BI TP C CH PHN NG

Bi tp s 1: Cho s :
CH3

CH3
CH
Cl2, Fe

, askt
B Cl2
C

NaOH

Cumen(A)

NaOH
t0, p

Cc chui phn ng u din ra theo t l mol 1:1, cc cht ghi trn s

u l sn phm chnh. Vit cc phng trnh phn ng v cho bit
c ch cc phn ng t A B, B C. Gii thch s to thnh sn phm
chnh ca 2 phn ng ny.
Bi tp s 2:

a. Cho s sau :

Hexin-3

HCl
C6H12Cl2
xt , t0

Vit c ch phn ng v cu trc ca sn phm to thnh.

b. Butin-2

Br2 , 1:1

Xc nh cu trc ca A v gi tn.
Bi tp s 3: Vit cng thc cc ng phn lp th khng i quang
( ng phn lp th i-a ) ca 2-clo-1,3-imetylxiclohexan v cho bit
cu trc sn phm to thnh khi cho cc ng phn tc dng vi
CH3ONa.
Bi tp s 4: Hon thnh cc chui phn ng sau:
a. CH3I
+ (CH3)2CHOb. CH3O+ (CH3)2CHI
c. (CH3)3CCH2I
+ C2H5Od. (CH3)3Br
+ CH3O-

Cl

e.
f.
g.

CH2Br
CH2O-

+ (CH3)3CO+ (CH3)2CHCH2O+ (CH3)2CHCH2Br

Bi tp s 5: Hon thnh cc phn ng sau:

CH3
C

CH3

a.

H2O

CH2Br

SN1, E1

CH3
CH3
CH3

CH2

CH2

b.

CH3

H2O
SN1, E1

Br
CH3
CH3

c.

CH

CH3

H2O
SN1, E1

CH3 Cl

CH2
CH

CH2

CH2Br

CH2

d.

H2O
SN1, E1

Bi tp s 6: Hy cho bit sn phm to thnh khi thc hin phn ng

hirat ho cc cht sau vi xc tc axit H+. Trnh by c ch phn ng.
a. propan-1,2-iol.
b. 2-metylpropan-1,2-iol.
c. 2-metylbutan-2,3-iol.
Bi tp s 7:
a. Vit phng trnh phn ng khi cho alyl clorua, benzyl clorua tc dng
vi dung dch KOH un nng.
b. Hp cht hu c X c cu to khng vng c cng thc C 4H7Cl v c cu
hnh E. Cho X tc dng vi dung dch NaOH trong iu kin un nng
thu c hn hp sn phm bn c cng thc C4H8O.
Hy cho bit cu trc ca X v cu hnh ca sn phm to thnh.
Bi s 8 : Vit cc phng trnh phn ng theo t l s mol 1:1 ca cc
cht sau y vi dung dch Br 2 trong CCl4. Gii thch s nh hng phn
ng :
a, CH2= CH- CH2- C

CH

b, CH2= CH- C

CH

c, (CH3)2C= CH- CH2- CH= CH2

d, CH3- CH= CH- CH2- CH= CHBr

Bi s 9 : Khi cho iso-butilen vo dung dch HCl c ha tan NaCl, CH 3OH c

th to ra nhng hp cht g ? Gii thch.
Bi s10 : Vit sn phm v gii thch c ch phn ng ca etilen vi :
a, Br2 trong CCl4

b, Br2 trong H2O

c, Br2 trong nc c pha

NaCl

Bi gii mu
Bi tp s 1:
CH3

CH3

CH3

CH3
CH

CH
0

Cl2

Fe, t

H Cl

(B)
Cl

CH3

CH3

CH3

CH3
Cl

CH
+

Cl2

askt
(C)

