Chapter 2.

Alkenes
 Alkene
Nomenclature
Cycloalkene

Cis and Trans

Alkenes Geometric Isomers
E and Z
configurations
Properties
Synthesis
Chemical Reaction
Reactions
 Revisit…
• Alkene
– Unsaturated hydrocarbon
– Contain double covalent bonds
– General formula CnH2n

Aliphatic Alkenes
Alkenes
Alicyclic Cycloalkene
 Physical properties
• Insoluble in water and soluble in polar solvents
• Have a density less than water
– Density is increasing with increasing no of C
• Boiling and melting points lower than alkane
eventhough they have the same no of C
– Both increasing with increasing C number
• 2 to 4 C alkenes: Exist as gases at room T
• 5 to 17 C alkenes: Exist as liquids
• Alkenes with >17 atoms exists as solids
 Alkene Nomenclature
• MUST account the double bond:
– Longest chain MUST contain the double bond
– Carbon that has the double bond must have the
lowest number
– Must indicate the position of the double bond
– Ending must be
• – ene (one double bond)
• - diene (2 double bond)
• - triene (3 double bond)
– Same rules for the side chains and halides
 Alkene Nomenclature
1 2 3 4
H2C CHCH CH2 1,3-butadiene
1 2 3 4 5 6 7
H2C CHCH CHCH CHCH3
1,3,5-heptatriene
 Cycloalkene Nomenclature
• Replace the -ane ending of the
cycloalkane having the same number of
carbons by -ene
• Number through the double bond in the
direction that gives the lower number to
the first-appearing substituent.

CH3 6-Ethyl-1-methylcyclohexene

CH2CH3
 Cycloalkene Nomenclature (cont.)
• 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 6 2

1 5 3
5 2 4
H3C CH3
4 3

1-methylcyclopentene 3,5-dimethylcyclohexene
 Geometric isomers
Can rotate about all
bonds
Alkanes
No geometric
isomers

Rigid bond
Geometric
Alkenes Cis and trans
isomers
Have geometric
isomers
E and Z confg.
Rigid but linear
bond
Alkynes
No geometric
isomers
Cis and trans
 Cis and trans (Cont.)
• cis – trans stereoisomerism (geometric isomer) in alkenes is not
possible IF the doubly bonded carbons bears two identical
substituents
• The essential requirement for this stereoisomerism - each carbon of
the double bond must have two different substituent groups (one
may be hydrogen)

Example 1: The left-hand double bond carbon has two identical substituents (A) so
stereoisomerism about the double bond is not possible (reversing substituents on the right-
hand carbon gives the same configuration).

In the next two examples (Example 1 and 2), each double bond carbon atom has two different
substituent groups and stereoisomerism exists, regardless of whether the two substituents on
one carbon are the same as those on the other.
 Cis and trans (Cont.)
• Alkenes nomenclature must specify whether a
given molecule is cis or trans if it is a
geometric isomer
 E and Z configuration
• Although the prefixes cis and trans can be used to distinguish
diastereomers 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.
 (E) : the higher priority groups are on opposite sides
of the double bond.
 (Z) : the higher priority groups are on the same side
of the double bond.
E is for "Enemies", which are on opposite sides
In Z isomers, the higher priority groups are on zee
zame zide.
 E and Z configuration (cont.)
• When atoms of higher atomic number are on the same side of
double bond, we say that the double bond has the Z configuration

• When atoms of higher atomic number are on opposite site of double

bond, we say that the double bond has the E configuration
 E and Z configuration (cont.)
• E/Z system is now recommended by IUPAC for the
designation of geometric isomerism.
• Use the sequence rules to assign the higher priority
* to the two groups attached to each vinyl carbon.
 E and Z configuration (cont.)

(Z) – 3-methyl-2-pentene
(3-methyl-cis-2-pentene)

(E)-1-bromo-1-chloropropene
 Synthesis of alkenes
Dehydrogenation of
Regioselectivity
alkenes

Dehydration of alcohol Zaitsev Rule

Synthesis of
alkenes
Saytzeff rule

Dehydrohalogenation of
Saytzeff rule
alkyl halides
 Synthesis of alkenes (cont.)
• Dehydrogenation of alkanes
– Elimination of H2 molecule
– Industrial synthesis of ethylene, propene
 Synthesis of alkenes (cont.)
• Dehydration of alcohol
– Loss of O and H from adjacent carbons
– Acid catalyst is necessary
 Synthesis of alkenes (cont.)
• Regioselectivity
– A reaction that can proceed in more than one
direction, but in which one direction predominates,
is said to be regioselective.
 Synthesis of alkenes (cont.)
• 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.
 Synthesis of alkenes (cont.)
• Saytzeff rule - A reaction that produces an alkene
would favor the formation of an alkene that has the
greatest number of substituents attached to the
C=C group
Dehydration of alcohols
H+
CH3CH2-CH=CH2 + H2O
CH3CH2-CH-CH3 1-butene
+
OH H
CH3CH=CH-CH3 + H2O
2-butanol
2-butene
major product
 Synthesis of alkenes (cont.)
• Dehydrohalogenation of alkyl halides
– Loss of H and X from alkyl halides
– In the presence of strong base in solvent i.e. NaOCH3 in
methanol, KOH in ethanol
 Synthesis of alkenes (cont.)
• Saytzeff rule - A reaction that produces an alkene
would favor the formation of an alkene that has the
greatest number of substituents attached to the
C=C group
Dehydrohalogenation of haloalkanes
CH3CH-CH-CH2 alcohol CH3CH2CH=CH2
KOH CH3CH=CH-CH3
reflux
H Br H 2-butene
1-butene
2-bromobutane (major product)