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1.5 Cyclic Alkanes / Alkenes

1.5.1 Structure
A hydrocarbon that contains carbon atoms joined to
form a ring is called a cyclic hydrocarbon.
When all carbons of the ring are saturated (sp
3
), the
hydrocarbon is called cycloalkane.
When a double bond (sp
2
), is part of the ring, the hydrocarbon
is called cycloalkene.
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1.5.2 Nomenclature
The system for naming members of this class is
straightforward. Alkane/Alkene names are preceded by the
prefix cyclo-
However, no numbering of the functional group is
needed in a cyclic alkene
Examples
3
4
Some definitions:
Angle strain: it is the strain induced in a molecule when the
bond angles are different from the ideal tetrahedral bond
angle of 109.5o.
Torsional strain: it is caused by repulsion between the
bonding electrons of one substituent and the bonding
electrons of a nearby substituent.
Steric strain: it is caused by atoms or groups of atoms
approaching each other too closely.
Total Strain Energies of Selected Cycloalkanes
0 Cyclohexane
25.9 Cyclopentane
110.9 Cyclobutane
114.2 Cyclopropane
Strain Energy (kJ/mol) Alkane
1.5.3 Ring Strain and the Structure of Cycloalkanes
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Generally speaking, cyclic alkanes found in nature have five
or six-membered rings. On the other hand, compounds with
three and four-membered rings are found much less
frequently. This observation suggested that alkanes with
five- and six-membered rings must be more stable than
those with three- or four-membered rings. It was proposed
that such instability could be explained on the bases of
angle strain. Ideally, an sp
3
hybridized carbon has bond
angles of 109.5. As a result, stability of a cycloalkane may
be predicted by determining how close the bond angle of a
planar cycloalkane is to 109.5
0
. The angles of an equilateral
triangle are 60
o
. Therefore, the bond angles in a planar
cyclopropane are compressed from the ideal bond angle
of 109.5
o
to 60
o
, a 49.5
o
deviation causing angle strain.
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As described earlier, normal sigma bond between two carbon
atoms are formed by the overlap of two sp
3
orbitals that
point directly at each other. In cyclopropane, overlapping
orbitals cannot point directly at each other.
Therefore, the orbital overlap is less effective than in a
normal C-C bond. Hence, the less effective orbital overlap
causes the C-C bond to be weaker and could be easily
broken i.e. reactive. For example, cyclopropane could be
readily hydrogenated to propane.
H
2
Cyclopropane
Propane
Pt
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Because the C-C bonding orbitals in Cyclopropane cannot
point directly at each other, they have shapes that resemble
bananas and, consequently, are often called banana bonds.
In addition to angle strain, three-membered rings have
torsional strain as a result of the fact that all hydrogen atoms
are eclipsed.
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Similarly, the bond angles in planar cyclobutane would
have to be compressed from 109.5
o
to 90
o
, the bond angle
associated with a planar square. Planar cyclobutane would
then be expected to have less angle strain than
cyclopropane because the bond angles in cyclobutane are
only 19.5
o
away from the ideal angle.
Considering angle strain as the only factor, it was predicted
that cyclopentane be the most stable of cycloalkanes
because its bond angles (108
o
) are closest to the ideal
tetrahedral one.
In addition, it may be predicted that cyclohexane, with bond
angles of 120
o
, would be less stable.
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Because three points define a plane, the carbons of
cyclopropane indeed lie in a plane as it cannot twist.
As a result cyclpropane is planar.
On the other hand, other cycloalkanes are not planar. They
are capable of twisting and bend in order to attain a
structure that minimizes the three different kind of strain
(angle, torsional, and steric strains) that destabilize a cyclic
compound.
Contrary to this prediction, it turned out that cyclohexane is
more stable than the five-membered ring! Why?
The assumption that all cyclic molecules are planar is not
accurate.
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Although planar cyclobutane would have less angle strain than
cyclopropane, it could have more torsional strain because it has eight
pairs of eclipsed hydrogens, compared with the six of cyclopropane.
