Trng THPT Chuyn Lo Cai

T Ha hc

CHUYN : HIN TNG CHUYN V TRONG PHN NG HU C

Trong hu ht cc phn ng ha hc hu c, trung tm phn ng l cc
nhm chc v ch c s bin i v cu to (cu trc) . Tuy nhin, nhiu phn
ng c s bin i khng ch v tr nhm chc m c s tham gia ca c gc
hidrocacbon to ra nhng sn phm khc d kin, l hin tng chuyn v trong
phn ng hu c.
Chuyn v gm 3 loi ch yu:
+ Chuyn v 1,2 (Thuc dy no).
+ Chuyn v 1,3 (Thuc dy khng no no).
+ Chuyn v t nhm chc vo vng thm (Thuc dy thm).
I. CHUYN V 1,2
I.1. Chuyn v 1,2 Nucleofin
L s chuyn v m nhm nguyn t hoc nguyn t chuyn i mang theo c
cp electron.
I.1.1. Chuyn v n nguyn t Cacbon
a. Chuyn v Vannhe-Mecvai:
Chuyn v nguyn t Hidro, gc Ankyl, Aryl n v tr C+ (To cacbocation
bn hn).
Loi chuyn v ny thng gp : Ancol/H+(P th, phn ng tch nc), dn
xut/Ag+, amin/HNO2, hidrocacbon (Anken/H+)...
VD:
CH3

CH3
C

CH3

+ HCl
CH2OH

CH3 C

- H2 O

CH3

CH3

(CH3)2C=CH-CH3

CH3
CH3 C

CH2Cl

CH2OH

- H2 O

CH2=C-CH2CH3

CH3

CH3

b. Chuyn v pinacol-pinacolon:
Chuyn v to cacboncaction bn hn (Do c s tng tc ca cp e ca
nguyn t O vi C+).
VD:
CH3 CH3

CH3 CH3
CH3 C
OH

C
OH

CH3

+ H+
- H2O

CH3 C

C
+

CH3

CH3

+
Chuyn v CH C
3

OH

OH

CH3

CH3
CH3

Pinacol
CH3 C
Pinacolon

CH3

CH3

Hay tng t trn (To cacbocation trung gian ging nhau)

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

CH3 CH3
CH3 C

OH

T Ha hc
CH3
-H+

+ Ag+
- AgBr

CH3

CH3 C

Br
C

OH

CH3

NH2

+ NaNO2,HCl

-H+

CH3 C

-NaCl, -N2

CH3

CH3
CH3

CH3 CH3
CH3 C

CH3

CH3

c th lp th: Do to ra cacbocaction trung gian dng cu ni nn chuyn v

Vanhe-Mecvai v chuyn v Pinacol-Pinacolon u lm quay cu hnh sn phm
(C).
Hng chuyn v:
+ Nhm dch chuyn mang theo c cp electron (Nh mt tc nhn Nu) nn nhm
no c tnh y electron mnh hn s b chuyn dch.
VD:
CH3C6H4

C6H4 CH3

C6H4 CH3
+

C6H5 C

+H
- H2O

C C6H5

OH

OH

C6H5

+
C

C C6H5

OH

C6H4 CH3

SPC

+ Vi Pinacol khng i xng, Cacbocation no cng bn s u tin c to ra.

VD:
C6H5
C6H5
C6H5 C
OH

C6H4 OCH3
C C6H4OCH3
OH

+ H+
- H2O

C6H5 C

+
Chuyn v
C C6H4 OCH3

OH C6H4OCH3
C6H5 OH
C6H5 C
+

Chuyn v

-H+

-H+

C C6H4 OCH3

SPC

SPP

C6H4OCH3

+ nh hng khng gian: o-Anizyl kh nng dch chuyn km p-Anizyl 1500 ln.
c. Chuyn v Vonfer
Chuyn ha -diazoxeton thnh xeten, tc dng vi H2O (Ancol) to ra axit (este).
VD:
RCOCHN2

+Ag2O
-N2

..

