chng l bo v cy khi b cn trng ph hi.
8.4. Cc steroit glucozit tim
Steroit -glucozit tim thng gp trong 11 h thc vt, ngoi ra khng thy trong cc sn phm thin nhin khc. Steroit -glucozit tim c hai dng l cacenolit v bufaienolit. Hai loi ny khng bao gi tn ti trong cng mt h thc vt. Cc cht tiu biu ca steroit loi ny l egoxigenin v benebrigenin. Chng c cu to nh sau:
O HO
CHO
O =O
=O
OH HO HO
OH
egoxigenin
8.5. Cc steroit khc
benebrigenin
Ngoi cc steroit m t trn ngi ta cn tch c mt s hocmon c bn cht steroit. Cc hocmon ny cng c trong thc vt. Hocmon sinh dc c to thnh tuyn sinh dc nam v n. Hocmon sinh dc iu khin s sinh trng ca c th v quyt nh tnh tnh, hnh dng, phong thi ca nam v n.
Hocmon sinh dc n ( estrogen) gm cc cht tiu biu nh estraiol, estron v estriol:

HO O HO OH
HO
HO
HO
estraiol
estron
estriol
Estraiol c to thnh trong bung trng, estron v estriol l sn phm oxi ho estraiol trong c th v c thi ra ngoi theo nc tiu. Hocmon sinh dc nam (anragen ) gm c testosteron v anrosteron. Testosteron c to thnh trong tinh hon. Cn anrosteron l dn xut ca testosteron, n c thi ra ngoi theo nc tiu. Cng thc ca chng nh sau: HO O
HO
testosteron
anrosteron
Hocmon v tuyn thng thn costicosteroit: T v tuyn thng thn ngi ta tch ra c gn 40 hocmon khc nhau. Cc hocmon ny iu khin s trao i cht khong, nc v gluxit trong c th. Tt c cc costicosteroit u l dn xut ca pregnan. Cc cht tiu biu ca nhm ny l: hirocortizon v cortizon. Cng thc ca hirocortizon v cortizon nh sau: CH2OH CH2OH C=O C=O OH OH HO O
O hirocortizon
cortizon
Cu hi v bi tp
1. Cu to ca D (+) glucoz, D(-) fructoz, mantoz, lactoz, saccaroz, tinh bt v xenluloz. 2. Phn ng cng hp ca cc monosaccarit. 3. Phn ng ngng t v este ho cc monosaccarit, ngha ca cc phn ng ny. 4. Phn ng oxi ho cc monosaccarit v i saccarit. 5. Phn ng thu phn ca cc i saccarit v poli saccarit. 6. Cu to v tnh cht ca lipit. Cho bit ngha ca phn ng thu phn trong qu trnh trao i cht ca c th sinh vt. 7. Cu to lng cc v im ng in ca cc axit amin. 8. Cho bit cng thc cu to v gi tn cc axit amin t nhin c cng thc phn t C3H7O2N; C3H7O2NS; C9H11O2N. Gii thch tnh cht lng tnh ca chng bng cu to v chng minh bng cc phn ng ho hc. 9. Phn ng ngng t cc axit amin v ngha ca n. 10. Cu to v phn ng thu phn protit, ngha ca phn ng ny. 11. Hon thnh cc phng trnh phn ng sau y: 11.1. Alanin + NaOH + HCl H+ + H2O + glixin D(+) glucoz + Tlens t0 + KMnO4 + H2SO4 + Cu(OH)2 D(-) fructoz + Phlinh + C6H5NH-NH2 t0 + KMnO4 + H2SO4 A + B isaccarit 2B isaccarit Tolens
Phlinh
1. 2. 3. 4.
Ti liu tham kho inh Vn Hng, Trn Th T- Ho hc hu c -NXB i hc v gio dc chuyn nghip, 1990 inh Vn Hng, Trn Vn Chin- Ho hc hu c- Trng i hc Nng nghip I, 1996 nh Rng, Nguyn H- Ho hc hu c-NXB i hc Quc gia H Ni, 1997 Robert Thornton Morison- Organic Chemistry- Allyl and Bacon, Inc. Boston 1970
Mc lc
Chng 1. i cng..
3 4 8 12 15 15
1. Cu to v c im ca Cacbon 2. Lin kt ho hc trong cc hp cht hu c 3. Phn loi cc hp cht hu c v phn ng hu c 4. C ch phn ng 5. Cu trc phn t hp cht hu c 6. nh hng tng h gia cc nguyn t v nhm nguyn t trong phn t hp cht hu c
Cu hi v bi tp Chng II. Hircacbon
24
31 32
1. Hirocacbon no (ankan, xicloankan) 2. Hirocacbon khng vng cha no (anken, ankaien, ankin) 3. Hirocacbon thm
Cu hi v bi tp Chng III. Dn xut ca hirocacbon
32 40 50
62 64
1. Dn xut halogen 2. Ancol v phenol 3. Hp cht cacbonyl (anehit v xeton) 4. Axit cacboxylic 5. Amin
Cu hi v bi tp
64 73 83 95 108
113
Chng IV. Cc hp cht t nhin
115
2. Gluxit (Hirat cacbon) 2. Lipit (cht bo) 3. Axit amin (amino axit) 4. Protit 5. Axit nucleic 6. Tecpenoit 7. Ancaloit 8. Steroit
Cu hi v bi tp
115 131 133 139 144 146 148 153

