Phn ng chuyn v l s di chuyn nguyn t hay nhm nguyn t t v tr

ny sang v tr khc ca mch cacbon gy ra s thay i mch cacbon hay bo ton

mch cacbon.
Phn ng chuyn v rt a dng phong ph, thng xy ra trong cc qu trnh
th, tch hay cng qua nhng cht trung gian nh cacbocation hay cacbanion. C th
phn bit 3 loi chuyn v ch yu sau y:
I. S chuyn v 1,2 nucleophin:
Chuyn v nucleophin l nhng qu trnh chuyn v trong nguyn t (hay
nhm nguyn t) chuyn dch ti mt trung tm ang thiu ht electron, mang theo c
cp e lin kt.
Y Y
A B A B
Hp cht hu c tham gia chuyn v c th l ion hay phn t. Thng v tr
chuyn v (A) l nguyn t C, cn v tr chuyn n (B) c th l C, O, N...
I.1. S chuyn v n nguyn t C:
I.1.1 Chuyn v Wagner-Meerwein:
Trong qu trnh th v tch nucleophin n phn t cng nh qu trnh cng
electronphin vo lin kt bi u sinh ra cacbocation. Nhng cacbocation c th
tham gia chuyn v lm cho 1 nguyn t H hay nhm akyl hay aryl v tr i vi
C(+) chuyn dch n C(+) .
R R' R R' R R'
-X -H+ R R'
R C C X R C C C C H C C
R R
R H R H R R

V d:
CH3 CH3
HCl chuyen vi
CH3 C CH2OH CH3 C CH2 CH3 C CH2 CH3
-H2O
CH3 CH3 CH3

Cl-
Cl
CH3 C CH2 CH3
CH3
S chuyn v c th xy ra khng ancol m cn nhiu loi hp cht khc
nh dn xut halogen, amin, hidrocacbon...
I.1.2. Chuyn v pinacolic:

1
 R R'' R R'' R''
+ -H2O
H
R' C C R''' R' C C R''' R' C C R''' (I)
+
-H H2O R OH
OH OH OH

R
-H+
RR'R''COR''' R' C C R'''
R'' OH
S chuyn v nh trn c th xy ra i vi bt k hp cht no c kh nng
to ra cacbocation tng t nh (I).
V d:

CH3 CH3 CH3 CH3

+
Ag CH3 C C CH3
CH3 C C CH3 CH3 C C CH3
-AgBr
OH Br OH CH3 OH CH3
+
-H
-N2 CH3
CH3 C C CH3
CH3 CH3 CH3 CH3
NaNO2,HCl O CH3
CH3 C C CH3 CH3 C C CH3
-N2
OH NH2 OH N2

V nhm b chuyn v mang theo c cp electron lin kt nh mt tc nhn

nucleophin cho nn khi c 2 nhm th, nhm d b chuyn dch hn l nhm c tnh
y electron mnh hn.
V d:
p-CH3C6H4 C6H4CH3-p C6H4CH3-p C6H4CH3-p

C 6H5 C C C6H5 C6H5 C C C6H5CH3-p + p-CH3C6H5 C C C6H5CH3-p

OH OH O C6H5 O C6H 5

94% 6%
Trong cc pinacol khng i xng hng chuyn v thng c qui nh bi
kh nng tch nhm OH tc l bi n nh tng i ca cacbocation trung gian. V
vy trong phn ng di y khng phi nhm p-anizyl m chnh nhm phenyl chn
v l ch yu.

2
 (p-CH3OC6H4)2COH-COH(C6H5)2

(p-CH3OC6H4)2COH-C(C6H5)2 (p-CH3OC6H4)2C-COH(C6H5)2

C6H4OCH3 -p C 6H 5
C 6H 5 C 6H 5
p -CH3OC6H4 C C C C
p -CH3OC6H4
C6H5
O O
p -CH3OC6H4
28% 72%
Ngoi ra hng chuyn v cn ph thuc vo cc yu t khng gian. V d nh
kh nng chuyn v ca o-anzyl km p-anizyl hn 1500 ln.
I.1.3.Chuyn v Vont.
Xut pht t phng php iu ch chuyn ho axit cacboxylic thnh ng
ng.

