2.

ALKENES
Nomenclature
The alkenes are unsaturated hydrocarbons that contain one double bond. They have the general
formula C
n
H
2n
and the double bond is known as olefinic bond or ethylenic bond.
e.g.
CH
2
= CH
2
Ethene
CH
3
CH = CH
2
Propene
CH
3
CH = CHCH
3
But 2 ene

METHODS OF PREPARATION
2.1. Dehydrohalgoenation
It is possible to form alkenes by base induced elimination from alkyl halides.

R R
H
R
R
X
base (B
-
or B
R
R R
R

Alcoholic KOH converts alkyl halide into alkene by a reaction called dehydrohalogenation
which involves removal of the halogen atom together with a hydrogen atom from a carbon
adjacent to the one having the halogen.

CH
3
CH
2
CH
2
Cl
KOH(alc) KOH(alc)
A
H
3
CHC CH
2
KOH(alc)
n-propyl chloride
isopropyl chloride
CH
3
CHCH
3
Cl


CH
3
CH
2
CH
2
CH
2
Cl
KOH(alc) KOH(alc)
A
n-butyl chloride 1-butene
C H
3
CH
2
CH CH
2


KOH(alc) KOH(alc)
A
H
3
CHC CHCH
3
sec-butyl chloride
2-butene 80%
+
CH
3
CH
2
CH CH
2
1-butene 20%
H
3
CH
2
C CHCH
3
Cl

Note: (i) Ease of dehydrohalogenation of alkyl halides is in order 3
0
> 2
0
> 1
0
.
(ii) Ease of formation of alkenes is in order
R
2
C = CR
2
> R
2
C = CHR > R
2
C = CH
2
or RCH = CHR > RCH = CH
2
> CH
2
= CH
2
and
same is the stability order of alkenes.
Also
C C
R
R H
H



>
C C
R
H H
R



~
C C
R
R H
H

Thus by general rule: More stable the alkene, the more easily it is formed

C C
X
H
C C
+
X +
H
2
O

Increasing rate of dehydrohalogenation is in the order.
RF < RCl < RBr < RI
Also greater the conjugation, greater is the stability (due to resonance) hence easier is the
dehydrohalogenation.

H
3
C CH
2
Br
CH CH
2
KOH(alc.)
CH
2
CH CH CH
2
(I)
(II)


H
3
C CH
2
Br
CH
2
CH
3
KOH(alc.)
(III)
(IV)
A
CH
3
CH CHCH
3

As II is more stable than IV hence dehydrohalogenation of I is easier than that of (III)

In case of elimination of HBr from 1 bromo 1 methyl cyclohexane, loss of bromide
provides a tertiary cation. This species is symmetrical and loss of proton from either of the
adjacent methylene groups leads to the same product, 1 methyl 1 cyclohexene in which
the double bond is in the ring (endocyclic) on the other hand loss of proton from the methyl
group produces methylene cyclohexane (Y) in which the double bond is outside the ring
(exocyclic). By saytzeff rule, the more highly substituted an alkene, the more stable it is
hence formation of 1 methyl 1 cyclohexene is favoured.
Br
CH
3 Br
CH
3
H
H
CH
3
H
H
H
(from methyl)
H
Fast
(from ring)
(X) major

Formation of less substituted alkene in an elimination reaction is referred to as a Hofmann
elimination.

Note: Hindered base gives Hofmann product as major isomer.


Br C H
3
Et
3
N
CH
3 CH
2
+
Minor
Major


C
CH
3
O
CH
3
C H
3 +
C
CH
3
Br
CH
3
H
2
C CH
3
Minor (satyzeff)
(CH
3
)
3
COH
C H
3
CH C
CH
3
CH
3
75
0
C
+
Less substituted
H
3
CH
2
C C
CH
2
CH
3
More substituted


Ex. 5. What are the various products due to loss of HBr from

CH
3
Br
CH
3

Sol.
CH
3
CH
3
Major
CH
3
CH
3
Minor
CH
3
CH
2
Minor


2.2. Dehydration of Alcohols
Alcohols undergo dehydration to give alkenes.

R CH
2
CH
2
OH
A
Conc. H
2
SO
4
R CH CH
2


C H
3
CH
2
CH CH
3
OH
A
Conc. H
2
SO
4
H
3
CHC CH CH
3

2.3. Dehalogenation
(i) Vicinal dihalides undergo dehalogenation in the presence of Zn, Ag or Mg.

R CH CH R
X X
A
Zn/C
2
H
5
OH
R CH CH R
+
ZnX
2


(ii) Geminal dihalides undergo coupling reaction Via dehalogenation to give alkenes.

