Alkanes

They are saturated hydrocarbons (they have only carbon-carbon single bonds). The molecular formula of
this group is CnH2n+2 (n is the number of carbon atoms).

A. Alkanes: Nomenclature

Although many different types of nomenclature, or naming systems, were employed in the past, today
only the International Union of Pure and Applied Chemistry (IUPAC) nomenclature is acceptable for all
scientific publications. In this system, a series of rules has been created that is adaptable to all classes of
organic compounds. For alkanes, the following rules apply.

1. Identify the longest continuous chain of carbon atoms. The parent name of the alkane is the IUPAC
assigned name for the alkane of this number of carbon atoms (see Table ). Thus, if the longest chain
of carbon atoms has six carbon atoms in it, the parent name for the compound is hexane.
 2. Identify the substituent groups attached to the parent chain. A substituent group is any atom or
group that has replaced a hydrogen atom on the parent chain.

3. Number the continuous chain in the direction that places the substituents on the lowestnumbered
carbon atoms.

4. Write the name of the compound. The parent name is the last part of the name. The name(s) of
the substituent group(s) and the location number(s) precede the parent name. A hyphen separates
the number associated with the substituent from its name. If two substituents are on the same
carbon of the parent chain, the number of the carbon they are attached to is written before each
substituent name. If the two substituents are identical, the numbers are both written before the
substituent name, and the prefix di is added to the name. Substituent group names are placed in
alphabetical order.

Applying the four nomenclature rules to the following compound

results in the name 2chloro3methylpentane. Notice that the parent name comes from the longest
continuous carbon chain, which begins with the carbon of the CH 3 group at the bottom of the structural
formula ( a) and goes to the carbon of the CH 3 group on the top right side of the formula ( b). This chain
contains five carbon atoms, while the straight chain of carbons from left to right contains only four
carbons. Starting the numbering from the top right carbon of the CH 3 group ( b) leads to 2,3
substitution, while numbering from the bottom right side CH 3 carbon ( a) leads to 3,4 substitution
(which is incorrect). This alkane is referred to as a branchedchain alkane because it contains an alkyl
group off of the main chain.

Applying the IUPAC nomenclature rules to a more complex alkane molecule

results in the name 5chloro2hydroxy4propylheptane. Notice that the names of the substituent
groups are in alphabetical order.

Finally, here is an example of a compound with a repeating substituent group.

This compound is called 2,4dichlorohexane.

B. Alkanes: Physical Properties

The alkanes can exist as gases, liquids, or solids at room temperature. The unbranched alkanes methane,
ethane, propane, and butane are gases; pentane through hexadecane are liquids; the homologues larger
than hexadecane are solids.

Branched alkanes normally exhibit lower boiling points than unbranched alkanes of the same carbon
content. This occurs because of the greater van der Waals forces that exist between molecules of the
unbranched alkanes. These forces can be dipoledipole, dipoleinduced dipole, or induced dipole
induced dipole in nature. The unbranched alkanes have greater van der Waals forces of attraction
because of their greater surface areas.

Solid alkanes are normally soft, with low melting points. These characteristics are due to strong
repulsive forces generated between electrons on neighboring atoms, which are in close proximity in
crystalline solids. The strong repulsive forces counterbalance the weak van der Waals forces of
attraction.

Finally, alkanes are almost completely insoluble in water. For alkanes to dissolve in water, the van der
Waals forces of attraction between alkane molecules and water molecules would have to be greater
than the dipoledipole forces that exist between water molecules. This is not the case.

C. Sources of alkanes:

The two major sources of alkanes are natural gas and petroleum. Natural gas consists of approximately
90 to 95% methane, 5 to 10% ethane, and a mixture of other relatively low-boiling alkanes (propane,
butane and 2-methylpropane). Petroleum is a thick, viscous, liquid mixture of thousands of compounds,
most of them hydrocarbons, formed the decomposition of marine plants and animals. The fundamental
separation process in refining petroleum is fractional distillation. All crude petroleum that enters a
refinery goes to distillation units, where it is heated to temperatures as high as 370 to 425C and
separated into fractions.

