QUY LUT TH ELECTROPHIN

VO VNG BENZEN
Ngi bin son:
Hoavang06
BENZEN (C
6
H
6
)
Vng benzen l mt vng hp bi 6 nhm C-H, mi nguyn t C
cn li mt ha tr;
Cc nguyn t C s dng ha tr ny to thnh 3 ni i ging nh
xiclohexadien.
3 ni i ny khng c nh m c s chuyn ch thng xuyn
gia cc ni n v ni i to thnh vng khp kn.
t- ng - ng v i
Cng thc Kekule (1865):
BENZEN (C
6
H
6
)
Quan nim hin i v cu trc ca benzen:
Benzen c cu to vng ng phng, 6 nguyn t C v 6 nguyn t H
nm trn mt phng l lc gic u.
Su nguyn t C trong benzen u trng thi lai ha sp
2
to thnh
mt phng s. Mi nguyn t C cn mt electron p cha lai ha xen ph
hai pha vi mc nh nhau to thnh h thng electron p gii to u
trn ton b phn t. Vng benzen l mt h lin hp bn vng v mt
nhit ng hc (nng lng thm ha E = 36 kcal/mol).
+
-
+
-
+
-
+
-
+
-
Phn ng th electrophin vng benzen (S
E
Ar)
Benzen tiu biu cho cc h thng thm, c im v cu trc ca benzen th
hin cc c im v tnh cht:
- Khuynh hng i vo phn ng th chim u th do phn ng th h
thng lin hp c bo ton.
- Khuynh hng i vo phn ng cng gim do phn ng cng h thng lin
hp b ph v.
Phn ng th electrophin S
E
Ar l phn ng c trng quan trng ca vng
benzen. Phn ng tng qut:
xc t c
H
+ E Y
-
s s
+
E
+ H Y
Tc nhn electrophin l cation E
+
hoc phn t E-Y.
Cc phn ng th S
E
Ar u cn s c mt ca cc cht xc tc.
Vai tr ca cht xc tc l lm tng qu trnh to tc nhn electrophin.
C ch phn ng th S
E
Ar
Phn ng xy ra theo 2 giai on:
Giai on 1: Tc nhn electrophin tn cng vo h thng electron p ca nhn thm
to thnh mt phc p; tip phc p chuyn thnh phc s:
E
(tr ng th i chuyn tip)
E
phc p phc s
H E
+
E
(tr ng th i chuyn tip)
E
phc p phc s
H E
+
Giai on 2: phc s l mt cation khng bn vi 4 electron p gii ton trn 5 nguyn
t C; nguyn t C th su ca vng lin kt vi E trng thi lai ha sp
3
. Phc s c
bn ha theo 2 cch:
+ Cng anion Y
-
to thnh h thng vng xiclohexadien (to sn phm cng)
+ Tch proton to li h thng electron p ca vng thm (to sn phm th).
E
(tr ng th i chuyn tip)
E
phc p phc s
H E
+
H
H
E
Y
(sn phm cng)
E
1. (+ Y )
2. (- H )
(sn phm th) phc s
H E
+
Khuynh hng
tch proton H
+

c u tin hn
do c mc nng
lng thp hn.
Mt s phn ng th S
E
Ar
Halogen ha
Benzen
Br
2
/FeBr
3
Brom benzen
Br
+ HBr
Br
2
+ FeBr
3
Br + [FeBr
4
]
C ch:
+ H
+
Br
Br
phc p phc s
H Br
+
Br
Nitro ha C ch:
Benzen
Nitro benzen
NO
2
+ H
2
O
HNO
3
/H
2
SO
4
HNO
3
+ H
2
SO
4
NO
2
+ 2HSO
4
+ H
2
O
NO
2
N
O

O

+

N
O

O

HSO
4
-
phc p phc s
+
H NO
2

Sunfo ha
C ch:
+ H
2
O
Axit benzen
sunfonic
SO
3
H
Benzen
H
2
SO
4
H
2
SO
4
SO
3
+ H
3
O + HSO
4

NO
2
N
O

O

+

N
O

O

HSO
4
-
phc p phc s
+
H NO
2

O

+

S
O

O

-
s
:
:
:
:
:
:
:
s
+
-
s
-
s
SO
3
phc s
+
H SO
3

HSO
4

SO
3
H
H
+
Mt s phn ng th S
E
Ar
Ankyl ha theo
Friedel-Crafts
C ch:
+ R - X
Benzen
(R : gc ankyl
X : halogen)
Alkyl benzen
R
AlX
3
khan
R X AlX
3