SOCl2 CH2N2 Ag2O

R CO OH R CO Cl R CO CH N N R C CH
-N2
i
nv O
uye
c h
R CH2 COOH H2 O
R CH C O
Diazometan cng c th kt hp vi andehit hay xeton cho phn ng chuyn v.
I.1.4. Chuyn v benzilic.
L phn ng chuyn ho -dixeton trong mi trng baz thnh -hiroxyaxit.
Ar
- Ar
HO Ar C C OH
Ar C C Ar Ar C C OH
O O O O O O

Ar Ar
H3O+
Ar C C OH Ar C C O
OH O OH O
Ngoi nhng xeton thm, mt s dixeton bo v xetoaxit cng tham gia chuyn
v benzilic.

3
I.2. S chuyn v n nguyn t nit
I.2.1. Cc phn ng chuyn v Hofmann, Curtius, Lossen, Schmidt
c im chung cc phn ng chuyn v ny l to ra mt cacbenoit trung gian
v nhm ankyl hoc aryl trong cacbenoit chuyn dch ni phn t n nguyn t
nit thiu ht electron.
* Chuyn v Hofmann:
BrO- OH- -
R C NH2 R C NH Br R C N Br -Br R C N
-H2O
O O O O

H2O O C N R
CO2 + RNH2 O C NH R
OH
* S chuyn v Curtus:
Xy ra khi phn ng tch bng nhit azit ca axit cacboxylic:
'
R OH O
R C N N N R C N O C N R R NH C
-N2 OR'
O O izoxyanat
Azit
Nu s chuyn v c tin hnh trong mi trng tr ta c th cho phn ng
dng sn phm izoxyanat, nhng nu thc hin trong dung mi c hidro linh ng ta
s c sn phm chuyn ho izoxyanat (thng l amin)
H2O
O C N R HO C NH R R NH2 CO2
O

p-CH3OC6H4N=C=O (86%)
6
6H
C

p-CH3OC6H4CON3 -N2
C2
H5

p-CH3OC6H4NHCOOC2H5 (86%)
OH

* S chuyn v Lossen:
Tng t nh trong phn ng Hofmann, trong s chuyn v Lossen mui ca
axit hydroxamic hoc hp cht tng t b phn tch trong mi trng kim thnh
izoxyanat.

4
 -
R C NH OH OH R C N OH R C N O C N R
-H 2O
O O O
* Chuyn v Schmidt:
L mt bin dng ca chuyn v Hofmann v Curtus nhng i t sn phm cng
ca azit v olefin hoc gia axit cacboxylic vi axit hidrazoic.

H+ HN3 -N2
R C OH R C R C N N N R C N
O O O O

CO2 RNH3 O C N R
Ngay sn phm cng ca azit vi anehit hay xeton cng chuyn thnh
azometin v chu chuyn ha tip theo trong mi trng khc nhau.
R' R' R' R'
C O H N+
N N
R C N N N R C N N N -N2
R C N
H -H2O
R OH H
chuyen vi

H2O
R C NH R' R C N R' +
R C N R'
-H
O OH +
-H R''OH
H N N N
R C N R' R C N R' R C N R'
+
-H
H N N N OR''
N N
N

Sn phm cng azit vi axit cacboxylic cng qua phn ng chuyn v trn cho
amin km mt cacbon so vi axit.
O OH OH OH
R C H N N N R C N N N -N2 R C N
+ R C N N N
H -H2O
OH OH H

H2O HO C N
CO2 + RNH3 R
I.2.2. Chuyn v Beckmann:
Chuyn v Bekman l qu trinh chuyn ha xetoxim hoc cc dn xut O axyl
ca chng to thnh amit th:
R C R' R C NHR' hay R ' C NHR
N OH O O
5
 Ta c th m t c ch ca s chuyn v Beckmann bng s sau:

R R' R R' R' H2O R' + HO R'

C +
H C -H2O C H2O C -H C
N N N N N
OH OH2 R R R

R R' O R'
XCl C -OX
- C
-HCl N NH
OX R

X: R''CO, R''SO2
Nhng dn xut loi R2C=N-X (X l OCOR, OTs ...) tham gia phn ng chuyn
v d hn, do d tch anion axit bn hn.
I.3. S chuyn v n nguyn t oxi:
I.3.1 Chuyn v Bayer Villiger
Trong phn ng oxi ha xeton bng peaxit xc tc bng axit:
R C R + R' C O OH R C OR + R' C OH
O O O O
C ch phn ng c m t nh sau:
O R R

