GS.TS.NGND.

O HNG CNG
CHUYN
TNG HP HU C
2011

1
CHNG I
CCH A NHM CHC VO PHN T CHT HU C V S
CHUYN HO GIA CH!NG
Qua trinh tng hp cac hp cht hu c thc cht la qua trinh chuyn hoa t mt
hp cht nay thanh mt hp cht khac duoi tac dung cua cac yu t nhu cac tac nhn phan
ung va diu kin phan ung. Qua trinh chuyn hoa do co th thuchin duc bng hai
phung phap c ban:
- Dua mt nhom chuc vao phn tu cua hp cht hydrcacbon.
- Chuyn hoa tung h giua cac nhom chuc voi nhau.
"#"# A NHM CHC VO PHN T HY$%CAC&ON
"#"#"# A NHM CHC VO AN'AN
D dua mt nhom chuc vao phn tu cua cac hp cht ankan co th su dung mt
trong cac phan ung sau dy tuy thuc vao yu cu va muc dich cua s tng hp.
"#"#"#"# P()* +*, (-./,0* (/12
C H X
2
C X HX
Phan ung xay ra theo c ch gc (S
R
) la thuong tao thanh hn hp nhiu san phm
khac nhau. Kha nng phan ung cua tac nhn halogen X
2
: Cl
2
~ Br
2
; con kha nng phan
ung cua nguyn tu Hydr trong ankan la:
Bc ba ~ Bc hai ~ Bc mt ~ CH
3
- H
"#"#"#3# P()* +*, 4567.0* (/12
C H
C CH
2
- H
CH
2
N
2
CH
2
C O
N
2
CO
Phan ung mtylen hoa cac hp cht ankan thuong tao ra mt hn hp cac san
phm khac nhau. Mt khac, phan ung loai nay co th xay ra theo 2 c ch:
"# C8 9(: 4567.0* (/1 6;<9 6=:>2
C H
C CH
2
- H CH
2
A
CH
2
C

250-400
0
c hoc chiu sang
hoc
Tia cc tim
hoc
2
3# C8 9(: 619( ? 9@*, (A>2
C H CH
2
C CH
3
C CH
3
"#"#"#B#P()* +*, *=6;C (/12
Phan ung thuong duc tin hanh trong tuong khi o nhit d cao voi axit nitric hoc
nit tetraoxyt lam tac nhn nitro hoa

CH
2
HNO
3
CH
3
- NO
2
H
2
O
470 C
0

Phan ung xy ra thuong kem voi oxi hoa ankan tao thanh CO
2
va H
2
O nn co hiu
sut khng cao. Mt khac khi tin hanh phan ung nitr hoa voi cac dng dng cua
mtan thuong xay ra s ct mach tao thanh hn hp san phm:
HNO
3
, 425 C
0
CH
3
CH
2
CH
3
CH
3
CH
2
CH
2
NO
2
CH
3
- CH - CH
3
NO
2
CH
3
CH
2
NO
2
CH
3
NO
2
"#"#"#D# P()* +*, E7*FC (/1
Phan ung nay co th duc thc hin bng tac nhn sunI hoa la axit sunIuric dc:
R - H HO - SO
3
H R - SO
3
H H
2
O
Tuy nhin phan ung nay dat hiu sut rt thp nn trong thc t thuong su dung
phan ung thay th hydr bng gc SO
2
Cl tao thanh ankynlsunIclorua nhu sau:
0
R - H R - SO
2
Cl HCl
SO
2
, Cl
2
, t C

"#"#"#G# P()* +*, CH7 (/12
Duoi nhng diu kin dc bit, ankan co th bi xy hoa hp cht C H va chuyn
v cac hp cht hydrxi hoc cac hp cht cacbonyl.
Vi du:

3

KMnO
4
C H H
3
C
CH
3
CH
3
C OH
CH
3
CH
3
H
3
C
R - CH
3
R - CH
2
- OH
CH
4
H - CHO
"#"#3# A NHM CHC VO AN'IN2
Vic dua mt nhom chuc vao phn tu anken co th thc hin duc bng phan ung
cng hp electrophin, cng hp raddical phan ung thay th va oxy hoa. Duoi dy la s d
cua mt phan ung c ban thuong duc su dung trong tng hp cac hp cht hu c.
"#"#3#"# P()* +*, 9@*, (A>2

C C XY
C C
X Y
Trong do XY H
2
, Br
2
, HCl, HBr, HI, H
2
SO
4
, HOH, HOCl...
Cac phan ung xay ra co th co s tham gia cua cac xuc tac thich hp cung co khi
khng cn s co mt cua xuc tac. Trong dai da s cac truong hp, phan ung cng hp con
xay ra theo quy tc Macpnhicp: Phan ung cng hp xay ra theo c ch gc (khi co s
tham gia cua cac cht xuc tac co kha nng tao thanh gc t do nhu poxit, peaxit...) thi
huong cua phan ung nguc voi quy tc Macpnhicp.
CH
3
CH CH
2
CH
3
CHBrCH
3
CH
3
CH
2
CH
2
Br
HBr
Cac phan ung cng hp cua mt s hp cht anken ri hydrcacbon hoc mtylen
s cho san phm ankyl hoa:

B
2
O
3
, khng khi
Khng khi, 600
0
C, NO
Khng co pexit
Co mt pexit
Theo Macpnhicp
Phan Macpnhicp
4

C C
C C R H C C
H R
axit
C C
CH
2
N
2
CH
2
C O
Hv
CH
2
Phan ung thay th nguyn tu hydr o vi tri allyl cua cac hp cht anken duc thc
hin o nhit d cao (khoang 600
0
C) voi cac tac nhn la clo Brm hoc N brmxucximit:
C C C X
2
Cl
2
, Br
2
C C C X
2
H X
Vi du:

0
CH
3
CH CH
2
Cl - CH
2
CH CH
2
Cl
2
, 600 C
Br
2
Br
2
600 C
0

"#"#3#B# P()* +*, /H= (/12
Phan ung oxy hoa cac hp cht lephin thuong tao thanh cac san phm chua xy la
ancol hoc andhyt tuy thuc vao tac nhn xy hoa. Vi du nu xy hoa cac hp cht
lephin bng tac nhn KMnO
4
lanh va long hoc dung dich peaxit HCOOOH thi s thu
duc hp cht glycol nhu sau:
C C KMnO
4
HCOOOH C C
OH OH
Mt khac s khac nhau gia cac phan ung xy hoa cua 2 tac nhn nay la vic tao
thanh cac san phm dng phn hinh hoc khac nhau. Phan ung xy hoa bng KMnO
4
thuong tao ra cac san phm dng phn Cis trai lai HCOOOH tao ra cac san phm dng
phn trans.

hoc
5
KMnO
4
H
2
O
2
, HCOOOH
H H
OHOH
cis - xyclopentadiol -1,2
H OH OH H

trans - xyclopentadiol -1,2

Nu tin hanh phan ung xy hoa bng tac nhn la hp cht zn thi san phm thu
duc la cac andhyt hoc xtn:
C O O C C C C C O
3
O O
O
H
2
O,Zn
Vi du:
CH
3
CH
2
CH CH
2
CH
3
CH
2
C O O CH
C CH
2
O
3
H
2
O, Zn
H H
CH
3
O
3
H
2
O, Zn
C O O CH CH
3
H
CH
3
CH
3
Phan ung nay thuong duc su dung d xac dinh cu tao cua phn tu olephin.
"#"#B# J- *(K4 9(+9 LM/ >(N* 6O -*P=*2
Tung t nhu cac phung phap dua mt nhom chuc vao hp cht anken, vic dua
mt nhom chuc vao phn tu ankin cung duc tin hanh bng phung phap cng hp hoc
thay th nguyn tu hydrlinh dng cua ankin.
"#"#B#"# P()* +*, 9@*, (A>2

C C
C C YZ C C
Y
Z
Y Z
YZ

Trong do: YZ H
2
,Cl
2
, Br
2
, HCl, HI, H
2
O
Cac phan ung xay ra theo huong dc thu v mt lp th tuy thuc vao vic su dung
cac hp cht xuc tac.
Vi du:

6

C C C C YZ
H
H
H
H
2H
2


C C
H
H
C C
H
H
C C

Phan ung cng hp voi nuoc thuong xay ra voi s co mt cua xuc tac la mi thuy
phn trong mi truong axit va tao thanh san phm la cac hp cht xtn:
C C
C C H
2
O
H
H
HgSO
4
, H
2
SO
4
C C
H OH
O
Vi du:
C C
C C H H
2
O
H
H
H
HgSO
4
, H
2
SO
4
C H
H
H
O
H
H
C C
C C H H
2
O
H
H
H
HgSO
4
, H
2
SO
4
O
CH
3
"#"#B#3# P()* +*, -*P7. (/12
Nguyn tu hydr thuc lin kt ni ba cua ankin rt linh dng dn dn cac hp cht ankin
co tinh axit yu. Vi vy no co kh nng tham gia voi cac phan ung voi cac kim loai kim
hoc voi cac ion kim loai nng.
Vi du:
C C H M C C H H

Ni, H hoc pd
Na hoc Li,NH
3
H
2
, pd hoc Ni B
dng phn trans
dng phn cis
7
Trong do:
M Ag , Cu

Hoc:

C C H Na C C Na 1/2H
2

Nu cho hp cht axetylua kim loai trn dy tac dung voi cac dn xut halogen thi s
thu duc cac san phm ankyl hoa:

- C C - M X - R - C C - R MX
"#"#D# J- 4@6 *(K4 9(+9 LM/ >(N* 6O (A> 9(Q6 6(84
Vic dua mt nhom chuc vao nhn thm cua cac hp cht hyddrrocacbon thm duc
thc hin boi cac phan ung xay ra theo c ch th electrophin (S
E
). Duoi dy la s d cua
mt s phan ung c ban thuong gp:
-R N=6;;C (/12
H
2
SO
4
ArH HONO
2
ArNO
2
H
2
O
SR ST*FC (/12
SO
3
ArH HOSO
3
H ArSO
3
H
2
O
9R H-./,0* (/1
ArH X
2
ArX HX (X
2
Cl
2
, Br
2
)
Fe
UR A*P7. (/1 6(0/ V;=W0* X C;-F2
ArH RCl ArR HCl
AlCl
3

UR A*P7. (/1 6(0/ V;=W0* X C;-F2
ArH ROCl ArCOR HCl
AlCl
3
0R N=6;;CYC (/12
ArH HONO ArN O H
2
O

NH3 long
8
,R AYC (/12
ArH Ar'N
2
X ArN N - Ar' HX
(R P()* +*, '/*S02
CO
2
COONa
OH
OH
125 c, 7atm
0
=R P()* +*, $-=48 X T=4-*2
CO
2
CHO
OH
OH
dung dich NaOH
Trong bang s d cua cac phan ung trn dy, cac phan ung e va g chi xay ra di
voi cac hp cht hydrocacbon thm hoat dng manh, con cac phan ung h va i chi co
ngha khi hp cht hydrocacbon thm tham gia vao phan ung la phenol.
Vic dua mt nhom chuc thu hai vao nhn thm cua hydrocacbon thm duc tun theo
mt s quy lut dinh huong nht dinh. Nguoi ta chia cac nhom th thanh 2 loai:
- Loai I: Cac nhom tng hoat (co kh nng lam tng mt d din tu cua nhn thm) -
dinh huong oct va para.
- Loai II: Cac nhom giam hoat (nhom ko din tu cua nhn thm) - dinh huong mta.
Kh nng hoat dng cua cac nhom th trong phan ung th electrophin rt khac nhau
va duc sp xp theo thu t nhu sau:
NHM TH LOI I NHM TH LOI II
Tng hoat manh Dinh huong mta
- NH
2
(-NHR, -NH
2
) - NO
2
- OH - N
()
(CH
3
)
2
Tng hoat va - CN
- OCH
3
(-OC
2
H
5
...) - COOH (COOR)
- NHCOCH
3
- SO
3
H
Tng hoat yu - CHO, COR
- C
6
H
5
Dinh huong Oct, para
- CH
3
(-C
2
H
5
,...) - F, - Cl, - Br, - I

Vic dua nhom chuc thu ba vao nhn thm khi d co mt cua 2 nhom th s lam phuc
tap s dinh huong cua phan ung th electrophin. Vi vy ta co th phn thanh cac truong
hp sau:
1. Nu hai nhm th cng nh hng vo mt v tr th s nh hng s x! ra
th"o chi#u c$a c%c m&i t'n sau(
CH
3
O
2
N
O
2N
SO
3
H
CN
NHCOOCH
3
). Nu hai nhm th nh hng *h%c nhau th s th"o +u! t,c(
- nh huong cua nhom hoat hoa manh (tng hoc giam hoat) s quyt dinh huong
cua phan ung S
E
so voi nhom hoat hoa yu.
- nh huong cua nhom tng hoat s quyt dinh huong cua nhom phan ung S
E
so voi
nhom giam hoat. S anh huong nay duc thay di theo dy sp xp sau:
- NH
2
~ - OH ~ - OCH
3
~ - NHCOCH
3
~ - C
6
H
5
~ - CH
3
~ Nhom dinh huong mta
Vi du:
HO
CH
3
HO
CH
3
NO
2
HNO
3
/H
2
SO
3
CH
3
CONH CH
3
CH
3
CONH CH
3
Br
Br
2
/Fe
CHO
HO
Br
2
/Fe
HO
CHO Br
Br
HO
CHO
Br
"#"#G# A MZT NHM CHC VO PHN T [\ V]NG THM N GI^N
Vic dua mt nhom chuc vao nhn thm di vong dn gian duc thc hin bng phan
ung th eleectrophin. Cac phan ung th xay ra o cac hp cht Iuran, tiophen, pirol uu tin
dinh huong vao vi tri s 2.
Vi du:

10
SO
3
H
O
: SO
3
O
COCH
3
O
(CH
3
CO)
2
O (C
2
H
5
)
2
O : BF
3
O
0 C
0
COC
6
H
5
O
C
6
H
5
COCl SnCl
4
S
N NC
6
H
5
N
C
6
H
5
N NCl
N
tiophen 2 - Bezoyltiophen
CH
3
Cl KOH
N
H
H
N
H H
CHO


Tung t nhu vic dua mt nhom th vao hp cht di vong 5 canh, vic dua mt
nhom chuc vao hp cht di vong 6 canh cung co th thc hin bng phan ung th
electrophin. Truong hp nay huong th uu tin vao vi tri 3 (hoc )

Iuran Iuran 2 sunI axit
2- axtylIuran
Pirol 2- (phenylaz) pirol
11
N
piridin
N
NO
2
N
SO
3
H
N
Br

N
Br
KNO
3
, H
2
SO
4
, 300 C
0
H
2
SO
4
, 350 C
0
Br
2
, 300 C
0

Phan ung th nuclphin cua hp cht piridin s cho ra cac san phm th vao vi
tri 2 hoc:
N
NaNH
2
NH
2
H
NH
2
NaNH
2
H
2
N N
N
C
6
H
5
- Li
NH
2
H
C
6
H
5
LiH
N N

"#3# S CHUYN HO TNG H_ GIA CC NHM CHC
"#3#"# CHUYN HO NHM CHC HY$%`Ya CbA ANOa V PHINOa
S chuyn hoa nhom hydrxyl cua cac hp cht ancol co th duc thc hin bng
mt s phan ung quan trong sau dy:
a- .hn /ng ha0og"n ho%(
Phan ung nay co th duc thc hin bng cac tac nhn halogen hoa nhu
hydrhalogenua HX, phtpho halogenua PX
3
, PX
5
, dinyl clorua SOCl
2
.
Phan ung voi hydrhalogenua:
ROH HX RX H
2
O
Phan ung xay ra theo c ch th Nuclphin, trong do kh nng phan ung cua HX
giam dn theo dy: HI ~ HBr ~ HCl, con kh nng phan ung cua ROH thay di theo dy:
Allyl benzyl ~ bc ba ~ bc hai ~ bc mt
Nhiu khi phan ung xay ra voi s chuyn vi.

Dun nong
Dun nong
12
Vi du:
CH
3
C
CH
3
H
H
OH
C CH
3
CH
3
C
CH
3
H
H
Cl
C CH
3
CH
3
C
CH
3
H
H
Cl
C CH
3
HCl
Hoc:
CH
3
C CH
2
OH
CH
3
CH
3
C CH
2
Cl
CH
3
CH
3
CH
3
C CH
2
CH
3
CH
3
Cl
CH
3 HCl

1 .hn /ng 2hot2ho ha0og"nnua(
R - OH + PX
n
RX + H PO
3 3
Trong do: PX
n
PBr, PL
3
, PCl
5
Vi du:
- CH - CH
3
OH
- CH - CH
3
Br
PBr
3
CH CH OH CH CH I
3

2 3
2
P + I
CH CH CHCH OH CH CH CHCH Cl
3 2
2
PCl
5
3 2 2
CH
3 CH
3

1 .hn /ng vi tioon!0 c0orua(

13
R - OH + SOCl
R - O - SOCl R - Cl + SO
2
2
piriin
-
HCl (khng bn)
1 .hn /ng t%ch 0o3i 'h!r%t ho%(
C

C
H OH
axi

C C + H O
2
Phan ung tach loai ancol xay ra theo c ch E
1
va E
2
voi s tham gia cua cht xuc tac
la axit. Kh nng tham gia phan ung tach loai cua ancol bin di theo dy:
ROH: bc ba ~ bc hai ~ bc mt
Huong cua phan ung tach loai xay ra sao cho tao thanh anken la bn vng nht. Ngoai
ra, phan ung tach loai cac ancol nhiu khi xay ra voi s chuyn vi.
Vi du:
CH CH CH CH OH
CH CH ! CHCH "# CH CH CH ! CH
2
H SO
2 $
2 3
3
3 2
2 2
3
%n n&ng (S'n ph() *h+nh)
c- .hn /ng ox! ho%(
Phan ung chuyn hoa nhom hydrxyl cua hp cht ancol bng phung phap xy hoa
tao thanh cac san phm khac nhau tuy thuc vao loai ancol va tac nhn, diu kin cac
phan ung. Duoi dy la s d c ban cua mt s phan ung:
Bc mt:
R - CH OH
2
C%, 25- C
-

R - C ! O
H
./nO
$
H01* .
2
Cr
2
O

2
H01* .
2
Cr
2
O
2

./nO

$
R - COHH
Bc hai:
R - C - HOH
R

./nO ,CrO , h01* . Cr O $ 2
2
2
3

R - C ! O
R
h01* C%, 25-
-
C
Bc ba:

14
R - C - OH
R



R
./nO (r%ng +nh h01* ki))
$
.hng ph'n 3ng
4+567
CH CH CH OH
C%, 25- C

3

2

2
CH CH C ! O + H
2
2 3
H
CH CH CHCH OH
CH
3
3
CH CH CH COOH
-
./nO
$

3 2 2
3 2
CH
3
OH
. Cr O
2

2
2

! O
"#3#3# CHUYN HO NHM AMIN%
Tung t nhu amnic, nguyn tu nit trong nhom amni mang cp din tu khng
phn chia d tao nn kh nng tham gia cac phan ung nuclphin cua nhom chuc nay. Sau
dy la s d cua mt s phan ung chuyn hoa c ban:
a- .hn /ng t3o mu4i(
RNH

R NH R N R N X
2

2

3

$


+ -
RNH + H RNH

+
+

2


3


+
+

R NH + H R NH

2

2

2


+
+

R N +H R NH
3

3


2

8rNHR rNR 8rNR X

8rNH



8
2

3

+ -
b, Ph'n 3ng ank9l h0: 7
RX
RX
RX
RX
RX RX
Vi du:

15
(n - C H ) NH + C H CH Cl (n - C H ) NCH C H
$ ;
2
< 5

2 $
; 2

2 <

5
n - C H NH n - C H NCH
3 2
2
3 2 3
CH I
3
H
3
CH I
CH
3

CH I
3
3 2 3
n - C H NCH n - C H NCH I
3

2 3
CH
3
CH
3
+ -
c- .hn /ng t3o thnh amit(
Bc mt
RNH
R C
O
N
H
R
R COCl
,
8rSO Cl 2
8r - S - N
O
O
R
H
Bc hai:
R NH
R C
O
N
R
R
R COCl
,
8rSO Cl 2
8r - S - N
O
O
R
R
2
Bc ba:

R N
R COCl
,
8rSO Cl 2
2
khng ph'n 3ng
khng ph'n 3ng
Vi du:

16

NH
2

(CH CO 3
)

2
O
- N - C - CH
3
O
H
C H SO Cl < 5 2
5%ng 5=*h NaOH

- N - S -
H
O
O
C H NCH
<
5 3
H
C H COCl
n - CH C H SO Cl
CH
5
<
3 < 5 2
3
- C - N
-
O
CH
CH
S - N
CH
C H
O
3
3
3
2
5
5%ng 5=*h NaOH
5- .hn /ng vi axit nit6(
Amin thm bc mt:

8rNH

8r - N

N
HONO
2
+
)%>i i?ini
Amin bo bc mt:
RNH R - N

N
HONO
2
+
H O
2

N + h@n hA p an*0l "# ankBn
2
Amin thm va bo bc hai:

HONO
8rNHR 8r - N - N ! O
h01*
R NH R N - N ! O
2

h01*
R
N - Nir0Ca)in
2

17
Amin thm bc ba:

HONO



NR O ! N
2


NR
2
Amin bo bc ba:
HONO



R N R N - N ! O + anDh9, xDn 3 2
"- .hn /ng t%ch 0o3i(
Phan ung tach loai cac hp cht amin d tao thanh cac anken chi co th thc hin
duc khi chuyn chung thanh ion amni bc bn. Co 2 phan ung tach loai c ban sau dy:
Phan ung tach loai theo Hpman:


- C - C -
H
NR
3
HO
,
%n n&ng
E C ! C F + R N + H O
3 2
Vi du:
CH - N - CH CH CH CH - N + CH !CHCH + H O 3 2 2 3
3
CH
CH
CH
CH
2
3 2
3
3
3
3
HO, %n n&ng
Phan ung tach loai theo Kopu:
8)in bG* ba

- C - C E C ! C F + R NOH
%n n&ng
H O 2 2
2
HO
N O R
R
O
Vi du:

18
R - CH - CH R - CH - CH RCH ! CH + CH - N - CH CH R


2
,
2
OH
3 2 2 2
H$- C
-
H O 2 2
2 2
N
H C CH CH R 3 2 2
,
N - CH CH R
H C -
3
2 2
,
O
"#3#B# CHUYN HO NHM HAaOGIN
a, Do co nhng cp din tu t do trn cac ocbital cua cac nguyn tu halogen nn cac hp
cht halogen tham gia phan ung th nuclophin. Duoi dy la s d cua mt s phan ung
th nuclophin thuong xay ra:
Phan ung San phm
R: X : Z R : Z : X -
R: X : OH R : OH : X ancol
R: X : H
2
O R : OH ancol
R: X : OR

R : OR

ete
R: X : C CR

R : C CR

ankin
R: X : Na R

R : R

ankan
R: X : I R : I ankyl idua
R: X : CN R : CN nitri
R: X : R

OO : R : COOR este
R: X : NH
3
R : NH
2
amin bc nht
R: X : NH
2
R

R : NHR amin bc hai

R: X : NH
2
R

R : NR

amin bc ba
R 7 X + 7 P(C H ) R 7 P (C H ) X )%>i ph0ph0ni
< 5
3
<
5 3
R: X : SH R : SH Tiol(mcaptai)
R: X : SR

R : SR

Tiete(sunIir)
R 7 X + 7 CH(COOC H ) R 7 CH (COOC H ) IJng hA p )alni*
2 5 2 2 5 2
R 7 X + 7 CH COCHCOOC H CH COCHCOOC H IJng hA p axDaxBa
5 2 3 5 2 3
KKK
R
Phan ung th nuclphin xay ra theo c ch S
N1
hoc S
N2
tuy thuc vao ban cht hoa
hoc cua dn xut halogen. S phu thuc do duc hiu qua s d bin di sau:

1
I>* L ph'n 3ng S Mng
N
2


RX ! CH X, bG* )L, bG* hai, bG* ba
3
I>* L ph'n 3ng S 2 Mng
N
Mt khac, cn chu thm rng phan ung xay ra theo c ch S
N
1 thuong kem theo s
chuyn vi:
Vi du:
CH - C - CH Nr
CH
CH
3
2
3
3
C H O
2 5
C H OH 2 5
CH - C - CH OC H khng *& *h%9On "=
CH
CH
3
3
3
2
2
5
S
N2
CH - C - CH CH
CH
OC H
CH - C ! CH - CH
CH
S
N
3
3
2 3
2
5
3
3
3
H
*hP*& Q'n ph()
*h%9On "=
a, Phan ung tach loai:
Cac dn xut halogen khng chi co tham gia chu yu vao cac phan ung th nuclphin
ma con tham gia cac phan ung tach loai, tao thanh cac hp cht khng no:

C C
H X
C ! C
NaCR
Phan ung tach loai cua cac dn xut halogen xay ra theo c ch E1 va E2. Khi nay
tham gia phan ung tach loai cua chung theo c ch E1 va E2 thay di nhu sau:
Bc ba ~ Bc hai ~ Bc mt.
c, Phan ung khu
Phan ung khu cac dn xut halogen co th xay ra bng Hydr voi s tham gia cua cac
xuc tac kim loai cung co th bng Hydr moi sinh (khu hoa hoc):
Khu xuc tac:

RX + H RH + HX
2
Ni

20
Khu hoa hoc:
RX + / + H RX + / +X
Vi du:
CCl CHCl
SB,H O
$
2
3
(CH ) CCl (CH ) C/gCl (CH ) CT
3 3 3 3 3 3
Nr
Nr
Na, CH OH
3
2,2 -ibr) n0r*aran
N0r*aran
"#3#D# CHUYN HO NHM ANHYT V `T%N2
Hoa hoc cua cac hp cht andhyt va xtn duc xac dinh boi s co mt cua nhom
cacbonyl ~ C O. Chinh nhom nay la trung tm cua s tn cng nuclophin. Vi vy,
phan ung chuyn hoa dc trung cho an dhyt va xtn la phan ung cng hp nuclophin.
Ngoai ra, andhyt va xtn con tham gia mt s phan ung khac nhu xi hoa, khu hoa,
ngung tu,... Sau dy la s d cua mt s phan ung c ban.
a, Phan ung xi hoa:
Andhyt:
RCHO h01* 8rCHC
8g(NH )
./nO
. Cr O

RCOOH h01* 8rCOOH
3 3
$
2 2 2
Vi du:
CH CHO + 28g (NH ) +3HO 8g +CH COO + $NH + 2 H O
3 3 3 3
2 3
Mtyl xtn:
R - C - CH h01* 8r - C - CH RCOO h01* 8rCOO + CHX
3 3 3
OX
O
O
Vi du:

21
C H - C - CH + 3OI C H COO + CHI +2HO
2 5 3
2 5 3
O
- - -
CH C ! CH - C - CH CHCl + CH C ! CHCOO.
CH
O
CH
3 3
3 3
3 3
.OCl
<-
-
b, Phan ung th:
- Khu hoa thanh ancol:
C OH
H + Ni, P h01* P5
Ui8lH h01* NaNH ,iVp hB0 H
C ! O
2
$ $
Vi du:
H
OH
O
H , Ni
2
C CH
O
Ui8l H H
+
CH CH
OH
3
$
- Khu hoa thanh hydrcacbon:
C ! O
Wn (Hg), HCl()
NH NH , NaCR
2 2
- C - H khX .lB)BnxBn
- C - H khX .iCnB - 40n?a
H
H

22
Vi du:
CH CH CH COCl
3 2
2 2

2
8lCl
3
CCH CH CH
2 2
3
O
Wn(Hg), HCl()
CH CH CH CH
2 2 2 3
O
NH NH , NaOH
2 2
H
H
- Khu hoa thanh pinacol:
C
khX h0: l- Y ng phZn X
C C
O
OH
OH
Pina*0l
Vi du:
2CH CCH CH C C CH CH C
3
3 3 3 3
/g, NBnCBn H O
2

C CH
3
O O O
/g
CH CH
CH CH
OH OH
3 3
3
3
C
O
/g + /gI , BB, bBnCBn
C C
HO

OH
2
- Amin hoa - khu hoa:
E C ! O + NH E C ! NH E CH - NH
3 2
H , Ni
2
Vi du:
CH (CH ) CHO CH (CH ) CH NH
NH , H , Ni
3 2 5
3 2
3 2
5
2 2
CCH CH - CH
O
NH
2
3 3
NH , H , Ni
3 2
- Phan ung cng hp rinha:

23
C + R/gX C R C R
O
O/gX
OH
H O
2
Phan ung xay ra theo c ch cng hp nuclphin A
N
: voi Iocmandhyt tao thanh
ancol bc mt, voi cac andhyt khac tao thanh ancol bc hai, voi xtn s tao thanh
ancol bc ba.
Vi du:

CH CH CHCH + H - C ! O CH CH CHCH O/gNr CH CH CHCH OH
H O
2
3
2 3 3 2 2 3 2 2
CH
3
CH
3
H
/gNr
/gNr + CH - C ! O CHO/gNr
CHOH
CH
H O
2
3
CH
3 H
3
n - C H /gNr + CH - C ! O n - C H CO/gNr n - C H C - OH
$ ; $ ; 3 $ ;
H O 2
CH CH CH
CH CH
3
3 3
3 3
d, Phan ung cng hp tao thanh xianhydric:
C + CN C CN
H
O
OH
Vi du:

24
CH - C ! O + NaCN
H
CH - C - CN CH - C - COOH
H H
OH OH
3 3 3
H SO
2 $
H O[HCl
2
CH - C ! O + NaCN CH - C - CN CH - C - COOH
O
CH
OH
CH
OH
3
3
3
3
3
CH ! C - COOH
CH
3
2
H O,H SO 2 2 $
e, Phan ung cng bisunIit:
C + Na HSO C SO Na
OH
+
-
3 3
-
+

O
Vi du:
C ! O + Na HSO
C SO Na
H
OH
H
$
3
CH CH CCH + Na HSO CH CH C - SO Na
3
2 3
$
3 2 3
O
CH
OH
3
g, Phan ung cng hp voi cac dn xut cua amnic.

