2023-10-20

Alkanes : Nomenclature, Chemical and Physical

Properties; and Preparation of Alkanes

Asst. Prof. Dr. Fuad O. Abdullah

Organic Chemistry l, course code: PHAR 205
Semester : 1
Week : 3
Date: 21-10-2023

Outline

◦ Hydrocarbons.
◦ Alkanes, cycloalkanes and their derivatives
◦ Alkyl group and types
◦ The IUPAC nomenclature of alkanes
◦ Preparation of alkanes and cycloalkanes

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Objectives

◦ Recognize of alkane classes

◦ Prepared alkane compounds

Hydrocarbons:
Hydrocarbons are compounds that only contain carbon and hydrogen atoms, and they can be classified as follows
depending on the bond types that are present within the molecules.

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Alkanes, cycloalkanes and their derivatives

 Alkanes are hydrocarbons that contain only single bonds.

 The carbon atoms of the molecule are arranged in chains (alkanes) or in rings
(cycloalkanes).
 Alkanes are said to be saturated hydrocarbons
Because their hydrogen content is at a maximum.

 The general molecular formula CnH2n+2

 The alkane family is characterized by the presence of tetrahedral carbon (sp3) atoms

 Methane butane are gases

 Pentane C17H36 are liquids

 C18H38 and higher are solids

Exercises:
• A saturated hydrocarbon contains 5
carbons. What is the formula?
C5H2(5)+2 = C5H12

• A saturated hydrocarbon contains 20

carbons. What is the formula?
C20H2(20)+2 = C20H42

Saturated = Single

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Alkyl Group (R)

 Alkyl group contains one less hydrogen than the corresponding
alkane.
 In naming this group the “-ane” is dropped and “- yl” is added.
 This group does not exist independently but occurs bonded to
another atom or molecule.

Types of Alkyl groups

Classified by the connection site

a carbon at the end of a chain (primary alkyl group)
a carbon in the middle of a chain (secondary alkyl group)
a carbon with three carbons attached to it (tertiary alkyl group)

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The IUPAC nomenclature of alkanes

In general, organic compounds are given systematic names by using the order prefix–
parent–suffix, Common names as well as systematic names are used for alkanes and
their derivatives.

 Identify the longest chain -parent

 number from the end closest to first branch
 Name the groups attached to the chain, using the carbon number as the
locator.
 Assemble the name, listing groups in alphabetical A-Z order using the full
name . (e.g. cyclopropyl before isobutyl).
 Use di-, tri-, etc., for multiples of same substituent
 combine number and name of substituent with parent name, separating
with hyphen

No. of
Prefix Carbon
atoms
Meth- 1 First, one has to identify and name the groups attached to the
Eth- 2 chain, and number the chain so that the substituent gets the
Prop- 3 lowest possible number. For example, one of the isomers of
But- 4 pentane is 2-methylbutane, where the parent chain is a four-
carbon butane chain, and is numbered starting from the end
Pent- 5
nearer the substituent group (methyl group). Therefore, the
Hex- 6 methyl group is indicated as being attached to carbon atom
Hept- 7 number 2.
Oct- 8
Non- 9
Dec- 10
Undec- 11
Dedec- 12

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Similarly, isobutane is the common name of one of the structural isomers of C4H10 (butane).
The longest continuous chain of carbons consists of three atoms in length, so the systematic
name is based on propane. Finally, since a methyl group appears on the second carbon, the
correct name is 2-methylpropane.
When more than one substituent is present, the location of each substituent should be
designated by an appropriate name and number. The presence of two or more identical
substituents is indicated by the prefixes di-, tri-, tetra- and so on, and the position of each
substituent is indicated by a number in the prefix. A number and a word are separated by a
hyphen, and numbers are separated by comma. For example, in 2,2-dimethylbutane, both
methyl groups are attached to carbon atom 2 of a butane chain. The names of the substituents
are arranged in alphabetical order, not numerical order, e.g. 3-ethyl-2-methylhexane, not 2-
methyl-3-ethylhexane.

Isomerism and physical properties

Compounds that differ from each other in their molecular formulas by the unit __ CH2 __ are
called members of homologous series. Thus, methane and ethane belong to a homologous
series of saturated hydrocarbons. Compounds that have same molecular formula but
different order of attachment of their atoms are called constitutional isomers.

Alkanes have similar chemical properties, but their physical properties vary with molecular
weight and the shape of the molecule.

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Structure and conformation of alkanes

Alkanes have only sp3-hybridized carbons. Methane (CH4) is a nonpolar molecule, and
has four covalent carbon–hydrogen bonds. In methane, all four CH bonds have the
same length (1.10 A° ), and all the bond angles (109.5) are the same. Therefore, all four
covalent bonds in methane are identical. Three different ways to represent a methane
molecule are shown here. In a perspective formula, bonds in the plane of the paper are
drawn as solid lines, bonds sticking out of the plane of the paper towards you are drawn
as solid wedges, and those pointing back from the plane of the paper away from you are
drawn as broken wedges.

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Cycloalkanes

Cycloalkanes are alkanes that are cyclic with the general formula CnH2n.
The simplest members of this class consist of a single, unsubstituted carbon ring, and
these form a homologous series similar to the unbranched alkanes.
The C3 to C6 cycloalkanes with their structural representations are shown below.

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Nomenclature of cycloalkanes

The nomenclature of cycloalkanes is almost the same as that for alkanes, with the
exception that the prefix cyclo- is to be added to the name of the alkane. When a
substituent is present on the ring, the name of the substituent is added as a prefix to the
name of the cycloalkane. No number is required for rings with only one substituent.

However, if two or more substituents are present on the ring, numbering starts from the
carbon that has the group of alphabetical priority, and proceeds around the ring so as to
give the second substituent the lowest number.

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Preparation of alkanes and cycloalkanes

1. Alkanes are prepared simply by catalytic hydrogenation of alkenes or alkynes.

2. Alkanes can also be prepared from alkyl halides by reduction, directly with Zn and
acetic acid (CH3COOH) or via the Grignard reagent formation followed by hydrolytic
work-up. The coupling reaction of alkyl halides with Gilman reagent (R’2CuLi, lithium
organocuprates) also produces alkanes.

Selective reduction of aldehydes or ketones, either by

Clemmensen reduction or Wolff–Kishner reduction yields alkanes.

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H.W Problems
Give the IUPAC name for each compound.

H.W Draw the structure corresponding to each IUPAC name

3-ethyl-2-methylhexane cyclobutylcycloheptane

4-isopropyl-2,4,5-trimethylheptane 6-isopropyl-2,3-dimethylnonane

2,2,6,6,7-pentamethyloctane 3-ethyl-1,1-dimethylcyclohexane

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H.W

Each of the following IUPAC names is incorrect. Explain why it is incorrect and give the correct IUPAC name.

Example Why its incorrect name ? Corrected

1,3-dimethylbutane

2-methyl-2-isopropylheptane

5,5,6-trimethyloctane

5-ethyl-2-methylhexane

2,2-dimethyl-4-ethylheptane

1-ethyl-2,6-dimethylcycloheptane

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