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C CH TRONG PHN NG HA HC HU C PHN NG TH PHN NG CNG

PHN NG TCH

C CH PHN NG TH NUCLEOPHIN:
S phn ng

RY

RY

X : I , Cl , Br , OH , OR , OSO2Ar Y- : OH- , RO- , RCOO- , I- , H2O , ROH, NR3

1. PHN NG TH SN2:
C ch lng phn t, mt giai on i qua trng thi chuyn tip
-

Y
V d:
HO

Y..... .....X ttct

+ CH3 Br

+ HO...CH3...Br

HO CH3

Br

S trn p dng trc tip cho trng hp X l halogen.

Khi X= OH hoc OR trc khi thc hin phn ng SN2 cn hot ho nhm OH hoc OR
V d: CH3OH + HI SN2 nhanh

CH3OH2 + I

CH3OH2 + I

+ I- - -CH2- - -OH2

I - CH3

H2O

Khi tc nhn nucleophin trung ha in ( R3N, ROH ) cp electron t do l tc nhn nucleophin


H H + H3C N - - - C - - - Br H H H H H3C N CH3 + Br H

H3C NH2 + H3C - Br

2. PHN NG TH SN1:
Phn ng n phn t, hai giai on to ra sn phm trung gian l cacbocation R+ giai on chm quyt nh tc phn ng
S : -C-X chm -C nhanh

-C V d:

-C-Y

Me3C - Br

chm

Me3C +

Br

Me3C

+ OH

nhanh

Me3C - OH

Khi X l OH hoc OR cn hot ho bng H+ hoc ZnCl2


+ H+ chm

Me3C - OH

Me3C OH2 nhanh

Me3C

OH2

Me3C

+ Cl

Me3C - Cl
chm

Me3C - OH

ZnCl2

Me3C O

ZnCl2

Me3C + Zn(OH)Cl2

H Me3C + Cl nhanh Me3C - Cl

3. PHN NG TH SNi:
Phn ng th SNi xy ra khi cho ancol tc dng vi SOCl2, PBr3, PBr5,Phn ng c bc 2, nhiu giai on, hnh thnh trng thi chuyn tip vng
C OH Cl
+

S=O

O C S Cl ankyl closunfit (2) O

Cl

HCl

O C Cl
+

SO2

C Cl ttct vong

S=O

V tc nhn Y- ( Cl- ) v trung tm phn ng C+ cng thuc mt phn t ankylclosunfit nn ngi ta gi l c ch SNi

4. PHN NG TH THEO C CH GC T DO (SR):


S phn ng theo c ch gc t do: R -H + X -Y RX + HY X - Y : Hal2 , SO2Cl2 , R3C- O- Cl , CCl3Br, CF3I, Phn ng xy ra c chiu sng hoc c cht khi mu c im: phn ng dy chuyn to ra sn phm trung gian l gc cacbo t do R. . C 3 bc chnh V d: phn ng halogen ho Bc khi mu: Bc pht trin: XX . X + RH . R + XX . . R + R . . X + X . . R + X

. 2X . R HX . RX + X

(*)

Tt mch:

R-R

X2
R-X

Bc quyt nh to thnh sn phm l bc pht trin mch, trong (*) l giai on chm

PHN NG TCH
1. PHN NG TCH E2:
Phn ng E2 l phn ng lng phn t, mt giai on, to thnh trng thi chuyn tip tng t SN2 v thng xy ra song song vi SN2

H C C X

H C C X ttct

YH

C=C

Trong

X: Cl, Br, I, +NR3 , OSO2Ar Y- : OH- , RO- , NR3


Br H C C H H H3C H Br H C C H H H3C C2H5 OH Br H

V d:

C2H5

C2H5

H C C H3C

H H

2. PHN NG TCH E2:


Tng t SN1, E1 l phn ng 2 giai on to sn phm trung gian l R+
S c ch:

H C C X

cham

H C C

H C C

nhanh

C C

X: Cl, Br, OSO2Ar, OH2

V d:

(CH3)3C

Br

cham

(CH3)3C

Br

(CH3)2C

CH3

nhanh

(CH3)2C

CH2

3. PHN NG TCH Ei:


C ch Ei gp trong cc phn ng nhit phn alkyl axetat (to ra anken v CH3COOH) ; ankyl xantogenat (to ra anken v CH3SH, COS) ; oxit amin bc 3 (to ra anken v hydroxyl amin th). 0 500 c H3C CH2 CH2 O C CH3 H3C CH CH2 + CH3COOH O Ankyl axetat
H3C CH2 CH2 O C S ankyl xantogenat S CH3
0 300 c

H3C

CH CH2 + COS

HS

CH3

CH3 H3C CH2 CH2 N CH3 Oxit amin bac


3

0 150 c

H3C

CH CH2

(CH3)2N OH

Phn ng mt giai on i qua trng thi chuyn tip vng:


C C H O C R O H O ttct vong
C C H S C S CH3 O H S ttct vong O S C C O H S C O SCH3 COS + CH3SH

C O O R
C C

H O C

O R

C C H O C R N R H O

C R N R ttct vong H O N R R C C

PHN NG CNG ELECTROPHIN (AE)


Phn ng qua nhiu giai on trong giai on tn cng ca tc nhn electrophin to cacbocation R+ l giai on chm quyt nh tc phn ng S c ch:
C=C
+

X X X cham C C
+

X C C
+

Y X Y nhanh C C

X-Y : Hal-Hal, Hal-Hal, , H-Hal , Hal-OH , H2SO4 , H2O

Trong mt s trng hp cacbocation tn ti di dng vng 3 cnh


C=C Br Br Br C C
+

Br

Ion bomoni C ch cng AE vo ni ba tng t c ch AE vo ni i

Mt s phn ng AE ca Anken v ankin:


- Phn ng cng halogen: phn ng xy ra trong iu kin khng chiu sng, c mt cht xc tc l axit Lewis (AlCl3 , FeCl3 ) hoc ch cn c dung mi phn cc nhit phng. Tin trnh lp th rt c th l cng trans + Flo : phn ng qu mnh lit, thng xy ra phn ng hy nn rt t dng. + Clo : c th cng vo ni i, cng c th gy phn ng hy nht l khi c tia la in hoc chiu sng.