25
H N - \ S'n ph()
H N - OH H9rxila)in C ! NOH ] xi)
H N - NH H9raCin C ! N - NH H9raC0n
H N - NHC H PhBn9lh9raCi C ! NNHC H PhBn9lh9raCi
H N - NHCONH SB)i*a*baCi C ! NNHCONH SB)i*a*baCi
2
2
2
2
2
2
< 5
2
< 5
2
2
Vi du:
CH OH ! O + H N - OH CH CH ! NOH + H O
3 2 3
H
2
CH ! O + H N - NHC H CH ! NNHC H +H O 2 < 5 < 5 2
H
CH COOH + H N - NHCONH CH C ! NNHCONH + H O
3 3 2 2 3 2 2
CH
3
H
h, Phan ung cng voi ancol tao thanh hp cht axtal:

C + 2ROH - C - OR + H O
H
+
2
O
OR
Vi du:

CH - C ! O +2C H OH CH - C - OC H + H O
HCl
H H
OC H
2
5
2 5 2 2 5 3 3
i, Phan ung Kaizar:
2 - C ! O - COO + - CH OH
NaCR )^ nh

-
2
H
Vi du:
2HCHO HCOO + CH OH
55 5-_ NaOH
2
k, Phan ung ngung tu:

26
8rCHO + (RCH CO) O 8r CH ! C - COOH
R
2 2
NaCR
"#3#G# CHUYN HO NHM A`IT CAC&O`YaIC V [cN `UT CbA
CH!NG
Tinh cht hoa hoc cua axit cacboxylic duc xac dinh boi s co mt cua nhom
cacbonxyl : - COOH. Nhom nay duc cu tao t nhom cacbonyl ( ~C O) va
hydrxyl (OH), do do phan ung chuyn hoa nhom - COOH cung chinh la s chuyn
hoa cua hai nhom nay. Duoi dy la s d chuyn hoa cua mt s phan ung c ban:
a- .hn /ng chu!7n ho% thnh c%c 58n xu9t axit(
R - C R - C (W ! Cl, OR , NH )
`
2
O
OH W
O
Chuyn hoa thanh cloranhydrat:

R - C + PCl

O
OH
SOCl
PCl
2
3
5
R - C
Cl
O
Vi du:
CH COOH + PCl 3 CH COCl + H PO 3
3 3 3
3 3
5- C
-
Chuyn hoa thanh este:
R - C + R - C R - C
O
O
O
OH Cl
OR
SOCl
R OH
3 `
`
R - C + R OH R - C + H O
O
OH
O
OR
2
H
`
.ha nMng ph'n 3ng R OH 7 NG* )L E NG* hai E NG* ba `
Chuyn hoa thanh amit:

27

R - C RCOONH R - C
NH %n n&ng
- H O
OH

O
3
2
O
NH2
R - C + R - C R - C
O O O
OH Cl NH
2
SOCl NH
2 3
4+567
CH COOH CH COONH CH CONH
NH
NH
3
3
3
$ 3 3 2
C H CH COOH C H CH COCl C H CH CONH
< 5 2 < 5
2
< 5 2
SOCl NH
2
3
:- ;h< ho%(
RCOOH RCH OH
2
Ui8l H
$
4+567
$ (CH ) C COOH + Ui8l H
(CH ) C CH O 8l Ui (CH ) C CH OH
2 3 3
H ,Ui 8lO
2 2
3
3 2 $
BB
$ 3
3
c- .hn /ng th7 hi=n tnh axit t3o thnh mu4i(
RCOOH RCOO + H
4+567
2 CH COOH + Wn (CH COO) Wn + H
2 3 3 2
CH (CH ) COOH + NaOH CH (CH ) COONa + H O
3 H- 3 2 H- 2
h- .hn /ng 'cac:ox!0 ho%(
C H COONa + NaOH (CaO) C H + Na CO
< 5 < < 2 3

-
C
NO
NO
COOH
O N + CO
NO
NO
H O, H
%n Qi
NO
2
2
2
2
2
2
2

28
CHNG II2
S PHN CdT V TeO THNH aIN 'fT CAC&ON X CAC&ON
Trong cac qua trinh phan ung hoa hoc, lin kt C X gia cacbon va mt nguyn tu X
khac (Co th la cacbon, xy, halogen...) trong phn tu cht hu c co kh nng dut ra theo
3 kiu khac nhau:
aK - C 7 X - C + X

*a*b*ai0n
bK - C 7 X - C + X
*K - C 7 X - C + X
*a*b*ai0n
h>* *a*b b 50
+
+
-
-

-
+
.iO% phZn *c 5=l9
.iO% phZn *c dng l9
Trong kiu phn ct thu nht tao ra mt ion voi nguyn tu cacbon thiu mt electrn
va mang din dung. Ion nay duc goi la cacbcation. Trong kiu phn ct thu hai ion
sinh ra mang din tich m goi la cacbanion. Do la hai kiu phn ct di ly. Cong kiu phn
ct thu ba phn ct dng ly, tao ra gc t do voi din tu t do o nguyn tu cacbon goi tt
la gc cacb t do.
S phn ct nhu trn co th xay ra duc khng hoc co th xay ra theo kiu nao, diu
do tuy thuc chu yu vao cu truc cua phn tu chua nhom C X va cac diu kin tin
hanh phan ung. S khao sat cac ion va gc t do cua cacbon co tm quan trong dc bit
trong vic tim hiu c ch cac phan ung hu c.
3#"#CAC&%CATION
Cacbcation la nhng cation ma trung tm din dung la nguyn tu caacbon. Co nhiu
loai cacbcation khac nhau:
Cacbcation co ba lin kt

o C
()
(ph bin nht). Thi du (CH
3
)
3
C
()
.
Cacbcation chi co hai lin kt

o C
()
. Thi du CH
2
CH
()
. C
6
H
5
()
.
Cacbcation khng kinh din (nonlassical carboncation) hay la cacbcation cu ni.
Trong do din tiach dung duc giai tao nho cac lin kt

hoc

o vi tri tung di xa
nguyn tu cacbon trung tm.
Cacbcation co s phi tri 5 (rt it gp). Thi du: CH
5
()
. Trong phn nay chu yu d
cp dn loai cacbcation thu nht.
3#"#"# NHNG PH^N NG TeO THNH CAC&%CATION
3#"#"#" C19 >()* +*, 9g6 .=5* P:6 C X ` 6(M*( 9-9SC9-6=/*
a. .h>n c,t 0i'n *t ? @ Aa0. Mun cho lin kt C Hal bi phn ct di ly diu kin tt
nht la Hal co kh nng hut electron manh, cacbcation sinh ra co cu truc tung di bn

2
va dung mi co kh nng ion hoa cao. Vi du triphnylclomtan la mt cht rn kt tinh
khng mau, khng tan trong nuoc va d tan trong C
6
H
6
hoc CHCl
3
cho dung dich khng
mau va khng dn din do s phn ly:
C H ) C - Cl (C H ) C + Cl

< 5
(
3
<
5 3
SO leng
2
+ -
L tt nhin cac ion sinh ra du bi sonvat hoa, trong cac dung mi nhu nitrmtan,
axtn... triphnylclomtan cung bi phn ly nhung o muc d yu hn. Vi dung dich
cacbcation dn din va co mau nn nguoi ta co th dung cac phung phap vt l d khao
sat. Chng han bng phung phap quang ph nguoi ta d thit lp duc rng o 0
0
c dung
dich 0,1M (C
6
H
5
)
3
C-Cl trong SO
2
long co chua 3,2 o dang ion con dung dich 0,01M
chua 21.
Trang thai cua lin kt C-Hal co th thay di r rt khi co tac dung cua cac mui
halgenua kim loai co kh nng tao mui phuc voi halgen trong C-Hal, nhu: SnCl
4
,
AlCl
3
, SbCl
5
, HgCl
2
... Thi du:
C H ) C - Cl + SbCl (C H ) CCl + SbCl (C H ) C + SbCl
< 5
(
3
5
< 5 3 < 5 3 5 <
+
-
Qua trinh phn ly o trn co th xay ra ngay trong cac dung mi khng phn cc nhu
benzen, ttraclorua cacbon... Dang chu la nhiu dn xut halgen, voi halgen o nguyn
tu cacbon bt doi, co th t raxemic hoa trong dung mi co kh nng ion hoa cao vi qua
trinh phn ly co tinh thun nghich.
Nu dn xut halgen khng t phn ly thanh cacbcation d raxemic hoa duc thi
nguoi ta co th nhng mui halogen kim loai nhu d noi trn. Hin tung raxemic hoa y
la c so cua mt phung phap khao sat qua trinh phn ly, dc bit la qua trinh phn ly cua
nhng cht co d phn ly km.
:- .h>n c,t 0i'n *t ?BCA. Lin kt C-OH rt kho t phn ly thanh cacbcation va
anion hydroxyl. Chng han triphnylcation la mt cht khng mau va trung tinh, khng
phn ly trong C
6
H
6
. Phn ly rt yu trong SO
2
long nhung trong axit sunIuric dc hay axit
Iomic co phn ly manh cho ta nhng dung dich mau vang da cam. Quang ph cua cac
dung dich nay ging quang ph cua dung dich (C
6
H
6
)
3
C
C H ) COH + 2H SO (C H ) C + H O + 2HSO
< 5
(
3 2 < 5 3
3 $
+
-
$
Vi phan ung trn d chuyn dung dich mt cht khng mau thanh dung dich cht co
mau (hoc mau thm hn) do hin tung tao mui cho nn nguoi ta cho do la mt vi du
cua hin tung halcrm (Hal-mui, rm-mau)

30
Cac ancolloai bo bc cao thi du (CH
3
)
3
COH cung co kh nng tao ra ion cacbni
trong axit sunIuric dc. Thi du trimtylcacbinol
c. .h>n c,t 0i'n *t ?B?. Lin kt C-C noi chung kho phn ly thanh ion. Tuy nhin
nhng dn xut thm cua metan nhu ttraphnylmtan, dimtylphnylmtan,...trong axit
sunIuric ddaclai co th cho ta nhng dung dich co mau va co tinh huynh quang khi
chiu tia tu ngoai vao, do hin tung tao thanh cacbocation.
So sanh quang ph electron cua dung dich trimtylcacbinol va dung dich
dimtylphnylcacbinol trong H
2
SO
4
dc voi dung dich trimtylphnylmtan nguoi ta di
dn kt lun rng trimtylphnylmtan bi phn ct thanh cation tecbutyl.
(CH ) C - C H (CH ) C
3 2 < 5 3 3
+
d. Mt s hp cht khac nhu este cua axit v c manh ROSO
2
H, ROSO
2
Ar, hoc hp
cht az trong nhng diu kin thich hp cung co th phn ly thanh cacbcation. Thi du:
R - N N R + N

+
2
+
3#"#"3# C19 >()* +*, 9@*, LM/ *h= WC= 6i/ 6(-*( 9-9SC9-6=/*
a. ?ng 2rDtDn vo n4i Di c$a an*"n( Khi co mt axit manh alken co th cng hp
prtn thanh cacbcation.
R C ! CR + H8 R C - CHR + 8
2
2
2 2
-
+
nu ion nay rt it bn no s chuyn hoa ngay. Vi du:
CH ! CH + H SO CH CH HSO CH CH OSO H
3 2 3
$ 2
3 $
2
2 2
+
D chung minh rng qua thc cacbcation co sinh ra t ken nguoi ta so sanh ph
electron cua 1,1- diphnyltylen va cua hai dung dich nay co ph kh kin rt ging nhau,
diu do chung to trong ca hai dung dich du tao ra cacbcation mtyldiphnyl mtyl.
:. ?ng 2rDn vo nhm ca:Dn!0(
Cac andhyt va xtn
,
- chua no voi d lin hp cao, co kh nng kt hp prtn
tao thanh cacbcation chua nhom hydrxy o ngay nguyn tu cacbon trung tm. Thi du:

31

- CH ! CH - C ! O + H SO - CH ! CH - C - OH + H SO
2 $
2
2
$ 2
-
+
Phan ung trn la mt phan ung halcrm.
Trong s cac phan ung tao thanh cacbcation chung ta con phai k dn cac qua trinh
tao thanh hp cht thm khng co vong bn nhu ion triphnyl-xycclpropenili, dication
ttraphenyl-xycclpropenili...
3#"#3#"# CQT 6;j9 P(C*, ,=-*2
V mt l thuyt ta co th cho rng cacbcation co cu truc phng tung t R
3
B hoc
cu truc hinh thap tung t R
3
N.
D giai quyt vn d nay ta co th dua vao s bin di nng sut quay cc cua dung
dich hp cht co cacbon bt di kiu R
1
R
2
R
3
C Hal. Ta bit rng khi hoa tan hp cht
trn vao SO
2
long s xy ra qua trinh thun nghich.
R - C - Cl R - C - Cl
R
R
R
R
H
2
3
H
2
3
+
-
Nu cacbcation co cu truc phng nhu triankyl bo thi trong qua trinh nghich Cl
(-)
co
th tn cng nguyn tu cacbon mang din dung t hai phia voi xac sut nhu sau:

C
R
R
H
2
+
+ Cl Cl - C - "# C - Cl
R
R
R
R
R
R
H
H
2
2
3 3
R
3
kt qua s tao ra bin th raxemic, va R
1
R
2
R
3
C-Cl trong SO
2
long s bi raxemic hoa.

32
Nguc lai nu ion co cu truc hinh thap nhu R
3
N thi trong qua trinh nghich Cl
(-)
chi co
th tn cng t mt phia thi.
C + Cl C
R R R R R R
H 2 3 H 2 3
+
-
Cl
kt qua la cu hinh cua phn tu phai duc bao toan.
Thc t cho thy rng cac phn ly thanh cacbcation nhu trn di voi hp cht cacbon
bt di lun lun kem theo s giam nng sut quay cc. D kin nay cung voi cac d kin
thc nghim khac chung to rng cacbcation co cu truc phng hay gn nhu phng.
Thuyt c lung tu cung cho kt qua tung t.
Trong truong hp cacbcation triarylmtyl ta hiu cu truc phng la ba truc xut phat
t nguyn tu cacbon mang din dung xuyn qua cac vi tri 1,4 cua vong benzen du o
trn mt mt phng. Con ba vong khng nht thit o trn mt phng do ma bi lch di
trong khng gian (do anh huong khng gian) tung t nhu ba canh cua mt chic quat
ban.
Trong cac cation xyclpropy ba lin kit C-C o trn mt mt phng, con vong
xyclpropan tao thanh mt phng khac nhau thng goc voi mt phng va noi va song
song voi truc cua obitan p con trng cua nguyn tu C
()
. Thi du:
Cu truc phng la diu kin cn d cho cacbcation tn tai . Vi th, khac voi
triphnyclomtan, 1-brmtryptyxen (A) trong SO
2
long khng cho dung dich mau va cung
khng dn din. Khac voi triphnylcacbinol, 1 hydrxytryptyxen (B) trong H
2
SO
4
dc
cung khong cho dung dich mau. Nhng diu do chung to chung rt kho tao ra cacbcation
hinh thap.

C
CH
3
CH
3
33
C
Nr
-
C
H
(8)
(N)
H
C
-
OH
C
3#"#3#3# CQT 6;j9 6=*( L= LM W@ Sk* Ll*, 6J8*, Wh=
D bn tung di cua cac ion cacbni co lin quan cht ch toi s phn b din
tich Ec9u trFc tinh viG trong toan b ion. Din tich cang duc giai toa rng ra nhiu
nguyn tu trong ion thi d bn tung di cang cao.
Mun tng d bn cua mt cacbcation co th dua vao nguyn tu cacbon mang
din dung nhng nhom co hiu ung lin hoph hoc lin hp dung:
H C - C C C C C C C O C
H
H
C
+ + + +
Vi vy, trong dy cation ankyl cung nhu trong dy cac cation arlmtyl, bc cua
cation cang cao d bn cua cation cang lon:
CH F CH CH F CH(CH ) F C (CH )
+

+

+

+

3
2
3 3 2 3 3
2
3
CH F CH C H F CH(C H ) F C (C H )
<
5 < 5
2
< 5
3

+ +
+
+
Dy thu hai thuong co d bn tung di cao hn dy thu nht vi hiu ung C cua
nhom aryl manh hn hiu ung H cua nhom ankyl. Tung t nhu vy, s co mt cua
nhom viryl o C (Cation alyl) lam cho d bn cua cation tng ln r rt:

CH - CH - CH F CH - CH ! CH
2 2 3
2 2
+
+
Kt qua tinh toan din tich dung theo cac phung phap hoa lung cung nhu cac
kt qua khao sat bng cac phung phap vt l d xac nhn co s giai toa din tich dung
trong cacbcation lin hp o trn. Thi du theo phung phap MO Hucken din tich dung
o mt s cacbcation duc giai toa nhu sau:

34
CH ! CH - CH C H CH C H
2
+ +
2
<
5 < 5
C (CH )
3 2
+
+ -,-5 - +-,-5 - +-,H$ - + -,-f

C C C + -,H$


C + -,-f
C
C H
< 5
5 <
C H
+-,52 +-,3H
- + -,H$ - + -,-f
Cac nhom th co hiu ung C hay H o vi tri para cua C
6
H
5
CH
2
hoc o vi tri

cua CH
2
CHCH
2
lam cho d bn tng ln; trai lai cac nhom th co hiu ung -C hoc H
o nhng vi tri do lam chop d bn gim di.
Trong nhng truong hp cacbtion khng kinh din, so d chung co d bn tung
di cao (So voi
CH
+

chng han) vi co s giai toa electron

cua lin kt C C hoc

electron

cua lin kt C C khng o vi tri lin hp di voi obitan trng ma o vi tri xa

hn. Thi du:
CH - CH
CH - CH
2
2
+
CH
CH
+
2
2
CH
CH
2
2
+
(Sinh ra tu CH
3
CHCH
2
Cl (Sinh ra t C
6
H
5
CH
2
CH
2
Br)
hoc t xicl-C
6
H
5
CH
2
Cl)
S xut hin tinh bn vng dc bit cua cac cation thm (thi du ion trpili) cung
do s lin hp va cac dc tinh khac cua vong thm gy nn.
3#3#CAC&ANION
Khac voi cacbcation co nguyn tu cacbn thit thu electron va mang din tich
dung, cacbanion co mt cp electron du o nguyn tu cacbon va mang din tich m. ia
loai ion nay co s lin quan cht ch; v diu kin tao thanh va tinh cht co nhng dim
tung t nhau hoc di lp nhau; vi th khi khao sat cacbanion cn lin h voi
cacbcation.
3#3#" S PHN aY aIN 'fT C X ` THNH CAC&ANION
3#3#"#"# =kT P=m* 6(Tn* .A= 9(/ E< >(N* .7 .=5* P:6 C X ` 6(M*( 9-9S-*=/*#
Mun cho lin kt C X d bi phn ct di ly thanh cacbanion diu kin tt nht la:
a. Cp electron o lin kt C X chuyn manh v phia nguyn tu cacbon, chng han cac
lin kt CK, CNa,... trong hp cht c kim; b. Cacbanion sinh ra co cu tao tung di bn

35
nhu cac anion triarrylmtyl chng han; c. Dung mi duc dung co kh nng ion hoa cao,
thuong amniac long, ete,...
Triphnylclomtan chi d phn ly thanh cacbcation thi. Nhung nu ta chuyn
nhng phn tu nay thanh dn sut natri (C
6
H
5
)
3
CNa trong amnic long chung lai cho ta
nhng dung dich dn din va co mau, do s tao thanh cacbanion va ion kim loai.
(C H ) C - H
(C H ) C - Cl
< 5 3
< 5 3
(C H ) C - CNa (C H ) C 7 Na
Na
NH leng
Na
3
< 5 3
< 5 3
+
NH
3
leng
Cacbanion cua nhng ankan dn gian co trong cac hp cht c nguyn t nhu cac
hp cht cua liti, natri, magi...; do do noi chung cac hp cht nay tham gia phan ung nhu
nhng cacbanion. Tuy vy, khng nn ngh rng cac hp cht y la nhng mui dn gian
kiu R
-
M

vi rng cac lin kt giua cacbon voi kim loai phn nao mang tinh cht cng
hoa tri.
3#3#"#3# S< >(N* .7 .=5* P:6 C X H LM .<9 C X H 6J8*, Wh=2
Lin kt C H cung co th bi phn ct di ly tao thanh cacbanion nu nguyn tu H
co d linh dng rt cao. Thi du triphnylmtan thc t khng tac dung voi kim duc
nhung tri (p-nitrophnyl) mtan lai tac dung duc voi NaOH tao ra dn xut natri d phn
ly thanh cacbanion.

(p - NO C H ) CH + NaOH (p - NO C H ) CNa + HOH
3
$ 2
< 2
<
$ 3
Qua trinh phn ly lin kt C H o dy chinh la qua trinh phn ly cua nhng axit
cho nn nguoi ta co th dung cac gia tri pKa lam muc do s phn ct di ly nay.
3#3#3 CU T$!C V Z &N TNG oI CbA CAC&ANION
3#"#3#"# CQT 6;j9 P(C*, ,=-*2
Nhin vao cng thuc cua cacbanion ta co th cho rng cac anion nay co cu truc mt
phng nhu cacbcation. Nhung cacbanion lai co cp electron con du, nn cung co th
chop rng chung co cu truc hinh thap.
D giai quyt vn d cu truc khng gian cua cacbanion nguoi ta co dung phung
phap do s bin di tinh quang hoat cua hp cht co cacbon bt di trong qua trinh tao
thanh cacbanion. Tuy vy phung phap nay gp nhiu kho khn cn ban. Vi th trong
tng thoi gian, tng nguoi co nhng nhn dinh khac nhau.
Hin nay noi chung nguoi ta d nht tri rng cacbanion co th co cu truc hinh thap
hay cu truc gn nhu thng tuy theo ban cht cua cac nhom th o nguyn tu cacbon mang
din tich m.
Nu gia nhom th va cp electron o C
()
khng co s lin hp thi cacbanion co
cu truc hinh thap theo mt cn bng gia hai dang:

36

C C
R
R
R
R
R
R
H
2
3
H
2
3
Vi th trong phan ung duoi dy cu hinh cua phn tu vn bao toan.
n - C H n - C H n - C H
CH C - T CH C CH C - H
C H SO C H SO C H SO
< H3
3
< 5 2 < 5
2
< 5 2
3 3
< H3 <
H3
OCH
3
HOCH
3
-
-
g
( I+nh khiV% h%ang hi*) ( j L inh khiV h%ang hi* ;-_)
Trai lai nu gia nhom th va cp electron o C
(-)
co s lin hp d cho anion tro v bn
vng thi anion do co cu truc phng hay gn nhu phng. Vi vy, ta thy trong qua trinh
sau dy co s raxmic hoa:
C H - C - COO C C H - C - H
CN CN
K K
C H
C H
2 5
2 5 2 5
g
-
ani0n h%ang h0^ *a*bani0n biVn hOraxD)i*
3#3#3#3# CQT 6;j9 6=*( L= LM W@ Sk* 6J8*, Wh=
ia cu truc tinh vi (s phn b mt d electron) va d bn tung di cua cacbanion
cung co mi lin quan: din tich m hay la mt d electron o nguyn tu cacbon trung tm
cang duc giai toa rng d bn cua cacbon cang cao. Nhng nhom th voi hiu ung C co
kh nng giai tao din tich m nhu vy, chng han tinh toan cho thy trong cac anion alyl
va benzyl din tich m o nguyn tu cacbon trung tm chi bng khoang dn vi din tich.

C C C --,H$

C
--,5- - --,-5
- --,H$
-
--,H2
- --,H$

37
Vi th tluen co pKa ( 38) nho hn cua tan ( 58) , triphnylmtan co pKa con nho
hn na
( 33). D bn cua cac cacbanion nhu C
6
H
5
CH
2
(-)
, (C
6
H
5
)
6
C
(-)
s tng ln khi tng ln o
vi tri para co nhom th gy hiu ung C ( thi du NO
2
, CN...) nguc lai s giam di khi co
nhom th C.
Nu nhng nhom th -C ni trc tip voi nguyn tu ccbnion s tng ln r rt (biu
hin o pKa). Thi du:

CH CN 25 CH (COOC H ) H3
CH (CN) HH CH (COCH ) ;
p.a p.a
3
2
2
2 3 2
2
5
3
Trong nhng truong hp do, din tich cua cacbanion phn b o 2 nguyn tu khac
nhau. Thi du:

CH - C ! CH COOC H KKK
K
K
K
O
3
2
5

Nhng nhom co hiu ung -1 hoc H ni voi C

(-)
cung lam tng manh d bn cua
cacbanion. Thi du: pKa(theo thang Xtrviz) cua CF
3
H : 28, (CF
3
)
3
CH : 11.
Cac anion vong thm nhu C
3
H
5
(-)
, C
6
H
5
2
... co tinh bn cao la do s lin hp va cac dc
tinh khac cua hp cht thm.
3#B PH^N NG TeO aIN 'fT CAC&ON X CAC&ON VpI S THAM GIA
CbA CAC&%CATION V CAC&ONANION2
3#B#"# PH^N NG TeO aIN 'fT CAC&ON X CAC&ON CbA CAC&%CATION
3#B#"#"# P()* +*, -*P7. (/12
a. Phan ung ankyl hoa cua cacbcation d tao ra lin kt cacbon-cacbon la phan ung
cng hp voi ankan. Vi du din hinh nht cua phan ung nay la s tao thanh 2,2,4
trimtylpetan duc dung lam nhin liu cho dng c t izbutan va izbutylen.

38
(H) CH - C ! CH + H CH - C - CH
CH
CH
+
+
3
3
3 3 3 2
(2) CH - C ! CH C - CH CH - C ! CH - C - CH
CH CH CH CH
CH CH
+
+
3 3 3 3
3
3
3 2 3 3 2 3
(3)
CH - C ! CH - C - CH + H - C- CH CH - C ! CH - C - CH + H - C - CH
3 2
3
3 3
2 3 3
CH CH CH CH CH
CH CH H CH
+
3 3 3 3
3
3 3 3
CH
3
+
Sau do phan ung lai tip tuc 2, 3; 2, 3...
b. Phan ung ankyl hoa cua cacbcation xay ra o cac hp cht thm theo c ch S
E
(phan ung Faiden-Crap). Trong phan ung nay d thit lp nn mt lin kt cacbon-cacbon
moi:
RCl + 8lCl 8lCl + R
R
R + C H C H
R H
C H + 8lCl C H - R + HCl + 8lCl
3 $
< < < 5
<
5
$ <
5 3
H
-

+
+
+
+
-
Bng phan ung nay co th diu ch duc nhiu hp cht thm co mach nhanh khac
nhau. Vi du:

3
C H + CH CH CH C H - CH CH CH + H
CH CH
C H + CH C - CH C H - C - CH + H
CH
< < 3
2 2 < 5
2 2 3
+
+
+
+
3 3
3
< < 3 3 < 5 3
8lCl
8lCl
3
3
3#B#"#3# P()* +*, 9@*, (A> LM/ -*P0*
Dy la phan ung cng hp tao thanh mt caacbcation moi voi s hinh thanh lin kt
cacbon-cacbon:
R + E C ! CF R - C - C
+ +
Phan ung nay co ngha quan trong trong qua trinh trung hp theo c ch cactionic.
Vi du phan ung trung hp izbutylen trong axit xay ra nhu sau:
(CH ) C ! CH (CH ) C CH ) C ! CH - C(CH )
3 2 2 3 2 3 2 2
3
2
H CH ! C(CH )
+
KKK 3 2 2
+ +
Trong nhng diu kin xac dinh duoi tac dung cua axit H
2
SO
4
s xay ra phan ung
dime hoa:
2CH - C ! CH
CH
H SO
2 $
CH CH CH - CH - CH - C - CH
CH
CH ! C - CH - C - CH
CH
CH - C ! CH - C - CH
CH
CH
CH
CH CH
3
3 3
2 2 3
3
3 3
3
3 3
3
3
3
3
2 3
H kNi
2
$ 3
3#B#"#B# P()* +*, *,J*, 6q 9;C6C*=92
Hp cht cacbonyl trong mi truong axit bi prtn hoa tao thanh cacbocation:

40
CH CH CH
CH CH CH
3 3 3
3
3 3
C ! O + H C ! O - H C ! OH
+
+
+
Cac hp cht tham gia phan ung ngung tu crtnic tao thanh lin kt cacbon cacbon
moi:
C - OH + CH - C -CH C - CH - C - CH
3 3
2 3
3
CH CH
CH O CH + OH O
3
3 3
+

2
- HOC
C - OH + CH - C - CH C ! CH - C - CH
CH CH
CH CH
O
O
- H
+
3 3
3
3
3 2 3 3
3#B#3# PH^N NG TeO aIN 'fT CAC&ON X CAC&ON CbA CAC&ANION2
Cacbanion duc tao thanh bng s tach di nguyn tu
-
hydr cua cac hp cht
cacbonyl. Vi vy cacbonion la mt baz manh tham gia cac phan ung tao lin kt cacbon-
cacbon nhu mt tac nhn nuclphin.
3#B#3#"# P()* +*, 9@*, (A> *T9.5C>(=* LM/ (A> 9(Q6 9-9S/*7.2
a. .hn /ng ngng tH anato0(
C ! O + - C - C ! O - C - C - C !O
O
+
-
Vi du: Phan ung tao thanh hp cht - hydrxibutandehyt t axxetandehyt xay ra theo
s d sau:

41
CH CHO + HO CH CHO + H O
3 2 2
-
-
H H
CH - C ! O + CH CHO CH - C - CH CHO
3 2 2
-
O

-
CH - C ! O + CH CHO CH - C - CH CHO
H H
O OH
3 2 2 3
-

-
:. .hn /ng ngng tH 2"c*in(
Phan ung cua anhydrit cua axit cacbonxylic voi cac andhyt thm tao thanh mi lin
kt cacbon-cacbon xay theo c ch cng hp nuclphin (phan ung Peckin).
CH - C


C H - CH ! O + C H - C - CH ! C
CH - C
O
O
O

CH - C

O
O
O
O
C H - CH ! CH - COOH + CH COOH
<
5 3

-
< 5 2 < 5
3
3 3
Cac phan ung tao lin kt cacbon cacbon xay ra theo c ch nay con tim thy o rt
nhiu hp cht khac nhau nhu o cac hp cht c kim loai, phan ung ReIocmatxki s duc
trinh bay trong phn sau:
3#B#3#3# P()* +*, 6(: *T9.0C>(=* r *(K4 -H7.
a. .hn /ng ngng tH c0aiI"n
Dy la phan ung tao thanh lin kt cacbon cacbon o hp cht -xtn. Vi du phan
ung diu ch tyl axetaxtat xay ra nhu sau:

42
CH COOC H + C H O C H OH + CH COOC H
CH - C - OC H + CH COOC H CH - C - CH COOC H
CH - C - CH COOC H + C H O
O
OC H
O
O
3 2 5 2 5
-
2 5 2 2 5
2 5
2 2
5 3 2
-
2 5
3 2 2 5 2 5
2 5
3
-
-
-
:JKng hL2 ma0Dnic(
Mt trong nhng phung phap tao lin kt cacboxylic duc da trn c so cua hp
cht etylmelonat goi la tng hp malnic. Trong phan ung nay nguyn tu -hydr cua
etylmalnat rt linh dng nn d dang bi thay th boi cac ion natri tao thanh cacbonion.
CH CH + C H OH
COOC H COOC H
COOC H

COOC H
2
2 5 2 5
2 5
5 2
5 2
C H ONa
2 5
-
Na
-
Cacbanion duc tao thanh rt d tham gia phan ung voi cac dn xut halogen tao
thanh cac san phm khac nhau:
CH CH + NaHal
COOC H COOC H
COOC H

COOC H
2
2 5 2 5
5 2
5 2
R - R - Ral +
Cac este malnic d bi thuy phn trong mi truong axit va sau do bi dcacboxyl hoa
boi nhit tao ra cac axit monocacboxylic:
CH CH + R - CH - COOH
COOC H COOH
COOC H

COOH
2
2 5
5 2
R - R -
HOHkH
+
C
- CO
2
-
2
Theo nguyn tc cua phan ung trn dy khng nhng co th tng hp duc axit kiu R
CH
2
COOH, R CHCOOH ma con tng hp duc cac diaxit kiu HOOC (CH
2
)
n

COOH.