R CH
2
CHX
2
+
CHX
2
CH
2
R
C = n
C = n

R CH
2
CH = CH CH
2
R
(C = 2n)

2.4. Thermal elimination reaction
The product formation takes place by Hofmann rule. Following compounds give thermal
elimination reactions.
(i) Acetates

C H
3
CH
2
CH
OCOCH
3
A
C H
3
CH CH
2


C H
3
CH
2
CH
2
OH
TsCl / Py
C H
3
CH
2
CH
2
OTs
CH CH
2
C H
3


(ii) Amine oxide
Thermal elimination of amine oxides is known as copper elimination.

C H
3
CH
2
CH
2
N
CH
3
CH
3
O
A
CH
2
C H
3
+
H
3
C N
CH
3
OH

(iii) Quaternary ammonium hydroxide
Thermal elimination of this compound is known as Hofmann elimination.

OH C H
3
N(CH
3
)
3
| , |
o
A
CH
2
C H
3
+
CH
3
C H
3
+
(CH
3
)
3
N
(Major)
(Minor)


2.5. By partial reduction of alkynes:

Alkynes undergo partial reduction to give alkenes in the presence of catalyst

R C C R
2
H / Lindlar ' s
Catalyst
2 2
Ni B/ H
3
(i) BH
3
(ii) CH COOH
( )
3
Na / NH
C C
R
H H
R
C C
R
H H
R
C C
R
H H
R
C C
R
H R
H
4
Pb BaSO
Quinoline

2.6. Wittig Reaction
Carbonyl compounds react with 1
0
and 2
0
alkyl halides in the presence of triphenyl phosphine
and strong base (RLi, NaH etc) to give alkenes. This reaction is known as Wittig reaction.

R CH
2
Br
( )
6 5 3
(i ) C H P
(ii) NaH
(iii)
C O
R'
R
C CH
R'
R
R
from carbonyl
compounds
loss of oxygen
from alkyl halides loss of H
and X from - carbon o



Note: For writing product remove H and X from the o - carbon of alkyl halide and oxygen from-
carbonyl carbon and join these two carbons (o - carbon and carbonyl carbon) by double bond.
2.7. Kolbe hydrocarbon synthesis
Electrolysis of potassium salt of succinic acid gives alkene at the anode

H
2
C
H
2
C
COO K
COO K
Electrolysis
CH
2
CH
2
+
2CO
2 +
H
2


Ex. 6. Explain which of the following reactions would provide a better synthesis of
2 pentene.
(i)
C H
3
Br
CH
3
CH
3
O
CH
3
OH

(ii)
C H
3
CH
3
Br
CH
3
O
CH
3
OH


Sol. (i)
C H
3
Br
CH
3
C H
3
CH
3
Only product

(ii)
C H
3
CH
3
Br
C H
3
CH
2
C H
3
CH
3
Mixture
Hence (a) is better

Ex.7. Compound A (C
7
H
15
Br) is not a primary alkyl bromide. It yields a single alkene (b) on
being heated with NaOC
2
H
5
/C
2
H
5
OH. Hydrogenation of B gave 2, 4 dimethyl pentane.
Identify compounds A and B.
Sol.
A :
C H
3
C H
3
Br
CH
3
CH
3
B :
C H
3
C H
3
CH
3
C H
3


PHYSICAL PROPERTIES
At room temperature alkenes differs in their physical state depending upon the number of
carbon atom.
C
2
C
4
: Gases
C
5
C
17
: Liquids
C
18
Onwards : Solids like alkanes

CHEMICAL PROPERTIES
Alkenes show
(a) Free radical attack (Substitution reaction)
(b) Ionic attack (Addition reaction)
The Type of reaction depends upon experimental conditions.

C H
3
CH CH
2
Cl
2
low temperatrue
CCl
4
Solution
gas phase
500 - 600
0
C
CH
3
CH
Cl
CH
2
Cl
(Ionic addition)
Propylene chloride
H
2
C CH CH
2
Cl
Alkyl chloride
(free redical substitution)

Some reactions of alkenes are given below

1. Conversion to alkanes (Heterogenous)

Relative rates of hydrogenation are as follows:
H
2
C = CH
2
> RCH = CH
2
> R
2
C = CH
2
, RCH = CHR > R
2
C > R
2
C = CR
2

The rate decreases as steric hinderance increases.
R
R
+
H
2
| |
3
2 6
B H
f r o m B H
R
R
H
BH
2
Alkyl borane
R
R
CH
3
COOH

2. Addition reactions
Addition of unsymmetrical reagents such as HX, HOX, H
2
O, H
2
SO
4
etc to unsymmetrical
alkenes such as propene occurs in accordance with Markonikovs rule which states that the
negative part of the addendum (adding regent) gets attached to that carbon atom of the double
bond which has least number of hydrogen atoms
e.g.