Hence, cyclobutane is not planar molecule-it is bent molecule. Although
this increases the angle strain never the less, the increase is
more than compensated for by the decreased torsional strain.
110.9
Cyclobutane
114.2 Cyclopropane
Strain Energy (kJ/mol) Alkane
Similarly, if cyclopentane were planar, it would have essentially no angle
strain. In this case however, its 10 pairs of eclipsed hydrogens would be
subject to considerable torsional strain. Consequently, cyclopentane
puckers, allowing the hydrogens to become nearly staggered
although in doing so it acquires some angle strain.
0 Cyclohexane
25.9 Cyclopentane
Strain Energy
(kJ/mol)
Alkane
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Such form is called the envelope conformation as the shape resembles
an envelope with the flap up.
In contrast to smaller rings, distortion from planarity in cyclohexane
relieves both the angle and torsional strain of the planar structure.
Once more, the internal angle in a planar hexagon is 120
o
, larger, not
smaller, than the ideal sp
3
angle. Deviation from planarity will decrease
both this angle and torsional strain from the six pairs of eclipsed
hydrogens in planar model.
Remarkably, this relaxation produces a molecule in which
essentially all of the torsional and angle strain is gone. This
energy minimum cyclohexane is called the chair form. In the
chair conformer of cyclohexane, all bond angles are 111
o
and all the adjacent bonds are staggered.
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Definitions
Equatorial carbon-hydrogen bonds are parallel to the ring
carbon-carbon bonds one bond away in chair cyclohexane.
Axial carbon-hydrogen bonds are parallel and pointing either
straight up or down in chair cyclohexane
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Cyclohexane rapidly interconverts between two stable chair conformations
because of the ease of rotation about its C-C bonds. Such process is called ring
flip. When the chair conformers interconvert, bonds that equatorial in one chair
conformer become axial in the other chair conformer and vice versa.
Definitions: Equatorial carbon-hydrogen bonds are parallel to the ring carbon-
carbon bonds one bond away in chair cyclohexane. Axial carbon-hydrogen bonds
are parallel and pointing either straight up or down in chair cyclohexane
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Cyclohexane can also exist in a boat conformation
Similar to the chair conformer, the boat conformer is free of
angle strain. However, the boat conformer is not as stable
because some of its bonds are eclipsed, giving torsional
strain to the molecule. In addition, the boat conformer is
further destabilized by the close proximity of the
flagpole hydrogens which causes steric strain.
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16
H
H
H
H
H
H
H
H
CH2
CH2
Newman projection of the chair conformer
In the boat form, the bonded atoms are in
the less stable eclipsed conformation,
whereas in the chair form, they are staggered
1
4
1
4
In the boat form, carbons 1, 4
Are pulled toward each other,
Causing steric interactions between
The flagpole hydrogens.
In the chair form, these same carbons are
bent away from each other, and thus are
not subject to mutual repulsion.
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It should be noted that while cyclohexane interconverts from one chair
conformer to the other, it can assume other conformations namely, half-chair
and twist-boat. As expected, because the chair conformers are the most stable
conformers, at any instant more molecules of cyclohexane are in chair
conformations than in any other one.
Interesting to note that it has been calculated that, for every thousand molecules
of cyclohexane in a chair conformation, no more than two molecules are in the
next most stable conformations-the twist-boat. Cis trans in cycloalkanes
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1.6 Functional groups
1.6.1 Definition
It is the part of a molecule where most of its chemical
reactions occur. Alkanes do not have a functional group. It
is the part that effectively determines the compounds
chemical and most of its physical properties.
1.6.2 Most common functional groups
Aldehyde Ketone Carboxylic acidCarboxylic ester Alcohol
Ether Alkene Alkyne
R C
H
H
OH
R C
H
O
C O
R
R
C
O
OH R
R O R
R C O R
O
R NH
2
R C NH
2
O
Amine
Amide
R C C R
C
H
H
C
R
R