UNIT-TWO

Functional Groups in Organic

Chemistry

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 2. Functional Groups in Organic Chemistry
2.1 The Importance of Classification of Organic Compounds According to
Their Functionality
 The structural features that make it possible to classify compounds into
families are called functional groups.
 The chemistry of organic materials is conveniently described by
categorizing compounds according to their functional groups.
 A functional group is an atom or a group of atoms within a molecule that
are responsible for the characteristic reactions of a molecule.
 The chemistry of every organic molecule, regardless of size and
complexity, is determined by the functional groups it contains.
 Chemically, a given functional group behaves in nearly the same way in
every molecule it’s a part of.

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• Why are compounds classified according to
their functional groups?
• One of the main reasons for classifying
compounds by their functional groups is that
it also classifies their chemical behavior. By
this we mean that the reactions of compounds
and, to some extent, their physical properties
are influenced profoundly by the nature of the
functional groups present.

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• In general functional groups are important in organic
chemistry because:
1) They are sites of predictable chemical behavior. A particular
functional group, in whatever compound it is found, undergo
the same types of chemical reactions. Because compounds
with similar functional groups undergo similar reactions

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2) Serve as the units by which we classify organic
compounds into families. It is very important to
arrange organic compounds into classes, according to
the particular functional groups that they contain.
This approach is very important to understand the
chemistry of organic compounds.
3) Serve as a basis for naming organic compounds.
4) Determine in large measure of the physical
properties of a molecule.

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 2.2 Introduction to the Common Functional Groups in Organic
Chemistry
2.2.1 Alkanes, Alkenes, Alkynes
Alkanes (Paraffine)
 Alkanes are hydrocarbons in which all the bonds are single bonds
 Alkanes have no functional groups
 Alkanes are called saturated hydrocarbons
 Open chain alkanes: - general formula, CnH2n+2 where n= 1, 2, 3,……
 Cyclic alkanes (cycloalkanes):- general formula, CnH2n where n= 3,4,5,…
 The formulas and structures of each successive compound differ from each
other by one methylene group (CH2) is called homologous series.
 E.g. CH3_H, CH3_CH2_H, CH3_ CH2_CH2_H
 The names of alkanes are derived from the Greek prefixes that indicate
the number of carbon atoms in the molecule, and ending with “-ane”.

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 Cont’d

For examples
 CH4 = methane, CH3-CH3 = ethane, CH3-CH2-CH3 = propane,
CH3-CH2-CH2-CH3 = butane

Naming of alkyl groups

 Alkyl groups (R) are formed by removing one hydrogen atom from an
alkane. They are named by dropping –ane from the name of the
corresponding alkane, and adding the ending –yl.

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 Cont’d

Naming of non-alkyl groups

 A number of non-alkyl groups are used in naming organic compounds,
some of their names are given below:
 —Cl = Chloro —I = Iodo —NO2 = Nitro —OH = Hydroxy
 —Br = Bromo —F = Fluoro —NH2 = Amino —NO = Nitroso

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 Naming system of alkanes
IUPAC System
 In general, organic compounds are given systematic names by using the
order locant -prefix–parent–suffix

The IUPAC rules for naming of alkanes are given below:

1. Select the longest continuous chain of carbon atoms; this chain determines
the parent name for the alkane.

2. Number the longest chain beginning with the end of the chain nearer the
substituent.

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 Cont’d
3. Use the numbers obtained by application of rule 2 to designate the location
of the substituent group.

4. When two or more substituents are present, give each substituent a number
corresponding to its location on the longest chain and list them alphabetically
order.

5. When two or more substituents are identical, indicate this by the use of the
prefixes di-,tri-,and so on.

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6. When branching first occurs at an equal distance from either end of the
longest chain, choose the name that gives the lower number at the first point of
difference.

7. If more than one substituent is attached to the parent hydrocarbon, the

chain is numbered in the direction that will result in the lowest possible
number in the name of the compound. The substituents are listed in
alphabetical (not numerical) order, with each substituent getting the
appropriate number.

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8) If a compound has two or more chains of the
same length, the parent hydrocarbon is the
chain with the greatest number of
substituents.

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 Classification of Carbon Atoms in Alkanes
What are primary, secondary ,tertiary and quaternary carbons?

Primary carbons, are carbons attached to one other carbon. (Hydrogens – although
usually 3 in number in this case
Secondary carbons are attached to two other carbons.

Tertiary carbons are attached to three other carbons.

Finally, quaternary carbons are attached to four other carbons.

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 Nomenclature of branched alkyl groups
• Removing hydrogen from an alkane results in an alkyl substituent (or an alkyl
group).
• Alkyl substituents are named by replacing the “ane” ending of the alkane with
“yl.” The letter “R” is used to indicate any alkyl group.

