Chng 2

Cc HIU NG IN T TRONG HA HU C

Mc tiu
1. Nu c cc loi hiu ng cm ng, hiu ng lin hp, hiu ng siu lin
hp v tnh cht ca chng.
2. Bit c mt s ng dng ca cc hiu ng trn.
Ni dung
Mt in t trong lin kt cng ha tr thng c phn b khng ng
u gia 2 nguyn t ca lin kt, khi y phn t cht hu c b phn cc. S
phn cc c th xy ra ngay trng thi tnh hoc cng c th ch xut hin
nht thi trng thi ng (khi phn t b tc ng bi cc yu t ca mi
trng). Bn cht ca s phn cc khc nhau cn tu thuc vo cu to phn t
(phn t c h thng lin kt nh th no). Nh vy cu to phn t c nh
hng n s phn b mt in t. nh hng gi l hiu ng in t
trong phn t.
C cc loi hiu ng:

Hiu ng cm ng I
Hiu ng lin hp C, M
Hiu ng siu lin hp H
1. Hiu ng cm ng (Inductive effect): K hiu l I
Kho st phn t n -propan C3H8 v phn t n-propylclorid C3H7Cl
H
H

C3 C 2 C1 H
H

n-propan
n-propan

H H
+3 +2 1+
H C C C Cl
3
2
1
H

n-propylclorur
n-propyclorid

Trong phn t n -propylclorid, lin kt C1 Cl b phn cc v pha nguyn

t clor v nguyn t clor c m in ln hn. Nguyn t clor mang mt phn
in tch m v nguyn t carbon mang mt phn in tch dng +. V C1
mang in tch dng nn cp in t lin kt ca lin kt C2 C1 b dch chuyn
v pha carbon C1. Kt qu l lin kt C2 C1 cng b phn cc theo. Nguyn t C2
mang mt phn in tch dng. n lt lin kt C3 C2 cng chu nh hng
nh vy v kt qu nguyn t carbon C3 mang mt phn in tch dng. Nhng
1+ >2+ >3+. Cc lin kt cng chu nh hng nh th v kt qu c s phn cc
22

ca lin kt C H. Hydro tr nn linh ng hn. Hin tng ny khng ch xy

ra vi phn t propan. Nh vy nh hng s phn cc ca lin kt C -Cl lm cho
cc lin kt khc b phn cc theo v ton phn t b phn cc.
Nguyn t clor l nguyn t gy nh hng cm ng.
S phn cc hay s chuyn dch mt in t trong cc lin kt gi l hiu
ng cm ng. Hiu ng cm ng k hiu l I hoc I (ch u ca inductive)
phn loi cc nhm nguyn t theo hiu ng cm ng ngi ta quy c
rng nguyn t hydro lin kt vi carbon trong C __ H c hiu ng I = 0. Nhng
nguyn t hay nhm nguyn t X c kh nng ht in t (CX) mnh hn
hydro c coi l c hiu ng - I (hiu ng cm ng m). Nhng nguyn t hay
nhm nguyn t Y c kh nng y in t (YC) mnh hn hydro c coi l
nhng nhm c hiu ng +I (hiu ng cm ng dng)

+I

H
I=0

-I

1.1. Hiu ng cm ng + I
Thng thy cc nhm alkyl (R-) v cc nhm mang in tch m.
Trong dy cc nhm alkyl, hiu ng cm ng +I tng theo phn nhnh
hay l bc ca nhm .

+I

CH3

CH2 CH3

CH CH3
CH3

CH3
C CH3
CH3

Trong dy cc nhm mang in tch m, nhm c m in nh hn l

nhm c hiu ng + I ln hn .
-O- < -S- < -Se1.2. Hiu ng cm ng - I
L hiu ng rt ph bin cc nhm khng no, cc nhm mang in tch
dng v cc nhm ng vi nhng nguyn t c m in ln (nh cc halogen,
oxy, nit).
S bin thin mc mnh yu ca hiu ng - I trong cc nhm nguyn t
tun theo mt s quy lut:

Nguyn t carbon lai ha sp c -I ln hn nguyn t carbon lai ha sp2 v sp3

-CCR > -CR1=CR2 > -CR2_CR3.

