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nh
ngha: l hin tng cng mt cng thc c nhiu cht khc nhau loi:
Phn
ng phn cu to (phng): cng cng thc phn t nhng khc cng thc cu to. ng phn lp th (khng gian gian) ): cng cng thc cu to nhng khc nhau v cch thc sp xp cc nguyn t trong khng gian gian. .
ng phn v tr
CH3 CH OH CH2 CH2 OH CH3
CH3
CH3
ng phn v tr tr: : tnh cht vt l khc nhau (khng nhiu), tnh cht ha hc tng ng. ng phn nhm chc: tnh cht vt l ha hc hon ton khc nhau nhau. .
Ceton
Enol
Amid
Imid
CH
NH
CH
OH
Imin
Enamin
Nitroso
Oxim
Trong mt s trng hp cht hu c c th tn ti cng mt lc hai dng cn bng khc nhau nhau. . S h bin c c l do s dch chuyn ca nguyn t H t nguyn t ny sang nguyn t khc Hai dng h bin khng th tch c do chng chng chuyn ha (bin i) lin tc qua li nh vy h bin khng phi hin tng ng phn phn. .
ng phn lp th (khng gian gian) ): cng cng thc cu to nhng khc nhau v cch thc sp xp cc nguyn t trong khng gian gian. . Cn c tn l ng phn cu hnh do cu hnh c nh ngha l cch thc sp xp trong khng gian ca cc nguyn t trong mt phn t. V d: phn t metan c cu hnh t din u.
H H
o C 109 28'
H H H
H H H
M HNH PHN T
biu din (trnh by by) ) cu hnh ca mt phn t hp cht hu c trn mt phng ngi ta c th dng cng thc chiu:
1. 2. 3.
Cng thc phi cnh Cng thc chiu Newman Cng thc chiu Fisher
Hai Ni nt Ni
ni trong mt phng c biu din bng nt lin nm pha trc mt phng c biu din bng m nm sau mt phng c biu din bng nt t
=
Sai
* Biu din cng thc phi cnh cho nhiu cacbon cacbon: :
-
Ni sang phi hng ra bn ngoi mt phng Ni sang tri hng ra pha sau mt phng Cc ni c v vung gc nhng tht ra gc ni l 109o28 28 Ni C-C gia v di ra cc nhm th ca 2 tm C sp3 khng chp ln nhau
Ni s c c l do s xen ph gia hai vn o theo hng trc lin nhn. Nh vy ni s c tnh i xng trc ngha l khi xoay 2 vn o xen ph, xen ph hay bn (nng lng) lin kt khng i. Do , 2 nguyn t ca ni s c th xoay quanh lin kt s.
sp3 s
sp3
sp3
C-H
C-C
Dn n hin tng phn t hu c c th tn ti di nhiu cu trng (cu dng khc nhau) nhau). . Cu trng: l cc dng khc nhau ca cu hnh c c do s quay quanh ni n s. V d: xt phn t n-butan
Cu trng i lch
Cu trng bn lch
CH3
H H CH3
H H H
CH3
CH3 H
CH3
CH3
CH3 CH3
Cu trng lch bn hn cu trng che khut rt nhiu, trong bn nht l cu trng i lch, cu trng che khut ton phn km bn nht.
Ni l gii hn v khng phi ni s quay t do hon ton m phi quay sao cu trng bn chim lng nhiu hn. S quay trong phn t hp cht hu c l lin tc do ta c th c v s cu trng khc nhau nhau. . Cn phn bit r gia hin tng cu trng v ng phn. phn .
Cu trng bn nht ?
Trc C-C c t thng gc vi mt phng chiu (t giy hoc tm bng). C xa c biu din bng ng trn trn, , C gn c biu din bng du chm tm ng trn . Cc ni ca C gn xut pht t tm ng trn trn, , Cc ni ca C xa xut pht t trn ng trn trn. . Cc ni to vi nhau gc 120o.
H H H CH3 H H H H H H CH3 H H
CH3
CH3
CH3 CH3
H H
H CH3
HCH3
Ni dc (Bc-nam nam) ) hng ra pha sau mt phng. Ni ngang (ng-ty ty) ) hng ra pha trc mt phng. Mch cacbon c t trn trc dc, cc ni vit bnh thng. Giao im gia ng ngang v ng dc chnh l tm cacbon cacbon. .
C A B D A D C B A D C B C
A D
C D
A C D
A C
G F G E C D A
A F G E
=
F G E
Trong trng hp nhiu C (t 2C tr ln ln), ), nu dng cu trng lch chiu th d ng t pha no chiu th u khng tha mn cng thc chiu Fisher (khng phi tt c cc ni ngang hng ra pha trc mt phng) do vy thu c hnh chiu sai sai. .
C1
C2
A2
A1
A D1 D1 D2 C1 B1 B1 B2 A2 A D2 C2 B2 A1
Nh vy chiu cng thc chiu Fisher ng ngoi vic chn gc nhn (hay mt phng chiu ng) trong mt s trng hp nu phn t cu trng lch th phi xoay v cu trng che kht ri mi chiu.
A A
D F G
C G E
F E
D A C
ng phn lp th
ng phn hnh hc
ng phn quang hc
ng phn hnh hc
nh ngha: l nhng hp cht c cng CTCT nhng cch sp xp ca nhng nguyn t hay nhm nguyn t khc nhau i vi mt mt phng quy chiu. Ty vo mt phng qui chiu l mt phng p (mt phng cha ni s v p) hay mt phng vng (xicloankan xicloankan) ) m ta ng phn hnh hc tng ng:
ng phn hnh hc ng phn ca ni i ng phn xiclan
ng phn hnh hc ca ni i
Hin tng ng phn c c l do c cu cng nhc ca ni i khc vi ni n khng th xoay c (nu khng s mt i s xen ph bn ca 2 vn o p). Nh vy nu trn 2 cacbon ni i c 2 nhm th khc nhau th ta s c 2 cch sp xp cc nhm th trong khng gian (i vi mt phng p - mt phng cha ni s v p 2 ng phn hnh hc.
H H H COOH
HOOC
COOH
HOOC
Ban u ngi ta s dng tn gi cis cis-trans, nhng tn gi ny c nhc im l trong trng hp trn 2 cacbon ni i c khng c 2 nhm th ging nhau c nn khng c c tn 2 ng phn quang hc c th c c. .
Cl
Cl
Br
Br
10
Cch gi tn E-Z
Bc 1: So snh u tin ca 2 nhm th trn mi cacbon ni i theo quy tc Cahn Cahn-Ingold Ingold-Prelog Prelog. . Bc 2: Gi tn - 2 nhm th u tin cng pha (Z) - 2 nhm th u tin khc pha (E) - (E), (Z) c t trong du ngoc n v t trc tn cht bi du gch ngang () - Trong trng hp c nhiu ni i th ta phi vit km theo s th t ni i. V d: (2E, E,4 4Z) (theo s th t t nh m ln).
H C C C
O C C O
C C C C
11
V d:
CH3
Cl F Cl I
CH3 H
H
Br I Br F
CH3
(Z)
(E)
(2E, E,4 4E )
CH3
trans (Z)
cis (E)
ng phn xiclan
-
Cc hp cht vng no c th c 3, 4, 5, 6, 7, 8, cacbon Nhng vng 3,4 rt km bn (qu cng), trn thc t cc cht vng ch yu l vng 5,6 (bn nht). Vng 7 tr ln rt t gp.
Mo hnh phan t
Dang n gian
12
- V d: Hp cht 1-Hidroxi Hidroxi-4-brom brom-ciclohexan c 2 ng phn hnh hc c trnh by dng n gin v cu trng gh.
OH Br H OH H Br
cis-1-Hidroxi-4-bromociclohexan
Br H OH H
trans-1-Hidroxi-4-bromociclohexan
H Br OH H
ng phn quang hc
Nm 1815 1815, , Jean Jean-Baptiste Biot pht hin mt s cht hu c lng hoc dung dch cc hp cht thin nhin nh: ng, axit tartic (dd dd), ), tinh du thng (l) c kh nng lm quay mt phng nh sng phn cc. (trc y ngi ta cng tm thy hin tng ny mt s tinh th v c bt i xng).
13
Nhng hp cht ny c gi l nhng cht c tnh trin quang hay c tnh quang hot. Tnh quang hot ca mt s hp cht hu c c gii thch l do tnh bt i xng trong phn t hp cht . C mt s nguyn nhn dn n tnh bt i xng nhng ph bin nht l trong phn t hu c c cha t nht mt C phi i xng hay cn gi l C th tnh (k hiu C*) C*). .
C PX
BX
HTQH
Tnh bt i xng
C nhiu cch bit (hay nh ngha) vt no i xng hay bt i xng. Vt bt i xng l vt khng c bt k yu t i xng no (nh tm i xng, trc i xng, mt phng i xng, ). Mt cch nh ngha khc khc, , vt i xng l l vt trng vi nh ca n qua gng. Ngc li, vt bt i xng l vt khng trng vi nh ca n qua gng.
14
Khng C*
C C*
15
CH3
CH COOH OH
- ng vi mt C*, c th c hai cch sp xp 4 nhm th trn C , hai cch sp xp ny nu trnh by trong khng gian l hai hnh i xng vi nhau qua gng phng v khng trng kht ln nhau nhau. . Nh vy, chng khng phi l cng mt cht m l hai cht khc nhau tc hai ng phn phn. . Trong ha hc ngi ta gi chng l hai i phn.
16
Bc 1: Da trn quy tc Cahn Cahn-Ingold Ingold-Prelog sp xp th t u tin 4 nhm th trn C phi i xng v nh s 1>2>3>4. Bc 2: Chn hng quan st ngc vi nhm c u tin thp nht (4) (tc nhn t C phi i xng n (4). Xem xt nhm 1 2 3 theo chiu kim ng h hay ngc li. Nu cng chiu kim cu hnh R, ngc chiu kim ng h cu hnh S.
17
Trng hp c 2 cacbon phi i xng, v d xt hp cht 2-Brom Brom-3clobutan .ng vi 1 C phi i xng ta c 2 cch sp xp l R, S. Nh vy ng vi 2 C phi i xng ta c th c 4 cch sp xp trong khng gian tc c 4 ng phn quang hc.
