Professional Documents
Culture Documents
PHN NG TCH
C CH PHN NG TH NUCLEOPHIN:
S phn ng
RY
RY
1. PHN NG TH SN2:
C ch lng phn t, mt giai on i qua trng thi chuyn tip
-
Y
V d:
HO
+ CH3 Br
+ HO...CH3...Br
HO CH3
Br
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
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
Me3C - OH
Me3C
OH2
Me3C
+ Cl
Me3C - Cl
chm
Me3C - OH
ZnCl2
Me3C O
ZnCl2
Me3C + Zn(OH)Cl2
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 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
. 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
V d:
C2H5
C2H5
H C C H3C
H H
H C C X
cham
H C C
H C C
nhanh
C C
V d:
(CH3)3C
Br
cham
(CH3)3C
Br
(CH3)2C
CH3
nhanh
(CH3)2C
CH2
H3C
CH CH2 + COS
HS
CH3
0 150 c
H3C
CH CH2
(CH3)2N OH
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
X X X cham C C
+
X C C
+
Y X Y nhanh C C
Br
HO
SO3H
H2O
CH3 CH CH3 OH
H2SO4
CH3CHO
R C
CH
Hg , H
80 c 0
2+ +
R C O
CH3
X Y
C OX
cham X Y
C O
Y C O
+
Y X nhanh C OX
C OH
H
OH
ROH
cham
O C OH
nhanh _H
OR C OH
H2O
C O
RO
cham
OR C O
ROH nhanh
OR C
+
OH
RO
Giai on chm l giai on tn cngca tc nhn nuleophin to ra anion, giai on nhanh l tch nhm X
cham
R C X nhanh O
R C Y O
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
Ar H
E ...... Ar ...... H
E Ar
nhanh
Ar E
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:
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
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
X R
tch HX
R
+HX cng arin
Y R