43
R
3#D# TeO aIN 'fT CAC&ON X CAC&ON &sNG CC HP CHT C 'IM2
3#D#"# PH^N NG CbA HP CHT G$INHA2
Khi cho Magi tac dung voi cac dung dich cua ankyl halogenua trong dityl ete khan
(C
2
H
5
)
2
O
Thi phan ung s xay ra rt mnh lit kt qua la Magi bi hoa tan va thu duc mt dung
dich moi. Dung dich do goi la tac nhn rinha. Tac nhn rinha la mt hp cht hoat
dng rt manh, no tac dung nhiu cac hp cht v c k ca nuoc, xy, CO
2
va voi mt s
lung rt lon cac hp cht hu c. Mt trong nhng huong quan trong cua phan ung cac
hp cht Magi la tao ra cac mi lin kt cacbon cacbon.
3#D#"#"# P()* +*, 9@*, (A> 9t- 619 *(N* G;=*(-2
Phan ung cng hp cua tac nhn rinha voi cac hp cht Cacboxyl (andehyt va
xtn). Cac este va cac dn xut cua tylenxit du cho ra san phm la cac ancol voi s
tao thanh cac mi lin kt cacbon cacbon moi. Trong phung phap nay san phm cua
loai ancol thu nhn duc tuy thuc vao dc dim cua cac tac nhn co chua xy duc su
dung.
a.Phan ung cua tac nhn rinha voi cac hp cht cacboxyl: T Focmandhyt HCHO
s tao thanh ancol bc 1, t cac andhyt tao thanh ancol bc 2
0
, va t xtn s tao thanh
ancol bc 3
0
.

44
H - C ! O + R/gX H - C - O/gX
R
H
H - C - OH (8*0l H
-
)
R
H
R - C ! O + R/gx R - C - O/gx H - C - OH (8*0l 2 )
- HOH
`
`
`
H
H H
R R
R - C ! O + R/gx R - C - O/gx H - C - OH (8*0l 3 )
R
R R
R
R
``
``
``
` `
-
Vic vn dung phung phap tng hp nay d thu nhn mt hp cht cn thit theo
mun cn phai cn cu vao cu tao cua san phm ancol. Mt nhom ankyl lin kt voi
nguyn tu cabon mang nhom - OH tao thanh t phn tu cua cac tac nhn rinha, hai
nhom con lai t hp cht cacbonyl, vi du co th thu nhn hp cht 2 phnylhecxanol -2
bng 2 s d phan ung sau:

45

- C + CH CH CH CH /gNr - C - CH CH CH CH
CH
O
CH
OH
3
3
3 2 2 2
2 2
2 3
8xDphBnn0n n - b%9l)agiD br)%a
PhDn9l)agiD br0)a /D9 - n - b%9lxDn
3 2 2 2 2 2 2 3
3
OH
CH
- /gNr + CH CH CH CH - C C - CH CH CH CH
CH
O
3
-

Nhu vy co th thu nhn 2-phnylhecxanol -2 t mt xtr thm voi tac nhn rinha
co 4 nguyn tu cacbon (1) hoc t mt xtn bo voi tac nhn rinha (2). Tuy nhin thc
nghim cho thy rng trong truong hp cu th nay thi tin hanh diu ch 2 -phnylhecxal
-2 theo s d (1) la tt nht.
b. Phan ung cng hp cua tac nhn rinha voi este la mt trong nhng phung phap
tt nht d diu ch ancol bc 3
0
. Phan ung xay ra theo hai giai doan: iai doan 1 tao ra
hp cht xtn va giai doan 2 la phan ung cua xtn voi tac nhn rinha tao ra ancol:

R - C R - C - R R - C - R R - C - R
O
OR
O
R
R
R
R
R /gx R /gx HOH
`` ``
`
``
``
``
``
``
`` ``
H 2

Nhu vy ancol bc 3
0
co th thu nhn duc t xtn hoc este bng phan ung cng
hp voi tac nhn rinha. Tuy nhin cac kt qua nghin cuu cho thy phung phap diu
ch ancol bc 3
0
t este la tt nht. Vi du triphnycacbinol co th thu nhn bng phan ung
cua phnylmagibromua voi este etylbenzoat hoc xtn benzphenon. Ca 2 qua trinh do
co th thc hin t axit benzic theo s d sau:

46
- COOH -

COOC H
- COCl - C -
O
PCl
C H k8lCl
C H OH, H
2C H /gNr
C H /gNr
5
2 5
+
2 5
< 5
< 5
< < 3
-
- C - OH
R rang qua s d cho ta thy rng phan ung chuyn hoa axit benzic thanh
triphnycacbinol bng tac nhn rinha qua buoc tao thanh este xay ra dn gian hn, it
giai doan hn.
c. Phan ung tao thanh lin kt cacbon cacbon cua tac nhn rinha voi xi tylen la
mt phung phap quan trong d diu ch cac ancol bc 1
0
. Phung phap nay co uu dim
lon so voi phan ung diu ch ancol bc 1
0
bng Iocmandhyt s tao ra duc san phm co
mach dai hn 2 nguyn tu cacbon so voi gc ankyl hoc aryl cua tac nhn rinha:
R - /gX + CH - CH RCH CH O/gx RCH CH OH
O
2 2 2 2 2 2
H
+
3#D#"#3# P()* +*, 9t- 919 *(N* G;=*(- LM >(N* 6O 9-9S/* 0.096;/>(=*2
a. .hn /ng vi c%c 58n xu9t Aa0og"n(
V nguyn tc tac nhn rinha co th tham gia phan ung voi cac dn xut halogen
theo c ch S
N
2 tao ra lin kt cacbon cacbon. Dy la mt trong nhng phung phap
thun tin nht d diu ch hydrocacbon no bc bn:
(C H ) C - Cl + C H /gNr (C H ) C + /g
Nr
Cl
< 5
3
< 5 < 5
$
(CH ) C - Cl + C H /gNr (CH ) C - C H + /g
Nr
Cl
3 5 3 2 3 3 2 5
Phan ung nay cung co th dung d diu ch cac hydrcacbon khng no:

47
Nr
Cl
CH CH - /gNr + ClCH - CH ! CH CH CH CH - CH ! CH + /g
3 2 2 2 3 2 2
2
Phan ung cua tac nhn rinha voi dn xut halogen cua axit cacboxylic s tao thanh
hp cht xtn. Trong thc t nguoi ta co th lai cho phan ung dng lai o giai doan tao ra
xtn hoc di xa hn na tao thanh amol bc 3.
RCOU R - CO - R R - C - OH
R/gNr R/gNr, HOH
`
`
R
R
`
`
b. Phan ung voi cac hp cht nitrin RC N
Nhom xian trong cac nitri R C N phan ung voi hp cht magi tao thanh lin kt
cacbon cacbon tung t nhu nhom cacbonyl:
R - /gNr + R - C N R - C - R R - C - R + /g
Nr
Cl
` `
`
N/gNr NH
HOH
Sau do nhom Imin bi thuy phn d tao thanh hp cht xtn:
R - C - R + HOH R - C - R + NH
NH O
` `
3
Phan ung nay co th su dung d diu ch cac xtn bo.
Vi du:
CH CH /gCl + CH - C N CH CH - C - CH
CH CH - C - CH CH CH - C - CH
3 2 3 3 2 3
3 2 3 3 2 3
HOH
HOH
N/gNr
NH O
hoc cac xtn thm:
C H - C N + R/gNr C H - C - R C H - C - R + /g +NH
< 5 < 5 < 5 2
Nr
Cl
N/gNr O
Trong do R - gc bo hoc thm.

48
9# P()* +*, 9t- (A> 9(Q6 4-,=5 Lu= 919 (A> 9(Q6 -*P0.R H)7 ;- 6(0/ 98 9(: 9@*, (A>#
S/ Lu= .=5* P:6 C v O 6(w .=5* P:6 WC= C v C P(K 6(-4 ,=- >()* +*, 9@*, (A> Lu= (A>
9(Q6 >(= P=4 (8*2

C C + R/gHal - C - O -
*hG)
R /gHal
Trong khi do:
C ! O + R/gHal - C - O - /gHal
nhanh
R
Tuy nhin s cng hp vao lin kt di co th thc hin duc khi lin kt do duc
hoat hoa bng mt nhom hut din tu:
Vi du:
x ! C - C ! O + R/gHal - C - C ! C - O/gHal
OR R OR
- C - CH - C ! O - C - C ! C - OH
R OR R OR
`
`
H O
3
+
` `
3#D#3# PH^N NG CC HP CHT C 'IM VpI CC PHN T CAC&ON
IaIT$OPHIN#
3#G#3#"# C19 (A> 9(Q6 98 N-6;= LM 98 a=6=2
Cac hp cht ankyl natri va ankyl liti co nhiu dim ging voi tinh cht cua cac hp
cht c magi nhung co kh nng phan ung cao hn. D tao thanh lin kt cacbon
cacbon, cac hp cht ankyl natri va ankyl liti duc su dung trong nhiu phan ung khac
nhau. Vi du phan ung tng hp Vuyc d diu ch cac hp cht ankhan xay ra theo s d
sau:
R - Hal + 2 Na + Hal - R R - R + 2 NaHal
Trong phan ung nay cac ankyl halogenua co phn tu lung cang cao thuong cho hiu
sut cao va phan ung thuong duc su dung d diu ch cac hydrcacbon mach dai:
2C H Nr C H
2- $H $- f2
nhanh
j ih9rph99l Nr0)%a PBhirli*0pin

4
Tuy nhin phan ung tng hp nay chi co ngha dung d tng hp ankan di xung R
R, con di voi cac ankan bt di R R

s tao ra mt hn hp nhiu san phm.

Cac hp cht ankyl c liti co th tac dung voi nhng hp cht co ni di, ni di lin
hp voi nhn thm va cac dien:
CH CH CH CH Ui + nCH ! CH CH CH CH CH (CH - CH ) Ui
(C H ) C ! CH + C HgUi (C H ) C ! CH C Hg
Ui
CH ! C - CH ! CH + RUi RCH - C ! CH ! CH Ui
3 2 2 2 2 2 3 2 2 2 2 2 n
< 5 2 2
$
< 5 2 2 $
2 2 2 2
CH CH
3 3
Cac ankan liti cng vao butadien -1,3 o cac vi tri 1,4 va 1,2 nhung nu tin hanh o
nhit d cao thi phan ung cng vao vi tri 1,4 la thun li. Phan ung duc su dung d tng
hp polibutandien co cu truc diu hoa tp th lam cao su ging cao su t nhin.
C ! C + CH ! C - CH ! CH C ! C CH CH Ui
H C H H C H
R - CH CH Ui R - CH CH C ! C
CH H
3
3
2 2
2 2 2 2
3
CH
3
P0li)B h0:
C ! C CH CH - R
H C H
R - CH CH C ! C
CH H
3
2 2
2 2
2
n
Khac voi hp cht c magi, c km tham gia phan ung voi cac hp cht cacbonnyl
tao thanh ancol bc ba co d phn nhanh cao. Vi du: trizpropylcacbinol co th duc diu
ch t izpropylxtn va izpropyl liti nhu sau:

50
CH - C - CH + CH - Ui CH - C - CH
CH CH CH
CH CH
CH
H C CH
CH CH CH CH CH
OUi
O
CH - C - CH
H C CH
H C CH
CH
OH
H C CH
HOH - UiOH
3 3 3
3
3 3
3
3
3 3
3
3
3 3
3 3
3 3
3#G#3#3# HA> 9(Q6 98 Px4R 9-64=2
Tung t nhu hp cht c magi, c km tham gia phan ung voi cac hp cht
cacbonyl tao thanh cac ancol khac nhau tuy thuc vao tac nhn cacbonyl tham gia phan
ung: Iocmadhyt ancol bc mt; andhyt ancol bc hai; xtn, clorua axit ancol
bc ba.
Diu dang luu la phan ung cua andhyt hoc xtn voi km va este cua cac axit -
halogen th ta duc - hydrxiaxit (phan ung ReIocmatxki).
NrCH COOCH CH + Wn NrWn - CH COOCH CH
CH CH - CH - CH COOCH CH CH CH - CH - CH COOCH CH
CH CH - CH - CH COOH
OWnNr OH
OH
CH CH CH !O
OHOHkH
+
2 2 3 2 2 3
3 2 2 2 3 3
2 2 2 3
3 2 2
3 2
HOH
D tao mi lin kt cacbon cacbon co th sue dung phan ung cua hp cht c catmi
voi hp cht clorua axit:
2RCOl + R C5 2R - C - R + C5Cl
O
`
2
`
2
Khac voi phan ung cua hp cht c magi voi clorua axit la sau khi tao ra san phm
xtn, hp cht magi tip tuc tac dung voi hp cht nay tao thanh ancol bc ba, trong khi
do hp cht c catmi co tinh hoat dng hoa hoc yu hn nn san phm thu duc chi dng

51
lai o hp cht xtn. Mt khac hp cht c catmi cung khng phan ung voi nhiu nhom
chuc khan nhau nhu NO
2
CN - , - COOR. Vi vy s co mt cua cac nhom chuc khac
trong phn tu clorua axit s khng gy can tro dn phan ung tng hp xtn. Vi du:

2O N COCl + (CH ) C5 2O N COCl + (CH ) C5
CH OCOCH CH COCl + (CH ) CHCH CH C5
CH OCOCH CH CO CH CH(CH )
2
3
2
2 3 2
3 2 2 3 2 2 2
2 2 2 2 3
2
2

52
CHNG B
PHNG PHP NG V My V]NG
B#"# PHNG PHP TeO V]NG AN'AN
Qua trinh thu nhn cac vong anken t cac hp cht hydrcacbon mach thng thuong
duc thc hin qua 2 giai doan phan ung:
a. Chuyn hoa mt hp cht mach h thanh hp cht mach vong bng phan ung dn
vong.
b. Chuyn hoa hp cht vong thu duc thanh hp cht vong cn thit phai diu ch,
vi du chuyn hoa xycloancol thanh xycloankan hoc xycloanken thanh
xycloankan.
B#"#"# AN'Ya HO T$C TIfP2
D chuyn hoa cac hp cht mach h thanh mach vong bng phung phap ankyl hoa
trc tip thi cac hp cht mach h cn phai chua 2 nhom chuc nhu halogen, ancol,
cacboxyl... Vi du phan ung d tao cac hp cht vong nho duc thc hin bng cac s d
sau dy:
(CH )
CH - X
CH - X
( CH )
CH
CH
Xl* : *
2 n
2
2
2 n
2
2
Trong phan ung nay n 1,2,3,4,5, - tuc la co th diu ch t xyclopropan dn
xyclohecxan. X va Y la cac nhom halogen, cacboxyl. Xac tac thuong hay dung la kim loai
kim hoc cac hn hp kim loai. Vi du xyclpropan duc diu ch t 1,3 dibrompropan
voi xuc tac natri kim loai theo phan ung sau:
CH Nr
CH Nr
CH
CH
2
2
2
2
CH CH
Na
+ 2NaNr
2 2
V thc cht dy la phan ung dong vong ni phn tu Vuyc nu phan ung nay duc
thc hin voi tac nhn tach loai la bt km trong ancol thi s co hiu sut cao hn.
D diu ch xyclobutn voi hiu sut cao konor d dung phan ung cua 1,4
dibrombutan voi hn hp Liti trong dung mi khng phn cc tetrarydoIuran:
CH - CH Nr CH - CH
CH - CH Nr CH - CH
+ 2 Ui - Hg + 2 Ui - Hg
2
2 2
2 2
2 2
2

53
Bng phung phap tung t cung co th diu ch xyclopental t 1,5 dibrompentan voi
hiu sut 75.
H C + 2Ui - Hg H C + 2UiNr + Hg
CH CH Nr CH - CH
CH CH Nr CH - CH
2 2
2 2 2 2
2
2 2 2
Tuy nhin truong hp cac hp cht vong co th diu ch bng phung phap Peckin
voi cac tac nhn phan ung la mui natri cua este nalnia va dn xut halogen:
CH + Na CH COOC H CH
CH Nr CH - CH COOC H
CH Nr CH Nr
2
2
2
2 2 2 5
2
+
2 5 2 2
2
Na CH COOC H
-NaNr
2

5 2
H C C (COOC H ) + NaNr + CH (COOC H )
CH
CH
2
2
2 2 5 2 2 2 5 2
+
D diu ch cac vong 5, 6 va cac hp cht da vong thuong su dung phung phap Piria
nhit phn mui canxi cua Diaxit cacboxylic.
CH - CH - C CH - CH
O
O
Ca C ! O + CaCO
CH - CH - C
O
CH - CH
2 2 2
2 2
3
2 2
C
-
O
2
Phan ung loai nay nu dung d diu ch xyclopentanon va xyclohecxanon thi co hiu
sut cao con voi cac vong co s nguyn tu cacbon lon hn thi co hiu sut rt thp. Phan
ung nay cung khng su dung duc d diu ch cac hp cht 3 hoc 4 vong.
Phung phap ngung tu cac dieste va cac dn xut cua no cung thuong duc su dung
d diu ch cac hp cht vong - phan ung Dicmon:

54
(CH ) - COOHC H C
CH - COOC H
(CH ) -- CH - COOC H
C H ONa
O
2
n
2 5
2 5
2 n
2 5
2 2 5
Trong diu kin tung t nhu vy s xay ra phan ung ngung tu cua hp cht nitrin:
(CH ) (CH ) C ! NH (CH ) C ! O
CH CN CH CH
CH CN CH - CN CH - CN
2 n
2
n 2
n
2
2 2 2
HOH
Phan ung ngung tu este lin phn tu cung co th su dung d diu ch hp cht vong.
Vi du phan ung cua dietylxalat voi este glutariat hoc dng dng axtn cua no s tao ra
cac vong xtn 5 canh:
O OC H CH - COOC H
C
C
O OC H
+ CH
CH - COOC H
O ! C - CH - COOC H
CH
O ! C - CH - COOC H
C H ONa
2 5
2 5 2 5
2
2 5 2 2 5
2 5
2
2 5
O OC H CH R
C
C
O OC H
+ C ! O
CH R
O ! C - CHR
C - O
O ! C - CHR
C H ONa
2 5
2 5
2 5
2
2
S ngung tu cua 2 phn tu este xuxinat s tao thanh hp cht vong 6 canh:

55

C
O OC H H C O - C
O
CH C
CH + CH
H C
C
O
OC H C
O OC H O C
O
CH - C
OC H
O
CH

H C
C - CH
O OC H
C H ONa
2 5
2
5 5 2
2
2 5
2
2
2 2
2 5
2
2 5
2
5
Phung phap ankyl hoa trc tip cung co th thc hin bng phan ung dong vong cac
hp cht hydrcacbon co 5 nguyn tu cacbon voi xuc tac Platin o nhit d 300
0
C.
CH - C - CH - CH - CH H C - C - CH
CH - CH + H
CH - CH
CH
CH
CH CH
3
3
3 3
3
2
2 2
2
3 2
2 3
P(3-- C)
-
Di voi cac khung hydr cacbon co lon hn 5 nguyn tu cacbon thi buoc du s tao
thanh vong 6 canh nhung tip sau do co th bi dhydr hoa thanh vong benzen nu nhu
vong khng co mt nguyn tu cacbon bc 4
0
.
CH - CH - CH - CH - CH - CH
H C CH
CH
H C CH
CH
+ 3H
3 2 2 2 3
2 2
2 2
2
2
3
S co mt cua nguyn tu cacbon bc bn s can tro qua trinh thm hoa :
CH - C - CH - CH - CH H C + H
CH CH
CH CH H C CH - CH
C CH

H C CH
2
CH
3 3
3
2
2 3
2 3
2
3 3
3 2 2
P

56
Phan ung ankyl hoa d thu nhn hp cht vong co quan sat thy o s chuyn hoa ln
nhau cua cac hp cht vong. Phan ung mo rng vong duc thc hin bng s tn cng
cua mt nguyn tu cacbon o mach nhanh cua vong vao khung cacbon cua vong (s
chuyn vi):
Vi du:
H CH - CH OH H C - CH
H C - CH
+ H O
CH
2
2
2
2
2
H SO
2 $
H C - CH H C CH + H O
H C - CH - CH OH
H SO
2 $
H C
CH
2 2 2 2 2
2
2 2
2
Phan ung cung co th xay ra theo huong nguc lai kem theo s hp vong:
CH - CH OH
OH
H
+
2
C ch chuyn hoa cua qua trinh chuyn vi trn dy xay ra theo s d sau:
S mo vong:
(CH ) - C - C (CH ) - C - C (CH ) - C - C

OH O
H
R
R
O
H
+ H
C
R
O
CH
R
CH
R
CH
R
+ H
2
2 n 2
n
2
n
+
+
2
2
H SO
-HOH
2
S hp vong:
OH
CH
OH
CH
3
3
3
3
CH
OH
CH
+
+H
-HOH
+
- CH
C ! O
CH
3
3
Cac phan ung ankyl hoa khng nhng chi dung d diu ch cac hp cht dn vong ma
cac hp cht da vong khac nhau. Vi du s tao thanh cac hp cht hai vong co th duc
thc hin theo cac phan ung sau:
a. JKng hL2 vu!c(

57
2 -
CH Cl + 2 Na - CH - CH
2 2 2
:. JKng hL2 :Mng s hN trL gi4ng c$a t%c nh>n c6 magi'(
-Nr + /g /gNr

-
! O + - /gNr

OH
c.Ngng tH c%c vOng an'h!t hoPc x'tDn vi nhau(

! O + - /gNr

O
O
5.;h< ho% c%c vOng x'tDn(
! O 2
/g - Hg
OH OH
". .hn /ng t3o thnh c%c hL2 ch9t s2iran(
CH CH COOC H
CH COOC H
COOC H
O
NaOH
2 2 2 5
2 2 5
2 5
OH OH
O
O
OH
OH
B#3# PH^N NG CZNG HP2

58
B#3#"# PH^N NG CZNG HP IN` X AN
Cac hp cht cacbonyl
,
khng no tham gia mt phan ung rt quan trong voi cac dien
lin hp duc goi la phan ung Dinx And. San phm cua phan ung nay la mt vong 6
canh duc hinh thanh do kt qua cac mi lin kt gia nguyn tu cacbon cua ni di trong
hp cht cacbonyl khng no. Duois dy la mt s vi du v phan ung cng hp Dinx
And:
CH C
CH C
CH
CH
H
H
C
C
O
O
O
+ O
O
O
2- C bBnCBr
-
N%aiBn -H,3
8nh9ri )alBi*
8nBh9 *iQ -H,2,3,< -Bra
h9rphaali*
2
2

5
CH HC
CH HC
CH
CH H
H
C ! O
+
2
2
CHO
H-- C
-
N%aiBn -H,3 8r*lDin
8nDh9 *iQ -H,2,3,< -Bra
h9rbBnCanDh9
N%aiBn -H,3
2
2
CH
CH
CH
CH
+
2- C bB9CBn
-
N% i Dn -H,3, H-- C
-
O
O
O
O

5,f,;,H- -IBrah9r - H,$ -naphh%in0n

p - NBnC0h%in0n
O
O
+
C
C
C
C
O
H
H
O
O
NBnCBn C
-
C
C - O
! O
O
X9*l0hB*xaiBn -H,3
Thc nghim d chung minh rng phan ung cng hp xay ra d dang nu Anken
(thuong goi la phn dienophin) duc th boi mt hoc nhiu nhom ko electron manh, thi
du nhu COOH,
- C - R, - C NKKK
O

60
Trong bang sau dy la mt s dienophin co kh nng phan ung cao.
MZT So CHT IIN%PHIN HOeT ZNG
TN CN THC

61
Ttraxiantylen
Crlonandhyt
Axitxinamic (els va trans)
Anhidrit malic
Dimtyl malic
1- Nitrpropen
Acrilnitrin
Acrlin
tyl acrital
N phnylmalimit
Dimtyl Iumaral
HC
HC
C
H
O
O
O
(CN) C ! C(CN)
CH CH ! CH - CHO
C H CH ! CH - COOH
2 2
3
< 5

C
C
H COOCH
H COOCH
3
3
CH CH - CH - NO
CH - CH - CN
CH - CH - CNO
CH - CH - COOC H
3
2
2
2
2 2 5
C
O
HC
HC
C
N - C H
O
< 5
H
C
C
COOCH
COOCH H
C H - CH ! CHNO
3
3
< 5 2

62

-Nitrositren
Mt trong nhng uu dim cua phung phap Dinx And la no xay ra rt dc thu v
mt lp th.
Dien phan ung o cu dang s-eis cua cac ni di cua no, boi vi ni di o san phm (mt
vong su) phai co cu hinh cis.
C C
C C
CH H CH H
CH H CH H
2
2
2
2
CH
CH
CH ! CH
2 2
CH
C
C
CH
H
H
2
2
2
2
CH
CH
C C
H

CH
2
2
2
H
CH
2
Mt dim dang chu na la cu hinh cua dien va cua cht dienphin vn gi nguyn o
san phm. Diu ddod co ngha la hai cht nay d cng hp cis voi nhau. Chng han
butadien phan ung voi dimtyleste cua axit Iumaric hoc axit malic trong tluen va
o nhit d 155
0
C d cho dimtyleste cua cac axit trans - hoc cis xyclhexen - 1
dicacbxylic -4,5.

63
CH OOC
H
- COOCH H
COOCH
CH OOC
H
H
COOCH
H
COOCH
3
3
3
3
3
3
j i)D9lBQB *ma axi ranQ -xi*lhBxBn -H-i*a*bx9li* -$,5
CH OOC
H
- COOCH H
COOCH
CH OOC
H
H
COOCH
H COOCH
3
3
3
3
3
3
j i)D9lBQB *ma axi ranQ -xi*lhBxBn -H-i*a*bx9li* -H,5
COOCH
3 H
cac thi du nay ta thy cu hinh cua cht dienphin duc gi nguyn .
Ta cung cn k dn mt dc dim na cua phan ung Dix And la trong nhiu
truong hp cac cht phan ung bi dinh huong v mt hoa lp th. Thi du phan ung cng
anhidrit vao xyclpentadien co th di theo hai con duong dn toi hai san phm khac nhau.
O
O
O
O
O
O
O
O
O
S'n ph() *ma Bn

64
O
O
O
O
O
O
O
O
S'n ph() *ma Bx
Trong thc t thuong hinh thanh dng phn end la san phm chu yu duy nht.
Phan ung Dix And co l xy ra theo mt c ch nhiu trung tm, trong do hai lin
kt

moi gia dien va cht dienphin hinh thanh dng thoi (Hoc hu nhu dng thoi).
Mt tin trinh phan ung dng thoi nhu vt co nhng yu cu rt cao v mt lp th, cac
di tung phan ung phai duc sp xp sao cho hai lin kt

co th hinh thanh cung mt

luc, phu hp voi diu nay cac phan ung Dix And thuong co entropi hoat hoa m
manh (t -20 dn -25 cal/d. Mol).
San phm phan ung cua cac tng hp dien thuong la cac cht trung gian cho nhiu
tng hp hu c. Bixicl -2,2,1 heptadien (2.5) (I) duc tng hp t xyclpentadien
va axtien voi hiu sut khoang 65. Cht nay phan ung voi hecxaclozxiclpentadien
mt cach hu nhu toan lung trong mt tng hp dien thu hai d thanh cht andrin II la
mt loai thuc tr su co hiu lc:
H
C
C
H
+
( I )
Cl
Cl
Cl
Cl
Cl
Cl
H
H
Cl
Cl
Cl
Cl
Cl
Cl
;
f
<
5
$
3 H2
2
H
H-
HH
( I ) ( II )
Trong s cac san phm cng hp Dix And cua hecxaclopentadien con co nhiu
loai thuc tr su khac va mt s plime chiu nhit.
Cac phan ung Dix And la thun nghich. Ta co th su dung tinh cht do cua phan
ung vao trong tng hp va sau khi thc hin cac bin di o cac san phm cng hp Dix
And ta lai co th tach chung ra thanh cac hp phn. Chng han cht tianhidrit cua axit

65
malic cng hp voi butalien, sau do san phm duc chuyn thanh dn xut ion III ri
tach ra thanh cac hp phn.
+ O O O + O
O O O O
Na Sx
2
HCl
( I )
O O O O
( II ) ( III ) ( I4 )
Mc du noi chung cac dien lin hp tac dung voi cac cht dienphin o vi tri 1,1 d
cho cac hp cht vong sau, nguoi ta cung bit co mt s phan ung cng 1,2 cho cac hp
cht vong 4. Rt co th ban cht cua cht dienphin la yu t qut dinh vic cng hp
theo 1,4 hoc 1,2. Chng han mc du tylen cng hp 1,4 voi butadien, ttraIlotyln lai
cng hp o 1,2:

CH ! CH - CH ! CH CH ! CH
+ H-- C CH - CH
S C ! CS S C CS
2 2 2
2 2
2
2 2
-
Trong khi do ttraIltylen cng vao xyclpentadien cho mt hn hp cac san phm
cng hp dong vong 1,2 va 1,4.

+ S C ! CS
2 2
190 C
0
+
S
S
2
2
3.2.2. PHN N CN HP CA CACBEN V NITREN VO ANKEN
La nhng hp cht hoa hoc hoat dng rt manh va trong cac phan ung voi cac hp
cht anken chung su dung nhom mtylen: CH
2
d tao thanh cac hp cht vong. Mtylen
va dn xut mtylen tham gia phan ung cng hp vao ni di (- C C -) theo s d sau:

66
C ! C + 7 CH C C
C ! C + 7 CH C C Cl
CH
l C
CCl
2
2
2
2
2
Cl
Cl
2
+ 7 CCl
CCl
2 2
Loai phan ung nay cung d duc Diaknp su dung d diu chinh mt s dn xut cua
axit cacbxylic:
C
H COOC H
C H - C ! C - C H
2 5
3 2 3 2
+ N ! N ! C
H
COOC H
H C - C - C - C H
C
C
COOC H H
H COOC H
2 5
3 2
2 5
2 5
2 3
+
Phan ung cung co th dung d tng hp xyclbutan t Anken:
CH ! C ! O H O C ! O
CH ! N ! N
+ CH + N
H C - C ! O
2
CH
+ CH ! N ! N
H C C ! O
H C CH
+ N
2
2
2
2
2
2 2
2
2 2
2
Mtylen va dn xut cua no co th tham gia phan ung cng hp vao h ni di cua
bn:

67
+ 7CH
CH
n0* - *ara5i Bn x9*l 0hBpari Bn
Tung t nhu vy clocacben tac dung voi benzen tao thanh ion tripili theo s d sau:
+ 7CH
CH
n0* - *ara5iBn x9*l0hBpariBn
+ Cl -
Cl
Cl
Cac hp cht cacben va diazmtan cung co th tham gia phan ung cng hp vao ni
ba (Chi co phan ung voi dn xut cua axetylen, nhung khng phan ung voi axtylen) tao
thanh vong khng no.
Vi du:
CH - C C + CH + 7 CH CH C ! C - CH
CH
CH - C ! C - CH + 7 CH
C H
Nr
CH C ! C - C H
CH
3 3 2 3
2
3
3 3
2 3
2
< 5
< 5


C H + C H
C H

Nr
-
< 5
< 5
< 5
Mtylen cung co th cng hp vao cac hp cht vong ete va mo rng vong hn:
+ 7 CH
O - CH
2
2
O
O
B#B# PHNG PHP TeO V]NG THM V [\ V]NG
B#B#"# TNG HP &INzIN V [cN `UT CbA &INzIN
Benzen co th duc tng hp bng phan ung trime hoa hp cht axtylen:

68
HC CH
+
HC
CH
HC
HC
Phan ung nay d duc nhiu nha hoa hoc nghin cuu voi cac xuc tac va diu kin phan
ung khac nhau.
D thu duc benzen Zelinxki d tin hanh phan ung trn than hoat tinh o nhit d 450
500
0
C. Trong khi do Repe d su dung xuc tac la dicabony ditriphenylphotphin Niken
(C
6
H
5
)
3
P]
2
Ni (Co)
2
va d thu duc dn xut th 1, 3, 4 cua Benzen. Bng vic su dung
xuc tac la Al(C
2
H
5
)
3
TiCl
4
] Xigler d thu nhn duc cac dn xut th 1, 3, 5 cua
benzen. Voi xuc tac la CrCl
3
Xeis d diu ch duc hp cht hecxaphnylbenzen t
diphnylxtylen:

C
+
C
C - C H
C
C H
C H
C - C H
C
C H
C H
C H
C H
C H
C H
H C
H C
<
5
<
5
< 5
< 5
< 5 < 5
5 <
5
<
<
5
< 5
< 5
< 5
b. Hp cht axtn duoi tac dung cua axit sunIuric dam dc s tao thanh 1, 3, 5
trimtylbenzen (mzitilen).
CH
C
O CH
CH
C
H C O
+ + 3H O
C - CH
O
CH
H C CH
CH
3
3
3
3
3
3 3
3
2
3
Phan ung cung xy ra tung t di voi cac xtn loai R-CO-CH
3
.
Vi du t axtphenon C
6
H
5
COCH
3
co th diu ch 1, 3, 5 triphnylbenzen.

