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Ti liu BDHSG

C ch phn ng hu c

C CH
1. 1.1 1.1.1 1.1.2 1.1.3 1.1.4
H3C
H3C

: CH3-CH2Cl + NaOH : CH2 = CH2 + HCl : CH3 CH2Br


KOH / ancol

CH3-CH2OH + NaCl CH3 CH2Cl CH2=CH2

CH2
C N

CH2
CH2 OH

CH2
CH3

CH3
H3C

H3C

CH

CH2
CH2

CH3
CH3

CH3 NH C
O

1.2 1.2.1 vi cc

) (hoc cng

h . as : Cl2 (k) + CH4(k) CH3Cl + HCl : (Substitute Radiccals - SR) 1: Khi mo phn ng: xy ra s phn ct ng li phn t clo to ra cc nguyn t clo (gc clo) hot ng: Cl Cl a's' Cl + Cl 2:Pht trin phn ng: cc gc clo tn cng vo lin kt C H cc phn t metan to gc metyl: CH4 + Cl CH3 + HCl CH3 + Cl2 CH3Cl + Cl 3: Kt thc phn ng: cc gc t do kt hp (ngu nhin) vi nhau thnh cc phn t Cl + Cl Cl2 CH3 + CH3 CH3 CH3 CH3 + Cl CH3Cl 1.2.2 ) vi cc baz : (CH3)3C Br + NaOH
H2O

(CH3)3C OH + NaBr
cham

1: Lin kt C Br b phn cc ha mnh do nh hng ca dung mi hoc xc tc, dn n b phn ct d li: (CH3 )3 C Br
(CH3 )3 C + HO

(CH3 )3 C

+ Br

2: Cc ion m ca dung mi hoc cht phn ng nhanh chng kt hp vi cacbocation


nhanh

(CH3 )3 C OH

2. 2.1

: : X

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG

C ch phn ng hu c

X
(1)

goc cacbo t do
+ -

cacbocation

(2)

cacbanion

(3) . 2.2 d . mang hiu ng cm ng dng +I (+Inductive: nhm c xu hng y e, do tr thnh nhm mang mt phn in tch dng) (+) (cacbocation), v nh hiu ng ny m in tch (+) c gim thiu. ( ) ( ) ) < (CH3 )3 C( ) CH3 < CH3CH( 2 < (CH3 )2 CH ,

CH3 CH2 CH( 2

CH2

CH CH( 2
)

( ( ) ) < C6H5CH( CH3 2 < (C6H5 )3 C

nhm mang mt phn in tch m)

-I (nhm c xu hng ht e, do tr thnh (-)

CH3 CH2 CH( 2


-

CH2

CH CH( 2

)
)

( ) ) < (p O2N C6H4 )3 C( C6H5CH( 2 < (C6H5 )3 C

CH3 2.3

CH3 CH2

(CH3 )2 CH (CH3 )3 C (ion) (lai ha sp2) 3 3 lai ha sp ).

120

+ C

120

(-)

cau truc phang cua cabocation

cau truc thap cua cacbanion

cau truc phang cua goc t do

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG 2.4

C ch phn ng hu c

R X

R R
-

X R

R X R R

C C

C O

R R

C C

C O

R
R
C H

H+

3. 3.1 ) + 3.1.1 phin a in tch dng) ha tr cha s dng nh: m : . .

I , OH , C2 H5O , H 2 O, C 2 H 5 O H, N H 3 , CH 3 N H 2 .... 3.1.2 hn electrophin ( a electron

: H 3O , N O 2 , SO3 , BF3 , AlCl3 ,.......

