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CLD 10302

ORGANIC CHEMISTRY
CHP2 : HYDROCARBON
ALKENE
Prepared By:
ARBANAH MUHAMMAD

TOPIC COVERED

Alkenes
Nomenclature of Alkenes
Naming of Cycloalkenes
Geometric Isomers
Properties of Alkenes
Synthesis of Alkenes
Principal Reactions of Alkenes

Introduction

Classification of
Hydrocarbon
Hydrocarbon
Aromatic

Aliphatic
Alkanes

Alkenes

Alkynes

CycloalkanesCycloalkenes

Saturated

Unsaturated

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkenes are
hydrocarbons that
contain a carbon-carbon
double bond.
H

H
C

Alkenes
Alkenes
H

C
H

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkenes whose carbon


atoms are joined in
rings.

CycloAlkenes
CycloAlkenes

General formula
Aliphatic hydrocarbons
Unsaturated hydrocarbon

CYCLOALKENES
Alkenes whose carbon atoms are joined in
rings
General formula Cn H2n-2 where n =3,4,5..
Eg:

Cyclopentene, C5H8

Cyclobutene, C4H6

E.G 1: Cycloalkene with substituents

CH3

CH3

1,3- dimethylcyclopentene

Naming Alkenes
We must account for double bond:
1.

Longest chain must contain the double bond ( = )

2.

Number of carbons so that the double bond has the


lowest number

3. Indicate the position of the double bond


4. Change ending to ene
5. Use the same rules for the substituent (side chains and
halides)

The ending of the alkenes with more than one


double bond should be change from -ene to:
diene if there are two double bonds
triene if there are three double bonds
1

H2C
1

H2C

CH CH
2

CHCH

1,3-butadiene

CH2
4

CHCH

CHCH3

1,3,5-heptatriene

E.G 2: Naming cycloalkenes

1
5

CH3

CH2CH3

6-Ethyl-1-methylcyclohexene
First appearing
substituent at double
bond

1) Replace the -ane ending of the cycloalkane


having the same number of carbons by -ene.
2) Number through the double bond in the
direction that gives the lower number to the
first-appearing substituent.

Number substituted cycloalkenes in the way that gives the

carbon atoms of the double bond the 1 and 2 positions.


That also gives the substituent groups the lower numbers
at
the first point of difference.
1

CH3

2
4

H3C

CH3

1-methylcyclopentene

3,5-dimethylcyclohexene

Geometric Isomer

Trigonal planar

2-butene

Alkenes nomenclature must specify whether a


given molecule is cis or trans if it is a
geometric isomer
Eg 1::

CH3

CH3
C=C
H

cis-2-butene

Larger group
on the same
side

CH3CH2

C=C
H

CH2CH3

trans-3-hexene

Larger group
on the
different side

CH2CH3

CH3CH2

C=C
H

CH2CH2CH3

trans-4- ethyl 3-heptene

CH2CH2CH3

CH3CH2
C=C
H

CH3

cis-4-methyl-3-heptene

However, Cis trans stereoisomerism (geometry


isomer) in alkenes is not possible when :
one of the doubly bonded carbons bears two identical
substituents

Using the prefix E and Z


Although the prefixes cis and trans can be used to
distinguish disastereomers when two alkyl groups are
bonded to the C C , they cannot be used when there
are three or four alkyl groups bonded to the C
C.
A completely unambiguous system for specifying
double bond stereochemistry has been adopted by the
IUPAC based on an atomic number criterion for
ranking substituents on the doubly bonded carbons.