..... .....
s
+
s
-
R
+ H - X + AlX
3

AlX
4

+
R H
R - X + AlX
3
R X AlX
3

..... .....
s
+
s
-
Dng ankyl halogenua lm tc nhn ankyl ho
di s c mt ca cht xc tc Liuyt:
C ch:
Axyl ha theo
Friedel-Crafts
+ HX
Benzen
(R : gc ankyl
X : halogen)
+ X - C - R
O

AlX
3
khan C R
O

Aryl alkyl xeton
s
+
s
-
R - C - X + AlX
3

O

R C O AlX
3

.....
X

:
:
R X AlX
3

..... .....
s
+
s
-
R
+ H - X + AlX
3
AlX
4

+
R H
C
+ H - X + AlX
3

s
+
s
-
R C O AlX
3

.....
X

:
:
R O
+
C H
O
R
AlX
4

Tc nhn axyl ha thng dng l cc axyl
halogenua RCOX hoc cc anhydrit axit (RCO)
2
O:
Quy lut th S
E
Ar
1. nh hng ca nhm th n s th S
E
Ar:
Mt nhm th R c sn nhn thm c nh hng n v tr ca cc nhm
vo sau gi l nhm nh hng.
xc t c
R
+
R
E E
S d nh vy l:

+ Khi benzen cha b th, mt electron 6 nguyn t C trong vng l
nh nhau vo ch thu c mt sn phm khi th ln u.

+ Khi th ln th hai, nhm th mi c th nh hng vo cc v tr ortho,
meta v para so vi nhm nh hng, s thu c mt hn hp 3 sn phm
ng phn c t l phn trm khc nhau.
Quy lut th S
E
Ar
Khi nhn thm c sn mt nhm th:
Da trn c s tc dng nh hng ngi ta chia lm 2 loi
nhm th:
Nhm th loi I: Tc dng nh hng nhm th vo sau u
tin vo v tr ortho v para so vi nhm th nh sn; ng thi
a s cc nhm th ny kch hot s th: gm cc nhm th
hot ha nhn thm (O-, -NR
2
, NH
2
, -OH, -OR, -NHCOCH
3
, -
CH
3
, -C(CH
3
), C
6
H
5
-) v mt s nhm th phn hot ha nhn
thm (halogen, -CH
2
Cl,)
Nhm th loi II: Tc dng nh hng nhm th vo sau u
tin vo v tr meta so vi nhm th nh sn; ng thi cc
nhm th ny th ng ha s th: gm cc nhm th phn
hot ha nhn thm (-NO
2
, -NR
3
, CF
3
, -CN, -COOH, -COOR, -
SO
3
H, -SO
2
R, -CHO, -COR.)
ortho
para
I
meta
II
OCH
3
ortho ortho
para
Loi I
CH
3
ortho ortho
para
Loi I
Loi I I
NO
2
meta
V d:
Quy lut th S
E
Ar
Khi nhn thm c sn nhiu nhm th:
Trng hp nhn thm c sn nhiu nhm th th v tr nhm th vo sau c
quyt nh bi nhm th c tc dng nh hng mnh hn.

Trng hp nhm th nh sn cng loi:
Da vo thc nghim lp c trt t nh hng cc nhm th nh sn cng loi
theo dy sau:
Nhm th loi I:
O
-
> -NR
2
> -NHR > NH
2
> -OH > -OR > -NHCOR > halogen (F > Cl > Br > I) >
> - OCOR > - R > -ankenyl
Nhm th loi II:
-NO
2
> -NR
3
> -CN > -COOH > -COOR > -SO
3
H > -CHO> -COR
OCH
3
Loi I
Cl
Loi I
ortho
para
Loi II
NO
2
COOH
meta
Loi II
OCH
3
Loi I
CH
3
Loi I
para
ortho
V d:
Quy lut th S
E
Ar
Trng hp nhm th nh sn khc loi:
Trng hp nhm th nh sn khc loi: nhm th loi I ng vai tr
nh hng nhm th vo sau.
V d:
NO
2
NHCOCH
3
Loi I
Loi I I
ortho
para
COOH
Loi I I
Cl
Loi I ortho
para
ortho
para
Loi I
OH
SO
3
H
Loi I I
NO
2
CH
3
Loi I
Loi I I
ortho
para
CH
3
Loi I
NO
2
Loi I I
para
CH
3
Loi I
NO
2
Loi I I
Tuy nhin quy lut th ch c tnh tng i v ngoi yu t in t cn ph
thuc vo cc yu t khng gian, iu kin phn ng, bn cht ca nhm
th
Gii thch quy lut th S
E
Ar
Quy lut th c xy dng trn c s thc nghim. Tuy nhin c th gii
thch quy lut th da trn c s yu t in t v ng hc.
Tu thuc vo bn cht nhm th m mt electron vng tng ln hoc
gim i, do kh nng phn ng th S
E
Ar s d dng hn hoc kh hn khi
khng c nhm th.

