Bui th su

Chng 2. Phn ng chuyn v phn t

Trong phn ng th, s xut v nhp ca cc nhm xy ra trn cng 1 nguyn t carbon theo
nguyn tc cu trc phn t thay i t nht. Nhng c nhng phn ng hu c s xut v
nhp xy ra khng trn cng mt nguyn t carbon v i khi c s thay i khung sn
carbon. Phn ng hu c km theo s thay i v tr nhm chc hay thay i khung carbon
gi l phn ng chuyn v phn t. Chuyn v ni phn t l s chuyn v m nhm dch
chuyn khng tch hn khi phn t v dch chuyn sang v tr khc trong cng phn t. Khi
trng thi trung gian c c cu vng. Chuyn v lin phn t l s chuyn v m nhm
dch chuyn tch khi phn t v dch chuyn sang v tr khc trong cng phn t hoc ti
phn t khc.Ta xt mt s phn ng chuyn v ni phn t trong h thng thiu in t v
h thng giu in t.
2.1. S chuyn v trong h thng thiu in t
H thng thiu in t l h thng cha nguyn t thiu in t, tc nguyn t ch c 6 in
t tng ha tr. Nguyn t c 6 in t c th l nguyn t trung ha hoc mang in tch
dng. Nguyn t thiu in t c th l carbon, nit, xy. Do thiu in t nn h khng
bn, to tin cho s chuyn v. Chuyn v trong h thiu in t cn gi l chuyn v thn
hch. Ta xt chuyn v ti 2 nguyn t k cn nhau, gi l s chuyn v 1,2, trong nguyn
t mang nhm dch chuyn l nguyn t i, nguyn t nhn nhm dch chuyn l nguyn t
n.

C A C A

Z Z

Cation carbonium
C C C C

R R

Carben C C
C C C C

R R R

Nitren C N C N
C N

R R
R

Cation oxonium C O C O C O

R R R

Trong h, A l nguyn t c 6 in t lp ha tr, do thiu in t. Nhm Z v tr s 2

di chuyn sang A cng i in t lin kt. A nhn in t t Z nn d 1 in t v mang
in tch m, ng thi c 8 in t tng ha tr. A c th l C, N, O tng ng vi cation
carbonium, carben, nitren, cation oxonium.
H thiu in t c th c to thnh do nhm L tch ra cng i in t lin kt, li
cation carbonium c nguyn t C thiu in t. Nhm Z tng tc vi C bng i in t
lin kt, cho trng thi chuyn tip vng 3. Z tip tc dch chuyn sang nguyn t C mi,

47
cho trung gian l cation carbonium mi l h thiu in t. H nhn 1 cht thn hch N
cho sn phm.

L N
-L N
C C C C C C C C C C

Z Z Z Z Z

Qu trnh phn ng c trnh by d hiu nh trn. Thc th phn ln chuyn v 1,2 xy ra

trong 1 giai on. Trng thi chuyn tip c biu din bng vng 3 mang in tch dng.
Ngi ta cho rng nhm Z v L tham gia vo trng thi chuyn tip, v c th c nhm N
cng tham gia vo trng thi chuyn tip.
L L
L

C C C C C C

Z Z Z

L N L N L
N

C C C C C C

Z Z
Z

S xut nhm L v s dch chuyn nhm Z xy ra cng lc, hoc nhm N cng tham gia
giai on ny. Thc nghim cho thy nhm dch chuyn lu gi cu hnh, nhm xut v
nhm dch chuyn v tr i lch nhau. Nh vy, cu to trng thi chuyn tip ny c
khng nh.
Trng thi chuyn tip thnh lp khi nhm dch chuyn Z ly in t to lin kt mi vi
C n trong khi lin kt c vi C i cha t. Ngoi ra gia nguyn t C i v C n c
mt phn lin kt biu din bng on thng ri. Nh vy vng 3 ny c lp bng 2 in
t v c s cng hng vng. Theo quy tc Huckel vng 3 ny c tnh thm v c tnh bn.
Nhm Z tng tc bng i in t lin kt, nh mt baz, hay mt cht thn hch, vi tm
thiu in t nh mt tm acid, hay tm thn in t. Phn ng cho mt h thiu in t mi
l ion carbonium. Ion ny c th nhn mt cht thn hch N hay tch 1 H linh ng cho
alcen, cng nh c th cho phn ng chuyn v vi cc nhm ti 2 C cho ra nhiu sn
phm khc nhau. Nhng thng ch c 1 phn ng chuyn v xy ra. D hiu rng nhm
dch chuyn l nhm c lc thn hch mnh hn. Khuynh hng di chuyn ca cc nhm
tng dn theo th t:
H < CH3 < C2H5 < i-C3H7 < t-C4H9 < C6H5
Cc nhm phenil dch chuyn tng dn theo th t:
48
 p-NO2-Ph < p-Cl-Ph < Ph < p-Ph-Ph < p-CH3-Ph < p-CH3O-Ph
Ta thy cc nhm alkil bc cng cao cng u tin, nhm phenil u tin hn nhm alkil, cc
nhm th y in t trn vng thm lm tng tnh u tin.
Trng hp nhm H dch chuyn: Vn o 1s ca H tng tc vi vn o 2p ca C mang
in tch dng, lin kt vi vn o sp3 ca C i cha t. Ti trng thi chuyn tip, lai
ha ca 2 carbon l trng thi gia sp3 v p.
H1s C2p C2p H1s

Csp3 Csp3

Trng hp nhm alkil R dch chuyn: Vn o bin HOMO ca R tng tc vi vn o

LUMO ca C carbonium. Ta thy cu hnh ca R c bo ton.
A
A
B B
C2p C C2p C
A

B
C

Csp3 Csp3

Trng hp nhm aril Ar dch chuyn: aril l h in t thm nn chuyn v ca aril ging
nh s th ni phn t qua giai on to trung gian cation ciclohexadienil.

2.1.1. S chuyn v n nguyn t carbon

1. Chuyn v pinacol
Nm 1859 Wittig nhn c pinacol, n nm 1860 ng pht hin pinacol trong dung dch
acid bin i thnh pinacolon.
CH 3 CH 3 CH 3

H 2SO 4
H 3C C C CH 3 H 3C C C CH 3

OH OH O CH 3
Pinacol Pinacolon

Sau nhiu phn ng ng tng t c nghin cu v phn ng ca Wittig tr thnh

phn ng u tin ca nhm phn ng mang tn chuyn v pinacol. Chuyn v pinacol l
phn ng ca 1,2-glicol trong mi trng acid b tch nc thnh hp cht carbonil.
Trong mi trng acid, nhm hidroxil b proton ha thnh nhm xut tt, s mt 1 phn t
nc lm C mang nhm xut tr thnh C thiu in t (carbonium). S dch chuyn nhm
alkil ti C k cn cng s tch 1 ion H to thnh sn phm ceton.

49
 R2 R3 R2 R3 R2 R3

H - H 2O
R1 C C R4 R1 C C R4 R1 C C R4

OH OH OH OH 2 OH

~R 2

R2 R2

-H
R1 C C R3 R1 C C R3

O R4 OH R4

Vi -glicol c cc nhm khc nhau, cn xc nh nhm OH b proton ha v nhm dch

chuyn. Ni chung, OH b proton ha v b tch ra di dng phn t nc l OH cho
carbonium bn hn, nhm dch chuyn l nhm u tin hn theo th t nu trn. Khuynh
hng nhm OH b tch ra theo th t sau:
R Ar R Ar

CH 2 < CH < CH < R < Ar

OH OH OH OH OH

Tuy nhin sn phm phn ng ph thuc vo iu kin phn ng. Khi cho 1,1-dimetil-2,2-
dipheniletilen-1,2-glicol vo H2SO4 m c v lnh, phn ng xy ra khc vi khi cho vo
acid acetic c vt acid sulfuric.
H 2SO 4 lanh Me C CPh 2

Ph 2C CMe 2 O Me

CH 3COOH Ph C CMe 2
OH OH
vet H 2SO 4
O Ph

Trong acid sulfuric m c l acid mnh, OH u i proton ha l OH ca C c 2 nhm

phenil cho carbonium bn, nhm dch chuyn l nhm metil. Trong acid yu l acid
acetic, s proton ha v tch nc xy ra cng lc vi s dch chuyn, m nhm phenil dch
chuyn u i hn nhm metil nn sn phm nhiu l sn phm c s dch chuyn ca nhm
phenil.
Mt s th d:
H2SO 4 Me C CPh2

Ph2C CMe2 O Me

ZnCl2 Ph C CMe2
OH OH

O Ph

Ph Ph Ph OCH 3

H
CH 3O OCH 3 Ph C C Ph OCH 3

OH OH O Ph
Ph

PhCH CHPh H
Ph CH CHO

OH OH

50
c im chung ca chuyn v trong h thiu in t l chuyn v thng xy ra trong 1 giai
on v nhm xut cng nhm dch chuyn ti cu trng phn ng v tr i lch. c
im v tr ca nhm dch chuyn quan trng hn th t u tin. Do chuyn v pinacol
cc ng phn lp th khc nhau cho sn phm khc nhau. Hn na, 2 nhm OH v tr 1,2
to lin kt hidro ni phn t ti cu trng bn lch. Do c im lp th c th hin r
trong cc trng hp ca phn ng chuyn v pinacol.
Chuyn v pinacol c m rng cho nhm hp cht -minoalcol khi ch bin vi acid
HNO2, -halohidrin khi ch bin vi bc, m vng epoxid trong mi trng acid. Cc hp
cht ny trong iu kin phn ng cho trung gian ion carbonium, chuyn v kiu pinacol cho
ceton.
R2 R3 R2 R3

HNO 2
R1 C C R4 R1 C C R4

OH NH2 OH N N - N2

R2 R3 R2 R3 R2 R2
Ag - AgBr
R1 C C R4 R1 R4 R1 R3
-H
C C C C R1 C C R3

OH Br OH Br Ag OH R4 O R4
2 3
R R R2 R3

H
R1 C C R4 R1 C C R4

O O
H

2. Chuyn v Wagner Meerwein

Chuyn v Wagner Meerwein l s tch loi nc t alcol trong acid qua trung gian l
cation carbonium. Chuyn v Wagner Meerwein do Wagner pht hin nm 1899 khi tin
hnh tch loi phn t nc t cc terpen 2 vng, nhng nm 1920 Meerwein nghin cu v
xut c ch.

OH

- H 2O

Borneol Camphen

V sau phn ng m rng cho cc hp cht c vng v khng vng vi nhm xut bt k c
th to carbonium nh OH, halogen, TsO... Sn phm phn ng c th l th, tch loi...
Me Me

-H C
Me Me
Me Me
H Me Me
Me CH Me Me CH Me CH Me Me
- H2O
Me Me Me Me
OH Cl CH

Me Cl Me

Chuyn v Wagner Meerwein trnh by trong nhiu giai on (tng t SN1), nhng trong
phn ln trng hp ch c 1 giai on xy ra (tng t S N2), khng c s to thnh ion
carbonium t do. S tch nhm OH xy ra cng lc vi s dch chuyn v c th c tc kch
nhm nhp. Do phn ng c bit tnh lp th. Nu xy ra qu trnh

51
 R

A B

Y X

th A v B c s nghch o cu hnh, R c s lu gi cu hnh. Bit tnh lp th ca chuyn

v Wagner Meerwein c biu din r nt trong bin i 3-fridelanol thnh 13(18)-
oleanen trong acid. Xy ra 7 dch chuyn.