6
Loai phan ung nay cung co th su dung d diu ch cac dn xut bn t cac hp cht
andhyt co nhom mtyl linh dng:

CHO CH
CH
+ CHO

HOOC
CH
COOH COOH
OHC COOH
COOH COOH
2
2
2



c. Mt trong nhng phan ung duc su dung rng ri d diu ch benzen la phan ung
thm hoa cac hp cht paraIin bng xuc tac platin o nhit d ~300
0
C:
CH - CH - CH - CH - CH - CH + $H
P
3 2 2 2 2 3 2
2 3 2 2 2 2 3
P
CH - CH - CH - CH - CH - CH - CH + $H
3
CH
3
Phan ung nay co th thc hin bng xuc tac Al
2
O
3
Cr
2
O
3
o nhit d trn 400
0
C.
d. Cac hp cht benzen cung co th duc diu ch bng phan ung dehydr hoa
xyclhecxan va xyclohecxadien voi xuc tac platin o nhit d cao.
+ 2 3
3
P
P
P
+
B#B#"#3# T{*, (A> 919 U| L}*, G 9i*(2
a. Phung phap quan trong va chung nht dung d tng hp cac hp cht di vong thm, 5
canh duc bt du bng 1,4 - dicacbonyl.

70
R C C R R C C R
CH - CH
O O
HC - CH
OH
OH
HC - CH
C C
S
R R
HC - CH
C C R R
NH
NH
R R C C
HC - CH
O
P O
2 5
2 2
P O
2 5
PS
2
3
5
Cac hp cht di vong 5 canh co th duc thu nhn bng phan ung nhit phn
(dcacbonxyl hoa) axit muxic nhu sau:

3
HO - CH - CH - OH
HO - CH CH - OH
O ! C C ! O
OH OH
NH
+ 2CO + 3 H O
+ 2 CO + $ H O
C

NH , C
-
-
2 2
2 2
O
Phan ung nay khng su dung d diu ch tiphen duc nhung tiphen co th duc
diu ch bng phan ung cua axit voi P
2
S
3
CH - CH
O
HOOC COOH
NH , C
3
-
2 2
c. D chuyn hoa ln nhau gia cac di vong thm va khng thm 5 canh lurep d su
dung xuc tac Al
2
O
3
o 400
0
C cho cac phan ung xay ra theo s d sau:

71
HnhR) Hnkhng hR)
O
S
NH
H S
HOH
HOH
H S
NH
2
NH
3
2
3
O
S
NH
H S
HOH
HOH
H S
NH
2
NH
3
2
3
d. Phan ung cng hp 1, 3 vao h ni di va ni ba cua tac nhn loai diazo, axit nit,
axit, oxit nitril, hp cht nitron... d cho php thu nhn mt s lung rt lon cac
hp cht di vong 5 canh khac nhau duoi dy la mt s vi du:

72
HK R - C C - R R - C ! C - R R - C - C - R
N ! N - CH 7 N CH 7 N C
K K K K
N
NH
K K
K K
NH N
K K K K
N ! N - N - R 7 N N - R
2K R - CH CH - R R - CH ! CH - R R - C - CH - R
- +
- +
2
2
2 2 2
+
-
3K R - C C - R R - C ! N - R
N ! N - CH 7 N CH 7 N CH
K K K K
N
K K
K K
K K
N
$K R - C N R - C ! N
N ! N - N - R 7 N N - R
K K
5K H - C ! N - OH R - C ! N - O R - C ! N - O
Cl
+
+
- + -
] xi niril
R - C ! N - O R - C O
H - C C - R H - C ! C - R
N
K K + -
+ K K
N
H - C C - R H C - CH - R
R - C ! N - O R - CH O
nir0l
- +
-
+
<K H - C ! N - OH R - CH ! N - O R - CH ! N - O
R
2
``
R
R
-
`
`
RI,HO
`
-
K K

73
e. Cac hp cht di vong 5 canh cung co th duc diu ch bng phan ung cua Shulte
nhu sau:
H O,C H O
HC C - C HC
NH ,C%Cl
H5- C
S NH
-
2 2
5
3
-
e. Ngoai cac phung phap chung d diu ch cac hp cht di vong 5 canh trn dy,
nguoi ta con su dung nhng phung phap d tng hp cac hp cht ring bit.
Vi du:
1. Phan ung diu ch Iuran va dn xut Iuran:

HO - CH - CH - OH
CH CH - CHO
OH OH
CHO
O
-3H O
2
2
HO - CH - CH - CH - CH - OH
O
2 2 2 2
"# P()* +*, W=kT 9(: 6=C>(0*2
8r OC H 8r COOC H 8r COOC H
CHCl

C ! O
C ! O CH
8r C N

+
! NH
O 8r
8r O
NH
Na
+
2 5
-
2 5 2 5
2
3# P()* +*, W=kT 9(: U=/>(0*2

74
CH CH CH CH + $S + 3 H S
S
2-- C
-
2
3 2 2 3
CH CH
CH CH
+
8l O
$-- - 5--C
2 3
-
+ H
2
H S
2
2C H - CH ! CH - C H + S
%n n&ng
S
S
S
H C C H
C H
H C
5 < < 5
< 5
5 <
< 5 < 5
R - CH - CH - C ! CH
o
C
R
O
`
R
R
CH
3
`
2
B# P()* +*, W=kT 9(: >=;/.2
R
R
`
+

CH
NOH
``
R - CH O ! C - R
C
R
O
`
2
R
NH
``
D# P()* +*, W=kT 9(: =*U/.2

75
CH ! CH - Cl
NH
+ C H ONa
NH
+ NaCl + C H OH
2
2 5 2 5
NH
+
CH
CH
- H
NH
2
2
2
N - N
CH
CH - CH
H
H
CH - CH
CH
N - N
3
3
H
C - CH
CH
CH
3
2
2
NH
CH
NH
- NH
3
3
B#B#3# TNG HP CC HP CHT [\ V]NG ~ CeNH2
-# T{*, (A> >=;=W=*2
Piridin co th thu nhn bng phan ung cua axetylen voi axianhydric (phan ung
Betlo):
CH
CH
N
+
CH
CH
N
CH
b. Cac dn xut cua Piridin co th diu ch bng phan ung cua andehyt R

CH
2
CHO voi
amniac khi co mt xuc tac Al
2
O
3
o 400
0
C nhu sau:

76
R - CH H C - R
CH CH
O
O
NH
H O - R
+ 3H O + H
CH R
R R
CH - R
CH
O
O
CH
R - CH CH
R
R - CH CH
CH
O K NH
O
+
R
R
RCH
N
N
+ H O + H
2
2
2
2
2
2 2
2 2
3
2 2
2
3
3
+
Dn xut Piridin cung co th duc diu ch bng phan ung cua cac dien voi
ankylinitril:
2
2
R N
CH
CH
CH
CH
+ C - R
N
B#D# PH^N NG My V]NG2
Phan ung mo vong cua cac hp cht vong xay ra duoi tac dung cua cac tac nhn khac
nhau theo nhng c ch khac nhau tuy thuc vao cu truc cua vong. Duoi dy la mt s
phan ung mo vong c ban thuong gp.
B#D#"# My V]NG &sNG PHNG PHP 'H HO
Do qua trinh tao thanh hp cht vong, cac nguyn tu cacbon d bi bin dang khoi
trang thai lai tao tung ung cau minh nn trong cac hp cht vong tn tai mt suc cng
(Suc cng Baye, suc cng Fitze...). Diu nay d dn dn cac hp cht vong tham gia mt
s phan ung khu hoa tung t nhu cac hp cht hydrcacbon khng no.
Vi du: Xyclpropan tham gia phan ung hdr hoa voi s pha v vong lin kt cacbon
cacbon o nhit d 80
0
C.

77

CH
2
H C CH
CH - CH - CH
2 2
3 2 3
H kNi
2
Trong khi do phan ung voi xiclbutan xay ra o 120
0
C.
H C - CH
H C - CH
CH - CH - CH
3 2 3
H kNi
2
- CH
2
2 2
2 2
Phan ung cung xay ra tung t di voi cac dn xut cua Xyclpropan va xiclbutan
nhnh tuy thuc vao s co mt cua cac nhom chuc khac nhau s thu duc cac san phm
khac nhau. Vi du phan ung hydr hoa izpropyl - xiclpropan va izpropenyl
xiclpropan s tao thanh cac san phm khac nhau nhu sau:
H C
H C
CH
2
2
CH - CH - CH CH - CH
CH CH
CH CH
3 3
3 3
3
3
H
2
H C
H C
CH
2
2
CH - CH - CH CH - CH - CH - CH
CH
CH
3
3
3
H
2
2 2
B#D#3# PH^N NG CZNG HP THIO C CHf IaICT$OPHIN2
Cac hp cht vong co th tham gia cac phan ung cng hp voi cac tac nhn
electrophin voi s pha vong. Phan ung thuong xay ra duoi tac dung cua cac
hydrhalogenua.
Vi du: phan ung cua xiclpropan va xiclbutan voi HBr xay ra nhu sau:
H C CH
(CH )

2
2 n
CH - (CH ) - CH Nr
3 2 2
2
HNr
n
Phan ung cung xay ra tung t khi su dung tac nhn electrophin la H
2
SO
4
hoc Brm.
H C CH
(CH )

2
2 n
CH - (CH ) - CH OSO H
3 2 2
2
n
3
Nr CH - (CH ) - CH Nr
2 2 2
n
2
H SO
Nr
2 $
2
Kt qua nghin cuu cac phan ung mo vong cho thy rng s co mt cua cac nhom th
ai din tu cua vong nhu COOH, - CHO... s lam cho phan ung pha vong xay ra kho

78
khn. Vi du cac dn xut ankyl hoa cua xiclpropan rt d dang phan ung voi axetat thuy
ngn:
R - CH - CH - R + Hg(OCOCH ) R - CH CH - HgOCOCH
CH CH

CH O CO R
2
3 2
2
3
2
Dc bit cac phan ung cua h lin hp vong voi ni di thuong xay ra theo quy tc
phan Macopnhicop:
H C - CH - C - C H + HNr CH - CH - CH - C - C H
CH

2
< 5
2 < 5 2 2 2
O Nr O
B#D#B# PH^N NG CZNG HP THIO C CHf NUCaI%PHIN2
Phan ung cng hp dn dn pa v vong theo c ch nuclonphin xy ra chu yu o cac
vong xtn, lactn... Vi du phan ung cng hp cua xianat Kali vao vong lactn xay ra
theo s d sau:
H C - CH CH - CH - CN
H C - C CH - C - O.
O + .CN
O O
2
2
2 2 2
2
Dy la phan ung rt quan trong dung d diu ch axit cacboxylic. Phan ung Buton voi
tac nhn rinha tao thanh cac hp cht xtancol:
H C - CH H C - CH
H C - C ! O H C - C
O + R/gCl
2
2
2 2 2
2
O
R
/gCl
R - C - CH - CH - CH OH + /g
OH
Cl
O
2 2 2
O
HOH
B#D#D# PH^N NG My V]NG &sNG MZT So TC NHN 'HC2
Cac hp cht vong khng no hoc xtn co th tham gia phan ung oxy hoa dn dn s
pha vong. Vi du hp cht xiclohexen bi pha v boi phan ung oxy hoa bng zn theo s
d sau:

7

O
O HOH
Wn
O ! CH - (CH ) - CHO
2
3
$
O - O
Phan ung xy hoa cung xay ra tung t di voi hp cht Xibtn nhu sau:
HC
HC
(CH )
2
(CH )
C ! O HOOC - (CH ) - COOH + HOOC - (CH ) - COOH
2 2
2
2
2 <
2
Mt s loai hp cht vong co th bi pha v boi phan ung thuy phn. Vi du hp cht
caprolactam bi thuy phn thanh axit aminocapric nhu sau:
H C CH
H C
C ! O

2
CH
H C - NH
2
2 2
2
2
H O,H
2
CH - (CH ) - COO
NH
$
+
+
-
Phan ung thuy phn dn dn s pha vong cua cac hp cht xtn cung co th xay ra
duoi tac dung cua anh sang.
CH
O
3
CH - (CH ) - COOH
2 5 5
H",H O
2

80
CHNG D
&^O V NHM CHC T$ONG TNG HP HU C
CHIfN aC CHUNG2
Trong tng hp hu c nhiu truong hp nguoi ta phai tin hanh bao v mt s
nhom chuc ma nhng nhom do nu o trang thai t do thi no co th tham gia vao mt
s phan ung hoa hoc theo nhng huong khng cn thit. Phung phap nay ngay cang
duc ung dung rng ri trong cng nghip san xut hoa cht nhm tao ra nhiu loai
san phm cn thit voi cht lung tt.
Trong lich su phat trin cua nghanh hoa hoc hu c truoc dy, nguoi ta d su
dung kha nhiu phung phap bao v nhom chuc khac nhau. Dc bit la trong nhng
nm gn dy, khi ma cac phan ung tng hp hu c duc thc hin voi cac hp cht
co nhiu nhom chuc khac nhau thi phung phap bao v cac nhom chuc lai cung duc
phat trin ht suc nhanh chong. Mt trong nhng thanh cng lon nht cua vic su dung
phung phap nay la s bao v cac nhom chuc trong cac phan ung tng hp cac cht
Peptit (vi du vic tng hp cac protit nhu Inxulin, Ribonuclazas). Vi vy vic nghin
cuu mt cach co h thng cac phung phap bao v cac nhom chuc tro nn ht suc
quan trong va cn thit cho nganh hoa hoc noi chung va nganh hoa hoc hu c noi
ring.
&^O V CC aIN 'fT C X H2
&^O V aIN 'fT C X H A`TIaIN:
Lin kt C H trong cac hp cht axtilen loai RC CH thuong cn duc bao v
trong cac phan ung diu ch cac hp cht c kim loai vi nguyn tu Hydro o dy rt
linh dng - co tinh axit.
Vi du:
C H U + RC CH RC CUi + C H

C H /gNr + RC CH RC C - /gNr + C H
< 5
i
< <
2 5 2 <
Vi vy, khi ta mun thu nhn mt hoa cht rinha n LiC
6
H
4
C MgBr (Vi du t n
Bromphnylaxtilen) (1) va magi) ma nu ta khng tin hanh bao v lin kt C H
bng mt tac nhn rinha va sau do cho tac dung voi hp cht c Liti thi s thu duc
hp cht cn thit (huong b).

81
n - NrC H C CH n - Nr/gC H C CH n - C H C C/gNr
(H)
n - NrC H C C/gNr
n - NrC H C C/gNr (b)
< $ < $ < 5
< $
< $
UiC H
< 5

/g
Trong phong thi nghim va trong cng nghip thuong hay su dung nhom Triankylsilyl
lam nhom bao v cho lin kt C H. Vi du co th dua nhom Trimtylsililclorua vao phn
tu hp cht Broma (2) sau do cho tac dung voi hp cht rinha va cui cung tai tao lai
lin kt C H bng phan ung thuy phn trong mi truong kim.
n - NrC H C C/gNr n - Nr/gC H C CSi/B
< $ < $
/g, IHS
3


3
CO , H O

$ < $ <
n - R /C H C CSi/B n - Nr/gC H C CSi/B
/B SiCl
3
R /H U
2 3
+
n - R /C H C CH n - HOOC C H C CSi/B
< 3 $ < $
3
HO, H O
+
3
-
n - HOOC C H C CH
< $
(2)
HO
Ngoai ra, nguoi ta cung thuong hay chon cac nhom nhu cacboxyl, -OH... d bao v
lin kt C H cac axtilen.
Vi du:
RC CH + NrC CCOOH R(C C) COOH R(C C) H
R (C C) COOH R (C C) H
2 2
3 3
Hoc la;
RC CH + NrC CCH OH R(C C) CH OH R(C C) H
R (C C) CHO R (C C) H
2 2 2 2
2 2
&^O V aIN 'fT C X H CbA HP CHT THM
Phan ung th electrophin la mt trong nhng phan ung rt c ban dung d tng
hp cac dn xut cua cac hp cht thm khac nhau. Phan ung th xay ra theo huong

82
uu tin vao nhng vi tri giau din tu cua vong thm. Vi vy, d huong phan ung vao
nhng vi tri cn thit ...(vi du vi tri co mt d din tu thp) thi cn phai bao v nguyn
tu hydr cua vi tri co mt d din tu cao.
Vi du phan ung brm hoa cht tecbutylbenzen s cho san phm chu yu la p
bromtecbutylbenzen. Vi vy d thu nhn san phm th octo thi cn phai bao v lin kt
C H cua vi tri Para nhu sau:

HNO
Nr kH SO
SBkHCl
C H - B* C H - B* C H - B*
H SO 8gSO
NO NO
$ ; $ ; $ ;
3
2
$ $
2 2
$
2 2
Nr
HNO
H PO
C H - B* C H - B*
Nr
$ ; $ ;
3 2
2
Nr
NH
2
a, D dinh huong oct va Para thuong nguoi ta su dung cac nhom bao v nhu:
cacboxyl, Nitr, SunI.
Vi du d thu nhn hp cht 2,6 diclophenol nguoi ta thc hin nhu sau:
OH
OH OH
OH
COOH COOH
x
C
Cl
Cl Cl Cl

-
Cac phan ung cung tin hanh tung t nhu vy khi su dung nhom bao v la
sunI:
OH
OH OH
p
OH
p
X
X
SO H
SO H
3
3
X
X CH
3
X CH
3
X Cl
Y NO
2
Y Br Y NO
2
b, D dinh huong mta thuong nguoi ta su dung cac nhom bao v nhu: amin,
halogen, tite... Vi du d diu ch cac dng phn mtacua cac hp cht ankylbenzen
co th tin hanh nhu sau:

83

X
X
R R
R R
NH NH
2 2
R CH
3
, Iz C
3
H
7
R C
6
H
3
, C
2
H
5
, Iz C
3
H
7
, tec C
4
H

X NO
2
X Br
Dc bit vic su dung nhom bao v la halogen co rt nhiu thun li vi sau khi
phan ung kt thuc, chung ta d dang bi khu di bng nhng tac nhn chon loc thich
hp.
Vi du:
x
C
-
I
I
CH CN
OCH C H
OCH
H CO OCH
OCH C H
HCO
OCH
OCH C H
HCO
CH CN
OCH
OCH C H
H CO
3 3
3 3 3
3
2
2
< 5
2 < 5 2 < 5
2
3
2 < 5
3
Ui8lH
$
&^O V aIN 'fT C X H HP CHT &O2
Muc dich chinh cua cac phung phap nay la nhm bao v cac lin kt C H cua
nguyn tu Hydr nm o vi tri

so voi nhom cacbonyl. D dat duc diu nay nguoi ta

d su dung cac phung phap bao v trc tip va khng trc tip.
a, Phung phap bao v trc tip: CH
2
~ C CH C
6
H
5
Vi du: Qua trinh bao v nguyn tu
H

d mtyl hoa hp cht decalon -1 o cacbon

C
3
nhu sau:

84
O
O O
CHC H
CHC H
/B9l h0:
Cl
CH
O
CHClC H
Cl
C H ONa
CH
O
OC H
C H
O
CH
O
CH
H O
COC H
HO
H
;
2
< 5
< 5
CH
3
3 3
2
< 5
2 5
< 5
2 5
3
+
3
< 5
-
3
Bao v bng phung phap trc tuyn cung co th thc hin qua phan ung chuyn hoa
thanh hp cht andhyt:
~ CH
2
~ CH CHO
CHO
CHO
O O
O O
R
R
:- .h6ng 2h%2 :o v= *hDng trc ti2
Dy la phung phap bao v cac nhom mtylen hoat dng bng cach khu cac
nhom cacbonyl bn canh va sau khi phan ung kt thuc thi khi phuc lai nhom
cacbonyl bng phan ung oxi hoa.
Vi du: Phan ung mty hoa o cacbon C
2
cua vong A tetrahydromdanon nhu sau:
O
OH
/B9l h0:
OH
CH
3
O
O
CH
3
CH
O
O
8
CH
N
NaNH
$
3
CH
O
3
3
&^O V NHM AMIN%2
&^O V CC NHM AMIN &C MZT V &C HAI2

85
Cac amin bc 1
0
va bc 2
0
la nhng hp cht rt d tham gia cac phan ung oxy
hoa va phan ung th. Vi vy d bao v cac nhom nay thuong nguoi ta thc hin bng
cach bao v cac lin kt N H cua cac amin. Duoi dy la mt s phung phap bao v
c ban:
Phng php Protn ho:
Dy la phung phap bao v cac nhom amin dn gian nht. Phan ung xay ra
trong mi truong axit va khi do nhom nhom amin chuyn hoa thanh Protn va ngn
cm cac phan ung th khng cn thit
NH NH h01* NH NH
H
H
2
+ +
+
3
+
Tuy nhin, phan ung nay khng ngn can duc cac phan ung oxy hoa.
Phng php selat ho
Dy la phung phap bao v cac nhom chuc amin rt co hiu qua bng s tham
gia cua cp electron t do cua nguyn tu Nit d tao thanh mt ni phuc (selat) voi
cac kim laoi chuyn tip. Vi du co th tin hanh phan ung Benzol hoa nhom Hydrxi
cua hp cht tirozin sau khi d bao v nhom amin bng phuc voi dng:
CH - CH - C
HO
H N HO
O
HO
O
2
2
CH - CH - C
2
2
H N O
C%
O
CH - CH - C
2
2
H N O
C%
C H COO
< 2
Phuc cht duc tao thanh sau phan ung co th thuy phn bng H
2
S d tai tao lai
hp cht amin axit ban du.
4.3.1.3. Phng php axyl ho
Dy la phung phap nhm bao v da vao kh nng d tao thanh cac hp cht
axyl cua cac nhom amio. Thng thuong trong phung phap nay hay su dung cac nhom
bao v nhu Iocmyl axtyl va benzoyl.
Vi du:
a- .hn /ng s< 5Hng 2h6ng 2h%2 :o v= Qocm!0 ho% 7 i#u ch c%c aminD axit(

86
CH (COOR) HON ! C(COOR)
HONH - CH(COOR) HONH - C(COOR)
H N - CH COOH
R ! CH C H
2 2 2
2 2
2
3
,
5 2
R
R
NaNO , 8*OH Wn, HCOOH
2
`
`
`
:- .hn /ng tKng hL2 s!nQani0amit tR ani0in:
NH
NHCHO
HCOOH, 0*
2
CHCHO
NH CHO
H NO S ClO S
2 2 2
2
c, Phan ung dung phung phap bao v nhom chuc axyl hoa (COCF
3
) d tng hp cac
hp cht glycozit:
N
O
O
CH
N
O
O
CH
OH
CH OH
CH O8* CH O8*
CH OH
H
N
CH OH
N
H
O8* O8*
HO NH 8*0 NHCOCS
NHCOCS
Nr
O8*
OH
8*O
NHCOCS
HO
NH
2
2 2
2 3
3
2
2
3
2
3
3
d, Phan ung tng hp ete cua dn xut piperidin bng phung phap bao v benzoyl
hoa nhom amin bc 2
0
:

87
N
CH Nr CH Nr
N N
CH CH COOC H
H
COC H COC H
CH CH COOC H
N
COC H
2 2
2 2 2 5
< 5 < 5
2 2 2 5
< 5
e, Phan ung bao v bng tao ra hp cht diaxyl:
N.
O
O
RX
O
N - R
O
H, H O
2
+
COOH
COOH
RN H +
+
3
D#B#"#D# P(J8*, >(1> -YC4567. (/12
Dy la phung phap da vao phan ung tao thanh cac nhom azmtin (cac baz
ship) bng phan ung cua cac nhom amin bc 1
0
voi cac andehyt va xtn.
Vi du: Phan ung chuyn hoa amin bc 1
0
thanh amin bc 2
0


O
O
O
O
CH CH NH
C H CHO
CH CH N ! CH - H H (CH) SO
2 2 2
< 5
2 2 < 5 2
$
O
O
CH CH - N ! CH - C H
CH
2 2
CH CH NHCH
O
O
C 2 2
+
3
< 5
3
-

88
D#B#"#G# P(J8*, >(1>2 N=6;/YC LM *=6;C (/12
Phung phap nitroz hoa duc thc hin chu yu voi cac amin bc 2
0
. Sau khi
kt thuc phan ung nhom amin duc phuc hi bng phan ung khu co xuc tac kim loai
hoc trong mi truong axit.
Vi du:
H C NH H C NH - NO H C - N - NO
N
N
N
CH C H
H C - N
CH C H
3
-
3 3
2 < 5
O
O
2 < 5
NH
H k Ni
2
Phan ung nitr hoa d tao lin kt N N nhm bao v nhom amin, chi co ngha
di voi hp cht arginin. Ou dy, nguoi ta su dung phung phap nay d tng hp Poly
Li arginin.
D#B#"#~# P(J8*, >(1> 6i/ 6(M*( 919 .=5* P:6 N X P LM N X S
Cac ete cua - aminoaxit tac dung voi dibenzylclphtphat duc su dung d bao
v nhom amin trong phan ung tng hp peptit.
``
R CH
O
P
NH - CH - CO - PBpi
R
O
O
O
NH - CH - CO - PBpi
R
O
HO
HO
H , HOH
pH ! $
H PO + H N - CH - CO - PBpi
3 $ 2
Nguoi ta cung su dung nhiu hp cht cua luu huynh d lam nhom bao v cac
hp cht amin:
a. Phan ung cua sunIenylclorua voi cac amin
R - NH
C H SCl
< 5
C H S
C H S
N - R RNH Cl
+ -
3
2
< 5
< 5
b. Phan ung cua IenanxylsynIonyclorua voi cac amin:

8
R - NH + C H COCH SO Cl RNHSO CH COC H
NSO CH COC H NH
R
R
`
R
R
`
WnkCH COOH
2 < 5 2 2 2 2 < 5
2 2 <
5
3
R X
`
c. Phan ung bao v bng s tao thanh hp cht N surIaxit:

NO
2
NO
2
NH
+N
NH
NHSO H NHSO H
NHSO H
NHSO H
N ! N - 8r
2
2
3 3
3
3
D#B#3# &^O V NHM N X NH
3
CbA NHM HY$AzIN2
D bao v nhom chuc N NH
2
cua Hydrazin trong tng hp hu c, nguoi ta d
su dung nhiu loai hp cht khac nhau.
a. Su dung nhom tec Butoxicacbonyl lam nhom bao v d tng hp 1 Benzoyl 1-
Benzythydrazin.
H N - NH B*-N%-OCONHNH B*-N%-OCONHN ! CHC H
B*-N%-OCONHNHCH C H B*-N%-OCONH-N-CH C H COC H
C H CH
NNH
C H CO
2 2 2 < 5
2 < 5 2 < 5 < 5
< 5 2
< 5
2
H
b. Su dung phan ung bao v Iocmyl hoa d diu chhp cht 1 aminobenzimidrazol
t 0 Nitrophenyl hydrazin:

0
NHNH
NO
2
NHNHCHO
NO
2
NH
NHNHCHO
N
N
CH
N
N
CH
3
3
NHCHO
NH
2
2
2
d. Bao v nhom N NH
2
bang andhyt - tng hp 1 amintetrazol.
H N - NH + C H - CHO C H - CH ! N - NH C H - CH ! N - N ! CH ! O - C H
2 2 < 5 < 5 2 < 5 2 5
N
N
N
N
N
N
N
N
C H - CH ! N
H N
< 5
2
D#B#B# &^O V NHM O X NH
3
CbA HY$%`YaAMIN2
D thu nhn cac hp cht O axyl va O ankyl cua Hydrxylamin thi cn phai bao v
lin kt N H. Diu nay co th dat duc bng nhiu phung phap khac nhau. Vi du co
th dung cac hp cht cacsonyl nhu sau:
CH
CH
C ! N - CH C H H N - OCH - C H
3
3
CH
CH
C ! O + H N - OH N - OH
3
3
CH
CH
C !
3
3
C H CH Cl
2
< 5 2
2 < 5 3
+
2 < 5
HCl
Phung phap bao v trn dy tuy rng duc su dung rt rng ri nhung trong mt s
truong hp khi dung phan ung thuy phn hp cht thu duc sau phan ung d tai tao lai
nhom amin thi pha huy lung lin kt O- Axyl hoc O- Ankyl. D khc phuc nhuc
dim nay nguoi ta thuong su dung nhom Tec Butoxi cacbonyl lam nhom bao v.

1
B* - N%OCON B* - OCONHOH
NO
Cl
NO
[ .OH
ONHCOO - N% - B*
NO
NO
CS COOH
NO
NO
ONH
NH OH
2
2
2
3
2
2
2
2
2
III#D# &^O V NHM AMIN &C B

X N$
B
D bao v cac nhom amin bc 3
0
nguoi ta tim cach chuyn hoa chung thanh mui
amni bc 4
0
hoc thanh cac hp cht nictin thanh mui cua Pirdin nhu sau:
N
N
HI N
N
CH
+
CH H
CH
N
N
H CH

+
3
3
+
3
3
+
N
N
3
CH
3
CH
CH I
3
D bao v nhom amin bc 3
0
cua Pinidin, trong cac phan ung chuyn hoa, nguoi
ta dung phung phap tao hp cht N oxit.
Vi du:

2
2
2
N N
NH CN
C H
C H
H C H C
O
3 3
2 5
5 5

2
N
NH
C H
H C
O
3
2

+
N
C H
H C
O
3
2
COOCH
3
5


+
N
C H
H C
3
2
COOCH
3
5
D#D# &^O V NHM CHC ANCOa
Ancol tham gia d dang vao cac phan ung ankyl hoa, axyl hoa, xy hoa, dhydrat
hoa... Vi vy trong rt nhiu cac phan ung tng hp d thu duc nhng san phm
cn thit thi phai bao v nhom ancol duc su dung rt rng ri trong cac phan ung
tng hp sterit, cac loai duong, glyxerit... Cac phung phap c ban thuong duc
su dung d bao v nhom chuc ancol thuong la ete hoa, axtal hoa va ketal hoa.
D#D#"# PHNG PHP ITI HO2
Nhom Hydrxy cua cac hp cht ancol rt d dang tham gia phan ungd d tao thanh
cac hp cht ete khac nhau. Duoi dy la mt s ete thuong duc su dung d bao v
nhom chuc ancol.
a. Ete metylic:
Cac nhom chuc hydrxyl trong hydrcacbon va trong ancol rt d dang mtyl hoa boi
dimtylsunIat trong mi truong kim hoc boi metyliodua voi xuc tac oxit bac. Dy
chinh la c so cua phan ung dung d bao v cac nhom chuc ancol bng phung phung
phap ete mtylic.
b. Ete Tec Butylic:
Nhom tec Butylic thuong duc su dung d bao v cac nhom chuc ancol trong cac
phan ung tng hp peptit steroit. Ete tec Butylic co th duc diu ch voi mt hiu
sut kha cao bng phan ung cua ancol va izbutylen voi Metylen clorua duc xuc tac
bng axit:

ROH + (CH )C ! CH ROC(CH )
3 2
3 3
H
+
Sau phan ung co th tach nhom bao v tec Butyl bng phan ung voi triIloaxtic axit
khan.
c. Ete alylic:

3
Trong rt nhiu truong hp dc bit la trong mi truong axit yu thi co th su dung ete
allylic d bao v nhom chuc ancol.
ROH + CH ! CH - CH Nr ROCH CH ! CH
NaOH
2 2 2 2
d. Ete Benzylic:
Nhom bao v benzyl duc ung dung rt rng ri d bao v cac nhom chuc ancol trong
cac tng hp duong, nucleozit, glyxrit, aminaxit. Phan ung bao v duc thc hin
bng s dun nong ancol voi benzyl clorua du trong dung mi khng phn cc. Vi du
phan ung chuyn D- glucoza thanh L sorboza duc bao v boi Ete benzylic nhu sau:
O
CH OH
OH
HO
OH
OH
O
C H CH Cl
C H CH O
OCH C H
OH
OCH C H
O
HCOCH C H
C H CH CH
HCOCH C H
HCOH
CH OCH C H
CH OH
HO
OH
OH
CH OH
2
< 5 2
2 < 5
< 5 2
2 < 5
2
2 < 5
< 5 2
2 < 5
2 2 < 5
2
e. Ete triarylmtylic:
Ete triarymtylic duc su dung rt rng ri d bao v nhom ancol bc 1
0
trong cac
phan ung tng hp duong, nucleozit, glyxerit va steroit. Hp cht bao v duc tao thnhI
khi cho ancol tac dung voi triphenylclomtan.
Vi du:
3
C Cl + ROH
H CO
C OR
H CO
3
Nhom bao v sau phan ung duc tac di bng phan ung thuy phn trong mi truong
axit.
I. Ete trimtysilic:
Nhom trimtyl silyl duc ung dung rng ri d bao v cac nhom chuc ancol trong
cacbon hydrat, steroit. Uu dim lon cua phung phap nay la nhom bao v rt d dang bi
dy di trong nhng diu kin phan ung khng khc nghit lm. Hp cht bao v thuong
duc thu nhn bng phan ung cua ancol voi trimtylclosilan.