C H
3
CH CH
2
+
H Br
o
H
3
C CHBr CH
3
2 - Bromopropane
o


C H
3
CH CH
2
+
OH Br
o
H
3
C CHOH CH
2
Br
Propylene Chlorohydrin
o


C H
3
CH CH
2
+
H
3
C CH CH
3
HO
3
SO
H O SO
3
H
C H
3
CHOHCH
3 +
H
2
SO
4
H
2
O


C H
3
C CH
2
CH
3
+
H OH
o o
C H
3
C
OH
CH
3
CH
3
Tert - butyl alcohol



Carbocations are the intermediates and the major products always results from more stable
carbocations. e.g.

C H
3
CH CH
2
CH
3
CH
2
CH
2
1- bromo propane (mirror prdcuct)
H
2
CCl CH CH
3
2
0
Carbocation
(More stable)
H
Br
CH
3
CH
2
CH
2
Br
Br
2- bromo propane (major prdcuct)
1
0
carbocation (less stable)
C H
3
CH CH
3
Br


In presence of peroxide, the addition of HBr to unsymmetrical alkenes occurs contrary to
Markovnikovs rule. e.g.
C H
3
CH CH
2
HBr
Benzoyl
peroxide
Propene
H
3
C CH
2
CH
2
Br
1- Bromo propane (Major product)
+
C H
3
CHBr CH
3
(minor product)
Anti markovnikovs addition is generally called peroxide effect or kharasch effect. In presence
of peroxides, the addition of HBr to unsymmetrical alkenes occurs by a free radical
mechanism.
e.g.
Initiation:
or h
Homolytic fission
R O O R 2RO
-
A v

Peroxide
RO H Br ROH Br
- -
+ +
Propagation:
(i)
3 2 3 2
CH CH CH Br CH CH CH Br
- -
= +
2
-
Free radical (more stable)
(ii)
3 2 3 2 2
CH CH CH Br HBr CH CH CH Br Br
- -
+ +
Termination: (i) Br Br Br Br
- -
+
(ii)
3 2
2CH CHCH Br
-
CH CH
CH
3
BrH
2
C
CH
3
CH
2
Br

Note: Peroxide effect is not observed with other halogen acids (HF, HCl or HI) since only HBr has
both steps exothermic while with HCl second propagation step involving the reaction of carbon
radical with HCl is endothermic and with HI, first propagation step involving the addition of
iodine radical to alkene is endothermic.
Because of the presence of double bond alkene readily undergoes electrophilic addition
reactions. Some important reactions of ethene are given below:
2
(i) H / Ni, 525 575K
3 3 catalytic hydrogenation
CH CH (Sabatier and Sendren' s reaction)

(iii) HX( X Cl,Br,I)
3 2 Reactivity HI HBr HCl
CH CH X(addition of halogen acids)
=
> >

Br
2
is discharged)
2 4 2
2 2 2
(ii) X ( X Cl,Br,I) / CCl or CS
2 2 2
Reactivity Cl Br I
XCH CH X(with Br , the orange colour of
=
> >

3 2 2
(x) O / Cu Cl
196 K

Ethylene halohydrin
2 2
(iv) HOX or X / H O
2 2
HO CH CH X(addition of hypohalous acid)
(Hydration of ethylene)
2 4 2
2 4
( v) Conc. H SO H O
3 2 3 3 2 2 4
( Addition of H SO ) Boil
CH CH OSO H CH CH OH H SO +
CH
2
=CH
2
-
Ethylene nitrosochloride
( vi) NOCl
2 2
Addition of Nitrosyl chloride
ON CH CH Cl
Reagent is discharged) Ethylene glycol
4
( vii) Cold alk. KMnO
2 2
Baeyer ' s reagent
HOCH CH OH (Pink colour of Baeyer ' s
Formic acid
2
(xii) O /
2 2
combustion
CO H O heat light
A
+ + +
CH
2
CH
2
O
2
H O
Boil
CH
2
OH
CH
2
OH
Epoxy ethane
Ethylene glycol
2
3
(ix) O / Ag, 575 K
or CH COOH

CH
2
O
O CH
2
O
2
Zn / H O
( ZnO)
2HCHO

Formaldehyde
Ethylene ozonide (ozonolysis)
4
( viii) KMnO KOH [O]
2 2 373 383 K
2HCOOH 2CO 2H O

+
Polythene
2
( xi) O (trace) 473 673 K
2 2 n under pressure
( CH CH ) (Polymerization)

Ex.8. Tetrachloromethane (Cl
2
C = CCl
2
) is non reactive towards Cl
2
but addition of AlCl
3
makes
it reactive explain.