CH3 Br
Br
CH3 H
i phn
Cl H CH3
Cl CH3
(2S,3S)-2-Bromo-3-clorobutan
H CH3 Br
(2R,3R)-2-Bromo-3-clorobutan
Br CH3 H
i phn
H Cl CH3
Cl H CH3
(2S,3R)-2-Bromo-3-clorobutan
(2R,3S)-2-Bromo-3-clorobutan
Khi trnh by 4 ng phn quang hc trn di dng cng thc chiu Fisher ta thy cng thc chiu ca hai i phn cng i xng vi nhau qua gng phng. Hai ng phn quang hc m khng phi l i phn ca nhau c gi l hai xuyn lp th phn phn. . (1), (2): cu hnh treo treo; ; (3), (4): cu hnh eritro
1CH3 H Cl 2 3 Br H
CH 3 Br H H Cl CH 3
(1)
4CH3
Xuyn lp th phn
(2)
CH3 H H Br Cl CH3
Br Cl
C H3 H H C H3
(3)
(4)
18
Nh vy cng nhiu C* ta cng c th c nhiu ng phn quang hc. Quy tc Van Hoff Hoff: : Nu c nC nC*, *, ta s c 2n ng phn quang hc. Nhng quy tc Van Hoff trong mt s trng hp li khng ng. V d: xt hp cht 2,3-Dibrombutan CH3 CH CH CH3
Br
CH3 H Br
Br
CH3 Br
CH3 Br H
Br
CH3 H
Br
H CH3
Br CH3
H CH3
Br
Br CH3
(2S,3S)-2,3-Dibromobutan
C H3 H Br H CH 3 Br
(2R,3R)-2,3-Dibromobutan
CH3 Br H
Br CH3 H
L mt
H Br C H3 H CH 3 Br
Br CH3
Br
H CH3
l do ng phn ny c mt mt phng i xng vung gc vi ni C2-C3. V cng v vy ng phn ny khng c tnh quang hot (khng c tnh trin quang) quang). . Ngi ta khng dng tn gi eritro na m gi ng phn ny l meso meso. .
CH3 Br CH3 Br Meso CH3 H Br
H CH3
Br
Nh vy quy tc Van Hoff khng ng m phi pht biu li l nu mt cht c nC* th c th c ti a 2n ng phn quang hc. Bt k yu t i xng no cng s lm gim s ng phn quang hc. ng phn quang hc no c cha t nht mt yu t i xng s khng c tnh quang hot (khng c tnh trin quang) quang). .
19
Lu khi c tn eritro eritro, , treo treo, , meso cho cc hp cht c 2C*: - Mch cacbon chnh phi t trn trc dc ca cng thc chiu Fisher. Fisher . t C s 1 ln trn cng cng. . - Nu 2 nhm th ging nhau cng bn eritro eritro, , khc bn treo. treo . Nhng khng phi lc no ta cng c c tn eritro eritro, , treo treo. .
1 CH3
Br
Br
Cl
CH 3
CH3
3 4 CH3
CH3
Br H Br CH3
H CH3
Cl
Cl
CH 3
H Cl
Sai
Cl
1 CH3 2
Br
Cl
Br
3 4 CH3 1 CH3
3 4 CH3
H CH3 Br
2 1 CH3
CH3 Cl H
Br
3 4 CH3
Cl
i vi nhng hp cht ha sinh quan trng nh cacbohidrat v amino axit (ngay c trong trng hp 2C*), phn bit cc ng phn quang hc ngi ta khng dng tn gi eritro eritro, , treo treo, , meso m dng tn gi D,L . Tn gi D,L bt ngun t lc ban u khi nghin cu glicerandehit, glicerandehit , Hermann Emil Fischer chn mt cch c on hp cht hu trin l D-(+) (+)-glicerandehit v hp cht t trin l (L)(L) -(-)-glicerandehit glicerandehit. .
CHO H OH CH2OH D-(+)-glicerandehit OH CHO H CH2OH (L)-(-)-glicerandehit
Da theo quy c ny ny, , ngi ta gi tn cc cacbohidrat khc khc. . Nh vy mun s dng tn gi D,L bt buc phi s dng cng thc chiu Fisher Fisher. .
20
t mch cacbon chnh trn trc dc. t cacbon c mc oxi ha cao nht v tr trn cng (COOH>CHO>(COOH>CHO> -C-OH) (chnh l C s 1). Da trn nhm OH cacbon phi i xng mang s nh v cao nht, nu nm bn tay phi hp cht c cu hnh D, nu nm bn tay tri hp cht c cu hnh L.
H HO H H CHO OH H OH OH CH2OH HO H HO HO CHO H OH H H CH2OH H HO HO H CHO OH H H OH CH2OH H HO HO H CHO OH H H OH CH2OH
H H H
HO HO HO
HO HO
HO H
H HO
L-(+)-eritrose
D-(-)-treose
L-(+)-treose
H HO H H
CHO OH S3 H R4 OH R5 OH CH2OH
R2 6
HO H HO HO
CHO H R3 OH S4 H S5 H CH2OH
S2 6
D-(+)-glucose
L-(-)-glucose
(2R,3S,4R,5R)-2,3,4,5,6-pentahidroxihexanal
(2S,3R,4S,5S)-2,3,4,5,6-pentahidroxihexanal
Gi tn D, L cho amino axit axit: : - t mch cacbon chnh trn trc dc. - t cacbon c mc oxi ha cao nht v tr trn cng (chnh l nhm COOH tc C s 1). - Da trn nhm NH2 C* mang s nh v thp nht, nu nm bn tay phi hp cht c cu hnh D, nu nm bn tay tri hp cht c cu hnh L.
COOH COOH H2N H CH2OH L-(-)-serin H COOH H2 N NH2 H CH2OH CH3 D-(+)-serin L-(-)-threonin OH H
21
Quy tc 1: Nu i ch 2 nhm th bt k ca mt C* trn cng thc chiu Fisher th ta s lm thay i cu hnh ca C* (chuyn sang dng i hnh hnh) ).
H Br R CH3 CH2CH3
i ch ln 1
CH3CH2
S CH3
Br
i ch ln 2
H CH3CH2 R Br CH3
- M rng:
Thay i v tr hai nhm th s l ln lm thay i cu hnh (chuyn sang dng i hnh hnh) ). Thay i v tr hai nhm th s chn ln khng lm thay i cu hnh hnh. .
- Tuy nhin cn lu l nhng iu trn ch ng vi trng hp mt C*, trong trng hp nhiu C th tnh th kt qu s phc tp hn.
CHO H HO H H R S R R OH H OH OH HO HO H H CHO S S R R H H OH OH
CHO H HO H H R S R R OH H OH OH HO H HO HO
CHO S R S S H OH H H
CH2OH (D)-(+)-glucose
CH2OH (D)-(+)-mannose
CH2OH (D)-(+)-glucose
CH2OH (L)-(-)-glucose
22
- Quy tc ny rt hu ch trong mt s trng hp khi ta v cng thc chiu Fisher c tn cu hnh, c th chiu ng th gc nhn li v cng kh khn d dn n nhm ln, khi ta c th chn gc chiu d chiu ri i ch s chn ln (thng l 2 ln) c c cng thc Fisher ng ca cht ri c tn cu hnh hnh. .
OH OH
CHO
CH 2OH
CHO
CH2OH H CHO H
OH
CH2OH D
Quy tc 2: Nu xoay cng thc chiu Fisher 1800 trong mt phng th ta s khng lm thay i cu hnh ca cht .
H Br R CH3 CH2CH3
CH3
Xoay 1800 trong mt phng
CH3CH2
R H
Br
Quy tc 3: Nu xoay cng thc chiu Fisher 1800 ngoi mt phng th ta s lm thay i cu hnh ca cht .
H Br R CH3 CH2CH3
CH 3 CH 2
S CH 3
Br
23
Quy tc 4: Nu xoay cng thc chiu Fisher 900 trong mt phng th ta s lm thay i cu hnh ca cht .
H Br R CH3 CH2 CH3
Br
CH3
CH2CH3
Cc ng phn lp th: Tnh cht vt l (nhit si si, , nhit nng chy, t khi, ha tan, ch s khc x, ) hon ton ging nhau nhau. . Tnh cht ha hc: hon ton ging nhau nhau. . ng phn quang hc c hot tnh quang hc khc nhau, nhau , hai i phn nu o cng iu kin th mt cht s lm quay mt phng nh sng phn cc sang tri tri, , mt cht s lm quay mt phng nh sng phn cc sang phi, vi tr tuyt i s gc quay bng nhau nhau. . Hot tnh sinh hc khc nhau nhau. .
24
Trong ha hu c c hai hiu ng v cng quan trng l hiu ng in t v hiu ng lp th. Hiu ng in t quan trng v n quyt nh phn cc do nh hng n tnh cht vt l, tnh cht ha hc ca hp cht hu c. Hiu ng in t c chia lm 3 loi: hiu ng cm, hiu ng lin hp (cng hng) v hiu ng siu lin hp (siu tip cch).
1. Hiu ng cm (hiu ng ca ni s): 1.1. nh ngha: l hiu ng dch chuyn in t sinh ra do s sai bit v m in ca hai nguyn t hoc nhm nguyn t.
- X c m in ln hn C X ht i in t ni C1-X, ht i in t ni ca C1-C2, nh hng truyn ngang qua cc ni ha tr lc ht gi l hiu ng cm (nh vy nhm gy hiu ng cm khng ch nh hng ln nguyn t gn trc tip gn n m cn nh hng n nguyn t xa hn).
+ C > X
1.3. c im: L s phn cc thng trc trng thi cn bn ca mt phn t. Hiu ng cm truyn dc trn dy carbon, cng cng yu dn khi cng xa X, trn thc t hiu ng cm s bng 0 khi lan truyn qua 3 hoc 4 ni (hiu ng cm gim rt mnh theo khong cch v bn cht n l lc Coulomb t l nghch vi bnh phng khong cch). Do C v H c m in gn bng nhau nn xem nh ni C-H khng c hiu ng cm (mc d C-H c phn cc mt t). H < C < I < Br < N < Cl < O < F
Hiu ng cm dng: cho hiu ng y in t (+I), thng l ankyl hoc nhng nhm mang in tch m. Hiu ng cm m: cho hiu ng rt in t (-I), thng l nhng nhm c m in ln hoc nhng nhm mang in tch dng.