Nhm mang in tch dng c hiu ng -I ln hn nhm c cng cu to

nhng khng mang in tch.
+

-OR2 > -OR

-NR3 > -NR2

23

 Cc nguyn t ca nhng nguyn t trong cng mt chu k nh hay trong

cng mt phn nhm chnh ca h thng tun hon, hiu ng -I cng ln
khi nguyn t tng ng cng bn phi (trong cng chu k) hoc cng
pha trn trong cng phn nhm).
-F > -Cl > -Br > -I
-F > -OR > -NR2 > -CH3.
-OR > -SR > -SeR
m in cng tng th hiu ng cm ng - I cng ln
Biu hin c th ca hiu ng cm ng l nh hng ca cc nhm th khc
nhau n lc acid v lc base ca cc acid carboxylic no v ca cc amin.
Trn bng 2-1, ngi ta nhn thy rng nu thay th hydro ca acid formic
bng cc gc alkyl c + I tng th kh nng phn ly ca acid gim. Cn ln lt thay
th cc hydro ca amoniac bng cc gc alkyl c +I tng th tnh base tng ln.
Hiu ng + I tng lm cho lin kt O __ H km phn ly.
H_COOH

CH3

C
O

Khi thay th hydro ca amoniac bng cc nhm c hiu ng + I, mt in

t trn nguyn t nit tng ln do tnh base ca amin tng.
CH3

..

H_NH2

CH3 N:

..

CH3 NH2

CH3

Bng 2.1. nh hng hiu ng cm ng n tnh acid base

Lc acid giam khi +I tang

Acid hu c

pKa (H2O.25o)

CH3CH2COOH

3,75
4,76
4,87

CH3CH2CH2COOH

4,82

HCOOH
CH3COOH

(CH3)2CHCOOH

4,86

Lc base tang khi +I tang

Base hu c pKa (H2O.25o)
NH3
CH3NH2
CH3CH2NH2
(CH3)2NH
(CH3)3N

9,10
10,62
10,63
10.77
9,8*

Ch : *S d tnh base ca trimethylamin khng tng l do hiu ng khng gian.

Hiu ng - I tng, lc acid tng. Khi thay th hydro ca CH3 trong acid
acetic bng cc halogen c m in khc nhau th tnh acid thay i. Nguyn
t halogen c hiu ng -I ht in t nh hng n s phn ly ca nhm O _H.
F CH2 C O H
O
pKa 2,58

24

Cl CH2C O H
O
2,85

Br CH2C O H
O
2,9

I CH2 C O H
O
3,16

H CH2 C O H
O
4,76

c im quan trng ca hiu ng cm ng l hiu ng cm ng lan truyn

trn mch lin kt v yu dn khi chiu di ca mch carbon tng ln.
CH3CH2CH2COOH
4,82
pKa

CH3CH2CHClCOOH

CH3CHClCH2COOH

2,86

4,05

CH2ClCH2CH2COOH
4,42

2. Hiu ng lin hp (cng hng)

2.1. H thng lin hp
H thng lin hp l mt h thng:

Cc lin kt bi (i, ba) lun phin vi lin kt n.

C=C-C=C-C=C-

( - )

C=C-C=C-C=O-

(- ).

H thng cha nguyn t cn cp in t p t do khng lin kt trc tip

vi nguyn t carbon c lin kt bi.

..

..

-C=C-O-R

( p- )

-C=C-Cl

Phn t cha h thng lin hp l phn t lin hp.

2.1.1. Phn loi h thng lin hp nh sau:

H thng lin hp -
H thng lin hp khng vng
CH2=C_CH=CH2
CH3

CH2=CH_CH=CH2
1,3-Butadien

CH2 = CH CH = O
Aldehyd acrylic

2-methyl-1,3-butadien (izopren)

CH2 = CH C N

CH2 = CH C = O

Acrylonitril

Acid acrylic OH

H thng vng
..
O

H thng lin hp p -
H thng lin kt lin hp do tng tc gia in t p t do vi lin kt .

..

..

CH2=CH_Cl

CH2=CH_OCH3

Vinylclorid

Methylvinyl ether

:OH

:NH2

Phenol

Anilin

2.1.2. c im ca h thng lin hp

Trong phn t khng ch c lin kt i hoc lin kt n ring:
25

CH2=CH_CH2_CH=CH2 ;

CH2=CH_CH=CH_CH3 ;

CH=CH_CH2_OCH3

Lin hp

Khng lin hp

Khng lin hp

Cc nguyn t to h lin hp lun nm trong mt mt phng v trc ca

cc oirbtal p song song vi nhau v thng gc vi mt phng cha cc lin kt .

Benzen

Butadien

phenol

Phn t lin hp bao gi cng c nng lng thp hn nng lng ca nhng
phn t khng lin hp tng ng. V mt in t gn nh gii ta ng u
trn cc nguyn t to h thng lin hp v to thnh mt orbital phn t gii
ta trn ton b phn t.
C

Orbital phn t trong h thng lin hp rt d bin dng v d phn cc khi

cu to ca phn t lin hp c mt nguyn t chnh lch v m in.
Nh vy trong h lin hp c s tng tc gia cc orbital p vi nhau. S
tng tc gi l hiu ng lin hp.
2.2. Hiu ng lin hp C (M)
Hiu ng lin hp l hiu ng sinh ra do s phn cc ca lin kt c lan
truyn trong h thng lin hp
Hiu ng lin hp c k hiu l C (Conjugate effect) hoc M (Mesomeric effect)
2.2.1. Phn loi hiu ng lin hp
Cn c vo s dch chuyn in t ca cc in t . C hai loi hiu ng
lin hp: Hiu ng lin hp + C v Hiu ng lin hp - C