20
19 21
Me Me Me
12 18 22

11 13 17
H H H Me Me
9 14 H
16
1
2 10 8 15
Me Me H Me
3 5 7
4
OH 6
Me H
H
Me

Nu cc dch chuyn xy ra th t ngang qua cc carbonium th bc tranh c m t nh

sau. OH b proton ha v loi 1 phn t nc thnh cation trn C3. H4 chuyn sang C3,
metil t C5 chuyn sang C4, H10 chuyn sang C5, metil ti v tr s 9 chuyn sang C10, H8
chuyn sang 9, metil t 14 sang 8, metil t 13 sang 14.Ti C13 c in tch dng, tch 1 H
ti C18 to 13(18)-en. Nhng c 7 dch chuyn xy ra ng thi nh 7 phn ng SN2 cng
lc. Cc dch chuyn biu din di dng s nh sau.

H 2O Me Me C1 Me C7 Me C 12 H H 2O

3 4 5 10 9 8 14 13 18

H H C6 H C 11 H C 15 Me C 19

H 2O
H Me C6 Me C 11 Me C 15 C 12 H 3O

3 4 5 10 9 8 14 13 18

H Me H C1 H C7 Me C 19

C th thy cc dch chuyn c bit tnh lp th. Cc nhm pha trn mt phng phn t
(on lin) sau dch chuyn vn pha trn, cc nhm pha di (on ri) vn pha di.
Th t u tin cc nhm dch chuyn trong phn ng l vn phc tp. Nu phn ng theo
kiu SN1, vai tr quan trng khng phi nhm dch chuyn, m cc nhm khng dch
chuyn, v chnh cc nhm ny lm bn carbocation mi to ra. Nu phn ng xy ra ging
SN2, bn cht nhm dch chuyn l quan trng, nhm no cho trng thi trung gian bn hn
u tin hn.
Trng hp cation norbornil. Cation 2-norbornil c khuynh hng chuyn v Wagner
Meerwein. S chuyn v d dng hn vi norbornan th ti exo, nhm dch chuyn l lin
kt C1 C6 do c v tr i lch vi nhm xut (theo kiu SN2). Nu nhm xut v tr endo,
nhm dch chuyn khng th l lin kt C1 C6 do khng v tr i lch. Do phn ng
bt u bng tch nhm X to carbonium, sau lin kt C1 C6 dch chuyn. Phn ng

52
theo kiu SN1. Phn ng chm hn nhiu so vi ng phn exo. Cht thn hch Y tc kch
thun li hn t hng exo.
7 7 3 3

4 4 4 4
5 3 5 3 7 Y 7
5 5
1
X
6 1 6 2 1 2
2 2 1 6 6
exo
Y
7 7 7 3

4 4 4 4
5 3 5 3 5 3 Y 7 5
1
6 1 1 1
2 6 2 6 2 2 6
endo
X
Y

3. Chuyn v Wolf
Chuyn v Wolf l chuyn v ca carben sinh ra t diazoceton di tc dng nhit hoc nh
sng t ngoi hoc xc tc bc. Carben l hp cht c carbon ha tr 2, c 6 in t tng ha
tri. Do thiu in t nn carben c khuynh hng cho phn ng chuyn v.
R R R
Ag2O
O C C N N O C C N N O C C N N
_ N2
CH 2 CH 2 CH 2

R' R' R'

R R

R O O R'
~H C CH CH R' C C
H
CH
Ag2O
O C C ceton khong no
R R
_ N2
CH 2 O C C CH 2 R' O C C CH 2 R'
~R
ceten
R'
carben

Carbocation thng c lm bn bng tng tc vi i in t khng phn chia ca xy

bn cnh (chuyn v pinacol) hoc nhn tc kch cht thn hch t bn ngoi (chuyn v
Wagner Meerwein), trong trng hp ny c tng tc ca i in t t do sinh ra do
dch chuyn ca R, to thnh ceten, hoc dch chuyn H, to thnh ceton khng no. Ceten
cng nhanh nc thnh acid, alcol thnh ester, amin thnh amid.
H 2O
RCH 2COOOH

R'OH
R CH C O RCH 2COOR'
R'NH 2
RCH 2CONHR'

T l sn phm ceten v ceton ph thuc vo nhit phn ng: nhit thp ceton khng
no nhiu hn, nhit cao (>50OC) cho nhiu sn phm l chuyn ha cht ca acid.
Phn ng c ng dng ko di mch acid thm 1 C. y l phn ng Arndt Eistert.
O O O O
SOCl2 CH 2N 2 1. Ag 2O
R C R C R C R CH 2 C
2. H 2 O
OH Cl CH 2 N2 OH

53
M rng vng ceton.
O
O O

- N2
+ CH 2 N 2 CH 2 N2 O +

Lm hp vng.
O

H COOEt
N2
EtOH

Bi tp:
1. Chuyn v ni phn t trong h thiu in t thng xy ra trong mi trng acid. Phn
ng c th xy ra trong mi trng baz khng, ti sao?
2. Trong phn ng chuyn v trong h thiu in t, cu hnh nhm dch chuyn c bo
ton. iu ny ni ln c im g ca c ch phn ng?
3. Trong chuyn v pinacol, nhm xut v nhm dch chuyn lun v tr i lch nhau. Mt
khc cu hnh carbon mang nhm xut lun b ngch o. iu ny ni ln c im g ca
c ch phn ng?
4. Gii thch c im ca phn ng chuyn v pinacol:
- OH ti C mang nhm phenil d tch ra hn OH ti C mang nhm alkil.
- Nhm phenil d dch chuyn hn nhm alkil.
- Nu 2 yu t trn tc ng khng cng chiu th phn ng xy ra theo chiu no, cho v d.
5. Trong chuyn v pinacol, 1,2-glicol lun c cu trng m ti 2 nhm OH v tr bn
lch do c lin kt hidro ni phn t. Vit c ch cc phn ng sau, lu c im ny ca
phn ng.
H 3C

eritro
CH 3CH 2COCH 3 + CH CHO

CH 3 CH CHCH 3 H
H 3C
treo
OH OH CH 3 CH 2COCH 3

6. Trong chuyn v Wagner Meerwein ca 3-fridelanol thnh 13(18)-oleanen ngi ta

cho rng c 7 dch chuyn u xy ra cng lc. iu ny c chng minh bng s kin g?
7. Vit c ch phn ng.

54
 CH 3 O
CH 3
OH H +
CH 3
CH 3 C CH 3
CH 3
OH
O

CH 3
CH 3
OH H
OH C CH 3

CH 3
O
Ph
Ph
OH H

CH 3 C CH 3

OH
O
Ph
Ph
OH H

OH C CH 3

CH 3
O

55
Bui th by
2.1.2. S chuyn v n nguyn t nit
Cc nhm alkil v aril c khuynh hng chuyn v n nguyn t nit thiu in t. Phn
ng ngang qua trng thi chuyn tip vng 3.

R C N X O C N X O C N R + X

R
O

hoc
R

C N X C N X C N R + X

Trng thi chuyn tip vng 3 thun li nu nhm di chuyn l aril v c cc nhm th y
in t. Cc d kin ph hp c ch ny l: phn ng bc 1; cu hnh R c lu gi,
nghin cu ng v nh du cho thy phn ng xy ra ni phn t; nhm R khng c s
thay i. Theo c ch ny, s tch X cng lc vi s dch chuyn ca R. Tuy nhin khng
phi lc no cng xy ra nh th, phn ng ph thuc vo iu kin c th v bn cht cht
nn.
1. Chuyn v Hofmann
Chuyn v Hofmann l phn ng ca amid khng th vi mui hipohalit Na (hoc hn hp
NaOH v halogen), sn phm l amin c t hn 1 carbon (nn cn gi l gim cp
Hofmann).
Br2/NaOH
R CO NH 2 R NH 2

Ha tan brom vo dung dch xut c dung dch mui hipobromit Na. Dung dch ny brom
ha nhm amin cho trung gian c H acid kh mnh. Trong mi trng phn ng hidro cn
li tch ra di dng proton, cho trung gian anion vi in tch m trn nit. S y in t
lm brom ra i cng i in t lin kt, li nit c 6 in t tng ha tr. Hp cht ny
ca nit gi l nitren. Nitren khng bn, lp tc cho phn ng chuyn v vi nhm dch
chuyn l R. S tng tc ca cc vn o p ca N v C to lin kt , cho sn phm phn
ng l alkil isocianat. Trong mi trng phn ng, isocianat b thy phn v phn hy thnh
amin c t hn 1 C so vi amid ban u.

Br2/NaOH H OH - Br
R C NH2 R C N Br R C N Br R C N
(NaOBr) - H 2O
O O O O
nitren

~R
O
- H 2O
RNH 2 + CO 2 R NH C O C N R O C N R
isocianat alkil
OH

Nitren thc t khng tn ti trong hn hp phn ng, s tch Br v s dch chuyn R xy ra

cng lc. Khi kho st s chuyn v ca amid c C bt i xng, ngi ta thy cu hnh ca

56
C khng tay i. Nh vy nhm dch chuyn i ngang qua vng 3 v to lin kt mi ngay
ti lin kt c b t.
O
Me Me Me
O

H C C H C H C N C O
N
NH 2 Et Et
Et

Nu phn ng thc hin trong alcol th nhn c sn phm l uretan.

R'OH
R N C O R HN C O

OR'

2. Chuyn v Lossen
Chuyn v Lossen l phn ng xy ra khi un acid hidroxamic O-acil ha vi baz, nhn
c sn phm isocianat. Trong mi trng nc, isocianat b thy phn thnh amin bc 1,
t hn 1 carbon so vi acid ban u.
HO H 2O
R1 C NH OCOR 2 R1 N C O R1 NH 2 + CO 2

Phn ng theo c ch tng t chuyn v Hofmann. Hidro ti nguyn t nit ca acid

hidroxamic O-acil ha c dng tch ra di dng proton bng baz, cho trung gian anion
y in t, lm nhm carboxil tch ra cng i in t lin kt. Lc ny nit cn 6 in t
tng ha tr nn thiu in t, lm nhm alkil dch chuyn sang nit, cho nitren. Tng t
nh chuyn v Hofmann, nitren khng bn nn thc t khng to ra m cng lc xy ra
chuyn v nhm alkil cng tng tc ca i in t t do trn N, cho sn phm isocianat,
thy phn thnh amin.
O O

C O R2 C O R2
1 1
R N R N R1 N C O

-R 2COO
H O O H2O
OH

R 1NH 2 + CO 2

Phn ng khng c s dng rng ri trong tng hp hu c v acid hidroxamic khng c

sn.
3. Chuyn v Curtius
Chuyn v Curtius xy ra khi phn hy bng nhit hoc bng quang cc azid acid, to thnh
isocianat.