3.2
1: Khi mo phn ng: Cl Cl a's' Cl + Cl 2:Pht trin phn ng: CH4 + Cl CH3 + HCl CH3 + Cl2 CH3Cl + Cl 3: Kt thc phn ng: Cl + Cl Cl2 CH3 + CH3 CH3 CH3 CH3 + Cl CH3Cl 3 do (SR)

Gi

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG ), khi

C ch phn ng hu c

: (v gc t do sinh ra s c n nh hn nh hiu ng +I). . t0 C 25 27 100 127 CI 1 1 1 1 CII 1,2 3,9 4,3 82 CIII 1,4 5,1 7 1600

cc C bc khc nhau ) %a n i ri .100 n i ri

: F2>>Cl2>Br2>>I2 : ri : kha nang phan ng cua H bac i

n i : so H bac i

3.3
X
+

( SE Ar )
X phn li t c sigma ( ).
X + X
+

+
phc phc

X + HA

, X+ benzen sang X+

vi .

3.3.1 : Benzen khng tc dng vi nc brm nhng phn ng d dng vi brm khan, khi c mt bt st lm xc tc (hoc FeCl3, AlCl3, ZnCl2 : gi l axit Lewis) Br + Br2 benzen * C che : Fe +Br2 FeBr3 FeBr3 +Br Br
Fe

+ HBr

Brombezen 2 giai on:

FeBr4

+ Br+

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG Giai on 1: xy ra chm: H + Br+ + Br

C ch phn ng hu c

Phc (sn phm trung gian) Giai on 2: xy ra nhanh: H Br Br +


H

+ H+

H+ + FeBr4 FeBr3 +HBr Khi nhn benzen c nhm y electron th phn ng xy ra d dng hn, v sn phm u tin th v tr o- v pCH3 Br CH3 + Br2

Fe

o-Bromtoluen CH3

Br p- Bromtoluen Ch : Nu chiu sng (khng c mt ca Fe) th toluen, etyl benzen khng th trong nhn benzen m th v tr (cacbon lin kt trc tip vi vng benzen) ca nhnh ankyl:
CH3
anh sang

CH 2Br

+ Br 2

+ HBr

Benzylbromua
CH 2CH 3
anh sang

CHBrCH

+ Br 2

+ HBr

1-brom-1-phenyletan 3.3.2 + HNO3


H2SO4 t0C

NO2 + H2O

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG * C che : H2SO4 HO NO2 + H+ H+ + HSO4

C ch phn ng hu c

H2O

NO2

N O 2 + H2O H2O NO2 Giai on 1: xy ra chm: NO2 H

+ N O2

Phc (sn phm trung gian) Giai on 2: xy ra nhanh: H NO2 NO2 +


H

+ H+ Nitrobenzen

3.3.3

s SO3 H
1700 1800 C

+ H2SO4

+ H2O

* C che : Trong trng hp ny, tc nhn electronphyl l SO3 ( mi sinh ra hoc do c sn trong olum) H2SO4 H3O+ + HSO4 + SO3 SO3 H +
SO3
HSO4 -H+

+ SO3 H +
SO3

SO3 H
H

3.3.4
AlCl3

a
CH3 + CH3Cl + HCl
C 2H5 + C2H5Cl
AlCl3

+ HCl

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG
CH2-CH3 + H2C
CH2

C ch phn ng hu c

C2H5 + C2H5OH
AlCl3

+ H2O

* Nu dng CH3CH2CH2Cl th c s ng phn ha, do ta thu c hn hp sn phm, trong sn phm chnh l C6H5CH(CH3)2 l sn phm chnh * C ch : - Electronphyl c to thnh do: CH3CH2 Cl + AlCl3 CH3CH2 OH + H+ CH2 =CH2 + H+
CH3 C H2 AlCl4

CH3 C H 2 H 2 O CH3 C H 2

C ch th tng t nh th Br2 3.3.5


COCH3 + CH3CO - Cl
AlCl3

+ HCl

* C ch :

CH3CO Cl + AlCl3 Giai on 1: xy ra chm:


+ CH 3 C O

CH3 CO + AlCl 4 COCH3 H

Phc (sn phm trung gian) Giai on 2: xy ra nhanh: H COCH3 COCH3 +


H

+ H+

3.4
3.4.1 Giai on 1:
R1 C R2 C R3
+

R1

R3 C R4
A + B

A B

(+)

C R2

R4

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG :
R1 R3 C R4
A B

C ch phn ng hu c ( )

B +

R1 C R2

R3 C
A

(+)

C R2

3.4.2
2

R4 ( H-Br; H-OH; HOSO3H.)