+ HCl

Cl

Cl

CH3

CH3

CH3
C

CH3
C

Cl
+

NaOH

OH
+ NaCl

(D)
Cl

:Cl

Nguyn t Cl lin kt trc tip vi vng benzen kh b thu phn do c s

gii to electron ca Cl vo vng benzen nh hiu ng +C.
CH3

CH3

CH3
C

CH3
C

OH

OH

+
:Cl

NaOH

t ,p
(D)
OH

NaCl

 C ch phn ng t A B
Phn ng theo c ch electrophin vo nhn thm SEAR.
3 Cl2

t0

+ 2 Fe

FeCl3 + Cl2
CH3

2 FeCl
_3
+

Cl ... FeCl4
CH3

CH3
CH

CH3
CH

+
Cl ... FeCl4

+
H

FeCl4

Cl
Phc

CH3

CH3

CH3

CH

CH3
CH

Cl

Cl

Phc
H

FeCl4

FeCl3

HCl

Do gc (CH3)2CH- c hiu ng +I l nhm th loi I nn nh hng

phn ng th tip theo vo v tr ortho v para. Nn giai on to
phc c th c hai phc sau :
CH3

CH3

CH3
CH

CH
+
H

CH3

(I)

Cl
H

(II)

Cl

Do gc (CH3)2CH- c s n ng v khng gian nn dn n Cl + kh tn

cng vo v tr ortho nn phn nc (II) kh hnh thnh hn. Cho sn
phm chnh l :

CH3

CH3
CH

Cl

C ch phn ng B C
Phn ng th theo c ch gc SR, gm cc giai on :
- Khi mo phn ng :

as

Cl2

2 Cl

- Pht trin mch :

CH3

CH3

CH3
CH
+

Cl

.
C

.
C

HCl

Cl

Cl

Cl
CH3

CH3

CH3

CH3

CH3
C

+ Cl2

Cl
.

Cl

Cl

C nh vy
- Ngt mch
.
.
Cl + Cl
.
.
R + Cl
.
.
R + R

.
V i gc t do R : Cl

Cl2
R
R

Cl
R

CH3
C.
CH3

Trong giai on pht trin mch c th sinh ra cc gc sau :

CH3

.
C

.
CH2

CH3

CH3

CH
(II)

(I)
Cl

Cl

Gc (I) bn hn do c hiu ng +C ca vng benzen v hiu ng +H. Gc

(II) km bn hn do ch c hiu ng +H.
Nn sn phm chnh l :
CH3

CH3
C

Cl

Cl

Bi tp s 2:
Cl
CH3

CH2

CH2

CH3 + 2 HCl

CH3CH2 CH2

CH2CH3

Cl

C ch :
CH3

CH2

CH2

CH3 HCl

CH3

CH2

CH2

CH3

H
Cl

HCl

Cl

CH3

CH3

CH3

CH2

CH2

CH2

H
H

Cl

Cl

Cl

Cl

CH2

CH3

CH2

CH3

CH2

CH3

b.Phn ng tun theo quy tc Maccopnhicop v theo hng cng hp trans.

Br
2 CH3

CH3

+ Br2

1:1
CH3
cng trans

CH3

Br
trans - (hay E-)2,3 -
ibrom-2-buten
Br
Br
CH3

CH3

Br

Br

CH3

CH3 Br

CH3

CH3

Br

Bi tp s 3:
CH3

Cl

CH3
CH3

CH3

CH3

Cl

Cl

H
H

(III)

H3C

CH3

CH3

CH3

H3C

Cl

Cl

C 2 H C
bn cnh
u
tch ra

CH3

(II)

(I)

H3C

Cl

CH3

CH3

Cl

Khng tch c vH
C bn cnh khng
ng
ph
ng v
u vtrcis
i
v i clo

Chc 1 H l tch c

CH3

CH3

1,3-
imetylxiclohexen
CH3

CH3

1,3-
imetylxiclohexen

Quy tc Barton Hassel : Phn ng tch nucleofin vng no ch chy

tt khi cc nhm th c tch ra v tr axial trans.
Bi tp s 4:
a. CH3I + (CH3)2CHOb. CH3O- + (CH3)2CHI
c.

CH3
I-

CH3

CH3OH + I- +

CH OCH3
CH2

CH

CH3

CH3
CH3

CH3
CH2I

CH3 C

OC2H5 + I -

CH2

CH3 C

+ C2H5O-

CH2

CH3

CH3

(Ph)

+ C2H5OH + I

C
CH2

CH3

Kh vvng ny nh km bn

d. (CH3)3CBr + CH3O-

CH2 = C (CH3)2 + CH3OH + Br-

e.

