The Alkanes Chapter 2

THE ALKANES:

STRUCTURE AND NOMENCLATURE

OF SIMPLE HYDROCARBONS

CHAPTER SUMMARY

Organic compounds are classified according to common structural

features that impart similar chemical and physical properties to the compounds
within each group or family.

2.1 Hydrocarbons: An Introduction

Hydrocarbons are composed only of carbon and hydrogen and fall into two
major classes - saturated and unsaturated. Saturated hydrocarbons or the
alkanes are entirely constructed of single bonds and have the general formula
CnH2n+2. Unsaturated hydrocarbons include the alkenes (CnH2n) in which
there is at least one carbon-carbon double bond; the alkynes (CnH2n-2) where
there is at least one carbon-carbon triple bond; and aromatic hydrocarbons
which appear to have double bonds but actually have a special structure that is
discussed in Chapter 6.

2.2 Molecular and Structural Formulas - Isomerism

Compounds are described by molecular formulas and structural
formulas. Molecular formulas describe the kinds of atoms and numbers of

21
Chapter 2 The Alkanes

each in a molecule. Structural formulas describe the bonding arrangements of

the atoms, that is, what atoms are bonded to one another and by what kinds of
bonds. Isomers are compounds with the same molecular formula but different
structural formulas. Structural isomers (skeletal, positional, and functional)
differ in the bonding arrangement of atoms; different atoms are attached to one
another. In stereoisomerism the same atoms are bonded to one another but
their orientation in space differs; conformational and geometric isomerism are
forms of stereoisomerism presented in this chapter.

2.3 Skeletal Isomerism in Alkanes

A. Isomers
Isomers are different compounds with the same molecular formula but
different structural formulas. Skeletal isomers differ in the arrangement of the
carbons in a set of isomers; there are differences in the carbon skeletons.
B. Drawing Structural Isomers
The rules and procedures for drawing structural isomers are the same
used for drawing electron dot formulas. Every atom in the molecular formula
must be used and each atom must have its valence satisfied. To draw a
structure, bond all atoms with a valence greater than one with single bonds.
Attach monovalent atoms to the polyvalent ones until all valences have been
satisfied. If there are insufficient monovalent atoms in the formula to
accomplish this, insert double bonds, triple bonds or draw cyclic structures
until it is possible to satisfy all valences. To draw isomers, vary the
arrangements of atoms and bonds to form different molecules.
C. Cycloalkanes
The simplest cycloalkanes have the general formula CnH2n; they have
two fewer hydrogens than the corresponding alkane and at least three of the
carbons are arranged in a ring.

2.4 Representations of Structural Formulas

In Chapter 1, electron dot formulas were used to describe covalent
compounds. More condensed respresentations involve replacing the electron
dots with lines (one for a single bond, two for a double bond, three for a triple
bond), grouping hydrogens on a carbon, grouping identical carbons, and using
stick diagrams in which each corner represents a carbon with sufficient
hydrogens to satisfy the valence.

22
The Alkanes Chapter 2

2.5 Positional Isomerism

Positional isomers differ in the position of a noncarbon group or of a double
bond or triple bond.

2.6 IUPAC Nomenclature of Alkanes

A. An Introduction to IUPAC Nomenclature
Many organic compounds have informal common names but the
accepted way of naming compounds is by the IUPAC system of
nomenclature.
B. Nomenclature of Continuous-Chain, Unbranched Alkanes:
The Basis for Organic Nomenclature
The base name of alkanes is derived from the Greek for the number of
carbons in the longest continuous carbon chain (Table 2.1 of the text)
followed by the suffix ane. The base name of cycloalkanes is based on the
Greek for the number of carbons in the ring with the prefix cyclo and the
suffix ane.
C. Nomenclature of Branched-Chain Alkanes
Branched-chain alkanes have a longer carbon chain, upon which the
name is usually based, with attached shorter carbon chains. These shorter
chains are called alkyl groups (Table 2.2 of the text) and are named by
changing the ane (of the alkane name) to yl. The positions of alkyl groups
are described with numbers; the longest carbon chain of an alkane is
numbered starting at the end that gives the lowest number to the first
substituent. Multiple numbers of identical alkyl groups are indicated with di,
tri, tetra, etc.
D. Nomenclature of Halogenated Hydrocarbons (Alkyl Halides)
The prefixes fluoro, chloro, bromo, and iodo are used to indicate the
presence of halogen in a molecule.

2.7 Conformational Isomerism

Conformational isomers are isomers in which the spatial relationship of
atoms differs because of rotation around a carbon-carbon double bond. Because
the rotation is unrestricted in most cases, conformational isomers are constantly
interconverting and are not isolatable. There are two extreme conformations. In
the eclipsed conformation, atoms on adjacent carbons are lined up with one
another and are as close together as possible; this is the least stable

23
Chapter 2 The Alkanes

conformational arrangement. In the staggered conformation, atoms on

adjacent atoms are staggered with one another and are as far apart as possible;
this is the most stable conformational arrangement. Staggered and eclipsed
forms are represented with sawhorse diagrams or Newman projections.
Sawhorse diagrams are essentially stick structures highlighting the two carbons
for which the conformations are being described. In a Newman projection the
carbon- carbon bond is described by a circle with three bonds emanating from
the center (the front carbon) and three from the perimeter (the back carbon).

