General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 5

Chapter 4

Alkenes & Alkynes

Alkene Nomenclature
 Alkenes
Alkenes

Alkenes are hydrocarbons that contain a

carbon-carbon double bond

also called "olefins"

characterized by molecular formula CnH2n

said to be "unsaturated"
 Alkene
AlkeneNomenclature
Nomenclature

H2C CH2 H2C CHCH3

Ethene Propene
or
Ethylene (Propylene is
(both are acceptable sometimes used
IUPAC names) but is not an acceptable
IUPAC name)
 Alkene
AlkeneNomenclature
Nomenclature

H2C CHCH2CH3 1-Butene

1) Find the longest continuous chain that

includes the double bond.
2) Replace the -ane ending of the unbranched
alkane having the same number of carbons
by -ene.
3) Number the chain in the direction that gives
the lowest number to the doubly bonded
carbon.
 Alkene
AlkeneNomenclature
Nomenclature

H2CCHCHCH2Br

CH3

4) If a substituent is present, identify its position

by number. The double bond is first then
alkyl groups and halogens when the chain is
numbered.
The compound shown above is
4-bromo-3-methyl-1-butene.
 Alkene
AlkeneNomenclature
Nomenclature

H2CCHCHCH2OH

CH3

4) If a substituent is present, identify its position

by number. Hydroxyl groups take
precedence over the double bond when the
chain is numbered.
The compound shown above is
2-methyl-3-buten-1-ol.
 Alkenyl
Alkenylgroups
groups

methylene H2C

vinyl H2C CH

allyl H2C CHCH2

Remember

isopropenyl H2C CCH3

 Cycloalkene
CycloalkeneNomenclature
Nomenclature

Cyclohexene

1) Replace the -ane ending of the cycloalkane

having the same number of carbons by -ene.
Structure and Bonding in
Alkenes
 Structure
Structureof
ofEthylene
Ethylene

bond angles: H-C-H = 117°

H-C-C = 121°
bond distances: C—H = 110 pm
C=C = 134 pm

planar
Bonding in Ethylene

σ
σ

σ σ
σ

• Framework of σ bonds
• Each carbon is sp2 hybridized
Bonding in Ethylene

• Each carbon has a

half-filled p orbital
Bonding in Ethylene

• Side-by-side overlap of half-

filled p orbitals gives a π bond
Isomerism in Alkenes
 Isomers
Isomers

Isomers are different compounds that

have the same molecular formula.
 Isomers
Isomers

Constitutional
Constitutionalisomers
isomers Stereoisomers
Stereoisomers
 Isomers
Isomers

Constitutional
Constitutionalisomers
isomers Stereoisomers
Stereoisomers

same connectivity;
different connectivity different arrangement
of atoms in space
 Isomers
Isomers

Constitutional
Constitutionalisomers
isomers Stereoisomers
Stereoisomers

consider the isomeric alkenes of

molecular formula C4H8
 H CH2CH3 H3C H
C C C C
H H H3C H

1-Butene 2-Methylpropene

H3C CH3 H3C H

C C C C
H H H CH3

cis-2-Butene trans-2-Butene
 H CH2CH3 H3C H
C C C C
H H H3C H

1-Butene 2-Methylpropene

H3C CH3

C C Constitutional isomers
H H

cis-2-Butene
 H CH2CH3 H3C H
C C C C
H H H3C H

1-Butene 2-Methylpropene

H3C H

Constitutional isomers C C
H CH3

trans-2-Butene
 Stereoisomers

H3C CH3 H3C H

C C C C
H H H CH3

cis-2-Butene trans-2-Butene
Stereochemical
StereochemicalNotation
Notation

cis (identical or
analogous substituents
on same side)

trans (identical or
analogous substitutents
on opposite sides)
 Naming Stereoisomeric
Alkenes by the E-Z Notational
System
 Stereochemical
StereochemicalNotation
Notation

CH3(CH2)6CH2 CH2(CH2)6CO2H

C C Oleic acid
H H

cis and trans are useful when substituents are

identical or analogous (oleic acid has a cis
double bond)
cis and trans are ambiguous when analogies
are not obvious
 Cl Br
Example
Example C C
H F

What is needed:

1) systematic body of rules for ranking

substituents
2) new set of stereochemical symbols other
than cis and trans
 The
TheE-Z
E-ZNotational
NotationalSystem
System

E : higher ranked substituents on opposite sides

Z : higher ranked substituents on same side

higher

C C

lower
 The
TheE-Z
E-ZNotational
NotationalSystem
System

E : higher ranked substituents on opposite sides

Z : higher ranked substituents on same side

lower

C C

higher
 The
TheE-Z
E-ZNotational
NotationalSystem
System

E : higher ranked substituents on opposite sides

Z : higher ranked substituents on same side

higher lower

C C

lower higher

Entgegen
 The
TheE-Z
E-ZNotational
NotationalSystem
System

E : higher ranked substituents on opposite sides

Z : higher ranked substituents on same side

higher lower higher higher

C C C C

lower higher lower lower

Entgegen Zusammen
 The
TheE-Z
E-ZNotational
NotationalSystem
System

Question: How are substituents ranked?

Answer: They are ranked in order of
decreasing atomic number.

higher lower higher higher

C C C C

lower higher lower lower

Entgegen Zusammen
 The
TheCahn-Ingold-Prelog
Cahn-Ingold-Prelog(CIP)
(CIP)System
System

The system that we use was devised by

R. S. Cahn
Sir Christopher Ingold
Vladimir Prelog
 CIP
CIPRules
Rules

(1) Higher atomic number outranks lower

atomic number

Br > F Cl > H

higher Br Cl higher

C C

lower F H lower
 CIP
CIPRules
Rules

(1) Higher atomic number outranks lower

atomic number

Br > F Cl > H

higher Br Cl higher

C C

lower F H lower
(Z )-1-Bromo-2-chloro-1-fluoroethene
* Do not remember the name just if it is E or Z
Physical Properties of Alkenes
 Dipole
Dipolemoments
moments

What is direction of
dipole moment?
Does a methyl group
H H donate electrons to the
double bond, or does it
C C withdraw them?
H H
µ =0D H3C H
C C
H H
µ = 0.3 D
 Dipole
Dipolemoments
moments
µ = 1.4 D
H H
C C
H H H Cl
C C Chlorine is
electronegative and
H H attracts electrons.

µ =0D H3C H
C C
H H
µ = 0.3 D
 Dipole
Dipolemoments
moments
µ = 1.4 D
Dipole moment H H
of 1-
chloropropene C C
is equal to the H Cl H3C H
sum of the
dipole moments C C
of vinyl chloride
and propene. H Cl
H3C H µ = 1.7 D
C C
H H
µ = 0.3 D
 Dipole
Dipolemoments
moments
µ = 1.4 D
H H
C C
Therefore, a
H Cl H3C H
methyl group
donates C C
electrons to the
double bond. H Cl
H3C H µ = 1.7 D
C C
H H
µ = 0.3 D