R C R R'COOH R C O
R C R R C O O C R'
-R' C OH
O OH OH
OH OH O

R C OR R C OR
- H+
O
OH
I.3.2. Chuyn v peoxit:
Khi phn hy nhiu hp cht hu c peoxit trong mi trng axit ngi ta thy
c hin tng chuyn v tng t chuyn v Bayer Villiger.
R
R C O OH H+
R C O ROH
R R
Phn ng tiu biu l phn ng oxi ho cumen:

6
 C6H5 C6 H 5 C6H5
H+
CH3 C O OH CH3 C O OH2 CH3 C O
-H2O
CH3 CH3 CH3

OH2
H2O
CH3 C CH3 + C6H5OH + CH3 C OC6H5 CH3 C OC6H5
-H
O CH3 CH3
Phn ng oxi ha mt dn xut hiroxy hoc dn xut amino ca benzandehit
nh peoxit hiro thay th nhm CHO bng nhm OH cng l mt trng hp ca
chuyn v peoxit.
H H H
H O
C HO C O OH O C O OH OH
O C O
OH OH OH OH OH
- -
H2O2 -HO -HO + HCOO-
NaOH

II. S chuyn v 1, 2 electrophin v ng ly:

II.1. S chuyn v 1,2 electrophin:
Phn ng chuyn v electrophin l nhng qu trnh xy ra vi nhm chuyn v
thiu electron hay mang in tch dng ti trung tm c mt electron ln hay mang
in tch m. Phn ng thng c tc dng ca baz v theo c ch electrophin do tn
cng ca trung tm electrophin vo trung tm nucleophin. Nhm chuyn dch s to
lin kt mi bng cch phi tr vi cp electron cha s dng trung tm chuyn n
(B) trong khi cp electron li trung tm chuyn i (A) s kt hp vi proton, phn
ng thng c tc dng ca baz.
R
R R H+
A B A B A B
H +
-H H
Di y l mt s phn ng chuyn v electrophin quan trng:
II.1.1 Chuyn v Stevens:
S chuyn v nhm ankyl hoc aryl t nguyn t nit (hoc lu hunh) ca
nhm amoni (hoc sunfoni) sang nguyn t C bn cnh gi l s chuyn v Stevens.
HO-
Z CH2 N(CH3)2 Z CH N(CH3)2 + H2O
R R
Z thng l nhng nhm ht electron nh RCO, ROOC, ...Cn nhm chuyn
dch R thng l alyl, benzyl...
7
 Phn ng xy ra nh l th electrophin ni phn t qua cht trung gian
cacbanion, phn ng xy ra vi s bo ton cu hnh di chuyn, vi s to thnh lin
kt C C v phn ct lin kt C N ng thi.
HO-
C6H5C CH2 N(CH3)2 C6H5C CH N(CH3)2 C6H5C CH N(CH3)2
-H2O
O CH2C6H5 O CH2C6H5 O CH2C6H5

II.1.2. Chuyn v Wittig:

S chuyn v mt te lm t lin kt C C c gi l chuyn v Wittig.
thc hin qu trnh ny ta phi dng nhng baz mnh nh phenyl liti, amiua natri, ...
C6H5Li O CHC6H5 H2O HO CHC H
O CH2C6H5 O CHC6H5 - 6 5
CH3 C6H6 CH3 -OH
CH3 CH3
S di chuyn gim dn theo dy cc nhm th sau:
CH2=CHCH3, C6H5CH2 > CH3, C2H5, p-O2NC6H4 > C6H5
II.2. S chuyn v 1,2 ng ly:
Tng t s chuyn v mt cacbocation, ta c th khi qut ho s chuyn v
mt gc t do bng s :
R
R
A B A B
Gc t do mi sinh ra phi t bn vng ho bng cc phn ng tip theo. Hng
chuyn v l to ra cc gc t do tng i bn vng hn.
II.2.1. Chuyn v aryl 1,2:
Loi chuyn v gc t do tng i ph bin hn c l chuyn v nhm aryl t v
tr 1 sang v tr 2.
V d: Khi c mt cht khi mo, (CH 3)3C-O-O-(CH3)3 trong clobenzen s b
phn hu ng thi lm chuyn dch nhm phenyl:
Khi mo: (CH3)3C-O-O-(CH3)3 (CH3)3C-O. (RO.)
Phn ng:
C6H5 C6H5 C6H5
- -CO
CH3 C CH2 C H + RO ROH CH3 C CH2 C CH3 C CH2
CH3 O CH3 O CH3