When atoms of higher atomic number are on the same side of


double bond, we say that the double bond has the Z configuration.
Higher

CI

Br
C

Lower

Higher
Lower

When atoms of higher atomic number are on opposite site of


double bond, we say that the double bond has the E configuration.
Higher

CI

Lower

* Refer to page 189 in our text book

C
H

Lower

Br

Higher

Physical
Properties

Physical Properties
Similar to alkanes
Solubility
Soluble in non polar solvent
Not soluble in water
Low density, boiling point and melting point
Properties vary based on chain size
Interesting physical properties
Alkenes with several double bonds will have a color
associated with them

Colored Alkenes

LYCOPENE : Tomato, Paprika And Watermelon (RED)

B-CAROTENE: Carrots and Yams (Yellow)

Physical Properties of Alkenes

Synthesis of alkenes
-Dehydrogenation
-Dehydration
-Dehalogenation

Synthesis of alkenes: Elimination reactions


Dehydrogenation of alkanes:
X=Y=H
Dehydration of alcohols:
X = H; Y = OH
Dehydrohalogenation of alkyl halides:
X = H; Y = Br, Cl

Synthesis of alkenes
Dehydrogenation of alkanes

Elimination of molecule H2

limited to industrial synthesis of ethylene, propene


H

Example
H
H
H

C
H

750C

ethane

H
C

+ H2

+
H

ethene (ethylene)

H2

Synthesis of alkenes
Dehydration of alcohol
Loss of H and OH from adjacent carbons.
Acid catalyst is necessary.
C

OH

H 2O

Example
H
H

C
H

H
C
H

H2SO4
OH
ethanol

160C

H
C

C
H

ethene (ethylene)

H 2O

Synthesis of alkenes
Regioselectivity in alcohol dehydration
H H
H OH H H
H C C C C H H2SO4 H C C C C H
H H
H
H
H H
H C H
H C H
80C
H
H
2-methyl-1-butene
2-methyl-2-butanol

H
H
H C C C C H
H
H H
+ H C H
H

2-methyl-2-butene

10 %

A reaction that can proceed in more than one


direction, but in which one direction
predominates, is said to be regioselective.

90 %

Synthesis of alkenes
Zaitsev Rule

When elimination can occur in more than one


direction, the principal alkene is the one formed
by loss of H from the carbon having the
fewest hydrogens.

OH

CH3

R
CH2R

CH2R
C

2H on this carbon
only 1H on this carbon

C
CH3

Synthesis of alkenes
Dehydrohalogenation of alkyl halides
Loss of H and halogen (X) from an alkyl halide
In the presence of strong base in solvent likewise
NaOCH3 in methanol, or KOH in ethanol
C

+ HX

Example
H
H

C
H

H
C
H

Cl

(Sodium ethoxide)
NaOCH2CH3
ethanol, 55C

Ethyl chlorides

H
C

+
H

ethene (ethylene)

HCl
Hydrogen
chloride

Reaction of Alkenes
Primarily reactions involve the double bond
The key reaction of double bond is addition reaction
(Breaking the bond and adding something to each carbon)
The major alkene reactions include additions of hydrogen
(H2),halogen ( CI2 or Br2), water (HOH) or hydrogen
halides (HBr or HCI)

+ A-B
A B

REACTION OF ALKENE

HYDROGENATION
HYDRATION
HYDROHALOGENATION
HALOGENATION
OZONOLYSIS

Reaction of Alkenes
1. Hydrogenation Addition of H2
Addition of a molecule of H2
Results in the formation of an alkane

Usually requires heat, pressure and a catalyst like Pt, Pd or Ni

Reaction of Alkenes

2. Hydration: Addition of H2O


The addition of water to an alkene
One carbon get an H, the other an OH
produces an alcohol

The reaction requires a small amount of acid to be present


to work

Reaction of Alkenes

Reaction of Alkenes

Reaction of Alkenes

Reaction of Alkenes

3. Hydrohalogenation
Addition of HX to an alkene
HX HF, HCI, HBr, HI
It follows Markonikovs rule where the H ends up on the
carbon with the most hydrogen to start with

Reaction of Alkenes

Reactions of alkenes
4. Halogenation: Addition of X2
The addition of halogen to an alkene
produces a haloalkane or alkyl halide

R C CR

X2

R C C R
X X

Simple laboratory test for unsaturation.

5. Ozonolysis of alkenes
1st step - reaction of alkene with ozone to form
ozonide.
2nd step - hydrolysis of ozonide to form aldehyde
and ketone.
R
R
O
C

H
R

+ O3

O
O
ozonide

R
R
C

H aldehyde

ketone R

H2O, Zn