2.8 Cycloalkanes - Conformational and Geometric Isomerism

A. Structure and Stability
Cycloalkanes are generally depicted with regular polygons though they
actually exist in three-dimensional conformations. Cyclopropane and
cyclobutane are less stable than other cycloalkanes since they are planar
(cyclopropane) or nearly so (cyclobutane) and have internal bond angles
significantly smaller (60o and 90o respectively) than the preferred tetrahedral
angle (109o). The larger cycloalkanes are able to pucker out of planarity and
assume tetrahedral angles.
B. Conformational Isomerism in Cyclohexane
Cyclohexane exists in two puckered conformations, the boat and chair
forms, that have tetrahedral bond angles. The boat form is less stable and
not preferred because of interactions between the two end or flagpole
carbons and because the hydrogens on the other adjacent carbons are
eclipsed. In the preferred chair form, atoms on adjacent carbons are
staggered and there are no flagpole type interactions. There are two
orientations of hydrogens in the chair conformation. Axial hydrogens are
oriented directly above or below the "plane" of the ring in an alternating
arrangement. Equatorial hydrogens protrude out along the perimeter of the
ring.
C. Drawing the Cyclohexane Chair
In drawing the cyclohexane chair, keep in mind that there are four
carbons in a plane. On one end there is a carbon oriented above the plane
and on the other end there is a carbon oriented below the plane. Each
carbon has an equatorial hydrogen oriented along the perimeter. There are
three axial hydrogens on alternating carbons above the ring and three on the
other carbons below the ring.

24
The Alkanes Chapter 2

D. Conformational Isomerism in Substituted Cyclohexanes

In a monosubstituted cyclohexane, the substituent can be either in an
equatorial or axial position. Equatorial positions are more spacious and in
substituted cyclohexanes they are preferred. Cyclohexane rings flip between
chair forms and establish an equilibrium. In the process of flipping, all
equatorial positions become axial and all axial positions become equatorial.
The equilibrium favors the chair in which substituents are equatorial. In
monosubstituted cyclohexanes, the conformation in which the substituent is
equatorial is favored. In disubstituted cyclohexanes where one group is axial
and one equatorial, the equilibrium favors the chair form where the larger
group occupies the more spacious equatorial position.
E. Geometric Isomerism in Cyclic Compounds
Disubstituted cycloalkanes exhibit geometric isomerism, a type of
stereoisomerism. If both groups are on the same "side" of the ring (both up
or both down) the isomer is termed cis. If they are on opposite "sides" (one
up and one down) the isomer is trans.

2.9 Hydrocarbons: Relationship of Structure and Physical Properties

The solid, liquid, and gas states of a compound differ in arrangements of
molecules, not in molecular structure. In the solid state the molecules are orderly
arranged and immobile with maximum intermolecular attractions. In the liquid
state, molecules are mobile but still there are intermolecular attractions. In the
vapor phase molecules are mobile and ideally there are no intermolecular
attractions. For these reasons, solids have a constant shape and volume, liquids
have a constant volume and variable shape, and gases assume the size and
shape of the container. Physical properties of hydrocarbons are related to
structure.
A. Melting Point, Boiling Point, and Molecular Weight
Melting points and boiling points generally increase with molecular weight
within a homologous series (a series of compounds in which each
succeeding member differs from the previous one by a CH2 group).
B. Melting Point, Boiling Point, and Molecular Structure
Branched chain hydrocarbons have less surface area and thus less
opportunity for intermolecular attractions; as a result, their boiling points are
lower than the straight chain isomers. However, their compact nature causes

25
Chapter 2 The Alkanes

them to fit more easily in a crystal lattice and thus they generally have higher
melting points.
C. Solubility and Density
Hydrocarbons are non-polar and insoluble in water and, because they
are less dense, they float on the surface of water.

CONNECTIONS 2.1: Petroleum

SOLUTIONS TO PROBLEMS

2.1 Alkanes, Alkenes, and Alkynes

H H H H H H

H C C C H H C C C H H C C C H

H H H H H H

2.2 Skeletal Isomers

H C H

H H H H H H

H C C C C H H C C C H

H H H H H H H

2.3 Skeletal Isomers

(a) All three of these structures are identical. In each, the longest continuous
chain of carbon atoms is six with a CH3 group attached to the second carbon
from the end.
(b) The first and last structures are the same. In each, the longest continuous
chain of carbons is six and there is a CH3 group bonded to the third carbon from
the end.

26
The Alkanes Chapter 2

2.4 Skeletal Isomers

Start with a chain of seven carbons.

CH 3CH 2CH 2CH 2CH 2CH 2CH 3

Now draw isomers with six carbons in the longest chain and vary the position of
the one-carbon chain.
CH 3 CH 3

CH 3CHCH 2CH 2CH 2CH 3 CH3CH 2CHCH 2CH 2CH 3

Now draw five carbon chains and place one two-carbon chain or two one-carbon
chains on it. If the two-carbon side chain is placed on either the first or second
carbon, it merely extends the longest chain. However, placing it on the third
carbon gives us another isomer.
CH2CH 3

CH3CH 2 CHCH2CH3

Now attach two one-carbon chains to the carbon skeleton.

CH 3 CH 3 CH 3 CH 3 CH 3
CH 3 CCH 2CH 2CH 3 CH 3CH 2 CCH 2CH 3 CH 3CHCHCH 2CH 3 CH 3CHCH 2CHCH 3
CH 3 CH 3 CH 3

Finally, draw a four carbon chain with three one carbon side chains.
CH3 CH3

CH3C CHCH3
CH3
2.5 Skeletal Isomers of Cycloalkanes: Five cyclic compounds of C5H10.
Start with a five-membered ring. Then use a four-membered ring with a one-
carbon side chain. Finally, draw a three-membered ring with either one two-
carbon side chain or two one-carbon side chains.
CH3 CH2CH 3 CH3 CH3 CH3

CH3

27
Chapter 2 The Alkanes

2.6 Representations of Structural Formulas

CH3
(CH3)2CH(CH2)3CHCH2C(CH3)3

2.7 Molecular Formulas from Structural Formulas

(a) C13H8N2O2 (b) C8H12 (c) C15H29Br

2.8 Positional Isomers

Two isomers of C2H4Br2

Br Br Br

CH3CH CH2 CH2

Br
Five isomers of C3H6BrCl
Br

CH 3CH 2CHBr CH3CH CH2 CH 2CH 2CH 2 CH3CH CH2 CH 3CCH 3

Cl Cl Br Cl Br Br Cl Cl

2.9 IUPAC Nomenclature

(a) Names of compounds in Example 2.1 as they appear:
hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,
and 2,3-dimethylbutane.

