1.

HIU NG CM NG
1.1 NH NGHA

H H H H H-C-C-C-C H H H H

Cl

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 H
H H C H F F C F CH = CH2 CH = CH2 H H C H

CH = CH2

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+ Carbocation

Z-

D ly heterolysis

Carbanion

CARBOCATION
C+
Carbocation (Lewis acid) O H H Water (Lewis base)

O H H

* Bc Carbocation
CH3 H3C C + CH3 Carbocation 3 CH3 H3C C + H 2 benzyl

~ ~

CH2

~ ~

C H

C+ H

H H3C C + H 1

H H C+ H methyl

allyl

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 + C

+

C C

Carbanion

Lewis acid