+ Brom : phn ng vo ni i mt cch m du v thun tin nht.


+ Iod : rt km hot ng, phn ng chm v thun nghch

- Phn ng cng hidro halogenua HX:


+ Phn ng thng bt u bng s hnh thnh phc + Tnh c th lp th khng cao. Tuy nhin nhiu phn ng xy ra theo kiu cng trans + Kh nng phn ng: tng theo lc acid
HF < HCl < HBr < HI

- Phn ng cng nc:


+ Anken: cng trc tip (xt H+) hoc gin tip nh H2SO4
CH3 CH=CH2
+

HO

SO3H

CH3 CH CH3 OSO3H

H2O

CH3 CH CH3 OH

H2SO4

+ Ankin: Cng nc to hp cht cacbonyl nh xc tc HgSO4 hoc cc mui Ag+ , Cu2+


HC CH Hg , H
0 80 c 2+ +

CH3CHO

R C

CH

Hg , H
80 c 0

2+ +

R C O

CH3

PHN NG CNG V TH VO HP CHT CACBONYL


- Phn ng cng nucleophin vo nhm C=O ca andehyt v xeton xy ra theo s :
Y C C O
+

X Y

C OX

X-Y :H-OH, H-CN, H-SO3Na , R-Li , R-MgHal ,LiAlH4

Phn ng lng phn t, hai giai on sn phm trung gian l mt anion


Y C C O
+

cham X Y

C O

Y C O
+

Y X nhanh C OX

- Phn ng c xc tc bi axit hoc baz


+ Xc tc axit hot ho nhm C=O
C O
+

C OH
H

OH

ROH

cham

O C OH

nhanh _H

OR C OH

+ Xc tc baz hot ho tc nhn


ROH OH RO
+

H2O

C O

RO

cham

OR C O

ROH nhanh

OR C
+

OH

RO

PHN NG TH NHM X NI VI C=O CA AXIT V DN XUT


Phn ng 2 giai on, lng phn t

Giai on chm l giai on tn cngca tc nhn nuleophin to ra anion, giai on nhanh l tch nhm X

- C ch SN2 (CO) trong mi trng baz hay trung tnh


Y R C X O
+

cham

R C X nhanh O

R C Y O

X:-Cl, -OCOR, -OR1, -NH2 Y: HO-, RO-, H2O, ROH, R3N

- C ch SN2 (CO) trong mi trng axit

R C X O

R C X hoac R C XH hoac R C OH OH O X

Y R C OH X
+

Y nhanh -X R C OH
-H

cham

R C OH X

R C Y O

Ngoi c ch SN2 (CO) trong nhng iu kin nht nh cn c th xy ra theo c ch SN1 hoc SN2

PHN NG TH NHN THM


1. C CH PHN NG TH ELECTROPHIN: Phn ng gia hp cht thm Ar-H v tc nhn E+ to ra sn phm Ar-E v H+ c th xy ra theo 3 c ch khc nhau: - C ch mt giai on: tng t c ch SN2 dy no
E
+

Ar H

E ...... Ar ...... H

E Ar

- C ch hai giai on n phn t: tng t c ch SN1 dy no


Ar H cham Ar + H cacbanion
Ar
+

nhanh

Ar E

- C ch hai giai on lng phn t:


Ar H
+

cham

H Ar E

nhanh

Ar E

2. PHN NG TH NUCLEOPHIN:
Phn ng th nucleophin vo hp cht thm c th xy ra theo cc c ch sau:

- C ch lng phn t, hai giai on: SN2 Ar


- C ch n phn t, hai giai on: SN1 Ar - C ch arin (c ch tch cng) a. C ch SN2 Ar: Xy ra khi v tr ortho hoc para trong nhn thm c nhm th Z vi hiu ng C mnh: NO2, CN, COR

Phn ng lng phn t, 2 giai on sn phm trung gian l mt anion vng tng t phc nhng mang in tch m

X
+Y

Y
+

Z
Anion trung gian

Nhm Z c tc dng lm gim in tch m nn lm tng bn ca anion trung gian Th d: Khi Z = NO2, X = Cl, Y- = C2H5O-, anion trung gian c cu to nh sau:

Cl

OC2H5

N O O

b. C ch SN1 Ar: Phn ng ny ch xy ra hp cht diazoni thm

Phn ng 2 giai on, n phn t


Ar N N
+ +

chm nhanh

Ar

N2

Ar

Ar Y

Trong Y : H2O, ROH, I c. C ch Arin: (c ch tch cng) Phn ng xy ra trong iu kin khc nghit - Nhit cao - p sut cao - Khi nhm X khng c hot ha Th d: 3500C, 350 atm C6H5 OH + NaCl C6H5 Cl + NaOH

c im: phn ng xy ra qua 2 bc


- Tch HX - Cng HY

Sn phm trung gian l arin

X R
tch HX

R
+HX cng arin

Y R

- X b tch cng vi H v tr ortho no linh ng hn - Y cng vo cacbon no ngho mt electron hn

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