(b) Names of nine isomers in Problem 2.4 as they appear:

heptane;
2-methylhexane and 3-methylhexane;
3-ethylpentane;
2,2-dimethylpentane; 3,3-dimethylpentane; 2,3-dimethylpentane;
and 2,4-dimethylpentane;
2,2,3-trimethylbutane

c. Structures from names

28
The Alkanes Chapter 2

CH3
CH 2CHCH 3 CH3 CH2CH 3 CH3

CH 3CCH 2CHCHCHCH 2CHCH 3

CHCH 3 CH3 CH3 CH2CH 3

CH3

1-isobutyl-3-isopropylcyclopentane 5,6-diethyl-2,2,4,8-tetramethylnonane

2.10 Alkyl Halide Nomenclature

Names of compounds in section 2.5 as they appear.
1-bromobutane, 2-bromobutane,
1-bromo-2-methylpropane, and 2-bromo-2-methylpropane.

2.11 Alkyl Halide Nomenclature

(a) Names of compounds as they appear in problem 2.8a:
1,1-dibromoethane and 1,2-dibromoethane
(b) Names of compounds as they appear in problem 2.8b..
1-bromo-1-chloropropane, 1-bromo-2-chloropropane,
1-bromo-3-chloropropane, 2-bromo-1-chloropropane, and
2-bromo-2-chloropropane

2.12 Skeletal and Positional Isomerism

CH 3CH 2CH 2CH 2CH 2Cl CH 3CH 2CH 2CHCH 3 CH 3CH 2CHCH 2CH 3

Cl Cl
1-chloropentane 2-chloropentane 3-chloropentane
CH 3
CH 3

CH 2CHCH 2CH 3 CH 3CCH 2CH 3

Cl Cl
1-chloro-2-methylbutane 2-chloro-2-methylbutane

29
Chapter 2 The Alkanes

CH 3 CH 3

CH 3CHCHCH 3 CH 3CHCH 2CH 2

Cl Cl

2-chloro-3-methylbutane 1-chloro-3-methylbutane

CH 3
H3C C CH 2Cl 1-chloro-2,2-dimethylpropane
CH 3

2.13 Newman Projections of Propane

H
CH 3 H3C
H H
Staggered Eclipsed

H
H H H H H
H

Most Stable Least Stable

2.14 Conformational Isomers of Butane

CH3 H 3C
H3C CH3 H CH3
H CH3 H H

H H
H H H H H H H 3C H H H
H CH3
Least Stable Most Stable

2.15 Cyclohexane Chair: Axial and Equatorial Positions

a) CH3 b) H c) Br

H
H CH3 H Br

30
The Alkanes Chapter 2

d) Br e) H
H H Br
Br

Br
H

2.16 Equilibrium between Chair Forms

(a) The equatorial position is more spacious and the isomer more stable.

ax Br more
stable
H
eq
eq
Br

H
ax

(b) The equatorial positions are more spacious and preferred in the equilibrium.

ax CH(CH 3)2
ax more
H eq H stable

H eq CH 3 CH(CH 3)2
eq eq
ax CH 3 H
ax

31
Chapter 2 The Alkanes

(c) The equilibrium favors the isomer in which the larger isopropyl group
is in the more spacious equatorial position.

ax CH(CH 3)2 more

H3C ax stable
H H
eq eq
eq eq
CH 3 CH(CH 3)2
H ax H ax

2.17 Geometric Isomerism in Cyclic Compounds

Br CH 3 Br H
CH 3 H
Br Br
H CH 3
H H H CH 3
H H
cis trans cis trans
1-bromo-2-methylcyclopentane 1-bromo-3-methylcyclopentane

2.18 Molecular Weights

(a) 16 (b) 46 (c) 342 (d) 264 (11x12 + 17x1 + 2x14 + 2x16 + 32 +23)

2.19 Skeletal Isomerism: Sections 2.3 and 2.6

(a) C8H18: Start with an eight-carbon chain. Then systematically make the
longest chain one carbon shorter. Arrange the remaining carbons in each case
on the chain in as many different ways as possible without extending the length
of the base chain. The following isomers are drawn in a logical, systematic
order.
CH3
CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 3 CH 3CHCH 2CH 2CH 2CH 2CH 3
octane 2-methylheptane

CH 3 CH 3
CH 3CH 2CHCH 2CH 2CH 2CH 3 CH 3CH 2CH 2CHCH 2CH 2CH 3

3-methylheptane 4-methylheptane

32
The Alkanes Chapter 2

CH 2CH 3 CH 3 CH 3

CH 3CH 2CHCH 2CH 2CH 3 CH 3CCH 2CH 2CH 2CH 3 CH 3CH 2CCH 2CH 2CH 3

CH 3 CH 3

3-ethylhexane 2,2-dimethylhexane 3,3-dimethylhexane

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3

CH 3CH CHCH 2CH 2CH 3 CH 3CHCH 2CHCH 2CH 3 CH 3CHCH 2CH 2CHCH 3
2,3-dimethylhexane 2,4-dimethylhexane 2,5-dimethylhexane
CH 3
CH 3 CH 3 CH 3 CH 2 CH 3