Sol.
C C
Cl
Cl Cl
Cl

Cl atoms are electron attracting hence they decrease nucleophilic nature of alkene, hence no
reaction with Cl
2
takes place. In presence of AlCl
3
, electrophilic nature of Cl
+
is
increased.

3 2 4
AlCl Cl AlCl Cl
+
+ +
Hence t - electrons of alkene are reactive

2 2 3 2
Cl C CCl Cl Cl C CCl

+
= +

3 2 4 3 3 3
Cl C CCl AlCl Cl C CCl AlCl

+ +


MECHANISM OF SOME IMPORTANT REACTIONS OF ALKENES

1. Mechanism of halogen addition:
The mechanism proposed is an ionic mechanism.
In the first step the exposed electrons of the t- bond of the alkene attacks the halogen in the
following way:

C
C
Br Br
o
o + C
C
Br
Bromonium ion
Br
Bromide ion

As e' s t of the alkene approach the bromine molecules, the electrons of bromine bromine
bond drift to make bromine molecule polarised. The more distant bromine develops a partial
negative charge and nearer bromine becomes partially positive. Polarization weakens the bond
and cleaves it heterolytically.
In second step, one of the bromide ions predicted in step I attacks one of the carbon atoms of
the bromonium ion. The nucleophilic attack results in the formation of a vicinal dibromide by
opening the three membered ring.

C
C
Br
+
Br
C
Br
Br

On reaction of cyclopentane with bromine in
4
CCl , anti addition occurs and the products of
the reaction are trans 1, 2 dibromocyclopentane enantiomers (as a race`mate)

2
4
Br
CCl

H
Br
Br
H
enantiomer

Addition of bromine to cis 2 butene gives racemic form of 2, 3 dibromobutane.
Bromine adds to trans 2 butene to form meso compound, thus the reaction is stereospecific
in nature.

CH
3
H
H
H
3
C
(2 Z) - but - 2 - ene
CH
3
H
Br
Br
H
CH
3
CH
3
H
CH
3
H
Br
Br

CH
3
CH
3
H Br
Br H
CH
3
CH
3
Br H
H Br


CH
3
H
C H
3
H
(2 E) - but - 2 - ene
CH
3
H
H
C H
3
Br
Br

CH
3
CH
3
H Br
H Br
CH
3
CH
3
H Br
H Br
CH
3
Br
C H
3
Br
H
H

2. Mechanism of halohydrin formation
It can be explained by the following mechanism:

C C
R
R
R
R
X X +

R R
R
R
X
+
X

+


R R
R
R
X
+
2
H O + R R
R
X
OH
2
R
H
+

R R
R
X
OH
R

If the alkene is unsymmetrical, the halogen ends up on the carbon atom with greater number of
hydrogen atoms.

CH
2
C H
3
C H
3
2 2
Br , H O
or HOBr

C H
3
Br
OH
CH
3

3. Syn - hydroxylation
Hydroxylation with permanganate is carried out by reaction at room temperature. Its a good
method for the synthesis of 1, 2 diols.

2 2 4
H C CH aq KMnO = +
OH
OH
ethylene glycol


C H
3
CH
2
4
3 2
i ) OsO
ii ) NaHSO / H O

C H
3
OH
OH
propylene glycol

Mechanism in both cases involves formation of cyclic intermediates, then in several steps, the
cleavage at oxygen metal bond takes place producing glycol and
2
MnO or Os metal.

R
R R
R
R R
R
O
R
O
Mn
O O
2
OH
H O

several steps
R R
R
OH
R
OH
MnO
2
KMnO
4


2
cold
2
H O / OH
MnO

+
H
OH
H
OH
cis - 1, 2 - cyclopentanediol

Cis 2 butene when treated with cold alkaline
4
KMnO gives meso glycol and trans 2
butene gives racemate.
4. Oxidation reactions of alkenes
(i) With cold dilute
4
KMnO (Baeyers reagent) alkenes give 1, 2 glycols.

