MODULE 3

ALKANES AND CYCLOALKANES

Learning Objectives:
1. Represent the structure of alkanes and cycloalkanes by means of complete or dash structural
formula.
2. Name alkanes and cycloalkanes using the IUPAC rules
3. Draw the structure of alkanes and cycloalkanes given their names.
4. Correlate the physical and chemical properties of alkanes and cycloalkanes with their structure.
5. Describe the reactions of alkanes.

Alkanes(acyclic) and cycloalkanes belong to a class of organic molecules called

hydrocarbons. Hydrocarbons contain only carbon and hydrogen. They are also members of a
larger class of compounds referred to as aliphatic. Simply put, aliphatic compounds are
compounds that do not incorporate any unsaturated aromatic rings in their molecular
structure.

Alkanes and cycloalkanes are called saturated hydrocarbons because they only contain
single bonds and contains the maximum number of hydrogens possible. Since they are
saturated, no other atoms can add to them. Alkanes contain open-chain structure and
cycloalkanes are cyclic.

Molecular and Structural Formulas of Alkanes and Cycloalkanes

General Formula of Alkanes: CnH2n+2

General Formula of Cycloalkanes: CnH2n

Cycloalkanes have two fewer hydrogen atoms than alkanes because another carbon–carbon
bond is needed to form the ring.
 All C atoms in an alkane are surrounded by four groups, making them sp3 hybridized and
tetrahedral and all bond angles are 109.5°. Methane, CH4, has a single carbon atom, and
ethane, CH3CH3, has two.

Table 3.1 The simplest alkanes with their structural formulas

Molecular Structural Molecular Structural

Name Name
Formula Formula Formula Formula
methane CH4 CH4 hexane C6H14 CH3(CH2)4CH3
ethane C2H6 CH3CH3 heptane C7H16 CH3(CH2)5CH3
propane C3H8 CH3CH2CH3 octane C8H18 CH3(CH2)6CH3
butane C4H10 CH3CH2CH2CH3 nonane C9H20 CH3(CH2)7CH3
pentane C5H12 CH3(CH2)3CH3 decane C10H22 CH3(CH2)8CH3

PRACTICE TEST

Solution

No. of Carbons 23 25 27
No. of Hydrogens (CnH2n+2) 48 52 56
ISOMERS

There are two different ways to arrange four carbons, giving two compounds with
molecular formula C4H10, named butane and isobutane.

Butane and isobutane are isomers, two different compounds with the same molecular
formula. They belong to one of the two major classes of isomers called constitutional or
structural isomers. Constitutional isomers differ in the way the atoms are connected to each
other.
PRACTICE TEST

CYCLOALKANES

Cycloalkanes have molecular formula CnH2n and contain carbon atoms arranged in a
ring. Think of a cycloalkane as being formed by removing two H atoms from the end carbons of
a chain, and then bonding the two carbons together. Simple cycloalkanes are named by adding
the prefi x cyclo- to the name of the acyclic alkane having the same number of carbons.
Cycloalkanes having three to six carbon atoms are shown in the accompanying figure. They are
most often drawn in skeletal representations.
NOMENCLATURE

A systematic method of naming compounds was developed by the International Union

of Pure and Applied Chemistry. It is referred to as the IUPAC system of nomenclature

The IUPAC system of nomenclature has been regularly revised since it was first adopted
in 1892. Revisions in 1979 and 1993 and recent extensive recommendations in 2004 have given
chemists a variety of acceptable names for compounds. Many changes are minor. For example,
the 1979 nomenclature rules assign the name 1-butene to CH2=CHCH2CH3, while the 1993 rules
assign the name but-1-ene; that is, only the position of the number differs. In this module, the
most generally used IUPAC conventions will be given, and often a margin note will be added to
mention the differences between past and recent recommendations.

Naming organic compounds has become big business for drug companies. The IUPAC
name of an organic compound can be long and complex, and may be comprehensible only to a
chemist.

As a result, most drugs have three names:

• Systematic: The systematic name follows the accepted rules of nomenclature and indicates
the compound’s chemical structure: this is the IUPAC name.