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B gio dc v o to Trng i hc nng nghip I - H Ni --------------------------

inh vn hng - trn vn chin Pgs.ts. inh vn hng (Ch bin)

1 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..1

2 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..2

CH3 -CH2 -OH

CH2 CH2 xiclohexan

6 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..6

CH3 -O -CH3 imetyl ete

CH3 CH3 -C =O axeton

OH CH3 -C =O axit axetic

mch khng phn nhnh

mch phn nhnh

Lin kt gia H-H, H-C, C-C

8 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..8

gia cacbon v nguyn t ca nguyn t khc nh oxi, nit...

11 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..11

Cc hp cht khng vng

Cc hp cht Cc hp cht vng khng thm vng thm

D vng khng thm

13 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..13

14 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..14

Tin trnh phn ng

Tin trnh phn ng

16 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..16

axit maleic (cis)

h axit fumaric (trans) ch3 c C

axit iso crotonic (cis) r2 r1

h axit crotonic (trans)

18 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..18

19 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..19

C ho h ch3 ho cooh (b) h

20 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..20

(ch3)2ch (ch3)2chch2 ch3 n ch2ch3.cl ; h si c6h5

ch3 ch3 ; c6h5 p n-c3h7

21 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..21

cooh h oh ch3 axit d(-)lactic ho

cooh h ch3 axit l(+)lactic

22 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..22

ch2oh D(+) glucoz

cng thc phi cnh cng thc Niumen

cng thc phi cnh

cng thc Niumen

23 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..23

26 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..26

; ch2 = ch - ch = ch - ch =O ; ch2 = ch -cl oh ;

Mt th d khc, trong phn t vinyl clorua:

Dy nhm th sau y gy ra hiu ng -C gim dn:

H khng phng khng xen ph

29 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..29

30 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..30

31 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..31

32 Trng i hc Nng nghip H Ni - - Gio trnh Ho hu c ..32

CH3 - CH- CH2- CH3 CH3 isopentan

CH3 CH3- C- CH3 CH3 neopentan

CH3 CH -CH3 isopropylxiclopentan

metylxiclopentan - ng phn v v tr nhnh Th d: CH3 CH2 -CH3

CH2 -CH3 1-metyl-2-etyl xiclohexan - ng phn hnh hc Th d: CH3

1.2. Phng php iu ch

CH2 -CH2 - CH2 + 2 Na Br Br

O OH MnO , t0 CH2 - CH2 2 C =O OH - H2O, -CO2 CH2 - CH 2

Thng thng ngi ta tin hnh cacboxyl ho mui cacboxylat. Th d:

CH2 - CH2 t0 C =O -CaCO3 CH2 - CH 2

c. in phn dung dch mui natri ca axit monocacboxylic

1.3. Tnh cht vt l