An alkyl group name followed by the name of the class of the compound (alcohol,
amine, etc.) yields the common name of the compound

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The hydrogen atoms attached to the primary (1o), secondary (2o) and tertiary (3o) carbon
atoms are referred to as primary, secondary and tertiary hydrogens respectively.

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 Three-Carbon Groups

• Numbering always begins at the point where the group is

attached to the main chain

• 1-Methylethyl is the systematic name; isopropyl is a

common name.

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 Four groups
• Butane and isobutane

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• If you examine the following structures, you
will see that whenever the prefix “iso” is used,
the iso structural unit will be at one end of the
molecule and any group replacing a hydrogen
will be at the other end

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• As the number of carbons in an alkane increases beyond
three, the number of possible structures increases.
• There are two possible structures for an alkane with
molecular formula C4H10. In addition to butane—a
straight-chain alkane—there is branched butane called
isobutane
• Compounds such as butane and isobutane that have the
same molecular formula but differ in the order in which
the atoms are connected are called constitutional
isomers—their molecules have different constitutions

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• Constitutional isomers may have different carbon
skeletons(chain) (as in isobutene and butane),
different functional groups (as in ethanol and
dimethyl ether), or different locations of a functional
group along the chain(positional) (as in
isopropylamine and propylamine).

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• There are five constitutional isomers with
molecular formula C6H14

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• It occasionally happens that a substituent on the
main chain has sub-branching. In the following case,
for instance, the substituent at C6 is a three-carbon
chain with a methyl sub-branch. To name the
compound fully, the complex substituent must first
be named.

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 Cont’d
Properties of Alkanes
 The first four alkanes are gases. While pentane and higher alkanes
(heptadecane or C17H36) are liquids.
 Alkanes are insoluble in water but soluble in non-polar solvents.
 Boiling point and melting point of alkanes show regular increases as
molecular weight increases. E.g pentane has higher boiling point than
butane.
 Alkanes react with oxygen with oxygen to produce CO2 and H2O and
release large amount of energy.

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 Cont’d
 Alkanes undergo a substitution of the alkane hydrogen atoms by chlorine.

CH4 + Cl2 + energy ——> CH3Cl + HCl

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Cycloalkane Nomenclature
Cycloalkanes are alkanes that contain a ring of three or more carbons.
They have the general formula CnH2n , n = 3, 4, 5…..
Cycloalkanes are named under the IUPAC system by adding the prefix cyclo to the
name of the unbranched alkane with the same number of carbons as the ring.
The smallest possible ring consists of cyclopropane, C3H6.

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• I f the ring has two different substituents,
they are cited in alphabetical order and the
number 1 position is given to the substituent
cited first.

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• I f there are more than two substituents on
the ring, they are cited in alphabetical order.
• The substituent given the number 1 position is
the one that results in a second substituent
getting as low a number as possible.
• If two substituents have the same low
number, the ring is numbered— either
clockwise or counterclockwise—in the
direction that gives the third substituent the
lowest possible number. :

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Alkenes (Olefins)
 Alkenes are hydrocarbons that contain a carbon-carbon double bond
(C=C) in their molecule.
 Alkenes have carbon-carbon double bond (C=C) functional groups
 Alkenes are called unsaturated hydrocarbons
- Acyclic alkenes: - general formula, CnH2n where n= 2, 3,……
e.g. CH3 CH2CH=CHCH3 = C5H10
- Cyclic alkenes (cycloalkenes):- general formula, CnH2n-2 where n= 3,4,5,..

 Structure
- Planar molecular geometry
- Bond angle: 120
- sp2 of carbon

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 degree of unsaturation
• Knowing the number of degrees of
unsaturation in a molecule is useful because
this number is related to how many multiple
bonds or rings are present in an unknown
compound.

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• What is the Degree of Unsaturation for
Benzene?
• SOLUTION
• The molecular formula for benzene is
C6H6. Thus,
• DoU= 4, where C=6, and H=6.
• 1 DoB can equal 1 ring or 1 double bond. This
corresponds to benzene containing 1 ring and
3 double bonds.

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One degree of unsaturation is equivalent to
•1 ring or 1 double bond (1 ππ bond).
•Two degrees of unsaturation is equivalent to 2 double bonds,
• 1 ring and 1 double bond, 2 rings, or 1 triple bond
(2 πbonds).
DoU Possible combinations of rings/ bonds

# of rings # of double bonds # of triple bonds

1 1 0 0

0 1 0

2 2 0 0

0 2 0

0 0 1

1 1 0

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Naming system of alkenes
IUPAC system
1. The systematic (IUPAC) name of an alkene is obtained by replacing the “-ane”
ending of the corresponding alkane with “-ene”,
2. Select the parent name by selecting the longest chain that contains the double
bond and change the ending of the name of the alkane of identical length
from -ane to -ene.