CH3 H > < C < CH3
<
<
+I
< S
>
< O
>
>
< CH3
<
CH3
> C N > > F > > Cl > > C O OH > > Br >
-I
> NO2 O N O
>
> SO3H O S O O
>
> I>
> OH >
> OR >
> C O
R >
> C O
OR >
> C C >
>
>
> C CH 2
1.5. ng dng: So snh mnh axit, baz. Gii thch bn ion: ion cng bn khi gn trng thi trung ha in (ngc li, trng thi cng mang in nhiu cng km bn) nhm no cng lm ion gn trng thi trung ha in s lm ion cng bn ngi ta ni nhm c tc dng an nh (lm n nh) ion.
C C carbanion
carbocation
-
Hot tnh hp cht tc (ng hc) phn ng (v d: phn ng cng thn hch ca carbonyl). nh hng phn ng tc thnh phn sn phm chnh, ph (v d: phn ng th thn in t ca cc dn xut ca benzen).
HA cng mnh
H+ + A-
X cng bn
V d:
CH3 CH 2 COOH
4,90 4,76
4,82
H CH2 COOH
4,52
CH2
CH CH2 COOH
CH2 COOH
4,35 3,00
Cl
CH3 CH CH2 COOH
HC C
4,05
Br
CH2 COOH
2,86
Cl
< <
Cl CH2 COOH
CF3 COOH
2,83
CH3 CH2 CH Cl
COOH
2,85
Rt mnh
>
>
CH3
AB
[A1B1] A + B [A2B2]
A1B1 A2B2
2. Hiu ng lin hp (cng hng) (hiu ng ca ni p): 2.1. Thuyt cng hng: i vi nhiu cht hu c nu ch biu din chng bng mt cng thc Lewis s khng gii thch c rt nhiu tnh cht vt l ha hc ca chng. V d:
Ngn hn ni n thng thng
C O
CH2
CH
CH
CH2
Di hn ni i thng thng
H H
H H H H
C
CH 2
CH
CH
CH 2
CH2
CH
CH
CH2
C O
C O
2.2. c im:
-
Phn bit gia h bin v lin hp: cng thc lin hp khng c tht (ch l cng thc) tng tng trnh by mt phn t di dng nhiu cng thc lin hp. Phn t hp cht hu c thc cht l s lai tp hay l trung bnh cng ca tt c cc cng thc lin hp. Tuy nhin s c nhng cng thc lin hp quan trng hn (bn hn) chim t l nhiu hn, c cng thc t quan trng hn chim t l t hn. c im khc vi hiu ng cm: lan truyn lin tip mnh khng gim theo ni, chng no cn tip cch ni p.
2.3. Cc h thng lin hp: a) p-s-p: (ni p tip cch vi nhau bi ni s) Nu ch i in t p no khi u cho s dch chuyn cng c tng ng nhau.
CH2 CH CH CH CH3
CH2 CH CH CH CH3
CH2
-
CH
CH
CH
CH3
CH2
CH
CH
CH
CH3
CH3
CH
CH
C O
CH3
b) p-s-p:
C O O H
C O
c) p-s-C+:
C CH C
CH
d) p-s-C+:
Cl C
Cl
e) Gc t do - in t p:
CH
CH
Tt c cc cng thc lin hp l cng thc Lewis Cch nhau bi du . Du ch chiu di chuyn in t Trong cc cng thc lin hp ch c i in t p hay p l dch chuyn cn tt c cc nguyn t khng thay i v tr. Phi tnh li s in t t suy ra in tch trn tng nguyn t (tuy nhin tng in tch th khng i). Thng ngi ta vit tt hai cng thc lin hp u v cui.
OH
OH OH
OH
OH
OH
OH
Cng hng m (-R): cho hiu ng rt in t, thng l nhng nhm chc bt bo ha. Cng hng dng (+R): cho hiu ng y in t, thng l nhng nhm mang in tch m hoc nhng nhm c cha nguyn t c i in t t do.
-R NO2 O N O O C O +R S > HN C O > > R > C O OR > C O NH2 > C C > C CH2 > SO3H O S O > C N > C O H > C O OH >
O R
NR F
> >
NH2 Cl
> >
OR Br >
> I
OH
>
* Nhn xt:
-
C ch 2 hiu ng khc nhau. C nhng nhm ch c mt hiu ng. a s cc nhm c hai hiu ng cng chiu, nhng mt s nhm cho hai hiu ng ngc chiu.
+R +I
-R -I
NO2 ,
SO3H ,
N ,
C O
H ,
C O
OH
C O
C O
OR ,
C O
NR2
+R -I
NR2
NH2
OR
OH ,
Cl
Br
HN C O
2.6. ng dng:
-
nh hng ln tnh axit, baz. nh hng ln di ni. nh hng ln hot tnh (kh nng phn ng) hp cht t quyt nh (ng hc) phn ng. nh hng ln nh hng phn ng (v d: phn ng th thn in t ca cc dn xut ca benzen).
CH3 CH2 CH
CH
CH3
HCl
CH3
H H C H
H H C H C C > H
C H
H C C C C > C
H C C C C > C
C C C C C
Phn ln cc ni trong hp cht hu c l ni cng ha tr thun ty rt bn, kh ct t hu nh tr v mt ha hc. Phn khung sn cacbon ny phn cc km nn khng tan trong nc, dy cacbon cng di cng km tan. Ngi ta gi chng l u k nc hay a du. Ngc li, phn nhm chc ha hc nu phn cc mnh c gi l u k bo hay a nc.
* Cc bc gi tn quc t ca hp cht hu c: - Trc y tn ca hp cht hu c thng l do nh ha hc tm ra n t cho, tn ny thng c gc Latinh xut pht t ngun gc hay c tnh ni bt ca hp cht . V d: Ure (urine), Morphin (morpheus), acid barbatiric (Barbara), - Nhu cu t ra phi c mt h thng c tn thng nht cho tt c cc hp cht hu c. Hip hi Ha hc thun ty v ng dng quc t quy tc c tn chun (danh php quc t hay IUPAC). - c tn quc t ca hp cht hu c, chng ta phi tin hnh 4 bc.
Bc 1: Xc nh nhm chc chnh. Th t u tin ca cc nhm nh chc c sp xp theo th t sau -COOH > -SO3H > -CO-O-COR > -COOR > -COX > -CONH2 > -CN > -CHO > -COR > -OH > -NH2 > -OR > -O-O-R
CH2 CH OH OH CH2 CH CH CH3 CH3 Cl
CH3 CH OH CH2 CH2 COOH
Bc 2: Xc nh mch chnh l mch cacbon di nht c cha nhm chc chnh. Trong trng hp c nhiu nhm chc chnh th mch chnh phi l mch cha tt c cc nhm chc chnh (hoc cha nhiu nhm chc chnh nht c th).
CH3 CH2 CH2 CH3 CH CH3 CH3 CH2 CH CH2 CH CH3
CH3
CH2 CH
COOH
Bc 3: nh s trn mch chnh theo tun theo cc quy tc u tin di y - nh s sao cho nhm chc chnh c s th t nh nht (trong trng hp c th nhiu nhm chc chnh th phi nh s sao cho tng s th t cc nhm chc chnh l nh nht). - nh s sao cho tng s th t nhm th l nh nht. - Khi va c nhm ankyl v nhm halogen th u tin nhm halogen c s th t nh hn. - Khi c nhiu nhm th tng ng th nh s sao cho nhm th c ch ci u tin ng trc trong vn a,b,c s th t nh hn.
1 2
1
CH2
2
CH
3
CH
4
CH
5 4
6 3
7 2
8
CH2
CH2 CH2 CH
5
CH3
4
CH3
2
Cl
1
CH3
5
CH3
4
Cl
2
Br
1
CH3
CH CH2 CH
CH CH2 CH
Bc 4: c tn tun theo cc quy tc sau - STT nhm th-tn nhm th + tn mch chnh. - Gia s v s l du phy (,) ; gia s v ch l du gch (-) - Nu c nhiu nhm th ging nhau th thm tip u ng : di, tri, tetra, penta, hexa, ... vo trc tn nhm th v phi lp li STT ca nhm th (STT c vit t nh n ln). i vi cc nhm th phc tp th s dng tip u ng bis, tris, tetrakis, - Cc nhm th c vit theo th t a,b,c (da vo ch ci u tin ca cc nhm th m khng bao gm cc tip u ng di, tri, tetra,
Nhm th
F Cl Br I
Tn gi
Flo(ro) Clo(ro) Brom(o) Iod(o)
Nhm th
OH NH2 NO2 NO CN
Tn gi
Hidroxi Amino Nitro Nitroso Ciano
- Gc hidrocacbon: gc xut pht t ankan tn ankan b an thm yl(il), nhng gc xut pht t anken, akin th ch cn thm yl(il).
Gc
CH3 CH2 CH3 CH2 CH2 CH3 CH CH3 CH2 CH2 CH2 CH3 CH2 CH CH3 CH CH2 CH3 CH3 CH3 C CH3 CH3 CH2 C CH3 CH3 CH3 CH3 CH3
Tn gi
Metyl Etyl n-propyl Isopropyl (i-propyl)
Vit tt
Me Et n-Pr i-Pr
Gc
Tn gi
Ciclohexyl
Vit tt
Phenyl
Ph
Benzyl
o-Tolyl
sec-butyl (s-butyl)
s-Bu
CH3 m-Tolyl
tert-butyl (t-butyl)
t-Bu CH3
p-Tolyl
Neopentyl
Gc
CH2 CH 1 CH 1 CH2 CH2 2 CH 2 CH 3 CH3 3 CH2
Tn gi
Metilen Etenyl (Vinyl) 1-Propenyl 2-Propenyl (Alyl)
Gc
Tn gi
C 1 C 1 CH2
CH 2 C 2 C 3 CH3 3 CH
u gc
1 2 3 CH2 CH2 CH
8
4 CH2
8-(4-clo-3-metylbutyl)
Gc c cha oxi:
Gc Tn gi
CH3 O Phenoxi
Tip u ng ch s C
1 Met 2 3 4 5 6 7 8 Et Prop But Pent Hex Hept Oct 10 Dec 11 Undec 12 13 14 15 16 17 18 Dodec Tridec Tetradec Pentadec Hexadec Heptadec Octadec 20 (E)Icos 30 Triacont 21 Hen(e)icos 31 Hentriacont 22 23 24 25 26 27 28 Docos Tricos Tetracos Pentacos Hexacos Heptacos Octacos 32 40 50 60 70 80 90 Dotriacont Tetracont Pentacont Hexacont Heptacont Octacont Nonacont
100 Hect
CH2 CH3
CH3
CH CH3
Isohexan
2. Tn quc t: - Cc ch n-, s-, t-, i- (vit tt ca normal, sec-, tert-, iso-) khng c tnh n khi sp th t theo vn a,b,c. Tuy nhin Iso (khng vit tt) v neo (khng c dng vit tt th c tnh)
3. Tn cicloankan: - Nu s cacbon trn dy nhnh s cacbon trn vng th xem vng l mch chnh.
CH CH3 CH3
Isopropylxiclohexan
- Nu s cacbon trn dy nhnh > s cacbon trn vng th dy nhnh l mch chnh.