4
ROH + (CH ) SiCl ROSi(CH )
3
3
3 3
D#D#3# PHNG PHP I`ITAa V 'ITAa HO2
a. Ete tetrahydrIiranylic:
Phan ung cua 2, 3 dihydr 4H- piran tac dung voi ancol trong mi truong axit tao
thanh ete tetrahydrpiranylic la c so cua phung phap bao v axtal:
O
+ HOR
O
H
OR
+
Phan ung nay duc su dung rng ri d bao v cac nhom chuc ancol trong cac phung
phap tng hp steroit, nucleotit. Ete tetrahydrpiranylic rt bn vng trong mi truong
kim, nhung d dang bi thuy phn trong mi truong axit d cho lai hp cht ancol ban
du.
b. Cac hp cht axetal.
Cho dn nay trong hoa hoc tac dung hu c chu yu vn su dung Tuy nhin,
trong mt s truong hp nguoi ta co su dung mt s axetal Ete tetrahydrpiranylic d
bao v nhom ancol theo phung phap axetal. Tuy nhin, trong mt s truong hp nguoi
ta co su dung mt s axeta khac nhu dn xut cua uridin, tetrahydrtiIuran,
tetrahydrtipiran.
S
OR
S OR
CH COOCH
3
N
O
HN
O
C
O P - O OOCHOC H
CH
3
2
3
2 5
2
c. Cac hp cht ketal:
Vic su dung nhom bao v tetrahydrpiranyl cho cac nhom chuc ancol quang hoat d
dn dn mt kho khn la tao thanh hn hp dng phn khac nhau. D khc phuc vn d
nay trong nhiu truong hp nguoi ta thay nhom tetrahydrpiranyl bng mt hp cht
axetal di xung (ketal). Nhng ketal thuong duc su dung d bao v nhom chuc ancol
trong cac phan ung tng hp nhu ketal axtn, ketal uridin, ketal cua dn xut
tetrahydr 4H piranon 4.

5
CH O
C
OR
CH CH
CH O
O - qr CH O
O
OR
3
3
3
3
3
D#D#B# PHNG PHP ISTI HO
Mt trong nhng phuong phap duc su dung rng ri nht d bao v cac nhom chuc
ancolcua cac phan ung xay ra trong mi truong axit hoc la trung tinh la phung phap
este hoa - tao thanh cac hp cht axetat, hoc la cac hp cht cacboxylat. Cac phan ung
axyl hoa nay thuong xay ra o nhit d thuong boi phan ung cua ancol voi anhydrit hoc
cloranhydrit cua cac axit cacboxylic trong piridin.
a. ?%c hL2 ch9t ax"tat(
Dy la phung phap duc su dung tung di rng ri d bao v nhom chuc ancol
trong cac hp cht steroit, cacbonhydrat, nuclozit... Hp cht bao v duc tao thanh
boi phan ung cua anhydrit axetic voi ancol cn bao v trong piridin. Sau khi phan ung
kt thuc thi nhom bao v duc tach ra bng phan ung thuy phn trong mi truong axit.
b. ?%c hL2 ch9t S"nIoat v 2 notro:"nIoat:
D bao v cac nhom chuc ancol dc bit la trong cac hp cht duong thng su dung
rng ri phung phap benzoat hoa. Phan ung tao thanh hp cht bao v xay ra gia
nhom ancol voi hp cht Benzoyl clorua trong piridin. So voi phung phap axetat hoa
thi phung phap nay xay ra trong nhng diu kin chon loc tt hn va it co cac phan
ung chuyn vi hn.
c. .h6ng 2h%2 Qocmiat ho%(
Phung phap nay co uu dim lon la d bi thuy phn d phuc hi lai ancol ban du ma
khng lam anh huong dn cac nhom bao v cua cac loai este khac. Hp cht bao v
duc tao thanh by phan ung cua nhom ancol voi axit Iocmic va sau khi kt thuc phan
ung nhom ancol duc tai tao lai boi phan ung thuy phn cua bicacbonat Kali trong ruu
metylic.
Vi du phung phap Iocmiat hoa duc su dung d bao v nhom ancol trong phan ung
chuyn hoa cht dhydrizoandrosteron thanh testosterron.

6

O
3
HO HCOO
HCOO
O O
OCOCH
OCOCH
3
D#D#D# PHNG PHP &^O V CC IOa2
Cac nhom chuc 1, 2 va 1, 3 glycol thuong duc bao v bng cac axtal va ktal vong
hoc cac este vong.
4.4.4.1. Cc axtal v ktal vng
Phung phap bao v cac hp cht glycol bng cac axtal va ktal vong duc ung dung
rng ri trong hoa hoc steroit, glyxerit, cacbon hydrat. Cac nhom bao v thuong duc
hinh thanh bng phan ung cua hp cht glycol voi cac hp cht cacbonyl tung ung
trong mi truong axit. Phan ung c th tin hanh trong cac dung mi nhu dixan ete,
benzen, tetrametylIocmamit hoc khng co dung mi. Cac nhom bao v loai nay bn
trong mi truong trung tinh va mi truong kim, d bi thuy phn boi axit. Sau dy la
mt vai phung phap hay duc su dung.
1. T't!0"nax"ta0(
Hp cht nay thu nhn duc bng phan ung cua glycol voi Iocmandhyt trong mi
truong axit. Nu phan ung tin hanh voi cac ancol da chuc thi thuong tao ra mt hn
hp nhiu san phm. Vi du nu cho Iocmandhyt tac dung voi D lucoxit trong HCl
thi s thu duc mt hn hp san phm diaxetal va triaxetal.
HO - CH
CH OH
OH
OH
OH
OH
HCHO
2
2
O - CH
CH OH
O
O
O
OH
2
2
O - CH
CH - O
O
O
O
O
2
2
+
). Ut!0i"n ax"ta0(

7
Hp cht nay duc ung dung chu yu trong tng hp cac loai duong. Nhom bao v
duc hinh thanh bng phan ung glycol voi axetandhyt, 1, 1 dimetxyetanol voi s
xuc tac cua axit. Vi du hp cht metyl 4,6 O etyliden - - D lucopiranozit
duc tao thanh bng phan ung trao di gia mtyl - - D lucopiranozit voi 1,1
dimetxietan voi xuc tac H
2
SO
4
.
HOCH
2
OCH
3
3
CH
3
- CH CH
3
CH
HO OH
OH
O OCH
3
3
HO OH
OH
O
OCH
3
OCH
3
O - CH
2
O
Etylidenaxetal la hp cht bn trong mi truong kim nhung d bi thuy phn trong
mi truong axit d tai tao lai hp cht ban du.
V. S"nI!0i"n ax"ta0(
Hp cht bao v nay duc ung dung rng ri trong tng hp duong va glyxrit.
Benzyliden axetal duc tao thanh bng phan ung cua cac glycol voi benzandhyt voi
xuc tac axit. Vi du phan ung tao thanh dn xut benzyliden axetal 1,2 va 1,3 cua
glyxrin xay ra nhu sau:

CH
2
- OH CH
2
- O CH
2
- O
CH - OH C
6
H
5
- CHO CH - O CHOH
CH
2
- OH CH
2
OH CH
2
- O
CHC
6
H
5
H

Benzyliden axetal rt bn trong cac diu kin phan ung khac nhau (tr axit). Mt khac
mi lin kt bao v cua hp cht cung d bi pha v bng phan ung khu co xuc tac.
Vi du:
C
6
H
5
- CH
O - CH
2
O
O
O
H
2
, Pd/c
O
O
HOCH
2
HO
OCH
3
Ngoai ra d bao v cac diol theo phung phap nay nguoi ta con su dung nhiu cac hp
cht khac nhau nhu dn xut cua benzeliden axetal, izopropy liden ketal,
xyclohecxyliden ketal. Vi duphan ung tao thanh hp cht bao v xyclohecxylide axettal
gia D KxicloIuranoza voi xuc tac H
2
SO
4
xay ra nhu sau:

O
O
OH
O
O
HOCH
2
O
OH
OH
OH
HOCH
2
H

4.4.4.. Cc este vng!

8
D bao v cac diol theo phung phap nay, thuong nguoi ta hay phenyborat vong.
Phung phap nay duc ung dung rt rng ri trong cac tng hp duong, nucloIit,
glyxerit. Cac hp cht cacbonat duc hinh thanh bng phan ung cua glycol voi Iocgen
trong piridin. Vi du cac nhom glycol cua D glucza duc bao v bng hp cht
cacbonat vong nhu sau:

O
OH
OH
OH
HOCH
2
O
OH
O
O
O
O - CH
O
O
COCl
2
/Piridin

T W=4 .u* *(Q6 9t- 919 (A> 9(Q6 S)/ Lm 9-9S/*-6 .M P(1 Sk* trong mi
truong axit va chi bi pha v trong mi truong kim.
Cac hp cht bao v phenolborat vong duc tao thanh khi cho glycol tac dung
voi axit phenylbonic trong cac dung mi nhu benzen axtn, dixan. Dy la nhng
hp cht bn o trong khng khi nhung rt bi pha v boi 1,3 propandion. Vi du phan
ung chuyn hoa - D - Kxylopiranozit thanh dn xut 3 0 axtyl bng phung phap
phenolborat vong xay ra nhu sau:
O
OCH
3
OH
OH
OH
C
6
H
5
(OH)
2
O
O
O
OCH
3
OH
1.(CH
3
CO)
2
O
2.HOCH
2
CH
2
CH
2
OH
B
C
6
H
5
O
OH
CH
3
COO
OH
OCH
3
D#G &^O V NHM CHC CAC&O`Ya
Trong tng hp rt nhiu khe cn thit phai bao v nhom chuc cacboxyl d tin
hanh phan ung tai cac vi tri khac va sau khi phan ung kt thuc thi tim cachs phn huy
nhom bao v d khi phuc lai nhom chuc cac boxyl ban du. Vi du nhom chuc
cacboxyl duc bao v trong phan ung tng hp penyxylin nhu sau:

N-CH
S
NH
CH
3
CH
3
COOH
N-CH
O
O
COOH
O
O
COO(CH
3
)
3
S
NH
CH
3
CH
3
COOCH
2
C
6
H
5
(C
6
H
5
)
3
C-NH-CH
S
NH
CH
3
CH
3
COOCH
2
C
6
H
5
(C
6
H
5
)
3
C-NH-CH
S
NH
CH
3
CH
3
COOCH
2
C
6
H
5
COO(CH
3
)
3 COOH
(C
6
H
5
)
3
C-NH-CH
S
N
O
CH
3
CH
3
COOCH
2
C
6
H
5
S
N
O
CH
3
COOH
1.H
2
/pd
2.H
3
O

H
2
N -CH
CH
3 N
CH
O
CH
N
CH
3
COOH
CH
3
S
O
Phung phap chu yu la phung phap este hoa.

100
D#G#"# PHNG PHP ISTI HO &sNG ANCOa2
D bao v nhom chuc cacbonyl nguoi ta tin hanh este hoa cac axit caboxyl hoc
la cac dn xut cua no bng cac ancol khac nhau. Sau dy la mt s phung phap c
ban:
a. Phung phap este hoa trc tip cac axit co th thu nhn duc cacboxylat cuar
mtyl, tyl, benzyl, cac dn xut benzyl.bng phung phan ung cua axit va ancol tung
ung. Cac phan ung nay thuong duc xuc tac bng axit v c hoc mt s axit a kim khac
nhau.
b. Phung phap este hoa bng phan ung cua halogenanhydrit axit voi ancol duc
thc hin trong mi truong kim. Phan ung nay thuong dung d diu ch tec-butyl
cacboxylat.
c. Phan ung este hoa cua cac anhydrit axit voi cac ancol co th duc xuc tac boi
axit hoc baz. Mt trong nhng uu dim lon cua phan ung nay la no tao thanh mn
este khi cho ancol tac dung voi ca anhydrit vong cua cac hp cht diaxit.
Vi du: Nguoi ta d ung dung uu dim do d tng hp glutamic nhu sau:
COOH
COO

NH
3
C
C
NHCOCH
2
C
6
H
5
O
O
O
C
6
H
5
OH COOH
COOCH
2
C
6
H
5
NHCOCH
2
C
6
H
5
CONH
2
COO

NH
3
d. Phung phap este hoa bng phan ung cua cac dn xut halogen voi cac mui cua
axit cacboxylic duc su dung d diu ch mtyl, tyl, benzyl cacboxylat.
e. Ngoai ra, d diu ch este nguoi ta con su dung cac phung phap nhu trao di
este, phan ung cua axit cacboxylic voi oleIin, voi diaIoankan, va nhng phung phap
khac.
D#G#3# NG [NG V PHNG PHP TCH CC NHM &^O V CbA
ISTI2
a. T't!0 v 't!0 "st": Dy la cac nhom bao v duc ung dung rng ri trong nhng
phan ung anlyl hoa va ngung tu. Cac nhom bao v nay co th duc tach ra bng phan ung
thuy phn boi axit hoc baz.
:. J"c @ Sut!0 "st": Hp cht nay rt bn trong cac phan ung thuy phn boi baz
nhung rt bi thuy phn boi axit. Vi vy, no thuong duc su dung d bao v cac nhom
caboxyl trong cac phan ung tng hp xay ra trong mi truong kim, dc bit la d diu
ch cac xtn.
Vi du:
C
6
H
5
CH
2
CH(COO tec Bu)
2
P O
2
N C
6
H
4
COCl

P O
2
N C
6
H
4
CO CH
2
CH
2
C
6
H
5
5. S"nI!0 v c%c 58n xu9t :"n!0 "st"(

101
Cac nhom bao v nay rt d dang tach di bng phung phap thuy phn. Nhom benzyl
co th bi tach di bng phung phap thuy phn trong mi truong kim hoc la trong mi
truong axit voi diu kin khc nghit. Tc d thuy phn cua cac este nay phu thuc vao
nng d cua axit, nhit d, thoi gian, phan ung .Uu dim v d bn cua cac nhom bao
v nay trong mi truong axit yu d duc ap dung d tng hp nhiu hp cht ma khng
th diu ch duc trong mi truong kim.
Ngoai ra, d bao v nhom chuc caboxyl trong tng hp hu c nguoi ta con su dung
nhiu nhom bao v khac nhau: 2,4 dinitr benzensunIophenyl, O nitrbenzhydryl,
benzilidenyl, phenylaxtyl.Sau phan ung nhng nhom chuc nay cung duc tach ra bng
phan ung thuy phn trong mi truong axit hoc baz.
D#~# &^O V CC NHM CHC ANHYT V `T%N
Nhom cacbonyl trong cac hp cht andhyt va xtn la nhom chuc rt linh dng, tham
gia nhiu phan ung khac nhau trong tng hp hu c. Vi vy, vic bao v no d tin
hanh mt phan ung theo mun co ngha rt lon. Duoi dy la mt s phung phap
quan trong thuong duc su dung.
D#~#"# A`TAa V 'TAa HO
4.".1.1. Cc phng php #$o v% #&ng 'xtal v (tal:
a- .h6ng 2h%2 1-V @ iDxD0an @ Nhm iDxD0an(
C O C
R'
R
R'
R
O
O
CH
2
CH
2
duc su dung d bao v cac nhom andhyt va xtn trong mi truong kim va trung tinh.
Kh nng tao thanh hp cht dixlan duc sp xp theo dy sau: Cac andhyt ~ Cac
xtn mach ho va xycl-hecxannon ~ xyclopentanon ~ , - xtn khng no ~ cac dn
xut xut -mn va dixtn ~ Cac xtn thm.
Duoi dy la mt vai phung phap diu ch cac dixlan t andhyt va xtn:
.h6ng 2h%2 trc ti2: Trong phung phap nay dixlan duc diu ch bng
phan ung cua cac hp cht cacbonyl voi tylenglycol trong mi truong axit. Phan ung
duc tin hanh voi s tham gia cua octeste, la tac nhn tach loai nuoc. Ngoai xuc tac
bng axit thuong nguoi ta su dung cac xuc tac nhu sunIoaxit, pirindin clohydrat. Di
voi cac xtn hoat dng manh thi co th su dung cac xuc tac nhu xyt selen, axit
malnic.
.h6ng 2h%2 trao Ki: C so cua phung phap nay la phan ung trao di gia cac
nhom chuc cabonyl voi cac hp cht dixolan cua cac xtn co nhit d rt thp.
Thuong hay su dung cac hp cht dixlan cua butanon 2, axtn. Phung phap nay
co th dung d bao v cho cac dixtn co kh nng phan ung tung t nhu nhau.
Tt s4 2h6ng 2h%2 *h%c: D diu ch cac dixolan trong tng hp hu c,
nguoi ta con su dung mt s hp cht nhu etylenxyt voi xuc tac clorua thic, sunIit
glycol.
:- ?%c 2h6ng 2h%2 ax"ta0 v *"ta0 vOng: S tao thanh cac hp cht axetal va ketal
vong duc thc hin boi phan ung cua cac andhyt va xtn voi ancadiol. Cac kt qua

102
nghin cuu cho thy rng kh nng tao thanh cac ketal bin di theo dy: 2,2
dimtyprpadiol 1,3 ~ etylenglycol ~ propadiol 1,3.
c. Phung phap diankylaxetal va dianxylxtal:
C O C
R'
R
R'
R
OR'''
OR"
S tao thanh cac diankylaxetal va dianxylxtal chu yu chi xay ra voi cac andhyt va
cac xtn hoat dng manh. Phan ung xay ra voi xuc tac axit gia cac hp cht
cacbonxyl voi cac ancol. Dy la cac hp cht tung di bn trong mi truong trung tinh
va mi truong kim.
4.".1.. Phng php ph)n h*+ axtal v ktal:
Cac axtal va ktal thuong duc phn huy d phuc hi lai cac nhom chuc cacbonyl
duoi tac dung cua axit. Tuy nhin tuy thuc vao cac hp cht axtal va ktal, cu th na
nguoi ta su dung axits thich hp. Thuong thi s tao thanh cac axtal va ktal cang d
dang bao nhiu thi s phn huy bng axit cang nh nhang by nhiu. Mt khac, s phn
huy cua cac ketal quang hoat thuong xay ra trong diu kin khc nghit voi cac tac
nhn la nhng axit v c.
D#~#3# POaYTI% V I% X A`TAa V 'TAa2
4."..1. 1,3 - .cxat/olan 0Polyt/oketal1:
C O C
R'
R
R'
R
CH
2
CH
2
O
S
Cac hp cht nay duc tao thanh khi cho xtn tac dung voi 2-mcaptoetanol trong
mi truong axit. Trong mt s truong hp cung co th chuyn hoa cac andhyt bng
phan ung nay. Ngoai ra cac polytiketal cung co th thu nhn bng phung phap nay t
cac dn xut cua mcaptoetanol va mcaptpropanol. So voi etylen glycol thi cac
phan ung cua cac andhyt va xtn xay ra voi mcaptoetanol d dang hn. Mt khac,
cung tung t nhu dixalan, cac polytiktal rt bn vng trong mi truong trung tinh
va baz nhung khng bn trong mi truong axit. Cac polytiktal thuong bi phn huy
boi cac axit v c trong ancol hoc dixan. Nhuc dim c ban nht cua phung phap
nay la vic tao thanh hp cht polytiktal dn dn s xut hin trung tm bt di va do
do co th tao thanh san phm la nhng dng phn quang hoc khng di quang.
4."... 2/t/aketal v 3/t/ktal:
Cac hp cht nay co th thu nhn bng phan ung cua cac hp cht cacbonyl. Voi
ankylmcaptan hoc dimcaptan trong mi truong axit. Thuong hay su dung cac tac
nhn phan ung nhu: 1,2 dimcaptotan, tylmcaptan. Cac Ditiaketal va ditiktal
du bn trong mi truong trung tinh va baz nhung khng bn trong mi truong axit.
D phn huy cac hp cht nay tt nht la su dung khng phai axit ma cac mui cua thuy
ngn (II) trong cac dung mi khac nhau.
D#~#B# CC [cN `UT INOa V NAMIN

103
Dy la phung phap bao v duc su dung rng ri trong hoa hoc sterit, dc bit la di
voi cac
,
- xtn chua no. Vi vy cac hp cht co ngha chu yu la cac dienol va
dienamin.
4.".3.1. Cc ete enol v t/enol:
C
R'
H
C
R
O
C
R
R'
O(S) R'' C
Phan ung chuyn hoa cac
,
- xtn chua no thanh cac ete dienol thuong xay
ra duoi tac dung cua este octIocmiat hoc 2,2 dimtxypropan trong ancol voi xuc
tac axit. D thu nhn ete dienol thuong su dung cac diol hoat dng manh, vi du nhu
benzylmcaptan.
Cac ete enol va dienol cung nhu cac dn xut cua chung rt bn trong mi truong
kim nhung rt d bi phn huy boi cac axit. Ngoai ra, d phuc hi lai cac nhom chuc
cacbony cung co th phn huy cac dienol bng mui thuy phn (II).
4.".3.. 4nan/n v cc 5*6/ c7a ena5/n:
R'
R'
R
C
R'
H
C O
C
C
N
Cac hp cht enamin thuong duc dung d bao v cac nhom andehyt va
,
- xtn
chua no trong cac hp cht sterit. D tai tao lai cac nhom cacbonyl ban du, co th thuy
phn cac enamin bng cac dung dich axit hoc bng kim long.
D#~#D# SIMICAC&AzONR O`IM V CC [cN `UT HY$AzON
4.".4.1. 8e5/cac#a9on:
C O C N NH CONH
2
Trong nhng truong hp, dc bit la trong hoa hoc sterit cac hp cht semicacbazon
duc diu ch rt d dang. Hp cht semicacbazon rt bn duoi tac dung cua NaBH
4
,
LiBH
4
va trong mi truong kim. Trong hoa hoc hydrat cacbon, hp cht semicacbazon
duc su dung d bao v nhom andhyt cua cac hp cht mach ho khi tin hanh phan
ung ankyl hoa cac nhom ancol. D phn huy cac semicacbazon d tai tao lai cac nhom
cacbonyl thuong tin hanh phan ung thuy phn trong axit manh.
4.".4.. .x/5
C O C NOH
Hp cht bao v laoi nay co d bn vng tung dung voi semicacbszon nhung phan
ung phn huy no xay ra kho khn hn. Phan ung thuy phn hp cht xim d tai tao lai

104
nhom cacbonyl ban du cung duc tin hanh trong mi truong axit nhung phai co thm
mt s cht xuc tac khac. Trong mt s truong hp co th su dung phung phap xi hoa
trong mi truong axit.
4.6.4.3. Dn xut hydrazon:
C O C N - NH NO
2
va C N - N
CH
3
CH
3
O
2
N
Hp cht 2,4 dinitrphenyl hydrazon duc su dung chu yu d dinh tinh andhyt va
xtn con d bao v nhom chuc thi it hn vi phan ung phn huy no xay ra rt khoa khn.
Tuy vy, trong cac phan ung tng hp va chyn hoa cac hp cht steroit hp cht nay
nhiu khi cung duc su dung. Nhom bao v thuong duc tach ra bng phung phap kh
voi cac tac nhn nhu clorua thic (II), clorua thic (III), Liti nhm hydrua..
Hp cht N, N dimtylhydrazon la mt trong nhng hp cht kha l tuong dung d bao
v cac nhom andhyt va xtn vi rng vic tai tao lai cac hp cht cacbonyl sau phan ung
duc thc hin trong nhng diu kin rt nh nhang trong mi truong trung tinh.

105
CHNG G
S %`I HO ? 'H
S xi hoa va s khu la hai hin tung co lin quan mt thit voi nhau va khng th
tach roi nhau duc, khng co s xi hoa nao ma lai khng co s khu dng thoi voi no.
Hai qua trinh do duc coi la mt: S xy hoa - khu. Trong thc t ta noi mt phan ung
nao do la xy hoahy la khu chi la quy uoc d nhn manh tng mt. S xy khoa - khu
la mt khai nim tung di phuc tap. Vi vy, truoc khi xt dn c ch phan ung nay ta
cn d cp dn vn d nay.
G#"# S %`I HO ? 'H V C CHf PH^N NG#
G#"#"# T-* *=m4 Lk E< CH7 (/1 ? P(O 6;/*, (/1 (lT 982
Truoc kia nguoi ta cho rng s xy hoa la qua trinh cng thm xy, con s khu la
qua trinh tach bot xy, hoc tng ham lung tung di cua hydr trong phn tu. Dinh
ngha do khng co tinh tng quat, tuy rng do s thun tin va thoi quen nguoi ta vn
dung no trong vic phn chia cac phan ung cua hp cht hu c.
Trong hoa v c, phan ung xy hoa- khu thuong dc trung bng s thay di hoa tri
hoc s chuyn dich mt s electron. Trong hoa hu c quan nim do khng duc dung
vi nguyn tu cacbon trong phn tu hu c lun lun co hoa tri 4, con nhng phan ung
co s chuyn dich hn cac electron thi it gp.
Vi nhng l trn, hin nay nguoi ta thuong dinh ngha s xy hoa - khu da trn c
so bin di cua nhng dai lung co tinh cht quy uoc goi la s xy hoa hoc bc xy
hoa.
S xy hoa la s din tich quy uoc cua nguyn tu, tinh duc khi gia thit rng phn
tu gm toan nhng in dn gian trai du kt hp lai. Noi mt cach khac, s xy hoa la
s din tich xut hin o nguyn tu trong phn tu nu nhu xay ra s dich chuyn hoan
toan tt ca cac cp electron lin kt v phia nguyn tu nao co d m din tung di lon
hn. ENu hai ngu!'n t< Wng nh9t 0i'n *t vi nhau th *hDng c s chu!7n ch - v
nh vX! *hDng 0m xu9t hi=n i=n ti%chG.
S xy hoa duc k hiu bng ch n (tR ting Ynh oxi5ation num:"r) va biu thi bng
s Ar rp cung voi du din tich va ghi o phia trn k hiu cua nguyn t. Thi du:
C - H
H - H
H - O - H
0 0
1 -2 1
H
H -
H
1
-4 1
1
1
C - H
H
H -
H
1
-2 -1
1
1
S xy hoa la mt khai nim co tinh hinh thuc, vi tt ca cac lin kt cng hoa tri gia
hai nguyn tu thuc hai nguyn t khac nhau du duc coi nhu la nhng lin kt ion din

106
hinh, ma thc ra khng phai nhu vy: phn lon cac lin kt do chi phn cc it nhiu ma
thi.
Mt nguyn t co th co nhiu s xy hoa khac nhau, tuy theo ban cht va s lung
cac nguyn tu lin kt voi nguyn tu cua nguyn t do trong phn tu. Thi du: cacbon co
s xy hoa (k hiu n
C
) t -4 dn 4 trong dy cac hp cht sau:
Hp cht: CH
4
CH
3
OH C CO CO
2
n
C
: -4 -2 0 2 4
Ta co th tinh s oxy hoa cho mt nguyn tu nht dinh trong phn tu bng cach ly
tng cng cac din tich xut hin o nguyn tu do khi cho ion hoa tt ca cac lin kt. Thi
du:
H
H
1
-1
1
1
1
C O H
H
H
1
1
-1
1
1
H H
1
-1
-1
-1
-1
C
H
-1
-1
-1
C C O H
H
1 1
-1 1
H
1 -1
-1
-1
-1
1
H
H
1
H
1
n
c
4 n
c
-2 n
c
(CH
3
) -3; n
c
(CH
2
OH) -1
Cung co th xac dinh s xy hoa trung binh cho cac nguyn tu cua mt nguyn t nht
dinh trong phn tu. Khi y ta phai tun theo mt s quy tc sau:
a. Tng dai s cac xy hoa trong phn tu lun lun bng o, trong ion bng s din tich cua
ion.
b. S xy hoa cua mt nguyn t o dang dn cht du bng 0.
c. Trong cac hp cht, hydr co s oxi hoa 1 ( tr truong hp cac hydrua kim loai, trong
do n
H

-1), xy co s oxi hoa -2 ( tr truong hp cac peoxyt va mt s hp cht khac),
kim loai co s oxy hoa dung va bng hoa tri cua no.
Thi du tinh s oxy hoa trung binh:
CH
4
n
C
4n
H
0
N
C
4(1) 0
n
C
-4
CH
3
OH n
O
4n
H
n
O
0
n
C
4(1) (-2) 0
n
C
-2
CH
3
CH
2
OH 2n
C
6n
H
n
O
0
n
C
6(1) (-2) 0
n
C
-2
CH
3
COOH 2n
C
4n
H
2n
O
0
2n
C
4(1) 2(-2) 0
n
C
-2

107
Ta nhn thy rng s oxy hoa trung binh cua cacbon chng han s trung voi s oxy hoa
tinh cho tng nguyn tu cacbon khi trong phn tu chi chua mt nguyn tu cacbon ( thi du
CH
4
, CH
3
OH,..) hoc chua 2 nguyn tu C ging ht nhau:
Thi du: CH
3
CH
3
, CHO CHO, ...
Trong cac thanh phn khac, s oxy hoa tinh cho tng nguyn tu bao gio cung la mt s
nguyn hoc 0, thi s oxy hoa trung binh co th la mt s thp phn, thi du s xy hoa
trung binh cua cacbon trong phn tu prpan bng 2,67, trong phn tu butan bng -2,5.
Bn canh khai nim s oxy hoa, trong hoa hu c con mt khai nim tung dung goi la
bc xy hoa. Theo dinh ngha, bc xy hoa cua nguyn tu cacbon la s nhom hydrxy co
th xut hin o nguyn tu cacbon, nu gia thuyt la phn tu bi thuy phn hoan toan.