3. Number the parent chain in the direction that gives the double bond carbons
get lower numbers.

4. Indicate the locations of the substituent groups. Carbon–carbon double bonds

take precedence over alkyl groups and halogens.

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5. When there are two or three double bonds in a molecule, the ending –ane of
the corresponding alkane is replaced by –adiene or –atriene to get the name of
the hydrocarbon.

H2C C CH2 H2C CH CH CH2

Propadiene 1,3-Butadiene

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• In cyclic alkenes, a number is not needed to
denote the position of the functional group,
because the ring is always numbered so that
the double bond is between carbons 1 and 2.

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Physical properties of alkenes

 The first three alkenes (ethene, propene and butene) are gases at
ordinary temperature.
 C5- C14 members of alkenes are liquids.
 More than C18 are solids.
 All alkenes are colorless and odorless, except ethene which has a
rather pleasant odor.
 Alkenes are only slightly soluble in water but dissolve freely in
organic solvents.
 In general the boiling points and melting points of alkenes increases
as the molecular weight increases.

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Nomenclature of Alkynes
 The IUPAC names of alkynes are obtained by dropping the ending –ane of
the parent alkane and adding the suffix –yne.
 Select the longest chain which contain C≡C bond as a parent chain.
 Number the chain from the end closer to the C≡C bond.
 Indicate the position of the C≡C bond by the number of the first carbon
atom involved in the triple bond.

Physical properties of Alkynes

 The first three members are gases, next eight are liquids and the higher
alkynes are solids.
 They all are colorless and odorless except acetylene which has a garlic
odor.

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 Cont’d
 Their boiling points and melting points show a regular increase with the
increase in molecular weights.
 Alkynes generally have slightly higher boiling points than the
corresponding alkenes.
 They are only slightly soluble in water but dissolve readily in organic
solvent such as benzene, acetone, and ethyl alcohol.

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 Sources of Aromatic Hydrocarbons
 From high temperature distillation of coal tar
 Heating petroleum at high temperature and pressure over a catalyst

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 Benzene
 Benzene (C6H6) is the simplest aromatic hydrocarbon (or arene).
 This aromatic hydrocarbon was first discovered in 1825 (by Micheal
Faraday) but its structure was not generally agreed upon until 1946.
 Unsaturated hydrocarbons such as alkenes, alkynes and dienes readily
undergo addition reactions, benzene does not.

 Benzene does react with bromine, but only in the presence of FeBr3 (a
Lewis acid), and the reaction is a substitution, not an addition.

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 Cont..
 August Kekulé proposed that benzene was a rapidly equilibrating mixture of two
compounds, each containing a six-membered ring with three alternating  bonds.
 In the Kekulé description, the bond between any two carbon atoms is sometimes a
single bond and sometimes a double bond.
 These structures are known as Kekulé structures.

Facts about benzene

• Formula is C6H6 and planar.
• Benzene resists addition reaction, undergoes substitution reactions.
• From x-ray, all of the C-C bonds in benzene are the same length and intermediate in
length between single and double bonds.
• i.e In benzene, the actual bond length (1.39 Å) is intermediate between the
carbon—carbon single bond (1.53 Å) and the carbon—carbon double bond (1.34
Å).

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Chemical reactions of benzene (Electrophilic Aromatic Substitution)

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 Bromination of benzene
Br
Fe B r 3
+ B r2 + HBr

Nitration of Aromatic Rings

HNO3 NO2
H2 O
H2SO4

Sulfonation of Aromatic Rings

S O 2O H
S O 3
+ H 2O
H 2 S O 4

Conversion of sulfonic acids

 Heating with NaOH at 300 ºC followed by neutralization with acid replaces the
SO3H group with an OH
S O 3H 1. N aO H , 300o OH

2 .H 3 O 
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Alkylation of Aromatic Ring (Friedel-Crafts Alkylation)

CH3
Cl CHCH3
+ CH CHCH A lC l3
3 3 + HCl

benzene 2 - c h lo r o p r o p a n e is o p r o p y l b e n z e n e

Acylation of Aromatic Ring (Friedel-Crafts Acylation)

O
O C
A lC l 3 C H 2C H 3 HCl
+ C H 3C H 2C C l

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 Nomenclature of Aromatic Compounds
I. Naming of Monosubstituted Benzenes
 Name the substituent and add the word benzene
CH2CH3 Br NO2

Ethyl benzene Bromo benzene Nitro benzene

 Some benzene derivatives have common names which are currently

accepted.
CH3
HO
HO H2N
O
Toluene phenol Aniline Benzoic acid

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