C CH PHN NG HU C

PHN LOI PHN NG HU C

4 loi chnh
1. Phn ng th (Substitution)

HNO3 H2SO4

NO2

PHN LOI PHN NG HU C

2. Phn ng tch (elimination)

H H C H

H C Br H

KOH HBr

H C H C

H H

PHN LOI PHN NG HU C

3. Phn ng cng (addition)

H C H C

H + Br H Br

CCl4

Br H C H

H C H Br

PHN LOI PHN NG HU C

4. Phn ng chuyn v (rearrangement)

H H3C C H3C CH3 C C

H H

H3C C H3C C

CH3 CH3

PHN LOI PHN NG HU C

PHN LOI PHN NG HU C

C ch phn ng
Da vo cch t lin kt cng ha tr: c 3 c ch chnh: 1. C ch phn ng ion: tc cht hoc cht trung gian hoc sn phm l ion.
SO3H +
+

SO3H

H
+

SO3H

Benzenesulfonic acid (95%)

C ch phn ng
2. C ch phn ng gc t do cht trung gian mang in t l gi l gc t do (free radical hoc radical).
:
:X

H : R Alkane

:X : H

Alkyl radical

C ch phn ng
3. C ch ng b (pericyclic) ch c s phn b li cc orbital lin kt.

+ Diene alkene Cyclohexene

Cyclic transition state

D ly v ng ly
1. S D LY (Heterolysis) Thng xy ra i vi cc lin kt b phn cc Cn mt tc nhn h tr c th tch ri hai ion ra
A B A+ + Ions BHeterolytic bond cleavage

2. S NG LY (Homolysis)
A B A

Homolytic bond cle

Radicals

R O O R
Dialkyl peroxide

heat

2 R O
Gc t radicals do alkoxyl alkoxyl

X X

heat or light

ng ly

D ly

D ly

Bond-Making

ACID-BASE
BRNTED-LOWRY Acid: cht c th cho mt proton H+ Base: cht c th nhn mt proton H+
H O H Base Acid (proton acceptor) (proton donor) + H Cl
+

H O H

Cl

H Conjugate acid Conjugate base of H2O of HCl

 Hng s acid Ka. Acid cng mnh khi Ka cng ln v ngc li

HA + H2O H3O+ AKa = HA Ka H3O
+

A-

Gi tr pKa = - log Ka. Acid cng mnh khi Ka cng ln hay pKa cng nh. Trong mt cp acid-base: dng acid cng mnh (pKa nh) th dng base lin hp ca n cng yu v ngc li.

nh hng ca dung mi
AH + Sol: an acid Dung solvent Acid mi A:() + SolH(+) conjugate conjugate Base lin hp Acid lin hp base acid

NH HNG CA pH N CU TRC

NH HNG CA pH N CU TRC

pKa (RCOOH) = 5 pKa (RNH3) = 10

+

ACID & BASE HU C

O H3C C O H Acetic acid A carboxylic acid (acid)
H R N H Amine1o (base) + H
+

H + O H Water (base) H3C C

H + H
+

O H

O Acetate ion (conjugate base of acetic acid)

H H N H
+

Hydronium ion (conjugate acid of water)

H O H Hydronium ion (acid)

H + O H Water (conjugate base of H3O+)

H Alkylammonium ion (conjugate acid of amine)

ACID & BASE HU C

Phn ng acid-base
Trong phn ng acid-base: dng acid mnh s phn ng vi dng base mnh v cho ra sn phm l cc dng acid v base yu hn
O H3C O Acetic acid pKa = 4.74 C H + CH3CH2OH Ethanol O + CH3CH2OH2+ H3C O Protonated ethanol Acetic acid pKa = - 2.5 (acid) C

KHI NIM ACID-BASE THEO LEWIS Acid: Cht c kh nng nhn cc i in t Base: Cht c kh nng cho cc i in t
H
+

NH3 Lewis base Base Lewis (electron-pair donor)

H NH3

Lewis acid Acid Lewis (electron -pair acceptor) Cl Cl Al +

NH3 Lewis base Base Lewis (electron-pair donor)

Cl Cl Al Cl

NH3

Cl Lewis acid Acid Lewis (electron -pair acceptor)

KHI NIM ACID-BASE THEO LEWIS Bt k mt cht no trong c nguyn t thiu in t u c tnh acid Lewis V d: BF3, AlCl3, ZnCl2, FeCl3,
R O H + ZnCl2 R O ZnCl2
+

H Br Br + FeBr3 Br Br
+

FeBr3

ACID-BASE THEO LEWIS

Reactive Intermediates CHT TRUNG GIAN PHN NG

S d ly mt lin kt gia carbon v mt nguyn t bt k c th to thnh: 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
Nguyn t carbon thiu in t C lai ha sp2 C tnh acid Lewis Cht thn in t (electrophile)
R3 R3 C R2 1200 R2 Oblique view Top view R1 120
0

1200 R1

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
+

~ ~

~ ~

H C H

C+ H

H H3C C + H 1

H H C+ H methyl

allyl

CARBOCATION

Alcol bc 3

Carbocation bn

CARBOCATION ALKYL
Orbital Orbital p trng

CARBOCATION ALKYL

CARBOCATION ALKYL

Carbocation khng th t cu trc phng

CARBOCATION ALLYL

CARBOCATION BENZYL

Mt s Carbocation l acid Lewis

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)
C + H A

C H

Carbanion Lewis acid C

C C

Carbanion

Lewis acid

CARBENE V CARBENOID Phn t trung ha in cha C ha tr 2 C trng thi lai ha sp2 L cht thn in t v nguyn t carbon cn mt i in t t c cu bt b bn vng.
CH 2
+ N N heat or light

CH2 +
Methylene

N N
Nitrogen

Diazomethane

Vacant p orbital

R
+

H H C
2

sp3 R
H H

R
sp orbital

C
H

Methylene (a carbene)

A carbocation

A carbanion

VIT C CH PHN NG

VIT C CH PHN NG

In reactions where the distribution of electrons is not symmetrical, the direction in which curved arrows are drawn may be significant.

This is not a plausible mechanism