D. Important uses of alkanes are as follows:

1. Petroleum and natural gas are largely mixtures of different alkanes. On refining, they give liquefied
petroleum gas (LPG), gasoline, kerosene, diesel, furnace oil and wax which are used as fuels.

2. Some higher alkanes are used as lubricating oils and as vaseline.

3. Alkanes are used as starting materials for the preparation of many other useful organic compounds.
For example, methane on chlorinate on gives chloromethane, dichloromethane, trichloromethane
(chloroform) and tetrachloromethane.
4. Carbon formed during decomposition of methane is in the form of finely divided particles and is
known as carbon black. Carbon black is used for making printers ink and paints. It is also used in rubber
industry.

5. Alkanes are also used as source of hydrogen.

E. Alkanes: Preparations

Alkanes are rarely prepared from other types of compounds because of economic reasons. However,
ignoring financial considerations, alkanes can be prepared from the following compounds:

1. Unsaturated compounds via catalytic reduction

2. Alkyl halides via coupling (Wurtz reaction)

3. Alkyl halides via Grignard reagent

4. Alkyl halides via reduction

Although organic chemists refer to the above diagrams as equations, they are not balanced. In
addition, not every product formed is shown. These diagrams are really reaction schemes.

F. Conformational analysis of alkanes

Conformational analysis of ethane

A conformational analysis is a study of the energetics of different spatial arrangements of atoms

relative to rotations about bonds. Conformational analyses are assisted greatly by a representation of
molecules in a manner different to skeletal structures. A representation of a molecule in which the
atoms and bonds are viewed along the axis about which rotation occurs is called a Newman
projection (Figure 1).

Figure 1: Newman projection of ethane

In a Newman projection, the molecule is viewed along an axis containing two atoms bonded to each
other and the bond between them, about which the molecule can rotate. In a Newman projection, the
"substituents" of each atom composing the bond, be they hydrogens or functional groups, can then be
viewed both in front of and behind the carbon-carbon bond. Specifically, one can observe the angle
between a substituent on the front atom and a substituent on the back atom in the Newman projection,
which is called the dihedral angle or torsion angle.

In ethane specifically, we can imagine two possible "extreme" conformations. In one case, the dihedral
angle is 0 and the hydrogens on the first carbon line up with or eclipse the hydrogens on the second
carbon. When the dihedral angle is 0 and the hydrogens line up perfectly, ethane has adopted
the eclipsed conformation (Figure 2). The other extreme occurs when the hydrogens on the first carbon
are as far away as possible from those on the second carbon; this occurs at a dihedral angle of 60 and is
called the staggeredconformation (Figure 2).
Figure 2: Conformations of ethane - staggered and eclipsed

The staggered conformation of ethane is a more stable, lower energy conformation than the eclipsed
conformation because the eclipsed conformation involves unfavorable interactions between hydrogen
atoms. Specifically, the negatively charged electrons in the bonds repel each other most when the bonds
line up. Thus, ethane spends most of its time in the more stable staggered conformation.

Conformational analysis of butane

In butane, two of the substituents, one on each carbon atom being viewed, is a methyl group. Methyl
groups are much larger than hydrogen atoms. Thus, when eclipsed conformations occur in butane, the
interactions are especially unfavorable. There are four possible "extreme" conformations of butane:
1) Fully eclipsed, when the methyl groups eclipse each other; 2) Gauche, when the methyl groups are
staggered but next to each other; 3) Eclipsed, when the methyl groups eclipse hydrogen atoms; and
4) Anti, when the methyl groups are staggered and as far away from each other as possible (Figure 3).