CH2 CH Cl CH2 CH3
1-Xiclopropyl-2-clobutan
II. Tnh cht vt l: - Khng tan trong nc, ch tan trong cc dung mi hu c khng phn cc, khng tan trong axit, baz long, dung dch H2SO4 lnh. - Nh hn nc. - Nhit si, nng chy thp. S C tng, nhit si, nng chy tng. - Cng s C, ng phn c nhiu dy nhnh hn s c nhit si, nng chy thp hn. C1-C4 : kh C5-C17 : lng C18 : rn
2H2
Ni t0
C H H
C H H
H Li H Al H H
H Al H H + H + Li
C H
3. Tng hp Wurtz:
2RX + Na t0 R-R + 2NaX
- Ch thch hp iu ch ankan i xng, khi dng 2 halogenua ankyl khc nhau th s to hn hp sn phm hiu sut thp.
RX + RX ' + Na t0 R-R + R'-R' + R-R + NaX
10
- Ankan cho kh nng chy tt: cho ngn la sng, khng khi. - Tuy nhin khi s C tng th kh nng chy cng gim. - So snh gia cc ankan > anken > ankin > aren. - Trong trng hp t chy nhng hydrocacbon c kh nng chy km hoc t chy trong iu kin thiu oxy th qu trnh t chy cho nhiu khi, mui than.
11
2. Phn ng halogen ha: - iu kin: nh sng t ngoi hoc 200-400oC - C ch: gc t do qua 3 giai on + Giai on khai mo (nhanh):
Cl Cl
Gc t do
hn
Cl
Cl
H
H
+ H
C H
C H
HCl
H H C H
+ Cl
Cl
C H
Cl
Cl
+ Giai on kt thc:
Cl
CH 3
+
+
Cl
Cl
Cl 2
CH 3Cl
CH 3
CH 3
CH 3-CH 3
CH4
+ Cl2
hn
CH3-Cl
HCl
- Trong trng hp ankan c nhiu loi hidro ta s thu c nhiu sn phm halogen ha. Sn phm chnh s l sn phm xut pht t gc t do bn nht .
H Cl C H H C H H C H
C C C C > C H C C > H H C C > H H C H
12
- phn ng: Cl2 > Br2 > I2 (I2 hu nh khng phn ng). Tuy nhin Br2 li c chn lc cao hn Cl2.
CH3 CH2 CH2 CH3 Cl2 CH3 CH2 CH2 CH2 Cl (30%) CH3 CH2 CH2 CH3 Br2 CH3 CH2 CH2 CH2 Br (2%) + + CH3 CH2 CH CH3 Cl (70%) CH3 CH2 CH CH3 Br (98%)
3. Phn ng nitro ha: - Xy ra pha kh, nhit cao, mch cacbon c th b ct t cho hn hp sn phm.
RH + HNO3 RNO2 + H2O
4. Phn ng cracking:
R CH2 CH2 R' to R CH CH2 + R'H
13
-butylen
2. Tn quc t:
CH3
Cl
4-Metylxiclohexen
5-Cloxiclohexadien-1,3
Khng tan trong nc, ch tan trong cc dung mi hu c khng phn cc, khng tan trong axit, baz long nhng tan trong dung dch H2SO4 lnh. Nh hn nc. Nhit si, nng chy thp. S C tng, nhit si, nng chy tng. Cng s C, ng phn c nhiu dy nhnh hn s c nhit si, nng chy thp hn. C2-C4 : kh C5-C18 : lng C19 : rn
III. iu ch:
1. Hidro ha ankin:
C C
+ H2 Pd to
C H
C H
2. Kh nc ancol:
-
iu kin: H2SO4 (170oC) hoc Al2O3 (400800oC) Kh nng phn ng: ancol III > ancol II > ancol I
3. Kh HX ca RX (halogenua ankyl):
-
iu kin: KOH/EtOH, to (un nng mnh) Kh nng phn ng: R-I > R-Br > R-Cl > R-F III > II > I
4. Kh X2 ca -dihalogenua (vic-dihalogenua):
C X C X + Zn to C C + ZnX2
ng dng: bo v ni i
Cng i xng Phn ng cng Cng bt i xng Phn ng ca anken KMnO4 Phn ng oxi ha O3
Thng s dng dung mi CCl4 (CHCl3, CH2Cl2). Phn ng xy ra d dng nhit phng. Khng nn s dng d X2 hoc thc hin trong iu kin nh sng v phn ng th s quan trng. Mt in t trn ni i cng ln, phn ng cng xy ra nhanh (cng nhiu nhm y in t gn ni i). ng dng: dng nhn bit ni i.
Tin hnh: c th sc kh HX vo anken hoc phn ng trong dung mi chung l axit acetic. Ring HI (KI + H3PO4) nh hng phn ng: quy tc Markonikov. C ch: cng thn in t qua 2 giai on. + Giai on 1: cng thn in t proton vo ni p to carbocation (chm). + Giai on 2: X tc kch vo C+.
Br
C C
H d+
H C C
Br d-
H C C
Br
d+
CH2 CH CH CH2
H
dCl
Butadien-1,3
CH2
CH
CH
CH3
CH2
CH
CH
CH3
Cl
Cl
CH2
CH
CH Cl
CH3
CH2 CH Cl
CH
CH3
Quy tc Markonikov
Nm 1869, Vladimir Markonikov kho st nhiu phn ng cng hidracid vo anken v a ra quy tc mang tn ng : Trong s cng hidracid vo ni i C=C, H s gn vo carbon mang nhiu H nht .
C
a b
a
H
a b
C
H+
CH3 CH 3 C CH3
C C H
> CH3
C CH3
> CH3
CH2 >
CH3
Tuy nhin, quy tc Markonikov ch l quy tc kinh nghim, cha tnh n hiu ng in t do trong mt s trng hp s khng d on c hoc d on sai sn phm chnh.
CH2 CH C O
CH2 CH C O H
HCl
CH2 CH2 C Cl
CH2 CH
O
C O H
d+
d-
CH3 CH > C
CH2
CH
C O
H+
CH2
CH2 > C O
(bn hn)
CH2
CH
CH2 Cl
HCl
Cl
CH2 C Cl
CH 3
CH3
HCl
CH3
C Cl
CH3
CH
CH 2 > Cl
CH2
CH
CH2 Cl
H+
CH2 CH2 CH2 > Cl
(bn hn)
CH2
CH2 C Cl
CH3
CH
>
CH3
CH3
H+
Cl
C Cl
CH3
(bn hn)
Nm 1933, Morrish S. Kharash v Frank R. Mayo kho st phn ng anken vi HBr vi s c mt ca peroxit (R-O-O-R):
CH2 CH CH 3
HBr Peroxit
Sn phm chnh khng tun theo quy tc Markonikov m tun theo quy tc Kharash (phn Markonikov). Lu : peroxit ch c nh hng vi HBr (khng c tc dng vi cc tc nhn bt i xng khc nh HCl, HI, H2SO4, H2O, ) C ch: Gc t do.
RO + H
Br
ROH
Br
Br
C Br
C Br
Br
C Br
C H
Br
+ Giai on kt thc:
C
a b
Br
a b
C
Br
.
H H > H C C >
C Br
C C C C > C
H H C H
C C
Tin hnh: sc kh anken vo H2SO4 , lnh hoc trn anken lng vo axit to thnh dung dch ng nht.
O
O
OH
S O
C H
S O
OH
C H
C OH
H2SO4
ng dng: + iu ch ancol t anken thu c trong s cracking du ha + Tch mt hp cht ra khi anken - nh hng: tun theo quy tc Markonikov
-
C ch:
C C
d+ H
dA
C H
+
H O H
C OH
C H
H-A
H
C O H
C H
10
Nm 1959, H.C. Brown tm ra phn ng cng H2O theo quy tc phn Markonikov - phn ng hidrobor ha
-
C ch: 2 giai on
H
C C
H BH2 C C
+
H
Boran
H C C 3 B
H 2O 2 OH -
H C C
OH
Triankyl boran
H
H
H
H
B
C
H C C
BH2
11
* Phn ng oxi ha: 5. Phn ng oxi ha vi KMnO4: a. iu kin oxi ha yu (KMnO4 long, lnh):
-1 -2 +7 0 -1 +4
3R
CH
3R
CH OH
CH2 + OH
2MnO2 + 2KOH
-diol
CH3
CO2
HOOC-COOH +
C CH3
C ch: 3 giai on
O
R1 C R2 C R4 R3
O
O3 CH2Cl2
O C C
chuyn v
R1 R2
R3 R4
R1 C R2 O
O C
R3 R4 O
R1 C R2 O
+
R3 O C R4
Ozonid
12
Tin hnh: sc kh O3 vo dung dch anken trong dung mi (CH2Cl2, CCl4). Sau cho dung mi bay hi thu c ozonid du st (khng bn, d n) ngi ta khng c lp m cho tc dng ngay vi H2O vi s c mt ca Zn (s c mt ca Zn l ngn H2O2 oxi ha andehit thnh axit). ng dng: Xc nh cu trc anken
H C H H C H
CH CH
CH3 C CH3
CH3
CH
CH
C CH3
Phn ng ozon gii phi tri qua hai giai on nn phi trnh by:
1)O3 2)H2O, Zn
7. Phn ng th H:
CH3 CH CH2 + Cl2 450oC Cl CH2 CH CH2 + HCl
13
Akin cui dy
Akin gia dy
I. Gi tn:
1. Tn thng thng: xem nh dn xut ca axetilen
CH3 C CH CH3 CH2 C CH
Metylaxetilen
Etylaxetilen CH3
CH3
CH3
CH3
CH
CH
Dimetylaxetilen
Isopropylaxetilen
II. Tnh cht vt l: - Ging ankan, anken (tan trong H2SO4 lnh). III. iu ch: 1. iu ch axetilen: a. T than v vi:
Than vi CaC2 + 2H2O Than cc 2000oC Cao Ca(OH)2 + C2H2 CaC2 H2O C2H2
b. Oxi ha metan:
6CH4 + O2 1500oC 2C2H2 + 2CO + 10H2
2. Kh 2HX ca dihalogenua ankyl (vic hoc gem): - Tc cht: NaNH2/NH3l (NaNH2 pkb -19; KOH pkb = 0,5).
2Na + 2NH3
H R C H X CH X
Fe(NO3)3 -33oC
2NaNH2 + H2
KOH EtOH
HX
C H
CH X
NaNH2 NH3l
halogenua vinyl
- Phn ng ny thng c dng iu ch ankin cui dy. Nhng v ankin cui dy c tnh axit nn ngi ta thng dng d NaNH2 (3:1) v s thu c mui axetilua natri thay v ankin. Sau cng phi thm vo dung dch axit chuyn ha mui natri thnh akin tng ng.
CH
CH2
X2
CH X
CH2 X
NaNH2 NH3l
CH
+ 2HX
vic-dihaloankan
H R C H
X CH X
NaNH2 NH3l
CH
+ 2HX
gem-dihaloankan
3. Kh X2 ca tetrahalogenua ankyl:
X C X X C X + Zn to
2ZnX2
- ng dng: bo v ni ba
NaNH2 NH3l
R' + NaX
Ankin cui dy
Axetilua natri
Cng i xng Phn ng cng Cng bt i xng Phn ng ca ankin Phn ng oxi ha (KMnO4)
X2
C X
C X
X2
C X
Dihaloanken
Tetrahaloankan
HX
C X
X
CH2
C X
CH2
HX
C X
CH3
gem-dihaloankan
R
R C X
R C X CH3
CH
>
CH2
CH2
H+
(bn hn)
HX
CH
C X
X
R C X CH R
HX
C X
CH2
gem
X
HC CH
HX
CH2 CH X
HX
H3C
CH X
HX
C X
CH
R'
CH
C X
R'
(hn hp sn phm)
X
R C X CH R'
HX
C X
CH2
R'
X
R CH C X R'
HX
CH2 C X
R'
H2O HgSO4
H2C
CH HO
c/v
H3C
CH O
Axetandehit
H2O HgSO4
CH OH
CH2
c/v
C O
CH3
Metylceton
H2O HgSO4
C OH
CH
R'
CH
C HO
R'
c/v
R C O CH2 R'
c/v +
R CH2 C O R'
CH
C HO
c/v
CH2 C O
1 ceton
- Lu :
R C CH
CH
CH HO
c/v
CH2
CH O
Andehit
HCN
C CN
CH2
CH
CH3COOH
CH2
OCOCH3
KMnO4
RCOOH
RCOOH
* Th hin tnh axit yu ca ankin cui dy: - Tnh axit ca akin cui dy c gii thch:
HA
R C CH
H+ H+
+ +
AR C C
rt e-
C
C
CH
CNa
+ NaNH2 + H2O
NH3l
CNa
+ +
NH3 NaOH
CH
8. To axetilua kim loi nng vi CuCl/NH3 v AgNO3/NH3 : - Dng nhn bit ankin cui dy
R R C C CH CH
+ +
[Cu(NH3)2]+ [Ag(NH3)2]+
R
R
C
C
CCu
CAg
+ +
NH3 NH3
+ +
NH4+ NH4+
Quy tc Huckel : + C cu vng phng. + Cng hng lin tc trong vng vng. . + C 4n+ n+2 2 in t p.
CiclooctatetraenCiclooctatetraen -1,3,5,7
Hp cht hydrocarbon thm quan trng nht l benzen. benzen . Vo u th k 15 15, , t vng ng Nam xut qua Chu u mt loi nha (benzoin) c chit xut t mt loi cy b (hoa cnh kin trng - hoa benzoin) lm hng liu. c rt nhiu nh ha hc quan tm nghin cu. Nm 1833 Eilhard Mitscherlich qua s chng ct nha benzoin (axit axetic) iu ch c mt cht m ng t tn l benzin benzin. . 1845, 1845 , Charles Mansfield c lp c benzen t hc n than . Bn nm sau ng pht trin thnh sn xut quy m cng nghip.
Mc d CTPT (C6H6) c xc nh t lu nhng trong mt thi gian di cc nh vn cha xc nh c CTCT ca n n. . 1865 1865, , Friedrich August Kekul ng trn mt bi bo ca Php ngh cu trc ca benzen. benzen . Nm sau, ng vit mt bi bo chi tit hn c trong cp nhiu bng chng c th : ch c 1 ng phn dn xut th mt ln v c 3 ng phn dn xut th hai ln. Cng v sau cc nh ha hc cng tm c nhiu hp cht c lin quan quan. . Hofman ngh t tn nhm hp cht ny l hidrocarbon thm (hng phng).
H H H
1,397
H H
>
Thiu nhit mol chun ca 1,3,5-ciclohexatrien l thuyt l 827 kcal/mol, benzen : 789 kcal/mol thp hn 38 kcal/mol (nng lng cng hng).
CH
CH2
CH2
CH3
CH2
CH3
Benzen khng phn ng vi Br2/CCl4; khng lm mt mu KMnO4 long lnh. Nh vy benzen bn hn mt xiclohexatrien l thuyt v khng th xp vo anken a chc.
NO 2
Br
Etylbenzen
- Nu trn nhn thm cha nhiu nhm th th phi nh s (theo quy tc) :
Me Me
NO 2 Cl
Br
NO 2
- Tuy nhin nu trn nhn thm cha nhm nh chc ha hc th mch chnh lc ny (bao gm benzen v nhm nh chc ) s c tn ring v nhm nh chc ng nhin nh s 1.
COOH 1
SO 3H 1
CHO 1
Acid benzoic
Acid benzensulfonic
Benzandehit
OH 1
NH 2 1
CH3 1
Phenol
Anilin
Toluen
Me NO2 1 NO 2
Br
OH 1 Br
COOH 1
OH
NO2
2. Tn thng thng :
Me
Me
Ph
Me
Toluen
8 7 6 5 4 1
o,m,p-Xilen
9 1 2 3 5 10 4
2 3
Biphenyl
6 5 7 8
8
2 3
7 6
9 4 10
Naptalen
CH CH2
Antrancen
Me
Phenantren
Me
CH
CH
Me
Me
Stiren
Cumen
o,m,p-Cimen
Mestilen
Stilben
- Ngoi cch nh s ch v tr 2 nhm th trn nhn thm vi nhau ngi ta cn dng cc tip u ng : orto, meta, para vit tt o-, m-, p- (c x nh s.
Y
orto
meta para
Cl Cl
Me
CHO
Br
Cl
a s l cht lng tr cc hp cht a nhn l cht rn. ng phn para thng c im chy cao hn v tan km hn ng phn orto, meta meta. .
* Phn ng th thn in t :
-
Cc phn ng th thn in t u c c ch ging nhau. nhau . Chng ch khc nhau bn cht v cch to ra tc nhn thn in t.
E+
E H
H
E+
H2SO4 H+ HSO4-
H2O
N O
Nitronium
NO2 H
NO2
O S O O
H2SO4
O
S O
HSO4-
H O S O O
HSO4SO3 H H
SO3H
+ H2SO4
SO3H
CH3 CH3
H3 O+ to
H2SO4
SO3H
10
3. Phn ng halogen ha :
-
FeBr3
d+ dBr3Fe...Br...Br
d+ dBr3Fe...Br...Br
Br H
Br
FeBr4-
+ FeBr3 + HBr
iu kin : xc tc AlCl3, to
R + RX AlCl3 to HX +
CH3
Cl
AlCl3
CH3 AlCl4
CH3
CH3 H
CH3
AlCl4-
+ AlCl3 + HCl
11
Phn ng ny rt kh dng n ankyl ha v nhm ankyl l nhm tng hot nhn thm lm cho nhn thm c th nhn thm nhiu nhm ankyl na dn n s a ankyl ha ha. . trnh s a ankyl ha ngi ta thng s dng lng tha benzen benzen. .
C(CH3)3 C(CH3)3
(CH3)3CCl AlCl3, to
C(CH3)3
Nu s dng halogenua c nhiu nhm halogen ta s thu c sn phm c nhiu nhn thm (a nhn) :
2
+ CH2 Cl CH2 Cl AlCl3 to
CHCl3
AlCl3 to
12
Phn ng ankyl ha Fridel Fridel-Crafts khng xy ra trong cc trng hp sau : + Khi R = vinyl hoc phenyl :
Cl +
Cl
+ Khi trn nhn thm c nhng nhm rt in t mnh nh : -NR3, -NO2, -SO3H, -CN, -CHO, COR, -COOH, -COOR hoc cc nhm amino nh : -NH2, -NHR, -NR2.
Phn ng ankyl ha Fridel Fridel-Crafts c mt nhc im l rt kh dng tng hp nhn thm c dy nhnh di do carbocation R+ c th chuyn v t bc I sang bc cao hn (bn hn) :
CH3
CH3
CH2
CH2
CH2
CH2
CH2
CH2
Cl
AlCl3 c/v
CH3 CH3
CH2 CH2
CH2 CH
13
C O
Cl
AlCl3
AlCl4
O
CO H
COR
AlCl4-
+ AlCl3 + HCl
orto
H H
meta para
14
a) phn ng :
OH
Cl
NO2
1000
6x10-8
- Nh vy c 2 loi nhm : + Nhm lm tng vn tc phn ng th thn in t tip theo c gi l nhng nhm tng hot. + Nhm lm gim vn tc phn ng th thn in t tip theo c gi l nhng nhm gim hot.