RCOCH

Chuyn v

Cacben

+H2O
RCH=C=O
+R'OH

R-CH2COOH
R-CH2COOR'

Chuyn v Vonfer dng trong tng hp axit , xeton.

VD:
R-COOH

+SOCl2

R-COCl

+CH2N2

RCOCHN2

+Ag2O

RCH2COOH
+ H2O, Vonfer

+CH2N2

CV

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

d. Chuyn v benzylic (Chuyn v Benzyl-axit benzilic)

T Ha hc

L s chuyn ha -dixeton/HO- thnh -Hidroxi axit.

ArCOCOAr

HO-

Ar O

Ar

CV

Ar - C - C - OH
O O

Ar - C - C - OH

H3O+

Ar O
Ar - C - C - OH

O-

OH

I.1.2. Chuyn v n nguyn t Nit

a. Chuyn v Hopman:
Amit chuyn ha thnh amin di tc dng ca BrO-/HO-.
.. CV
-BrHOBrOR-CO-NH2

R-CO-NHBr

R-CO-N Br

R-CO-N :

R-N=C=O

+ H2O
-CO2

R-NH2

b. Chuyn v Curtius
R-CO-N3

-N2, to

R-CO-N :

CV

R-N=C=O

+ H2O
-CO2

R-NH2

(Azit)
Nu phn ng trong dung mi khng c hidro linh ng, phn ng dng li
giai on to isoxianat.
c. Chuyn v Lotxen
R-CO-NH-OH

+ HO-H2O

R-CO-N - OH

-HO-

R-CO-N :

CV

+ H2O

R-N=C=O

-CO2

R-NH2

(Axit Hidroxamic)
d. Chuyn v Schmidt

Nh vy, cc chuyn v Hopman, Curtius, Lotxen v Schmitdt u qua h/c

isoxianat, ch khc iu kin v cht ban u.
e. Chuyn v Backman
Chuyn ha xetoxim (V cc dn xut O-Axyl ca chng) thnh cc amit
th. Xc tc thng axit nh: H2SO4; PCl5; RSO2Cl; BF3; P2O5...
C ch:
R

R'

R'

+C

+H

C
N

+ H2 O

-H2O, CV
OH

HO

-H

R'

O
C

R'

NH

V mt lp th: Trong chuyn v Backman, vi cc xetoxim khng i xng (c

phh), nhm b chuyn v v tr anti (i) vi nhm -OH.
VD:

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

T Ha hc

C6H5
p-CH3OC6H4

ete

OH

p-CH3OC6H4

PCl5

C=N
C6H5

PCl5

C=N

OH

ete

C6H5
C - NH

p-CH3OC6H4
C6H4OCH3 - p

O
C6 H 5

C - NH

I.1.3. Chuyn v n nguyn t Oxi

a. Chuyn v Bayer-Viliger
Nm 1899, nh ha hc c Baeyer v nh ha hc Thy S Villiger trong
lc nghin cu v phn ng m vng hp cht Xeton vng bng peroxi axit hoc
hydro peroxit, h pht hin ra Xeton s c chuyn ha thnh este v Xeton vng
chuyn ha thnh lacton hoc hydroxi axit tng ng. V vy loi phn ng ny
c dt tn l Phn ng oxi ha chuyn v Baeyer-Villiger

Xeton

Este

Xeton

Lacton

C ch phn ng

Phn ng Baeyer-Villiger c nhng c im sau:

+ S chuyn v u tin xy ra so vi nhng phn ng khc.
VD: Hp cht , bt bo ha xeton cho phn ng oxi ha chuyn v vi nhm
carbonyl thay v oxi ha ni i.
+ Nhm tham gia chuyn v thng theo th t:
alkyl bc 3> xyclohexyl> alkyl bc 2 > aryl > alkyl bc 1 > metyl.
+ S chuyn v xy ra c lu gi cu hnh lp th ca nhm chuyn v.
+ Nhiu loi tc nhn oxi ha c th s dng cho phn ng ny vi hot tnh gim
dn tng i nh sau: axit CF3COOH >axit monopermaleic > axit
monoperphtalic > axit 3,5-dinitroperbenzoic > axit p-nitroperbenzoic > axit mclo peroxi benzoic ~ axit performic > axit perbenzoic >axit peracetic >> H2O2.
+ Vi -dixeton c th b oxh B-V thnh anhidrit axit, cn -dixeton th khng.
a. Chuyn v Hidropeoxit:
Chuyn v ny xy ra khi phn hy hp cht peoxit, bn cht tng t
chuyn v Bayer-Viliger.
VD:

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

CH3

C6H5
C O-O-H
CH3

-H2O

CH3

C 6 H5
C O+

T Ha hc
CV

(CH3)2C+-O-C6H5

+ H2 O

(CH3)2C=O + C6H5OH

CH3

Andehit salixilic + H 2O2/NaOH

o-Hidroxi phenol (pyrocatechol)

I.1. Chuyn v 1,2 electronfin, ng li

Nhm chuyn v khng mang theo cp electron lin kt (ng vai tr nh tc
nhn electronfin), to lin kt mi vi cp eletron ca nguyn t chuyn n.
a. Chuyn v Steven:
+
Z-CH2-N(CH2)2
R

HO-H2O

Z-CH-N(CH2)2
R

(Z ht e: RCO; ROOC ...

R: Anlyl;

Benzyl...)
b. Chuyn v Wittig:
Chuyn ha ete di tc nhn baz mnh: C6H5Li; NaNH2...
VD:
CH3 - O - CH2C6H5

+ C6H5Li
-C6H6

CH3 - O - CH C6H5

CV

O - CH C6H5
CH3

+ H2O
-HO-

HO - CH C6H5
CH3

Kh nng chuyn dch ca cc gc: Anlyl, benzyl > metyl; etyl > phenyl.
c. Chuyn v 1,2 Halogen ( Chuyn v 1,2 ng li )
t-C4H 9OCl
CH3CHClCH2Br (SPP) + CH 3-CBr(Cl)CH3 (SPC)
VD: (CH3)2CHBr
(Sn phm chnh u tin hng to ra gc t do bn hn)
II. CHUYN V 1,3
a. Chuyn v Anlylic
Trong phn ng th ca dn xut Anlyl: RCH=CH-CH2X /NaOH
VD:
CH3CH=CHCH2OH (40%)
CH3CH=CH-CH2Cl + NaOH

(CH3)2C=CH-CH2Cl + Na2CO3

H2 O

CH3CH(OH)CH=CH2 (60%)
CH3CH=CHCH2OH (15%)

CH3CH(OH)CH=CH2 (85%)

b. Chuyn v Xeton-Enol (Hin tng Tautome)

Xut hin hp cht c H linh ng: Hp cht Cabonyl; hp cht cha
nhm: -NH-CO- ; > CH-NO2 ; > CH-NO ... Nhng s chuyn ha Xeto-Enol c
nhiu ngha hn c.
Di xc tc H+ hoc HO-, hp cht Cacbonyl b Enol ha nhanh to ra mt
cn bng.
T l Xeto/Enol trng thi cn bng ph thuc vo nhit , nng , dung
mi v c bit l cu trc.
Nu trong phn t c nhm gy -C mnh lin hp vi h Enol th dng
Enol chim t l ln.
VD:
Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

CH3COCH3

T Ha hc
CH3C(OH)-CH2
0,00025%

CH3COCH2COCH3

CH3COCH2COH=CH2
80%

Cn bng Xeto-Enol

Xeto ha xt axit

Enol ha xt axit

Enol ha xt bazo

III. CHUYN V VO VNG THM

Chuyn v vo vng thm ch yu l cc phn ng mang c th th
Electronfin vo vng benzen (Nhm chuyn v ng vai tr nh mt tc nhn
elctronfin).
Cc chuyn v vo vng thm thng t cc nguyn t d t nh Oxi, Nit.
III.1. Chuyn v t nguyn t oxi vo vng thm
a. Chuyn v Frai (Fries)
Chuyn v nhm axyl trong este ca phenol vo vng thm di xt axit
Lewis (AlCl3, ZnCl2, FeCl3...)
nhit thp, u tin chuyn v vo v tr Para. Khi vng hm c sn
nhm y e (Hot ha vng) th chuyn v Frai cng d thc hin.