• Generic: The generic name is the official, internationally approved name for the drug.

• Trade: The trade name for a drug is assigned by the company that manufactures it. Trade
names are often “catchy” and easy to remember. Companies hope that the public will
continue to purchase a drug with an easily recalled trade name long after a cheaper
generic version becomes available.

In the world of over-the-counter anti-inflammatory agents, the compound a chemist calls

2-[4-(2-methylpropyl)phenyl]propanoic acid has the generic name ibuprofen. It is marketed
under a variety of trade names including Motrin and Advil.
The parent name for one carbon is meth-, for two carbons is eth-, and so on. (See table 3.1)

Naming Substituents

Carbon substituents bonded to a long carbon chain are called alkyl groups.

• An alkyl group is formed by removing one hydrogen from an alkane.

An alkyl group is a part of a molecule that is now able to bond to another atom or a
functional group. To name an alkyl group, change the -ane ending of the parent alkane to -yl.
Thus, methane (CH4) becomes methyl (CH3 –) and ethane (CH3CH3) becomes ethyl (CH3CH2 –).
R denotes a general carbon group bonded to a functional group. R thus denotes any alkyl
group.

Naming three- and four-carbon alkyl groups is more complicated because the parent
hydrocarbons have more than one type of hydrogen atom. For example, propane has both 1°
and 2° H atoms, and removal of each of these H atoms forms a different alkyl group with a
different name, propyl or isopropyl.
 Because there are two different butane isomers to begin with, each having two different
kinds of H atoms, there are four possible alkyl groups containing four carbon atoms, each
having a different name: butyl, sec-butyl, isobutyl, and tert-butyl.

The names isopropyl, sec-butyl, isobutyl, and tert-butyl are recognized as acceptable
substituent names in both the 1979 and 1993 revisions of IUPAC nomenclature.
EXAMPLES
PRACTICE TEST
 When an alkane is composed of both a ring and a long chain, what determines whether
a compound is named as an acyclic alkane or a cycloalkane? If the number of carbons in the ring
is greater than or equal to the number of carbons in the longest chain, the compound is named
as acycloalkane.
Physical Properties of Alkanes
Alkanes contain only nonpolar C –C and C – H bonds, and as a result they exhibit only
weak van der Waals forces. Table 4.2 summarizes how these intermolecular forces affect the
physical
Chemical Properties of Alkanes

Alkanes are not very reactive when compared with other chemical species. This is
because the backbone carbon atoms in alkanes have attained their octet of electrons through
forming four covalent bonds (the maximum allowed number of bonds under the octet rule;
which is why carbon's valence number is 4).
These four bonds formed by carbon in alkanes are sigma bonds, which are more stable
than other types of bond because of the greater overlap of carbon's atomic orbitals with
neighboring atoms' atomic orbitals. To make alkanes react, the input of additional energy is
needed; either through heat or radiation.

Physical and Chemical Properties of Cycloalkanes

The physical properties of cycloalkanes are similar to those of alkanes, but they have
higher boiling points, melting points and higher densities due to the greater number of London
forces that they contain.

Some of the physical and chemical properties of cycloalkanes are given below:

1. The first four classes of cycloalkanes are said to be in gaseous state in the room
temperature
2. These saturated hydrocarbons are said to have their boiling points ranging between 10 –
20 K.
3. These compounds are also reported exhibiting higher melting points and densities
4. These are also called as saturated hydrocarbons since saturated compounds form ring
structure
5. Since the electronegativity between the carbon-hydrogen bonds is found to be too less
for these compounds, they are said to be not having any polarity between the bonds.
6. These class of saturated hydrocarbons is said to be insoluble in water, and the
cycloalkanes in liquid form are said to be the good form of solvents for other organic
compounds.
7. The molecule of cycloalkane gets destroyed when burned.
8. Cyclopropane is said to be the most reactive compound when compared to other
cycloalkanes.
EXERCISES

3.1 Classify each carbon atom in the following compounds as 1°, 2°, 3°, or 4°.

3.2 Identify and name the parent in each of the following compound.

3.3 Write IUPAC names for these alkanes

3.4 Write the IUPAC name for each cycloalkane