CYCLOALKANES

Objectives

After completing this section, you should be able to

1. name a substituted or unsubstituted cycloalkane, given its Kekulé structure, shorthand

structure or condensed structure.
2. draw the Kekulé, shorthand or condensed structure for a substituted or unsubstituted
cycloalkane, given its IUPAC name.
3. draw all possible cycloalkane structures (substituted or unsubstituted) that correspond
to a given molecular formula.

Study Notes

Provided that you have mastered the IUPAC system for naming alkanes, you should find that
the nomenclature of cycloalkanes does not present any particular difficulties. Concentrate on
the examples in which the substituent or substituents is or are an alkyl group, a halogen, or
both.

Cycloalkanes are cyclic hydrocarbons, meaning that the carbons of the molecule are arranged
in the form of a ring. Cycloalkanes are also saturated, meaning that all of the carbons atoms
that make up the ring are single bonded to other atoms (no double or triple bonds). There are
also polycyclic alkanes, which are molecules that contain two or more cycloalkanes that are
joined, forming multiple rings.

Introduction

Many organic compounds found in nature or created in a laboratory contain rings of carbon
atoms with distinguishing chemical properties; these compounds are known as cycloalkanes.
Cycloalkanes only contain carbon-hydrogen bonds and carbon-carbon single bonds, but in
cycloalkanes, the carbon atoms are joined in a ring. The smallest cycloalkane is
cyclopropane.

Figure 4.1.1:
If you count the carbons and hydrogens, you will see that they no longer fit the general
formula CnH2n+2

. By joining the carbon atoms in a ring,two hydrogen atoms have been lost. The general
formula for a cycloalkane is CnH2n

. Cyclic compounds are not all flat molecules. All of the cycloalkanes, from cyclopentane
upwards, exist as "puckered rings". Cyclohexane, for example, has a ring structure that looks
like this:

Figure 4.1.2: This is known as the "chair" form of cyclohexane from its shape, which vaguely
resembles a chair. Note: The cyclohexane molecule is constantly changing, with the atom on
the left, which is currently pointing down, flipping up, and the atom on the right flipping
down. During this process, another (slightly less stable) form of cyclohexane is formed
known as the "boat" form. In this arrangement, both of these atoms are either pointing up or
down at the same time

In addition to being saturated cyclic hydrocarbons, cycloalkanes may have multiple

substituents or functional groups that further determine their unique chemical properties. The
most common and useful cycloalkanes in organic chemistry are cyclopentane and
cyclohexane, although other cycloalkanes varying in the number of carbons can be
synthesized. Understanding cycloalkanes and their properties are crucial in that many of the
biological processes that occur in most living things have cycloalkane-like structures.

Glucose (6 carbon
Ribose (5 carbon sugar) Cholesterol (polycyclic)
sugar)

Although polycyclic compounds are important, they are highly complex and typically have
common names accepted by IUPAC. However, the common names do not generally follow
the basic IUPAC nomenclature rules. The general formula of the cycloalkanes is CnH2n
where n

is the number of carbons. The naming of cycloalkanes follows a simple set of rules that are
built upon the same basic steps in naming alkanes. Cyclic hydrocarbons have the prefix
"cyclo-".

Contents

For simplicity, cycloalkane molecules can be drawn in the form of skeletal structures in
which each intersection between two lines is assumed to have a carbon atom with its
corresponding number of hydrogens.

same as same as

Cycloalkane Molecular Formula Basic Structure

Cyclopropane C3H6

Cyclobutane C4H8

Cyclopentane C5H10

Cyclohexane C6H12

Cycloheptane C7H14

Cyclooctane C8H16

Cyclononane C9H18

Cyclodecane C10H20
IUPAC Rules for Nomenclature

1. Determine the cycloalkane to use as the parent chain. The parent chain is the one with
the highest number of carbon atoms. If there are two cycloalkanes, use the
cycloalkane with the higher number of carbons as the parent chain.
2. If there is an alkyl straight chain that has a greater number of carbons than the
cycloalkane, then the alkyl chain must be used as the primary parent chain.
Cycloalkane acting as a substituent to an alkyl chain has an ending "-yl" and,
therefore, must be named as a cycloalkyl.

Cycloalkane Cycloalkyl
cyclopropane cyclopropyl
cyclobutane cyclobutyl
cyclopentane cyclopentyl
cyclohexane cyclohexyl
cycloheptane cycloheptyl
cyclooctane cyclooctyl
cyclononane cyclononanyl
cyclodecane cyclodecanyl

Example 4.1.1

The longest straight chain contains 10 carbons, compared with cyclopropane, which only
contains 3 carbons. Because cyclopropane is a substituent, it would be named a cyclopropyl-
substituted alkane.

3) Determine any functional groups or other alkyl groups.

4) Number the carbons of the cycloalkane so that the carbons with functional groups or alkyl
groups have the lowest possible number. A carbon with multiple substituents should have a
lower number than a carbon with only one substituent or functional group. One way to make
sure that the lowest number possible is assigned is to number the carbons so that when the
numbers corresponding to the substituents are added, their sum is the lowest possible.
 (1+3=4) NOT (1+5=6)

5) When naming the cycloalkane, the substituents and functional groups must be placed in
alphabetical order.

(ex: 2-bromo-1-chloro-3-methylcyclopentane)

6) Indicate the carbon number with the functional group with the highest priority according to
alphabetical order. A dash"-" must be placed between the numbers and the name of the
substituent. After the carbon number and the dash, the name of the substituent can follow.
When there is only one substituent on the parent chain, indicating the number of the carbon
atoms with the substituent is not necessary.