Phn loi nhm th nh vng:
Nhm th hot ha nhn thm: gm cc nhm th th hin cc hiu ng
dng (+C, +I, +H) y electron vo vng lm tng kh nng tham gia phn ng
SE ca vng benzen thun li cho phn ng S
E
Ar.
V d: cc nhm th O-, -NR
2
, NH
2
, -OH, -OR > -NHCOR

Nhm th phn hot ha nhn thm: gm cc nhm th th hin cc
hiu ng m (-C, -I) ht electron vo vng lm gim kh nng tham gia phn ng
S
E
ca vng benzen kh khn cho phn ng S
E
Ar.
V d: cc nhm th NO
2
, COOR, -CN

Trng hp nhm th c cc hiu ng I v C tc dng theo chiu
hng ngc nhau (v d halogen, -OH, -NR
2
(-I, +C) th da vo tr s s ca
phng trnh Hammet: cc halogen c tr s Hammet s dng th phn hot ha
nhn thm, cn nhm OH, -NR
2
c tr s s m th hot ha nhn thm.
Gii thch quy lut th S
E
Ar
trng thi tnh (trng thi c bn)
Nhm th nh sn loi I c hiu ng +I, +C : y electron vo vng. Do s lin hp
electron trong vng nn cc v tr ortho v para mt electron tng hn:
ortho
para
I
I

-
I I
I
Nhm th nh sn loi II c hiu ng -I, -C : ht electron t vng ra. Do s lin hp
electron trong vng nn cc v tr ortho v para xut hin in tch dng, v tr meta c
in tch dng nh nht:
meta
II

II
II II II
Nhm th c hiu ng -I, +C (v d cc halogen F, Cl, Br, I) ht electron
t vng ra lm xut hin in tch dng ln nht v tr ortho v para
nn tc nhn electrophin u tin vo v tr meta (l v tr c in tch dng
nh nht.
(X: halogen)
:
X

Gii thch quy lut th S

E
Ar
trng thi ng
Tc nhn electrophin tn cng to phc s. Nu vng benzen c sn mt
nhm th Y th c 3 phn ng cnh tranh nhau vo cc v tr ortho, meta, para.
V vy cn xt mc nng lng ca phc s do phn ng s u tin tao phc c
nng lng thp hn.
Do phc s l mt tiu phn giu nng lng nn mc nng lng ca n
cng thp nu in tch dng gii to cng nhiu. Bn cht ca nhm th nh
sn Y ng vai tr ln trong vic gii to in tch dng trn phc s.
ortho
para
Y
E +
meta
s
o
s
m
Y
E
H
Y
E
H
s
p
Y
H
E
+
+
+
Gii thch quy lut th S
E
Ar
trng thi ng
Y l nhm th loi I (c hiu ng +I, +C): gy hiu ng dng y electron vo vng
benzen lm gim in tch dng trn phc s, c bit gim nhiu cc phc s
o
v s
p
do
in tch ca hai phc nm gn nhm th Y nht v nng lng hot ha cc phc
s
o
v s
p
nh Nhm th E u tin vo v tr ortho v para.
Y l nhm th loi II (c hiu ng -I, -C): gy hiu ng m ht electron ca vng
benzen, v th khng nhng gii to in tch dng m cn lm tng in tch dng ca
phc s, m tng nhiu nht phc s
o
v s
p
(do in tch dng ca hai phc nm gn
nhm th Y nht). v tr meta khng nh vy nn nng lng hot ha ca phc s
p
nh
hn Nhm th E u tin vo v tr meta.
ortho meta
+

o

p

m > =
Y
H
E
E
H
Y
+
para
+
E
H
Y
(Y: nhm thlo i II)
Y
(Y: nhm thlo i I)
Y
ortho meta
+
Y
H
E
E
H
Y
+
para
E
H
Y
+

o

p

m < =
Gii thch quy lut th S
E
Ar
trng thi ng
Y l nhm th c hiu ng -I, +C nh halogen:
trng thi ng phc s c tnh electrophin mnh, l mt h thiu ht electron, do
s c mt ca cp electron cha s dng lun chim u th nn halogen th hin
hiu ng +C> -I, ch yu y electron vo vng benzen nh cc loi nhm th
loi I khc. Do trng thi ng (phc s) l giai on quyt nh ca phn ng nn
halogen tuy l nhm th phn hot ha nhn thm nhng vn u tin nh hng
vo cc v tr ortho v para.
ortho meta
+

o

p

m <
=
X
H
E
E
H
X
+
para
+
E
H
X
: : :
:
X
(X: halogen)
(X: halogen)
:
X