C CH PHN NG

L xem xt cc phn ng di ba gc :
Cc giai on ca phn ng
Bn cht ca s t v thnh lp cc ni c trng ca
phn ng
Trng thi chuyn tip ca phn ng
Gii thch sn phm sinh ra ph hp vi qu trnh thc
nghim.

PHN NG HU C
C IM
-Din ra vi tc chm
-Cc phn ng thng thun nghch, hiu sut phn ng
khng cao.
-Cc phn ng thng xy ra theo nhiu hng khc nhau
to thnh hn hp sn phm.
dng nhit, xc tc v k thut thc hin phn ng
PHN LOI
1. Phn ng th (Substituation)
CH3-H + Cl2
CH3-Cl + HCl
2. Phn ng cng
CH2=CH2 + Cl-Cl Cl-CH2CH2-Cl
3. Phn ng tch loi
H-CH2-CH2-OH CH2=CH2 + H2O

PHN LOI PHN NG HU C

4. Phn ng oxi ha kh
CH3-CH=O + H2 CH3-CH2-OH
CH2=CH2 + [O] + H2O HO-CH2-CH2-OH
5. Phn ng chuyn v: c th lm thay i khung Carbon.

C6H5

CH CH CH2

C6H5

CH CH CH2
OH

OH
R'
C N OH
R

R C N R'
O H

1.S phn ct lin kt

+ Phn ct ng ly: to cc gc t do
Cl Cl
CH3 H

hv

Cl

Cl

CH3

+ Phn ct d li: To cc ion, carbocation, carbanion

CH3
CH3

CH3

Br

CH3

CH3
C6H4NO2p
pO2NC6H4

C6H4NO2p

Br

C
CH3

OH

C6H4NO2p
pO2NC6H4

C
C6H4NO2p

2.Cc kiu c ch phn ng

+ C ch Nucleophil(thn hch-ht nhn)
+ C ch Electrophil(thn electron-in t)
+ C ch gc t do

d
Cl

d
< CH3

OC2H5

Cl

CH3 O C2H5
NO2

NO2
CH4

Cl

CH3

HCl

CH3

Cl2

CH3

Cl

I. Phn ng th
1.Phn ng th gc t do:
Gm ba giai on
2504000c
X2
2X.
Hoc nh sng t ngoi (h)
2X. + RH
HX
+ R.
R.
+ X2
RX
+ X.
X.
+ X.
X2
R.
+ R.
RR
X.
+
R.
RX

: Giai an khi mo
: Giai an truyn i

: Giai an kt thc

Phn ng th Cl2, Br2 vo alkan theo c ch gc t do

2. Phn ng th thn hch

Cht thn hch: l 1 anion m hoc phn t trung ha c
mang 1 i in t t do
Cc cht thn hch in hnh: HOH, RNH2, CN- , R
MgX, HOa). Th thn hch lng phn t SN2: L phn ng bc hai,
giai an chuyn tip c c hai cht.
Nu

C Y

Nu

Nu C

Cht nn
Sn phm
Cht thn hch
Trng thi chuyn tip
Nhm xut.
(nghch chuyn
cu hnh)
H
H
H
HO

C Br
H

Br

HO
H

HO

H
H

Br

Phn ng th thn hch

b.Th thn hch n phn t SN1: L phn ng bc
mt Trng thi trung gian qua ion cacbonium
C Y

Vd:

+ HX

SN1

CH3
CH3
CH3 C OH
CH3

H Br

C Nu

Nu C

Hn hp tiu trin

CH3
CH3 C OH

Nu

CH3
CH3 C X

H2O

CH3
CH3
CH3 C OH2
CH3

- H2O

CH3
CH3 C
CH3

Br

CH3
CH3 C Br
CH3

Bng so snh iu kin ca phn ng th thn hch

SN2

SN1

Cht nn

Thch hp cho CH3X

v RX nht cp.
RX tam cp khng cho
phn ng SN2

Thch hp cho cho cht

nn no to thnh ion
carbonium bn.
RX tam cp, R X loi
alil, benzyl

Tc cht thn hch

Cn cht thn hch

mnh, baz yu

Khng nh hng

Nhm xut

Cn nhm xut tt ( Cc
anion bn, baz yu).

Cn nhm xut tt ( cc
anion bn, baz yu ).

Dung mi

Dung mi phn cc phi

proton.

Dung mi phn cc: H2O,

Ru

Cht xc tc

Mui Ag+ thm vo hn

hp s xy ra phn
ng nhanh hn.

3. Phn ng th thn in t trn nhn

phng hng (SE).
Cht thn e: l ion hay phn t c kh nng nhn mt i
e, bao gm: cc tc cht dng in nh H+; cc cht
trung ha in nh Br2; Cc axit Lewis nh AlCl3; Cc
ion kim lai c cha vn o trng nh Ag+, Pt2+.
Nhn phng hng rt giu in t
E

H
E

H
E

E
A
HA

Phn ng th thn in t

Cl2

Vai tr ca Fe:

Fe

Cl

Fe

0
30 c
+

Cl2

FeCl3

Cl
Cl

Cl

Fe Cl
Cl

HCl

Cl
Cl

Cl

Fe Cl
Cl

Cl

FeCl4

II. Phn ng kh (phn ng tch loi)

L phn ng trong c hai nguyn t hoc mt nhm
nguyn t b lai khi cht nn.
Tc nhn phn ng l cc baz mnh.
Cc Baz mnh in hnh:
OH-(KOH, NaOH) < RO(KOH/Alcol) < RCC- (RCC-Na+) < NH2-(Na+NH2-)
1. Phn ng kh E2
CH3CH2CHCH3
CH3CH2O
H
CH3
H

