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
Y

RY

RY

X : I , Cl , Br , OH , OR , OSO 2Ar
Y- : OH- , RO- , RCOO- , I- , H2O , ROH, NR3

1. PHN NG TH
2
SC
N :
ch lng phn t, mt giai on i qua trng thi chuyn tip
Y

ttct

V d:
HO

Y..... .....X

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 S N2

cn hot ho nhm OH hoc OR
V d:
CH3OH + HI

CH3OH2 + I

SN2

nhanh

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
H3C NH2 + H3C - Br

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

H
H3C N CH3 + Br
H

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 :

chm

-C-X

-C

-C
nhanh

-C-Y

V d:
Me3C - Br

Me3C

chm

+ OH

nhanh

Me3C +

Br

Me3C - OH

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

+ H+

Me3C - OH

Me3C - OH

Me3C OH2
nhanh

+ Cl

Me3C

ZnCl2

chm

Me3C O

Me3C

Cl

OH2

Me3C - Cl

ZnCl2

chm

Me3C + Zn(OH)Cl2

H
Me3C

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

Cl

HCl

O
C
S

Cl
ankyl closunfit
(2)

O
C

Cl

SO2

S=O
Cl
ttct vong

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:

Tt mch:

XX
.
X + RH
.
R + XX
.
.
R + R
.
.
X + X
.
.
R + X

.
2X

.
R

HX
.
RX + X
+

(*)

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

H C

C X

YH

ttct
Trong

X: Cl, Br, I, +NR3 , OSO2Ar

Y- : OH- , RO- , NR3

V d:

C2H5

H
+

H C
H3C

Br
C H
H

H
C2 H 5

H C
H3 C

Br
C H
H
C2H5 OH
Br

H
C

H3C

C
H

C=C

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

H C

cham

nhanh

H C

X: Cl, Br, OSO2Ar, OH2

V d:

(CH3)3C

(CH3)2C

Br

cham

CH3 nhanh

(CH3)3C

(CH3)2C

Br

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
0

H3C

CH2 CH2 O C

CH3

300

H3C

CH CH2 + COS

HS

CH3

S
ankyl xantogenat

CH3
H3C

CH2 CH2 N

CH3
Oxit amin bac

0
150 c

H3C

CH CH2

(CH3)2N OH

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

C

H
S

O
S

CH3

R
N
O

ttct vong

O
S

COS + CH3SH

SCH3

C
C

O
O

ttct vong
C C

O C

R
H

N
O
ttct vong

R
O

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:

X
C=C

X X cham

X
C

nhanh

Y X
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 (AlCl 3 , 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

H2 O

CH3 CH CH3

OSO3H

OH

+ Ankin: Cng nc to hp cht cacbonyl nh xc tc

HgSO4 hoc cc mui Ag+ , Cu2+
2+ +

HC

CH

Hg , H
0
80 c

CH3CHO

R C CH

2+ +

Hg , H
0

80 c

R C CH3
O

H2SO4

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
C C O

X Y

cham

Y
C O

nhanh

Y
C O

Y
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

OH

OR

nhanh
_H

+ Xc tc baz hot ho tc nhn

ROH

C O

RO

OH

cham

RO

OR
C

H2O

ROH
nhanh

OR
C

OH

RO

OH

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
O

cham

R C

nhanh

X:-Cl, -OCOR, -OR1, -NH2

Y: HO-, RO-, H2O, ROH, R3N

R C Y
O

- C ch SN2 (CO) trong mi trng axit

R C

R C

X hoac R C

OH

Y
R C OH
X

cham

XH hoac R C OH

R C OH
X

Y
nhanh
-X

R C OH

-H

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

Ar

- C ch hai giai on n phn t: tng t c ch

SN1 dy no
cham

Ar H

Ar + H
cacbanion

Ar

nhanh

- C ch hai giai on lng phn t:

Ar H

cham

H
Ar E

nhanh

Ar E

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

+Y

Y
+

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:

OC2H5

Cl

N
O

b. C ch SN1 Ar:
Phn ng ny ch xy ra hp cht diazoni thm
Phn ng 2 giai on, n phn t
+

chm

Ar N N
+

Ar

nhanh

Ar

N2

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 Cl + NaOH

C6H5 OH + NaCl

c im: phn ng xy ra qua 2 bc

- Tch HX
- Cng HY
Sn phm trung gian l arin

X
R

R
+HX
cng

tch
HX
arin

- X b tch cng vi H v tr ortho no linh ng hn

- Y cng vo cacbon no ngho mt electron hn