Cl
+ (CH3)3CO-

f.

+ (CH3)3COH + Cl-

CH2Br

CH2OCH2CH(CH3)2

+ (CH3)2CHCH2O-

g.

+ BrCH2CH2CH(CH3)2

CH2O-

+ Br-

+ (CH3)2CHCH2Br
CH2

CH3

CH3

CH2OH

+ Br-

Bi tp s 5:
a.
CH3

CH3
CH3

CH2Br

CH3

H2O
SN1, E1

CH3

CH2

CH3

CH3

CH2

CH3

CH3

OH
CH3
CH3

C
CH3

CH2

CH2

CH3

CH

CH3 + CH2

CH3

CH3
CH3

C
CH3

C
CH3

CH2

CH3

CH3

CH3
2 CH3

CH2

OH
CH2

CH2 CH3

CH3CH2
H2O

CH3

CH

CH3

SN1, E1

CH2 CH3

C
CH3

Br
CH3

CH2

b.

CH2

CH2 CH3

c
CH3
3 CH3

CH3

CH

CH3

H2O

CH3

SN1, E1

CH3 Cl

CH3
CH3

CH3

Chuyn v

CH3

CH3

CH

CH3

CH

CH3

CH3

CH3

CH3 CH3
sn phm
chnh

CH3

OH

CH3

CH3

CH3

d.
CH2
CH

CH2

CH2Br

CH2

CH2

SN1, E1

CH2

CH2

CH2

CH2

Chuyn v
hi
rua

CH2

CH3

CH2

CH

CH3

M vng

CH2

CH2

Bi tp s 6:
a)
CH3 CH
OH

CH2 H
OH

CH3

CH2

CH2

CH3

CH2
CH

OH
CH2

CH2

CH3

CH2
CH2
C

CH2

OH
C

CH2

CH2

CH2

CH2

CH

CH2

H
C

CH2

CH2

H2O

CHO + H2O

CH3

CH

CH2

OH

OH

CH3

Chuyn v

CH3

CH

CH

.CH2

OH

OH2

CH2

CH3

-H

CH3

CH

CH3

-H2O

CH2

OH
CH3

CH2

OHC

CH

OH
CH3

C ch :

Chuyn v
hi
rua

CH

CH2

OH

OH

CH2

CH3

b.CH3

CH H

CH2

OH OH

H
-H2O

-H2O

OH

OH2

OH

CH3

.CH2

CH3

CH

CH2
OH

CH3CH2 CHO
CH3

CH3

CH

C CH2CH3

CHO + CH3

(cchtr
nh by t ng t c
u a.)
CH3

CH3
c. CH3

CH

CH3

H
-H2O

CH3

CH

CH3 +CH3

O CH3
(cchtr
nh by t ng t c
u a.)

OH OH

C CHO
CH3

Cn lu : Trong trng hp mt nguyn t cacbon COH c hai

nhm th khc nhau th nhm no c tnh cht y electron mnh
hn s b chuyn dch.
Bi tp s 7:
a. CH2

CH

CH2Cl + KOH

CH2

CH

CH2OH + KCl

CH2OH

CH2Cl
+

KOH

b. Vi cu hnh E, C4H7Cl c 3 cu trc sau :

KCl

CH3

CH3
C

..
Cl

C2H5
C

CH3
C

..
Cl

H
CH2Cl

H
III

II

I
C4H7Cl

C4H8O :

t0

C4H7OH

I v II rt kh thu phn do s lin hp gia cp electron khng lin kt

ca Cl v ni i. Tho mn iu kin trn l III.
CH3

H
C

- Cl

(-)

CH3

H
C

CH2Cl

chuy
n v

CH3

CH

CH

CH2

CH2

H
OH
CH3

OH

(-)

CH3

H
C

*
CH

(-)

CH

CH2

OH

C
CH2OH

(Bi
n thra xemic)

(Dng E)