CH 3CH 2CH CHCH 2CH 3 CH 3CH CHCH 2CH 3 CH 3CH 2 C CH 2CH 3

CH 2

CH 3

3,4-dimethylhexane 3-ethyl-2-methylpentane 3-ethyl-3-methylpentane

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3

CH 3C CHCH 2CH 3 CH 3CCH 2CHCH 3 CH 3CH C CH 2CH 3

CH 3 CH 3 CH 3

2,2,3-trimethylpentane 2,2,4-trimethylpentane 2,3,3-trimethylpentane

H3C CH 3 CH 3 CH 3CH 3
H3CCH CH CHCH 3 H3C C C CH 3
CH 3CH 3

2,3,4-trimethypentane 2,2,3,3-tetramethylbutane

33
Chapter 2 The Alkanes

(b) three isomers of C9H20 with eight carbons in the longest chain: write the
longest chain straight across. Don't put anything on the chain that would make it
longer.
CH 3 CH 3

CH 3CHCH 2CH 2CH 2CH 2CH 2CH 3 CH3CH 2CHCH 2CH 2CH 2CH 2CH 3
2-methyloctane 3-methyloctane
CH 3

CH 3CH 2CH 2CHCH 2CH 2CH 2CH 3

4-methyloctane

(c) 11 isomers of C9H20 with seven carbons in the longest chain:

CH 2CH 3 CH 2CH 3

CH 3CH 2CHCH 2CH 2CH 2CH 3 CH3CH 2CH 2CHCH 2CH 2CH 3
3-ethylheptane 4-ethylheptane

CH 3 CH 3 CH 3

CH3CCH 2CH2CH2CH2CH3 CH3CH2CCH 2CH 2CH 2CH 3 CH3CH2CH 2CCH 2CH2CH3

CH 3 CH 3 CH 3

2,2-dimethylheptane 3,3-dimethylheptane 4,4-dimethylheptane

CH 3CH 3 CH 3 CH 3 CH 3 CH 3

CH 3CHCHCH 2CH 2CH 2CH 3 CH 3CHCH 2CHCH 2CH 2CH 3 CH 3CHCH 2CH 2CHCH 2CH 3

2,3-dimethylheptane 2,4-dimethylheptane 2,5-dimethylheptane

CH 3 CH 3 CH 3CH 3 CH 3 CH 3

CH 3CHCH 2CH 2CH2CHCH 3 CH 3CH 2CHCHCH 2CH 2CH 3 CH 3CH 2CHCH 2CHCH 2CH 3

2,6-dimethylheptane 3,4-dimethylheptane 3,5-dimethylheptane

(d) Eight isomers of C9H20 with five carbons in longest chain: Draw a five-
carbon chain across the paper in a straight line. Arrange the remaining four

34
The Alkanes Chapter 2

carbons in as many ways as possible without making the chain longer. The ways
to consider arranging the remaining four carbons are: a) one four-carbon chain;
b) a three- and a one-carbon chain, c) 2 two-carbon chains; d) 1 two- and 2
one-carbon chains; and e) 4 one-carbon chains. Variations a) and b) are not
usable as there is no way to place a four- or three-carbon unit on a five-carbon
chain without extending the longest chain.

CH3 CH3 CH3

CH2 CH2 CH3 CH2
CH3CH 2 C CH2CH 3 CH3CH 2CH CCH3 CH 3CHCHCHCH 3

CH2 CH3 CH3 CH3

CH3
3,3-diethylpentane 2,2-dimethyl-3-ethylpentane 2,4-dimethyl-3-ethylpentane

CH3
CH2 CH3 CH3 CH3 CH3
CH3CH CCH2CH3 CH3C CCH2CH3 CH3C CH2 CCH3

CH3 CH3 CH3 CH3 CH3 CH3

2,3-dimethyl-3-ethylpentane 2,2,3,3-tetramethylpentane 2,2,4,4-tetramethylpentane

CH3 CH3 CH3 CH3 CH3 CH3

CH3C CH CHCH3 CH3CH C CHCH 3

CH3 CH3

2,2,3,4-tetramethylpentane 2,3,3,4-tetramethylpentane

(e) four isomers of C10H22 with nine carbons in the longest chain:

CH3 CH3

CH 3CHCH 2CH 2CH 2CH 2CH 2CH 2CH 3 CH3CH 2CHCH 2CH 2CH 2CH 2CH 2CH 3
2-methylnonane 3-methylnonane

35
Chapter 2 The Alkanes

CH3 CH3

CH 3CH 2CH 2CHCH 2CH 2CH 2CH 2CH 3 CH3CH 2CH 2CH 2CHCH 2CH 2CH 2CH 3
4-methylnonane 5-methylnonane

(f) two isomers of C10H22 with only two alkyl groups on a six carbon chain:

CH2CH 3 CH2CH 3

CH 3CH 2CCH 2CH 2CH 3 CH

3CH 2CHCHCH 2CH 3

CH2CH 3 CH2CH 3
3,3-diethylhexane 3,4-diethylhexane

(g) six isomers of C10H22 with five carbons in the longest chain:

CH3 CH2CH 3 CH3 CH2CH 3 CH3 CH2CH 3

CH 3CH CCH 2CH 3 CH 3C CCH 2CH 3 CH 3C CHCHCH 3

CH2CH 3 CH3 CH3 CH3 CH3

3,3-diethyl-2-methylpentane 3-ethyl-2,2,3-trimethylpentane
3-ethyl-2,2,4-trimethylpentane

