Alkanes

Alkanes are organic compounds that consist entirely of single-

bonded carbon and hydrogen atoms and lack any other functional
groups. Alkanes have the general formula CnH2n+2CnH2n+2 and can
be subdivided into the following three groups: the linear straight-
chain alkanes, branched alkanes, and cycloalkanes. Alkanes are
also saturated hydrocarbons. Alkanes are the simplest and least
reactive hydrocarbon species containing only carbons and
hydrogens. They are commercially very important, being the
principal constituent of gasoline and lubricating oils and are
extensively employed in organic chemistry; though the role of pure
alkanes (such as hexanes) is delegated mostly to solvents. The
distinguishing feature of an alkane, making it distinct from other
compounds that also exclusively contain carbon and hydrogen, is its
lack of unsaturation. That is to say, it contains no double or triple
bonds, which are highly reactive in organic chemistry. Though not
totally devoid of reactivity, their lack of reactivity under most
laboratory conditions makes them a relatively uninteresting, though
very important component of organic chemistry. As you will learn
about later, the energy confined within the carbon-carbon bond and
the carbon-hydrogen bond is quite high and their rapid oxidation
produces a large amount of heat, typically in the form of fire.

Nomenclature of Alkanes

The names of all alkanes end with -ane. Whether or not the carbons are
linked together end-to-end in a ring (called cyclic alkanes or cycloalkanes)
or whether they contain side chains and branches, the name of every
carbon-hydrogen chain that lacks any double bonds or functional groups
will end with the suffix -ane.

Alkanes with unbranched carbon chains are simply named by the number
of carbons in the chain. The first four members of the series (in terms of
number of carbon atoms) are named as follows:

1. CH4 = methane = one hydrogen-saturated carbon

2. C2H6 = ethane = two hydrogen-saturated carbons
3. C3H8 = propane = three hydrogen-saturated carbons
4. C4H10 = butane = four hydrogen-saturated carbons

Alkanes with five or more carbon atoms are named by adding the suffix -
ane to the appropriate numerical multiplier, except the terminal -a is
removed from the basic numerical term. Hence, C 5H12 is called pentane,
C6H14 is called hexane, C7H16 is called heptane and so forth.

Straight-chain alkanes are sometimes indicated by the prefix n- (for

normal) to distinguish them from branched-chain alkanes having the same
number of carbon atoms. Although this is not strictly necessary, the usage
is still common in cases where there is an important difference in
properties between the straight-chain and branched-chain isomers: e.g. n-
hexane is a neurotoxin while its branched-chain isomers are not.

1 Number of Hydrogen to Carbons

This equation describes the relationship between the number of hydrogen
and carbon atoms in alkanes:

H = 2C + 2

where "C" and "H" are used to represent the number of carbon and
hydrogen atoms present in one molecule. If C = 2, then H = 6.

Many textbooks put this in the following format:

CnH2n+2

where "Cn" and "H2n+2" represent the number of carbon and hydrogen
atoms present in one molecule. If Cn = 3, then H2n+2 = 2(3) + 2 = 8. (For
this formula look to the "n" for the number, the "C" and the "H" letters
themselves do not change.)

Progressively longer hydrocarbon chains can be made and are named

systematically, depending on the number of carbons in the longest chain.

The following table contains the systematic names for the first twenty
straight chain alkanes. It will be important to familiarize yourself with
these names because they will be the basis for naming many other
organic molecules throughout your course of study.

2 Drawing Hydrocarbons

Recall that when carbon makes four bonds, it adopts the tetrahedral
geometry. In the tetrahedral geometry, only two bonds can occupy a plane
simultaneously. The other two bonds point in back or in front of this plane.
In order to represent the tetrahedral geometry in two dimensions, solid
wedges are used to represent bonds pointing out of the plane of the
drawing toward the viewer, and dashed wedges are used to represent
bonds pointing out of the plane of the drawing away from the viewer.
Consider the following representation of the molecule methane:
 Figure 1: Two dimensional representation of methane

In the above drawing, the two hydrogens connected by solid lines, as well
as the carbon in the center of the molecule, exist in a plane (specifically,
the plane of the computer monitor / piece of paper, etc.). The hydrogen
connected by a solid wedge points out of this plane toward the viewer, and
the hydrogen connected by the dashed wedge points behind this plane
and away from the viewer.

