Cycloalkanes

Cycloalkanes are types of alkanes that have one or more rings of carbon atoms in
the chemical structure of their molecules. Cycloalkanes consist of only carbon (C)
and hydrogen (H) atoms and are saturated because there are no multiple C-C bonds to
hydrogenate (add more hydrogen to). A general chemical formula for cycloalkanes
would be: CnH2n where n = number of C atoms and H number
of rings in the molecule. Substituted cycloalkanes are named in a fashion very similar to
that used for naming branched alkanes. The chief difference in the rules and procedures
occurs in the numbering system. Since all the carbons of a ring are equivalent (a ring has
no ends like a chain does), the numbering starts at a substituted ring atom.
Hydrocarbons having more than one ring are common, and are referred to
as bicyclic (two rings), tricyclic (three rings) and in general, polycyclic
compounds. The molecular formulas of such compounds have H/C ratios that decrease
with the number of rings. In general, for a hydrocarbon composed of n carbon
atoms associated with rings

Nomenclature of Cycloalkanes
Cycloalkanes are named by adding the prefix “cyclo” to the alkane name. In addition to
being saturated cyclic hydrocarbons, cycloalkanes may have multiple substituents
or functional groups which further determines their unique chemical properties. The
most common and useful cycloalkanes in organic chemistry are cyclopentane and
cyclohexane, though other cycloalkanes varying in the number of carbons can be
synthesized.
The rules for naming cycloalkane resembles the rules for naming noncyclical alkanes:
1. In the case of cycloalkanes with an attached alkyl substituent the ring is the parent
hydrocarbon. There is no need to number the position of a single substituent on a
ring.
2. If the ring has 2 different substituents they are cited alphabetical order and
position is given to the substituents cited first.
IUPAC Rules for Nomenclature
1) Determine the cycloalkane to use as parent chain. The parent chain is one with
the most amount of carbon atoms. If there are two cycloalkanes, use the
cycloalkane with more carbons as the parent chain.
2) If there is an alkyl straight chain that is greater in the number of carbons than the
cycloalkane, 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.
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.

Conformation of Cycloalkanes
A cyclohexane conformation is any of several three-dimensional shapes that a
cyclohexane molecule can assume while maintaining the integrity of its chemical bonds.
A cyclohexane conformation is any of several three-dimensional shapes that a
cyclohexane molecule can assume while maintaining the integrity of its chemical bonds.
Cyclohexane conformations have been extensively studied in organic chemistry because
they are the classical example of conformational isomerism and have noticeable
influence on the physical and chemical properties of cyclohexane.

Chair Conformation
This conformation is not flat but is folded into the shape of a lawn chair, so it is called the
chair conformation. While the chair is typically drawn from such a perspective view, keep
in mind that the chair actually has thrThe best way to visualize the chair conformation is
to build one for yourself using a molecular model kit. You should verify that the chair has
no eclipsing interactions. ee-fold rotational symmetry. That is, it can be rotated by 120 or
240 degrees and look identical. This can also be seen in a Newman projection down a set
of two C-C bonds. Notice how this resembles two Newman projections of ethane joined
together by - CH 2 - groups:

There are two distinctive types of C-H bonds on the chair. One set is comprised of C-H
bonds that extend vertically up and down and are called axial bonds. The other set
consists of C-H bonds that extend out to the periphery of the ring and are called
equatorial bonds. Each carbon has one axial bond and one equatorial bond.

Boat conformation

In the basic boat conformation (C2v symmetry), carbons C2, C3, C5 and C6 are coplanar,
while C1 and C4 are displaced away from that plane in the same direction. Bonds C2-C3
and C5-C6 are therefore parallel. In this form, the molecule has two perpendicular planes
of symmetry as well as a C2 axis. The boat conformations have higher energy than the
chair conformations. The interaction between the two flagpole hydrogens, in particular,
generates steric strain. There is also torsional strain involving the C2-C3 and C5-C6
bonds, which are eclipsed. The twist-boat conformation, sometimes called twist (D2
symmetry) can be derived from the boat conformation by applying a slight twist to the
molecule about the axes connecting the two unique carbons. The result is a structure
that has three C2 axes and no plane of symmetry.
Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers and Amines
Alkanes contain carbon and hydrogen atoms. Because the electronegativities of carbon
and hydrogen are similar, the bonds in alkanes are nonpolar. Alkanes are neutral
molecules. The molecules of an alkane are held together by induced-dipole-induced-
dipole interactions which are known as van der Waals forces. Van der Waals forces are
the weakest of all the intermolecular attractions. The magnitude of van der Waals forces
that hold alkane molecules together depend on the area of contact between the
molecules. The greater the area of contact, the stronger are the van der Waals forces and
the greater the amount of energy needed to overcome the forces.

Boiling Point increases as the size of alkane increases. Because the strengthen of van der
Waals forces depends on the area of contact between the molecules, branching in a
compound lower its boiling point because it reduces the area of contact. Thus, if two
alkanes have the same molecular weight, the more highly branched alkane will have a
lower boiling point.

Uses of Alkanes and Cycloalkanes

The uses of alkanes and cycloalkanes are defined by the carbon number: C1 , C4 ,
natural gas, petroleum gas, C5 , C12 , motor fuel, C12 , C13 , kerosene, C15 , C25 , diesel,
C16 - C30 -- heavy oil, >C25 , petroleum jelly or paraffin wax, and residue asphalt.

Background Information for Alkanes and Cycloalkanes

Alkanes and cycloalkanes are nonpolar and do not have intermolecular hydrogen
bonding. These compounds are hydrophobic, do not dissolve in water, and are less
dense than water. The boiling points and melting points of alkanes and cycloalkanes
increase with increasing molecular weight. The conformations of ethane are eclipsed
and staggered. The conformations of butane are totally eclipsed, gauche, eclipsed, and
anti. Smaller rings are more likely to undergo ring opening reactions. The main
conformations of cyclohexane are chair and boat. The chair conformation of cyclohexane
is the most stable, with the hydrogens furthest apart. The boat conformation of
cyclohexane is the least stable, with the hydrogens the closest. The boiling point of a
series of ethers, alkyl halides, alcohol or amines also increase with increasing molecular
weight because of the increase in van der Waals forces. The C – Z bond (Z denotes N, O,
F, Cl, or Br) is polar and more electronegative than the carbon to which they are
attached. Molecules with polar bonds are attached to one another because they can
align in the positive end of one molecules to negative end of another. These attractive
forces called dipole-dipole interaction, stronger than van der Waals forces, but not as
strong as ionic or covalent bonds.

Ethers have higher boiling points than alkanes.

Alcohols have much higher boiling points than alkanes or ethers of comparable
molecular weight. Alcohols can form Hydrogen bonds A hydrogen bond is a special kind
of dipole – dipole interaction that occurs between a hydrogen that is bonded to an
oxygen, a nitrogen, or a fluorine. A hydrogen bond is stronger that other dipole – dipole
interactions. The reason why alcohols have much higher boiling points than alkanes or
ethers. Primary and secondary amines also form hydrogen bonds, so these amines have
higher boiling points than alkanes.

An amine has lower boiling point than an alcohol. Primary amine has a higher boiling
point than a secondary amine and secondary amine has higher boiling point than a
tertiary amine.