CHAPTER 5

REACTION OF ALKENES,ALKYNES AND AROMATIC COMPOUNDS

ADDITION REACTIONS OF ALKENES
1) 2) 3) 4) 5)

Addition of hydrogen halides Halogenation Hydration Hydrogenation Oxydation

Addition of Hydrogen Halides

The reaction of HX (X = Cl, Br, I) with double bond of alkene.

Example:

Markovnikov’s Rule: In addition of HX to an

C=C of an unsymmetrical alkene, the H attaches to the carbon with fewer R substituents and the X attaches to the carbon with more R substituents.

Mechanism of the reaction:

Since carbocations are involved as intermediates in the reaction, Markovnikov’s rules can be restated. - In the addition of HX to an alkene, the more

highly substituted carbocation is formed as an intermediate rather than less highly substituted one.

Anti-Markovnikov’s rule: In addition of HX

to an C=C of an unsymmetrical alkene, the H attaches to the carbon with more R substituents and the X attaches to the carbon with few R substituents. Example: H2O2 CH3CH=CH2 + HBr CH3CH2CH2Br
Free radical mechanism .

Exercise

exercise

Halogenation

Addition of X2 (X = Cl, Br, I) in the presence of CH2Cl2 to an C=C of an alkene.
X2 X X X = Cl,Br,I

•Mechanism of the reaction
H3C H H3C H

Cl
CH3

Cl

ClH

H

Cl

CH3

H3C

H

CH3

ClH

H

H

Cl

CH3

Cl

CH3

Cl

Halohidrin – the reaction of an alkene with X2 in the presence of H2O to give a molecule with both OH and X.

Hydration

The reaction of an alkene with water in presence of light sulphuric acid as a catalyst to yield an alcohol.

Markovnikov’s rule is also applied in this reaction.

Example: CH3CH=CH2 + H2O

H2SO4

CH3CH(OH)CH3

Mechanism of the reaction:

Exercise

Hydrogenation
Reduction of alkenes  React with H2 in the presence of catalyst such as Pt, Pd, Ni to form corresponding saturated alkanes.

Example:

Oxidation
a)

Combustion -Reaction of an alkene with O2 CH2=CH2 + O2 2CO2 + H2O Hydroxylation -React with warm and concentrated KMnO4 to form two carbonyl compounds - C=C will break into two fragments

d)

Hydroxylation 1)

2)

-React with cold KMnO4 to form 1,2-diol or glycol KMnO
CH3CH=CH2 cold
4

CH3CH(OH)CH2(OH) 1,2-propanediol
OH

KMnO4 cold
OH

CH3

H C OH CH3

CH3C(CH3)=CH(CH3)

KMnO4 cold

H3C

C OH

C) Ozonolysis The reaction of an alkene with ozone, O3 to give aldehyde and ketone.

O3

H2O Zn

O

O

In ozonolysis, aldehyde does not undergoes further reaction of oxidation to give carboxylic acid.

Mechanism of the reaction

ADDITION REACTION OF ALKYNES
1) Hydrogenation
H H3C C CH 2H2 H3C C H H C H H

2) Halogenation
H3C C CH Br2 H3C C C H Br Br

3) Hydrohalogenation
Cl H3C C CH 2HCl H3C C Cl H C H H

Electrophililic addition mechanism reaction:
H3C C CH 2HCl H3C

Cl C Cl

H C H H

H3C

C

CH

H

H3C

C

CH2

Cl

H3C

C Cl

CH2

H3C

C Cl

CH2

H+

H3C

C Cl

CH3

Cl
Cl
-

H3C

C Cl

CH3

4) Addition of water to alkynes (hydration)

AROMATIC COMPOUNDS

Benzene, C6H6 – aromatic hydrocarbon
Resonance form of benzene- Kekule structure

Electrons delocalization – resonance effect.  Resonance – differ in the position of electrons, not in atom

Nomenclature of the aromatic compounds

Nomenclature:

Reaction: Electrophile Substitution

Mechanism of Electrophile Substitution

a)Halogenation

b) Friedel Craft Alkylation

Friedel Craft Acylation

Exercise

c) Nitration

d)sulfonation

Orientation of Substitution
Directive effects Ortho-para * R = CH3, C2H5
1)
• • •

Meta NO2, C=OR,
C=OOR, SO3H CN, NR3

OH, OCH3 X = F, Cl, Br Ph

2) Activating and Deactivating Groups Activating group -group that increases the reactivity of aromatic compound to electrophile substitution. -Ortho & para director Deactivating group -group that decreases the aromatic reactivity compound to electrophile substitution -meta director

Example:

Example: