ALKANES AND

CYCLOALKANE

The synthesis of vitamin B12 took 11 years, required 90 steps, and involved the work of
nearly 100 people
Alkanes
Hydrocarbons:

1) Alkanes: CnH2n+2 (saturated)

i) Cycloalkanes: CnH2n (containing a single ring)

ii) Alkanes and cycloalkanes are so similar that many of their properties can
be considered side by side.

2) Alkenes: CnH2n (containing one double bond)

3) Alkynes: CnH2n–2 (containing one triple bond)
Physical Properties
Physical Properties
Physical Constants of the Hexane Isomers
Physical Properties
Branching of the alkane chain lowers the boiling point

1. Boiling points of C6H14: hexane (68.7 °C); 2-methylpentane (60.3 °C);

3-methylpentane (63.3 °C); 2,3-dimethylbutane (58 °C); 2,2-dimethylbutane
(49.7 °C).

2. As the molecular weight of unbranched alkanes increases, so too does the

molecular size, and even more importantly molecular surface areas.
1) Increasing surface area ⇒ increasing the van der Waals forces
between molecules ⇒ more energy (a higher temperature) is required to
separate molecules from one another and produce boiling.

3. Chain branching makes a molecule more compact, reducing the surface

are~ 21 ~and with it the strength of the van der Waals forces operating
between it and adjacent molecules ⇒ lowering the boiling.
Nomenclature of Alkanes
The Unbranched Alkanes
Nomenclature of Alkanes
Numerical Prefixes Commonly Used in Forming Chemical Names
Nomenclature of Alkanes
NOMENCLATURE OF UNBRANCHED ALKYKL GROUPS
Nomenclature of Alkanes
NOMENCLATURE OF BRANCHED ALKYL GROUPS
Nomenclature of Alkanes
1. Locate the longest continuous chain of carbon atoms; this chain
determines the parent name for the alkane

2. Number the longest chain beginning with the end of the chain nearer
the Substituent

3. Use the numbers obtained by application of rule 2 to designate the location

of the substituent group

4. When two or more substituents are present, give each substituent a number
corresponding to its location on the longest chain-The substituent groups
are listed alphabetically

5. When two or more substituents are identical, indicate this by the use of the
prefixes di-, tri-, tetra-, and so on

6. In deciding on alphabetically order disregard structure-defining prefixes that

are written in italics and separated from the name by a hyphen. Thus
“tert-butyl” precedes “ethyl”, but “ethyl” precedes “isobutyl”.
Nomenclature of Alkanes
Nomenclature of Cycloalkanes
Nomenclature of Cycloalkanes
Nomenclature of Cycloalkanes

BICYCLIC COMPOUNDS
Conformational Analysis
SIGMA BONDS AND BOND ROTATION
1. Conformations: the temporary molecular shapes that result from
rotations of groups about single bonds.
2. Conformational analysis: the analysis of the energy changes that a
molecule undergoes as groups rotate about single bonds.

3. Staggered conformation: allows the maximum separation of the

electron pairs of the six C—H bonds ⇒ has the lowest energy ⇒ most
stable conformation.
4. Eclipsed conformation: maximum repulsive interaction between
the electron pairs of the six C—H bonds ⇒ has the highest energy ⇒

least stable conformation.

Conformational Analysis of Ethane

Potential energy changes that

accompany rotation of groups about the
carbon-carbon bond of ethane
Conformational Analysis of Butane
Important conformations of butane I – VI

1) The anti conformation (I): does not have torsional strain ⇒ most stable.

2) The gauche conformations (III and V): the two methyl groups are
close enough to each other ⇒ the van der Waals forces between them
are repulsive ⇒ the torsional strain is 3.8 kJ mol−1 (0.91 kcal mol−1).
3) The eclipsed conformation (II, IV, and VI): energy maxima ⇒ II, and IV
have torsional strain and van der Waals repulsions arising from the
clipsed methyl group and hydrogen atoms; VI has the greatest energy due

to the large van der Waals repulsion force arising from the eclipsed
methyl groups.
Conformational Analysis of Butane

Energy changes that arise from rotation about the C2–C3 bond of
butane
Conformational Analysis of Cycloalkane
The carbon atoms of alkanes are sp3 hybridized ⇒ the bond angle is 109.5°.
Conformational Analysis of Cyclohexane
The most stable conformation of the cyclohexane ring is the “chair”
conformation
Conformational Analysis of Cyclohexane

1. The C—C bond angles are all 109.5° ⇒ free of angle strain.

2. Chair cyclohexane is free of torsional strain:

3. When viewed along any C—C bond, the atoms are seen to be perfectly
staggered.

4. The hydrogen atoms at opposite corners (C1 and C4) of the

cyclohexane ring are maximally separated.
Conformational Analysis of Cyclohexane

Boat conformation of cyclohexane

Conformational Analysis of Cyclohexane
Boat conformation of cyclohexane:

1) Boat conformation of cyclohexane is free of angle strain.

2) Boat cyclohexane has torsional strain and flagpole interaction.
i) When viewed along the C—C bond on either side, the atoms are found to

be eclipsed ⇒ considerable torsional strain.

ii) The hydrogen atoms at opposite corners (C1 and C4) of the
cyclohexane ring are close enough to cause van der Waals repulsion ⇒
flagpole interaction.
Conformational Analysis of Cyclohexane

The relative energies of the various conformations of cyclohexane

 Preparation of Alkane
1. Catalytic hydrogenation
 Preparation of Alkane
REDUCTION OF ALKYL HALIDES
 Preparation of Alkane
ALKYLATION OF TERMINAL ALKYNES

Alkylation: the formation of a new C—C bond by replacing a leaving

group on an electrophile with a nucleophile
 Reactions of Alkanes

1. Halogenation
Mechanism of halogenation

• 1. Initiation

• 2. Chain propagation
Mechanism of halogenation reaction

• Chain Termination
 Reactions of Alkanes
2. Combustion (important use of
alkanes)