)
C C
Br Br Br

C
Br

cham

C
Br

Br

ion ankenbromoni
-

anken bromoni
Br

Br

C
Br

nhanh

C
Br

,x

, b che chn, k trans-

BrBr

Br

Br Br

HCl -

3.4.3
-

axit
Br

C
H

C
Br

-Br

C
H
+

cham

( )

C
H

+Br

nhanh

C
H

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG ca X 1 axit th CH2=CH2<R-CH=CH2 R-CH=CH-R<R2C=CH2<R2C=CHR H2SO4 2SO4


R CH CH2 H2SO4ac

C ch phn ng hu c

=C

R CH CH3
OSO3H

H2O t0

R CH CH3
OH
2SO4

3.4.4 khng d
2SO4

HSO4

CH2

CH2 H3O

H 2O

CH2
H

CH2
+

cham

CH3 C H 2

CH3 C H 2
H2 O

CH3 CH2 OH2

nhanh

CH3 CH2 OH H

CH3 CH 2 3 CH 2 CH 2
H3O

H 2O
+

CH3CH 2CH 2CH 2 C H CH3


nhanh

chuyen v

CH3CH 2CH 2 C H CH 2CH3


nhanh

H2 O

H2 O

CH3CH 2CH 2CH 2 CH CH3 H

CH3CH 2CH 2 CH CH 2CH3 H

OH
66%

OH
34%

2+

(Hg(OCOCH3)2

ran (THF)

H2 O
R CH CH 2
CH 3COO

R CH CH 2
+

R CH CH 2
OH HgOCOCH3

CH3COO Hg OCOCH3

HgOCOCH3
9

Ngi son: GV. Trn Trng Ngha

THPT Quang Trung

Ti liu BDHSG * 4R CH CH 2 + NaBH 4 + 4OH


OH HgOCOCH3 4R CH CH 3 NaB(OH ) 4
OH

C ch phn ng hu c
4Hg 4CH 3COO

l .
H C H B H H H H H C R H B H H H C C

H C C H B H H H

H R

H C H BH2 H C

H R

Ankyl boran RCH2CH2BH2


2O2

(RCH2CH2)3B

(RCH2CH2 )3 B 3H2O2 OH

3RCH2CH2OH

B(OH)4
p

3.4.5 3C

- , Me3 N -, -COOH g
Br

C F3 C H CH 3
CF3 CH CH2 HBr

CF3 CH CH 3
Br

kem ben
C F3 CH C H 3
Br

san pham phu

CF3 CH CH 3
Br

ben hn

san pham chnh

3.5
khong co peoxit cham
(CH3 )2 C CH 2 HBr

(CH3 )2 C CH3
Br

co peoxit nhanh

(CH3 )2 CH CH 2
Br

Ngi son: GV. Trn Trng Ngha

10

THPT Quang Trung

Ti liu BDHSG : Khi o:

C ch phn ng hu c

ROOR
RO + HBr

2RO
ROH + Br

Br +CH3CH=CH2

CH3CH

CH2Br

CH3CH
Br + Br

CH2Br +HBr
Br2

CH3CH 2 CH 2 Br + Br

CH3CH CH3CH

CH2Br + CH3CH CH2Br + Br

CH2Br

CH3(CH2Br)CH CH(CH2Br)CH3

CH3CH 2 CH 2 Br

3.6

nucleophin ( SN )
a X,

nh H2 O,N H3 ..... Vd: C2H5 Br + OH (CH3)3C Br + OH C2H5 OH + Br (CH3)3C OH + Br : (v vy mi gi l S C2H5 OH + Br


H O ....C H 2 ....Br CH 3
-

.. ..

HO ,C2 H5O ,CN , Br ,....