C
C
Cl
C
H
2
O
H
2
O
C
C
OH
C
OH H
C Cl
C
C
OH
OH
C
OH
OH
O
H
2
O
H
2
O

Theo quan nim nay thi cacbon trong phn tu hu c co th co 5 bc oxy hoa khac nhau:
0, 1, 2, 3, va 4. (Xem bang trang sau).
Khai nim oxy hoa ( v *h%i ni=m :Xc ox! ho% c&ng vX!) cho php hinh dung muc d
tung di kha nng oxy hoa hay khu cua mt cht. S oxy hoa cang lon thi kha nng oxy
hoa E ha! 0 : *h< G cang tng, va kha nng khu E ha! : oxi ho%G cang giam. T dy ta co
th dinh ngha: Qua trinh oxy hoa la qua trinh lam tng s oxy hoa o cht phan ung vag
lam giam s oxy hoa o tac nhn phan ung, con qua trinh khu la qua trinh nguc lai. Noi
chung, oxy hoa - khu la qua trinh bin di s oxy hoa Eha! :Xc ox! ho%G

bc xy hoa:1
bc xy hoa:2
108
Dinh ngha trn v s oxy hoa - khu co tinh cach tng quat va bao ham duc tt ca cac
dinh ngha cu. Trong hoa hu c, ngoai nhng phan ung oxy hoa - khu bng cac tac nhn
oxy hoa hay cac tac nhn khu.
&)*, >(N* ./i= 919 *(K4 *,T75* 6O 6(0/ Sn9 /H7 (/1 9t- 9-9S/*#

10
NG* x9 h0:
*ma *a*b0n 1* r- ng
Nh&) ng%9Dn X Ih+56
CH [ RCH
C /
$ 3
C Ui C /gNr
C ! C
C X
C
C Hal [ C O [ C C N S ,
CH ! CH [ RR C ! CRR
2
`
`
-
H
C
X
X
C
! p
C
! C X
C
Hal
Hal
C
OH
OH
C
S
S
[
[
C
! O [
C
! S [
C

! N [
C
! C - Hal [
C
! C - OH
C
! C
C
! CH RC ! CR
2
C
! N


C
! CX
2
C
! CX
2
- C - X
p
- C - OH
O
- C - Hal
p
C
! C(OH)
2
3
$
- CX - CHal [ -C(OR)
- C
! W
CX CHal 7 C(OR)

$ $
$
p ! CX O ! CCl 7 S ! C(OR)
p ! C ! p S ! C ! S
! W C - X N C - OH 7 N C - Cl
! !

110
Sh CH7 (/1 9t- 9-9S/* 6;/*, 4@6 Eh >(N* 6O (lT 98 LM T1 6;w*( CH7 (/1 ? P(u

-$ -3 -2 -H - H 2 3 $
CH CH - OH
R - CH R - CH OH R - CHO R - COOR
CH - CH CH ! CH CH ! CH
HCHO HCOOH CO
3
3 3 2 2
3
2
2
Sb x9 h0:
Sb khX

$
Thng thuong nhu xy, hydro, pemanganat kali, axit crmit . con nhiu phan ung khac
cung duc coi la phan ung xy hoa - khu. Thi du cac phan ung halgen hoa hoa va nitro
hoa hydrocacbon, phan ung dhalgen hoa dn xut dihalgen, phan ung dcacbxyl hoa
axit cacbxylic.v.v. Trong khi do nhng phan ung nhu thuy phn dn xut halogen va hp
cht c kim, este hoa va thuy phn este. khng thuc loai phan ung xy hoa khu.
Khi cn bng phung trinh phan ung xy hoa khu trong hoa hu c nguoi ta cung
ap dung nguyn tc thng bng s xy hoa nhu trong hoa v c. Thi du co s d phan
ung:
CH
3
CH
2
OH KMnO
4
H
2
SO
4
CH
3
COOH MnSO
4
K
2
SO
4
H
2
O
-1
7
3 2
Trong do tanol la cht khu vi s xy hoa cua cacbon tng 4 dn vi (t -1 o tanol dn 3
o axit axtic) con pemanganat kali la cht xy hoa, vi s xy hoa cua mangan giam 5 dn
vi (t 7 o KmnO
4
dn 2 o MnSO
4
). D dam bao nguyn tc thng bng s xy hoa ta
phai ly 5 phn tu tanol va 4 phn tu pemanganat kali, con s phn tu H
2
SO
4
duc ly
sao cho tung ung voi s ion Mn
2
va K
2
sinh ra trong phan ung. Do do ta co th vit:
5CH
3
CH
2
OH 4KmnO
4
6H
2
SO
4
5CH
3
COOH 4MnSO
4
2K
2
SO
4
11H
2
O
Nhu vy quan nim v xy hoa khu da theo s bin di s xy hoa co th trong ca hoa
v c ln hoa hu c.
G#"#3# C8 9(: >()* +*, CH7 (/1 ? P(O
Dinh ngha trinh bay o trn v xy hoa - khu khng noi ln diu gi v c ch cac
phan ung do ca. Ta bit rng phan ung xy hoa - khu co th xay ra theo kiu dng ly hay
di ly. Tuy vy c ch xy hoa - khu la mt vn d rt phuc tap, vi c ch do rt da dang
va thuong bin di nhiu tuy theo ban cht cua tac nhn xy hoa - khu duc dung. Nhiu
nguoi d c gng h thng hoa cac c ch xy hoa - khu vao mt s loai nht dinh. C
ch cua cac phan ung xy hoa - khu duc tp trung noi dn o 5.2 va 5.3. Duoi dy la mt
s loai c ch xy hoa - khu ph bin.
Z.1.).1. ?hu!7n 5ch trc ti2 "0"ctron(
S d tng quat:

111
A e B
hoc B e A
Thi du:
Khu hp cht cacbnyl bng halri kim loai:
R
2
C O e R
2
C - O ...
Chuyn hoa gi ion va gc t do:
R R R
e
-
e
-
e
-
e
-
()
(- )
Z.1.).). ?hu!7n 5ch ngu!'n t< h!rD(
S d tng quat:
A H Z A - H Z
Thi du:
R H Cl HCl R ...
hoc:
R H - CR
3
RH CR
3
...
' '
Z.1.).V. ?hu!7n 5ch ion h!rua
S d tng quat:
()
(- )
A H Z AH Z
Thi du:
()
R H - R' RH R'
()
hoc:
...
(- )
()
R
2
C O LiAlH
4
R
2
CH - O Li AlH
3
Z.1.).[. ?hu!7n 5ch cP2 "0"ctron
S d tng quat:
A: Z A -~ Z
Thi du:
Br - Br Br - Br ()Br
Br
C
C
C
C
C
C
hoc:

112
R
3
N: O - O - H R
3
N - O - H HO R
3
N O H
2
O
H
() () (-) (-)
Z.1.).Z. J3o "st" trung gian(
Cht phan ung va tac nhn tac dung voi nhau tao thanh este trung gian (thuong la
este v c), sau do este bi phn tich:
() (-)
... A - C - B -~ A - C - B Z H
H
OZ O
Z thuong la CrO
3
H, MnO
3
, SeO
2
H.Thi du:
()
RCH O HMnO
4
R - C - OH R - O O MnO
H
OMnO
3
OH
B

G#3# C19 >()* +*, CH7 (/12
Z.).1. \x! ho% 0i'n *t

c$a A!rDcac:on
Ta bit rng nng lung phn ly cac lin kt

trong phn tu alkanthungI khng

khac nhau nhiu, cho nn it co phung phap xy hoa lam dut mt cach chon la hoc lin
kt C C hoc lin kt C H ma khng dung dn phn tu noi chung. Tuy vy, nng
lung phn ly cua cac lin kt C H bc ba hay cac vi tri alyl va benzyl yu hn cac lin
kt

khac mt cach r rt, do do ta co th chi xy hoa cac lin kt do ma phn con lai
cua phn tu vn duc nguyn vn. Thi du:
CH
2
CHCH
3
CH
2
CHCHO
O
2
CuCl
2

O
2
(CH
3
)
2
C - H (CH
3
)
2
C - OOH (CH
3
)
2
CO C
6
H
5
OH
C
6
H
5
C
6
H
5
C
6
H
5
CH
3
C
6
H
5
CHO
C
6
H
5
CH
3
C
6
H
5
COOH
(CH
3
CH)
2
O
CrO
3
KMnO
4
Phan ung xy hoa cac arylalkan bng Cr(VI) d duc nghin cuu tung di nhiu.
Tluen bi xy hoa thanh axit benzic, diphnylmtan tao ra benzphnon con
triphnylmtan tao ra triphnylcacbinol. Tc d xy hoa phu thuc nhiu cu tao cua

Prpen Acrlin
Cumen Hydpcxylcumyl
113
hydrcacbon. Trong truong hp xy hoa, nhom p mtyl lam tng tc d, con nhom p
nitr lam giam tc d, hiu ung no duc t hp tuyn tinh voi o

, p -1,4. Nu hai
nguyn tu hydr tham gia phan ung duc thay bng dteri, tc d phan ung s giam 6,4
ln, diu do chung to rng tc d phan ung xay ra s phn cach lin kt C H. Tuy vy
c ch cua giai doan nay noi ring cung nhu toan b phan ung noi chung con chua r
rang.
Phan ung xy hoa nhom alkyl o nhn thm bng pemaganat kali cung thuong tao
ra axit. Cac dn xut th o nhn cua toluen bi xy hoa tao thanh axit benzic tung ung.
So voi Cr
IV
thi Mn
VII
thuong xy hoa manh hn.
Chng han 2-5 dibrm-p-xylen bi xy hoa ca hai nhom mtyl boi penmanganat
Kali, nhung chi xy hoa mt nhom myl boi axit crmic.
Bt k cht xy hoa la Cr
VI
hay Mn
VII
, phan ung xy hoa nhom alkyl voi vong
benzen thuong xay ra o vi tri u (tao ra cac axit benzic tung ung). Tuy vy, cn luu
rng nhom alkyl bc 3 thi du t- butyl rt kho bi xy hoa vi khng con nguyn tu u
hydr.
G#3#3#"# %`Y HO aIN 'fT

CbA HY$%CAC&ON
G#3#3#3# %YC* >(N*
C C C C C O O C
O O
O
O
3
Zn
AcOH
Hp cht co ni di C C tac dung voi zn sinh ra znit. Co th phn lp duc znit,
nhung nguoi ta thuong dem phn huy no bng cach khu thanh hai phn tu hp cht
cacbnyl. Cung co th khu znit thanh hai phn tu alcol (tac dung cua LiAlH
4
) hoc xy
hoa thanh xton va cacbxylic (tac dung cua H
2
O
2
).
C ch cua giai doan tao thanh znit co th nhu sau:
O O
O
O
3
C C C C C - C
O
O
3
O
O
O
()
(-) Alken
C
C C
O
O
O C
()
(-)
Nu qua thc co tao ra san phm trung gian III va Iv nhu d nu o s d trn thi III
co th Dime hoa

znit (III) (IV)
114
()
(-)
C O
O O
C C
O C
() (-)
O
O C
O
(III)
(V)
hoc chuyn hoa thanh hydrpexyt.
Trong mt s truong hp, thi du zn hoa (CH
3
)
2
CC(CH
3
)
2
, nguoi ta d tach
duc san phm V, va nu duc zn hoa trong mtanol co th phn lp duc
hydrpexyt:
(CH
3
)
2
C - OCH
3
O - OH
Mt dn chung na v c ch zn hoa o trn la s tao thanh cac san phm cho:
theo c ch do nu xut phat t mt alken khng di xung RCH CHR ta phai duc 3
znit khac nhau:
RCH CHR RCH CHR' R'CH CHR'
O
O O
O
O O
O
O O
Trong thc t, khi zn hoa nhng hp cht nhu penten-2, hexen-2, lat mtyl.
nguoi ta d phn lp duc ca ba loai znit trn o cac dang dng phn cis-trans tung
ung.
Cac hp cht co ni ba C C va hp cht thm bi zn hoa kho hn alken.
G#3#3#3# =(7W;CH7 (/12
C C C C
OH OH
Mun cng hai nhom OH vao ni di (dihydrxy hoa) co th dung OsO
4
hoc
KmnO
4
trong mi truong kim. Do la nhng phan ung cng theo kiu cis.
Khi dung cht xy hoa la OsO
4
c ch phan ung nhu sau:
C C C C
O O OH OH
C C
HOH
OsO
2
(I)
Nguoi ta d phn lp duc este vong trung gian I.

115
Khi dung KmnO
4
trong mi truong kim, ta co c ch:
C C
C
C
MnO
4
MnO
4
MnO
4
C O
C O
H
2
O
C
OH
C
OH
(Mn
VII
)
(Mn
VII
) (Mn
VII
)
H
2
MnO
4
MnO
4
2-
MnO
2
(Mn
V
) (Mn
V
) (Mn
V
)
(-) (-) (-)
(-)
(-)
MnO
4
Hin nay, tuy chua phn lp duc este vong Mn
V
nhung d co chung co khac v c ch
trn, cu th la khi dung Mn
18
O
(-)
4
nguoi ta thu duc:
H
18
O - C - C -
18
OH
. Ngoai ra, d
chung minh rng phan ung chay theo kiu cis, nguoi ta dihydrxy hoa axit d,l-tactric,
dung nhu d doan theo c ch trn.
Mun trans-dihydrxy hoa ni di CC nguoi ta dung H
2
O
2
va axit Iomic. Trong
truong hp nay, axit peIomic sinh ra t H
2
O
2
va axit Iomic pxy hoa ni di theo kiu
cng cis, sau do pxit sinh ra s bi thuy phn theo c ch S
N
2 voi s quay cu hinh, kt
qua xt toan b thi phan ung chay theo kiu trans:
H - C - OH H
2
O
2
H - C - O - OH H
2
O
O O
Epxy hoa:
C O C
C
C C
C HO
H O
O
O
H
O H
Thuy phn:
()
()
C
O
C
C
O - H
C
C
OH
2
HO
C
C
HO
OH
-H
H
2
O
H
Do dc tinh cng trans cua phan ung, khi cho H
2
O
2
va HCOOH tac dung voi
xyclohexen ta duc trans-1,2-xyclohexandiol

116
()
HCOOH H
2
O
H
2
O
2
OH
O
OH
H
G#3#3#B# OH7 (/1 9g6 4i9(2
- C C - - C O O C -
H H OH OH
- C C - - C O O C -
H
OH
- C C - - C O O C -
Ni di CC co th bi oxy hoa ct mach theo cac s d trn nho tac dung cua
nhiu cht oxy hoa khac nhau, ph bin la cac cht oxy hoa pemanganat va bicromat trng
mi truong axit.
C ch phan ung con chua duc r rang. Cung co th trong phan ung d sinh ra
nhng san phm trung gian la glycol hoc este cua no.
Ni ba CC thuong kho bi oxy hoa hn ni di. Axtylen bi oxy hoa bng
pemanganat kali tao thanh mt hn hp san phm trong do co axit xalic.
Vong thm cung co th bi oxy hoa dut mach boi cac cht oxy hoa manh. Khi oxy
hoa benzen va naphtalen bng V
2
O
5
ta duc ln lut anhydrit malic va anhydrit phtalic.
G#3#B# %`Y HO AaCOa2
G#3#B#B# %H7 (/1 4C*C-.9/. 6(M*( (A> 9(Q6 9-9SC*7.
CHOH C O
S oxy hoa cac alcol bc mt va bc hai bng pemngnat kali xay ra rt chm
trong dung dich trung tinh, nhung thuong lai rt nhanh trong dung dich baz va axit
manh.
Khao sat phan ung xy hoa benzhydrol (C
6
H
5
)
2
CHOH trong dung dich trung tinh
va baz, nguoi ta thy: V k alcolMnO
4
-
OH
-
hiu ung dng vi o 25
0
C khi oxy hoa
(C
6
H
5
)
2
CDOH co gia tri bng 6,6; benzphnn sinh ra khng chua oxy t pemngnat
kali. T cac d kin do nguoi ta d nghi c ch phan ung nhu sau:
(-)
(C
6
H
5
)
2
CHOH HO (C
6
H
5
)
2
CHO H
2
O
(C
6
H
5
)
2
CHO MnO
4
(C
6
H
5
)
2
C O HMnO
4
HMnO
4
MnO
4
HO 2MnO
4
H
2
O
nhanh
(-)
(-)
(-)
(-) (-)
2- 2-
2-
Khao sat phan ung oxy hoa alcol izppylic bng axit cromic nguoi ta thy tc d
phan ung trong dung dich axit axetic lon hn trong dung dich axit v c voi cung gia tri
v H
0
; khi thay th nguyn tu u-hydro bng dteri o 25
0
C tc d giam 6,6 ln, trong khi
do thay th cac nguyn tu

- hydro bng dteri hu nhu khng lam thay di tc d phan

ung:
(CH
3
)
2
CH - OH (CH
3
)
2
CDOH (CD
3
)
2
CHOH

chm
117
T cac d kin nguoi ta d nghi c ch phan ung nhu sau:
(CH
3
)
2
CHOH HCrO
4
2H (CH
3
)
2
CHOCrO
3
H
2
H
2
O
() (-) ()
CH
3
C C
O - CrO
3
H
2
CH
3
CH
3
O BH HCrO
3
()
()
(Cr )
VL
()
CH
3
H
: B
(Cr )
IV
Sau do:
()
3Cr Cr 2Cr
III
IV IV
H
Hoc:
()
3Cr Cr 2Cr
IV
IV
Cr (CH
3
)
2
CHOH Cr (CH
3
)
2
C O
III V
V
-H
5.2.3.2. xy hoa ct mach 1,2 diol
Cac 1,2 diol co dc tinh khac va mnalcol o ch chung bi xy hoa boi axit peidic va
ttraxtat chi lam dut lin kt

- C - OH
C - OH
- C - OH
C - OH

- COH - COH -
Khi xy hoa bng HIO
4
phan ung di qua mt este vong trung gian:
- C - OH
C - OH
HIO
4
- C - O
C - O
IO
3
H
- C - OH
C - OH
HIO
3

HIO
4
hoc
Pb(CH
3
COO)
4
Tc d: 1,0 0,16 1,0
118
Nhng thi nghim dung
18
O d cho thy rng nguyn tu xy cacbnyl o san phm
cung chinh la nguyn tu xy glycol.
C ch tao este vong trung gian cua phan ung trn d duc xac nhn bng cac d
kin dng hoc va quang ph, dn chung dc bit la cac glycol voi hai nhom trans-OH thi
du trans-,10-dcalindiol khng phan ung voi axit peidic.
OH
OH
HIO
4
Khi xy hoa 1,2 -ddioolbng Pb (CH
3
COO)
4
nguoi ta cung co nhiu d kin cho
thy phan ung xay ra theo c ch vong. Thi du phan ung co bc mt ni di voi mi cht
phan ung giam di, cis-ddiolbi xy hoa nhanh hn trans-diol tung ung.C ch vong nhu
sau:
- C - OH
C - OH
Pb ( CH
3
COO)
4
Pb(CH
3
COO)
2
- C - OH
C - OH

-2CH
3
COOH Pb(CH
3
COO)
2
- C - O
C - O
Tuy nhin, co mt s trans-1,2-ddiol lai d phan ung hn dang cis tung ung. Vi
du truong hp ,10 dihydrphnantren-,10 -ddiol dang trans phan ung nhanh hn dang
cis ,4 ln, trans ,10 decalindiol khng phan ung voi HIO
4
nhung lai bi xy hoa boi
Pb(CH
3
COO)
4
. Nhu vy, co th o dy phan ung d xay ra theo c ch khng vong.
Pb(CH
3
COO)
2
-CH
3
COOH -2CH
3
COOH
OH
OH
O
O
Pb(CH
3
COO)
2
O
O
Pb(CH
3
COO)
2
1,2-diol cung co th bi xy hoa ct mach boi axit crmic va phan ung cung chay
theo c ch este vong trung gian.
G#3#D# %`Y HO AaIHYT V `T%N

11
G#3#D#"# %H7 (/1 S*, 619 *(N* LC 982
Cac hp cht cacbnyl, nht la aldhyl co th bi xy hoa boi cac hp cht xy hoa
khac nhau nhu Mn
VII
, Cr
VI
, Cu'', Ag
I
, Ce
IV
.
Nghin cuu phan ung xy hoa aldhyt thm bng KmnO
4
trong dung dich trung
tinh nguoi ta thy rng phan ung co bc mt di voi aldhyt cung nhu di voi
pemanganat, hiu ung dng vi dteri bng 7, nu dung KMn
18
O
4
,
18
O s xut hin trong
thanh phn phn tu cua axit thm sinh ra, cac nhom th o vong thm chi co anh huong
yu dn tc d phan ung (p -0,25).
Ta co th m ta c ch phan ung xy hoa do bng s d sau:
ArC MnO
4
H Ar - C OMnO
3
(-)
H
H
OH O
Ar - C - O - MnO
3
ArCOOH BH MnO
3
H
OH
()
() ()
: B
Phan ung xy hoa aldhyt bng axit crmic co nhiu nt tung t phan ung xy
hoa alcol cung bng tac nhn do. C ch phan ung nhu sau:
RC - H HCrO
4
H RC - H RC HCrO
3
H
3
O
:OH
2
OH
O
O
OH
O
- CrO
3
H
(-) ()
()
Trong truong hp dung C
6
H
5
CDO nguoi ta thy hiu ung dng vi bng 4,3, diu
do chung to giai doan phn ct lin kt cacbon-hydr quyt dinh tc d chung cua phan
ung.
ia hai phan ung xy hoa aldhyt va xy hoa alcol bng axit crmic co hai dim
khac nhau dang k. Mt la, cac nhom th hut electron xuc tin s xy hoa aldhyt (p
1,02) nhung lai lam giam nh tc d xy hoa alcol (p -1,0). Hai la thay th dung mi

chm
120
nuoc bng axit axetic khng lam tng manh tc d xy hoa aldhyt nhu d thy khi xy
hoa alcol.
Khac voi andhyt, xtn tung di kho bi xy hoa boi pemangant kali va axit
crmic. Tuy vy cac xtn vong d dang bi xy hoa thanh axit dicacbxylic. Thi du:

O
COOH
COOH
Co th cac xtn d tac dung duoi dang enol tao ra este v c trung gian, sau do este nay
bi thuy phn:

(-)
- C - C - - C C - - C - C -
O H OH
OH OCrO
3
H
2
()
()
- C - C - - C - C -
- H
()
O OH O OCrO
3
H
2
H
2
CrO
4

Dang chu la nhom u-metylen cua xtn cung nhu aldhyt co th bi xy hoa thanh
cacbnyl thu hai nho tac dung cua xyt selen:
- C - CH
2
- SeO
2
- C - C - Se H
2
O
-H
2
O
O
AeOH
O O
Trong phan ung trn, tac nhn xy hoa trc tip co l la axit selen: axit nay tac
dung voi lin kt a cua dang enol theo s d:

xy hoa tip
thuy phn
CrO
3
Hoc HNO
3
Axitadipic
121
- C - CH
2
- - C CH - - C CH -
H
2
SeO
3
-H
2
O
O OH O - SeO
2
H
- C - C - - C - CH -
O O O O - SeOH
- Se
- H
2
O
5.2.4.2. xy hoa bng tac nhn hu c:
Nhng phan ung xy hoa aldhyt bng cht hu c con co th duc coi la phan
ung khu di voi cht hu c do. Nhng phan ung nay thuong chay theo c ch chuyn
dich in hydrua, ma tiu biu hn ca la phan ung Cannizar va phan ung Tissenc.
a. Khi co tac dung cua mt baz manh nhu NaOH chng han cac aldhyt thm va
aldhyt bo khng co nguyn tu a-hydr s tham gia phan ung Cannizar, trong do mt
phn tu aldhyt bi xy hoa thanh cacbxylic tung ung, con phn tu aldhyt bi xy hoa
thanh alcol tung ung. Trong phan ung nay, thoat tin aion HO
(-)
tac dung vao nguyn tu
cacbon-cacbnyl cua mt phn tu aldhyt:

R - C - H HO R - C - H R - C - H
O O O
OH O
(-) (-)
(-)
(-)
(-)
HO
Sau do aion sinh ra s chuyn in hydrua sang nhom cacbnyl cua phn tu aldhyt
thu hai:
(-)
R - C - H C O R - C H - C - O R - C H - C - OH
O H O H O H
OH R OH R O R
(-)
(-)
H
2
O
hoc

122
(-)
R - C - H C O R - C H - C - O R - C H - C - OH
O H O H O H
O R O R O R
(-)
(-)
(-) (-)
H
2
O
Phan ung trn co bc mt di voi b va bc hai di voi andhyt, phan ung cua
RCHO trong D
2
O - kim tao ra alcol khng chua deteri, diu do co s chuyn dich trc
tip hydr t phn tu andhyt thu nht sang phn tu andhyt thu hai.
Phan ung Cannizar co th xay ra gia hai nhom C O cua mt phn tu (Thi du:
C
6
H
5
CO CHO) hoc gia hai nhom C O cua hai phn tu khac hn nhau(thi du:
(CH
3
O)
2
C
6
H
3
CHO va HCHO
2
.
b. Tt ca cac aldhyt khng co hoc co u-hydr noi chung du tac dung duc voi
alkxyt nhm, khi y mt phn tu aldhyt bi xy hoa tao ra axit cacbxylic, con phn tu
khac bi khu tao ra alcol, hai san phm nay o dang este (Phan ung Tisenco):
RCHO RCHO RCOOCH
2
R
Al(OR')
3
Khi dung hn hp hai aldhyt khac nhau ta co th thu duc toi bn este
RCOOCH
2
R', R'COOCH
2
R, RCOOCH
2
R va R'COOCH
2
R'. Tung t phan ung
Cannizar, phan ung Tisenc chay theo c ch chuyn dich in hydrua:
RC RC RC - O - CHR RC - O - CH
2
R
Al(OR')
2
O CHR
Al(OR')
3
O O Al(OR')
3
O Al(OR')
3
O
H H H
(-) (-)
G#B# CC PH^N NG 'H
5.3.1. KHU LIN KT B CACBON CACBON
5.3.1.1. Khu bng hydr trn b mt cht xuc tac kim loai
Bt k co nhom th la dy electron cac lin kt bi cacbon-cacbon du co th bi
hydr hoa trn b mt cht xuc tac kim loai. Nhng cht xuc tac hay dung la Ni, Pt, Rd,
Ru. va CuCr
2
O
4
. Khu hoa va dhydr hoa la nhng qua trinh thun nghich di voi nhau.
Qua trinh hydr hoa phat nhit (28-33kcal/mol), con qua trinh dhydr hoa thu nhit.
C ch cua phan ung hydr hoa trn b mt cht xuc tac kim loai la mt vn d phuc tap
con chua duc giai quyt tron vn.
Phan ung hydr hoa lun lun xay ra theo kiu cis. Vy cac alkyn bi hydr hoa tao
thanh cis-alken.

123
RCH
2
- C C - CH
2
R C C
RCH
2
CH
2
R
H H
H
2
,Pd
quinlin
Cac axit dimtylmalic va dimtylIumaric khi bi xy hoa tao ra nhng dng phn
khac nhau cua axit dimtylsucxinic:
CH
3
COOH
COOH
CH3
CH
3
COOH
COOH
CH3
CH
3
COOH
H
COOH
H
CH
3
H
2
/Ni
H
HOOC
H
CH
3
CH
3
COOH
H
COOH
CH
3
HOOC CH
3

H
Axit dimtylIumaric
D, L -
Mz-
H
2
/Ni
V kh nng phan ung, alkyn d bi hydr hoa hn alken. Nu so sanh kh
nng phan ung hydr hoa cua cac lin kt bi cacbon-cacbon voi cac lin kt b khac ta
co thu t gn dung nhu sau:
RC O ~ RNO
2
~ RC CR ~ RC O ~ RCH CHR ~RC O ~
Cl
H
H
~ dn xut cua naphtalen ~ RC O ~ O dn xut cua benzen

OR
'
Vong benzen khi d bi hydr hoa thuong khng dng lai o giai doan cng mt
phn tu hydr, vi anken d bi hydr hoa hn vong benzen rt nhiu. Thi du mt mol
benzen tac dung voi mt mol hydr khng cho xycllexadien hay xyclhexen ma cho 1/3
mol xyclhexan. Trong diu kin nhu vy naphtalen bi khu cho ta ttrahydrnaphtalen
(ttralin). Tuy vy, di voi nhng hp cht thm nhiu vong ngung tu hn nhu antraxen,
phnantren ta lai d dang cho phan ung dng o giai doan cng hydr vao hai nguyn tu ,
10 vi nhng vi tri nay hoat dng hn ca:

124

H
2
xt
H
2
xt
Benzen Xyclhexan
Antraxen
,10- Dihydrantraxen

H
2
xt
H
2
xt
Napncaten Tetralin
Phenantren
,10- Dihydrantraxen
G#B#"#3# '(O S*, 919 619 *(N* P(192
Cac alken -1 d dang bi khu boi hydrua nhm tao thanh alken:
RCH CH
2
AlH
3
(RCH
2
CH
2
)
3
Al RCH
2
CH
3
H
3
O Benzen
()
Diboran cung khu duc alken tung t nhu vy

RCH CH
2
B
2
H
6
(RCH
2
CH
2
)
3
B RCH
2
CH
3
H
()
Tc d cng diboran vao anken s giam khi s nhom alkyl o ni di tng ln.
Khi dung diboran d khu alkyl ta duc cis.alken.
RCH
2
C CC
2
R RCH
2
CH C - B RCH
2
CH
2
R
C C
H H
RCH
2
3
B
2
H
6
H
3
O
()
Trai lai nu dung cht khu la natri trong amniac long ta s duc trans-Anken:
2Na
2 2
CH R
RCH
2NH C C
RCH C CCH R C C
RCH
CH R
-2NaNH
2 H
H
2
2
2
( )
( ) -
( ) -
( )
Na
Na
2
Dung natri-amniac d khu vong thm ta duc san phm cng 1,4 la
xyclhexadien khng lin hp:

125
H H
H H
H
H H
H
H H
H H H H
Na
NH
Na
NH
3 3
Na
()
Nd
Cac nhom th dy electron (thi du OCH
3
) trong vong benzen dinh huong phan ung
tao ra dn xut 2,5 dihidr, trong khi do cac nhom th hut electron (thi du COOH) lai
dinh huong tao ra dn xut 1,4-dihydr:
OCH OCH COOH H COOH
H
H
H
H
H H
3 3
Naphtalen bi hydr hoa boi natri-tanol truoc tin cho ta 1,4-dihydrnaphtalen
nhung cht nay khng bn, no chuyn hoa ngay thanh 1,2- dihydrnaphtalen (ca hai phan
ung du toa nhit)
Napal Bn H,$-j i h9r- H,2 -j i hi r
NapalBn NapalBn
Na
C HOH
<
5
G#B#3 'H AaIHYT V `T%N2
G#B#3#"# '(O 6(M*( -.9/.2
Aldhyt va xtn noi chung d bi khu thanh alcol bc mt va bc hai. Cac cht khu
co th la: natri trong ruu, hydr trn niken Rany, hydrua litinhm, hydrua natribo.
a. ;h< :Mng ]iY0A
[
v NaSA
[
(
V thc cht cac phan ung nay la phan ung cng nucleophin vao nhom cacbnyl:
(-)
R - C O R - C OAlH
3
R - C O Al R - C OH
R' R'
H
R'
H
R'
H
4
RR'C O
H
2
O
(-)
H - AlH
3
(-)
Cac hydrua kim loai nhu LiAlH
4
thuong khng khu lin kt bi cacbon cacbon
vi th chung co th khu chon loc nhom C O cua hp cht cacbnyl chua no.
Thi du:
C
6
H
5
CH CH - CH O C
6
H
5
CH CH - CH
2
OH
LiAlH
4
ete -10
0
C
Tuy vy o diu kin nhit d phong phan ung khu trn tao ra alcol no
C
6
H
5
CH
2
CH
2
CH
2
OH.

