IUPAC Naming of Organic

Compounds with Functional

Groups
With the ability to identify functional groups, next we will learn how to give
IUPAC names to compounds containing several functional groups by following a
set of rules.

IUPAC NOMENCLATURE of COMPOUNDS with FUNCTIONAL

GROUPS

1. Find the longest carbon chain containing the functional group with the highest
priority (see Table 2.3). This chain determines the parent name of the compound.
2. Change the ending of the parent alkane/alkene/alkyne to the suffix of the highest
priority group, which gives the parent name of the compound (usually, drop the
last letter “e” before adding the suffix, except for nitrile where the “e” is kept).
3. Number the chain from the end closest to the highest functional group.
4. The other groups are named as substituents by using the appropriate prefixes.
5. Assign stereochemistry, E/Z or R/S, as necessary (details in Chapter 5).

For naming purposes, the functional groups are assigned with priorities (Table
2.3). If the compound includes more than one functional group, the one with
the highest priority is the “parent structure” and determines the “parent name”; the
other groups will be regarded as “substituents”. The “suffix” is used to indicate the
name of the parent structure, and the “prefix” is for the substituent. The order of
the groups listed in Table 2.3 is based on the decreasing order of priority, where
the carboxylic acid group is in the highest priority. The groups in the subordinate
table have no difference in terms of priority, and they are usually listed in
alphabetic order.
Table 2.3 Naming Priorities of Common Functional Groups
 Table
2.4 Subordinate Groups

We will go through several examples for more details about the naming rules.

1.

The parent structure is the 6-carbon carboxylic acid with a double bond, so the last
name comes from “hexene”. To add the suffix, the last letter “e” will be dropped,
so the parent name is “hexeneoicacid”. A number is necessary to indicate the
position of the double bond, so the name is “4-hexenoic acid”. The carboxylic acid
group is always in the #1 position, so it is NOT necessary to include that number
for the position.

2.

This is a ketone based on a cycloalkane, so the last name comes from

“cyclohexane”. By adding the suffix, it becomes “cyclohexanone”, and the
complete name is “3-ethylcyclohexanone”.
Homologous series:

 A homologous series is a collection of compounds with the same general formula that
differ only in the carbon chain length.
 Compounds in a homologous series often have a fixed set of functional groups,
resulting in chemical and physical properties that are comparable.
 For example, homologous series of alkane: CH4, C2H6, C3H8, etc. are homologous.
 They differ from each other by -CH2 unit.

The characteristics of homologous series:

 The functional group of the members of the homologous series is the same.
 The general formula is the same for all members.
 Members of homologous series have nearly identical chemical properties due to the
same functional group.
 Members of homologous series have a general method of preparation in common.

What is Isomerism?
Isomerism is the phenomenon in which more than one compounds have the same
chemical formula but different chemical structures.
Chemical compounds that have identical chemical formulae but differ in properties
and the arrangement of atoms in the molecule are called isomers. Therefore, the
compounds that exhibit isomerism are known as isomers.

The word “isomer” is derived from the Greek words “isos” and “meros”, which mean
“equal parts”. This term was coined by the Swedish chemist Jacob Berzelius in the
year 1830.

Isomerism Types

There are two primary types of isomerism, which can be further categorized into
different subtypes. These primary types are Structural
Isomerism and Stereoisomerism. The classification of different types of isomers is
illustrated below.
Structural Isomerism
Structural isomerism is commonly referred to as constitutional isomerism. The
functional groups and the atoms in the molecules of these isomers are linked in
different ways. Different structural isomers are assigned different IUPAC names
since they may or may not contain the same functional group.

The different types of structural isomerism are discussed in this subsection.

Chain Isomerism
 It is also known as skeletal isomerism.
 The components of these isomers display differently branched structures.
 Commonly, chain isomers differ in the branching of carbon
  An example of chain isomerism can be observed in the compound C 5H12, as illustrated
below.

