ALKENE

L TNH
Tng t alkane: Khng tan trong nc Tan trong dung mi khng phn cc T trng, Nhit si, Nhit nng chy thp v bin thin theo khi lng phn t a s alkene c nhiu ni i s c mu

DANH PHP

HA TNH
Phn ng c trng: phn ng cng
C C + A B A C C B

Lun km theo s ta nhit

CNG VI ACID BRNSTED MNH

CH2=CH2 + H3O+ HCH2CH2OH + H+

C CH
:Nu R1 R2 C C R3 R4 + E
+

H R1 R2 C
+

Nu R3 R1 R2 C C

H R3 R4

R4 Carbocation

H C+ C+ H
+

CH2+
H H C H
+

C+ H

QUY TC MARKOVNIKOV

QUY TC MARKOVNIKOV

QUY TC MARKOVNIKOV

HBr/Peroxide: Anti Markovnikov

CH3CH=CH2 HBr Peroxide CH3CH-CH2 H Br
Main Product

Peroxide: C6H5O OC6H5

C ch gc t do

HBr/Peroxide: Anti Markovnikov

CHUYN V CARBOCATION Phn ng qua trung gian carbocation chuyn v carbocation

CHUYN V CARBOCATION
H C C H 3-Methyl-1-butene H C H + H Cl H3C H CH3 C C H 2 carbocation Cl H H3C H3C C C H C H H + H3C H3C H Cl C C H
+

H3C H3C

H C

H H

Hydride shift H3C

CH3
+C

H C C H

H H

3 carbocation Cl H C H H

H Cl 2-Chloro-3-methylbutane

2-Chloro-2-methylbutane

CHUYN V CARBOCATION

CNG VI ACID LEWIS

Hypohalous Acids
X2 + H2O HOX + HX

OXYMERCURATION HYDROBORATION

Khng c s chuyn v carbocation

OXYMERCURATION: MARKOVNIKOV
OAc CH3 Hg OAc HgOAc CH3 :OH2 :O H
+

Hg

OAc
:

H2O, THF 1-Methylcyclopentene +

CH3 OAc

OAc CH3 OH

HgOAc CH3 OH + HOAc An organomercury intermediate NaBH4

1-Methylcyclopentanol (92%)

HYDROBORATION: ANTI-MARKOVNIKOV
+

H CH3 H2B

CH3

H2O2

CH3

H B H H BH3 H CH3 Partial 3 cation (more stable transition state)

OH

HO

H H
+

CH3

CH3 H B H H Partial 2 cation

BH3

(less stable transition state; not formed)

LP TH ?

E C

Nu C

E C C
H H + A B

syn

A B H H

anti

Nu syn addition (a) anti addition (b)

A H H B

CNG ANTI

CNG ANTI

CNG ANTI

HYDROBORATION: CNG SYN

+

H CH3 H2B

CH3

H2O2

CH3

H B H H BH3 H CH3 Partial 3 cation (more stable transition state)

OH

HO

H H
+

CH3

CH3 H B H H Partial 2 cation

BH3

(less stable transition state; not formed)

OXYMERCURATION: CNG ANTI

OAc CH3 Hg OAc
+

Hg

OAc :OH2
:

HgOAc CH3 :O H
+

H2O, THF 1-Methylcyclopentene +

CH3 OAc

OAc CH3 OH

HgOAc CH3 OH + HOAc An organomercury intermediate NaBH4

1-Methylcyclopentanol (92%)

YU T LP TH TC NHN PHN NG LP TH

HX X2 HOX RSCl Hg(OAc)2 BH3

syn + anti anti anti anti anti syn

C CH

C CH

PHN NG DIOL HA

EPOXY HA

OXY HA CT T NI I (OXIDATIVE CLEAVAGE) TCNHN: KMnO4, H3O+, t Ozon gii

OXY HA BNG KMnO4, H3O+, t

H C H R C H R' C R R R CO2 O c O c R' OH

OXY HA BNG KMnO4/H3O+/ t

CH3 CH3 O KMnO4 H 3O
+

CH3CH

CH3COOH KMnO4 H3O+

CH3

CH3

CH3CHCH2CH2CHCH CH3 CH3

CH2

CH3CHCH2CH2CHCOOH CH3 CH3 + CO2

OZON GII (OZONOLYSIS) OXDATIVE WORK-UP

OZON GII (OZONOLYSIS) REDUCTIVE WORK-UP

OZON GII

PHN NG GC T DO

IU CH ALKENE
1. Tch HX t Alkyl Halide
Quy tc Zaitsev

Br CH3CH2CHCH3

CH3CH2O Na CH3CH2OH

CH3CH=CHCH3 + CH3CH2CH=CH2
2-Butene (81%) 1-Butene (19%)

IU CH ALKENE
Br CH3CH2CCH3 CH3
CH3CH2O Na+ CH3CH2OH

2-Bromo-2-methylbutane

CH3CH=C-CH3
2-Methyl-2-butene (70%)

CH3CH2C=CH2 CH3
2-Methyl-1-butene (30%)

CH3

Tch HX t Alkyl Halide

Base mnh v nng cao (CH3CH2ONa, t-BuOK, NH2, OH,) Alkyl halide 2, 3 Gia nhit Phn ng tch E2

Cnh tranh gia E2 vi SN1 & E1

CH3 H3C C CH3 CH3CH2OH Br CH3CH2O Na
+

CH3 H3C C CH3 Ethyl tert-butyl ether (3%) CH3 H3C C CH3 Ethyl tert-butyl ether (80%) OCH2CH3 + OCH2CH3 +

H3C C CH2 H3C 2-Methylpropene (97%) H3C C CH2 H3C 2-Methylpropene (20%)

IU CH ALKENE
2. Tch H2O t Alcohol

CH3 CH3COH CH3

tert-Butanol

H2SO4

CH2=C-CH3 CH3
2-Methyl-1-propene

IU CH ALKENE
3. Tch X2 t vic-dihalide