C C

KOH/C2H5OH

CH3CH CHCH3

Br

Br
H
CH3
Br

CH3CH2O

CH3
H

C C

H
CH3
Br

CH3
H

H
C C
CH3

2. Phn ng kh E1
L phn ng bc mt, trng thi trung gian qua ion cacbonium. Vn tc
phn ng ch ty thuc vo nng cht nn.
CH3
CH3
H
Etanol
CH3 C
Br + C2H5ONa
C C
0
25
CH3
H
c
CH3
C ch:
CH3
CH3

C
CH3

Br

-Br

CH3
CH3

H
C C H
H

C 2 H5 O

CH3
CH3

C C

H
H

S cnh tranh ca phn ng E v SN

Cc baz thng c mang i e nn cng c tnh thn hch.
*Phn ng E2 bao gi cng km theo SN2.
CH3CH2Br + C2H5O-Na+ Etanol 550
CH3CH2OCH2CH3 + CH2=CH2
Etanol
E (10%)
CH3 CH Br + C2SN
H5O2(90%)
Na
0
CH
CH2 O CH CH + CH
CH
55

CH3

CH3

SN2(21%)
E2(79%)
*Phn ng E1 bao gi cng km theo SN1
CH3
CH3

C
CH3

Br

H2O, Etanol
650 c

CH3
CH3

C
CH3

OH

SN1(64%)

CH3
CH3

C C

H
H

E1(36%)

CH3

Ch
Thng khng c s gii hn r rng gia E1, SN1, E2,
SN2.
+ Dung mi phn cc v ion cacbonium bn thng u
tin E1 v SN1.
Dung mi t phn cc v ion cacbonium t bn thng
u tin E2 v SN2.
+ Tc nhn tnh thn hch mnh, baz yu thng cho
phn ng th.
Tc nhn thn hch yu, tnh baz mnh thng cho
phn ng kh.

III.Phn ng cng
1. Cng thn in t vo ni i C = C
Phn ng xy ra theo hai giai on:
+ Giai on I (chm): To onium vng hoc hp cht trung
gian l ion carbonium.
+ Giai on II (nhanh): cht thn hch tc kch vo cht
trung gian
a/. Cng HA vo ni C=C
C

C
H A

I
C

A
II

C H
C A

C H
A C

*Quy tc cng Markovnhicov

S cng tc nhn bt i xng E+X vo mt alken bt
i xng, th phn dng E+ s gn vo nguyn t C
ni i sao cho to nn cht trung gian carbocation bn
nht.
CH3
CH3

CH3
CH3

CH3
C CH2

C CH2

HBr

CH3

C Br
CH3

CH3
CH3

H
C CH2

Br

CH3
CH3

C Br
CH3

b/.Cng Br2, Cl2 vo alken

Thng l cng trans v phi tri qua giai on trung gian
onium vng.
H
C
CH3

Br Br
H - Br

Br
C

Br

Br

CH3

H
CH3 a

C
b

H
CH3

a
Br
H
CH3

(2R, 3R)2,3dibromobutan
(2S,3S)2,3dibromobutan

H
CH3
Br

b
H
CH3
Br

Br
C

H
CH3

Lu :
S hin din ca trung gian onium vng hay carbonium
c xc nhn khi mi trng phn ng c s hin din
ca cc ion X-, NO3-, H2O ta s c sn phm tng
ng.
X

CH2=CH2

Br2

Br
CH2

CH2

Hay CH2Br

CH2

NO3
H2 O

CH2Br

CH2Br

CH2Br

CH2ONO2

CH2Br

CH
OH2

X : Br, Cl, I

CH2Br

+ Khi cng HBr vo anken c s hin din ca perocid hay

peracid ROOR(anti Macconhikov).
+ Phn ng cng qua trung gian carbocation nn c th
xy ra chuyn v.
+ Cng hidro xc tc kim loi: Phn ng thuc lai cng Cis

CH
OH

2. Phn ng cng thn hch vo ni C=O

C ch tng qut:

Nu

Nu

C
O

+ Nu xc tc l acid:
C

C
O

Nu

Nu

O
+ Nu xc tc l baz:

Nu
C
OH

OH

Nu
C
O

H B

Nu
C
OH

Cc v d
- Cng alcol
R C R'

R"

OH

R'

- Phn ng ester ha
R C O H

R C O H

R C O
O

H O R'

R'

R'

R C
O H

OH

O H

R C O H

O H
R'

OR"

H2O

R'

O H

R C O H
O H

O H

IV. Phn ng sc hp aldol

Trong mi trng baz, cc aldehit v ceton c H s sc
hp.
+ Giai an u l s kh H bi baz to thnh enolat;
+ Carbanion s ng vai tr cht thn hch, s cho phn
ng cng thn hch vo phn t carbonil th hai to
aldol
R CH C H
H

OH

R CH C H

O
R
RCH2CHCHCHO
OH

HO H
OH

R CH C H Hay R CH C H
O
O
R
RCH2 C H
RCH2CHCHCHO
O