RCON 3 R N C O + N2
(h)

Phn ng xy ra theo c ch tng t phn ng Hofmann. Azid acid b nhit phn thnh
nitren, l h thiu in t ti N. Nhm alkil dch chuyn n N cng i in t lin kt cho
sn phm isocianat.
O
- N2 ~R - H 2O
R' C N N N R C N R RNH 2 + CO 2
O C

O N

57
Trong iu kin khan nc v khng c alcol, isocianat nhn c vi hiu sut cao. Cng
nh chuyn v Hofmann, nitren thc t khng tn ti, m s nhit phn tch phn t kh nit
xy ra cng lc vi s dch chuyn nhm alkil.

R C N N N C N R + N2

O O

Tuy nhin phn hy quang ha azid acid, nitren to thnh trong qu trnh phn ng nh mt
cht trung gian.
O

R' C N N N R C + N2

O N

Khi nhit phn alkilazid, sn phm nhn c l imin. S chuyn v xy ra tng t, nhng
c khc bit l c to thnh trung gian alkilnitren. Trong trung gian ny c th c chuyn v
ca aril, alkil hoc hidro.

R 3C N N N R2C NR + N2

Cicloazid v arilazid nhit phn cho chuyn v cng s m rng vng.

NR
R N3
R N

N3

NHPh

(Lu : y khng phi l chuyn v Cutius v cht u khng phi l azid acid, do trung
gian isocianat khng to thnh. Phn ng ny c chuyn v tng t chuyn v Cutius).
Azid acid c iu ch t azid Na v clorur acid hoc hidrazid acid v acid nitr .
O O

R C + NaN 3 R C + NaCl
Cl N3
O O O
HONO
- R'OH
R C + H 2N NH 2 R C R C + H 2O

OR' NH NH 2 N3
hidrazid acid

4. Chuyn v Schmidt
Chuyn v Schmidt l phn ng xy ra khi cng acid hidrazoic vo hp cht carbonil nh
aldehid, ceton, acid carboxilic, trong s c mt ca acid mnh. Cng ceton cho amid hoc
tetrazol ty thuc mi trng s dng l nc hoc khan nc.

58
 R' R' H R' N N
- H 2O
C O + H N N N R' N N N C N

R' R'
OH - N2

~R R'
H 2O
R' C NHR R' C N R R' C N R C N

O OH HN 3 R'

N R'
N
N
-H
R' R' C
N
N N N N
tetrazol
H

S tch nhm N2 v s dch chuyn R xy ra cng lc. Nhm dch chuyn l nhm v tr
trans vi nhm ra i. Khi tch loi 1 phn t nc, nhm ln hn s v tr trans vi nhm
diazonium. Do trong ceton khng i xng, th t di chuyn cc nhm nh sau:
t-Bu > Ph ~ i-Pr > Et > Me
Nh vy vi ceton, phn ng trong dung dch nc ging nh thm nguyn t N vo gia
CO v nhm alkil. Acid carboxilic trong mi trng acid mnh hoc acid Lewis chuyn v
thnh amin vi 1 nguyn t carbon t hn.
H - H 2O
R C OH R C OH R C OH 2 R C

O OH O O

HN 3 -H
H 3O - N2
RNH 2 + CO 2 R N R C N
C O R C N N N

O O

5. Chuyn v Beckmann
Chuyn v Beckmann l phn ng chuyn v ca oxim to thnh t aldehid hoc ceton, di
tc dng ca acid mnh hoc c mt PCl5, cho sn phm l amid th.
R' R' OH R' O
H2N-NH 2 H ~R H 2O
C O C N C N R' C N R R C
- H 2O
R
-H
R R NHR

Phn ng tng t chuyn v Schmidt, s tch OH di dng phn t nc xy ra cng lc

vi s dch chuyn R, trong nhm R v tr trans vi OH s dch chuyn. Khng c
cation nitrenium t do. Khuynh hng cc nhm dch chuyn ging nh trong phn ng
Schmidt.
2.1.3. S chuyn v n nguyn t xi
Khi xi c nhm xut ra i cng i in t lin kt, ta c h cha nguyn t xi thiu in
t. S chuyn v n nguyn t xi lm xi tr v trng thi bnh thng.
R R

C O C O + X

59
Nhm xut X thng l HO, RCOO... S xut v nhp thng xy ra cng lc v khng

c s to thnh cation R C O

1. Phn ng oxid ho Baeyer Villiger

Phn ng Baeyer Villiger xy ra khi cho aldehid hay ceton tc dng vi peracid trong mi
trng acid, c s gn thm nguyn t xy vo v tr gia nhm carbonil v nhm alkil hay
aril ca aldehid hoc ceton, cho sn phm l ester.
R1 R2 + R3 ~R2
C C O OH
R1 C O R2 + R 3COOH

O O
O

Ngi ta thy trong trng hp phn ng ca acetophenon c O carbonil nh du trong

phn ng vi acid m-cloroperbenzoic, sn phm cha O nh du trn nhm carbonil ch
khng phi trn phn alcol. Mt khc nghin cu ng v 14C cho thy phn ng c hiu ng
ng v. Nh vy s dch chuyn nhm phenil xy ra cng lc vi s tch nhm carboxil
trong giai on chm ca phn ng. C ch phn ng c th trnh by nh sau.
H
O O

AcOH O

- AcO O Cl
H O

Cl

O
H O
O Cl
O
~Ph HO
O +
O
O

Phn ng xy ra theo kiu chuyn v trong h thiu in t. Peracid c O hidroxil cng i

in t t do nh cht thn hch tc kch vo nhm C=O ca hp cht carbonil. S t ni
d li lin kt O-O lm xut hin O thiu in t (6 in t tng ha tr). S dch chuyn
nhm phenil cng s tng tc ca nhm OH lm O in t, cho sn phm l ester, trong
nhm dch chuyn nm trong phn alcol.
Phn ng thng dng vi acid peracetic, perbenzoic, c bit thun li vi CF3COOOH.
Tnh u tin dch chuyn cc nhm theo th t: alkil bc 3 > ciclohexil > aril > alkil bc 2 >
alkil bc 1 > metil. Cc nhm aril th: p-MeO-Ar > p-Me-Ar > p-Cl-Ar > p-Br-Ar > m-
MeO-Ar > p-O2N-Ar. Nhm th y in t lm tng, nhm th rt in t lm gim u
tin. Aldehid phn ng vi peracid cho acid.
RCHO + R'COOOH RCOOH + R'COOH

-Diceton c th enol ha khng cho phn ng, -diceton chuyn ha thnh anhidrid acid,
ceton vng thnh lacton.

60
 R 3COOOH
R1 C C R2 R1 C O C R2 + R 3 COOH

O O O O
O
O
RCOOOH
O + RCOOH

2. Phn ng oxid ha Dakin

Oxid ha Dakin l phn ng ca aldehid hoc ceton thm c hot ha bng nhm OH
v tr orto hoc para, vi peroxid hidro trong dung dch kim, cho sn phm l ester, b thy
phn trong mi trng phn ng thnh phenol.

H 2O 2, NaOH
OH CHO OH HO + HCOOH
45 - 50OC

Trong mi trng baz, peroxid hidro di dng mui Na tc kch thn hch vo nhm C=O
ca hp cht carbonil. S t d li lin kt O-O to nguyn t xi thiu in t. Nhm phenil
dch chuyn cng i in t lin kt n xi thiu in t to tm thiu in t mi trn C.
Tng tc ca O in tch m v C thiu in t cho sn phm l ester. Trong mi trng
kim v c un nh, ester b thy phn thnh phenol v mui ca acid formic.
O O
H ~Ar
OH OH OH O

H O H

O H OH O
HO
O

OH HO + HCOO

Bi tp
1. Theo c ch phn ng, chuyn v n nguyn t nit thiu in t c th chia thnh 2
nhm. Hy xp cc phn ng chuyn v n nit thiu in t thnh 2 nhm v cho bit
khc bit gia 2 nhm.
2. Ti sao trong s chuyn v n nguyn t N thiu in t, nhm dch chuyn u tin hn
l nhm c cha nhm y in t, v phenil u tin hn alkil?
3. Ti sao ni nitren khng to thnh trong qu trnh phn ng nh mt cht trung gian?
4. Trong chuyn v Hofmann, dung dch halogen trong xut rt thn li cho phn ng xy ra.
Hy phn tch tc dng ca halogen trong phn ng ny. T c th dng cht khc thay
th halogen trong phn ng ny c khng?
5. Ti sao chuyn v Lossen ch dng c cho acid hidroxamic O-acil ha m khng dng
cho acid hidroxamic RCONHOH?
6. Ti sao nhit phn azid acid khng nhn c nitren nhng quang phn li nhn c
nitren nh 1 cht trung gian?
7. Gii thch hin tng sau: acid dy di cho chuyn v Schmidt d dng hn acid thm,
ceton mch thng hoc vng d hn ceton thm.
61
8. Phn ng chuyn v Becmann lun cho sn phm l amid th. Ti sao sn phm amid
khng th khng to thnh?
9. Chuyn v Beckmann xy ra khi c s tch nhm OH ca oxim trong mi trng acid
di dng phn t nc. S tch nhm OH cn d dng hn nu chuyn nhm hidroxil
thnh nhm tosilat. Vit c ch phn ng chuyn v Becmann khi s dng clorur
benzensulfonil thay cho acid. T c th xut thay acid bng nhng cht phn ng no
khc?
10. Oxid ha theo Dakin dng cho aldehid hoc ceton thm c hot ha bng nhm OH
ti v tr orto hoc para. Nu aldehid hoc ceton thm khng c nhm hot ha th phn ng
c th xy ra nh th no?
11. V tr nhm dch chuyn thng quan trng hn th t u tin. Vit c ch 2 phn ng
sau thy r s quan trng .

a/ PhCOOOH

O O
O

b/ PhCOOOH
O

O O

62
Bui th tm
2.2. S chuyn v trong h thng giu in t
H thng giu in l h c cha nguyn t mang in tch m (anion). Chuyn v trong h
thng thiu in t thng xy ra trong mi trng acid v c s to thnh cation ca
nguyn t c 6 in t. Nguyn t thiu in t c coi l tm acid nn h bn trong mi
trng acid. Ngc li vi h thiu in t, h giu in t thng c to thnh trong mi
trng baz, thng l baz mnh, hidro linh ng b loi to anion. H giu in t c
coi l baz nn tn ti trong mi trng baz. H giu in t khng bn nn c bn ha
bng s chuyn v.
Z Z Z
baz
A B A B A B
-H
H

Nhm dch chuyn Z c tnh acid lm bn tm B.