CH 2CH 3 CH 3 CH 3 CH 3 CH 3 CH 3CH 3

CH 3CH C CHCH 3 CH 3C C CHCH 3 CH 3C CH-CCH 3

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3

3-ethyl-2,3,4-trimethylpentane 2,2,3,4,4-pentamethylpentane

2,2,3,3,4-pentamethylpentane

36
The Alkanes Chapter 2

(h) the isomer of C13H28 with the shortest longest chain possible

CH3 CH 3 CH3
CH 2
CH 3C C CCH 3 3,3-diethyl-2,2,4,4-tetramethylpentane
CH
CH3 CH 2 CH3
3

(i) five cyclic compounds of C5H10

CH3 CH2CH 3 CH3 CH3 CH3

CH3
Names in order: cyclopentane; methylcyclobutane; ethylcyclopropane
1,1-dimethylcyclopropane; 1,2-dimethylcyclopropane

(j) twelve cyclic compounds of C6H12

CH3 CH2CH 3 CH3 CH3

CH3
CH3

CH3 CH3
Names in order: cyclohexane; methylcyclopentane; ethylcyclobutane;
1,1-dimethylcyclobutane; 1,2-dimethylcyclobutane; 1,3-dimethylcyclobutane.

CH3 CH3 CH3 CH3

CH CH2CH 3 CH3
CH2CH 2CH3 CH3 CH2CH 3
CH3

CH3 CH3 CH3

Names in order: propylcyclopropane; isopropylcyclopropane;

1-ethyl-1-methylcyclopropane; 1-ethyl-2-methylcyclopropane;
1,1,2-trimethylcyclopropane; 1,2,3-trimethylcyclopropane.

37
Chapter 2 The Alkanes

(k) five compounds of C8H16 that have a six-membered ring

CH 2CH 3 H3C CH 3 CH 3 CH 3
CH 3
CH 3

CH 3
CH 3
Names in Order: ethylcyclohexane; 1,1-dimethylcyclohexane
1,2-dimethylcyclohexane; 1,3-dimethylcyclohexane;
1,4-dimethylcyclohexane

(l) 12 isomers of C9H18 that have a six-membered ring

CH 3
CH 2CH 2CH 3 CHCH 3 CH 3
H3C CH 2CH 3
CH 2CH 3

Names in Order: propylcyclohexane; isopropylcyclohexane;

1-ethyl-1-methylcyclohexane; 1-ethyl-2-methylcyclohexane

CH 3 CH 3 H3C CH 3 H3C CH 3
CH 3

CH 2CH 3 CH 3
CH 2CH 3

Names in Order: 1-ethyl-3-methylcyclohexane;

1-ethyl-4-methylcyclohexane; 1,1,2-trimethylcyclohexane;
1,1,3-trimethylcyclohexane

38
The Alkanes Chapter 2

CH 3 CH 3 CH 3
H3C CH 3
CH 3 CH 3

CH 3 H3C CH 3
CH 3 CH 3
Names in Order: 1,1,4-trimethylcyclohexane;
1,2,3-trimethylcyclohexane; 1,2,4-trimethycyclohexane;
1,3,5-trimethylcyclohexane

2.20 Nomenclature of Alkanes: Section 2.6

Names are included with structures in Problem 2.l9.

2.21 Positional Isomers: Section 2.5

Each carbon that can have a hydrogen replaced with a chlorine is numbered.
Identically numbered carbons produce the same isomer upon chlorination.
1 5
CH3 CH3
a) CH3CH 2CH 2CH 2CH 2CH 3 b) 1 CH 3CCH 2CH 2CHCH 3
1 2 3 3 2 1 2 3 4 5
CH3
3 isomers 1 5 isomers

1 5 1 1 Cl
c) CH3 CH3 CH3 d)

CH 3CHCH 2CHCH 2CHCH 3 1 1

1 2 3 4 3 2 1
1 isomer
5 isomers

2.22 Skeletal and Positional Isomerism: Sections 2.3 and 2.5

a) three isomers of C2H3Br2F
H Br Br Br Br H

H C C F H C C F H C C F

H Br H H Br H

1,1-dibromo-1-fluoroethane 1,1-dibromo-2-fluoroethane

1,2-dibromo-1-fluoroethane

39
Chapter 2 The Alkanes

(b) four isomers of C3H6Br2

Br

CH 3CH 2CHBr CH 3CCH 3 CH 3CH CH 2 CH 2CH 2CH 2

Br Br Br Br Br
Br
Names in Order: 1,1-dibromopropane; 2,2-dibromopropane;
1,2-dibromopropane; 1,3-dibromopropane
(c) twelve isomers of C4H8BrF

Br Br

CH 3CH 2CH 2CH CH 3CH 2CHCH 3 CH 3CH 2CHCH 2 CH 3CHCH 2CH 2

F F F Br F Br
Names in order: 1-bromo-1-fluorobutane; 2-bromo-2-fluorobutane;
1-bromo-2-fluorobutane; 1-bromo-3-fluorobutane

CH 2CH 2CH 2CH 2 CH3CH 2CH CH2 CH 3CHCH 2CH 2 CH3CH CHCH3
F Br Br F Br F Br F
Names in order: 1-bromo-4-fluorobutane; 2-bromo-1-fluorobutane;
3-bromo-1-fluorobutane; 2-bromo-3-fluorobutane

CH3 CH3 CH3 CH3

CH 3CHCHBr CH3 C CH2 CH3C CH2 CH2 C CH2

F F Br Br F F H Br

Names in order: 1-bromo-1-fluoro-2-methylpropane; 1-bromo-2-fluoro-

2-methylpropane; 2-bromo-1-fluoro-2-methylpropane; 1-bromo-3-fluoro-
2-methylpropane

(d) 6 isomers of C4H8Br2 with four carbons in the longest chain

Br Br Br Br

CH 3CH 2CH 2CH CH 3CH 2CCH 3 CH 3CH 2CHCH 2

Br Br

1,1-dibromobutane 2,2-dibromobutane 1,2-dibromobutane

40
The Alkanes Chapter 2

Br Br Br Br Br Br

CH 3CHCH 2CH 2 CH 2CH 2CH 2CH 2 CH 3CHCHCH 3

1,3-dibromobutane 1,4-dibromobutane 2,3-dibromobutane

(e) nine isomers of C5H10Br2 with four carbons in the longest chain
For simplicity let us just show the required carbon skeleton and move the two
bromines around systematically. First, place two bromines on the same carbon.

