Lecture 3

Classification and
Nomenclature of Organic
Compounds
Types of organic compounds
• There are more than 6 million organic compounds. In dealing with such a
large number of compounds some classification is essential.
There are five main types of organic compounds.

(1) Aliphatic Compounds

(2) Saturated and Unsaturated Compounds
(3) Aromatic Compounds
(4) Alicyclic Compounds
(5) Heterocyclic Compounds
 (1) Aliphatic Compounds.
Compounds which consist of open-chain of carbon atoms.
• There is no limit to the number of atoms involved.

(2) Saturated and Unsaturated Compounds.

Compounds which contain only carbon and hydrogen are called hydrocarbons.
• A hydrocarbon is said to be saturated if it contains only C-C single bonds.
• A hydrocarbon is said to be unsaturated if it contains C=C or C≡C multiple bonds.
• There is no limit to the number of atoms involved.

The term unsaturation is also sometimes used to describe a compound containing multiple bonds
between other pairs of atoms, e.g. C=O, C≡N.
(3) Aromatic Compounds.
Benzene and all compounds that have structures
and chemical properties resembling benzene are
called aromatic compounds.

(4) Alicyclic Compounds.

Non aromatic cyclic compounds which consist
only of carbon atoms are called alicyclic or
carbocyclic compounds.

(5) Heterocyclic Compounds.

Cyclic compounds in which the ring atoms are of
carbon and some other element (For example, N,
Sor O) are called heterocyclic compounds.
 Functional Groups

The hydrocarbon
the functional
portion remains
group is the action
inert
group

A Functional Group is a Site of Chemical Reactivity in a Molecule

• A functional group is an atom or group of atoms in a molecule that gives the

molecule its characteristic chemical properties.
• Double and triple bonds are functional groups. Other examples include -Cl, -
Br, -OH,-NH2 groups.
 The following table shows some common functional groups and the
corresponding classes of compounds.

• We often use the symbol R- to represent

the hydrocarbon portion to which the
functional group is attached.
• Thus R- can be CH3-, CH3CH2
(CH3)2CH-, or any other group of C and
H atoms with one free valence by which
the functional group is attached.
 ➢ Each functional group undergoes characteristic reactions.
➢ By recognizing the functional group in a molecule, it is possible to predict the
reactions which that molecule will undergo.

A molecule can contain more than one functional group. It is then said to be Polyfunctional,
and the properties of each functional group may be modified by the presence of the others

The concept of functional group is important to organic chemistry for three

reasons:
1) Functional groups serve as basis for nomenclature (naming) of organic compounds.
2) Functional groups serve to classify organic compounds into classes (families). All
compounds with the same functional group belong to the same class.
3) A functional group is a site of chemical reactivity in a molecule. Compounds in the
same class have similar chemical properties.
 Homologous Series
A homologous series is a series of
compounds in which adjacent members
differ by a CH2 unit. The individual
members are called Homologs.
The homologous series of alcohols

The general characteristics of a homologous series are:

1) All compounds in the series contain the same elements, the same functional group and
can be represented by a general formula.
2) The molecular formula of each homolog differs from one above and one below it by a
CH2 unit.
3) All compounds in the series can be prepared by similar methods and they have similar
chemical properties.
4) There is a gradual variation in physical properties with increasing molecular weight.
Principles of Nomenclature
• In early days of organic chemistry, each new compound was given an
individual name based on the source, some property, or some other trivial
reason.
• Thus formic acid, HCOOH, was so named as it was obtained by distillation of
red ants (Latin, formica = ants).
• A group of sedatives was named barbiturates after the name of a woman
Barbara.
• The structure of many of these compounds was not known at that time.
• An ordinary name given to a compound without reference to its structure is
called a Common Name or Trivial name. The common names are like
nicknames.
• With the rapid growth of organic chemistry, it became impossible to give common names to
such a large number of compounds.
• In 1957, the International Union of Pure and Applied Chemistry evolved a scheme for
giving systematic names to organic compounds on the basis of structure which is known as
the IUPAC System.
• IUPAC Name is the systematic name of a compound derived from its structural formula by
applying IUPAC rules.

• One organic compound can have only one IUPAC name. It is superior to a common
name as it gives an insight into the structure of the molecule. Knowing the IUPAC
name of a compound, we can at once write its structural formula.
• The common names identify compounds while the IUPAC names represent structures.