Nhng nhm tng hot l nhng nhm y t vo trong nhn thm lm cho nhn thm in t hn phn ng tt hn. Nhng nhm gim hot l nhng nhm rt t ca nhn thm lm cho nhn thm km in t hn phn ng km hn.
OCH3 NH C CH3 O R -H F Cl Br I NO CH O C O OR C O OH C O R SO3H
in giu in giu
NH2
OH
C N
NO2
R R R
-I, +R
-I, -R
15
b) nh hng :
-Y -NO2 -COOH -SO3H -Cl -Br -I -Me -OH orto 7 22 21 35 43 45 63 50 meta 91 76 72 1 1 1 3 0 para 2 2 7 64 56 54 34 50
NH2 OH
C nhng nhm quyt nh phn ng th thn in t tip theo cho sn phm ch yu l ng phn orto, para c gi l nhng nhm nh hng orto, para para. . C nhng nhm quyt nh phn ng th thn in t tip theo cho sn phm ch yu l ng phn meta c gi l nhng nhm nh hng meta meta. . Hon ton quyt nh bi hiu ng cng hng.
OCH3 NH C CH3 O R -H F Cl Br I NO CH O C O OR C O OH C O R SO3H C N NO2 N R R R
QUY TAC HOLLEMAN Nhom nh hng orto, para Nho m nh hng meta
+R
-R
16
Gii thch :
OH OH OH OH OH
O N
O N
O N
O N
O N
O N
NH2
OH
OCH3
NH C CH3 O
-H
Cl
Br
NO
CH
C O
OR
C O
OH
C O
SO3H
C N
NO2
R R R
QUY TAC HOLLEMAN Nho m tang hoat nh hng orto, para Nhom gia m hoat nh hng orto, para Nhom giam hoa t nh hng meta
HNO3 H2SO4
NO2
NO2
p-Nitrotoluen
17
Br/FeBr3 to
Me
Me
Cl2 as
18
KMnO4 to
CH3COOH
KMnO4 to
Hexaclociclohexan
19
R'
C OH
Ru III
R''
OH
Phenol
Ancol metyl
Ancol etyl
Ancol t-butyl
Ancol alyl
CH3
CH
CH
CH2 OH
CH2 OH
Ancol crotyl
Ancol benzyl
HC
CH2OH
Ph
CH
CH
CH2 OH
Ancol propagyl
Ancol cinamyl
Ancol capryl
Ancol lauryl
b) Cch 2: Ru + tn gc hidrocarbon + ic
CH3 CH3 OH CH3 CH2 OH CH3 C CH3 OH
Ru metylic
Ru etylic
Ru t-butylic
CH2 OH
Ru isoamylic
Ru benzylic
Metylvinylmetanol
Phenylmetanol
Trimetylcarbinol
CH2OH
Etilen glycol
Glycerin
Pentaeritritol
2. Tn quc t:
-
Etandiol-1,2
Propantriol-1,2,3
Et OH
2-Metylxiclohexanol
2-Etylxiclohexandiol-1,4
Lu : cch gi tn quc t cn cho php mt cch c tn na - xem nhm OH l nhm th (hidroxi) trn mch chnh l hidrocarbon.
CH2 OH CH2 CH2 CH Cl CH2 Cl
1,2-Diclo-5-hidroxipentan
1
CH3
2
CH OH
3
CH Br
4
CH3
4
CH3
3
CH OH
2
CH Br
1
CH3
3-Brombutanol-2
2-Brom-3-hidroxibutan
2-Propenol-1 (Prop-2-en-1-ol)
3-Butenol-2 (But-3-en-2-ol)
2-Xiclohexenol
II. Tnh cht vt l: 112C: lng, >12C: rn - C kh nng to lin kt Hidro: + Lin phn t nhit si, nng chy cao hn hydrocarbon, halogenua, ete c cng s carbon .V d: etanol (78,9oC), hexan (69oC), Dietylete (34,6oC). + Vi H2O ancol tan rt tt. Tuy nhin s C tng th tan gim. - Metanol v etanol c kh nng ha tan rt nhiu cht hu c k c nhng cht km phn cc dng lm dung mi.
-
C
1)BH3 2)H2O2, OH phn Markonikov
C O
H2
Ni to
CH2
OH
Ru I
C O
R'
H2
Ni to
CH OH
R'
Ru II
Mg
MgX
+ Cb
Ca
Cb
tm giu in t
H
- + R MgX +
H+ H2O
R-CH2OH
XMgOH
O -
OMgX
H
1 Mg(OH)2 MgX 2 2
- + R MgX +
R'
R'
H+ H2O
CH OH
R'
XMgOH
O -
OMgX
R'
R'
R''
- + R MgX +
R'
R''
H+ H2O
C OH
R''
XMgOH
O-
OMgX
- + R MgX +
CH2
CH2 O -
CH2
CH2 OMgX
H+ H2O
R-CH2-CH2-OH
XMgOH
RMgX
1) HCHO 2) H3O+
R-CH2OH
Ru I (+1C)
RMgX
1) RCHO 2) H3O+
CH OH
R'
Ru II
R'
RMgX
1) RCOR 2) H3O+
C OH
R''
Ru III
RMgX
1) O 2) H3O+
R-CH2-CH2-OH
Ru I (+2C)
Lu khi thc hin phn ng vi hp cht Grignard khng c c mt cc hp cht c cha hydro axit (d yu) nh : RCOOH, H2O, ROH, RCCH,
R'COOH + RMgX
RH
RH
+
+
R'COOMgX
OHMgX
OH R'OH
R'C
+ +
RMgX RMgX
RMgX
RH
R'OMgX
CH
RH
R'C
CMgX
V hp cht Grignard phn ng vi hi H2O v kh CO2 trong khng kh nn khi va iu ch phi s dng ngay.
1. Tnh axit:
ROH RO- + H+
CH3OH > Ru I > II > III pka = 15,4 EtOH(16) Me3COH(18,6) CF3CH2OH: pka = 12,43
RONa + H2O
ROH + NaOH
CH3
CH2
ONa
Etoxit natri
RCOOH
H2SO4 to
RCOOR + H2O
Phenol khng phn ng este ha vi axit cng iu kin. Mun thc hin phn ng este ha phenol ngi ta phi dng hp cht c hot tnh mnh hn : anhidric axit hoc clorua axit.
OH
+ CH3COOH
H2SO4 to
OCOCH3
OH
CH3 C O C CH3 O O
piridin
OCOCH3
CH3 C Cl O
CH3COOH
piridin
HCl
ZnCl2 pha trong dd HCl c gi l thuc th Lucas ng dng nhn bit bc ca ancol. Ru III: phn ng nhanh Ru II: chm Ru I: khng phn ng
R-OH + HCl ZnCl2 RCl + H2O
Phn ng xy ra s cho hin tng : ban u hn hp phn ng s c yn mt lc s t t tch lm hai lp cht lng.
10
Phn ng ca ru vi HX to halogenua c nhc im l tnh axit qu mnh ca HX c th nh hng n cc nhm chc khc trn hp cht hu c. Ngoi ra khng th iu ch clorua ankyl bc I t ru bc I.
11
5. Phn ng kh nc:
-
iu kin: H2SO4 (170oC) hoc Al2O3 (400-800oC). Kh nng phn ng: ancol III > ancol II > ancol I nh hng phn ng tun theo quy tc Zaixep. Tuy nhin khi dng d ancol v thc hin phn ng nhit thp th 2 phn t ancol c th kh mt phn t nc cho ete.
2CH3-CH2-OH H2SO4 140oC CH3-CH2-O-CH2-CH3 Dietylete Etoxietan + H2O
CH OH
R'
CuO
to
C O
R'
Cu
H2O
12
X2/NaOH
lng d
CHX3
RCOONa
I2 + 2NaOH
CH3 C R O
2NaI +
2H2O
+ 3I2 + 4NaOH
13
Do I2 tan rt km trong nc nn thng phi thm iodua (I-),v d KI. Cc phn ng haloform nht l phn ng idoform dng nhn bit ru c cu trc l: CH3 CH R v iodoform l cht rn mu vng
OH
CH3 CH CH3 OH
Propanol-2
CH3
Lu : R = H
CH3 CH H OH
CH3 CH2 OH
Ru I
14
OH CHO
Me
OH
o-,m-,p-Cresol
Salicilandehit
NH C O
CH3
Axetaminophen
OH OH
OH
OH
OH
Catechol
Resorcinol
OH
Hidroquinon
OH Cl
OH Cl
OH Cl Cl
Cl Cl Cl Cl
Cl Cl
Cl
Hexaclorophen
Pentaclophenol
II. Tnh cht vt l: - Cc phenol u l cht rn c nhit nng chy thp (do c lin kt H lin phn t). - Tan km trong nc. - Thng b chy nc, b xn mu do b oxi ha trong khng kh. - Gy bng lnh. - ng phn para c nhit nng chy, nhit si cao hn ng phn orto, meta.
HCl
C6H5Cl
+ 2NaOH
C6H5ONa + HCl
OH
SO3 H2SO4
CH3
CH3
1) NaOH, to 2) H3O+
Axit p-toluensunfonic
- Nhc im: thc hin nhit cao t nhm chc no tn ti sau phn ng (ch thch hp iu ch cc ankyl phenol.
OH
OH
OH
OH
OH
O
+ H3O+
bn nh cng hng
- Nhng nhm rt in t v tr orto, para lm tng tnh axit, ngc li nhng nhm cho in t v tr ny lm gim tnh axit.
OH NO2 NO2
pka = 0,6
NO2
- Khc vi ancol, phenol phn ng c vi NaOH, KOH, (dung dch kim long):
C6H5OH + NaOH C6H5ONa + H2O
2. Phn ng to ete:
ArOH
NaOH
ArO
+ R
ArOR +
OH
O Na
OCH3
+ CH3 I
NaOH
Metoxibenzen (Anisol)
3. Phn ng este ha: - Phenol hu nh khng phn ng este ha vi axit carboxylic xc tc H2SO4 phi dng tc cht c hot tnh mnh hn: clorua axit hoc anhidric axit.
