ALKENES (OLEFINS)

Alkenes form a homologous series of unsaturated hydrocarbons containing a carbon-carbon double

bond with the general formula CnH2n.

Alkenes are found in nature as well. Ethene is responsible for ripening of fruits, 1-octene is a
constituent of lemon oil, octadecene is found in silver fish, butadiene is found in coffee, lycopene
and carotenes (C40H56) give the attractive colour of red, orange and yellow colours of watermelons,
tomatoes, carrots, and other fruits and vegetables. Vitamin A is derived from carotene. Hence, the
world would be much less colourful place without alkenes.

PHYSICAL PROPERTIES

i. Physical State

These double-bonded compounds are colourless and odourless in nature. However, ethene is an
exception because it is a colourless gas with a faintly sweet odour. The first three members of the
alkene group are gaseous in nature, the next fourteen members are liquids and the remaining
alkenes are solids.

ii. Solubility

The alkenes are insoluble in water due to their nonpolar characteristics. But are completely
soluble in nonpolar solvents such as benzene, ligroin, etc.

iii. Boiling Point

1
The boiling points of the compounds increase as the number of carbon atoms in the compound
increases. When alkenes are compared with alkanes, it is found that the boiling points of both are
almost similar, as if the compounds are made up of the same carbon skeleton. The boiling point
of straight-chain alkenes is more than branched-chain alkenes just as in alkanes.

iv. Melting Point

The melting points of these double-bonded compounds depend upon the positioning of the
molecules. The melting point of alkenes is similar to that of alkanes. However, cis-isomer
molecules have a lower melting point than trans- isomers as the molecules are packed in a U-
bending shape.

Table showing melting and boiling points of some alkanes and alkenes

Alkanes Formula Mpt (o Bpt Alkene Formula Mpt Bpt

C)
(o C) (o C) (o C)

Methane CH4 -182 -164

Ethane C2H6 -183 -89 Ethene C2H4 -169 -104

Propane C3H8 -188 -42 Propene C3H6 -185 -47

Butane C4H10 -138 -1 1-Butene C4H8 -185 -6

Pentane C5H12 -130 36 1-Pentene C5H10 -138 30

Hexane C6H14 -95 69 1-Hexene C6H12 -140 63

Heptane C7H16 -91 98 1-Heptene C7H14 -119 94

Octane C8H18 -57 125 1-Octene C8H16 -102 121

v. Polarity

Alkenes are weakly polar just like alkanes but are slightly more reactive than alkanes due to the
presence of double bonds. The π electrons which make up the double bonds can easily be
removed or added as they are weakly held. Hence, the dipole moments exhibited by alkenes are
more than alkanes. The polarity depends upon the functional group attached to the compounds
and the chemical structures.

2
NOMENCLATURE OF ALKENES

In accordance with the IUPAC system, an alkene is named by dropping the ending -ane from the
corresponding alkane and replacing it with suffix -ene.

Where required, the position of the double bond is specified by appropriate number between the
stem name and ending -ene except for ethene and propene without positional isomers.

Example

Name the following organic compounds using the IUPAC System:

(a) CH3CH CH2 (b) CH3CH2CH CH2 (c) CH3CH CHCH3

(f) CH3C CCH2CH2CH3

(d) CH3C CH2 (e) CH3C CHCH2CH3

CH3 CH3
CH3
CH3

Solution:

(a) Propene (b) But-1-ene (c) But-2-ene (d) 2-methylpropene

(e) 2-methylpent-2-ene (f) 2, 3-dimethylhex-2-ene

Question

(a) Draw the structure of the following organic compounds:

i. 3, 3-dimethylcyclopentene

ii. 6-bromo-2, 3-dimethylpent-2-ene

iii. 3, 6-dimethyloct-3-ene

iv. 5-bromo-4-chlorohept-1-ene

v. 4-ethyl-3-methylcyclohexene

(b) Name the following organic compounds:

3
 CH2CH3

(i) BrCH2CH2CH CCH3 (ii)

CH2CH2CH3
CH3 CH3

(iii) CH2CH3 (iv) CH3CH2CH CHCH2CHCH2CH3

Br

cis– and trans- Isomerism (Geometric Isomerism) In Alkenes

cis-trans isomerism is also possible for alkenes. As in small rings, rotation about pi bonds is also
constrained: due to the “side-on” overlap of pi bonds, one can’t rotate a pi bond without
breaking it. This stands in contrast to conventional sigma bonds (single bonds) in acyclic
molecules, where free rotation is possible: witness 1,2-dichloroethane (below left).