126
Dung NaBH
4
lam cht khu co uu dim la tinh chon la cao va co th thc hin
phan ung trong mi truong nuoc. NaBH
4
khng khu cac nhom C C, COOH, COOR.
v tinh khu chon la, xem bang XV-3)
b. Khu bng izproopylat nhm:
Mt s alcolat kim loai, dc bit la izprpylat nhm co kh nng khu aldhyt va
xtn thanh alcol tung ung theo mt qua trinh thun nghich.
C O (CH
3
)
2
CHOH CH - OH (CH
3
)
2
C O
R
R'
R
R'
(i-C
3
H
7
O)
3
Al
Qua trinh thun, dung d khu hp cht cacbny, duc goi la phan ung Mecvai-
Pondoo-Vecly, con qua trinh nghich, dung d xy hoa alcol, duc goi la phan ung
Openao.
Ban cht cua cac phan ung trn la qua trinh chuyn dich ion hydrua t alcolat
nhm sang nhm cacbnyl qua mt trang thai chuyn tip vong:
CH
3
CH
3
C
O H
CH
3
CH
3
C
O H
CH
3
CH
3
C
O
(i - C
3
H
7
O)
2
Al
R
C
O R'
(i - C
3
H
7
O)
2
Al
C
O R'
R
(i - C
3
H
7
O)
2
Al
C
O R'
R
HH

Dn chung v s chuyn dich ion hydrua la khi dung izprpylat nhm co chua

- dteri RRCDOH.
Khi khu bng izprpylat nhm nguoi ta chung ct cho axtn thoat ra khoi mi
truong phan ung va cn bng v bn phai. Trai lai khi mun xy hoa alcol nguoi ta dung
du axtn va dung t-butylat nhm lam xuc tac, vi cht nay khng con

- hydr d co th
khu axtn ma chi co th chuyn alcol cn oxy hoa thanh alcolat tung ung.
G#B#3#3# '(O 6(M*( (7W;C9-9S/* */2

RCR' RCH
2
R'
O
Co mt s phung phap khu nhom C O thanh nhom CH
2
, quan trong nht la
phung phap Kizne VnI va phung phap clemmenxen.
Trong phung phap clemmenxen nguoi ta dun nong aldhyt hoc xtn hn hp
km trong axit clohydric dm dc. C ch cua phan ung con chua r rang, chi bit rng
san phm trung gian khng phai la mt alcol vi cht nay khng bi khu thanh hydrcacbon
trong diu kin noi trn.
Nu trong phn tu andhyt va xtn co nhng nhom th khng bn trong mi
truong axit, thi tt nht nn dung phung phap Kizne VnI. Theo phung phap nay

127
hp cht cacbonyl duc chuyn thanh hydraz tung ung, ri dun hydrazon voi kim dc
hoc tylat natri:
R
C O NH
2
- NH
2
R
C N - NH
2
R
CH
2
N
2
R
R
R
-H
2
O
C
2
H
5
ONa
200
0
C
C ch cua giai doan chuyn hoa hydrazon thanh hydrcacbon co th duc m ta bng s
d sau:
R
C NNH
2
R
C NNH
2
R
C - N NH
C
2
H
5
O
(-)
(-)
R
R' R' R'
R'
CH
2
C
2
H
5
O
(-)
R
R'
CH
(-)
R
R'
CH - N N
(-)
-N
2
Phung phap Kizne VnI duc Hoang Minh Long cai tin bng cach dun trc
tip hp cht cacbnyl voi hydrazin va kim trong tylenglycol duoi ap sut thuong (vi
th co tn goi phung phap Hoang Minh Long). Cram lai cai tin thm bng cach dung i-
butoxyt kali lam baz va dimtylsunIxyt lam tng dung mi, do do co th thc hin phan
ung ngay o nhit d phong ma hiu sut dat duc vn cao.
G#B#B# 'H A`IT CAC&O`YaIC V CC [cN `UT CbA CH!NG2
Axit cacbxylic RCOOH khng bi khu bng cac ch khu thng thuong, nhung lai
d bi khu boi LiAlH
4
, va mt vai cht khac tao thanh alcol bc nht:
RCOOH RCH
2
OH
LiAlH
4
C ch cua phan ung do co th nhu sau:

128
RCOOH LiAlH
4
H
2
AlH
3
RCOO Li
LiAlH
4
RCH
2
OH R - CH O R - C - OLi
H
O
()
()
()
1.LiAlH4
2.H
2
O
Li
2
O
(-)
(-)
(-)
(-)
Li
Este d bi khu hn axit cacbonxylic, phan ung khu este bng LiAlH
4
, xay ra tung t
phan ung khu aldhyt va xtn.
(-)
R - C O R - C - O R - C O R - CH
2
OH
R' R'
H
H
2.H
2
O
(-)
H - Al H
2
(-)
1.LiAlH
- RO
Ngoai LiAlH
4
, este con co th bi khu boi mt s cht khac nhu hydr trn cromit
dng, natri trong tanol.
Phung phap khu este thanh alcol bng natri trong tanol duc goi la phung phap
Buv-Blng. Truoc khi tim ra LiAlH
4
, phung phap Buv-Blng duc dung rt ph bin.
Clorua va anhydrit axit cung d bi khu boi LiAlH
4
, thanh alcol bc nht:
RCOOCOR 2RCH
2
OH
RCOCl RCH
2
OH
LiAlH
4
LiAlH
4
Clorua axit co th bi khu boi hydr trn cht xuc tac Pd tao thanh alcol, qua cht
trung gian la aldhyt:
RCOCl RCHO RCH
2
OH
H
2
xt
H
2
xt
D ngn can giai doan chuyn aldhyt thanh alcol nguoi ta dung BaSO
4
lam cht
dc di voi Pd (phung phap khu Rzenmun):

RCOCl RCHO
H
2
Pd-BaSO4
Mun khu clorua axit thanh aldhyt ta con co th dung cac cht khu la liti hydrua
hoc tri-t-butxy nhm hydrua. Trong truong hp dung cht khu la hn hp natri trong
te ta s duc este cua endiol:
4RCOCl 4Na C C 4NaCl
RCOO OCOR
R
R

12
'( **, >()* +*, 9t- 4@6 Eh *(K4 9(+9 Wh= Lu= 919 9(Q6 P(O P(19 *(-T2
P()* +*, H7W;C
(/1 9K
Hj9 619
a=A.H
D
6;/*, 560
&
3
H
~
6;/*,
THV
N-&H
D
6;/*,
06-*/.
N-&H
D

A.C.
B
6;/*,
W=,.=40
RCH CHR RCH
2
CH
2
R
TCHO RCH
2
OH
RCOR RCHOHR
RCHO
RCOCl
RCH
2
OH
RCOOR RCH
2
OH
ROH
RCOOH RCH
2
OH
RCOO
(-)
RCH
2
OH

-
-
-

-
-

-
-
-

THF: ttrahydrIuran, diglime: (CH

3
OCH
2
CH
2
)
2
O
G#B#D# 'H CC HP CHT CHA NIT2
S khu cac hp cht chua nhm C N, - C N va CONH
2
. noi chung
tung t s khu hp cht cacbnyl, san phm sinh ra thuong la amin. Thi du cac xim bi
khu bng LiAlH
4
thanh amin bc nht:
C NOH CHNH
2
R
R'
R
R'
LiAlH
4
Phan ung khu xim chay chm hn phan ung khu xtn. Amit bi khu boi
LiAlH
4
(NaBH
4
khng co tac dung) tung t este. C ch phan ung khu do nhu sau:

130
R - C - NH
2
RC - NH R - CH - NH
O
AlH
4
O O
(-)
(-)
AlH
4
(-)
(-)
(-)
RCH
2
- NH
2
RCH
2
- NH R - CH NH
H
2
O AlH
4
(-)
(-)
Amit, xim cung nhu nitrin du co th bi khu bng hydr nho cht xuc tac kim
loai.
Cac hp cht nitr va nhng dn xut th cua chung rt d bi khu bng nhiu tac
nhn khac nhau. S khu trong mi truong axit hoc khu bng hydr trn cht xuc tac kim
loai thuong cho ta hp cht amin:
RNO
2
RNH
2
S khu nhom nitr trong mi truong kim phuc tap hn nhiu vi co nhng phan
ung ngung tu gia cac san phm khu khac nhau:
RNO RNO RNHOH
2
Chr khX, ki )
HA p *hr
nir
HA p *hr HA p *hr 8)i n
ni rC h9rx9a)i n0
RNO RNO
RN - NR RN - NHR
OH OH OH
- H O
2
2
- H O
RN NR RN NR
HA p *hr aC
O
HA p *hr
aCx9
RNHNHR
HA p *hr
H9rC
Tuy s khu hp cht nitr phuc tap nhu vy, nhung nu chon cac cht khu thich
hp nguoi ta co th cho phan ung uu tin dng lai o mt giai doan nht dinh nao do.

Cht khu, axit
H
2
, Pt, Pd hoc Ni
RNH
2
131
CHNG ~
S CHUYN V\
Trong nhng chung truoc, chung ta thuong khao sat cac phan ung cua hp cht
hu c trn c so cua nguyn tc bin di cc tiu cu tao, ngha la tha nhn rng trong
phan ung trong phan ung hoa hoc chi cac nhom chuc thay di, con phn gc hydrcacbon
vn duc bao toan. Nguyn tc do to ra dung dn trong rt nhiu truong hp, va rt b ich
trong vic xac dinh cu truc phn tu bng con duong hoa hoc.
Tuy vy, ta bit co nhng trung hp khng theo nguyn tc bin di cc tiu.
Chng han, co nhng phan ung th, trong do nhom th di vao phn tu lai khng vao ch
vn co nhom th di ra truoc dy, ma lai vao nguyn tu khac thuong la o canh do. Hin
tung nay duc goi la chuyn vi. Hin tung chuyn vi rt da dang va phong phu. Ta
phn bit ba loai chuyn vi chu yu.
a. Chuyn vi 1,2 la loai chuyn vi t vi tri 1 dn vi tri 2 trong phn tu hp cht
thuc dy tro.
b. Chuyn vi 1,3 t vi tri 1 dn vi tri 3 trong phn tu hp cht thuc dy chua no.
c. Chuyn vi t nhom chuc vao vong thm trong dy thm.
Chung nay s noi v s chuyn vi 1,2 va chuyn vi t nhom chuc vao vong thm.
~#"# S CHUYN V\ "R3 NUCa%PHIN
Nhng qua trinh chuyn vi, trong do nguyn tu (hay nhom nguyn tu) chuyn dich
toi mt trung gian dang thiu hut electron, mang theo ca cp electron lin kt, duc goi la
chuyn vi nuclphin.
A B A B
R R
^( Nhm chu!7n 5ch( Y( v tr chu!7n i S( _ tr chu!7n n
Hp cht hu c tham gia chuyn vi co th la ion hay phn tu. Thuong thuong vi
tri chuyn di (A) la nguyn tu cacbon, con vi tri chuyn dn (B) co th la cacbon, xy,
nit.

132
R
C C
C CR
()
()
R
C
C OR
() ()
R
C
C NR
O
N
..
Nu R la nguyn tu co chua cp electron chua su dung (Z) nhu halgen, xy, luu
huynh, nit. s chuyn vi 1,2 co th di qua buoc trung gian tao thanh vong ni ba canh
khng bn:
C
()
()
()
C
Z
CH
3
- C - CH - CH
3
CH
3
- C - CH - CH
3
CH
3
- C - CH - CH
3
CH
3
Br CH
3
CH
3
CH
3
O:
O
CH
3
OH OCH
3
Ag
AgBr
H
2
O
Thi du:
Nu R la nguyn tu cacbon hoc hydr, dc bit khi R la nguyn tu cacbon thm
thi san phm trung gian co th la mt ion cu ni:

133
C
()
C
Z
CH
3
- CH - CH
2
CH
3
- CH - CH
2
CH
3
- CH - CH
2
Thi du:
H
H H
() ()
()
Vi vy, trong qua trinh chuyn vi thuong xay ra s quay cu hinh cua nguyn tu
cacbon o vi tri chuyn dn cung nhu o vi tri chuyn di.
Da s cac qua trinh chuyn vi 1,2 nuclphin du la chuyn vi ni phn tu, nhom R
khng tach ra o trang thai t do ma lun lun gn voi cac phn tu cht phan ung theo mt
cach nao do. Diu nay duc chung minh bng cac thi nghim cho va bng cach xac nhn
s bao toan cu hinh cua cac nhom R quang hoat.
~#"#" S CHUYN V\ fN NGUYN T CAC&ON
~#"#"#"# C(T7* L| V-*(0 X M09L-=2
Trong cac qua trinh th va tach nucleophin dn phn tu cung nhu trong qua trinh
cng electrphin vao lin kt bi cacbon cacbon du sinh ra cacbcation. Nhng
cacbcation do co th tham gia chuyn vi, lam cho mt nguyn tu hydr hoc nhom alkyl
hay aryl o vi tri u di voi C
()
chuyn dich C
()
dn do. Thi du:
CH
3
- C -CH
2
- OH
CH
3
CH
3
CH
3
- C -CH
2
CH
3
CH
3
CH
3
- C -CH
2
- CH
3
CH
3
HCl
-H
2
O
() ()
Cl
Cl
(-)
(-)
CH
3
- C -CH
2
- Cl
CH
3
CH
3
CH
3
- C -CH
2
- CH
3
Cl
CH
3
D chung minh s chuyn dich cacbcation sinh ra t alcol nepentylic nguoi ta d
dung ph hng ngoai va ph CTN d xac dinh cu tao cua cac alken sinh ra t
(CH
3
)
3
CCD
2
OH. Kt qua cho thy phan ung d sinh ra alken phu hp voi s d tao thanh
cacbcation trung gian nhu sau:

chuyn vi
Alcol nepentylic
Clorua nepentyl Clorua t-amyl
134
CH
3
()
()
(CH
3
)
2
C - CD
2
OH (CH
3
)
2
C - CD
2
(CH
3
)
2
C - CD
2
OH CH
2
CCD
2
CH
3
CH
3
CH
3
(CH
3
)
2
C CDCH
3
-D
()
H
-H
2
O
-H
()
()
Loai phan ung lam thay di b khung cacbon nhu kiu trn duc goi la chuyn vi
Vanhe-Mecval. S chuyn vi do co th xay ra khng nhng o alcol ma con o nhiu loai
hp cht khac nhu dn xut halgen, amin, hydrcacbon. Thi du:
CH
3
() ()
CH
3
CH
3
CH
3
()
H
2
O
()
(CH
3
)
2
C - CH
2
Br (CH
3
)
2
C - CH
2
(CH
3
)
2
C - CH
2
- CH
3
(CH
3
)
2
C CH
3
(CH
3
)
2
C - CH
2
- CH
3
OH
-H
()
(CH
3
)
2
C - CH CH
2
(CH
3
)
2
C - CH - CH
3
(CH
3
)
2
C - CH(CH
3
) (CH
3
)
2
C C(CH
3
)
2
-H
()
-H
()
H
()
S chuyn vi Vanhe-Macvai co tinh dc thu lp th r rt: diu do cho thy rng
cacbcation trung gian khng phai la cacbcation cu ni. Thi du khi cho tsylat cua cac
3 phnylbutanol -2 tac dung voi axit axtic ta s duc cac axtat tung ung, voi cu hinh
lp th khac nhau, tuy theo cu hinh cua tsytal ban du:

CH
3
()
-OTs
(-)
H
CH
3
H
H
CH
3
C
6
H
5
CH
3
OTs
H
H
CH
3
C
6
H
5
CH
3
OAc
H
C
6
H
5
CH
3
H
OAc
CH
3
H
AcOH
-H
()



Tsylat rytr Ion phnni
Axtat rytr
(quang hoat)
135
CH
3
()
-OTs
(-)
H
CH
3
H
H
CH
3
C
6
H
5
CH
3
OTs
H
H
CH
3
C
6
H
5
CH
3
OAc
H
C
6
H
5
CH
3
H
OAc
CH
3
H
AcOH
-H
()
~#"#"#3# C(T7* L| >=*-9/. X >=*-9/./*2
Thi du co tinh cach kinh din nht v chuyn vi pinacol pinaclon la chuyn hoa 2,3
dimtylbutandiol -2,3 (pinacol) trong mi truong axit thanh 3,3 dimtyl butanon -2
(pinaclon):
CH
3
- C - C - CH
3
CH
3
CH
3
()
OH OH
H
CH
3
- C - C - CH
3
CH
3
CH
3
OH OH
2
-H
2
O
()
CH
3
- C - C - CH
3
CH
3
OH CH
3
()
(I)
CH
3
- C - C - CH
3
CH
3
CH
3
O CH
3
()
-H
CH
3
- C - C - CH
3
CH
3
OH CH
3
()
(II)
S chuyn vi cacbocation I II co th xay ra di voi bt ki hp cht nao co kha nng
tao ra cacbocation tung t I. Thi du:

Tsylat rytr Ion phnni
Axtat rytr
(quang hoat)
Pinaclon
136
CH
3
- C - C - CH
3
CH
3
CH
3
OH Br
CH
3
- C - C - CH
3
CH
3
OH CH
3
()
CH
3
- C - C - CH
3
CH
3
CH
3
OH N
2
()
CH
3
- C - C - CH
3
CH
3
OH CH
3
()
CH
3
- C - C - CH
3
CH
3
CH
3
OH Br
-N
2
CH
3
- C - C - CH
3
CH
3
O CH
3
()
-H
Ag
-AgBr
()
NaNO
2
-HCl
Tung t nhu trong s chuyn vi Vanhe-Mecval, cation I sinh ra ttrong s
chuyn vi pinacal-Pinacolon khng phai la mt cabotion t do voi cu truc phng, vi
xut phat t hp cht quang hoat voi C

d quay cu hinh (quang hoat). Thi du:

()
()
H CH
3
C
6
H
5
OH
C
6
H
5
N
2
H
CH
3
C
6
H
5
C
6
H
5
H
CH
3
C
6
H
5
C
6
H
5
OH
O
-H
(-)
-N
2
Nhu vy, nhom phnyl bi chuyn dich d tin cng nguyn tu C

t phia di
lp voi phia co nhom N
2
()
(sinh ra t nhom NH
2
). Trong truong hp tao ra
cacboncation kinh din voi cu truc phng thi nhom C
6
H
5
t phai tin cng C

t hai
phia voi xac sut nhu nhau va tao ra san phm raxemic.
Vi nhom bi chuyn vi mang theo ca cp electron lin kt nhu mt tac nhn
nuclphin, cho nn khi co hai nhom th, nhom d bi chuyn dich hn chinh la nhom
co tinh dy electron manh hn. Thi du trong phan ung duoi dy hu nhu chi nhom p-
tlyl chuyn dich:
C
6
H
5
- C - C - C
6
H
5
C
6
H
5
- C - C - C
6
H
4
CH
3
- P CH
3
C
6
H
4
- C - C - C
6
H
5
p-CH
3
C
6
H
4
C
6
H
4
CH
3
- p C
6
H
4
CH
3
- p C
6
H
4
CH
3
- p
OH OH O C
6
H
5
O C
6
H
5
4
6

137
Trong cac pinacol khng di xung huong chuyn vi thuong duc quyt dinh boi
kh nng tach nhom OH, tuc la boi d n dinh tung di cua cacbocation trung gian, vi
vy trong phan ung duoi dy khng phai nhom p-anyzyl ma chinh nhom phnyl chuyn
vi la chu yu:
(p-CH
3
OC
6
H
4
)
2
C - C(C
6
H
5
)
2
OH OH
(p-CH
3
OC
6
H
4
)
2
C - C(C
6
H
5
)
2
(p-CH
3
OC
6
H
4
)
2
C - C(C
6
H
5
)
2
OH
OH
(p-CH
3
OC
6
H
4
)
2
C - C(C
6
H
5
)
2
(p-CH
3
OC
6
H
4
)
2
C - C(C
6
H
5
)
2
O
O
C
6
H
4
CH
3
- p C
6
H
5
()
()
28 72
Ngoai ra, huong chuyn vi con phu thuc vao cac yu t khng gian. Chng han
kh nng chuyn dich cua o anazyl km p anizyl hn 1500 ln.
~#"#"#B# C(T7* L| VC*F82
Khi co mt Ag
2
O cac

- diazxtn chuyn vi thanh xten la cht co kh nng

phan ung rt cao va d dang tac dung voi nuoc (hoc alcol) trong mi truong, tao thanh
axit cacbxylic (hoc este):
() ()
R - C - CH - N N R - C - CH O C CH - R O C - CH
2
- R
O O OH
Ag
2
O
-N
2
H
2
O
..
Cacben xeten
Khac voi cac phan ung chuyn vi pinacol pinacolon va Vanhe-Macvai, trong s
chuyn vi VnI nhom th R khng chuyn dich dn nguyn tu cacbon mang din dung
cua cacbcation, ma chuyn dn nguyn tu cacbon trung hoa voi lop vo electron chua du
cua mt cacbon.
S chuyn vi VnI duc dung trong tng hp Acn Aixt d chuyn hoa mt axit
cacbxylic thanh dng dng cao k tip, theo s d sau:
RCOOH RCOCl RCOCHN
2
RCH
2
COOH
SOCl
2
CH
2
N
2
Ag
2
O, H
2
O
-HCl
VonIo

138
Cung co th dung s chuyn vi vnI vao vic chuyn hoa mt xtn thanh dng dng
cao hn hoc mo rng vong xyclalkann. Thi du:
O O
CH
2
N
2
O
CH
2
- N N
(-)
Trong nhng phan ung do, huong canh tranh dang k la dng vong tao thanh xyt
tylen.
~#"#"#D# C(T7* L| S0*Y=.=92
Chuyn vi benzilic hay con goi la chuyn vi benzil axit benzilic la phan ung
chuyn hoa

- dixtn trong mi truong baz thanh

- hydrxyaxit. Dn gian va tiu

biu nht la truong hp chuyn vi benzyl thanh axit benzilic (vi th co tn goi trn). Phan
ung bt du bng tung tac gia baz va mt nhom cacbnyl, sau do nhom aryl chuyn
dich dn nhom cacbnyl thu hai mang theo ca cp electron lin kt:
()
Ar - C - C - Ar Ar - C - C - OH Ar - C - C - OH
HO
(-)
O O O O O O
Ar Ar
(-)
Ar
(-)
Ar - C - C - OH
OH O
Ar
Ar - C - C - O
OH O
H
3
O

Nu thay NaOH bng CH
3
Ona ta s thu duc este mtylic cua

- Hydrxyaxit:
(-)
ArCO - COAr CH
3
O ArC - COOCH
3
OH
Chu rng khng th dung cac alcolat nhu C
2
H
5
ONa va i-C
3
H
7
Ona thay cho CH
3
Ona
duc, vi nhng alcolat do khu ArCOCOAr thanh ArCHOH COAr. Mt khac phan ung
khng xay ra khi dung C
6
H
5
Ona, co l vi phnolat co tinh baz yu.
S chuyn benzilic thuong chi xay ra o cac

- di xtn thm, bao gm ca cac dixtn

ni vong nhu , 10 phnantrenquinn. Khi trong vong bn co nhom th hut electron kh
nng chuyn dich nhom chua vong do giam di.

XyclhexaNn Xyclheptanon
- dixetn
- Hydrxyaxit
13
Ngoai cac dixtn thm, mt s dixtn bo va xtaxit cung tham gia chuyn vi
benzilic. Thi du:
HOOC - CH
2
- C - C - CH
2
COOH HOOC - CH2 - C - CH
2
COOH
O O COOH
OH
1.KOH
~#"#3# S CHUYN V\ fN NGUYN T NIT
~#"#3#"# C19 >()* +*, 9(T7* L| HC>4-*R CT-6=T6R aC6H0*R S4=6
Dc dim chung cua cac phan ung chuyn vi nay la tao ra mt cacbenit trung gian va
nhom alkyl hoc aryl trong cacbenit do chuuyn dich ni phn tu dn nguyn tu nit
thiu hut electron.
Trong s chuyn vi Hpman mt amit khng co nhom th chiu tac dung cua
hypbromit kim (hoc kim va brm cung vy) chuyn thanh izxyanat la cht co kh
nng phan ung cao, nn bi huy phn ngay thanh amin bc nht km amit mt nguyn tu
cacbon.
OH
R - C - NH
2
R - C - NH - Br R - C - N - Br R - C - NH :
O
O O O
BrO
HO
(-)
(-)
(-)
CO
2
H
2
NR O C - NH - R O C N - R
Trong nhng diu kin thich hp, nguoi ta d tach ring duc cac san phm trung gian
N- brmamit, izxyanant.
iai doan quyt dinh tc d phan ung trong s d trn la tach Br
()
ra khoi anion
brmamit, tuy nhin rt co th la s chuyn dich nhom R xay ra gn nhu dng thoi voi s
tach Br
(-)
, tung t mt phan ung th S
N
2 ni phn tu. Nhu vy, ta co th d doan rng tc
d phan ung s cang lon nu tinh cht nhuong electron cua R cang manh. Diu d doan
nay d duc cac kt qua thc nghim xac nhn, khi do tc d phan ung cua cac benzamit
co chua nhng nhom th khac nhau trong vong benzen.
S chuyn vi Hpman co th ap dung tt cho amit cua cac axit bo cung nhu axit
thm. Thi du:

Axit xtpinic Axit xitric
Amit N - Brmamit
Amin Axit cacbomic Izxyanot
140
(CH
3
)
3
CCH
2
CONH
2
(CH
3
)
3
CCH
2
NH
2
NaOBr
4
CONH
2
Br
Br
NH
2
C
C
NH
O
NH
3
COOH
Br
2
KOH NaOCl
O
S chuyn vi Cuatiut xay ra khi phn tich bng nhit azit cua axit cacbxylic tao ra
izxyanat, ri izxyanat lai chuyn hoa thanh san phm bn.
O O
R - C - N
3
R - C - N: O C N - R
-N
2
Cht azit khoi du co th diu ch t clorua axit va azidua natri, hoc bng cach cho
axit nit tac dung voi hydazit cua axit.
Nu s chuyn vi duc tin hanh trong dung mi tr (Thi du: benzen) ta co th cho
phan ung dung o san phm Izxyanat, nhung nu thc hin trong dung mi co hydr linh
dng ta s duc san phm chuyn hoa Izxyanat do (thuong la amin). Thi du:
(CH
3
)
2
CHCH
2
COCl (CH
3
)
2
CHCH
2
CON
3
-N
2
NaN
3
(CH
3
)
2
CHCH
2
NH
2
(CH
3
)
2
CHCH
2
N C O
H
2
O
p-CH
3
OC
6
H
4
COOC
2
H
5
p-CH
3
OC
6
H
4
CONHNH
2
p-CH
3
OC
6
H
4
COOC
2
H
5
p-CH
3
OC
6
H
4
CON
3
p-CH
3
OC
6
H
4
C O
HONO
C
2
H
5
OH
-N
2
H
2
NNH
2
85
86
Trong s chuyn vi Ltxen mui cua axit hydrxamict hoc hp cht tung t bi phn
tich trong mi truong kim thanh izxyanat, tung t nhu trong phan ung Hpman:
O O
R - C - NH - OH R - C - N - OH R - C - N: O C N - R
-N
2
OH
-H
2
O
(-)
(-)
O

Azit Izxyanat
Clorua izvalryl
Izbutylamin 70
141
Trong thc t nguoi ta thuong khng tc hin s chuyn vi Ltxen voi cac axit
hydrxamit t do, ma voi cac dn xut O-axyl cua chung (RCNHAc), vi nhu vy dat
duc hiu sut cao hn. C ch phan ung trong truong hp do vn khng thay di, chi
khac o ch gion bi tach khng phai la HO
(-)
ma la ArO
(-)
.
Cung nhu phan ung Hpman, phan ung Ltxen duc xuc tin khi nhom th trong gc
phnyl chuyn dich co tinh dy electron, trai lai cac nhom th hut electron lam cho phan
ung chm lai. Ngoai ra, tc d cua phan ung Ltxen con phu thuc vao ban cht nhom th
trong vong benzen o nhom bi tach Oac theo mt quy lut nguc lai: nhom th hut electron
lam tng tc d, con nhom dy electron lam giam. Nhng d kin do la bng chung xac
nhn thm rng giai doan quyt dinh tc d phan ung la tach nhom Oac o dang AcO
(-)
.
S chuyn vi Smit la mt bin dang cua cac chuyn vi Hpman va Cuatiut. Do la phan
ung gia axit cacbxylic voi axit hydrazic khi co mt H
2
SO
4
tao ra azydua axyl, sau do
azydua axyl tham gia chuyn vi:
C ch phan ung voi axit cacbxylic nhu sau:
O
O
R - C - OH R - C R - C - N - N N
-N
2
HN
3
H
(-)
O
CO
2
RNH
3
O C N - R R - C - N :
H
()
()
()
()
()
O
iai doan quyt dinh tc d phan ung la tao ra ion axyli. Cac axit bo tham gia
phan ung voi hiu sut tt nht khi R mach dai. Nu R la aryl, hiu sut phan ung bin
dng, tt nht la khi aryl co nhom th an ng khng gian (thi du truong hp axit
mzitic).
Ngoai axit cacbxylic, ta con thy phan ung Smit voi xtn tao ra amit.
Trong truong hp do, c ch phan ung tung t phan ung Becman (Xem duoi). Ta
co th m ta c ch do nhu sau:

Axit hydrxamic Izxyanat
Cation axyli Axylazit
Izxyanat
142
OH O
R - C - OH R - C - R R - C - N - N N
HN
3
H
(-)
O
()
()
()
()
OH
R - C - NH - R R - C N - R R - C - N :
O
OH
R
Trong phan ung trn mt hoc ca hai nhom R co th la alkyl hoc aryl. Noi chung
cac dialkylxtn va xtn vong d tham gia phan ung hn alkyl aryl, xtn va
diarylxtn. Di voi alkyl arylxtn, nhom chuyn dich thuong la aryl, Thi du:
C
6
H
5
- CO - CH
3
CH
3
- CO - NH - C
6
H
5
HN
3
H
()
77
~#"#3#3# S< 9(TT7* L| &094-*2
Chuyn vi becman la qua trinh chuyn hoa xtxim hoc cac dn xut O-axyl cua
chung tao thanh amit th:
R - C - R R - C - NHR' R' - C - NHR
N - OH
O
O
Phan ung trn duc xuc tin nho cac tac nhn axit nhu H
2
SO
4
, PCl
5
, SO
3
, RSO
2
Cl
BF
3
, P
2
O
5
. Trong nhng diu kin thng thuong chi co mt s it aldxim tham gia phan
ung, nhung nu dung dung axit plyphtphoric lam cht xuc tac ta co th mo rng din
tich cac aldoxim tham gia chuyn vi.
Trong s chuyn vi becman khng co s trao di trc tip gia nhom R va OH
(nhom OH t dung mi di vao san phm). Diu nay d duc chung minh bng cach cho
benzphnxim chuyn vi trong H
2
18
O.
(C
6
H
5
)
2
C NOH C
6
H
5
CO - NHC
6
H
5
Ta bit rng xim cung nhu anilit sinh ra khng co kh nng trao di oxi voi
18
O trong
H
2
18
O cho nn s trao di ni phn tu cac nhom R va OH khng th dn dn anilit chua
18
O duc. Song, trong thi nghim trn nguoi ta lai thy anilit chua
18
O o nhom cacbnyl
voi ty l
18
O/
16
O nhu o nuoc dung luc du. R rang s chuyn vi d xay ra theo cach tach
nhom OH va cng nuoc.
Ta co th m ta c ch cua s chuyn vi Becman bng s d sau:

hoc
143
H
()
C
N
OH
R R'
C
N
OH
2
R R'
C
N
R'
C
N
R'
C
N
R'
R
R R
H
2
O OH
-H
2
O
H
2
O
-H
()
X-Cl
-HCl
C
N
Ox
R R'
-Ox
C
NH
R'
R
O
x R''CO R''SO
2
...
()
(-)