R C O Cl
C O
C O
COOMe
COOH OH
CH3OH to
OH
Axit salicilic
Ac2O to Aspirin
CH3
+ AcOH
HO
HO
O N CH3
Ac2O to
O N CH3
Morphin
Heroin
* Phn ng ca vng thm: - OH l nhm tng hot mnh, nh hng orto, para.
OH
Br OH Br
Br2
Br
Chng IV
Hp cht Carbonyl
C O
Andehit
C O
Xeton (R, R H)
R'
CH3
CH Cl
CH2
CHO
CH3
CH CH3
CH2
CHO
Ph
CH
CH
CHO
b-Clobutirandehit
Isovalerandehit
Xinamandehit
CHO OH
CHO
OMe
CH3
Salicilandehit
o,m,p-Toluandehit
CHO
Anisandehit (ngoi l)
CH3-CH2-CHO
Metanal
Etanal
Propanal
CH3
CH2
CH Cl
CHO
CH3
CH CH3
CH2
CHO
2-Clobutanal
3-Metylbutanal
- Nh chc: dial
HOC CH2 CH2 CH2 CH2 CHO
Hexandial
CHO Cl
CH3
Xiclopentancarbandehit
CHO
2-Clo-3-metylxiclohexancarbandehit
CHO
Benzencarbandehit (Benzandehit)
2-Naptalencarbandehit
C O
Metanoil (Formil)
Benzoil
CH3
C O
C O
CH3
Ac2O
Anhidric axetic
Dimetyl xeton
CH3
C O
CH CH3
CH3
CH3
CH CH3
C O
CH CH3 CH3
Diisopropyl xeton
Axetophenon
O C CH2 CH2 CH3
Propiophenon
O C
n-Butirophenon
Benzophenon
Propanon
4-Metylpentanon-2
CH3
CH
CH
C O
CH3
3-Pentenon-2
Xiclohexanon
CH3
C O
C O
CH3
Butandion
3-Oxobutanoat metyl
I. iu ch: 1. T ru:
R-CH2-OH + CuO to R-CHO + Cu + H2O
CH OH
R'
CuO
to
C O
R'
Cu
H2O
2. Ozon gii:
CH3 CH2 CH CH C CH3
CH3
HCHO + HOC-COH + O
C CH3
3. T ankin:
HC CH
H2O HgSO4
H3C
C O
Axetandehit
R C C R'
H2O HgSO4
C O
CH2 R'
CH2 C O
R'
Hn hp 2 xeton
R C CH
H2O HgSO4
C O
CH3
R-CHCl2
2NaOH
CH OH
2NaCl
R-CHO
H2O
R-CHCl2 R-CCl2-R
+ +
2NaOH 2NaOH
R-CHO
R C O
+
R' +
H2O H2O
+ +
2NaCl 2NaCl
H2
Pd-BaSO4 to
R-CHO
HCl
Phn ng ca carbonyl
Phn ng oxh-kh
- C=O cng phn cc, carbonyl cng c hot tnh vi cc tc nhn thn hch
H C O H
>
C O
>
C O
R'
>
CH3
C O
CH CH3
OH
O C R R'
:Nu (a)
R R'
C Nu
H+
R R'
C Nu
OH
Nu
:Nu-H (b)
R R'
C Nu H
H+
R R'
C Nu H
-H2O
R
C R'
- V d:
CH3 C CH
NaNH2 NH3l
CH3
C Na
CH3
CH3
C O
CH3
CH O
CH3
H2O
CH3
CH OH
CH3
HCN+KCN
C O
CN
HCN
C OH
CN
OH
ng dng
C OH
CH2
NH2
SO2Na OH
CH
OH
SO2ONa
CH3
C O
CH3 +
SO2Na OH
OH
Sn phm cng bisunfit (Tan trong nc nhng khng tan trong NaHSO3 bo ha d)
SO3Na
CH OH
Me
SO3Na
HCl
C O
+ NaCl + SO2
+ H2O
C OH
SO3Na
Na2CO3
C O
CH3
+ Na2SO3 + NaHCO3
10
4. Phn ng ancol gii: - Xc tc: axit (do ROH c tnh thn hch yu)
H
H O C
O C
H+
ROH
H O C O H R
OH2
OH C OR
H3O+
Hemiaxetal Hemixetal
H+
+
ROH
R
H2O
OR
O C
OR
H3O+
R O H
H 2O
Axetal Xetal
11
O C
OH
ROH
H+
C OR
Hemiaxetal Hemixetal
OH C OR
OR
ROH
H+
C OR
H2O
Axetal Xetal
OR C OR
H3O+
2ROH
1) LiAlH4 2) H3O+
CH2
C OCH3
CH2 OH
O C OCH3
OH
H+
1) LiAlH4 2) H3O+
O CH2OH
H3O+
CH2OH
CH2
CH2 OH
+
OH
12
OH C NH2
+ NH3
-H2O
C NH2 H
NH
Imin
OH C NHR
-H2O
+ RNH2 Amin I
C NHR H
H
NR
Imin
H Ca C O
+ RNHR' Amin II
Ca C R
H
O N R' H
Ca C
OH R N R'
-H2O
C C N
R R'
Enamin
O + R N R' R''
Amin III
+ NH2 OH Hidroxilamin
OH
Oxim
NH2
Hidrazon
NH2 NH
N NH
Phenylhidrazin
NO2
C O
Phenylhidrazon
NO2
NH2 NH
NO2
N NH
NO2
2,4-Dinitrophenylhidrazin (DNP)
2,4-Dinitrophenylhidrazon
13
- Cc sn phm ca cc phn ng trn thng l nhng cht rn, kt tinh c nhit nng chy xc nh nn thng c dng nhn bit carbonyl c bit l DNP. Carbonyl phn ng s cho kt ta mu vng ti cam
O C C H
H+
cng mnh
cng bn
C O
C H
C O
1,3-Dixeton (pka 9)
C O
C H
C O
C O
C H
C O
14
C O
C O
CH3
CH3 O
NaNH2 - Ha
C O
CH2
C O
CH2
Carbanion
R
1)NaNH2 2)RX
C O
CH R
1)NaNH2 2)RX
C O
C R
15
Br2
C O
Ca
HBr
X2/NaOH chm
C O
CH2X
X2/NaOH nhanh
C O
CHX2
X2/NaOH nhanh hn
C O
CX3
O
OH
O
O C R CX3 OH
C R CX3
C R OH
CX3
O C R O
CHX3
16
C O
CH3
X2 +
NaOH
C O
CH2X
NaX +
H2O
C O
CH3
+ 3X2 + 3NaOH
C O
CX3
+ 3NaX + 3H2O
C O
CX3
+ NaOH
C O
ONa
CHX3
C O
CH3
+ 3X2 + 4NaOH
C O
ONa
+ 3NaX + 3H2O +
CHX3
H H Ca H C O H
CH3
C O
H
CH3 CH O a CH2 C O H
-H+
Ca H
C O
carbanion
H2O
a CH
CH3
CH
C O
-H2O
CH3
CH OH
a CH2
C O
b-Hidroxiandehit
17
CH3
CH OH
CH2
C O
CH3CHO + HCHO
OH
to
CH2 CH 2 OH C O H
C O
Ca H
C O
a CH2 CH2 O
C O
H2O
CH2 OH
a CH2
C O
carbanion
CH3
CH3
CH OH
CH3
CH2
C O
CH3
C OH
CH2
C O
CH3
CH3
C O
+ CH3
C O
CH3
OH
to
CH3
C OH
CH2
C O
+ CH3 CH
OH
CH 2
C O
CH3
CH3 C CH 3
CH3
Ca H
C O
CH3
H2O
CH3
C OH
a CH2
C O
CH3
CH3 C CH 3
H Ca H C O H
CH3
H2O
CH3
C OH
a CH2
C O
CH3 C H
H Ca H C O CH3
CH3
CH O
a CH2
C O
CH3
H2O
CH3
CH OH
a CH2
C O
CH3
18
H2
Ni to
CH2
OH
Ru I
Ru II
- Lu nu dng LiAlH4:
O C R R'
H
O R R' C H
OH
H3O+
R R'
C H
H2/Ni
to
CH3 CH CH C O H
CH3
CH2
CH2
CH2 OH
1) LiAlH4 2) H3O+
CH3
CH
CH
CH2 OH
19
- LiAlH4 l cht kh rt mnh (kh c axit, este thnh ru I) NaBH4 kh yu hn v chn lc hn (ch kh andehit, xeton). 12. Phn ng oxi ha: - Xeton xem nh khng b oxi ha. iu kin oxi ha mnh lit b ct t cho hn hp axit khng c gi tr tng hp.
CH 3 CH2 CH2 CH 2 C O CH2 CH 3
KMnO4
to
- Andehit phn ng vi mt s thuc th c tnh oxi ha yu nh : Tollens, Fehling, Benedict (Cu2+), ... Ngoi ra, nhng thuc th ny cn c dng nhn bit cc ng kh.
20
phn ng
RCOOH + Ag
RCH=O
21
HO OH
OH
22
C O
OH
gc Hy Lp). Thng s dng: iso, sec, tert, neo. Cn s dng nh s theo mu t Hy Lp: a, b, g
C O
OH
CH3
C O
OH
CH3-CH2-COOH
CH3
CH
CH2
COOH
CH3-(CH2)4-COOH Axit caproic (caper d) CH3-(CH2)10-COOH Axit lauric (laurus nguyt qu) CH3-(CH2)16-COOH Axit stearic (stearin m ng vt)
H H
OH
Axit cis-9-octadecenoic
O
HO
Axit cis,cis-9,12-octadecadienoic
O
HO
Axit linolenic
HO
CH3
C O
C O
COOH
CH3
C O
CH2 COOH
COOH
COOH OH
CH3
Axit o,m,p-toluic
Axit salicilic
COOH COOH
COOH
COOH
COOH
COOH
Axit phtalic
Axit isophtalic
Axit terephtalic
HOOC-(CH2)3-COOH
HOOC-(CH2)4-COOH
COOH
HOOC
COOH
HOOC
Axit maleic
Axit fumaric
COOH
COOH
CH3 CH OH COOH
OH OH COOH
HOOC
CH2
C OH
CH2
COOH
Axit citric
2. Tn quc t:
Axit + Tn mch hidrocarbon + oic (khng cn STT)
HC C COOH
CH3 HC CH COOH
Axit propinoic
Axit 2-butenoic
Axit 3-etyl-6-metyloctandioic
a chc:
CH2 COOH HOOC CH2 CH2 CH CH2 CH2 CH2 COOH
Axit 4-carboximetyloctandioic
Axit 2-hidroxipropan-1,2,3-tricarboxylic
Axit pentan-1,3,5-tricarboxylic
Br
Axit 3-brombenzencarboxylic
Axit benzen-1,2-dicarboxylic
COOH COOH
COOH
Axit xiclohexan-1,2-dicarboxylic
Axit 1-xiclopentencarboxylic
3. Tn este, mui: Tn este: tn gc axit b ic thm at + tn gc ankyl (p dng vi c tn thng thng v tn quc t) carboxylat ankyl.
CH3 C O O CH2 CH2 CH CH3 CH3
Benzoat natri
axit thm u l cht rn. To lin kt hidro lin phn t nn c nhit si, nhit nng chy cao hn cc nhm chc hu c khc c cng s C. To lin kt hidro vi H2O nn tan tt trong nc.