Hence, we can have molecules such as cis-1,2-dichloroethene [boiling point 60°C] and trans-1,2-
dichloroethene [boiling point: 48°C] which can be separated from each other due to their differing
physical properties.

4
We can also use the cis–trans nomenclature to distinguish isomers such as 2-methyl-3-hexene
(above right). In the cis isomer, the two hydrogens are on the same side of the pi bond, and in
the trans isomer, the two hydrogens are on the opposite side of the bond.

As with rings, the minimum requirement for cis-trans isomerism in alkenes is that each carbon is
bonded to two different groups, and that the two carbons have at least one substituent in
common. As with rings, cis-trans isomerism isn’t possible if one of the carbons of the double bond
is attached to two identical groups, as with 1,1-dibromo-1-propene, below.

Ambiguous Names Where Cis/Trans Isomerism Is Possible

A quick digression: one consequence of our newfound appreciation of geometrical isomerism is

that many simple-sounding molecule names are actually ambiguous.

For instance, the descriptor “3-hexene” does not unambiguously describe a specific molecule. To
nail down the specific molecule, we need to specify cis– or trans– 3-hexene.

5
Note that 1-hexene is still OK, since the 1-position of 1-hexene is attached to two identical groups
(hydrogens) and thus no cis–trans isomers are possible.

Cis– Trans- Isomerism for Cyclic Alkenes

cis- and trans can also be applied to alkenes in rings. For example, on paper it’s possible to
draw cis– and trans– cyclohexene, since the pi bond fulfills the requirements for cis-
trans- isomerism. In reality, trans-cyclohexene is impossibly strained. For this reason, for ring
sizes 7 and below, it’s safe to ignore writing “cis”: the configuration is assumed.

At ring sizes of 8 and above, we do need to put a cis– or trans- in the name, because the trans–
isomer becomes feasible. (Imagine trying to kiss yourself on the tailbone if you had the neck of a
giraffe: suddenly not impossible!)

6
Solution for When “Cis” and “Trans” Fails: The E/Z System

We saw that cis and trans fails in rings when the two carbons lacked a common substituent. It also
fails for alkenes under these circumstances.

Case in point: try to apply cis and trans to the alkene below:

See the problem?

In the absence of two identical groups, we have no reference point!

On the left, the chlorine is cis to Br and trans to F. But does that really justify calling the isomer
“cis”? How do we decide?

7
What we need is some way to determine priorities in these situations.

The E and Z Notation for Alkenes

Thankfully, we can apply the ranking system developed by Cahn, Ingold, and Prelog for
chiral centres for this purpose.

The protocol is as follows:

• Each carbon in the pi bond is attached to two substituents. For each carbon, these
two substituents are ranked (1 or 2) according to the atomic numbers of the atom
directly attached to the carbon. (e.g., Cl > F)
• If both substituents ranked 1 are on the same side of the pi bond, the bond is given the
descriptor Z (short for German Zusammen, which means “together”).
• If both substituents ranked 1 are on the opposite side of the pi bond, the bond is given
the descriptor E (short for German Entgegen, which means “opposite”).
So, Z resembles “cis” and E resembles “trans”. (Note: they are not necessarily the same and do
not always correlate: see Note 2 for an example of a cis alkene which is E . The E/Z system
is comprehensive for all alkenes capable of geometric isomerism, including the cis/trans alkene
examples above. We often use cis/trans for convenience, but E/Z is the “official”, IUPAC
approved way to name alkene stereoisomers].

One easy way to remember Z is to say “Zee Zame Zide” in a German accent.

Here’s a practical example:

8
ISOMERISM

Chain isomerism,

9
Positional isomerism,

Functional isomerism,

cis- and trans isomerism

SYNTHETIC PREPARATIONS OF ALKENES

Alkenes are generally prepared by elimination of one atom or groups from two adjacent carbon
atoms mainly from alcohols and halo alkanes.

The ease of dehydration of alcohols is: 3o Alcohol> 2o>1oAlcohol while the ease of
dehydrohalogenation of halo alkanes is 3o> 2o>1o

1. From Alcohols

Alcohols are heated with excess concentrated sulphuric acid or orthophosphoric acid. The
temperature of dehydration depends on the structure of the alcohol.