By using IUPAC name system you can translate structures into names
and names into structures
Alkanes.
• Alkanes are hydrocarbons that contain only single bonds.
• The first four members of the series are known by their common names :
Methane, Ethane, Propane, and Butane.
• The names of larger alkanes are derived from the Greek prefixes that indicate the
number of carbon atoms in the molecule.
pentane has 5 carbons, hexane has 6, and so on.
• In the common system all isomeric alkanes have the same parent name.
• For example, two isomeric C4H10 alkanes are known as butanes.
• The names of various isomers are distinguished by prefixes.
• The prefix indicates the type of branching present in the molecule.

(1) Meaning of the Prefix n-.

Prefix n- is used for those alkanes in which all carbons are in one continuous
chain. The prefix n- stands for normal or straight-chain.

(2)Meaning of the Prefix Iso-.

Prefix iso- is used for those alkanes which have a methyl group (CH3-) attached
to the second last carbon atom of the continuous chain.
 (3) Meaning of the Prefix Neo-.
Prefix neo- is used for those alkanes which have two methyl groups attached to the second last
carbon atom of the continuous chain.

In the common system of naming alkanes, the following prefixes are

encountered very often. Memorize their meaning.
n- Alkane is unbranched.
iso- Alkane contains (CH3)2CH- and no other branches.
neo- Alkane contains (CH3)3C- and no other branches.
Classification of Carbon Atoms
The structural formulas of alkanes contain four types of carbons:

(1) Primary Carbon. A carbon atom attached to one other (or no other)
carbon atom.
(1° carbon; 1°= primary)
(2) Secondary Carbon. A carbon atom attached to two other carbon atoms.
(2° carbon; 2° = secondary)
(3) Tertiary Carbon. A carbon atom attached to three other carbon atoms.
(3° carbon; 3° = tertiary)
(4) Quaternary Carbon. A carbon atom attached to four other carbon
atoms.
(4° carbon; 4° = quaternary)
Hydrogen atoms attached to 1°, 2°,3° carbon atoms are often referred to as
primary, secondary and tertiary hydrogen atoms.
Alkyl Groups. An alkyl group is formed by removing one hydrogen atom from an
alkane and symbolized by R-.
• Alkyl groups are named by dropping -ane from the name of the corresponding
alkane, and adding the ending -yl.
• The grouping R-(e.g.CH3CH2-) is not a compound and must be bonded to
another atom or group of atoms.

Nonalkyl Groups. A number of nonalkyl groups are used in naming organic

compounds. Their names are given as:
The IUPAC system is much the same for all classes of organic compounds.
IUPAC Rules for Naming Alkanes

Rule 1. Select the longest continuous carbon chain.

• This chain does not have to be that portion of the molecule that is written
horizontally. This is a mistake made by many students.

Rule 2. Name the longest chain.

• The longest carbon chain is chosen as the basis for the name.
• These are the Parent Names.

The longest continuous chain has four carbon atoms.

Thus, the compound is named as a butane (parent name).
Rule 3. Number the longest chain.
• The carbon atoms in the longest chain are numbered.
• The numbering is started from that end which will give numbers having the
lowest value to carbons carrying substituents.

✔ ✘
Rule 4. Identify the substituent.
• Name the substituent. Indicate its position by the number of the carbon atom
to which it is attached.

The attached group is located on carbon 2 of

the chain, and it is a methyl group.
Rule 5. Prefix the position number and name of the substituent onto the parent name.
• The whole name is written as one-word.
• Notice that the number and name of the substituent are separated by a hyphen.

The following additional rules are used when more than one substituent is attached to the
longest continuous carbon chain.
Rule 6. Identify the substituents by names and position numbers.
• When the same substituent is present two or more times in the molecule, prefixes di-,
tri-, tetra-, penta-, etc. are used.
• Position of each substituent is indicated by a separate number.
• These position numbers, separated by commas, are put just before the name of the
substituent, with the hyphen before and after the numbers when necessary.

Rule 7. When two or more different substituents are present, their names are arranged
in alphabetic order and added to the name of the parent alkane, again as one word.
 Consider the following structural formula:

• Identify the longest chain.

• Identify the alkyl groups.
• Write the IUPAC name.
• Always remember: (a) Numbers are separated from each other by commas: (6) Numbers are
separated from names by hyphens; (c) Prefixes di-, tri- are not taken into account in alphabetizing
substituent names.

4-Ethyl-2,3-dimethylheptane.
Consider the following IUPAC name: 3,3-Diethyl-5-methyldecane
Cycloalkanes.
• Cycloalkanes are alkanes in which carbon atoms are arranged in a ring.
• They are named by attaching the prefix cyclo- to the name of the alkane having the same
number of carbons as in the ring.

• Substituted cycloalkanes are named as alkylcycloalkanes.