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

VD:

T Ha hc
OCOCH3

OH

OH
AlCl3, 165oC

AlCl3, 25oC

CH3CO

CH3

CH3

CH3
95%

CH3CO
80%

b. Chuyn v Claizen
Khi un nng ete Anlyl chuyn ha thnh o-Anlyl phenol.
OCH2CH=CH2

OH
CH2CH=CH2

200oC

90%

III.2. Chuyn v t nguyn t Nit vo vng thm

a. Chuyn v nhm Ankyl
un nng mui Halogen ca Aryl ankyl amin, nhm ankyl s chuyn dch
n v tr o- hoc p- ca nhn thm.
VD:
NR2

NHR

NHR
HHal, to

R
NHR

NH2

NH2
HHal, to

b. Chuyn v Octon (Chuyn v nguyn t Halogen)

un N-Clo axetanilit vi HCl (HBr), thu c o- hoc p- Clo (Brom)
axetanilit.
N(Cl)COCH3
HHal, to

NHCOCH3

NHCOCH3

Hal

Hal

c. Chuyn v nhm Aryl azo

Chuyn v nhm Aryl azo ca diazo aminobenzen thnh p-aminoazobenzen

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

T Ha hc

N=N-NH-Ar

N=N-Ar

HHal, to

NH2
Nu v tr p- c nhm th, s chuyn v vo v tr od. Chuyn v Fis - Hep(Chuyn v nhm Nitrozo )
Cho hp cht c nhm Nitrozo ca amin thm tc dng vi HCl, to.
N(NO)CH3

NHCH3

NHCH3

HHal, to

NO

NO

e. Chuyn v benzydin
Cho Hidrazobenzen/H+ to ra Benzidin
H+

-NH-NH-

NH2

H2N

(70%)

Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

T Ha hc
IV. BI TP VN DNG
Bi 1: Hy d on sn phm to thnh trong cc qu trnh chuyn v sau:
Xiclo heptanon.
a. Xiclo hexanon + CH2N2
b. Xyclohexanon + 1. H2N-OH; 2. H+
Caprolactam
(CH3)3CCH2NH2
c. (CH3)3CCH2CONH2 + NaOBr
CH3

H3C
H+

-NH-NH-

d.

CH3
H

OH

OH

(C6H5)2C-C(CH3)C 6H5

OH

g.

OH

f.

NH2

H3C

(C6H5)2C-C(CH3)2

e.

H2N

H+

OH

OH

h. p-CH3OC6H4-COCOC6H5

HO-

i. 2,2-dimetyl propan-1-ol + H+
k. Xiclopentyl metanol + H+
Bi 2: Hy gii thch
1. 3-metylbuten-1 tc dng vi axit clohidric to ra cc sn phm, trong c A
l 2-clo-3-metylbutan v B l 2-clo-2-metylbutan. Bng c ch phn ng, hy gii
thch s to thnh hai sn phm A v B.
2. 2-metylbuten-2 phn ng vi axit clohidric. Trnh by c ch ca phn ng, cho
bit sn phm chnh v gii thch?
3. But-3-en-2-ol tc dng vi dd HBr to thnh 3-brombut-1-en v 1-brombut-2en. Hy gii thch?
4. Ho tan hexa-1,4-dien-3-ol (A) trong H2SO4 ri sau mt thi gian pha long dd
th thu c A v 2 ancol ng phn cu to ca n.
(BT1,2 HS t gii)
Bi 3. Cho ancol A c CTCT:
H3C