The reaction involves removal of water molecules hence known as dehydration reaction

The 1o and 2o alcohols follow the same mechanism while 3o alcohols undergoes partial ionization
generating 3o carbocations

10
Example

Conc.H2SO4 CH3CH CH2 + H2O

CH3CH2CH2OH o
180 C
Mechanism

+ -
CH3CH2CH2OH H OSO3H CH3CH2CH2OH2 + OSO3H

+ -H2O
CH3CH CH2 OH2 CH3CH CH2

H -
OSO3H

Example

OH

Conc. H3PO4
+ H2O
176oC

Mechanism
+
OH2
OH
H+

+
OH2
-H2O
-H3PO4
-
H OPO3H2

Example

Conc.H2SO4
(CH3)3C OH (CH3)2C CH2 + H2O
170oC

Mechanism
+
(CH3)3CH + -
(CH3)3COH OH
-H2SO4
(CH3)2C CH2 H -
OSO3H (CH3)2C CH2

11
Example

Conc. H2SO4
CH3(CH2)2CH2OH CH3CH CHCH3
180oC

Write the mechanism of the above reaction.

2. From Haloalkanes

Halo alkanes are heated with a strong base to generate an alkene.

i. Dehydrohalogenation of alkyl halides.

Halo alkanes are heated with a strong base such sodium amide in liquid ammonia or sodium
ethoxide in ethanol in order to remove hydrogen halide i.e.

EtONa / EtOH RCH CHR'

RCH2CHR'
Heat

Example

CH3CH2OK / CH3CH2OH CH3CH CH2

CH3CH2CH2Br
Heat

Mechanism
-Br-
CH3CH CH2 Br CH3CH CH2
-CH3CH2OH
H
-
OCH2CH3

Example

CH3CH2CHCH3 KOH / EtOH CH3CH CHCH3

Heat
Cl

Mechanism
KOH + EtOH EtOK + H2O

12
 Cl
-Cl- CH3CH
CH3CH CHCH3 CHCH3
-EtOH
-
H OEt

Example

NaNH2 / Liq.NH3
(CH3)3C Br (CH3)2C CH2
Heat
Mechanism

(CH3)3C Br (CH3)3C + + Br-

-NH3
(CH3)2C CH2 H -
NH2 (CH3)2C CH2

ii. Dehalogenation of Vicinal dihalides

When vicinal dihalides are heated with Zinc, alkenes are formed i.e.

Br

Zn
CH3CHCHCH3 CH3CH CHCH3
Heat
Br

N.B. On a large scale, alkenes are obtained by cracking of petroleum products

REACTIONS OF ALKENES

Alkenes undergo electrophilic addition, reduction by hydrogen, oxidation and polymerization

reactions. Alkenes undergo Electrophilic addition since they are electron rich species.

1. Addition of Hydrogen to Alkenes

Alkene react with hydrogen in the presence of a metal catalyst to produce the corresponding
saturated alkane addition products. Platinum, nickel and palladium can be used as catalysts

13
 Catalyst
C C + H2 C C

An alkene An alkane

Examples,

H2 / Ni
RCH CHR' RCH2CH2R'
150oC
e.g.
H2 / Ni
CH3CH CH2 CH3CH2CH3
o
150 C

Platinum and palladium are the most common catalysts for alkene hydrogenation. Palladium is
normally used as a very fine powder “supported” on an inert material such as charcoal (Pd/C) to
maximize surface area. Platinum is normally used as PtO2, a reagent called Adams’ catalyst. The
reaction is a heterogeneous one, that is, it takes place on the surface of insoluble catalyst particle.
The reaction occurs with Syn stereochemistry- both hydrogen atoms add to the double bond from
the same face.

CH3
H
H2, PtO2
CH3CO2H Solvent
H
1,2-Dimethylcyclohexene CH3
cis-1,2-Dimethylcyclohexane

The first step is the adsorption of hydrogen onto the catalyst surface. Secondly, complexation
between catalyst and alkene that occurs as a vacant orbital on the metal interacts with the filled
alkene pie orbital. Lastly, hydrogen is inserted into the double bond. The reaction is so sensitive
to the steric environment around the double bond, as a result, the catalyst often approaches only
the more accessible face of an alkene, giving rise to a single product.