Chuyn v:
C6H5
CH3 C CH2 CH3 C CH2 C6H5
CH3 CH3
(A) (B)
Bn vng ha:
8
 C6H5 H C6H5
C CH2 C H C CH2 C6H5 + CH3 C CH2 C
CH3 C CH2 C6H5 +CH3 CH3
CH3 CH3 O CH3 CH3 O
(C)
Hoc
C6H5 C6H5 C6H5 C6H5
CH3 C CH2 +CH3 C CH2 C H CH3 C CH3 + CH3 C CH2 C
CH3 CH3 O CH3 CH3 O
(D)
Ngoi cc sn phm trn trong mt s trng hp cn thu c c sn phm
ime ha gc (A).
II.2.2. Chuyn v halogen 1,2:
Khi clo ha bromua izopropyl bng t C4H9OCl ta c hn hp sn phm gm
CH3CHClCH2Br v (CH3)2CClBr:
Cl
t - C4H9OCl
CH3 CH CH3 o CH3 CH CH2Br + CH3 C CH3
-78 C
Br Cl Br
15% 60%
S to thnh CH3CHClCH2Br cho thy c s chuyn v gc t do trung gian
theo s :
CH3 CH CH3
Br
-HCl Cl (t - C4H9Cl)

CH3 C CH3 CH3 CH CH2

Br Br
(be
n hn) (ke
m ben hn)

Cl (t - C4H9Cl)
CH3 CH CH2 Br
Cl Cl (t - C4H9Cl)
CH3 C CH3 CH3 CH CH2 Br
Br Cl
60% 15%
III. S chuyn v t nhm th vo vng thm:
Phn ln nhng phn ng chuyn v vo vng thm l nhng phn ng chuyn
dch mt nhm X t d nguyn t Z vo v tr ortho hoc para va vng.

9
 Z X Z H Z H
X
+

X
y Z = O khi X = ankyl, aryl, .
Z = N khi X = ankyl, halogen, hiroxy, nitro, nitrozo, azo, sunfo,
Hu ht cc phn ng chuyn v trn c xc tc bng axit v s tn cng ca
nhm X vo vng thm c tnh cch mt phn ng th electrophin. Ta gi l phn
ng chuyn v electrophin vo vng thm.
Nhng phn ng chuyn v nucleophin vo vng thm (v d chuyn v nhm
OH phenylhiroxylamin) tng i t gp.
III.1. S chuyn v t nguyn t oxi vo vng thm:
III.1.1 Chuyn v Frai:
Khi c tc dng ca axit Lewis (AlCl 3, ZnCl2, FeCl3.) nhm axyl trong este
ca phenol chuyn dch vo v tr ortho, para ca vng:
R
R
C R
O O OH C O
C
O
1.AlCl3
+ +
2.H3O
OH
R l ankyl hoc alyl
Ngi ta cho rng qu trnh chuyn v Frai tng t qu trnh axyl ha theo

Friden Crap. Di tc dng ca cht xc tc, este to ra cation axyli R C O , cation
ny s tn cng vo cc v tr ortho, para ca vng thm:
OAlCl2 O OH O
O C C
O +
R H3O R
O C R OAlCl3 C R

AlCl3 OAlCl2 OH
-HCl

H3O+

C C
R O R O

Phn ng Frai lun to ra hn hp hai sn phm ng phn. Nhit thp thun

li cho s to thnh ng phn para.
V d:
10
 OH COCH3 OH
CH3CO
AlCl3, 25 C
o
AlCl3, 165oC

CH3 CH3 CH3

COCH3
80% 95%
Khi v tr para b chim th ch to thnh sn phm ortho.
V d:
COCH3 OH
CH3CO
AlCl3
nitrobenzen

CH3 CH3
95%
III.1.2. Chuyn v Claizen
Khi un nng cc alyl aryl ete s chuyn thnh ortho-alylphenol theo mt phn
ng gi l chuyn v Claizen.
V d:
OCH2CH=CH2 OH
o CH2CH=CH2
200 C

90%

Phn ng theo c ch ni phn t nh sau:

14
CH2 14
CH2 CH CH2
O CH O CH
CH2 OH
CH2 CH2
H

III.2. S chuyn v nguyn t nit vo vng thm

III.2.1. Chuyn v nhm ankyl
Khi un nng cc mui halogenhirat ca arylankylamin, nhm ankyl s chuyn
dch n v tr ortho hoc para ca nhn thm.
V d:
HHal
C6H5NR2 o - hoa
c p - RC6H4NHR
to
HHal
C6H5NHR o - hoa
c p - RC6H4NH2
to