3 2 2 3 2
CH CH CH H O O CH CHOH CH OH = + +
Propene From
4
KMnO Propylene glycol

(ii) With hot alkaline
4
KMnO
Cleavage of C = C bond takes place leading to formation of carboxylic acids, ketones and
2 2
CO H O + depending upon structure of alkene.

4
KMnO ,KOH
3 2 3
373 383 K
e.g. CH CH CH 4[O] CH COOH HCOOH

= + +
Propene
Acetic acid
[O]
2 2
CO H O +


C CH
2
CH
3
C H
3
2 - methyl propene
4
KMnO , KOH
373 383 K
3 [O]

+
C O
CH
3
C H
3
HCOOH
[O]
2 2
CO H O +


C C
CH
3
C H
3
CH
3
CH
3
2, 3 - dimethyl - 2 - butene
4
KMnO , KOH
373 383 K
2 [O]

+
C O
CH
3
C H
3
2
Acetone

Hence by identifying the products formed during alkaline
4
KMnO oxidation, it is possible to
determine the position of the double bond in an alkene molecule.
(iii) With ozone alkenes first give ozonides which upon reductive cleavage with Zn dust and
2 2
H O or H / Pd gives aldehydes / ketones or a mixture of these depending upon the structure
of alkene.


2 2
CH Cl
3 2 3
196 K
e.f. CH CH CH O = +
Propylene
CH
3
CH CH
2
O O
O
Zn
H
2
O
3
CH CHO HCHO +


This two step conversion of alkene into ozonide followed by decomposition with
2
Zn/ H Oto give aldehydes / ketones or a mixture of these is called reductive ozonolysis.
If however ozonide is decomposed with
2
H O, the initially formed aldehydes are further
oxidized to the corresponding acids by
2 2
H O produced in the reaction. This is called
oxidation ozonolysis.
The oxidation reactions of alkenes are summed up as follows:


C C
O
epoxide
C
6
H
5
CO
3
H
HCO
3
H
4 4
MnO or OsO

cis - 1, 2 - diol
H
C C
OH
OH
trans - 1, 2 - diol
(anti - addition)
(By syn - addition)
O
3
(ozonolysis reaction)
ketone + aldehyde
H
2
O
2
acid + ketone
Z
n
,

H
2
O

o
r

C
H
3
S
C
H
3
H
C
OH
C
OH
C C
Alkene




Ex. 9. C
5
H
10
represents three isomeric alkenes A
1
, A
2
and A
3
. Each on hydrogentation gives 2
methyl butane. A
1
and A
2
on oxymercuration demercuration gives the same 3
0
alcohol. A
2

and A
3
on hydroboration oxidation gives different 1
0
alcohol. Assign structures to A
1
, A
2
and
A
3
and explain the reactions.
Sol.
A
1
, A
2
or A
3

H
2
C H
3
CHCH
2
CH
3
CH
3

This shows that each of A
1
, A
2
and A
3
have same C chain only position of C = C is to be
decided

oxymercuration 0
1 2
demerocuration
A , A 3 Alcohol
hence A
1
and A
2
have

C
CH
3
CH
3

or
H
2
C C CH
3
CH
3
grouping

hydroboration oxidation 0
1 3
A and A 1 Alcohol
This indicates presence of (CH
2
=) grouping at the terminal. Hence
CH
3
C CHCH
3
CH
3
A
1
is

CH
3
CH
2
C CH
2
CH
3
A
2
is

A
3
is
CH
3
HC
CH
3
CH CH
2


A
1
or A
2

oxymercuration
demercuration
C H
3
C CH
2
CH
3
OH
CH
3
3
0
alcohol (X)


A
2

hydroboration
oxidation

1
0
alcohol (Y)
CH
3
CH
2
CHCH
2
OH
CH
3


A
3

hydroboration
oxidation

1
0
alcohol (Z)
CH
3CHCH
2
CH
2
OH
CH
3

Y and Z are different 1
0
alcohols


Ex.10. An olefin was treated with ozone and the resulting product on reduction (reductive
ozonolysis) gave 2 pentanone and acetaldehyde. What is the structure of olefin? Write the
reaction.
Sol.
Alkene is C C
CH
2
CH
2
CH
3
CH
3
C H
3
H
(z) - 3 - methyl hex - 2 - ene
H
3
C CH
2
CH
2
C CH
CH
3
C H
3
3
O

O
CH
O
C
O
CH
3
C H
3
H
3
CH
2
CH
2
C
H
2
O / Zn
H
3
CH
2
CH
2
C
C O
C H
3
O CH
CH
3


Ex. 11.
2
Conc.H
2
SO
4

Explain mechanism.

Sol.
H
H


H