C C Br C

C C C C Br C C C C Br C C C C

Br Br Br

1,1-dibromo-3-methylbutane 1,1-dibromo-2-methylbutane
2,2-dibromo-3-methylbutane

Now put a bromine on carbon-1 and vary the position of the other bromine.

C C C
C C C C C C C C C C C C
Br Br Br Br Br Br

1,2-dibromo-2-methylbutane 1,4-dibromo-2-methylbutane
1,3-dibromo-2-methylbutane

Finally, draw isomers in which the bromines are on the middle two carbons and
the two carbons on the other end.

C Br C C

C C C C C C C C C C C C

Br Br Br Br Br

1,3-dibromo-2-ethylpropane 1,2-dibromo-3-methylbutane
2,3-dibromo-2-methylbutane

41
Chapter 2 The Alkanes

(f) five isomers of C6H13Cl with four carbons in the longest chain.
Again let us draw the carbon skeletons, there are two, and vary the position of
the chlorine.

C C C

C C C C C C C C C C C C
Cl C Cl Cl
C C

1-chloro-2,2-dimethylbutane 1-chloro-3,3-dimethylbutane
3-chloro-2,2-dimethylbutane

C C C C

C C C C C C C C

Cl Cl

1-chloro-2,3-dimethylbutane 2-chloro-2,3-dimethylbutane

2.23 Nomenclature of Halogenated Alkanes: Section 2.6D

The names are with the structures in Problem 2.22.

2.24 Nomenclature of Alkanes: Section 2.6

(a) propane (b) decane (c) octane

2.25 Nomenclature of Alkanes: Section 2.6

(a) 4-methylnonane; (b) 5-propyldecane; (c) 2,5-dimethylhexane;
(d) 4-ethyl-2-methylhexane; (e) 2,2,4,6-tetramethylheptane;
(f) 6-propyl-2,4,4-trimethyldecane (longest chain is not written straight across the
page); (g) 2-cyclobutylhexane; (h) 3,3,5,7-tetramethyldecane (note that the
longest chain is not written straight across the page; the two fragments below are
part of the longest chain.)
(i) 2,2,3,3-tetramethylbutane; (j) ethylcyclopropane;
(k) isopropylcyclopentane; (l) 1-butyl-4-t-butylcyclohexane;
(m) 2,2-dimethylbutane; (n) 2,4-dimethylhexane;
(o) 4-ethyl-2,2-dimethylhexane

42
The Alkanes Chapter 2

2.26 Nomenclature of Halogenated Alkanes: Section 2.6D

(a) triiodomethane; (b) 2-bromo-3-methylbutane;
(c) 1,3-dibromo-4-fluoro-2,4-dimethylpentane

2.27 IUPAC Nomenclature: Section 2.6

CH3 CH3 Cl
Cl Cl
(a) CCl 2F2 (b) CH 3CCH 2CHCH 3 (c)

CH3 Cl
CH3 CH2CH 3 CH Cl
3
Cl
(d) CH 3CCH 2CHCH CHCH2CH3

CH3 CH2CH 2CH3

2.28 Conformational Isomers: Section 2.7

In each case, draw the compound, determine what three groups are on each of
the carbons to be placed in the Newman projection, draw the Newman projection
with the bonds for the front carbon emanating from the center of the circle and
those of the back carbon coming from the perimeter, and put the three groups on
each carbon. Rotate between staggered and eclipsed conformations to get the
extreme forms.

H H H H
(a)
OH H OH
H C C OH
H H H
H H
View H H
H H
front to back

43
Chapter 2 The Alkanes

H H

(b) HOCH 2 CH 2OH HO C C OH

H H
View
front to back
HO
HO OH
H OH
OH H OH
H H

H H
H H H H H
H
H HH H HO
OH

H CH3 H H
(c)
OH H OH
H C C OH
H H H
H H
View H
front to back CH3H CH3

2.29 Conformational Isomerism in Substituted Cyclohexanes:

Section 2.8 B-D
In doing these problems, remember that equatorial positions are roomier than
axial positions and substituents occupy equatorial positions preferentially when
possible. If there are two groups on the cyclohexane chair, the conformation in
which the larger group is equatorial, or, if possible, both groups are equatorial, is
preferred.

(a)
H ax

CH2CH 3 eq
ethylcyclohexane

44
The Alkanes Chapter 2

(b) most stable chair forms of 1,2-; 1,3-; and 1,4-dimethylcyclohexane

ax
H H ax H ax
CH3 CH3 CH3
eq eq
H ax eq
eq
CH3 CH3
eq
H ax
CH3
eq
H ax

(c) least stable chair forms of compounds in part b

CH3 ax CH3 ax CH3 ax

H H H
eq ax CH3 eq eq
eq
H H
eq eq
CH3 ax H

ax CH3

(d) 1,2-dimethylcyclohexane with one group axial and one equatorial

CH3 ax

H eq

CH3 eq

H ax

45
Chapter 2 The Alkanes

(e) most stable chair form of 1-butyl-3-methylcyclohexane with one group axial
and one equatorial
H ax
ax CH2CH 2CH2CH3 eq the larger group
CH3 is in the roomier
equatorial
eq H position

