1.

HIU NG CM NG
1.1 NH NGHA

H H H H

H-C-C-C-C

Cl

H H H H

Hiu ng cm ng c vit tt
bng ch I (inductive effect) v c
biu din bng mi tn thng () t
nguyn t c m in nh n
nguyn t c m in ln.

1.2 PHN LOI

1.3 C IM CA HIU NG CM NG

 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.
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.

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.

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.

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.

Lin kt gia hai nguyn t c m in khc

nhau l lin kt cng ha tr phn cc, mt electron
b lch v pha nguyn t c m in ln hn,
nguyn t c m in km hn do b thiu ht
electron nn s mng mt phn in tch dng. S
phn cc lin kt C-Cl khng ch c nh lin kt
m lan truyn theo mch lin kt ca phn t lm
xut hin cc in tch dng cc nguyn t khc
cho n tn nhm carboxyl. Tc dng ny lm tng
cng s phn cc ca lin kt O H, lm n nh
nhm carboxylat COO- do lm tng lc acid.

i vi cc nhm I

 m in cng ln th hiu ng I cng ln.

Ph thuc trng thi lai ho:
-CH2=CH2 < -C6H5 < - CCH

i vi cc nhm +I
Cc nhm c hiu ng + I l nhng nhm
c m in thp hn nguyn t bn cnh.

2. HIU NG LIN HP
2.1 NH NGHA

Cc loi h lin hp thng gp

H lin hp -: Khi cc lin kt bi cch nhau ng
1 lin kt n th to thnh 1 h lin hp gi l h lin
hp -.

H lin hp -p: Khi 1 lin kt bi cch 1 obitan p

c cp electron mt lin kt n th to thnh 1 h lin
hp gi l h lin hp -p.

Bn cht ca hiu ng lin hp

Bn cht: Cc electron hoc p khi tham gia trong h
lin hp th khng cn c tr ring 1 v tr no m
chuyn dch trong ton h lin hp. Khi cc nhm
nguyn t lin hp vi nhau th mt electron v p
b thay i ngi ta gi l hiu ng lin hp (C).
Nh vy bn cht ca hiu ng lin hp l hin tng
dch chuyn electron trong h lin hp, gy nn s phn
cc ca cc lin kt trong h .

CH2= CH-CH = O

CH2= CH- Cl

N=O
O

2.2 PHN LOI

2.2.1 HIU NG LIN HP DNG (+C)

2.2.2 HIU NG LIN HP M (-C)

Lu : C mt s nhm nh vinyl v phenyl du ca

hiu ng lin hp khng c nh, tu thuc vo bn cht
nhm th m chng lin kt.

2.3 C TNH CHUNG CA HIU NG LIN HP

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.

S d c iu v trong (IV) 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.

Khc vi hiu ng cm ng, hiu ng lin hp gy ra

s phn b xen k u n cc v tr giu v ngho
electron . Nhm gy hiu ng +C lm xut hin cc v
tr giu electron (k hiu -) xen k vi cc v tr khng
giu electron. Nhm gy hiu ng C lm xut hin cc
v tr ngho electron (k hiu +) xen k vi cc v tr
khng b ngho electron. Tc dng ny lan truyn trong
ton mch lin hp, khc vi hiu ng cm ng, n hu
nh khng b gim khi ko di mch lin hp.

V d 1: Sp xp cc hp cht sau theo tnh acid gim dn

(gii thch l do).
CH3-CH2-NH2; CH3-CH2-OH v CH3-CH2-CH3
Sp xp cc base lin hp ca cc cht trn theo tnh
base tng dn.
Oxy c m in mnh hn nit v nit c m
in mnh hn carbon, v th ni O-H phn cc hn ni
N-H v hn ni C-H.
CH3-CH2-OH > CH3-CH2-NH2 > CH3-CH2-CH3
Cc base lin hp ca cc cht trn c sp xp
theo tnh base tng dn l do mt hp cht c tnh acid
cng yu th base lin hp ca n cng mnh.

V d 2: Ion amonium NH4+ c pKa = 9,25 cn

metylamonium CH3-NH3+ c pKa = 10,66. Hi amoniac
NH3 v metylamin CH3-NH2, hp cht no c tnh base
mnh hn?