Figure 3: Conformations of butane: fully eclipsed, gauche, eclipsed, and anti

The fully eclipsed conformation is clearly the highest in energy and least favorable since the largest
groups are interacting directly with each other. As the molecule rotates, it adopts the relatively stable
gauche conformation. As it continues to rotate, it encounters less favorable eclipsed conformation in
which a methyl group eclipses a hydrogen. As rotation continues, the molecule comes to the anti
conformation, which is the most stable since the substituents are staggered and the methyl groups are
as far away from each other as possible. An energy diagram is a graph which represents the energy of a
molecule as a function of some changing parameter. An energy diagram can be made as a function of
dihedral angle for butane (Figure 4).
Figure 4: Energy diagram for conformations of butane as a function of dihedral angle

Clearly, the anti and gauche conformations are significantly more stable than the eclipsed and fully
eclipsed conformations. Butane spends most of its time in the anti and gauche conformations.

There is one final, very important point. At room temperature, approximately 84 kJ/mol of thermal
energy is available to molecules. Thus, if the barrier to a rotation is less than 84 kJ/mol, the molecule will
rotate. In ethane and butane, the barriers to rotation are significantly less than 84 kJ/mol. Therefore,
even though the eclipsed conformations are unfavorable, the molecules are able to adopt them. In
reality, since these conformations are not as stable, the molecules will quickly pass through them at
room temperature and return a staggered conformation. Molecules are constantly converting between
different staggered conformations all the time, quickly passing through eclipsed conformations in
between. Thus, in alkanes, no single "true" conformation exists all the time; the molecule instead
constantly converts between conformations, spending more time in those that are more stable. This
constant conversion lies in stark contract to alkenes, which adopt the cis- or trans- (E- or Z-)
conformations and retain them at room temperature; they do not interconvert because the barrier to
rotation is too high.

G & H. Alkane Reactions and Mechanisms

The alkanes and cycloalkanes, with the exception of cyclopropane, are probably the least chemically
reactive class of organic compounds. Despite their relative inertness, alkanes undergo several important
reactions that are discussed in the following section.
1. Combustion
The combustion of carbon compounds, especially hydrocarbons, has been the most important source of
heat energy for human civilizations throughout recorded history. The practical importance of this
reaction cannot be denied, but the massive and uncontrolled chemical changes that take place in
combustion make it difficult to deduce mechanistic paths. Using the combustion of propane as an
example, we see from the following equation that every covalent bond in the reactants has been broken
and an entirely new set of covalent bonds have formed in the products. No other common reaction
involves such a profound and pervasive change, and the mechanism of combustion is so complex that
chemists are just beginning to explore and understand some of its elementary features.

CH3-CH2-CH3 + 5 O2 > 3 CO2 + 4 H2O + heat

Two points concerning this reaction are important:

1. Since all the covalent bonds in the reactant molecules are broken, the quantity of heat
evolved in this reaction is related to the strength of these bonds (and, of course, the strength of
the bonds formed in the products). Precise heats of combustion measurements can provide
useful iinformation about the structure of molecules.
2. The stoichiometry of the reactants is important. If insufficient oxygen is supplied some of the
products will consist of carbon monoxide, a highly toxic gas.

CH3-CH2-CH3 + 4 O2 > CO2 + 2 CO + 4 H2O + heat

Heat of Combustion
From the previous discussion, we might expect isomers to have identical heats of combustion. However,
a few simple measurements will disabuse this belief. Thus, the heat of combustion of pentane is 782
kcal/mole, but that of its 2,2-dimethylpropane (neopentane) isomer is 777 kcal/mole. Differences such
as this reflect subtle structural variations, including the greater bond energy of 1-CH versus 2-CH
bonds and steric crowding of neighboring groups. In small-ring cyclic compounds ring strain can be a
major contributor to thermodynamic stability and chemical reactivity. The following table lists heat of
combustion data for some simple cycloalkanes and compares these with the increase per CH2 unit for
long chain alkanes.