CH3
C

OH

CH3

Khi ehiat ha ancol A thu c 3 ankaien lin hp. Vit CTCT, gi tn 3

ankaien lin hp? Trnh by c ch phn ng?
HD:
Phm Duy ng - Chuyn hu c

Trng THPT Chuyn Lo Cai

T Ha hc

-H+

H+
-H2O
OH

-H+

-H+

Bi 4. Tin hnh phn ng gia 3,5,5-trimetyl xiclohex-2-enon v n-butyl magi

ioua. Sau , thu phn hn hp bng dung dch HCl 4M thu c hp cht B. B
b chuyn thnh nm ng phn, k hiu t D1 n D5 c cng thc phn t
C13H22. Vit cng thc cu to ca cc ng phn D1, D2, D3, D4, D5 v gii thch
s hnh thnh chng?
HD:
Hb

HO
H+

1 .BuMgBr
2. H 2 O

Ha

- Hb

- Ha

- H2O

D3

D2

CV
D1
H+
- H O
2

D5

D4

Bi 5. X l - halogen xeton Vi baz mnh to thnh cc sn phm chuyn v.

S chuyn v ny gi l phn ng Favorski. - cloxiclohexanon s chuyn v thnh
metylxiclopentancacboxilat khi c mt CH3ONa trong ete. Hy xc nh c ch
ca phn ng ny.
O
Cl
CH3ONa

ete

COOCH3
NaCl

HD:

Phm Duy ng - Chuyn hu c

10

Trng THPT Chuyn Lo Cai

O

T Ha hc

Cl CH3O

Cl

OCH3

CH3O

CH3OH

OCH3

OCH3

O
H2O
OH

Bi 6. Hy vit cu to cc cht t A n E:
O
COOH
OH

(CH3CO)2O
CH3COOH

COOH

thay i v tr

Br 2

H3C

H+

chuyn v Fries

(B: sn phm chnh)

(CH3)3CNH2
HBr

LiAlH4

OH

(Trong ph hng ngoi

khng cn cc m C= O na)

HD:
OH

OH

OOCCH3

A:

COOH

COOH

COOH

; B

CH3CO

;C

BrCH2CO
CH2OH

COOH
OH

OH

D: (CH3)3CNHCH2CO
; E: (CH3)3CNHCH2CH(OH)
Bi 7. Anlylmagie bromua (A) phn ng vi acrolein to thnh cht B, sau khi
thy phn B s c sn phm C duy nht. un nng C nhn c cht D. Cho D
phn ng vi C6H5Li thu c sn phm E. un nng E khi c vt iot th c F
c cng thc C12H14.
1. Hon thnh s dy phn ng trn (vit cng thc cu trc ca cc cht hu
c trn t C n F).
2. Ghi k hiu c ch cc giai on ca phn ng di dng cc mi tn trong s
, tr giai on to thnh F.
HD:

Phm Duy ng - Chuyn hu c

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Trng THPT Chuyn Lo Cai

T Ha hc

+
CH2=CH-CH2-MgBr
AN
cng 1, 4

+
CH2 = CH-CH = O
thu phn

H3O+

CH2=CH-CH2-CH2-CH=CH2-OMgBr
B

CH2=CH-CH2-CH2-CH=CH-OH

tautome ho

CH2=CH-CH2-CH2-CH2-CH=O
D

Hoc:
CH2=CH-CH2-MgBr
AN
H2O
+
CH2=CH-CH2-CH-CH=CH2
CH2=CH-CH2-CH-CH=CH2
cng 1, 2
-MgBr(OH)
CH2=CH-CH=O
B OMgBr
C
OH
o

OH

H bin

t
Chuyn v 3, 3

C6 H 5

OH
H2O

H
OLi

xeto-enol

D
C6 H 5
H
E OH

C6H5Li
AN

Vt iot, to
- H2O

C6 H5

TI LIU THAM KHO

[1] C s l thuyt ha hc hu c - GS.TS Trn Quc Sn - NXBGD 1979.
[2] Bi tp ha hu c - GS.TSKH Ng Th Thun - NXBKHKT 2001 v 2008.
[3] thi HSGQG cc nm.
[4] Advanced Oganic Chemistry - Part B - Reactions and Synthesis - Kluwer
Academic Publishers - New York - 2002.
[5] Name Reactions - Phil S.Baran - La Jollan - 2006

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