Also, alkenes are much more reactive than most other unsaturated functional groups towards
catalytic hydrogenation, and the reaction is therefore quite selective as shown below. Other
functional groups such as aldehyde, ketone, esters and nitrile survive normal alkene hydrogenation
with conditions unchanged, although reaction with these function groups does occur under more
vigorous conditions.

14
 H2
O
O
Pd/ C in ethanol
2-Cyclohexenone Cyclohexanone (Ketone NOT reduced)

O
O

H2
O
O
Pd/ C in ethanol
Methyl-3-phenylpropanoate
Methyl-3-phenylpropenoate
(Aromatic ring NOT reduced)

N N
H2

Pd/ C in ethanol
Cyclohexylidene acetonitrile Cyclohexyl acetonitrile
(Nitrile NOT reduced)
This reaction is quite applicable in food industry, where unsaturated vegetable oils are reduced to
produce the saturated fats used in margarine and cooking products. Vegetable oils are triesters of
glycerol OHCH2CH(OH)CH2OH with three long chain carboxylic acids called fatty acids. The
fatty acids are generally polyunsaturated and their double bonds invariably have cis
stereochemistry. Complete hydrogenation yields the corresponding saturated fatty acids but
incomplete hydrogenation often results in partial cis- trans- isomerization of the remaining double.
When eaten and digested, the free trans- fatty acids are released, raising blood cholesterol levels
and contributing to potential coronary problems.

2. Addition of Halogens to Alkenes

This reaction is usually carried out in an inert solvent such carbon tetrachloride. Chlorine and
Bromine reacts rapidly with alkenes to yield 1, 2- dihalides in a process called halogenation.
Fluorine is too reactive and difficult to control for most laboratory applications, and iodine does
not react with most alkenes.

The reddish- brown colour of bromine is turned colourless therefore the reaction is used to test for
presence of carbon-carbon double bond and the number of double bonds since the mole ratio is
1:1(Alkene: Bromine)

15
 X2 /CCl4
RCH CHR' RCHCHR' X2 = Cl2 or Br2

X X

CCl4 CH3CHCH2Br
CH3CH CH2 + Br2

Br

The mechanism involving carbocation seems plausible at first sight. However, it does not explain
the stereochemistry of the addition reaction. That is, the mechanism does not tell which product
stereoisomer is formed.

+ Cl Cl CH3 CHCH2Cl + Cl-

Propene

CH3CHClCH2 Cl

When the halogenation reaction is carried out on a cycloalkene, such as cyclopentene, only the
trans- stereoisomer of the dihalides addition products is formed rather than the mixture of cis- and
trans- isomers that might have been expected if a planar carbocation intermediate were involved.

H Br
Br - Br

Br H Br Br

trans- 1,2- Dibromocyclopentane cis- isomer

Sole product
The explanation for the observed antistereochemstry of addition was proposed that the reaction
intermediate is not a carbocation but instead a bromonium ion, R2Br+, formed by addition of Br+
to the alkene. Similarly, a chloronium ion contains a positively charged divalent chlorine, R2Cl+.
The bromonium ion is formed in a single step by interaction of the alkene with Br2 and
simultaneous loss of Br-.

16
 Br

Br
Br+
+ Br-
C C
C C

An alkene A bromonium ion

Reaction with Br- ion in the second step could then occur only from the opposite, unshielded side
to give trans- product.
Top side open to attack

:Br: - H Br

H H
Br Br Br H
Br
Cyclopentene
A bromonium ion intermediate trans- 1,2-
Dibromocyclopentane

3. Addition of Hypohalous acids to Alkenes: - Halohydrin Formation

Reaction of alkenes with hypohalous acids HO - Cl or HO- Br to yield 1,2- halo alcohols,
called halohydrins. The reaction takes place indirectly by reaction of an alkene with either Br2
or Cl2 in the presence of water.
X

X2
C C C C + HX
H2O
OH

Mechanism

17
 Br+
H CH3

+ Br Br C C + Br-
C C
H
H3C H CH3
H3C H
But-2-ene

OH2

Br CH3 Br CH3

H C C H + H3O+ H C C H

CH3 OH CH3 O

H H
3- bromo-2-butanol

:OH2
Other examples

Br2 /H2O CH3CHCH2Br

CH3CH CH2

OH

In practice, few alkenes are soluble in water, and bromohydrin formation is often carried out in a
solvent such as aqueous dimethyl sulfoxide CH3SOCH3 (DMSO) using a reagent called N-
bromosuccinimide (NBS) as a source of Br2.