• The substituents on the ring are named and their position are indicated by numbers.
• The ring is numbered so that the substituents are given the lowest possible numbers.

The ring designated as a substituent if the alkane chain

contains a greater number of carbon atoms than the ring.
Alkenes. Alkynes.
• Alkenes are hydrocarbons that contain a carbon- • Alkynes are hydrocarbons that contain a carbon-
carbon triple bond.
carbon double bond.
• Their common names are obtained by changing the • The simplest alkyne, HC≡CH, is commonly called
acetylene.
ending –ane of the corresponding alkane to –ylene • alkynes adopt the parent name like acetylene with the
(alkylene). substituents’ name added as a prefix.

IUPAC rules for naming Alkenes. IUPAC rules for naming Alkenes.
• Select the longest carbon chain containing the double bond. • Select the longest carbon chain containing the triple bond.
• Name the longest chain. The name is obtained by dropping • Name the longest chain. The name is obtained by dropping
the final –ane from the name of the corresponding alkane, the final –ane from the name of the corresponding alkane,
and adding the ending –ene (alkene). and adding the ending –yne (alkyne).
• Number the chain from the end closer to the double bond. • Number the chain from the end closer to the triple bond.
• Indicate the position of the double bond by the number of • Indicate the position of the triple bond by the number of
the first carbon atom involved in the double bond ( lowest the first carbon atom involved in the triple bond ( lowest
numbered). numbered).
• Alkyl groups and other substituents are numbered, named, • Alkyl groups and other substituents are numbered, named,
and placed as prefixes in alphabetic order. and placed as prefixes in alphabetic order.
 Alkenes containing two double bonds are named as Alkynes containing two triple bonds are named as
alkadienes alkadiynes

In naming cycloalkenes, number the ring to give the double bonded carbons the
numbers 1 and 2.
Chose the direction of numbering so that the substituents get the lowest numbers.
The position of the double bond is not indicated because it is known to be between C-1
and C-2.
Ethyl chloride spray
A skin “refrigerant”, used as topical anesthetic. It
is used in sports injuries to relieve muscle pain.
 Alkyl Halides
• Alkyl halides are organic compounds in which a halogen atom is attached to carbon.
They have the general formula:

• Alkyl halides are classified as Primary (1°), Secondary (2°), or Tertiary (3°), depending
upon whether the halogen atom X is attached to a primary, secondary, or tertiary carbon.
Structure:
• Alkyl halides consist of an alkyl group linked to a halogen.
• The carbon linked to the halogen is sp3 hybridized and tetrahedral.
• The carbon–halogen bond length increases and the bond strength decreases as
the halogen increases in size.

• The C–halogen bond (C–X) is a polar σ bond where the halogen is slightly
negative and the carbon is slightly positive.
Nomenclature:
• In the Common system, the alkyl group attached to halogen atom is named first followed
by the halide name – chloride, bromide, iodide, or fluoride – as two words (alkyl halide)

IUPAC System rules:

• Select the longest carbon chain containing the halogen atom and name the alkyl halide as a
derivative of the corresponding alkane.
• Number the chain from the end closer to the halogen atom so that the carbon carrying the halogen
atom given the lowest possible number.
• Indicate the position of the halogen atom by a number and its type by the fluoro-, chloro-, bromo-,
or iodo.
• Name other substituents and indicate their positions by numbers.
The IUPAC names of alkyl halides are written as one–word name.
 Method of preparation
(1) Halogenation of alkanes.
Alkanes (hydrocarbons) react with Cl2 or Br2 in the presence of UV light or at high
temperature (400 °C) to give alkyl halides along with poly halogen derivatives.

This method is not used in the laboratory because of the difficulty of separating the products.

(2) Addition of halogen acids (hydrogen halides) to alkenes.

Halogen acids (HCl, HBr, HI) add to alkenes to yield alkyl halides. The mode of addition
follows Markovnikov rule, except for the addition of HBr in the presence of organic
peroxides (RO-OR).
(3) Action of halogen acids (hydrogen halides) on alcohols.
Alcohols react with HBr or HI to produce alkyl bromides or alkyl iodides. Alkyl chlorides
are produced by the action of dry HCl in the presence of zinc chloride.
(4) Action of phosphorous halides on alcohol.
Alcohols react with phosphorus halides (PX5 or PX3) to form alkyl halides.

(5) Action of thionyl chloride on alcohols.

Alcohols react with thionyl chloride (SOCl2) in the presence of pyridine to produce alkyl chloride.

Pyridine (C5H5N) act as abase, absorbs hydrogen chloride as it is formed.

Review Questions