Cyclic Aliphatic Compounds

The cyclic organic compounds that are involves carbon atoms arranged to
form rings

Nomenclature
Cyclic aliphatic hydrocarbons are named by prefixing cyclo- to the name of
the corresponding open-chain hydrocarbon having the same number of
carbon atoms as the ring. For example:
The lowest combination of
numbers being used, for simple
cycloalkenes and cycloalkynes the
doubly- and triply-bonded carbons
are considered to occupy positions
1 and 2. For example:

For convenience, aliphatic rings are often represented by simple geometric figures: a
triangle for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane, a
hexagon for cyclohexane, and so on. ft is understood that two hydrogens are located
at each corner of the figure unless some other group is indicated. For example:
Industrial source
The petroleum from certain areas, (in particular California) is rich in
cycloalkanes, known to the petroleum industry as naphthenes. Among these
are cyclohexane, methylcyclohexane, methylcyclopentane, and 1,2-
dimethylcyclopentane. These cycloalkanes are converted by catalytic reforming
into aromatic hydrocarbons, and thus provide one of the major sources of these
important compounds
Preparation

Preparation of alicyclic hydrocarbons from other aliphatic compounds generally

involves two stages: (a) conversion of some open-chain compound or compounds
into a compound that contains a ring, a process called cyclization. (b) conversion
of the cyclic compound thus obtained into the kind of compound that we want: for
example, conversion of a cyclic alcohol into a cyclic alkene or of a cyclic alkene
into a cyclic alkane

dihalide can bring about coupling between two alkyl groups that are part of the
same molecule

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Reactions
Reactions of small-ring compounds:Cyclopropane and cyclobutane

Besides the free-radical substitution reactions that are characteristic of

cycloalkanes and of alkanes in general, cyclopropane and cyclobutane undergo
certain addition reactions These addition reactions destroy the cycldpropane
and cyclobutane ringn systems, and yield open-chain products. For example:
 Stability of Cycloalkanes: The
Baeyer Strain Theory
• In 1885, Baeyer proposed a theory to explain the apparent lack of
cyclic alkanes having certain ring sizes. More specifically only 5 and 6
membered cycloalkane rings were known but smaller and larger rings
could not be prepared.

• Baeyer theorized that when carbon is bonded to four other atoms, the
angle between any pair of bonds is the tetrahedral angle 109.5. But the
ring of cyclopropane is a triangle with three angles of 60, and the ring
of cyclobutane is a square with four angles of 90. In cyclopropane or
cyclobutane, therefore, one pair of bonds to each carbon cannot
assume the tetrahedral angle, but must be compressed to 60 or 90 to
fit the geometry of the ring.
These deviations of bond angles from the "normal" tetrahedral value
cause the molecules to be strained, and hence to be unstable compared
with molecules in which the bond angles are tetrahedral. Cyclopropane
and cyclobutane undergo ring-opening reactions since these relieve the
strain and yield the more stable open chain compounds. Because the
deviation of the bond angles in cyclopropane (109.5 - 60 = 49.5) is
greater than in cyclobutane (109.5 - 90 =19.5), cyclopropane is more
highly strained, more unstable, and more prone to undergo ring-opening
reactions than is cyclobutane.

Baeyer concluded that cyclopropane would be the most strained followed

by cyclobutane. Cyclopentane would be strain free while cyclohexane
would show a substantial amount of strain energy. Rings larger than
cyclohexane would be impossibly strained and not capable of existing.10
Bayer’s Proposed Bond Angle Strain
 Measurements of Energy
Strain in a Cyclic Compound
•Heats of combustion can be used to measure the total
amount of energy strain in a compound. The notion here is
that the more strained a compound, the higher is its energy
content and the more heat delivered per CH2 unit upon
combustion to CO2 + H2O.
Alkane + O2 CO2 + H2O + Heat
 Bayer’s Theory Busted
Heats of combustion data indicate that Baeyer's theory was
not fully correct. Cyclopropane and cyclobutane are quite
strained but cyclopentane is more strained then first
predicted while cyclohexane is less strained. For larger
rings, there is no regular increase in strain and rings of
more than 14 carbons are strain free.

Why was Baeyer's theory incorrect?

Baeyer assumed that all cycloalkanes are flat when in fact

most adopt a puckered 3-D conformation. Furthermore, he
did not consider the contribution of torsional strain to the
overall strain energy of a molecule.
 The Nature of Ring Strain
• Rings larger than 3 atoms are not flat
• Cyclic molecules can assume nonplanar
conformations to minimize angle strain
and torsional strain by ring-puckering
 Conformations of cycloalkanes
Let us look more closely at the matter of puckered rings, starting with cyclohexane, the
most important of the cycloalkanes.

First, there is the chair form, If we sight along each of the carboncarbon bonds in turn, we
see in every case perfectly staggered bonds

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Let us look at the boat conformation. This is not a very happy arrangement.
Sighting along either of two carbon-carbon bonds, we see sets of exactly eclipsed
bonds, and hence it is less stable because of torsional strain. In addition, there is
van der Waals strain due to crowding between the "flagpole" hydrogens.

the boat conformation exactly eclipsed bonds

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Equatorial and axial bonds in cyclohexane

Let us return to the model of the chair conformation of cyclohexane.

Although the cyclohexane ring is not flat, we can consider that the carbon
atoms lie roughly in a plane. If we look at the molecule in this way, we see
that the hydrogen atoms occupy two kinds of position: six hydrogens lie in the
plane called equatorial (e). while six hydrogens lie above or below the plane
called axial (a).

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1,3-Diaxial interaction in methylcyclohexane. Axial CH3 more crowded than equatorial
CH3 . So the equatorial methylcyclohexane more stable than axial methyl cyclohexane

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Cis- and Trans- in cyclohexane conformation

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