N2

N2

:
CH 3

C2H5 Br + OH

C H 2 Br HO

HO CH 2 CH 3 Br

CH 3 C H H Br

CH 3 CH 3

HO

HO
H

C
H

Br

HO

C H H

+ Br

dn

SN2
11 THPT Quang Trung

Ngi son: GV. Trn Trng Ngha

Ti liu BDHSG
R1 C R2 R3 X R1

C ch phn ng hu c

Nu

R1

Nu
R2

X
R3

Nu

C R2 R3

S
1: 2: : 1: 2: :

N1

2g

(CH3)3C Br + OH

(CH3)3C OH + Br

(CH3 )3 C Br (CH3 )3 C

cham

(CH3 )3 C
nhnh

+ Br
)
N2

+ HO

(CH3 )3 C OH
m
N1

N1 N2

3.7 anken Vd: C2H5- Br + H


CH3 H3C C Br

h HX
ancol

CH2 = CH2 + H2O + Br-

CH3 + HO

ancol

H2C

CH
ancol

CH3 + H2O +Br


H2C CH

CH 2

CH3

+ H2O +Br

H3C

CH Br
2

CH 2

CH3 + HO

ancol

H3C
2

CH

CH

CH3
N2

+ H2O +Br

:
ancol

C2H5- Br + H

CH2 = CH2 + H2O + Br-

HO

H CH2 CH2 Br

H O ......H......CH 2 HOH CH2

CH 2 ....Br

CH2 Br

Ngi son: GV. Trn Trng Ngha

12

THPT Quang Trung

Ti liu BDHSG
HO
-

C ch phn ng hu c

HO H H H

H H H Br HOH H H

C
H H

Br

H H Br
-

b) C cacbocation
+ 1

:
CH3 H3C C Br
CH3 H3C C CH 3
CH3 H3C C+ CH3
H

CH3 + HO

ancol

H2C

CH

CH3 + H2O +Br

CH3 Br
ancol

H3C

C+ CH3

+Br

H2C

C CH3

CH3 +

*C ch: th SN2 u tin vi ancol bc 1, 1 baz : C2H5OH + HBr


N2

SN1 u tin vi ancol bc 3 C2H5 Br + H2O

(th nucleophin lng phn t)


C2 H5 O H 2 Br

C2H5OH + HBr
Br C2 H5 O H 2

C2 H 5 Br H 2O

Ngi son: GV. Trn Trng Ngha

13

THPT Quang Trung

Ti liu BDHSG :
CH 3 C H
-

C ch phn ng hu c
CH 3 OH + HBr H C H CH 3 CH 3

O 2 H + Br

H CH 3 C H H

Br

O2 H

Br
H

O2 H
H

Br

C H H

+ H2O

: (CH3)3C OH +HBr
N1:

O H2
H

O H2

(CH3 )3 C Br H 2O

2
H

(CH3)3C OH +HBr 1: 2:

(CH3 )3 C O H 2 Br

(CH3 )3 C OH2 H
(CH3 )3 C Br

(CH3 )3 C + H3O
(CH3 )3 C Br

- Kh nng phn ng: HI>HBr>HCl Ancol bc 3>bc 2>bc1 * Dng thuc th Lucas( HCl c+ZnCl2) - Ancol bc 3 phn ng nhanh nhit thng to lp cht lng nh du ni ln b mt - Ancol bc 2 phn ng chm, to dung dch hi - Ancol bc 1 khng phn ng nhn bit bc ancol + i vi axit hu c :
2 4 CH3COOH + C2H5OH CH3COOC2H5+H2O 3) Phn ng tch nc ( hirat ha) a) Tch nc t 1 phn t ancol anken + i vi ancol bc 1: 1 anken 0 0 CH3-CH2-CH2-OH H 2 SO4 , t 170 C CH3-CH=CH2+H2O + i vi ancol bc 2 : thng cho h h anken CH 3 CH 2 CH=CH 2 + H 2 O

H SO t 0

CH3 CH 2 C H CH 3 OH

H 2SO4 , t 0 1700 C

(spp) CH 3 CH=CH CH 3 + H 2O (spc)

Ngi son: GV. Trn Trng Ngha

14

THPT Quang Trung

Ti liu BDHSG
CH 3
3:

C ch phn ng hu c

CH 3 C H CH 3 OH
: : CH3 CH2 OH

CH 3 C H=CH 2 + H 2O CH 3
1
H 2 SO4 , t 0 170 0 C

CH2 = CH2 + OH

H2SO4

HSO4
CH 3CH 2 O H 2

CH3CH2OH + H+

HSO 4

CH 2 CH 2
HSO 4
H H H

O2 H
HSO 4

H 2SO 4 + H2C

CH2 + H 2O

H H

C
H H

C
O H2

O H2 H 2SO 4
H H

H H

H 2O
:
CH3 CH 3 C H CH 3 OH CH 2 C H CH 3 + H 2O CH 3

H2SO4

HSO4

(CH3 )3 C OH H

(CH3 )3 C OH2

Ngi son: GV. Trn Trng Ngha

15

THPT Quang Trung

Ti liu BDHSG
CH3 H3C C CH 3
CH3 H3C C+ CH3
H

C ch phn ng hu c
CH3

OH2

H3C

C + + H 2O CH3

H2C

C CH3

CH3 +

*Quy tc Zaixep: trong phn ng tch

, nhm -OH u tin tch vi H ca cacbin bc cao


H 2 SO4 , t 0 140 0 C

b)Tch nc t 2 phn t ancol CH3OH + HOCH3 C ch : N2

CH3OCH3 + H2O
H 2 SO4 , t 0 140 0 C

: CH3CH2OH + HOCH2CH3

C2H5OC2H5 + H2O

H3C CH2

H3C O: H

CH2 OH +

CH3CH 2 O 2 H

CH2 H3C

O2 H

CH3CH 2 O CH 2 CH3 + H 2O
H

CH3CH 2 O CH 2 CH 3 + H +

Ngi son: GV. Trn Trng Ngha

16

THPT Quang Trung

Ti liu BDHSG 1: . 2: - 3-clopentan 3: a) (CH3)3CCH(CH3)OH b) (CH3)3CCH2OH


HCl HCl

C ch phn ng hu c - -

(CH3)2CClCH(CH3)2

(CH3)3CCH(CH3)Cl

(CH3)2CClCH2CH3 : -

4: p-CH3OC6H4CH2OH>C6H5OH>p-ClC6H4CH2OH>p-O2NC6H4CH2OH 5: 3-phenylbut-1-en trong H2SO4 - 2-phenylbutan-2-ol. Gi 6: : BrCH 2CH 2 Br (37%)

CH 2
a)

CH 2

Br2 H 2O

BrCH 2CH 2OH


Cl2 CH3OH
0

(63%) (50%) (35%) (15%)


trm nh sau

CH3CH(OCH3 )CHClCH 2CH 3


CH3CH CHCH 2CH3

CH3CHClCH(OCH3 )CH 2CH3 CH3CHClCHClCH 2CH3


2-clo-2-metylbutan : 28,4% 4-clo-2-metylbutan : 12,2% I , CII, CIII.
peoxit

b) 7: 100 1-clo-2-metylbutan : 24,4%; 3-clo-2-metylbutan : 35%;

i 8:

CH3CH CH2 HBr


.

9: a) 10:
CH3 CH CH 2 BH3

: CH3CH CH2

Hg(OCOCH3 )2 / THF

NaBH4 / NaOH

propen

propen

H 2O 2 / OH

, B, C, D. . 11: a) p-nitroclobenzen, clobenzen, 2,4-dimetylbenzen b) 1,3-dimetylbenzen; 1,4-dimetylbenzen; toluen; 1,3,5-trimetylbenzen c) p-CH3C6H4COOH; p-HOOCC6H4COOH; p-CH3C6H4CH3; C6H5CH3 Ngi son: GV. Trn Trng Ngha 17 THPT Quang Trung

Ti liu BDHSG

C ch phn ng hu c

GII
1: . - a) SN2 b) SN1 2: - 3-clopentan brompentan khi Brb) ZnCl2 2RX + ZnCl2 Cacbocation CII
l