Theo s d trn thi s chuyn vi Becman trong mi truong axit manh bt du qua
trinh prtn hoa oxim, con khi co mt clorua axit X-Cl thi tao ra dn xut axit RR

C
NOX. D xac minh s tao thanh dn xut axyl do nguoi ta d diu ch no va thm chi cho
dn xut do tham gia chuyn vi trong mi truong trung tinh khng co tinh cht xuc tac.
Ngoai ra, nguoi ta con thy rng nu axit X-OH cang manh, tuc la nu XO
(-)
cang bn thi
anion nay cang d tach ra khoi phn tu va tc d phan ung cang tng nhu sau: CH
3
COCl
ClCH
2
COCl C
6
H
5
SO
2
Cl. Khi tng d cc phn cua dung mi tc d chuyn vi cung
tng ln C
6
H
6
C
6
H
5
Cl (CH
3
)
2
CO CH
3
NO
2
. Diu do chung to ion hoa (tao ra RC
()

NR quyt dinh tc d cua phan ung.
Hin nay, no con kho ma khng dinh rng trong s chuyn vi Becman s phn ct
lin kt N-O va s chuyn dich nhom R co xay ra dng thoi hay khng. Du cho hai qua
trinhg do khng dng thoi thi s chuyn dich nhom R cung phai din ra ngay tuc khc sau
khi lin kt N-O bi dut. Chung co la nhom R d tin cng nguyn tu nit t phia di lp
voi nhom OH bi tach, tuc la s chuyn vi xay ra uu tin voi nhom R nao do o vi tri anti
voi nhom OH.
D chung minh quy lut trn v hoa lp th cua phan ung nguoi ta xac dinh cu
hinh cua san phm chuyn vi xut phat t hai dng phn hinh hoc cua mt xtxim khng
di xung. Kt qua cho thy rng chi nhom R nao anti di voi nhom OH moi bi chuyn
dich:

144
OH
O
C N
C
6
H
5
p-CH
3
OC
6
H
4
C N
C
6
H
5
p-CH
3
OC
6
H
4
PCl
5
ete
OH
C N
C
6
H
5
p-CH
3
OC
6
H
4
C N
C
6
H
5
p-CH
3
OC
6
H
4
PCl
5
ete
O
D chung minh dc tinh ni phn tu cua s chuyn vi nguoi ta tin hanh chuyn vi
dng thoi hn hp hai xim co nhom th khac nhau va thy khng tao ra san phm
chuyn vi cho.
S chuyn vi Becman duc dung trong tng hp hu c, dc bit trong vic tng
hp

-caprlactam d san xut plycaprlactam (capron hay peclon):

NH
H
()
Becman
H
2
NOH
-HOH
O
NOH
O

~#"#B# S CHUYN V\ fN NGUYN T %`Y2
~#"#B#"# C(T7* L| &-=8? V=.=,=82
Trong phan ung Bai-Viligi, xtn chiu tac dung cua peaxit chuyn thanh este:
RCR R'C - O - OH RC - OR R'C - OH
O O O O
Ta co th m ta c ch phan ung do nhu sau:

Xyclohexanon Xyclhexanxim Caprlactom
Xtn Este
145
()
O
O
R - C - R R - C - R R - C - O - O - C - R'
OH
OH OH
R
-()
O
R - C - OR R - C - OR R - C - O - R' - C - OH'
OH OH
R
()
-H
()
D chung minh rng nguyn tu xy cacbnyl cua este chinh la nguyn tu xy cua
xtn ban du, nguoi ta cho benzphnol chua C
18
O tac dung voi axit pebenzic, kt
qua la thu duc benzat phnyl cung chua nhom C
18
O
O
C
6
H
5
- C - C
6
H
5
C
6
H
5
C - OC
6
H
5
C
6
H
5
COOH
O
18
O
18
Khi dung

-phnyltyl cung quang hoat:

CH
5
CHCCH
3
C
6
H
5
CH - O - CCH
3
CH
3
O
CH
3
O
Diu do chung to nhom C
6
H
5
CHCH
3
bi chuyn dich vn gi nguyn cu hinh va
phan ung chuyn vi co dc tinh ni phn tu. D kin trn cung cho thy rng nhom

-
phnyltyl d chuyn dich hn nhom mtyl. Noi chung di voi cac xtn khng di xung
kh nng chuyn vi cua cac gc R tng theo thu t: mtyl alkyl bc I alkyl bc II
alkyl bc III.
Cac

-dixtn co kh nng enol hoa khng th bi xy hoa theo Bai-Viligi

duc, nhung

-dixtn co th bi xy hoa thanh anhydrit axit:

Xtn
Este
Quang hoat Quang hoat
146

RC - CR RC - O - CR
O O O O
R'COOOH
~#"#B#3# C(T7* L| H7W;C>0CH=62
Khi phn huy nhiu hp cht pexyt khac nhau nguoi ta thy co hin tung chuyn
vi tung t chuyn vi Bai-Viligi.
R - C - O - OH R - C O ROH
R'
R
R
H
()
Thi du co ngha thc tin la phn huy hydrpexyt cumyl (diu ch t
izprpylbenzen bng cach xy hoa boi xy). C ch phan ung nhu sau:
CH
3
- C - O - OH
C
6
H
5
H
CH
3
CH
3
- C - O - OH
2
C
6
H
5
CH
CH
3
- C - O
C
6
H
5
CH
3
H
2
O
() ()
CH
3
- C O HOC
6
H
5
CH
3
- C - OOC
6
H
5
CH
3
- C - OC
6
H
5
CH
3
CH
3
CH
3
H
()
H
2
O
()
()
()
OH
iai doan cui cung o s d trn la giai doan thuy phn smiaxtal.
Phan ung xy hoa mt dn xut hydrxy hoc dn xut amin cua benzal-dhyt
nho pcxyt hydr thay th nhom CHO bng nhom OH cung la mt truong hp cua
chuyn vi pxyt.
~#3# CC 'IU CHUYN V\ "R3 IaICT$%PHIN V NG aY
~#3#"# S< 9(T7* L| "R3 0.096;C>(=*2
Ta goi chuyn vi electrphin la nhng qua trinh chuyn vi trong do, nhom chuyn
dich (R) o dang electrphin, khng mang theo cp electron lin kt. Nhom chuyn dich do
s tao nn lin kt moi bng cach phi tri voi cp electron chua su dung o trung tm
chuyn dn (B), trong khi do cp electron o lai trung tm chuyn di (A) s kt hp voi
prton. Thuong thuong phan ung bt du bng mt qua trinh tach prton ra khoi trung
tm B nho tac dung cua baz.

Baz-Viligi
Hydrpexyt cumyl
147
H
-H
()
()
A - B
R
H
A - B:
R
A - B
R
H
S chuyn vi 1,2 electrphin co th tao ra san phm bn hoc it bn, d ri lai
chuyn hoa tip thanh san phm bn hn. Duoi dy s trinh bay mt vai phan ung chuyn
vi electrphin quan trong.
~#3#"#"# C(T7* L| `65L0*2
S chuyn vi nhom alkyl hoc aryl t nguyn tu nit (hoc luu huynh) cua nhom
amni (hoc sunIni) sang nguyn tu cacbon bn canh goi la s chuyn vi Xtven:
()
OH
Z - CH
2
- N(CH
3
)
2
Z - CH - N(CH
3
)
2
H
2
O
(-)
R R
Nhom th Z thuong la nhng nhom hut electron nhu R'CO, R'OOC. con nhom
chuyn dich R thuong la alyl, benzyl, -Iluorenyl, 3-phnylprpacgyl,.
Ta co th hinh dung c ch cua s chuyn vi Xtven qua thi du sau:
()
OH
()
(-)
C
6
H
5
C - CH
2
- N(CH
3
)
2
C
6
H
5
C - CH - N(CH
3
)
2
C
6
H
5
C - CH - N(CH
3
)
2
(-)
O O O CH
2
C
6
H
5
CH
2
C
6
H
5
CH
2
C
6
H
5
Nhu vy la trong phan ung sinh ra mt ylit trung gian. Dc tinh ni phn tu cua s
chuyn vi Xtven duc xac nhn bng php thi nghim cho (khng thy co s chuyn vi
cho) va dung nguyn tu danh du
14
C. Thi du khi thc hin chuyn vi ring r hai cht:
()
()
CH
2
C
6
H
5
CH
2
C
6
H
5
p - Br - C
6
H
4
COCH
2
- N(CH
3
)
2
C
6
H
5
COCH
2
- N(CH
3
)
2
14
Ta ln lut duc hai san phm

() ()
CH
2
C
6
H
5
CH
2
C
6
H
5
p - Br - C
6
H
4
COCH - N(CH
3
)
2
C
6
H
5
COCH - N(CH
3
)
2
14
Nu cho chuyn vi hn hp hai hp cht amni o trn ta cung chi duc hai san
phm do chu khng duc san phm chuyn vi cho:
CH
2
C
6
H
5
CH
2
C
6
H
5
p - Br - C
6
H
4
COCH - N(CH
3
)
2
C
6
H
5
COCH - N(CH
3
)
2
14

va
va
va
148
Cac nhom th o vi tri mta va para trong nhom benzyl co anh huong nht dinh dn
tc d chuyn vi: nhom hut electron xuc tin phan ung, con nhom dy electron thi kim
hm.
CH
3
H,CH
3
Cl, Br, I NO
2
nh huong cua cac nhom th o gc phnaxyl ArCOCH
2
co phn yu hn: dang cu
la nhng nhom th hut electron lai lam giam tc d phan ung.
V phung din hoa lp th cua s chuyn vi Xtven, nguoi ta thy rng nhom
chuyn dich vn giu nguyn cu hinh sau phan ung.
Thi du:
HO
()
(-)
C
6
H
5
COCH
2
- N(CH
3
)
2
C
6
H
5
COCH
2
- N(CH
3
)
2
CH
3
- CH - C
6
H
5
CH
3
- CH - C
6
H
5
`.1.).1.). ?hu!7n v _ittic
S chuyn o mt t lam dut lin kt C-O va hinh thanh lin kt C-C duc goi la
chuyn vi Vittic. D thc hin qua trinh nay, nguoi ta phai dung nhng baz manh nhu
phnyl liti, amidua natri.
Thi du:
CH
3
CH
3
(-)
O - CHC
6
H
5
O - CHC
6
H
5
O - CHC
6
H
5
HO - CHC
6
H
5
CH
3 CH
3
C
6
H
6
C
6
H
5
Li
Khao sat kh nng chuyn dich cua gc R trong cac Iluorenyl te khac nhau,
nguoi ta thy co trt t sau: alyl, benzyl ~ mtyl, tyl ~ phnyl.
C
6
H
6
C
6
H
5
Li
OR H
R
OH
Dang chu la khi nhom chuyn dich co trung tm bt di nhu trong truong hp
duoi dy, thi sau phan ung nguoi ta thy co s razmic hoa mt phn cung voi s gi
nguyn cu hinh:
2H
2
O
()
C
4
H

Li
O
CH
2
C
6
H
5
CH
3
CH
C
2
H
5
HO - CH - C
6
H
5
CH
3
CH
C
2
H
5

Quang hoat Cac dng phn dia
Quang hoat Mt phn raxmic hoa:
Mt phn gia nguyn cu hinh
14
S raxmic hoa mt phn cho thy rng co th con co mt c ch chuyn vi khac
na xay ra song song voi c ch nu trn.
~#3#3# S CHUYN V\ "R3 NG aY
S chuyn vi 1,2 dng ly km ph bin rt nhiu so voi nhng s chuyn vi 1,2 di ly.
Tung t nhu s chuyn vi o mt cacbcation, ta co th khai quat hoa s chuyn vi o mt
gc t do bng s d:
A - B
R
A - B
R
c t do moi sinh ra phai t bn vng hoa bng cac phan ung tip theo. Huong chuyn
vi la tao ra gc t do tung di bn hn nhu d nu.
~#3#3#"# C(T7* L| -;7. "R32
Loai chuyn vi gc t do tung di ph bin hn ca la chuyn vi nhom aryl t vi tri 1
sang vi tri 2. Thi du: khi co mt cht khi mao pxyt di-t-butyl aldhyt

-
phnyllizvalric trong clobenzen s bi phn huy dng thoi lam chuyn dich nhom
phnyl:
Khi mao:
CH
3
(CH
3
)
3
C - O - O - C(CH
3
)
3
(CH
3
)
3
C - O (RO:)
CH
3
- C - CH
2
- C - H RO'
C
6
H
5
O
CH
3
CH
3
- C - CH
2
- CH ROH
C
6
H
5
O
CH
3
CH
3
- C - CH
2
CO
C
6
H
5
Chuyn vi:

Phan ung:
150
CH
3
CH
3
- C - CH
2
C
6
H
5
O
CH
3
CH
3
- C - CH
2
C
6
H
5
CH
3
CH
3
- C - CH
2
C - H
C
6
H
5
(A)
(B)
CH
3
CH
3
- C - CH
2
C
6
H
5

H
CH
3
- C - CH
2
C
6
H
5
C
6
H
5
(C)

O
CH
3
CH
3
- C - CH
2
- C
C
6
H
5
CH
3
- C - CH
2
CH
3
- C - CH
2
C - H CH
3
- C .. CH
3
CH
3
- C - CH
2
- C
C
6
H
5
CH
3
CH
3
CH
3
CH
3
O O
C
6
H
5
C
6
H
5
C
6
H
5
(D)
Thc nghim cho thy rng trong phan ung trn sinh ra hai san phm (C) va (D)
voi ty l 1:1, dat hiu sut chung ~70.
Ta nhn thy o giai doan chuyn vi nhom phnyl chuyn dich chu khng phai
nhom mtyl. Diu nay cho php ngh rng trong phan ung d tao ra mt gc trung gian
cu ni, tung t nhu cacbcation cu ni.
C - C

Bn vng hoa:
hoc:
151
Co l gc trung gian nay duc hinh thanh sau khi d tao ra gc (A) vi nhu trn d
thy trong phan ung sinh ra san phm tung ung voi (A) la (D), va trong mt s truong
hp con thu duc ca san phm dime hoa gc (A) do.
~#3#3#3# C(T7* L| (-.C,0* "R32
n dy s chuyn vi nguyn tu halgen t vi tri 1 sang vi tri 2 bn canh cung d
duc chu . Thi du khi clo hoa brmua izprpyl bng t-C
4
H

Ocl nguoi ta duc mt hn

hp san phm gm CH
3
CClCH
2
Br va (CH
3
)
2
CClBr:
CH
3
- CH - CH
3
CH
3
CH - CH
2
Br CH
3
- C - CH
3
Br Cl Br
Cl
t-C
4
H

OCl
-78 C
0
(15)
(60)
S tao thanh CH
3
CClCH
2
Br cho thy s chuyn vi gc t do trung gian theo s d:
CH
3
- CH - CH
3
Cl CH
3
- C - CH
2
Br Br
Cl
-HCl
(15)
(T - C
4
H

OCl)
CH
3
- CH - CH
2
Br CH
3
- CH - CH
2
Br
(T - C
4
H

OCl)
L tt nhin, huong chinh cua phan ung la tao ra gc t do o nguyn tu cacbon bc
hai (CH
3
)
2
CBr, vi gc nay bn hp gc bc nht tham gia chuyn vi o trn. Do do 2-
brom-2-cloprpan chim ty l cao hn 1-brom-2-cloprpan:
CH
3
- CH - CH
3
CH
3
- C - CH
3
CH
3
- C - CH
3
Br Br
Cl
(60)
(T - C
4
H

OCl)
T - C
4
H

OCl
-HCl
Br
~#B# S CHUYN V\ T NHM THf VO V]NG THM2
Phn lon nhng phan ung chuyn vi vao vong thm la nhng phan ung lam
chuyn dich mt nhom X t di nguyn tu Z vao vi tri oct hoc para cua vong:

152
Z
X
Z
H
x

Z
H
x
dy Z O khi X alkyl, aryl.; Z N khi X alkyl, halgen, hydrxy, nitr, nitrz,
az, sunI.
Hu ht cac phan ung chuyn vi trn duc xuc tac bng axit va s tn cng cua
nhom X vao vong thm co tinh cach mt phan ung th electrphin. Ta goi do la phan ung
chuyn vi electrphin vao vong thm.
Nhng phan ung chuyn vi nuclphin vao vong thm (thi du chuyn vi nhom OH
o phnylhydrxylamin) tung di it gp.
~#B#D# S CHUYN V\ T NGUYN T %`Y VO V]NG THM2
~#B#"#"# C(T7* L| V;-=2
Khi co tac dung cua axit Liuyt (AlCl
3
, ZnCl
2
, FeCl
3
.) nhom axyl trong este cua
phnyl chuyn dich vao cac vi tri oct va para cua vong:
O
C
O
R OH
C
O
R

O
C
R
OH 1.AlCl
3
2.H
3
O
()
R la alkyl hoc alyl.
Cac kt qua thi nghim cho cho thy rng chuyn vi Frai co tinh cach lin phn
tu. Tuy vy, c ch cua s chuyn vi nay chua duc xac dinh hoan toan dy du, nguoi ta
cho rng qua trinh chuyn vi Frai tung t qua trinh axyl hoa theo Friden-Crap. Duoi tac
dung cua cht xuc tac, este tao ra cation axyli RC
(-)
0, cation nay s tin cng cac vi tri
oct va para cua vong thm:

153
O
C
O
R
OH
C
O
R
OH
AlCl
3
()
Cl
3
AlO CR
(-)
Cl
2
AlO
O
C
R
O
H
3
O
()
C
O
R
Cl
2
AlO
C
O
R
H
3
O
()
-HCl
Do tinh cht electrphin cua qua trinh chuyn vi nn khi trong vong co nhom th
dy electron, phan ung s tro nn d dang hn.
Phan ung Frai lun lun tao ra mt hn hp hai san phm dng phn, nhit d thp
la diu kin thun li cho s tao thanh dng phn para. Thi du:
AlCl
3
,25 C
OH
COCH
3
CH
3
OCOCH
3
CH
3
OH
CH
3
CH
3
CO
0
0
80 C
AlCl
3
,165 C
0
0
5 C
L tt nhin khi vi tri para d bi chim thi chi tao thanh san phm oct. Thi du:
OCOCH
3
CH
3
OH
CH
3
CH
3
CO
AlCl
3
Nitrobenzen
~#B#"#3# C(T7* L| C.-=Y0*2
Khi dun nong alyl aryl te s chuyn thanh oct-alylphnol theo mt phan ung goi
la chuyn vi claizen. Thi du:
CH
3
OCH
2
CH CH
2
CH
3
OH
CH
2
CH CH
2
0
0
200 C
Nghin cuu s chuyn vi alylphnyl te co danh du bng
14
C hoc co nhom th vi
tri para, nguoi ta d d nghi mt c ch ni phn tu nhu sau:

154
CH
2
O
CH
C O
H
CH
2
CH
CH
2
OH
CH
2
C
CH
D chung minh rng trong phan ung co hinh thanh dienn trung gian I nguoi ta d
cho thm anhydrit malic vao mi truong phan ung va thy co xay ra phan ung Dix-do
gia dienn va anhydrit do. Hn na, trong mt s truong hp nguoi ta con diu ch duc
dienn voi hiu sut dinh lung. Thi du:
O
H
3
C
O
CH
3
CH
2
CHCH
2
Br
H
3
C
CH
3
CH
2
CH H
2
(-)
C
6
H
6
15 C
0
-Br
(-)
D chung minh c ch ni phn tu cua s chuyn vi nguoi ta tin hanh phan ung
cho voi hn hp hai te I va II. Nu phan ung xay ra theo c ch ni phn tu thi chi sinh
ra hai san phm III va IV; trai lai nu phan ung xay ra qua giai doan tao thanh thi ngoai
cac san phm III va IV con tao ra V va VI. Thc t khng tim thy V va VI.
OCH
2
CH CH
2
D D
OCH
2
CH CHC
6
H
5

CH
2
CH CH
2
OH
D
D

CHCH CH
2
OHC
6
H
5

CH
2
CH CH
2
OH
D
D

CH
2
CH CH
2
C
6
H
5
OH
(I)
(II)
(III) (IV) (V) (VI)
Trong truong hp cac vi tri oct d bi chim nhom alyl cua t s chuyn dich dn
vi tri para. Nguoi ta goi do la s chuyn vi para-Claizen. Nu tt ca cac vi tri oct va para
du bi chim thi khi dun nong khng xay ra s chuyn vi nao ca.
Rt co th s chuyn vi para-Claizen cung phai qua buoc chuyn vi oct, sau do
moi xay ra s chuyn vi tip dn vi tri para:

155
OCH
2
CH CH
2
CH
2
CH CH
2
OH
CH
2
CH CH
2
R
R
O
R R
CH
2
O
R R
CH
2
H
R R
CH
D chung minh c ch chuyn vi hai ln noi trn, nguoi ta d dung alyl 2,6-
ddialyl-phnyl t co danh du bng
14
C o vi tri

cua mt nhom oct-alyl; sau khi

chuyn vi nguoi ta duc 2,4,6-trialylphnol trong do nguyn tu
14
C phm hoc o vi tri

cua nhom p-alyl hoc o vi tri

cua nhom o-alyl.

OCH
2
CH CH
2
CH
2
CH CH
2
CH
2
CH CH
2
CH
2
CHCH
2
CH
2
CH CH
2
OH
CH
2
CH CH
2
14
CH
2
CH CH
2
14
CH
2
CH CH
2
CH
2
CHCH
2
14

CH
2
CHCH
2
OH
CH
2
CH CH
2
CH
2
CHCH
2
14

Nu nhu nhom alyl chuyn dich trc tip t nguyn tu xy dn vi tri para thi d
khng sinh ra san phm co
14
C o p-alyl.
~#B#3# S CHUYN V\ T NGUYN T NIT VO V]NG THM#
~#B#3#"# C(T7* L| *(K4 -.P7.2
Khi dun nong cac mui halgenhydrat cua alkyl s chuyn dich dn vi tri oct hoc
para cua nhn thm. Thi du:
C
6
H
5
NR
2
o
-
p
-
RC
6
H
4
NHR
HHal
t
0
C
6
H
5
NHR o
-
p
-
RC
6
H
4
NH
2
HHal
t
0
Co l phan ung bt du bng mt qua trinh th nuclephin d tach dn xut
halgen Rhal ra khoi mui halgenhydrat, sau do Rhal s tac dung voi nhn thm theo c
ch th electrphin. Thi du:

hoc
hoc
156
C
6
H
5
NH
2
R Hal RHal C
6
H
4
NHR
C
6
H
5
NH
2
R RHal RC
6
H
4
NH
3
Hal
()
()
(-) (-)
(-)
Phu hp voi c ch trn, trong mt s truong hp nguoi ta d tach duc Rhal trung
gian, va khi thay di Hal
(-)
ty l cac san phm o/p cung thay di.
Dang chu la phn tu chuyn vi nhom alkyl nhu trn co th xay ra khi dun amin t
do voi CoCl
2
. Khi y phan ung mang tn Ryli-Hickinbttm. C ch cua s chuyn vi
Ryli-Hickibttm chua r rang.
~#B#3#3# C(T7* L| *,T75* 6O H-./,0*
S chuyn vi nguyn tu Halogen t nguyn tu Nit vao vong Benzen goi la chuyn
vi Octn. Thi du: Khi dun N-Cloaxtanilit trong axit axtic hoc nuoc co clorua hydr ta
duc o
-
va p
-
cloaxtanilit.
C
6
H
5
- N - COCH
3
Cl - C
6
H
4
- NH - COCH
3
Cl
HCl
Nguoi ta cho rng trong phan ung trn clorua hydr d tac dung voi cloaxtanilit
sinh ra axtanilit va clo, sau do clo tac dung voi vong thm cua axtanilit theo c ch
electrphin:

C
6
H
5
N - COCH
3
HCl C
6
H
5
NH - COCH
3
Cl
2
ClC
6
H
4
NH - COCH
3
HCl
Cl
Tc d cua phan ung trn tun theo phung trinh: v~ [cloaxtanilit] [H
()
]
[Cl
()
. Nu thay HCl bng HBr ta s thu duc o
-
va p- brmaxtanilit. Nhng d kin do
chi co th giai thich duc da trn c ch d nu cu th la theo s d sau:

C
6
H
5
N - COCH
3
HBr C
6
H
5
NH - COCH
3
Br - Cl BrC
6
H
4
NH - COCH
3
HCl
Cl
Nhu vy s chuyn vi Octn thuc loai chuyn vi lin phn tu
~#B#3#B# C(T7* L| *(K4 -;;7.-YC2
Thi du tiu biu v chuyn vi nhom arrylaz la phan ung chuyn hoa
diazaminbenzen thanh p-aminazbenzen:
C
6
H
5
N N - NHC
6
H
5
p
-
NH
2
C
6
H
4
N NHC
6
H
5
HCl
hoac C
6
H
5
NH
2
HCl
Trong truong hp vi tri para d bi chim nhom arylaz s chuyn dich dn vi tri
oct. Thi du:

157
HCl
p-CH
3
C
6
H
5
NH
2
p- CH
3
C
6
H
4
N N - NH CH
3
p
-
CH
3
C
6
H
4
N N
CH
3
NH
2
Nu thay p-CH
3
C
6
H
4NH
2
bng
C
6
H
5
NH
2
trong phan ung trn ta s duc 4-mtyl-4'-
aminazbenzen. Diu nay cho thy phan ung chuyn vi nhom arylaz thuc loai chuyn
vi lin phn tu.
Nghin cuu dng hoc cua phan ung nguoi ta d xac dinh duc tc d chuyn hoa
cua diazaminbenzen ty l voi nng d cua anilinclohydrat; nu ly mui cua amin voi
axit khac thay cho anilinclohydrat thi tc d phan ung phu thuc lc cua axit do. Diu nay
cho php ta gia thit rng chinh axit t do d tham gia vao qua trinh chuyn vi. Dang chu
na la phan ung cua clorua phnyldiazni voi anilin co th xay ra theo hai huong khac
nhau tuy theo pH cua mi truong:
()
(-)
C
6
H
5
N
2
Cl H
2
NC
6
H
5
C
6
H
5
N N - NHC
6
H
5
C
6
H
5
N N - C
6
H
4
NH
2
Da trn cac d kin thc nghim o trn nguoi ta cho rng s chuyn vi nhom
arylaz xay ra qua hai giai doan tao thanh ion aryldiazni va amin t do, sau do ion
arydiazni s tac dung vao nhn thm cua amin theo c ch electrophin:
()
C
6
H
5
N - NHC
6
H
5
C
6
H
5
N
2
C
6
H
5
NH
2
C
6
H
5
N NC
6
H
4
- NH
2
- p
HCl
~#B#3#D# C(T7* L| *(K4 *=6;CYC C(T7* L| V=E8 X H0>
Khi co mt axit clohydric, nhom nitrz cua nitrzamin thm s chuyn dich vao
nhn thm. Thi du:
HCl
C
6
H
5
N - N - CH
3
o
-
p
-
NOC
6
H
4
- NH - CH
3
NO

C ch chuyn vi Fis-Hep tung t c ch chuyn vi Octn. Duoi tac dung cua
axit, nitrzamin bi phn tich thanh amin va clcorua nitrozyl (NOCl) hoc ion nitrzni;
sau do la qua trinh nitrz hoa nhn thm theo c ch electrphin:


pH lon hn
pH nho hn
va
158
CH
3
()
NO
C
6
H
5
N H
CH
3
()
H
C
6
H
5
N NO O N - C
6
H
4
NHCH
3
H
()
Co nhiu d kin thc nghim xac nhn c ch chuyn vi gia cac phn tu va
nu. Chng han, khi cho vao hn hp phan ung mui nitri natri mui nay s tao ra NO
hoc NOCl). Hiu sut phan ung chuyn vi s tng; trai lai nu cho thm r (cht nay d
kt hp voi NO va NOCl) ta s khng thu duc dn xut nitrz ma chi duc amin bc
hai.
~#B#3#G# C(T7* L| S0*Y=W=*2
Khi cho axit manh tac dung ln hydrazbenzen s xay ra s chuyn vi lam dut lin
kt nit nit va hinh thanh ln kt cacbon cacbon tao ra benzidin (4,4
diaminbiphnyl):
NH - NH
H
()
H
2
N NH
2
Trong phan ung chuyn vi cua hydabenzen ngoai benzidin la san phm cua s t
hp o,p (chim ~ 30) va lung rt nho cac san phm t hp khac.
H
2
N
NH
2
NH
2
NH
2
NH NH
2
NH
2
-NH
Nu ca hai vi tri para trong phn tu hydrazobenzen ban du du d bi chim ca boi
cac nhom th. Con nu chi co mt vi tri para bi chim thi phan ung co th tao ra cac dn
xut th cua diphnylin, p-xemidin va o-xmidin.

Hydrzbenzen Benzidin
Diphenylin 0-Benzidin p-Xemidin o-Xemidin
15
Vn d c ch cua s chuyn vi benzidin la vn d phuc tap duc nhiu nguoi
quan tm t du th ky nay.
Khi cho hn hp hai hydrazbezen cung chuyn vi nguoi ta khng thu duc san
phm cho, diu do cho thy s chuyn vi xay ra theo kiu ni phn tu. Khao sat dng
hoc cho thy rng phan ung chuyn vi thuong co bc hai di voi H
()
, va khi thay hydr o
vi tri para cua hydrazobenzen bng dtri, tc d noi chung khng thay di. Nhu vy giai
doan phn ct lin kt C H khng quyt dinh tc d chung cua phan ung va tiu phn
trc tip tham gia phan ung la hydrazbenzen d prton hoa hai ln ArNH
3
- NH
2
Ar.
Rt co th c ch chuyn vi benzidin nhu sau:
2H
()
H
2
N............NH
2
NH
2
NH
2
NH - NH
NH
2
NH
2
D
D
NH
2
- NH
2
D
D
()
()
2D
()
D D
()
()
D D
.................
Theo c ch trn thi phan ung bt du bng qua trinh prton hoa hai nguyn tu nit
cua hydrazbenzen tao thanh dication. Diu nay d duc moi nguoi tha nhn. Tuy vy,
cac chi tit v nhng giai doan tip theo, nht la v cu tao cua trang thai chuyn tip con
chua duc tra loi dy du va thng nht. Diu nay chc chn la trong mi truong phan ung
phai sinh ra dication cua benzidin nhu mt san phm trung gian.

() ()
+

160
MC aC
Chung 1: Cach dua nhom chuc vao phn tu cht hu c va s chuyn hoa giua
chung..............................Trang 1
Chung 2: S phn ct va tao thanh lin kt Cacbon Cacbon.......Trang 28
Chung 3: Phung phap dong va mo vong...............Trang 52
Chung 4: Bao v nhom chuc trong tng hp hu c.............Trang 80
Chung 5: S xy hoa - khu....................Trang 105
Chung 6: S chuyn vi......................Trang 131

161