Hiu ng lin hp - C
Nu thay th nguyn t hydro trong nhm CH2 ca butadien bng nhm
CH = O, nhm ny tham gia lin hp vi orbital phn t ca butadien. Nh c
c tnh phn cc ca nhm CH =O nn ton b orbital mi hnh thnh ca
phn t b dch chuyn mt phn v pha nguyn t oxy.
CH2

CH CH

CH

CH

Nhm CH = O c hiu ng lin hp theo c ch ht in t nn c gi l

nhm c hiu ng - C.

26

Cc nhm c hiu ng - C l nhng nhm khng no c cng thc chung

C =Y, CZ v mt s nhm khc khng cha carbon nh - NO2, - SO3H...
Hng chuyn dch in t trong h thng c nhm vi hiu ng - C c m
t bng mi tn cong. Nhm c hiu ng -C thng c thm hiu ng cm ng - I.
Cc nhm chc c hiu ng -C :

..

C ..
O
: Cl
:
..

..

C O
..
H

..

C O
..
CH3

..

C O
..
: OR
..

..

..

C O
..

C O
..

:OH
..

: NH
.. 2

..

C O
..
: O.. -

CR = O > CR > CR = CR2

NO2 > O N
> O CR
Hiu ng lin hp +C
Cc nguyn t hay nhm nguyn t c hiu ng lin hp +C l nhng
nhm c kh nng y in t. Cc nhm ny thng c nguyn t mang
cp in t p t do. Chnh cp in t p ny lin hp vi cc lin kt
trong h thng lin hp.

..

..

CH2=CH_OCH3

CH2=CH_Cl
.. :

-NH2 > -OH ; -O- > -OH

Cc nhm c hiu ng + C :

-F > -Cl > -Br > -I

-NR2 > -OR > -SR > -SeR

Cc nhm c hiu ng + C thng c thm hiu ng cm ng - I.

Hiu ng lin hp c ng dng rng ri gii thch c ch phn ng,
cc cu to trung gian, bn ca cc ion, tnh acid -base ...

Hiu ng lin hp c nh hng n s dch chuyn in t. Chng c cc

cng thc trung gian hay cn gi l cng thc gii hn nh sau:
V d:
Butadien-1,3:
CH2

CH

CH

CH2

CH2

+
CH

CH

CH2

+
CH2

CH

CH

CH2

CH3

+
CH

CH

CH O

Aldehyd crotonic:
CH3 CH CH

Phenol

+
CH3 CH CH CH

CH O

:OH

+OH

+OH

+OH

OH
-

Hp cht c h thng lin hp cng di th c nhiu cng thc gii hn.

bn ca cc cng thc gii hn ph thuc vo khong cch gia 2 in tch tri
du. in tch tri du cng xa nhau th cng thc gii hn cng bn.
27

 Khc vi hiu ng cm ng, nh hng ca hiu ng lin hp khng b

gim i khi h lin hp ko di.
V d: Nguyn t hydro trong nhm CH3 ca aldehyd crotonic linh ng do
nh hng ca hiu ng lin hp.
H

: CH3 CH CH CH
aldehid
crotonic
Aldehyd
crotonic

Nu ko di mch aldehyd crotonic bng cc nhm vinyl th hydro ca nhm

CH3 vn cn linh ng.
H

: CH2

CH

CH

CH

CH

CH

CH CH

Hiu ng lin hp lm thay i trung tm phn ng:

V d: C hp cht sau:
..
C

CH

NH2

CH

CH

+
NH2

CH

O-

Trong h thng lin hp p -, cp in t p khng lin kt trn nguyn t N

lin hp vi h thng lin kt . Nhm NH2 gy hiu ng lin hp + C.
Nhm NH2 c tnh base c kh nng tc dng vi proton H+. Nhng do hiu ng
lin hp, H+ khng tc dng vo nhm amin NH2 m tc dng vo nguyn t oxy
ca nhm carbonyl.
C CH CH
O

+
NH 2 + H+

C CH CH

+
NH 2

OH

nh hng ca hiu ng lin hp ch xy ra trong h thng phng:

V d: Phenol (I) c tnh acid v nhm OH c hiu ng lin hp +C.
p-Nitrophenol (II) c tnh acid mnh hn phenol v nhm -NO2 c hiu ng lin hp
- C. Thay 2 nhm CH3 vo v tr orto so vi nhm OH c cht (III). Cht (III) c
tnh acid gim cht t so vi (II). Nhng a 2 nhm CH3 vo v tr orto so vi nhm
NO2 c cht (IV). Cht (IV) c tnh acid yu hn (II). iu chng t 2 nhm
CH3 lm cho nhm NO2 khng c hiu ng lin hp - C nh hng n chc phenol.
OH

OH

OH

OH

CH3

CH3

CH3
I

pKa

9.98

NO2
II
7,16

NO2
III
7,21

CH3
NO2
IV
8,24

S d c iu v trong (III) nhm NO2 khng nm trong cng mt phng

vi vng benzen. Hai nhm CH3 c cn tr khng gian lm cho nhm NO2 b lch
ra khi mt phng ca vng benzen. Hiu ng lin hp ca nhm NO2 khng pht
huy tc dng.
28

CH3

..