Hp cht c tnh acid cng mnh th th base lin

hp ca n cng yu. Vy do ion amonium NH4+ c
tnh acid mnh hn metylamonium CH3-NH3+ nn
base lin hp ca n l amoniac NH3 s c tnh base
yu hn so vi metylamin CH3-NH2

3. HIU NG SIU LIN HP

Bn cht: L hiu ng lin hp ca cc lin kt C-H
hoc vng no nh vi cc lin kt bi C=C, CC cch cc
lin kt C-H hoc vng no nh 1 lin kt n.
H
H

CH = CH2

CH = CH2

H
H
H

H
CH = CH2

H
F
F

C
F

C
H

CH = CH2

3.1 HIU NG SIU LIN HP DNG (+H)

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
2bromopentan. 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.

Cc nhm alkyl thng gy hiu ng

siu lin hp dng (+H) v ln ca
hiu ng bin i theo trt t ngc
vi trt t v ln hiu ng +I ca
chng:

3.2 HIU NG SIU LIN HP M (-H)

4. HIU NG KHNG GIAN

4.1 HIU NG KHNG GIAN LOI 1 (S1)

4.2 HIU NG KHNG GIAN LOI 2 (S2)

4.3 HIU NG ORTHO

5. NH HNG CA CC HIU NG LN TNH

ACID-BASE V BN CA CARBOCATION
5.1 NH HNG CA HIU NG CM LN TNH ACID

5.2 NH HNG CA HIU NG LIN HP, HIU NG

SIU LIN HP LN TNH ACID

 a s hp cht hu c c tnh axit khi c lin kt

Z-H phn cc, m ph bin nht l cha nhm - O-H.
Nu lin kt O-H cng phn cc v nu tch H+ m
anion to ra cng bn th tnh axit cng ln. V vy:
Trong hp cht nu O-H lin kt vi nhm ht
electron th tng tnh axit, ngc li vi nhm y
th tnh axit gim.
ancol < nc < phenol < axit cacboxylic
i vi ancol : bc 1 > bc 2 > bc 3

 i vi phenol: Tnh axit ph thuc vo

bn cht v v tr ca cc nhm th: tr v
tr ortho c nhiu ngoi l, cn cc nhm
th c hiu ng +C v tr para th c tnh
axit yu hn meta, nhng c nhm ht e
(hiu ng C) th v tr para s mnh hn
v tr meta v khi hiu ng lin hp
pht huy tc dng.

 i vi axit cacboxylic
Axit no: Mch cacbon cng di th tnh axit cng
gim, thay H bng cc nhm ht electron th tnh
axit cng tng.
Axit dicacboxylic
bc 1 c tnh axit tng, nhng bc th 2 c
nhm COO- y electron nn c tnh axit gim
r rt.
ng phn cis c tnh axit cao hn trans.

 Nhm khng no cng gn nhm COOH th tnh axit

cng tng, tr trng hn lin kt i C=C v tr .

5.3 NH HNG LN TNH BASE

Tnh baz ca hp cht hu c

a s cc baz do c cp electron cha s dng nn
kt hp c vi proton. Nu mt eletron cng cao
v cng linh ng th tnh baz cng ln. V vy:
Tnh baz ca amin > ancol > nc.
Baz cng mnh th tnh axit cng yu v ngc
li axit cng yu th baz lin hp ca n cng
mnh.
- Tnh axit: C6H5OH > H2O > C2H5OH
- Tnh baz :C6H5O- < HO- < C2H5O-

Tnh baz ca cc hp cht cha nit

i vi cc hp cht cha nit, ni chung c tnh
baz, nu mt electron cng ln th tnh baz cng
mnh.

i vi amin: amin bo > amoniac > amin thm.

Cc amin thm c nhm th: tnh baz ph

thuc vo bn cht v v tr ca nhm th
nhn.

5.4 NH HNG LN BN CA CC CARBOCATION

Carbocation: ion dng vi in tch dng

trn C
Carbanion: ion m vi in tch m trn C

D ly
heterolysis

C+

Z-

Carbocation

D ly
heterolysis

Carbanion

CARBOCATION
C+

O H

O H
H

H
Water
(Lewis base)

Carbocation
(Lewis acid)

* Bc Carbocation
CH3
H3C C +
CH3
Carbocation 3

CH3
H3C C +

CH2

~~

H
2

~~

C
H

benzyl

C+
H

allyl

H
H3C C +
H
1

H
H C+
H
methyl

CARBANION

Ion m cha carbon ha tr 3

L nhng base Lewis mnh
Phn ng vi proton H+ hoc nhng tm mang in
tch dng (thiu in t)
L cht thn hch (Nucleophile)

H A

C H

Carbanion Lewis acid

C

Carbanion

Lewis acid

C C