In drawing hydrocarbons, it can be time-consuming to write out each atom

and bond individually. In organic chemistry, hydrocarbons can be
represented in a shorthand notation called a skeletal structure. In a
skeletal structure, only the bonds between carbon atoms are represented.
Individual carbon and hydrogen atoms are not drawn, and bonds to
hydrogen are not drawn. In the case that the molecule contains just single
bonds (sp3 bonds), these bonds are drawn in a "zig-zag" fashion. This is
because in the tetrahedral geometry all bonds point as far away from each
other as possible, and the structure is not linear. Consider the following
representations of the molecule propane:

Figure 2: Full structure of propane and skeletal structure of propane

Only the bonds between carbons have been drawn, and these have been
drawn in a "zig-zag" manner. Note that there is no representation of
hydrogens in a skeletal structure. Since, in the absence of double or triple
bonds, carbon makes four bonds total, the presence of hydrogens is
implicit. Whenever an insufficient number of bonds to a carbon atom are
specified in the structure, it is assumed that the rest of the bonds are
made to hydrogens. For example, if the carbon atom makes only one
explicit bond, there are three hydrogens implicitly attached to it. If it
makes two explicit bonds, there are two hydrogens implicitly attached,
etc. Note also that two lines are sufficient to represent three carbon
atoms. It is the bonds only that are being drawn out, and it is understood
that there are carbon atoms (with three hydrogens attached!) at the
terminal ends of the structure.

3 Alkyl Groups

Alkanes can be described by the general formula CnH2n+2. An alkyl group is

formed by removing one hydrogen from the alkane chain and is described
by the formula CnH2n+1. The removal of this hydrogen results in a stem
change from -ane to -yl. Take a look at the following examples.

The same concept can be applied to any of the straight chain alkane
names provided in the table above.

Molecular Formula Condensed Structural

CH4 CH4

C2H6 CH3CH3

C3H8 CH3CH2CH3

C4H10 CH3(CH2)2CH3

C5H12 CH3(CH2)3CH3

C6H14 CH3(CH2)4CH3

C7H16 CH3(CH2)5CH3

C8H18 CH3(CH2)6CH3

C9H20 CH3(CH2)7CH3

C10H22 CH3(CH2)8CH3

C11H24 CH3(CH2)9CH3

C12H26 CH3(CH2)10CH3

C13H28 CH3(CH2)11CH3
 Molecular Formula Condensed Structural

C14H30 CH3(CH2)12CH3

C15H32 CH3(CH2)13CH3

C16H34 CH3(CH2)14CH3

C17H36 CH3(CH2)15CH3

C18H38 CH3(CH2)16CH3

C19H40 CH3(CH2)17CH3

C20H42 CH3(CH2)18CH3

4 Using Common Names with Branched Alkanes

Certain branched alkanes have common names that are still widely used
today. These common names make use of prefixes, such
as iso-, sec-, tert-, and neo-. The prefix iso-, which stands for isomer, is
commonly given to 2-methyl alkanes. In other words, if there is methyl
group located on the second carbon of a carbon chain, we can use the
prefix iso-. The prefix will be placed in front of the alkane name that
indicates the total number of carbons. Examples:

 isopentane which is the same as 2-methylbutane

 isobutane which is the same as 2-methylpropane

To assign the prefixes sec-, which stands for secondary, and tert-, for
tertiary, it is important that we first learn how to classify carbon
molecules. If a carbon is attached to only one other carbon, it is called
a primary carbon. If a carbon is attached to two other carbons, it is called
a seconday carbon. A tertiary carbon is attached to three other carbons
and last, a quaternary carbon is attached to four other carbons.
Examples:

 4-sec-butylheptane (30g)
 4-tert-butyl-5-isopropylhexane (30d); if using this example, may
want to move sec/tert after iso disc

The prefix neo- refers to a substituent whose second-to-last carbon of the

chain is trisubstituted (has three methyl groups attached to it). A neo-
pentyl has five carbons total. Examples:
  neopentane
 neoheptane

5 Alkoxy Groups

Alkoxides consist of an organic group bonded to a negatively charged

oxygen atom. In the general form, alkoxides are written as RO -, where R
represents the organic substituent. Similar to the alkyl groups above, the
concept of naming alkoxides can be applied to any of the straight chain
alkanes provided in the table above.