2.30 Conformational Isomerism in Substituted Cyclohexanes: Section 2.8

(a) bromocyclohexane

Br
H

equatorial Br
axial less stable more stable H

(b)
arrows show
ring flipping Br Br
H
H H

H Br
Br Br Br
H
H one Br axial
diaxial diequatorial
less stable more stable one Br equatorial

(c) 1-ethyl-3-methylcyclohexane

CH3CH 2
CH3 H CH3 arrows show ring flip;
axial groups become
H equatorial and vice-versa
CH2CH 3
H
H more stable
less stable both groups equatorial
both groups axial

46
The Alkanes Chapter 2

ax CH2CH 3 ax
eq H H eq H eq
more stable - larger
CH3 group in roomier
equatorial position
less stable- CH3 CH2CH 3
larger group eq
ax H ax
in crowded axial
position

(d) 1-ethyl-4-methylcyclohexane

ring flip CH2CH 3 H

H CH3 more stable - both
groups equatorial

H less stable- CH2CH 3

both groups axial
CH3 H

ring flip CH2CH 3 CH3

H more stable - larger
H
group in more spacious
equatorial position

CH3 less stable- CH2CH 3

larger group in more
H crowded axial position H

(e) 1,3,5-tribromocyclohexane

Br
more stable- H H H H
ring less stable - two
only one Br Br Br's in crowded
in crowded H axial positions
axial position; flip Br
other two in Br Br Br
spacious equatorial H

2.31 Conformational Isomerism in Cyclohexane: Section 2.8B

The structures show a one-carbon bridge between the first and fourth carbons of
the ring. In the boat form, the first and fourth carbons are directed toward one
another and are easily tied together by the single bonds to the CH2 bridge.
However, in the chair form, these two carbons are so far removed from one

47
Chapter 2 The Alkanes

another that they cannot be bridged by a single carbon. The two single bonds
are not long enough nor can they be conveniently directed in the necessary
geometry.

CH3 CH 2
CH2
O CH3
H CH3 CH3
CH2 CH3

CH3 O CH3 O
CH3 CH3
H
Camphor Boat Form Chair Form

2.32 Conformational Isomerism

CH 3 CH 3
In the first compound,
H H both conformers have
one methyl axial and
one equatorial. They
are the same. You
CH 3 can bottle this isomer.It
H3C identical structures H is the sole component
H of the equilibrium.

H
CH 3 The diaxial conformer
H3C
H is in equilibrium with the
diequatorial. The di-
equatorial is virtually the
exclusive component
CH 3 of the equilibrium. The
methyls diaxial methyls diequatorial H diaxial essentially
H
less stable more stable cannot exist.
CH 3

2.33 Geometric Isomerism: Section 2.8E

(a) 1,2-dimethylcyclopropane

CH3 CH3 CH3 H

cis trans

H H H CH3

48
The Alkanes Chapter 2

(b) 1-bromo-3-chlorocyclobutane
Br Cl Br H

cis trans

H H H Cl

2.34 Geometric Isomerism: Section 2.8E

(a) 1,2-dimethylcyclohexane
CH3 CH3
CH3 H
trans
cis

H H
H CH3

(b) 1,3-dimethylcyclohexane
CH3 CH3
CH3 H
cis trans

H H
H CH3

(c) 1,4-dimethylcyclohexane
CH3 H
CH3 CH3
trans
cis
H CH3
H H

2.35 Geometric Isomerism: Section 2.8E

(a) 1,2-dibromo-3-chlorocyclopropane

Br Cl Br H Br Cl

Br Br H
H H H Cl H H

H H Br

49
Chapter 2 The Alkanes

(b) 1,2,3-tribromocyclopropane

Br Br Br Br

Br H
H H H H

H Br

(c) 1,2,4-tribromocyclopentane

Br Br Br H Br Br
Br Br H

H H H Br H H
H H Br

(d) 2-chloro-1,4-dibromocyclopentane

Br Br H Br Br H Br Br
Cl Cl Cl H

H H Br H H Br H H
H H H Cl

2.36 Geometric Isomerism in the Cyclohexane Chair: Section 2.8

To understand cis and trans on the u ax
cyclohexane chair, first draw the chair
eq d eq
and insert bonds for the axial and
equatorial positions (these are labeled ax u u
in the diagram). Then note on each ax u
carbon, one bond can be considered eq d d ax u eq
up (u) and one down (d) relative to one
another. In disubstituted cyclohexanes, d d ax
if both groups are up or both down the eq u eq
isomer is cis. If they are up/down or
down/up, the isomer is trans. Rationalize d ax
this with the chart in the textbook Problem
2.36. For example,in 1,2-disubstituted
cyclohexanes, up/up or down/down is cis u/u or d/d
ax/eq or eq/ax and up/down or down/up is trans u/d or d/u
ax/ax or eq/eq.

50
The Alkanes Chapter 2

(a) cis 1,2-dimethylcyclohexane

CH 3 ax,u ax,u
CH 3 cis is up/up or down/down
H which is ax/eq or eq/ax in
this case. The two
CH 3 H conformations are essentially
CH 3 identical and of equal
eq,u eq,u stability.
H
H

(b) cis 1-bromo-3-chlorocyclohexane

Br ax,u
Cis is ax/ax or eq/eq in
ax,u H 1,3-disubstituted chairs
since this is u/u or d/d.
Cl The eq/eq is more stable
Cl since the two large groups
eq/u are in the more spacious
H H
Br equatorial positions.
less stable more stable
eq/u
H
(c) trans 1,4-diethylcyclohexane

ax,u CH 2CH 3 eq/d H 1,4 trans is u/d or

H CH 3CH 2 d/u or di-ax or di-eq.
In di-equatorial, the
two large substituents
are in the more
spacious positions.
H less stable more stable CH 2CH 3
CH 2CH 3 ax,d eq/u
H