2.2.1. Chuyn v Stevens
Chuyn v Stevens l chuyn v ca mui amonium bc 4 hay mui sulfonium di tc dng
ca baz mnh thnh amin bc 3 hay tioeter (mercaptan).
R1 R1
NaNH 2
A CH 2 N R2 A CH N R2

R3 R3

A l nhm rt in t (RCO, ROOC ...). A rt in t, cng vi N rt in t lm H ca

nhm metilen linh ng, di tc dng ca baz mnh b tch ra di dng proton, li i
in t lin kt trn C, to ilur, l h giu in t. S dch chuyn R3 lm trit tiu in tch,
cho c cu bn. Nhm di chuyn thng l nhm allil, benzil.
R1 R1 R1
NaNH 2 ~R 3
A CH 2 N R2 A CH N R2 A CH N R2

R3 R3 R3
ilur

Th d:

OH
(CH 3)2N CHCOPh (CH 3)2NCHCH 2OPh
(CH 3)2NCH 2COPh

PhCH 2 CH 2Ph
CH 2Ph

OH
PhCOCH 2SCH 3 PhCOCHSCH 3 PhCOCHSCH 3

CH 2Ph CH 2Ph CH 2Ph

2.2.2. Chuyn v Wittig

Chuyn v Wittig l chuyn v ca eter di tc dng ca baz rt mnh l alkil hay arillitium,
thnh alcol. H trong eter c tnh acid yu hn trong mui amonium hay sulfonium nn baz
dng mnh hn.
R 3Li
R 1 CH 2 O R2 R 1CH OLi + R 3H

R2

63
Di tc dng ca baz rt mnh, eter b tch proton thnh carbanion. Nhm metil tng tc
vi i in t p trn carbanion, chuyn v thnh alcol.

PhLi H 3O
CH 3 O CH 2Ph CH 3 O CHPh Li Li O CHPh OH CHPh
- PhH
CH 3 CH 3

2.2.3. C ch chuyn v Stevens v Wittig

Chuyn v Stevens v Wittig c im chung l tch proton trong mi trng baz to ra
carbanion, l h giu in t. Nhm dch chuyn tng tc bng vn o LUMO vi vn
o HOMO ca carbanion. n gin, ta xem R tch ra nh R v nm trong s tng tc
vi 2 tm mang in tch m l C v A (A l N, S hoc O). Vn o trng ca R c th l
sp2 hoc sp3, tng tc c th theo trc vung gc hay song song (theo Mebins). Trong
trng hp u cu hnh ca nhm di chuyn b nghch o, trong trng hp sau cu hnh
c bo ton.

R LUMO
C

C A C A HOMO

hay

Nhm s thy r l c 2 trng hp u khng th thc hin c do tr ngi lp th qu

ln. Do c th ngh phn ng phi xy ra trong 2 giai on: R c tch ra v gn vo
C. Trong trng hp phi nhn c sn phm tiu trin. Thc t cho thy sn phm
nhn c ch yu c lu gi cu hnh.

Cht Nhm dch chuyn % SP lu gi cu hnh

Chuyn v Stevens

PhCOC H _N Me2CH(Me)Ph CH(Me)Ph 97

CH 2=CHC H_N Me2CH(Me)Ph CH(Me)Ph 90

Chuyn v Wittig

PhC H-OC(Me)(Et)Ph C(Me)(Et)Ph 80 90

PhC H-OCH(Me)Ph CH(Me)Et 62

CH 2 =CHC H-OCH(Me)Et CH(Me)Et 74

Xut hin mu thun: phn tch tng tc vn o cho thy trng thi chuyn tip khng c
cu to vng 3, nhng thc nghim ng h trng thi chuyn tip vng 3. T gi thit
rng t dng ilur tch ra 1 trung gian c hot tnh rt mnh, mnh n ni phn ng rt
64
nhanh v cu hnh cha kp thay i. Trung gian c hot tnh mnh nht l gc t do. Thc
t cho thy trong cc phn ng chuyn v trn c s t ni ng li.

OH
(CH 3)2NCH 2COPh (CH 3)2N CHCOPh (CH 3)2N CHCOPh (CH 3)2N CHCOPh

CH 2Ph PhCH 2 PhCH 2 PhCH 2

(CH 3)2NCHCH 2OPh

CH 2Ph

C ch phn ng qua giai on to cp gc t do trn N v nhm benzil. C cho N 1 in t

t do v tr thnh gc t do. Gc t do benzil tng tc nhanh vi gc t do mi to thnh
cho sn phm chuyn v. Gc t do sinh ra trong cc phn ng ny c chng minh bng
ph cng hng t ht nhn.
Lin kt n k tm anion d dng t ni ng li. Cc phn ng chuyn v ny xy ra
nhit thp, chuyn v Wittig thc hin -60OC. Bnh thng c th ngh rng cc tng
tc in t xy ra nh sau.

ArCH O ArCH O ArCH O

R R R

Nhng thc t phn ng thng khng xy ra nh vy. y c dch chuyn 1 in t. Nu

thay cc mi tn bng mi tn 1 cnh biu din tng tc ca 1 in t, ta c bc tranh ca
phn ng. Gc t do R v ArCH c to thnh.

ArCH O R ArCH O R

Gc R dch chuyn n gc ArCH t c ly gn trong thi gian ngn, gc R cha kp sp xp

li. Cu hnh c bo ton.
2.2.4 Chuyn v Favorsky
Trong khi nghin cu -diclorceton, Favorski d nh iu ch -diceton bng phn ng
thy phn -diclorceton trong dung dch kim. Nhng thay v nhn c diceton, ng
nhn c acid metacrilic t cht u l metil--dicloretilceton.
Sau nhm ca Favorski p dng phn ng cho nhiu hp cht -haloceton khc v m ra
phn ng chuyn v mang tn ng. Chuyn v c cng b ln u vo nm 1895. Chuyn
v Favorski l phn ng ca baz thn hch vi -haloceton qua trung gian l ciclopropanon,
ty thuc baz thn hch cho sn phm l chuyn ha cht ca acid carboxilic. Vi baz l
hidroxid kim loi kim, alcoxid, amin, sn phm l mui ca acid carboxilic, ester, amid.

65
 R
R'O
R'O C C

O
R

HO
Cl O C C

R C Cl O
R

O R'NH 2
R'NH C C

H 2O2 + CO 2

C ch phn ng l ti tranh lun thi gian di. Ban u ngi ta cho rng phn ng bt
u bng s cng thn hch ca baz thn hch vo nhm carbonil.
X R R

R C C + OR' R'O C C R'O C C

O O X O

Nu phn ng xy ra theo c ch ny th t -clorbenzilmetilceton ch bin kim phi nhn

c acid -phenilpropionic. Thc t phn ng cho sn phm l acid -phenilpropionic.
Nh vy phn ng khng xy ra theo c ch ny.

PhCHCOCH 3 + HO PhCH(CH 3)COOH (khong xay ra)

Cl PhCH 2 CH 2COOH

Favorski xut c ch ngang qua trung gian ciclopropanon, nhng khi iu kin thc
nghim v l thuyt cha cho php chng minh. n nm 1951 Loftfield dng phng php
nguyn t C nh du chng minh c ch phn ng i qua trung gian vng 3.
HO * *
* O COOH + COOH
*
*
*

Cl

i-C 5H 11ONa
O COOC 5H 11 + COOC 5H 11
*
*
*

Cl

Phn ng bt u bng s tch proton v tr pha bn kia carbon mang clor, tip theo l th
thn hch ni phn t cng s ra i nhm xut clor, to thnh vng ciclopropanon. Baz thn
hch cng vo nhm carbonil, O y in t cng s m vng 3 cho sn phm phn ng.
Trong giai on u, ion alcoxid tc dng khng phi nh cht thn hch m nh baz, tch
ly proton. Sau ion alcoxid cng vo nhm carbonil ca ciclopropanon nh cht thn
hch, tham gia vo sn phm. Gia on chm ca phn ng l th thn hch ni phn t cho
trung gian l ciclopropanon. Do y l hp cht vng nh cng nn nh nng lng cao.
Tip theo l cng thn hch ca baz thn hch v m vng, do gii phng nng lng nhiu
nn phn ng xy ra nhanh. Ngi ta khng nhn thy c ciclopropanon t do trong qu
trnh phn ng.

66
 H

C C RO C C SN 2 C C

C Cl
- ROH
C Cl - Cl C
chm
O O
O

RO

ROH
C C C C C C
H

C C
C

O OR O OR O OR

Nu trung gian ciclopropanon khng i xng, s m vng 3 u i hn ti pha cho ra

carbanion bn hn
Cl

PhCH CH 2
RO PhCH 2CH 2COOR
Ph CH C CH 3
C
O
Cl
O
H 3C H 3C CH 3
H 3C C CH 3 RO C
H 3C C C CH 2
H 3C COOR
H 3C
C
O

Chuyn v Favorski lm hp vng haloceton vng.

Cl

EtO
COOEt

Nu phn ng trong dung dch km v c mt peroxid hidro, sn phm l alcen v thot kh

carbonic.

H 2O 2
C C C C + CO 2 + HO

C OH C

O O OH
O
O OH

C ch ngang qua trung gian ceton vng 3 khi -haloceton c H linh ng ti v tr .

Chuyn v Favorski dng nh cng xy ra khi ti C khng cha H.
CH 3 CH 3

HO
Cl C C Ph Ph C COO

CH 3 O CH 3

Cl Ph
EtO

C Ph COOEt

67
 y phn ng xy ra khng theo c ch qua trung gian ciclopropanon, m theo c ch
biu din ti trang 66 (c ch tranh ci v b ph nhn). Do theo c ch khng phi l
chuyn v Favorski nn phn ng c gi l chuyn v ging Favorski (quasi-Favorskii
rearrangement).
Bi tp
1. S chuyn v trong h thiu in t thng xy ra trong mi trng acid hoc trung
tnh, nhng ti sao s chuyn v trong phn ng oxid ha Dakin li xy ra trong mi trng
baz?
2. Ti sao cho rng s chuyn v trong h giu in t khng i qua trng thi chuyn tip
l vng 3? Nu thc s c to thnh gc t do trong phn ng th chuyn v trong h thng
giu in t c c coi l chuyn v lin phn t khng?
3. Theo s chung ca phn ng chuyn v trong h giu in t, s chuyn v thng
i t h giu in t ny sang h giu in t khc. Nh vy phn ng phi thun nghch.
Nhng cc phn ng chuyn v Stevens, Wittig v Favorski u xy ra d dng v mt
chiu. Da vo c im c th ca 3 phn ng cho gii thch iu ny.
4. Chuyn v Stevens dng cho cc mui amonium v sulfonium c nhm A rt in t.
Nu khng c nhm rt in t th phn ng c xy ra khng?
5. Chuyn v Wittig c th thc hin nhit rt thp. Dng c im c ch gii
thch c im ny ca phn ng.
6. Ti sao c th xp chuyn v Favorski vo nhm chuyn v trong h giu in t kiu
1,2? Tm giu in t l tm no? Ch ra nhng khc bit trong c ch phn ng chuyn v
Favorski vi chuyn v Stevens v chuyn v Wittig.
7. chng minh c ch phn ng chuyn v Favorski, Loftfield thc hin phn ng vi
2-clorciclohexanon c C14 ti v tr 1 v 2. Kt qu phn tch cho thy trong sn phm c
50% C14 ti C nhm carbonil, 25% ti C v 25% ti C. Dng cc s liu trn chng
minh rng phn ng khng xy ra theo c ch tranh ci (trang 66), trong phn ng bt
u bng s cng baz thn hch.
8. Trung gian ciclopropanon khng i xng trong phn ng chuyn v Favorski c th
m vng ti 2 v tr v cho 2 sn phm. Nhng thc t ch nhn c 1 sn phm. Gii thch
s m vng trung gian ciclopropanon ca 1-chloro-1-phenylpropan-2-one v 3-chloro-3-
methylbutan-2-one trong dung dch alcoxid natri.
9. Vit cc phn ng sau.
a/ CH3COCCl2CH2CH3 + HO
b/ CH3CHBrCOCH2Br + EtO
c/ CH3CHBrCHBrCOCH3 + EtO
d/ CH3CH2CHClCOPh + EtO

