QUY LUT TH ELECTROPHIN VO VNG BENZEN

Ngi bin son: Hoavang06

BENZEN (C6H6)

Cng thc Kekule (1865): 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 -

BENZEN (C6H6)
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 sp2 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 (SEAr)

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 SEAr l phn ng c trng quan trng ca vng benzen. Phn ng tng qut:

H + s+ sE Y xc t c

+ H

Tc nhn electrophin l cation E+ hoc phn t E-Y. Cc phn ng th SEAr 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 SEAr
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 E + H

phc p

phc s+
(tr ng th i chuy ti n p)

Giai on 2: phc s l mt cation khng bn s 4 electron p gii ton trn 5 nguyn phc vi phc p t C; nguyn t C th su ca vng lin E th i chuy trng thi lai ha sp3. Phc s c kt (tr ng Hvi E n ti p) bn ha theo 2 cch: + Cng anion Y- to thnh h thng+vng xiclohexadien (to sn phm cng) E + Tch proton to li E thng electron p ca vng thm (to sn phm th). h
E + 2. (- H ) H
phc p

phc s

1. (+ Y )

(tr ng th i chuy ti n p) E

H Y E

(sn phm cng)

phc s

Khuynh hng tch proton H+ c u tin hn do c mc nng lng thp hn.

(sn phm th )

Mt s phn ng th SEAr
Halogen ha
Br
Br2/FeBr3

C ch:

Br2

FeBr3
Br H

Br

+ [FeBr4]
Br

+
Brom benzen

HBr

Br

Br

H+

Benzen

phc p

phc s

Nitro ha
NO2
HNO3/H2SO4

C ch:
O

HNO3 + H2SO4

NO2 +
NO NO2 2 HH

2HSO4 + H2O
NO NO2 2
HSO4 4HSO
-

O O N N ++

+
Nitro benzen

H 2O

+ N + N O

Benzen

phc p

phc p

phc s

phc s

Sunfo ha
SO3H
H2SO4

C ch:
O: s-

H2SO4

SO3 +
SO3 H

H3O + HSO4
SO3 SO3H H+

: :

+
Axit benzen sunfonic

H2O

s+ S : O: s

Os

HSO4

Benzen

phc s

Mt s phn ng th SEAr
C ch:
Dng ankyl halogenua lm tc nhn ankyl ho di s c mt ca cht xc tc Liuyt:
R - X + AlX3
H s+ sR ..... X..... AlX3
Alkyl benzen

Ankyl ha theo Friedel-Crafts

R
AlX3 khan

s+ s..... X..... AlX3 R

R + AlX4 R

+
Benzen

R-X

(R : gc ankyl X : halogen)

H - X + AlX3

Axyl ha theo Friedel-Crafts

O +
Benzen

C ch:

s+ sR ..... X..... AlX3

H cc axyl Tc nhn axyl +ha AlX4 thng dng + l - X + AlX3 halogenua RCOX hoc cc anhydrit axit (RCO)2O:

R - C - X + AlX3 O
AlX3 khan

X
O H C R + AlX4 + H - X + AlX3 R C O

X-C-R
(R : gc ankyl X : halogen)

C O
Aryl alkyl xeton

R + HX
R s+ sC O ..... AlX3 X

: :

: :

s+ sC O ..... AlX3

Quy lut th SEAr

1. nh hng ca nhm th n s th SEAr: Mt nhm th R c sn nhn thm c nh hng n v tr ca cc nhm vo sau gi l nhm nh hng.
R + xc t c R

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 SEAr

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-, -NR2, NH2, -OH, -OR, -NHCOCH3, CH3, -C(CH3), C6H5-) v mt s nhm th phn hot ha nhn thm (halogen, -CH2Cl,) 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 (-NO2, -NR3, CF3, -CN, -COOH, -COOR, SO3H, -SO2R, -CHO, -COR.)
I ortho para

II

meta

V d:
ortho

Lo i I CH3 ortho para ortho

Lo i I OCH3 ortho

Lo i I I NO2

meta para

Quy lut th SEAr

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- > -NR2 > -NHR > NH2 > -OH > -OR > -NHCOR > halogen (F > Cl > Br > I) > > - OCOR > - R > -ankenyl Nhm th loi II: -NO2 > -NR3 > -CN > -COOH > -COOR > -SO3H > -CHO> -COR V d:

Lo i I OCH3 ortho Cl Lo i I para ortho

Lo i I OCH3 CH3 Lo i I para

Lo i I I NO2 Lo i I I COOH meta

Quy lut th SEAr

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:
ortho para Lo i I NHCOCH3 NO2 Lo i I I ortho para SO3H Lo i I I Lo i I OH Lo i I CH3 NO2 Lo i I I para

Lo i I CH3 ortho para NO2 Lo i I I

Lo i I CH3 ortho

Lo i I I COOH Cl Lo i I para

NO2 Lo i 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 SEAr

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 SEAr 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 SEAr. V d: cc nhm th O-, -NR2, NH2, -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 SE ca vng benzen kh khn cho phn ng SEAr. V d: cc nhm th NO2, COOR, -CN Trng hp nhm th c cc hiu ng I v C tc dng theo chiu hng ngc nhau (v d halogen, -OH, -NR2 (-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, -NR2 c tr s s m th hot ha nhn thm.

Gii thch quy lut th SEAr

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:
I ortho para 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:
II meta II II II II

:
X (X: halogen)

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.

Gii thch quy lut th SEAr

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.
Y ortho Y + E meta + Y para + H E E + Y H E

so

sm

sp

Gii thch quy lut th SEAr

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 so v sp do in tch ca hai phc nm gn nhm th Y nht v nng lng hot ha cc phc so v sp nh Nhm th E u tin vo v tr ortho v para.
Y Y H + E H (Y: nhm thlo i I) ortho para + E + H E meta Y Y

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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 so v sp (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 sp nh hn Nhm th E u tin vo v tr meta.
Y Y H + E H (Y: nhm thlo i II) ortho para + E + H E meta Y Y

>

Gii thch quy lut th SEAr

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.

X H + E H ortho

X + E +

:
X H E meta

(X: halogen) (X: halogen)

para

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