NBS is stable, easily handled compound that slowly decomposes in water to yield Br2 at a
controlled rate. Bromine itself can be also used in the addition reaction, but it is more dangerous
and more difficult to handle than NBS.

18
 O

Br N

Br

O
N-Bromosuccinimide
H2O, DMSO
OH
Styrene 2-Bromo-1-phenylethanol

4. Addition of Water / Hydration to Alkenes

Alkenes react with cold concentrated sulphuric acid to form alkyl hydrogen sulphate which reacts
with water on heating to form alcohol.

H2SO4 H2O
RCH CHR' RCHCH2R' RCHCH2R'
Heat

OSO3H OH

H2SO4 H2O
CH3CH CH2 CH3CHCH3 CH3CHCH3
Heat
OSO3H OH

Mechanism

The mechanism follows Markovnikov’s rule.

19
 + H OSO3H
CH3 CHCH3
Propene

OSO3H

H2 O CH3CHCH3
CH3CHCH3
OSO3H
O
H
H
OSO3H

CH3CH(OH)CH3
2-Propanol

5. Addition of Hydrogen Halides to Alkenes

Hydrogen halides react with alkenes forming alkyl halides.

HX
RCH CHR' RCHCH2R' X=Cl,Br and I

In the reaction above, the hydrogen atom from hydrogen halide adds itself to the carbon atom of
the double bond with the larger number of hydrogen atoms. Also, the halogen adds itself to the
carbon atom in double bond with lower number of hydrogen atom thus these are known as
Markovnikov’s rule.

HBr
CH3CH CH2 CH3CHCH3

Br

Mechanism

- CH3 CHCH3
+ H Br CH3CHCH3 + Br
Propene Br

20
 Example

H3CH2C

CH2CH3
+
H Cl -Cl-

CH2CH3 CH2CH3
+

Cl
Cl-

N.B. The hydrogen bromide is usually generated by action of concentrated Sulphuric acid on
sodium bromide.

6. Addition of Hydrogen Bromide to Alkenes in presence of Peroxide

In this reaction, the bromine atom adds itself to the carbon atom of the double bond having higher
number of hydrogen atoms with hydrogen atom (from Hydrogen bromide) to lower carbon atom.

This observation is known as anti-Markovnikov’s rule.

HBr
RCH CH2 RCH2CH2Br
Peroxide
e.g.
HBr
CH3CH CH2 CH3CH2CH2Br
Peroxide
Mechanism
.
RO OR 2OR
. .
RO H Br ROH + Br

CH3CH CH2 Br CH3CHCH2Br

CH3CHCH2Br + HOR CH3CH2CH2Br + OR

21
 7. Oxidation of Alkenes: Epoxidation and Hydroxylation

This decreases electron density on carbon by either forming C-O, C-N, C-X or breaking C-H bond.

Epoxidation

Alkenes are oxidized to give epoxides on treatment with a peroxy acids (RCO3H), such as meta-
chloro peroxybenzoic acid. An epoxide, also called an oxirane, is a cyclic molecule with an oxygen
atom in a three membered ring.

Example
Cl

O
+
CH2Cl2
O +
O
1,2-Epoxycycloheptane
OH
m-chloroperoxybenzoic acid Cl CO2H

Mechanism

H
C
O O + RCOOH
O
C
O C

R
Epoxide

Also, halohydrins can generate epoxides. Halohydrins are prepared by addition of HO-X to
alkenes. Heating halohydrins with a base eliminates HX and produces epoxides.
Cl

Cl2 NaOH + H2O + NaCl

HO
Heat
H2O
O
trans-2-chlorocyclohexanol
Cyclohexene 1,2-Epoxycyclohexane

22
Epoxides undergo acid catalyzed hydrolysis to give the corresponding diols also called glycols.
Hydroxylation is the net result of Epoxidation and hydrolysis reactions- adding –OH group to each
of the two double bond carbon atoms.

C O OH
Epoxidation +
H3 O
C C C C
C

OH
A 1,2-diol

Mechanism

H H

OH
H3 O+
O H

H
O H
O
1,2-Epoxycyclohexane
:OH 2
H
H

OH2

H
OH

+ H 3O +

H
OH

trans-1,2-cyclohexanediol (86%)

23
Hydroxylation, can be done using Osmium tetroxide, OsO4. The reaction occurs with Syn
stereochemistry. The cyclic intermediate formed maybe reduced with sodium hydrogen sulphate
in the presence of water.