HO
e/ CO

Br

68
 Bui th chn
Chng 3. Phn ng trn h thm
3.1. Tnh thm
Hp cht thm c dng ch cc cht c mi c tch ra t du thm, du chng ct than
... Ngy nay t thm c dng vi ngha hon ton khc. Tnh thm c hiu l kh
nng mt s hp cht khng no d cho phn ng th m kh cho phn ng cng, bn vi
cht oxid ha, vi nhit ... i din cho cc hp cht thm l benzen, cng thc phn t l
C6H6. Cc nguyn t carbon v hidro to vng 6 phng vi 3 lin kt i v 3 lin kt n.
C 6 nguyn t carbon u tng ng. di lin kt C-C l 1,397, gc ha tr 120O.
Lin kt ca cc nguyn t carbon to thnh do xen ph vn o sp2, 6 vn o p ca 6
nguyn t C to h in t khp kn do c s xen ph bn. S cng hng khp kn ny
m bo cho tnh khng c nh ca cc in t . Chnh h in t khp kn ny gii
thch tnh bn ca benzen.
Theo thuyt vn o phn t (MO), 6 vn o p ca 6 nguyn t C t hp thnh 6 vn o ,
trong 3 vn o lin kt v 3 vn o phn lin kt. Nm 1931 Huckel p dng thuyt vn
o phn t cho cc hp cht polien n vng cng hng phng (thuyt HMO) v a ra
quy tc xc nh tnh thm (quy tc Huckel). Cc hidrocarbon n vng cng hng phng
c tnh thm nu trong vng c (4n+2) in t . Theo HMO, mc nng lng cc vn o
p ca mt s vng polien nh sau.

Cc vn o di mc l vn o lin kt, s lp y cc vn o ny lm phn t bn.

Cc vn o nm ngang mc l vn o khng lin kt, in t trn vn o ny khng
lm tng cng nh khng lm gim tnh bn phn t. Cc vn o nm trn mc l vn
o phn lin kt, in t vn o ny lm gim tnh bn phn t. Theo thuyt HMO, trong
benzen c 6 in t p u nm trn vn o lin kt, do benzen bn v c tnh tr ha
hc. Ciclobutadien c 4 in t p phn b trn vn o lin kt v vn o khng lin kt,
trong 2 in t c thn. 2 in t ny lm phn t butadien khng bn, d cho phn ng
cng nh lin kt i C=C c lp.
Quy tc Huckel p dng tt cho cc hidrocarbon n vng, vng mang in tch, hp cht d
vng. i vi hidrocarbon a vng ngng t, quy tc Huckel c p dng nu cc lin kt
chung ca 2 vng khng gy nhiu lon ng k so vi 1 vng ln, m ch lm cho vng

69
phng. Xt naptalen v azulen trong so snh vi n vng c 10 C (vng [10]annulen).
Naptalen v azulen u c 10 in t cng hng khp kn v to vng phng. Lin kt
chung ca 2 vng lm tng tnh phng ca h, lm tng tnh khng c nh ca cc in t .
C naptalen v azulen u c nng lng thp hn [10]annulen, v u c tnh thm r rt.
Naptalen khng mu, nhng azulen c mu xanh dng m. Azulen ch yu tn ti di
dng lng ion gm anion ciclopentadienil v cation tropil.

Naptalen Azulen
i vi cc h c nhiu vng khc vic suy xt tng t. Ring cc vng c nguyn t C
chung 3 vng, quy tc Huckel khng p dng c.
Bn cnh tnh thm ngi ta cn c khi nim tnh khng thm v tnh phn thm. Tnh
khng thm l tnh khng thay i mc nng lng ca h khi trong h c s cng hng
khp kn. S phn thm l s tng mc nng lng (gim tnh bn) ca h khi c s cng
hng vng khp kn. Mt s th d (trch t: Carey F. A., Sundberg R. J. (2007) Advanced
Organic Chemistry, Part A: Structure and Mechanisms, 5th Edition, Prenum Press, New
York, trang 743).

H thm l h giu in t nn phn ng c trng l th thn in t. Trong iu kin khc

nghit hoc vi c cu c bit, h thm c th cho phn ng th thn hch.
3.2. Phn ng th thn in t
Phn ng th thn in t trong h thm c nghin cu y v s dng nhiu trong
cng nghip. Cc cht thn in t c chia ra thnh nhm thn in t mnh, va v yu.
3.2.1. Cht thn in t
- Cht thn in t mnh gm ion nitronium NO2, phc clor v brom vi acid Lewis
(FeCl3, AlBr3, AlCl3, SbCl5...), cc ion H2OCl, H2OBr, RSO2, HSO3
- Cht thn in t va gm cc phc halogenur alkil v acil vi acid Lewis (RCl.AlCl3,
RBr.GaBr3, RCOCl.AlCl3...), phc ca alcol vi acid Lewis v Bronsted mnh (ROH.BF3,
ROH.H3PO4, ROH.HF...).
- Cht thn in t yu gm cation diazonium ArN2, iminium CH2=NH2, nitrosonium
NO, dioxid carbon CO2.

70
Cht thn in t mnh: tc dng c vi cc dn xut benzen c nhm th rt v y in
t. Cht thn in t va: tc dng c vi benzen v dn xut cha nhm th cho in
t (-NO2, -SO3H, -COR, -CN...) v halogen. Cht thn in t yu: ch tc dng c vi
dn xut benzen cha nhm th y in t mnh (-OH, OR, -NH2, -NR2, -O...). Bng di
y cho thy s to thnh mt s cht thn hch mnh, va v yu trch t ti liu: Carey F.
A., Sundberg R. J. (2007), Advanced Organic Chemistry, Part A: Structure and
Mechanisms, 5th Edition, Prenum Press, New York, trang 743.

3.2.2. C ch phn ng
S th thn in t trn h thm xy ra theo kiu cng tch. Cht thn in t ban u
tng tc vi cc vn o ca h thm, to thnh phc . Tip tc phn ng, cht thn
in t tin gn li 1 trong cc C v xc lp lin kt vi C ny. Carbon chuyn t lai ha
sp2 sang sp3, h thm b ph v, do nng lng h rt cao, h khng bn. a h v
trng thi bn, 1 proton c tch ra ngang qua phc v cho sn phm th.

71
 X
X X

+ X X H H + H

phuc

Khi cho lung kh DCl i qua dung dch benzen trong n-hexan -78oC, ngi ta nhn c
phc phn t vi t l l 1:1. Phc ny khng mu, khng dn in. Nh vy trong dung
dch khng c ion v mnh phn t mang in tch. Bng phn tch nhiu x tia X cc tinh
th phc benzen v cc hidrocarbon thm khc vi cc cht thn in t khc nhau, xc
lp cu to cho nhn qua vn o ca cc phc ny. y l phc . Cc aren l baz , c
th to phc kiu cho nhn vi cc acid Lewis cng nh DCl khng phn ly. Khi nhit
tng, phc nhanh chng b phn hy.
Khi cho AlCl3 vo dung dch DCl trong benzen hay benzen th, dung dch dn in v c
mu. S dn in chng t trong dung dch c ion hoc phn t mang in tch. Phn tch
ph cng hng proton v 13C cho thy c to thnh phc ion.

C6H6 + DCl + AlCl3 C6H6D AlCl4

y l phc . Phc to thnh nhit thp, khi tng nhit phc b phn hy. Phc
c th phn hy thnh sn phm hay cht u, ty thuc s tch cht thn in t hay tch
proton, mnh no tch d hn. Thng thng tch proton d hn nhiu, v trong nhiu
trng hp phc to thnh khng thun nghch. Vi cc aren v cht thn in t khc
nhau bn phc khc nhau.
Me Me
Me

H
BF3 0OC
Me BF4 Me C 2 H5
Me + C2H5F
- 80OC C 2H5

Me Me 90%
Me

Me Me Me

AgBF4 H
Me Me
BF4 Me COC 2 H5
+ C2H5COF
CH3NO2
COC 2 H5
- 60OC
Me Me Cl

Giai on chm ca nhiu phn ng th thn in t h thm l giai on to phc . Gin

nng lng tng qut cho thy c 2 phc trc v sau phc .
TC2
TC3

TC1 H E

TC4
Z
E
Z E
+ E
H
Z
Z E

+ H
Z

72
Thc t ng hc phn ng th thn in t trn h thm ty thuc trng hp c th. Cht
thn in t mnh c mc nng lng cao, trng thi chuyn tip mc gn cht u. Khi
ta c trng thi chuyn tip sm. Trng hp ny c trng cho cc phn ng ta nhit.
in tch dng phn b trong vng t, do t c s khc bit v tr phn ng trn vng
benzen c sn nhm th.Vi cht thn in t yu, trng thi chuyn tip mc gn phc ,
ta c trng thi chuyn tip tr. Lin kt to hon chnh, in tch dng phn b trong
vng v tp trung nhiu hn v tr orto v para i vi nhm th c sn trong vng
benzen. Phn ng thu nhit. Hnh biu din di y trch t ti liu: Carey F. A., Sundberg
R. J. (2007), Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th Edition,
Prenum Press, New York, trang 789.

Kho st hiu ng ng v gip lm sng t c ch phn ng. Vi tng phn ng c th,

hiu ng ng v khc nhau. Hiu ng ng v kH/kD hoc kH/kT ca mt s phn ng c
trch t ti liu: Carey F. A., Sundberg R. J. (2007), Advanced Organic Chemistry, Part A:
Structure and Mechanisms, 5th Edition, Prenum Press, New York, trang 790. Phn ng c
hiu ng ng v kH/kD hoc kH/kT khi giai on tch proton khi phc cho sn phm l
giai on chm.