- -

II N1

N2

N2 N1

3-

2R+ + ZnCl 2 4
III

CH3CH 2CH2 C HCH3 Cl


3: a) (CH3)3CCH(CH3)OH b) (CH3)3CCH2OH
HCl
HCl

(CH3)2CClCH(CH3)2

(CH3)3CCH(CH3)Cl

(CH3)2CClCH2CH3 3
N2

CH3 H3C C CH 2 OH 2
+

CH3 H3C C CH3


+

CH3 CH 2 H3C C + CH 2 CH3

CH3

4: p-CH3OC6H4CH2OH>C6H5OH>p-ClC6H4CH2OH>p-O2NC6H4CH2OH
N1

:
3

5: - H2C CH CH CH3 CH3

NO2 -

3-phenylbut-1-en trong H2SO4 - H3C + CH CH CH3 CH3

HO H3C CH 2 + C CH3 CH3

H 2O H

H3C

CH 2

C CH3

CH3

Ngi son: GV. Trn Trng Ngha

18

THPT Quang Trung

Ti liu BDHSG 6: a) :

C ch phn ng hu c

BrCH 2CH 2 Br CH 2
Br2 H 2O

(37%) (63%)

CH 2
b)

BrCH 2CH 2OH

CH3CH(OCH3 )CHClCH 2CH 3


CHCH 2CH3
Cl2 CH3OH

(50%) (35%) (15%)

CH3CH

CH3CHClCH(OCH3 )CH 2CH3 CH3CHClCHClCH 2CH3

CH 3 CH CHClCH 2CH 3
3

CH 3CHCl CH CH 2CH 3
-

15% 7: 1000 1-clo-2-metylbutan : 24,4% 2-clo-2-metylbutan : 28,4% 3-clo-2-metylbutan : 35% 4-clo-2-metylbutan : 12,2%
I

, CII, CIII.

8:

CH3CH CH2 HBr


.

peoxit

1) ROOR 2) RO + HBr

2RO
ROH + Br

Br +CH3CH=CH2

CH3CH

CH2Br

CH3CH
3) Br + Br

CH2Br +HBr
Br2

CH3CH 2 CH 2 Br + Br

CH3CH CH3CH

CH2Br + CH3CH CH2Br + Br

CH2Br

CH3(CH2Br)CH CH(CH2Br)CH3

CH3CH 2 CH 2 Br

3>2>1 9: : CH3CH CH2


Hg(OCOCH3 )2 / THF

NaBH4 / NaOH

Ngi son: GV. Trn Trng Ngha

19

THPT Quang Trung

Ti liu BDHSG

C ch phn ng hu c

H2 O
CH3 CH CH2
CH 3COO

CH3 CH CH 2
+

CH3 CH CH2
OH HgOCOCH3

CH3COO Hg OCOCH3

HgOCOCH3

4CH3 CH CH 2 + NaBH 4 + 4OH OH HgOCOCH3

4CH3 CH CH3 NaB(OH )4 4Hg 4CH3COO OH

10:
CH3 CH CH 2 BH3 A
propen

propen

H 2O 2 / OH

, B, C, D. .
H C H B H H H H H C CH3 H B H H H H H C C CH3 H B H H H C C CH3 H BH2 H H C C CH3 H

CH3CH2CH2BH2 (C3H7)3 (CH3CH2CH2 )3 B 3H2O2 OH

(C3H7)2

3CH3CH2CH2OH

B(OH)4

11: a) p-nitroclobenzen, clobenzen, 2,4-dimetylbenzen b) 1,3-dimetylbenzen; 1,4-dimetylbenzen; toluen; 1,3,5-trimetylbenzen c) p-CH3C6H4COOH; p-HOOCC6H4COOH; p-CH3C6H4CH3; C6H5CH3 ) clobenzen >p-nitroclobenzen> 2,4-dimetylbenzen b) 1,3,5-trimetylbenzen >1,3-dimetylbenzen>1,4-dimetylbenzen> toluen c) p-CH3C6H4CH3> C6H5CH3 >p-CH3C6H4COOH>p-HOOCC6H4COOH;

Ngi son: GV. Trn Trng Ngha

20

THPT Quang Trung