6 Three Principles of Naming

1. Choose the longest, most substituted carbon chain containing a
functional group.
2. A carbon bonded to a functional group must have the lowest
possible carbon number. If there are no functional groups, then any
substitute present must have the lowest possible number.
3. Take the alphabetical order into consideration; that is, after applying
the first two rules given above, make sure that your substitutes
and/or functional groups are written in alphabetical order.
7 Example 1

What is the name of the following molecule?

8 Solution

Rule #1: Choose the longest, most substituted carbon chain containing a
functional group. This example does not contain any functional groups, so
we only need to be concerned with choosing the longest, most substituted
carbon chain. The longest carbon chain has been highlighted in red and
consists of eight carbons.
Rule #2: Carbons bonded to a functional group must have the lowest
possible carbon number. If there are no functional groups, then any
substitute present must have the lowest possible number. Because this
example does not contain any functional groups, we only need to be
concerned with the two substitutes present, that is, the two methyl
groups. If we begin numbering the chain from the left, the methyls would
be assigned the numbers 4 and 7, respectively. If we begin numbering the
chain from the right, the methyls would be assigned the numbers 2 and 5.
Therefore, to satisfy the second rule, numbering begins on the right side of
the carbon chain as shown below. This gives the methyl groups the lowest
possible numbering.

Rule 3: In this example, there is no need to utilize the third rule. Because
the two substitutes are identical, neither takes alphabetical precedence
with respect to numbering the carbons. This concept will become clearer
in the following examples.

9 Example 2

What is the name of the following molecule?

10 Solution

Rule #1: Choose the longest, most substituted carbon chain containing a
functional group. This example contains two functional groups, bromine
and chlorine. The longest carbon chain has been highlighted in red and
consists of seven carbons.
Rule #2: Carbons bonded to a functional group must have the lowest
possible carbon number. If there are no functional groups, then any
substitute present must have the lowest possible number. In this example,
numbering the chain from the left or the right would satisfy this rule. If we
number the chain from the left, bromine and chlorine would be assigned
the second and sixth carbon positions, respectively. If we number the
chain from the right, chlorine would be assigned the second position and
bromine would be assigned the sixth position. In other words, whether we
choose to number from the left or right, the functional groups occupy the
second and sixth positions in the chain. To select the correct numbering
scheme, we need to utilize the third rule.

Rule #3: After applying the first two rules, take the alphabetical order
into consideration. Alphabetically, bromine comes before chlorine.
Therefore, bromine is assigned the second carbon position, and chlorine is
assigned the sixth carbon position.

11 Example 3

What is the name of the follow molecule?

12 Solution
Rule #1: Choose the longest, most substituted carbon chain containing a
functional group. This example contains two functional groups, bromine
and chlorine, and one substitute, the methyl group. The longest carbon
chain has been highlighted in red and consists of seven carbons.

Rule #2: Carbons bonded to a functional group must have the lowest
possible carbon number. After taking functional groups into consideration,
any substitutes present must have the lowest possible carbon number.
This particular example illustrates the point of difference principle. If
we number the chain from the left, bromine, the methyl group and
chlorine would occupy the second, fifth and sixth positions, respectively.
This concept is illustrated in the second drawing below. If we number the
chain from the right, chlorine, the methyl group and bromine would
occupy the second, third and sixth positions, respectively, which is
illustrated in the first drawing below. The position of the methyl, therefore,
becomes a point of difference. In the first drawing, the methyl occupies
the third position. In the second drawing, the methyl occupies the fifth
position. To satisfy the second rule, we want to choose the numbering
scheme that provides the lowest possible numbering of this substitute.
Therefore, the first of the two carbon chains shown below is correct.

Therefore, the first numbering scheme is the appropriate one to use.

Once you have determined the correct numbering of the carbons, it is
often useful to make a list, including the functional groups, substitutes,
and the name of the parent chain.

Rule #3: After applying the first two rules, take the alphabetical order
into consideration. Alphabetically, bromine comes before chlorine.
Therefore, bromine is assigned the second carbon position, and chlorine is
assigned the sixth carbon position.

Parent chain: heptane 2-Chloro 3-Methyl 6-Bromo

6-bromo-2-chloro-3-methylheptane

13 Problems

What is the name of the follow molecules?