73
Hiu ng ng v khng r rng trong phn ng nitro ha, halogen ha, trong khi phn ng
acil ha, sulfon ha, nitroso ha v ghp cp diazo c giai on chm l deproton ha. Hiu
ng ng v cho thy vi cc cht thn in t yu nh trong phn ng nitroso ha v ghp
cp diazo, vn tc phn ng ph thuc hon ton vo vn tc tch proton. Nhng trong 2
trng hp ca phn ng ghp cp diazo, nhm sulfon v tr 8 cho hiu ng ng v, trong
khi v tr 4 khng c hiu ng ng v. Chung quy c 4 loi c ch cho phn ng th thn
in t h thm, biu in bng gin nng lng trch t ti liu: Carey F. A., Sundberg
R. J. (2007), Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th Edition,
Prenum Press, New York, trang 791.

Trng hp (a), giai on xc nh vn tc phn ng l giai on hot ha cht thn in t.

c trng cho loi c ch ny l vn tc phn ng khng ph thuc vo nng hp cht
thm. Trong trng hp (b), giai on chm l giai on to thnh phc , trng thi chuyn
74
tip sm, vn tc phn ng ph thuc vo nng c cht thn in t v hp cht thm.
Trng hp (c) cng c giai on chm l to phc , nhng trng thi chuyn tr. Trong
trng hp (d) giai on chm l giai on tch proton v thm ha thnh sn phm, c
trng l hiu ng ng v ti v tr th.
Trong trnh by c ch phn ng th thn in t trn h thm ta nn lu s to thnh v
c cu cht thn in t v c cu phc .
3.2.3. Phn ng th thn in t trn benzen c 1 nhm th
Ti trng thi chuyn tip trc phc , gia benzen th v cht thn in t c phn b
in tch dng. Nu trng thi chuyn tip sm, in tch dng ch yu phn b trn cht
thn in t, nu trng thi chuyn tip tr, in tch dng ch yu trn vng thm. Nu
trn vng benzen c 1 nhm th, c th c 4 trng hp phc .
X X X
X E
H

E
H

E E H
orto meta para ipso

T cc phc ca v tr tc kch orto, meta v para, 1 proton c tch ra, nhng t phc ca
v tr ipso nhm tch ra l X di dng X. S th ipso c trng cho cc dn xut kim loi
ca benzen, v kim loi b thay th d hn hidro. i vi cc dn xut khc, s th ch xy ra
trn cc v tr orto, meta v para. Ta xt cc trng hp ny.
Benzen c 1 nhm th c th c hot tnh vi tc kch thn in t mnh hn hoc yu hn
so vi benzen khng th. Cc nhm th lm tng hot tnh vng benzen l nhm c hiu ng
y in t, do nh hng para v orto. Nhm th gim hot tnh l nhm c hiu ng
rt in t, do nh hng meta. Ngi ta chia nhm th thnh 2 loi:
- Nhm th loi 1 nh hng para v orto: OH, OR, OCOR,SH, SR, NH2, NHR, NR2,
NHCOR, -N=N-, CH3, CH2R, CHR2, CR3, CH2Cl, CH2OH, CH2NH2, CH2NR2, CH2COOH,
CH2CH2COOH, F, Cl, Br, I.
- Nhm th loi 2 nh hng meta: SO3H, NO2, COOH, COOR, CONH2, COCl, SO2R,
NO, CHO, COR, CN, CCl3, CF3, NH3, , NR3, PR3, SR2, SAr, CH2NR3, POR2,
B(OH)2
Mt s nhm th khng nh hng r rng nh CF3, CHCl2, CH2NO2, CH2CH2NO2,
CH2CH2NR3, CH2PR3, CH2SR2...
Nhm th loi 1, tr halogen, u tng hot vng benzen. Nhm tng hot mnh nht l O
trong ion phenolat. Nhm tng hot mnh l R2N, NHR, NH2, OH, OR, OAC,v SR. Nhm
tng hot yu l cc nhm alkil. cc halogen u lm gim hot h thm. Nhm th loi 2
u gim hot vng benzen, vn tc phn ng chm hn benzen, v thng ch cho th 1
ln.
Tnh nh hng cc nhm th c gii thch bng tnh bn ion arenonium (phc ) trung
gian. Nhm th c th lm bn hoc lm km bn cation ny, do s chn lc v tr phi
ph hp phc bn hn c. Ta xt cc phc trung gian c th c trong phn ng th thn
in t ca anisol, clorobenzen v nitrobenzen.

75
 OCH3 OCH3 OCH3 OCH3
E E E E

H H H H

OCH3 OCH3 OCH3 OCH3

H E H E H E H E

OCH3 OCH3 OCH3

E E E

H H H

Cc phc ca s th para v orto ca anisol c bn ha do c tng tc y in t ca

nhm MeO v trong 1 cng thc gii hn c tng tc trc tip ca C v nhm OMe, do
s th vo v tr para v orto trn anisol xy ra nhanh hn th trn benzen. Phc ca
th meta khng c s bn ha do trong cc cng thc gii hn khng c tng tc trc
tip ca C v nhm OMe. Do phn ng trn v tr meta xy ra nhanh hn so vi benzen,
nhng chm hn so vi phn ng ti v tr para v orto.
Cl Cl Cl Cl
E E E E

H H H H

Cl Cl Cl Cl

H E H E H E H E

Cl Cl Cl

E E E

H H H

Cc phc ca clorobenzen trong phn ng th ti v tr para v orto gn ging vi trng

hp anisol, ion cloronium trong 1 cng thc gii hn gp mt phn vo tnh bn ca phc .
Nhng do clor l nhm rt in t nn ion ny km bn hn ion oxonium trong trng hp
anisol. Do phn ng th ti v tr para v orto trn clorobenzen xy ra chm hn trn
benzen. Phc ca th meta c tnh km bn mnh do tng tc tnh in ca tm C mang
in tch dng vi u dng ca lng cc carbon clor. Do d vn tc phn ng trn v
tr meta chm hn vn tc phn ng trn orto v para.

76
 O O O O O O
N N N

E E E

H H H

O O O O O O
N N N

H E H E H E

O O O O O O
N N N

E E E

H H H

Cc phc trong s th thn in t ca nitrobenzen u c tng tc tnh in ca tm C

mang in tch dng vi u dng ca lng cc carbon NO2 do nhm nitro rt in t.
Do phn ng th ti tt c cc v tr ca nitrobenzen u chm hn phn ng vi benzen.
Phc ca th orto v th para c tnh km bn cao hn do trong 1 cng thc gii hn c
lin kt 2 tm mang in tch dng. Trong phc ca th meta 2 tm mang in tch
dng cch nhau 1 hoc hn 1 nguyn t C nn bn hn phc ca th orto v th para.
nh lng nh hng nh hng ca nhm th, ngi ta dng i lng vn tc ring f
(partial rate factors). Vn tc ring ti v tr orto, meta, para l t l vn tc phn ng th
thn in t ti 1 v tr tng ng trn benzen c 1 nhm th vi vn tc th trn 1 v tr
ca benzen khng th. f c tnh theo cng thc:
6 Kbenzen the (ty le san pham Z)
f =
y Kbenzen

trong y l s v tr tng ng trong benzen 1 nhm th.

V d: nitro ha toluen trong hn hp acid nitric v anhidrid acetic nhanh gp 23 ln benzen
trong cng iu kin, hn hp phn ng cha 63% sn phm orto, 34% para v 3% meta.
Vn tc ring tng v tr trong toluen trong phn ng ny c gi tr sau.
6 . 23 . 0,63
forto = = 43,5
2.1

6 . 23 . 0,03
fmeta = = 2,1
2.1

6 . 23 . 0,34
fpara = = 46,9
1.1
Cc con s ny cho thy vn tc phn ng nitro ha toluen ti v tr para nhanh hn nitro
ha trn 1 v tr ca benzen 43,5 ln, ti meta nhanh hn 2,1 ln v ti orto nhanh hn 46,9
ln. Vn tc ring ti cc v tr orto, meta v para ca mt s phn ng trn toluen c dn
77
trong bng sau (trch t ti liu: Carey F. A., Sundberg R. J. (2007) Advanced Organic
Chemistry, Part A: Structure and Mechanisms, 5th Edition, Prenum Press, New York, trang
788).

Vn tc ring cho bit tnh chn lc ca phn ng v ca cht nn. Tnh chn lc ca phn
ng v ca cht nn thng bin thin cng chiu. Cht thn in t mnh thng c tnh
chn lc thp vi phn ng v vi cht nn, v ngc li. Khi cht thn in t c tnh chn
lc cao, t l sn phm orto/para thng thp v rt t sn phm meta to thnh. Tnh chn
lc ca cht thn in t c tnh theo cng thc
fparatoluen
Sf = lg
fmetatoluen

Sf cao thng c trng cho cht thn in t yu, cht thn in t mnh c Sf thp. Bng
di y cho cc gi tr vn tc ring v tnh chn lc ca mt s phn ng th thn in t
trn toluen.

STT Phn ng Ktoluen/Kbenzen fo fp fm Sf

1 Brom ha: Br2/CH3COOH, 606 600 2420 5,5 2,644

25OC

2 Clor ha: Cl2/CH3COOH, 344 6117 820 4,95 2,219

25OC

3 Acetil ha: CH3COCl, AlCl3, 128 4,5 749 4,8 2,195

ClCH2CH2Cl, 25OC

4 Benzoil ha: PhCOCl, AlCl3, 117 32,6 626 4,9 2,107

ClCH2CH2Cl, 25OC

5 Deuteri ha: D2O, CF3COOD, 156 253 421 3,8 2,044

70OC

6 Proton ha: HF, BF3, heptan, 59,5 103 145 3,1 1,670
20OC

78
 7 Brom ha: HOBr, HClO4, dd. 36 76 59 2,5 1,373
50% diocxan/nc, 25OC

8 Clor ha: HOBr, HClO4, dd. 20,6 134 32 4,0 1,311

50% diocxan/nc, 25OC

9 Nitro ha: HNO3/CH3NO2, 20,5 38,9 45,7 2,3 1,363

25OC

10 Sulfon ha: PhSO2Cl, AlCl3, 7,7 6,8 30,2 2,1 1,160

25OC

11 Thy ngn ha: Hg(OAc)2, 6,5 5,7 23 2,2 1,014

AcOH, 25OC

12 Metil ha: CH3Br, GaBr2, 5,5 9,5 11,8 1,7 0,842

toluen, 25OC

13 Isopropil ha: Me2CHBr, 1,75 1,8 5,1 1,4 0,554

GaBr3, toluen

14 t-Butil ha: Me3CBr, GaBr3, 1,6 0,0 6,6 1,6 0,625

toluen, 25OC

Theo chiu t trn xung tnh chn lc gim dn, hot tnh cht thn in t tng dn. Vi
cht thn in t yu, trng thi chuyn tip tr c cu to gn ging phc . Lin kt ca
carbon ca cht thn in t vi vng thm rt cht ch, phn ln in tch dng phn b
trong vng thm. Do vng thm c sn nhm th nn tnh dng in ti cc v tr khc
nhau c gi tr khc nhau ln. Trong trng hp ny nhm th trong vng thm nh hng
mnh ln vn tc phn ng ti cc v tr phn ng ca vng thm, ni cch khc, tnh chn
lc ca tc cht cao. Vi cht thn in t mnh, trng thi chuyn tip to thnh sm, cu
trc trng thi chuyn gn cht u hn phc . in tch dng phn b ch yu trn cht
u, trong vng thm khng nhiu, do s khc bit v tnh dng in ca cc v tr trn
vng thm khng nhiu. Nhm th nh hng t ln s khc bit vn tc phn ng ti cc v
tr ca vng thm, ni cch khc, tnh chn lc ca tc cht thp.
3.2.4. Mt s phn ng th thn in t trn h thm
1. Phn ng nitro ha
C nhiu tc nhn nitro ha, thng s dng hn c l acid nitric trong hn hp vi acid
sulfuric hay acid nitric trong dung mi hu c nh acid acetic, nitrometan... Ngoi ra c th
dng mui nitronium nh NO2BF4, acetilnitrat AcONO (anhidrid to thnh khi cho acid
nitric phn ng vi anhidrid acetic).
Benzen khng th phn ng vi hn hp acid nitric v acid sulfuric m c 45 50OC.
Cht thn in t trong cc tc nhn nitro ha l ion nitronium NO2. Ion nitronium to
thnh trong hn hp acid nitric v acid sulfuric hoc khng c acid sulfuric.