(d) cis 1-ethyl-4-methylcyclohexane

CH2CH 3 ax,u CH3 ax,u Cis is u/u or d/d

which as shown is
H H ax/eq or eq/ax for 1,4
disubstitution. The
conformer in which the
larger ethyl group is
CH2CH 3 equatorial is the more
CH3 less stable more stable
stable since equatorial
eq,u
eq,u H positions are more spacious
H
(e) trans 1-ethyl-3-methylcyclohexane

51
Chapter 2 The Alkanes

ax,u
Trans is u/d as shown
less CH2CH 3 here. The more stable
stable more
stable conformer has the
H larger ethyl group
H in the more spacious
H equatorial position and
the smaller methyl
CH3 CH3 group in the more
CH2CH 3
ax,d crowded axial position.
eq,d eq,u
H

2.37 Molecular Formulas

One approach to this problem is to bond continuously all the atoms with valences
greater than one and insert the described rings and multiple bonds (the big arch
represents one ring.

C C C C C C C N N O S

Now put lines on each atom corresponding to the number of monovalent atoms
will be necessary to satisfy the valence. Note below you need eight monovalent
elements.

C C C C C C C N N O S

There are two bromines in the molecule so you still need six hydrogens to
provide a total of eight monovalent atoms.

2.38 Physical Properties: Section 2.9

(a) Boiling points increase with molecular weight within a homologous series.
Both examples are alkanes; ethane has the greater molecular weight.

(b) These two compounds are isomers and have the same molecular weight.
The unbranched isomer has greater surface area and thus there are more
opportunities for intermolecular attraction. The greater the attractions between

52
The Alkanes Chapter 2

molecules, the more energy necessary to break these attractions and the higher
is the boiling point. The branched isomer has less surface area and less
intermolecular interactions as a result.

(c) CBr4 has the higher molecular weight and thus the higher boiling point.

(d) Cyclohexane is more symmetrical and compact and consequently forms a

more stable crystal lattice. Such a lattice requires more energy to disrupt and
cyclohexane has a higher melting point.

(e) Melting points generally increase with molecular weight (all other factors
being equal) since it requires more energy (higher temperatures) to give the
heavier molecules enough motion to break out of a stationary crystal lattice.

2.39 Combustion: Connection 2

(a) CH4 + 2O 2 CO2 + 2H 2O

(b) C3H8 + 5O 2 3CO 2 + 4H2O

(c) 2C8H18 + 25O2 16CO 2 + 18H 2O

2.40 Petroleum Fractions: Connection 2

(a) Gas - any hydrocarbon with 1-4 carbons; for example CH4, the main
component of natural gas.

(b) Gasoline - any hydrocarbon with 5-10 carbons; for example

CH3 CH3
CH 3CCH 2CHCH 3
CH3

53
Chapter 2 The Alkanes

(c) Kerosene - any hydrocarbon with 11-18 carbons; for example

CH3(CH2)10CH3

(d) Gas-Oil - any hydrocarbon with 15-18 carbons such as CH3(CH2)16CH3

(e) Wax-Oil - hydrocarbons with 18-20 carbons; CH3(CH2)17CH3

(f) Wax - high molecular weight hydrocarbons usually with 20 or more carbons;
for example CH3(CH2)22CH3

Activities with Molecular Models

1. Make molecular models of the three skeletal isomers of C5H12. Note the
tetrahedral geometry of each carbon. Also observe the increasing
compactness of the molecules with branching.

The models are shown in question 2.

2. For each of the three isomers you made in exercise 1, see how many
different places you can remove a hydrogen and attach a bromine. In each
different case, you have made a positional isomer. How many can you make
for each? Does symmetry within each molecule influence the number of
possible positional isomers?

The following models have an arrow directed at each carbon that could exchange
a hydrogen for a bromine. There are five such places in the first structure but
only three of them will give different isomers. The two carbons labeled 1 will
both give 1-bromopentane, for example. The two labeled 2 will both give 2-
bromopentane, and the one labeled 3 will give 3-bromopentane.

54
The Alkanes Chapter 2

Monobromination sites and number of isomers possible

2 1
1
1 1

4
3 1 1
2 3
1 2 1
3 isomers 4 isomers 1 isomer

3. Make a model of ethane, C2H6. Rotate the two carbons relative to each other
around the carbon-carbon bond. Make the staggered and eclipsed
conformations.

staggered eclipsed

55
Chapter 2 The Alkanes

4. Using your models from exercise 3, remove one hydrogen and replace it with
a bromine. Find the one staggered and one eclipsed conformation. Now
replace a second hydrogen, on the other carbon, with a bromine. Find the
two staggered and two eclipsed conformations.

The Br symbol is put into one of the hydrogens on one carbon to show where you
should place a bromine and what two conformations you will see.

Br
Br

In the following models, there are two bromines, one on each carbon. In the first
structure they are totally eclipsed. To get the other three models, the rear carbon
is rotated to give staggered, eclipsed, and finally another staggered.

Br
Br Br Br Br Br

Br
Br

5. Make a model of the chair form of cyclohexane. Notice that each carbon-
carbon bond is in a staggered conformation. Identify the axial and equatorial
hydrogens.

6. Using the model from exercise 5, remove one axial hydrogen and place a
methyl (CH 3) group in its place. Replace the hydrogen and put the methyl group
in the place of an equatorial hydrogen.

56
The Alkanes Chapter 2

Cyclohexane Methylcyclohexane (equatorial) Methycyclohexane (axial)

(more stable)

7. Using the model from exercise 6, make 1,2-dimethylcyclohexane with both

methyl groups axial, one axial and one equatorial, and both equatorial.

With 1,3-dimethylcyclohexane

With 1,4-dimethylcyclohexane

57