O R C O H O H O C R
KMnO4 to
R C C R'
RCOOH
RCOOH
COOH
KMnO4 to
CH3COOH
b. T ru I, andehit:
R-CH2-OH R-CH=O
[O]
RCOOH
Cl
H 2O
RCOOH + HCl
C O
N
H 2O
H+
2RCOOH
+ H+ + 2H2O H 2O
C O
NH2 + H+ +
C O
OR'
NaOH
to
RCOONa + ROH
H+
RCOOH
C O
OR'
H+
to
RCOOH
+ ROH
3. T tc cht Grignard:
- + R MgX
+O
C O
C O
OMgX
H+ H2O
C O
OH
RMgX
1) CO2 2) H3O+
RCOOH
Axit (+1C)
RMgX
1) HCHO 2) H3O+
R-CH2OH
[O]
RCOOH
4. Tng hp malonic:
pka 17-19
H C O a C
R
NaNH2 -Ha
C O
C O
a C
pka 13
H EtO C O C H C O OEt
EtOOC
EtOOC
NaOEt EtOH
CH EtOOC
X
EtOOC
CH
COOH
H3O+ to
CH COOH
-CO2
R-CH2-COOH
EtOOC CH EtOOC R
EtOOC
EtOOC
NaOEt EtOH
EtOOC
X
EtOOC
C R
H3O+ to
COOH R C R COOH
-CO2
CH R
COOH
EtOOC CH EtOOC R
EtOOC
EtOOC
NaOEt EtOH
EtOOC
R'
X
EtOOC
C R'
COOH
H3O+ to
C R' COOH
-CO2
CH R'
COOH
- O
Tuy cng cha nhm C=O nhng axit carboxylic li khng cho phn ng cng thn hch nh carbonyl (phn ng vi CN-, NaHSO3, NH3, )
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1. Tnh axit:
R C O O H
H+ +
C O
C O
ka ca axit carboxylic khong 10-5 (pka5). Tnh axit mnh hn phenol, ancol nhng yu hn cc axit v c mnh nh: HCl, H2SO4,
R-COOH > HOH > ROH > RC CH > R-H
Nhng nhm rt in t lm tng tnh axit, nhng nhm y in t lm gim tnh axit. i vi axit thm nhng nhm rt in t v tr orto, para lm tng tnh axit, ngc li nhng nhm cho in t v tr ny lm gim tnh axit.
Axit carboxylic th hin tnh axit qua cc phn ng : + Phn ng vi kim loi: Na, Zn, + Phn ng vi oxit kim loi: CaO, + Phn ng vi baz: NaOH, NH3, + Phn ng vi mui ca axit yu: CaCO3,
11
OH
PCl5
C O
Cl
POCl3 + HCl
+ SOCl2
C O
Cl
SO2
HCl
b. Anhidric axit:
2R C O OH
P2O5 - H 2O
C O
C O
c. Amid:
RCOOH + NH3 to RCOONH4
RCOONH4
RCONH2 + H2O
d. Nitril:
R C O NH2
P2O5
12
3. Phn ng th Ha (Hell-Vohhard-Zelinsky):
R CH2 COOH
+ Br2
CH Br
COOH
+ HBr
NH3 ng dng
CH NH2
COOH
CH Br
COOH
a-amino acid
OH
CH OH
COOH
a-hidroxi acid
4. Phn ng kh:
RCOOH LiAlH4 RCH2OH
13
NH2
NH
R'
N R''
R'
Amin I
Amin II
Amin III
p-Phenylendiamin
CH3
o-Anisidin
m-Toludin
Piridin
Piperidin
2. Tn quc t: a. Amin I:
Cch 2: Ankylamin (tn gc hidrocarbon + amin) ch thch hp cho cng thc n gin
CH3
CH3-CH2-NH2
NH2
CH NH2
Etylamin
Xiclohexylamin
1-Metylbutylamin
CH3-CH2-NH2
NH2
CH NH2
Etanamin
Xiclohexanamin
2-Pentanamin
NH2
NH2-(CH2)6-NH2
H2N
NH2
1,2-Propandiamin
1,6-Hexandiamin
1,2,4-Benzentriamin
Diphenylamin
Dietylmetylamin
N-Etyl-N-metylbutanamin
N-(2-cloetyl)propanamin (2-cloetylpropylamin)
N CH3
N-Metylanilin
N,N-Dimetylanilin
2-Metylaminoetanol
Axit 4-aminobenzoic
4-Amino-2-butanon
e. Mui amoni:
CH3 CH3 CH2 N CH3 OH CH3 CH2 CH3
Etyldimetylpropylamonium hidroxit
II. Tnh cht vt l: Phn cc hn ankan nhng km hn ancol, axit. Tr amin III, amin I, II c kh nng to lin kt hidro lin phn t. Nhit si, nng chy cao hn cc nhm chc khc nhng thp hn ancol, axit. Gia cc ng phn amin I c im si cao nht, amin III c im si thp nht. Mi kh chu: c, nc tiu (ging m phn hy).
NH3, to
RNH2 + NH4X
X + RNH2
R2NH2X
NH3, to
R2NH + NH4X
X + R2NH
R3NHX
NH3, to
R3N
+ NH4X
X + R3N
R4NX
Rt kh dng phn ng u v cng v sau N cng c hot tnh cao hn hp sn phm. Mun thu c sn phm n ankyl ha phi dng d NH3. V d:
CH3(CH2)6CH2Br + (2)NH3 I (45%) + II (43%) + III,IV(t) PhNHCH2Ph (85-87%)
(4)PhNH2 + (1)PhCH2Cl
Aryl halogenua phn ng kh khn, phi thc hin phn ng nhit cao, p sut cao.
C6H5Cl + 2NH3 340oC 340atm C6H5NH2 + NH4Cl
C2H5OH + C2H5NH2
(C2H5)2NH + NH4Cl
2. T nitro:
NH2
Fe/HCl
H2O
LiAlH4 H2/Ni
R-CH2-NH2
C O
NH2
LiAlH4
R-CH2-NH2
H2NR -H2O
H2/Ni
CH
NH R
Imin
4. Phn ng Gabriel:
O C N C O H
O C
O C
KOH C2H5OH
N C O
X
C O
phtalimit
Kali phtalimit
O
H3O+
OH
+
C O OH
RNH2
IV. Tnh cht ha hc: 1. Tnh baz: N ca amin c i in t t do Xt v tnh baz: III > II > I > amin thm Amin phn ng vi axit cho ra mui v c cho mui ha tan trong nc. Ngi ta li dng iu ny tch amin ra khi nhng hp cht trung ha khc.
RNH2
+ HCl
RNH3Cl
Axit carboxylic:
R C O
R C O OH
OH
+ 2RNH2
to
C O
NHR' + H2O
+ 2R2NH
to
C O
NR'2
+ H2O
Clorua axit :
R C O R C O Cl
+ 2RNH2
R
Cl
+ 2NH3
C O
C O
NH2
+ NH4Cl
NHR'
R'NH3Cl
C O
Cl + 2R2NH
C O
NR'2
R'2NH2Cl
Anhidric axit:
(CH3CO)2O + RNH2
CH3 C O NHR
+ CH3COOH
Sn phm ca phn ng ancyl ha - amid thng c dng bo v nhm amin. Anilin khng th phn ng trc tip trong cc phn ng th thn in t (tr phn ng halogen ha) m phi bo v nhm amino trc ri mi tin hnh phn ng, sau kh nhm bo v tr li nhm amino.
NH2
NH3 NO3
NH2
NH3 HSO4
HNO3 H2SO4
SO3 H2SO4
Anilinium nitrat
Anilinium hidrosunfat
NH2
AlCl3
NH2AlCl3
tnh baz rt yu
NH
C O
CH3
Ankyl/ancyl ha Fridel-Crafts
NH2
NHCOCH3
NHCOCH3
(CH3CO)2O - CH3COOH
HNO3 H2SO4
NH2
NO2
H3O+ - CH3COOH
NO2
HNO2 rt km bn nhit thng nn phi to ra bng cch cho mui (NaNO2, KNO2) phn ng vi axit mnh (HCl, H2SO4, o HNO3) nhit thp 0-5 C.
O N O
H+ o 0-5 C
H+
O H
-H2O
ion nitronium
10
Amin no bc I:
RNH2 + HNO2 ROH + N2 + H2O
NO
p-Nitro-N,N-dimetylanilin
11
Amin thm bc I:
H
N O
ArNH 2
ArNH
H+
ArN
- H+
ArN
-H2O
ArN
O H
H+
ArN
OH
NH2
N Cl
NaNO2/HCl 0-5 C
o
Diazonium clorua
NCl
H2O
I
N2 +
HCl
KI
Cl
N2
CuCl
+
Br
N2
CuBr
N2
12
CN
CuCN
N2
H3O+
COOH
H3PO2
N2
V d: iu ch 1,3-Dibrombenzen t benzen
Br
Br2 FeBr3 HNO3 H2SO4
NO2 Br
Br
Fe/HCl
NH2
Br
Br
Br
Br2 FeBr3
Br NH2
NaNO2/HCl o 0-5 C
Br N NCl
H3PO2
Br
13