2H2SO4 + HNO3 NO2 + 2HSO4 + H3O

3HNO3 H3O + NO2 2NO3

Nitro ha c th coi nh trn 2 giai on.

79
 NO 2
H NO 2
-H
NO 2 +

Z Z

Giai on chm ca phn ng c th l giai on to thnh cht thn in t hoc giai on

to phc , ty thuc hot tnh cht nn.

Phn ng nitro ha t nhy vi nhm alkil trong vng benzen. Toluen b brom ha nhanh
gp 600 ln so vi benzen, nhng b nitro ha ch nhanh hn 27 ln. Chng t trng thi
chuyn tip ca nitro ha l chuyn tip sm, ngha l gn ging cht u hn phc .
Trong hn hp HNO3 H2SO4 tnh chn lc phn ng v chn lc v tr rt thp. Vi cc
hn hp nitro ho c nng ion nitronium thp nh HNO3 CH3NO2 hay HNO3
(CH3CO)2O, tnh chn lc tng dn, khc bit trong vn tc phn ng ca cc cht nn khc
nhau tng ln. Nu cht nn c nhm th gim hot, nng lng hot ha tng ln, trng thi
chuyn tip dch chuyn ra xa. Khi y tnh chn lc vi cht nn tng ln. p-Nitrotoluen
khong 200 ln hot tnh hn nitrobenzen. Nh vy nh hng ca nhm metil trong trng
thi chuyn tip tng ln 10 ln (xem bng trang trc trch t ti liu: Carey F. A.,
Sundberg R. J. (2007) Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th
Edition, Prenum Press, New York, trang 798)
2. Halogen ha
Trong phn ng halogen ha aren, hot tnh halogen gim dn theo dy: Cl2 > Br2 > I2. Cht
thn in t c th l halogen phn t, phc halogen vi acid Lews. Cc acid hipohalogen
(ClOH, BrOH, IOH) l tc nhn halogen ha yu, nhng trong mi trng acid l cc tc
nhn hologen ha mnh. Thng dng dung dch Cl2 v Br2 trong acid acetic. Halogen phn

80
t dng cho cht nn hot tnh cao, vi cht nn hot tnh thp cn c xc tc acid Lewis
hoc acid Bronsted.
H H

Cl.....Cl.....FeCl3 Cl FeCl 4
+ Cl Cl + FeCl 3

Clor v brom trong acid acetic phn ng vi trng thi chuyn tip tr, gn phc . Tnh
chn lc phn ng halogen ha cao. Vn tc ring fp ca brom ha toluen khong 2400,
trong khi ca nitro ha toluen khong 50. Khi c mt Cl hoc Br trong vng benzen, vn tc
halogen ha tip theo gim xung 7 8 ln, khc vi phn ng nitro ha, vn tc a nhm
nitro th 2 gim 107 ln. Do phn ng clor ha v brom ha thng cho sn phm di- v
trihalogen. Vi cc aren c nhm th gim hot, halogen ha c tnh chn lc vi cht nn
cao. Brom ha benzen, toluen, anisol khng cho thy c hiu ng ng v. Nhng brom ha
dn xut cng knh ca anisol nh dn xut N,N-dimetilanilin hay 1,3,5-trialkil cho thy c
hiu ng ng v. Hiu ng ng v trong h cng knh thng do cc yu t lp th. C th
brom kch thc ln kh chim v tr phng do cn tr ca nhm th ln. Cng c th nhm
th ln cn tr dung mi hay baz tch proton.

81
Bui th mi
3. Alkil ha Fiedel Crafts
Alkil ha aren trong s c mt xc tc l acid Lewis hoc acid proton gi l alkil ha theo
Friedel Crafts. Aren c th c alkil ha bng cc tc nhn halogenur alkil, alcol v alcen
trong s xc tc ca acid Lewis. Hot tnh xc tc ca acid Lewis th t trong dy: AlBr3 >
GaBr3 > AlCl3 > GaCl3 > FeCl3 > SbCl5 > TiCl4 > BF3 > BCl3 > SnCl4 > SbCl3. Tc nhn
thng dng l halogenur alkil v xc tc thng dng l AlCl3.
Acid Lewis tng tc vi halogenur alkil, to phc phn cc trong C mang 1 phn in
tch dng. Phc to thnh tng tc nh cht thn in t vi aren. C th c s to thnh
ion carbenium nu gc alkil c cu trc thun li, th d cation t-butil.
AlCl3
R X R X AlCl3 R + AlCl4
R

+ R AlCl4 H
+ AlCl3 + HCl
AlCl4

Alkil ha theo Friedel Crafts c tnh chn lc phn ng v tc cht thp, trng thi chuyn
tip sm. phn ng ca halogenur alkil gim dn theo dy: Ph3CX > Ph2CHX >
PhCH2CX > CH2=CHCH2X > R3CX > R2CHX > RCH2X > CH3X. Kh nng to phc ca
halogenur vi acid Lewis gim mnh t flourur, clorur, bromur n iodur, v y cng l
th t hot tnh ca halogenur. Do iodur alkil khng c dng lm tc nhn alkil ha.
S khc bit trong hot tnh ln n ni c th alikl ha chn lc u alikl c F trong s c
mt Br trong cng phn t.
BF3
C 6H 6 + FCH 2CH 2Br C 6H 5CH 2CH 2Br
20 O C
4h (94%)

Alkil ha theo Friedel Crafts c 3 hn ch.

- Sn phm alkil ha c hot tnh vi cht thn in t cao hn cht u nn thng xy ra
s a alkil ha. gim a alkil ha ngi ta dng lng d aren nh dung mi.
- Trong qu trnh phn ng tc nhn alkil ha thng b ng phn ha, do cho nhiu sn
phm.
CH 2CH 2CH 3 CH 3CHCH 3

AlCl3, C 6H 6
+ CH 3CH 2CH 2Cl +
50O C

(35%) (65%)

Clorur isopropil sinh ra trong phn ng do clorur n-propil ng phn ha. Clorur alkil bc 2
hot tnh hn alkil bc 1 nn sn phm isopropil nhiu hn sn phm n-propil.
- Trong sn phm alkil ha thng c chuyn v. Metil ha toluen cho hn hp cc ng
phn para, meta v orto. Trong mi trng phn ng c HCl v acid Lewis, sau mt thi
gian ch c mt sn phm l ng phn meta. Cc phn ng chuyn v l qu trnh thun
nghch, ng phn meta l ng phn bn hn nn sau mt thi gian trong hn hp phn
ng ch c ng phn meta.

82
 CH 3

CH 3 H CH 3
-H
H

H ~ CH 3 CH 3
CH 3

-H
CH 3 H
CH 3 CH 3
CH 3
CH 3
CH 3 CH3

Alcol v alcen trong s c mt acid mnh c th lm cht thn in t cho phn ng alkil
ha.

R 3COH + H R 3CH 2OH 2 R 3C

R 2C=CHR' + H R2CCH 2R'

S to thnh cation carbenium c chng minh bng ph NMR.

Cc aren c nhm th rt in t nh NO2, NO, CN, COOR... khng cho phn ng alkil ha
theo Friedel Crafts. Amin thm, phenol cng khng cho phn ng alkil ha theo Friedel
Crafts v acid Lewis to phc cho nhn vi N v O lm gim hot aren.
4. Acil ha Friedel Crafts
a nhm acil vo h thm bng tc nhn acil ha di tc dng xc tc ca acid Lewis gi
l acil ha theo Friedel Craft. Tc nhn acil ha l halogenur acil v anhidrid acid. Cc
cht ny tc dng vi acid Lewis to phc kiu cho nhn vi t l 1:1 v 1:2. Tc nhn thn
in t c th l phc cho nhn hoc ion acilium.
O

R C X
+ MX n R C O + MX n-1
O O

R C X + MX n R C X MX n

Giai on chm ca phn ng l tc kch ca 1 trong cc cht thn in t (RCO ,

RCOCl.AlCl3) vi aren. Tc cht ph thuc vo iu kin c th ca phn ng. Khi acil ha
aren bng clorur acid, xc tc AlCl3, trong dung mi phn cc khng proton (nitrobenzen,
nitrometan), cht thn in t l ion acilium. Trong dung mi phn cc nh (clorur metilen,
diclorometan, tretachorur carbon) cht thn in t l phc. Halogenur acid thm to thnh
mui acilium d hn halogenur acid dy bo. Vi phc cho nhn, c ch phn ng m t
nh sau.