Position Isomerism
 The positions of the functional groups or substituent atoms are different in position
isomers.
 Typically, this isomerism involves the attachment of the functional groups to different
carbon atoms in the carbon chain.
 An example of this type of isomerism can be observed in the compounds having the
formula C3H7Cl.

Functional Isomerism
 It is also known as functional group isomerism.
 As the name suggests, it refers to the compounds that have the same chemical formula
but different functional groups attached to them.
  An example of functional isomerism can be observed in the compound C 3H6O.

Metamerism
 This type of isomerism arises due to the presence of different alkyl chains on each side
of the functional group.
 It is a rare type of isomerism and is generally limited to molecules that contain a divalent
atom (such as sulphur or oxygen), surrounded by alkyl groups.
 Example: C4H10O can be represented as ethoxyethane (C 2H5OC2H5) and methoxy-
propane (CH3OC3H7).

Tautomerism
 A tautomer of a compound refers to the isomer of the compound which only differs in the
position of protons and electrons.
 Typically, the tautomers of a compound exist together in equilibrium and easily
interchange.
 It occurs via an intramolecular proton transfer.
 An important example of this phenomenon is Keto-enol tautomerism.

Ring-Chain Isomerism
 In ring-chain isomerism, one of the isomers has an open-chain structure whereas the
other has a ring structure.
 They generally contain a different number of pi bonds.
 A great example of this type of isomerism can be observed in C 3H6. Propene and
cyclopropane are the resulting isomers, as illustrated below.
Stereoisomerism

This type of isomerism arises in compounds having the same chemical formula but
different orientations of the atoms belonging to the molecule in three-dimensional
space. The compounds that exhibit stereoisomerism are often referred to as
stereoisomers. This phenomenon can be further categorized into two subtypes. Both
these subtypes are briefly described in this subsection.

Geometric Isomerism
 It is popularly known as cis-trans isomerism.
 These isomers have different spatial arrangements of atoms in three-dimensional space.
 An illustration describing the geometric isomerism observed in the acyclic But-2-ene
molecule is provided below.
Optical Isomerism
 Compounds that exhibit optical isomerism feature similar bonds but different spatial
arrangements of atoms forming non-superimposable mirror images.
 These optical isomers are also known as enantiomers.
 Enantiomers differ from each other in their optical activities.
 Dextro enantiomers rotate the plane of polarized light to the right whereas laevo
enantiomers rotate it to the left, as illustrated below.

What is Conformation?

In alkanes, the distribution of electrons in a sigma molecular orbital is symmetrical

around the internuclear axis of the C-C bond. Thus, it permits the possibility of free
rotation about the C-C single bond. Due to this rotation, different spatial
arrangements of carbon atoms in space are observed which can change into one
another. Such spatial arrangement of carbon and hydrogen atoms which can be
converted into one another by rotation around a C-C single bond is called
conformation or conformer or rotamer. Alkanes can thus have an infinite number of
conformations by rotation around C-C single bonds. However, this rotation is not
completely free due to repulsive interactions between the electron clouds of C-H
bonds. This repulsive interaction is termed as torsional strain.

Conformational Isomers
Let us understand the fundamentals of conformation with the example of ethane. If
we observe the ball and stick model of ethane and rotate one carbon atom keeping
another carbon atom stationary about the C-C axis. We will observe that the
rotations will result in an infinite number of spatial arrangements of hydrogen atoms
attached to one carbon atom with respect to the hydrogen atoms attached to the
 other carbon atom. These different arrangements are better known
as conformational isomers or conformers.

Predominantly, these can be broadly classified into two different cases:

1. Eclipse conformation
Conformation in which hydrogen atoms are attached to two carbons stay nearest to
each other as possible is known as eclipsed

2. Staggered conformation
Confirmation in which hydrogen atoms attached to two carbons are as far as
possible with respect to each other is known as staggered The staggered
conformation is thus relatively more stable in comparison to eclipse conformation as
there are minimum repulsive forces, minimum energy due to many separations
between the electron clouds of C-H bonds.