CH3

O
H C O
OsO4
Os
2-Butene Pyridine H C O
O

CH3

A cyclic Osmate intermediate

H2S OR NaHSO4/H2O

CH3CHCHCH3

OH OH
cis-2,3-Butanediol (87%)
Mechanism

O O O O
+ Os Os
O O O
O (VIII) (VI)

H 2S

OH

OH
1-Methyl-cyclohexane-1,2-diol

24
 8. Oxidation of Alkenes: Cleavage to Carbonyl compounds

There are powerful oxidizing reagents that cleave C = C bonds to produce two carbonyl
compounds.

Ozonolysis: Ozone (O3) is the most useful reagent.

When a stream of oxygen is passed through a high voltage electrical discharge, oxygen adds
rapidly to an alkene at low temperature to give cyclic intermediate called a molozonide, which
rearranges to form an ozonide.

3O2 2O3

O O O
O O
C C O3
C C
CH2 Cl2, -78o C C C
O
An alkene
An ozonide
A molozonide

Zn
CH3 CO2H/ H2O

C O + O C

The ozonide is treated with a reducing agent such as Zinc metal in acetic acid to convert it to
carbonyl compounds. The net result of the Ozonolysis/ reduction sequence is that the C = C bond
is cleaved and oxygen becomes double bonded to each of the original alkene carbon.

Example

1. O3
O +
2. Zn, H3O+
O
Isopropylidenecyclohexane Cyclohexanone Acetone

25
Several oxidizing reagents other than ozone also cause double bond cleavage. For example,
potassium permanganate (KMnO4) in neutral or acidic solution cleaves alkenes to give carbonyl
containing products. If hydrogen atoms are present on the double bond, carboxylic acids are
produced. If two hydrogen atoms present on a carbon atom, CO2 is formed.

KMnO4
CH3CH = CH2 CH3COOH + CO2
H3O+
In addition to direct cleavage with ozone or KMnO4 an alkene can also be cleaved by initial
hydroxylation to a 1,2- diols followed by treatment with periodic acid, HIO4, if the two –OH groups
are in an open chain, two carbonyl compounds result. If the two –OH groups are on a ring, a single
open chain dicarbonyl compound is formed.

Example,

CH3
CH3 OH
O
OH HIO4 I O
OH H2O, THF
O
H O
H

O
6-Oxoheptanal

HIO4
2O
H2O, THF O O
OH OH
I
O Cyclopentanone
OH
O

Cyclic periodate intermediate

26
 9. Oxidation of Alkenes: Oxymercuration

When an alkene is treated with mercury (II) acetate Hg(O2CCH3)2, often abbreviated as Hg(OAc)2
in aqueous tetrahydrofuran, THF, electrophilic addition of Hg2+ to the double bond rapidly occurs.
The intermediate organomercury compound is then treated with sodium borohydride, NaBH4 and
an alcohol is produced. The reaction yields Markovnikov’s product.

1. Hg(OAc)2 , H2O/THF
HO
2. NaBH4
1- Methylcyclopentene
1- Methylcyclopentanol

CH3 CH3

HgOAc OH

Hg(OAc)2 H2 O
HgOAc
H H
1- Methylcyclopentene Mercurinium Organomercury compound

NaBH4

HO

1- Methylcyclopentanol

10. Addition of Carbenes to Alkenes: Cyclopropane synthesis

A carbene, R2C: is a neutral molecule containing a divalent carbon with only six valence electrons
in its valence shell. It is highly reactive and generated only as a reaction intermediate, rather than
an isolable molecule. Because they are electron- deficient, carbenes behave as electrophiles and
react with Nucleophilic C = C bonds. The reaction occurs in a single step without intermediates.

27
 R
R
R C

C C + C : C C
R

The carbene can be generated by treatment of chloroform, CHCl3 with a strong base KOH. Loss
of a proton from chloroform gives trichloromethanide anion, - CCl3, which expels a Cl- ion to yield
dichloro carbene : CCl2

Mechanism

Examples
Cl Cl
H

KOH CH3 + KCl

+ CHCl3 H

2-Pentene
H3 CH2C

H
Cl
KOH
+ CHCl3 + HCl
Cl

28
Simmons – Smith reaction produces non – halogenated Cyclopropane. It uses carbenoids – a metal
complexed reagent with carbene – like reactivity.