Ceton thm baz hn halogenur acid, do to phc bn hn vi acid Lewis. Do acil ha

bng halogenur acid cn nhiu hn 1 ng lng xc tc, cn acil ha bng anhidrid acid
cn 2 mol acid Lewis, v c 2 O carbonil.
chn lc trong phn ng acil ha khng cao (xem bng trch t ti liu: Carey F. A.,
Sundberg R. J. (2007) Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th

83
Edition, Prenum Press, New York, trang 812). Theo s liu trong bng, ion alkilacilium
(acetil, propionil) c t l o/p thp hn cc ion thm. Nu chn lc ph thuc vo cc yu
t lp th, kt qu phi ngc li. C th cho rng i vi cc ion acilium thm, cht thn
in t l ion acilium, cn trong trng hp dy bo c phn ng ca phc cng knh ca
alkil halogenur vi acid Lewis.

i khi phn ng acil ha theo Friedel Crafts c hiu ng ng v yu. Hiu ng ng v

chng t giai on tch proton khng hon ton nhanh hn s to thnh phc , v c
trng hp phc to thnh thun nghch.
Acil ha theo Friedel Crafts khng c 3 hn ch nh trong phn ng aklil ha. Phn ng
th 1 ln v ceton thm khng th phn ng tip v b gim hot. Phn ng khng km ng
ha v chuyn v. Tc nhn acil ha mnh nht l anhidrid acid hn tp ca acid carboxilic
v acid trifluorometansulfonic thng c iu ch trc tip trong hn hp phn ng. Tc
nhn ny acil ha benzen v cc aren khng cn xc tc.
5. Ghp cp diazo
Ion diazonium l cht thn in t yu, ch phn ng c vi aren c nhm y in t
mnh.
O
O

ArN N +

N NAr

Ion arildiazonium to thnh khi diazo ha amin thm, bn nhit thp. Ion nitrosonium
tng tc nhm amin cng s tch 1 phn t nc.
H

ArNH 2 + H
HONO ArN N O + H 2O

H
ArN N O ArN N OH ArN N + H 2O

84
Aril vi nhm th rt in t lm tng tnh thn in t, nhm y in t lm gm tnh thn
in t. c im c ch phn ng ghp cp diazo l trong iu kin xc nh giai on xc
nh vn tc phn ng l giai on tch proton. iu ny c xc nh bng hiu ng ng
v. Mt khc phn ng c xc tc bng baz. Do cc hp cht c th phn ng ghp cp
diazo khng nhiu nn khng c s liu v tnh chn lc ca phn ng. D sao c th d
on rng phn ng c tnh chn lc cao.
3.3. Phn ng th thn hch
Phn ng th thn hch trn h thm c th biu din nh sau.
N

Nu h thm c nhm th X rt in t, h thm tr nn ngho in t v c th cho phn

ng th thn hch. ta ni h thm c tng hot i vi tc kch thn hch. Trong iu kin
khc nghit (nhit cao, baz mnh) v vi cht thn hch mnh, h thm c th cho phn
ng th thn hch m khng cn c nhm th tng hot (rt in t).
3.3.1. Phn ng th thn hch trong h thm hot ng
H thm hot ng l h thm c 1 hoc nhiu nhm rt in t nh NO2, NO, RSO2, N2,
CN... C nhiu cht thn hch c th cho phn ng nh HO, RO, RS, RNH2, NH2NH2...
Ging nh trong phn ng th thn in t, ban u c tng tc lin phn t cho cht trung
gian c c cu ging phc (phc ipso). Tuy nhin phc ny khng mang in tch
dng m mang in tch m. Ta gi phc anion. Nm 1902 Meisenheimer phn lp c
phc anion t 2,4,6-trinitrophenetol vi ion metilat.
OC 2H 5 OCH 3
C 2H 5O OCH 3

O 2N NO 2 O 2N NO 2 O 2N NO 2

CH 3O - C 2H 5 O

NO 2 NO 2 NO 2

Ph nhiu v tia X cho thy phc phng c cc nhm nitro nm trong mt phng vng
benzen, 2 nguyn t O ca 2 nhm metoxil nm trong mt phng vung gc. Gc bng
gc t din, gc bng 100O.

Phc anion c tnh bn ph thuc vo tnh khng c nh (chuyn ng t do ca in t)

ca 1 hoc mt s nhm rt in t.
Nu trn vng benzen ti v tr para v orto c 2 nhm th rt in t mnh (NO2, SO2R,
CN...) v nhm xut km (Z l H, OR, OAr...) th phc anion c th c lp hay nhn
dng. Nu nhm xut l halogen hay nhm OSO2R, cng nh nu ch c 1 nhm rt in t
mnh, phc khng nhn bit c do b nhanh chng chuyn thnh sn phm.

85
 Z Nu Z Nu O Z Nu Z Nu
Z Nu

NO 2 N NO 2 NO 2 NO 2
O

N NO 2 NO 2 NO 2 NO 2

O O

Z Nu O

N
O

N

O O

Nh vy c ch phn ng th thn in t trn h thm hot ng c th biu din trn 2

giai on: cng thn hch to thnh trung gian phc ipso v tch nhm xut cho ra sn
phm. Giai on chm ca phn ng trong phn ln trng hp l giai on cng thn hch.
Nu nhm xut l halogen, khc vi phn ng SN2, vn tc phn ng gim dn theo chiu: F
> Cl > Br ~I. Ta bit nng lng ct d li lin kt C F l ln nht nn giai on tch nhm
xut khng phi l giai on chm ca phn ng.
Nu phn ng th thn hch xy ra trn h thm c nhiu nhm xut, ta c nh hng phn
ng. Ta xt trng hp phn ng ca cc pentafluorophenil do F xut nhanh hn cc
halogen khc v bn thn 5 nhm F lm tng hot mnh vng benzen. C th ngh rng,
phn ng th thn hch hon ton ngc vi phn ng th thn in t, ngha l nhm nh
hng orto v para trong phn ng th thn in t th nh hng meta trong phn ng th
thn hch. Pentafluoronitrobenzen phn ng vi amoniac cho hiu sut 95% vi hn hp sn
phm gm 95% 2-nitro-3,4,5,6- v 4-nitro-2,3,5,6-tetrafluoroanilin.
NO 2 NO 2 NO 2

F F F NH 2 F F

NH 3
+

F F F F F F

F F NH 2

Cc nhm NH2, OCH3, O, cng nh CH3 nh hng meta. Fluor v halogen nh hng
meta.
F F

F F F OMe

+ MeO

F F

F F

F OMe

+ MeO

F F

86
nh hng i khi b nh hng bi yu t lp th. Khi un trong ng nghim kn hn hp
2,5-dinitro-meta-xilen vi dung dch amoniac c s thay th nhm nitro ti v tr 2 "cht
chi" ch khng phn ng ti v tr 5 trng tri.
NO 2 NH 2

Me Me Me Me

+ NH 2 + HNO 2

NO 2 NO 2

Nhm nitro ti v tr 2 do yu t lp th vi 2 nhm metil bn cnh nn khng cng phng

vi vng benzen, do khng lm bn phc anion nu s th xy ra ti v tr 5. Phn ng
tng t xy ra vi 2,3-dinitrotoluen.
Me Me

NO 2 NH 2

+ NH 2 + HNO 2

NO 2 NO 2

3.3.2. Phn ng th thn hch trong h thm khng tng hot

Halogenur aril c trng t nht 1 v tr orto cho phn ng th thn hch vi cht thn hch
mnh. Cht thn hch mnh ng thi l baz mnh, tch H linh ng nht l ti v tr orto
vi halogen. Carbanion to thnh nhanh chng tch halogen cho ra trung gian khng mang
in tch c hot tnh rt cao. Trung gian ny gi l aryn, c ch c tham gia trung gian ny
gi l c ch aryn, thng l benzyn.
X X

-X
+ Nu
- HNu

Z Z Z

Cc h thm khng tng hot khi c mt cht thn hch mnh hoc trong iu kin nhit
cao cho phn ng th thn hch theo c ch benzyn. Di y mt s th d.
Me Me Me

Cl OH

350 -400 O C
+ NaOH +
ap suat
OH
Cl NH 2

NH 2

NH 3
+ KNH 2 +
long
- 33O C

Me Me Me

87
 Cl OH OH

* *
NaOH *
340 OC

(58%) (42%)

Hn hp sn phm to thnh cho thy trung gian benzyn cho phn ng vi cht thn hch ti
2 v tr ca lin kt 3.
Carbon trong c cu benzyn c lai ha sp, ngha l c gc 180O. Nhng trong vng 6 khng
th c gc ha tr 180O. C th ngh rng lin kt th 2 ca benzyn nm trn mt phng
ca vng benzen c th c to thnh bng xen ph ca vn o sp2. S xen ph ny yu
hn nhiu lin kt thng thng.

Benzyn c hot tnh rt cao nn khng th tch v c lp c. S tn ti ca benzyn ch xc

nh c bng phng php ph. Benzyn nhanh chng cng cht thn hch k c cht thn
hch yu, v chn lc thp. phn ng ca benzyn gim dn trong cc cht thn hch:
RS > Ph3C > PhCC > ion enolat > PhO ~I > Br > Cl > ROH ~H2O.
Khi cho hn hp bromobenzen v o-deuteribromobenzen lng bng nhau phn ng vi
lng thiu amidur, ngi ta thy trong aren khng phn ng lng deuteribromobenzen
nhiu hn bromobenzen. Nh vy deuteribromobenzen c phn ng km hn
bromobenzen, ngha l H hay D c tch ra bng NH2 trong giai on chm ca phn
ng.
Br

NH 2 NH 2
Br
H (cham) - Br NH 2 /NH 3

H
NH 2
Br
(cham)

Aryn th cho cng thn hch ti 2 v tr khc nhau c th vi vn tc khc nhau. Khi cho
amidur kali trong amoniac lng phn ng vi orto-, meta- hay para-halobenzen th, ch c 2
benzyn to thnh. T 2 benzyn c th c 4 carbanion (xem hnh trang sau).
T dn xut orto v para ch c 1 benzyn to thnh l I v II, t dn xut meta c c 2
benzyn. Mi benzyn cng cht thn hch cho 2 trung gian carbanion. Carbanion no bn
hn th u tin to sn phm hn. Do trong carbanion, vn o cha i in t t do trn C
mang in tch m nm trn mt phng vng benzen nn khng c cng hng vi h in
t ca benzen. Do cc nhm th nh hng ti tnh bn ca carbanion bng hiu ng
cm. Cc nhm I lm bn carbanion IV hn III v VI hn V. Cc nhm +I, ngc li, lm
bn carbanion III hn IV v V hn VI.

88
 NH 2
Hal NH 2

NH 3

NH 2 X
X X NH 2 orto
orto III

Hal NH 2
NH 2
X NH 3
I
IV X

NH 2

X
meta
NH 3 X
meta
NH 2

NH 2 X
Hal V
X
II

H 2N H 2N
X
para NH 3

X X
VI para

Hiu ng cng hng ca nhm th, tuy khng quan trng bng hiu ng cm, cng c vai
tr trong tnh bn carbanion. Nu cht thn hch c i in t t do (trong trng hp ny
l nhm amin) v nhm th c hiu ng R, c th c cng hng ca i in t t do vi
nhm th, lm gim nng lng trang thi chuyn tip. Bng di y hiu sut phn ng
(%) XC6H4Br vi KNH2/NH3.

orto-XC6H4Br para-XC6H4Br
X
orto meta meta para

F <1 > 99 20 25 75 80

CN 10 15 85 > 90 05 95 100

OCH3 05 95 100 45 50 50 55

CH3 55 45 60 40

O 85 90 10 15 100 0

F l nhm th I mnh, cho hu nh sn phm meta (qua I) v nhiu para (qua II). CN c I
ngang vi F nhng ng thi c R mnh. Cng hng ca nhm NH2 vi CN lm tng tnh
bn anion VI m khng lm tng tnh bn anion V. Nh vy c hiu ng cm v cng hng
u thun li cho s to thnh sn phm meta t II. T I, cng hng ca CN vi NH2 trong
III m khng c trong IV, nhng trong trng hp ny hiu ng cm quan trng hn. Nh
vy, vi nhm th CN, sn phm para t II nhiu hn sn phm meta t I. Nhm metoxil
tng t F, nhng hiu ng yu hn. Nhm metil c hiu ng +I yu, O c +I mnh v +R
mnh nn c nh hng ngc vi CN.

-----------HT----------

89