Cycloalkane CH2 Units H25 H25 Ring Strain

(CH2)n n kcal/mole per CH2 Unit kcal/mole

Cyclopropane n=3 468.7 156.2 27.6

Cyclobutane n=4 614.3 153.6 26.4

Cyclopentane n=5 741.5 148.3 6.5

Cyclohexane n=6 882.1 147.0 0.0

 Cycloheptane n=7 1035.4 147.9 6.3

Cyclooctane n=8 1186.0 148.2 9.6

Cyclononane n=9 1335.0 148.3 11.7

Cyclodecane n = 10 1481 148.1 11.0

CH3(CH2)mCH3 m = large 147.0 0.0

The chief source of ring strain in smaller rings is angle strain and eclipsing strain. As noted elsewhere,
cyclopropane and cyclobutane have large contributions of both strains, with angle strain being especially
severe. Changes in chemical reactivity as a consequence of angle strain are dramatic in the case of
cyclopropane, and are also evident for cyclobutane. Some examples are shown in the following diagram.
The cyclopropane reactions are additions, many of which are initiated by electrophilic attack. The
pyrolytic conversion of -pinene to myrcene probably takes place by an initial rupture of the 1:6 bond,
giving an allylic 3-diradical, followed immediately by breaking of the 5:7 bond.

2. Halogenation
Halogenation is the replacement of one or more hydrogen atoms in an organic compound by a halogen
(fluorine, chlorine, bromine or iodine). Unlike the complex transformations of combustion, the
halogenation of an alkane appears to be a simple substitution reaction in which a C-H bond is broken
and a new C-X bond is formed. The chlorination of methane, shown below, provides a simple example of
this reaction.

CH4 + Cl2 + energy > CH3Cl + HCl

Since only two covalent bonds are broken (C-H & Cl-Cl) and two covalent bonds are formed (C-Cl & H-Cl),
this reaction seems to be an ideal case for mechanistic investigation and speculation. However, one
complication is that all the hydrogen atoms of an alkane may undergo substitution, resulting in a
mixture of products, as shown in the following unbalanced equation. The relative amounts of the
various products depend on the proportion of the two reactants used. In the case of methane, a large
excess of the hydrocarbon favors formation of methyl chloride as the chief product; whereas, an excess
of chlorine favors formation of chloroform and carbon tetrachloride.

CH4 + Cl2 + energy > CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl

The following facts must be accomodated by any reasonable mechanism for the halogenation reaction.

1. The reactivity of the halogens decreases in the following order: F2 > Cl2 > Br2 > I2.
2. We shall confine our attention to chlorine and bromine, since fluorine is so explosively
reactive it is difficult to control, and iodine is generally unreactive.
 3. Chlorinations and brominations are normally exothermic.
4. Energy input in the form of heat or light is necessary to initiate these halogenations.
5. If light is used to initiate halogenation, thousands of molecules react for each photon of light
absorbed.
6. Halogenation reactions may be conducted in either the gaseous or liquid phase.
7. In gas phase chlorinations the presence of oxygen (a radical trap) inhibits the reaction.
8. In liquid phase halogenations radical initiators such as peroxides facilitate the reaction.

The most plausible mechanism for halogenation is a chain reaction involving neutral intermediates such
as free radicals or atoms. The weakest covalent bond in the reactants is the halogen-halogen bond (Cl-Cl
= 58 kcal/mole; Br-Br = 46 kcal/mole) so the initiating step is the homolytic cleavage of this bond by heat
or light, note that chlorine and bromine both absorb visible light (they are colored). A chain reaction
mechanism for the chlorination of methane has been described.
Bromination of alkanes occurs by a similar mechanism, but is slower and more selective because a
bromine atom is a less reactive hydrogen abstraction agent than a chlorine atom, as reflected by the
higher bond energy of H-Cl than H-Br.

I. Spectral analysis of organic compounds

UV Vis