(ex: 1-chlorocyclobutane or cholorocyclobutane is acceptable)

7) If there is more than one of the same functional group on one carbon, write the number of
the carbon two, three, or four times, depending on how many of the same functional group is
present on that carbon. The numbers must be separated by commas, and the name of the
functional group that follows must be separated by a dash. When there are two of the same
functional group, the name must have the prefix "di". When there are three of the same
functional group, the name must have the prefix "tri". When there are four of the same
functional group, the name must have the prefix "tetra". However, these prefixes cannot be
used when determining the alphabetical priorities.

There must always be commas between the numbers and the dashes that are between the
numbers and the names.

Example 4.1.2
 (2-bromo-1,1-dimethylcyclohexane)

Notice that "f" of fluoro alphabetically precedes the "m" of methyl. Although "di"
alphabetically precedes "f", it is not used in determining the alphabetical order.

Example 4.1.3

(2-fluoro-1,1,-dimethylcyclohexane NOT 1,1-dimethyl-2-fluorocyclohexane)

8) If the substituents of the cycloalkane are related by the cis or trans configuration, then
indicate the configuration by placing "cis-" or "trans-" in front of the name of the structure.

Blue=Carbon Yellow=Hydrogen Green=Chlorine

Notice that chlorine and the methyl group are both pointed in the same direction on the axis

of the molecule; therefore, they are cis. cis-1-chloro-2-methylcyclopentan

9) After all the functional groups and substituents have been mentioned with their
corresponding numbers, the name of the cycloalkane can follow.

Reactivity

Cycloalkanes are very similar to the alkanes in reactivity, except for the very small ones,
especially cyclopropane. Cyclopropane is significantly more reactive than what is expected
because of the bond angles in the ring. Normally, when carbon forms four single bonds, the
bond angles are approximately 109.5°. In cyclopropane, the bond angles are 60°.

With the electron pairs this close together, there is a significant amount of repulsion between
the bonding pairs joining the carbon atoms, making the bonds easier to break.

Alcohol Substituents on Cycloalkanes

Alcohol (-OH) substituents take the highest priority for carbon atom numbering in IUPAC
nomenclature. The carbon atom with the alcohol substituent must be labeled as 1. Molecules
containing an alcohol group have an ending "-ol", indicating the presence of an alcohol
group. If there are two alcohol groups, the molecule will have a "di-" prefix before "-ol"
(diol). If there are three alcohol groups, the molecule will have a "tri-" prefix before "-ol"
(triol), etc.

Example 4.1.4

The alcohol substituent is given the lowest number even though the two methyl groups are on
the same carbon atom and labeling 1 on that carbon atom would give the lowest possible
numbers. Numbering the location of the alcohol substituent is unnecessary because the
ending "-ol" indicates the presence of one alcohol group on carbon atom number 1.

2,2-dimethylcyclohexanol NOT 1,1-dimethyl-cyclohexane-2-ol

Example 4.1.5
 3-bromo-2-methylcyclopentanol NOT 1-bromo-2-methyl-cyclopentane-2-ol

Example 4.1.6

Blue=Carbon Yellow=Hydrogen Red=Oxygen

trans-cyclohexane-1,2-diol

Other Substituents on Cycloalkanes

There are many other functional groups like alcohol, which are later covered in an organic
chemistry course, and they determine the ending name of a molecule. The naming of these
functional groups will be explained in depth later as their chemical properties are explained.

Name Name ending

alkene -ene
alkyne -yne
alcohol -ol
ether -ether
nitrile -nitrile
amine -amine
aldehyde -al
ketone -one
carboxylic acid -oic acid
ester -oate
amide -amide
Although alkynes determine the name ending of a molecule, alkyne as a substituent on a
cycloalkane is not possible because alkynes are planar and would require that the carbon that
is part of the ring form 5 bonds, giving the carbon atom a negative charge.

However, a cycloalkane with a triple bond-containing substituent is possible if the triple bond
is not directly attached to the ring.

Example 4.1.7

ethynylcyclooctane

Example 4.1.8

1-propylcyclohexane

Summary

1. Determine the parent chain: the parent chain contains the most carbon atoms.
2. Number the substituents of the chain so that the sum of the numbers is the lowest
possible.
3. Name the substituents and place them in alphabetical order.
4. If stereochemistry of the compound is shown, indicate the orientation as part of the
nomenclature.
 5. Cyclic hydrocarbons have the prefix "cyclo-" and have an "-alkane" ending unless
there is an alcohol substituent present. When an alcohol substituent is present, the
molecule has an "-ol" ending.

Glossary

 alcohol: An oxygen and hydrogenOH hydroxyl group that is bonded to a substituted

alkyl group.
 alkyl: A structure that is formed when a hydrogen atom is removed from an alkane.
 cyclic: Chemical compounds arranged in the form of a ring or a closed chain form.
 cycloalkanes: Cyclic saturated hydrocarbons with a general formula of CnH(2n).
Cycloalkanes are alkanes with carbon atoms attached in the form of a closed ring.
 functional groups: An atom or groups of atoms that substitute for a hydrogen atom in
an organic compound, giving the compound unique chemical properties and
determining its reactivity.
 hydrocarbon: A chemical compound containing only carbon and hydrogen atoms.
 saturated: All of the atoms that make up a compound are single bonded to the other
atoms, with no double or triple bonds.
 skeletal structure: A simplified structure in which each intersection between two
lines is assumed to have a carbon atom with its corresponding number of hydrogens.

 Name the following structures.

 Blue=Carbon Yellow=Hydrogen Red=Oxygen Green=Chlorine

 13) 14) 15)

 16)
  17)

 18) 19)