Bi tp s 8
a, CH2= CH- CH2- C

CH + Br2

CH2Br- CHBr- C

CH

Kh nng phn ng cng electrophin ca lin kt i (C sp ) cao hn lin

2

kt ba (Csp) do m in Csp > Csp nn kh nng gi eletron ca Csp

bn hn.
1,4
1

+Br2

CH2 = CH - C = CH

3,4

1,2

b,

CH2Br-CH=C = CHBr
CH2=CH-CBr = CHBr

CH2Br-CHBr-C = CH

C 3 sn phm cng : cng 1,4 ; cng1,2 ; cng 3,4 do c s lin hp

gia cc lin kt ca lin kt i v lin kt ba.
6

c, (CH3)2C = CH - CH2- CH = CH2 + Br2

(CH3)2CBr- CHBr - CH2 -CH = CH2

Do C5 c hai nhm CH3 y electron v pha lin kt i nn mt

electron lin kt C5 = C4 cao hn lin kt C2 = C1 nn kh nng phn ng
electrophin ca C5 = C4
6

d, CH3-CH = CH - CH2 -CH = CHBr + Br2

CH3CHBr - CHBr - CH2 - CH = CH2

Kh nng cng AE ca lin kt C5 = C4 cao hn lin kt C2 = C1 do C5 = C4

c
nhm CH3 y electron lm tng mt electron, cn C2 = C1 c Br ht
electron
lm gim mt electron.
Bi tp s 9
Sn phm phn ng l hn hp gm :
;

CH3
CH3 - C - CH3
OH

CH3
CH3 - C- O-CH3
CH3

CH3 - CBr - CH3

CH3
CH3 - CCl - CH3
OH

Gii thch da vo c ch phn ng

-Trong dung dch c cc qu trnh phn li :
HBr

H+ + Br-

NaCl

Na+ + Cl-

-Do trong dung dch c 4 tc nhn l Br-, Cl-, H2O v CH3OH c

kh nng kt hp vi cacbocation. Phn ng theo c ch cng
electrophin (AE).
-Trc ht tc nhn electrophin(H +) tn cng vo C- to
cacbocation (giai on chm) :
CH3

+ -

CH3

CH2

+ chm

CH3 - C - CH3
CH3

-Sau l qu trnh kt hp cacbocation vi cc tc nhn Br -, Cl-,

H2O v CH3OH to thnh sn phm (giai on nhanh) :

CH3
CH3 - C (+)

Br-

CH3
CH3 - C - Br

nhanh

OH

CH3

CH3
CH3 - C (+)

Cl-

CH3
CH3 - C - Cl

nhanh

OH

CH3

CH3
CH3 - C (+)

HOH

nhanh

OH

CH3
CH3 - C - OH

H+

CH3

CH3

CH3

nhanh CH - C - O - CH
3
3

CH3 - C (+) + CH3OH

H+

CH3

OH

Bi tp s 10
H
H

C =C

H
H

CCl4
+ Br2(dd)

Br

H-C-C-H
Br H

C ch :
Giai on chm (quyt nh tc phn ng) to ra

cacbocation.

CH2 = CH2 + Br

Br

CH2 - CH2 - Br

Giai on nhanh :
Br

CH2 - CH2 - Br + Br-

CH2 - CH2
Br

b, Trong dung mi nc c sn phm Br-CH2-CH2-OH (etilenbromhirin) theo c ch

HBr + HOBr {H+, Br-, HOBr}

phn ng : Br2 + H2O

+

CH2=CH2 + Br - OH

Br

Br

CH2-CH2 + OH -

CH2-CH2
OH

Br

CH2-CH2

Br
CH2 - CH2
Br

+ Br -

Ngoi ra c th c :
c, Tng t nh b, nhng cn c :
+

Br

Br

CH2-CH2

+ Cl-

CH2-CH2
Cl

Khng to ra 1,2 - icloetan do khng c tc nhn Cl +

Nh vy : Mun cho phn ng ch to ra BrCH2-CH2Br phi tin hnh phn ng trong
dung mi tr ( v d : CCl4)