Aliphatic Cyclic Hydrocarbons

Introduction to cyclic hydrocarbons

Organic compounds containing carbon and hydrogen atoms only and the
carbon atoms in them form one or more ring/s (closed C-chain) is/are known
as cyclic hydrocarbons.
Non-aromatic hydrocarbons in which carbon atoms form one or more
closed C-chain rings are aliphatic cyclic hydrocarbons. In this section, you will
introduce cyclic hydrocarbons with one C-chain ring only. Cycloalkanes and
cycloalkenes are the two major organic classes of this type of cyclic hydrocarbons.
Cycloalkanes are aliphatic cyclic hydrocarbons having single bonds between
C-atoms in the ring. The general formula is the same with those of alkenes; CnH2n
Cycloalkenes are cyclic hydrocarbons with one double bond between two Catoms in the carbon ring and their general formula is exactly the same with alkynes
family; CnH2n2.
Since alkenes and cycloalkanes have the same general formulae (the same
as alkynes and cycloalkenes are), we can deduce that these pairs of organic
classes are structural isomers, differing in their internal structures.

Nomenclature

Cycloalkanes with a single ring are named analogously to their normal alkane
counterpart of the same carbon content: cyclopropane, cyclobutane, cyclopentane,
cyclohexane, etc.
IUPAC nomenclature; use the prefix cyclo- before the parent name.

Properties
Cycloalkanes are similar to alkanes in their general physical properties, but have
higher boiling and melting points and densities. This is due to stronger London
forces because the ring shape allows for a larger area of contact. Cycloalkanes
exhibit almost the same degree of un-reactivity as alkanes, due to their unreactive
C-C and C-H bonds; however, the ring strain (see below) can cause cycloalkanes
to be more reactive.

Baeyer (Ring) strain

Baeyer strain theory or ring theory explains specific behavior of chemical
compounds in terms of bond angle strain. It was proposed by Adolf von Baeyer in
1885 to account for the unusual chemical reactivity in ring opening reactions of
cyclopropanes and cyclobutanes where this angle strain is relieved.
The carbon atoms in cycloalkanes are sp3 hybridized. In cyclopropane and
cyclobutane there is a deviation from the ideal tetrahedral bond angles of 109,5. In
this way, the potential energy increases and an overall destabilizing effect.
Eclipsing of hydrogen atoms is an important destabilizing effect, as well. Ring strain
is highest for cyclopropane, in which the carbon atoms form a triangle and therefore
have 60 C-C-C bond angles. The ring strain, calculated by subtraction of 60 from
109,5 therefore is approximately 49,5.

Cyclobutane has the carbon atoms in a square with approximately 90 bond angles.
Its ring strain is therefore slightly less, 19,5. For a theoretical planar cyclopentane
the C-C-C bond angles would be 108 very close to the measure of the tetrahedral
angle. Thus, from cyclopentane their rings and molecules are very stable.

Reactions
Cycloalkanes having three or four C-atoms undergo addition (hydrogenation and
halogenation) reactions performed by a catalyst. These processes are ring-opening
reactions.
Cycloalkanes having more than five carbon atoms undergo substitution reactions,
where one hydrogen atom from the ring replaces with a halogen atom (no ring
strain, low potential energy and stable ring).

Exercises
1. Name the following organic compounds.
a) CH2 = C(CH3) CBr2 CH2 CH2 CH3

b)

c)

d) CH3 CH = C = C(CH3) C(CH3)2 CH3

e) CH3 C C CHCl CH3

f) CH2Cl = CCl2

g)

2. Write balanced equations for the following reactions:

a)
b)
c)
d)
e)
f)
g)
h)
i)
j)
k)

pent-1-yne + ammoniacal solution of copper(I) cloride

polimerization of vynyl chloride
hydration of 2-methylhex-3-yne
halogenation (Br2) of cyclobutane
hydrohalogenation of 3,4-dimetylpent-1-yne
combustion of hexene
halogenation of cyclohexane
hydration of ethene
hydration of ethyne
halogenation of 4,5,5-trimethylhept-1-ene
dehalogenation of 2,2,3,3-tetraiodohexane

3. Write condensed structural formulas for the compounds given below:

a) 8-bromo-2,7,8-trimethyl-non-4-yne

c) propadiene

d) propyne

b) trans-1,2-dichlorocyclopropane

e) cis-1,2-dichlorocyclopropane

Which of these are isomer pairs (sets) and determine the main type and sub-type of
each set (be more specific).
Isomers: _____________________;
Types and sub-types: ___________________________________________________________
__________________________________________________________________________