11
 C l phn ng bt u bng mt qu trnh th nucleophin d tch dn xut
halogen RHal ra khi mui halogenhydrat, sau RHal s tc dng vi nhn thm
theo c ch th electrophin.
V d:
C6H5NH2RHal RHal + RC6H5NH2
C6H5NH2 + RHal RC6H4NH3Hal
III.2.2 Chuyn v nguyn t halogen
S chuyn v nguyn t halogen t nguyn t nit vo vng benzen gi l
chuyn v Octn.
Khi un nng N-cloaxetanilit trong axit axetic hoc nc c mt hidro clorua ta
c octo v p-cloaxetanilit
HCl
C6H5 N COCH3 Cl C6H4 NH COCH3
H2O
Cl
Phn ng xy ra theo c ch:
C6H5 N COCH3 + HCl C6H5NH-COCH3 + Cl2
Cl
C6H5NH-COCH3 Cl2 Cl C6H4 NH COCH3 + HCl
III.2.3. Chuyn v nhm aylazo
Phn ng tiu biu ca chuyn v nhm arylazo l phn ng chuyn ho
iazoaminobenzen thnh p-aminoazobenzen.
HCl
C6H5 N N NHC6H5 p - H2N C6H4 N NC6H5
hoa
c C6H5NH2 + HCl

Phn ng xy ra theo c ch electrophin nh sau:

C6H5 N N NHC6H5 HCl C6H5N2 + C6H5NH2 p - H2N C6H4 N N NC 6H5
III.
2.4. Chuyn v nhm nitrozo (chuyn v Fis Hep)
Khi c mt ca axit clohiric, nhm nitrozo ca nitrozamin thm chuyn dch
vo nhn thm.
HCl
C6H5 N COCH3 o -vap - NO C6H4 NH CH3
NO
C ch ca chuyn v Fis-Hep tng t c ch ca chuyn v Octon:

12
 CH3 CH3
C6H 5N + H+ C6H5N + NO+
NO H
CH3
C6H5N + NO+ O N C6H4 NH CH3 + H+
H
III.2.5. Chuyn v benziin
Khi cho axit mnh tc dng ln hyrazobenzen s xy ra s chuyn v lm t
lin kt N-N v hnh thnh lin kt C C to ra benziin.
H+
NH NH H2N NH2

Trong phn ng chuyn v hirazobenzen ngoi benziin l sn phm ca s t

hp p, p ta cn c sn phm ca s t hp o, p v nhng lng rt nh cc sn
phm t hp khc.
NH2 NH2 NH2 H2N

NH2 NH NH2 NH

Phn ng xy ra theo c ch ngh nh sau:

2H+
D NH NH D D NH2 NH2 D

H2N H 2N

H2N NH2

D D
-2D

D D
NH2 NH2

13
I. S chuyn v 1,2 nucleophin.
I.1. S chuyn v n nguyn t C.
I.1.1 Chuyn v Wagner-Meerwein.
I.1.2. Chuyn v pinacolic.
I.1.3.Chuyn v Vont.
I.1.4. Chuyn v enzilic.
I.1.5. Chuyn v benzilic.
I.2. S chuyn v n nguyn t nit
I.2.1. Cc phn ng chuyn v Hofmann, Curtius, Lossen, Schmidt
I.2.2. S chuyn v Beckmann
I.3. S chuyn v n nguyn t oxi.
I.3.1 Chuyn v Bayer Villiger
I.3.2. Chuyn v peoxit.
II. S chuyn v 1, 2 electrophin v ng ly.
II.1. S chuyn v 1,2 electrophin.
II.1.1 Chuyn v Stevens.
II.1.2. Chuyn v Wittig.
II.2. S chuyn v 1,2 ng ly.
II.2.1. Chuyn v aryl 1,2.
II.2.2. Chuyn v halogen 1,2.
III. S chuyn v t nhm th vo vng thm.
III.1. S chuyn v t nguyn t oxi vo vng thm.
III.1.1 Chuyn v Frai.
III.1.2. Chuyn v Claizen.
III.2. S chuyn v nguyn t nit vo vng thm.
III.2.1. Chuyn v nhm ankyl.
III.2.2 Chuyn v nguyn t halogen.
III.2.3. Chuyn v nhm aylazo.
III.2.4. Chuyn v nhm nitrozo (chuyn v Fis Hep).
III.2.5. Chuyn v benziin.

14