..

HO

HO

N O

N O

II

IV

O
CH3

3. Hiu ng siu lin hp (Hyperconjugate effect)

Ngoi s lin hp - v p - nu trn cn c s lin hp - gia cc
orbital ca cc lin kt C H trong nhm alkyl v orbital ca ni i, ni ba
hay vng thm.
H

C C C

CH3

C C C

H
22lin
ktket
lien

H
3
lin
3 lienkt
ket

H H

H H

H H

CH3

C C C

CH3

C
H

CH3

11lien
lin kt
ket

33lin
ktket
lien

S tng tc lin hp gia orbital ca lin kt C - H vi orbital ca lin

kt i, ba hoc h thng lin hp gi l hiu ng siu lin hp.

Hiu ng siu lin hp c k hiu l H.

Hiu ng siu lin hp khng nhng lm thay i bn cht ca lin kt
i m cn lm thay i c tnh cht ca lin kt n C - H.
Hiu ng siu lin hp lm thay i hng cng hp vo lin kt i.
V d: Trong phn t 2-penten, nhm C2H5 c hiu ng + I ln hn nhm CH3.
Phn t 2-penten cng hp vi HBr ng l phi to thnh 3-bromopentan.
Nhng thc t thu c 2-bromopentan. iu chng t nh hng siu lin
hp ca nhm CH3 ln hn nh hng siu lin hp ca nhm C2H5 nh hng
n hng cng hp.
H

H C CH CH

CH2

CH3 + HBr

H C CHBr CH2

CH2

CH3

Hiu ng siu lin hp nh hng n tnh cht linh ng ca lin kt C H trong gc alkyl.
V d: Nguyn t hydro trong nhm CH3 ca aldehyd acetic d dng b ct
t trong mi trng kim to carbanion.
H
H C CH
H

HO -

H
H C CH

O + H2 O

Carbanion

Carbanion to thnh c h thng lin hp p - . V vy carbanion ny c th

c cng thc gii hn:
H
H C CH

H
H C CH

Hin tng trn cn th hin trong hp cht ester ethylacetoacetat

CH3COCH2COOC2H5. Lin kt C H ca nhm CH2 c siu lin hp vi nhm
29

carbonyl C =O. Hydro ca CH2 tr nn linh ng v d dng b ct t trong mi

trng base to thnh carbanion.
CH3 C
O

H
..
C C
H O

OC2H5

+ OH -

C C OC2H5 + H2O
O H O
Carbanion

CH3 C

Carbanion to thnh c h thng lin hp p - do c th c cc cng thc

gii hn.
CH3 C

C C
OC2H5
O
.. : H O
Carbanion

CH3 C

:O
.. :

C
H

OC2H5

Hiu ng siu lin hp tng theo s lng lin kt C _H v tr .

CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C -

Hiu ng siu lin hp v hiu ng cm ng +I lun xy ra cng hng.

Hin tng phn b li mt in t cn c th c trong cc trng hp
h thng carbanion v carbocation.
V d: Carbocation allylic CH2=CHCH+ v carbanion allylic CH2=CHCH-.
+
CH2=CH_CH2

CH2=CH_CH2

Trong carbocation c hin tng dch chuyn in t t lin kt n orbital

trng ca nguyn t carbon. Trong carbanion c hin tng dch chuyn cp in
t t do ca carbon n lin kt .

Bi tp
1. Pht biu nh ngha v hiu ng cm ng, hiu ng lin hp v siu lin hp.
2. So snh hiu ng cm ng v hiu ng lin hp v bn cht, c tnh v quy lut.
3. Cn c vo hiu ng in t c th c so snh v gii thch tnh acid ca cc
cht trong cc dy sau:
a- n-C4H8ClCOOH, nguyn t clo cc v tr khc nhau .
b- m-ClC6H4(CH2)nCOOHn = 0,1,2 .
c- m-ClC6H4(CH2)nCOOHn = 0,1,2
4. Vit cng thc gii hn ca sn phm to thnh khi:

a-

NH2 C NH2
NH

+ H+

Guanidin
b-

30

C CH2 C CH2
O
O

+ HO -