Example

11. Hydroboration of Alkenes

This refers to the addition of hydrogen- boron bond to a C-C, C-N and C-O double bonds, as well
as C-C triple bonds. It produces organoboranes compounds, which react with a variety of reagents
to produce useful compounds, such as alcohols, amines and alkyl halides.

For Alkenes:

It is anti- Markovnikov’s reaction

H BH2
H

BH3 H B
RCH = CH2 R(H)C CH2
H
R(H)C CH2

2RCH = CH2

(RCH2CH2)3B

29
 1. B2H6
HO
2. H2O2
1-Methylcyclohexene (90%)
2-Methylcyclohexanol
Oxidation of organoboranes with basic hydrogen peroxide yields alcohol.

H BH2 OH

H2O2, HO- H
BH3
H3C H C C H
THF
2-Methyl-2-pentene CH2CH3
CH3 CH2CH3

2-Methyl-3-pentanol

Also,

OH

H2 O2
3 +
3 B H2O, NaOH
THF

B(OH)3

The reaction is useful because of regioselectivity

30
 CH3

H
BH3 H2O2, HO- HO
THF BH2

H
1-Methylcyclopentene Trans- 2-methylcyclopentanol

12. Polymerization Reaction

Alkenes undergo addition polymerization to form polymers. The mechanism of polymerization is

by radical mediated, cationic and anionic catalyzed. Ethene polymerizes to form polyethene which
is an important plastic material used as packing material.

O2 or Peroxide
n CH2 CH2 * CH2CH2 *
1500atom, 200oC
n

Historically, ethylene polymerization was carried out at high pressure and temperature in the
presence of catalyst such as benzoyl peroxide, although other catalysts and reaction conditions are
now more often used. The key step is the addition of a radical to the ethylene double bond, a
reaction similar in many respects to what takes place in the addition of the electrophile.

Radical mechanism

Initiation
O O

O O

O Heat O .
2 = 2 BzO

Benzoyl peroxide

. .
H2C = CH2 BzOCH2CH2
BzO

Chain propagation step

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 . .
BzOCH2CH2 CH2 = CH2 BzOCH2 CH2CH2CH2

Repeat many times

.
BzO (CH2CH2 )nCH2CH2

Chain termination step

The chain process is eventually ended by a reaction that consumes the radical. Combining the two
growing chains is one possible chain termination reaction.

.
2 RCH2CH2 RCH2 CH2CH2CH2R

Examples of Polymers synthesized from Alkenes.

Monomer Polymer Trade/ Common Uses

name of polymer

Ethylene H2C = CH2 Polyethylene Packaging, bottle

Propene H2C = CHCH3 Polypropylene Molding, rope, carpets

(Propylene)

Poly (vinyl chloride) Insulation, films, pipes

Chloroethylene H2C = CHCl
Tedlar
(Vinyl chloride)

Polystyrene Foam, molding,

Styrene H2C = CHC6H5

Tetrafluoroethylene F2C = CF2 Teflon Caskets, non-sticky coatings

Orlon, Acrilan Fibers
Acrylonitrile H2C = CHCN

H2C = CCO2CH3 Plexiglas, Lucite Paints, sheets, moldings

Methylmethacrylate

CH3
H2C = CHOCOCH3 Poly (vinylacetate) Paint, adhesives, foam
Vinyl acetate

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 13. Cycloaddition of alkenes

Alkenes undergo diverse Cycloaddition reactions. Most notable is the Diels- Alders reaction with
1, 3 – dienes to give cyclohexene.

C
+
C

Diene Dienophile Cyclohexene

Assignment

A hydrocarbon A contains 87.8% carbon. Its relative molecular mass is 82. A decolorizes bromine
and in presence of Nickel it reacts with hydrogen to form B. 0.1g of A was found to absorb 27.3cm3
of hydrogen (measured at s.t.p). B does not decolorize bromine.

(a) Determine the:

(i) Empirical formula

(ii) Molecular formula of A.

(b) Calculate the:

(i) Number of moles hydrogen that reacted with one mole of A

(ii) Number of double bonds in the molecule of A

(c) Write the possible Isomers of A.

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