UNIT – ONE

Introduction to Organic Chemistry

Introduction
The main reason for the presence of millions of carbon compounds is the unique property
of carbon called catenation. Catenation is the ability of atoms of the same element to join
together forming short or long chains and rings.
Other elements that show this property are sulphur, silicon and boron.
Classification of Organic Compounds
The functional group is the part of a molecule or a compound that determines the chemical
properties of the molecule or compound.
the most common classification of organic compounds including alkanes, alkenes, alkynes,
aromatics, alcohols, aldehydes, ketones, carboxylic acids and esters.
SATURATED HYDROCARBONS
Hydrocarbons are organic compounds composed of the elements carbon and hydrogen
only.
They can be classified as saturated and unsaturated hydrocarbons.
Saturated Hydrocarbons are those compounds of carbon and hydrogen containing only
carbon-carbon single bonds. Ex: alkane
Unsaturated Hydrocarbons are those compounds of carbon and hydrogen possessing
one or more multiple bonds (double or triple bonds) between carbon atoms.
Example: alkenes, alkynes and aromatic hydrocarbons.
Alkanes or Paraffins
Alkanes have the general formula CnH2n+2
A group of compounds in which each member of the group differs from the next member by a–
CH2, is called a homologous series.
Physical Properties of Alkanes
From C1 to C4 are gases.
From C5 to C17 are liquid
Above C17 are solids at room temp.
 Weak intermolecular forces called Van der Waal’s forces hold their molecules together.
 Strength of these forces increases with the increasing molecular mass of the alkanes.
 They are non polar
 The density, melting point, and boiling point of the homologous series of alkanes
increase as the carbon number increases
 For alkanes of the same carbon number, branched-chain isomers have lower boiling
points than the straight-chain (normal) alkanes. e.g., the boiling points of n-pentane, iso-
pentane and neo-pentane are 36°C, 28°C and 9.5°C, respectively.
Nomenclature of Alkanes
The name of alkanes containing suffix and prefix,
Suffix is indicating functional group, prefix is indicating number of carbons.
Ex: C2H6- Hexane
Common Names of Alkanes
Lower members of the alkane homologous series have common names.
The prefixes used in the common names are n- (normal), ‘iso-’ and ‘neo-’.
The prefix n- is used when all the carbon atoms form a continuous chain.
Ex: CH3-CH2-CH2-CH2-CH3 ( n-Pentane)
Iso- is used when all of the carbon atoms form a continuous chain, except for the one
next to the last carbon.

Ex: ( Isopentane)
Neo- is used when the central carbon is bonded to four other carbon atoms.

Ex:
( Neohexane)
IUPAC System of Nomenclature of Alkanes
It is difficult to have common names for the more branched and complex alkanes.
Example: Give the IUPAC name of:

3-bromo-4-ethyl-2,2,5-trimethyl octane.
Isomerism
The existence of two or more chemical compounds with the same molecular formula but
different structures is called isomerism.
From C1 to C3 have only one possible structure.
The compounds that have the same molecular formula but different structures are
called isomers.
Alkanes exhibit a type of structural isomerism called chain or skeletal isomerism.
For example, butane has two isomers, and pentane has three isomers.
Preparation of Alkanes
They are mainly obtained by fractional distillation of petroleum.
Methode of preparation of alkanes are:
1. Hydrogenation

2. Wûrtz Synthesis (reaction): is involves the reaction of a halogenated alkane with sodium
 3. Decarboxylation: Heating sodium salt of an organic acid with soda lime (mixture of
sodium hydroxide and calcium oxide)

Methane
Methane is the main constituent (about 90%) of natural gas.
Chemical Properties of Alkanes
Alkanes are generally not considered to be very reactive organic compounds.
The major reactions of alkanes are the following:
1. Combustion Reactions:

2. Substitution Reaction: The reaction of chlorine and bromine with alkanes proceeds in
presence of heat or sunlight. This type of reaction is called photochemical reaction.
Chlorination of methane involves
i) Chain Initiating Step:

ii) Chain Propagating Step:

iii) Chain Terminating Step:

3. Elimination reaction:

Cycloalkanes
Cycloalkanes are saturated hydrocarbons
Uses of Alkanes
They are used as fuels, solvents, raw materials to makealkenes, alcohols, soaps, detergents and
plastics.
UNSATURATED HYDROCARBONS
Alkenes, alkynes, and arenes (aromatic compounds) all contain carbon–carbon multiple
bonds and are unsaturated hydrocarbons.
Alkenes or Olefins
Alkenes are unsaturated hydrocarbons with functional group of double bond.
The general formula of alkenes is CnH2n.
Their name end with “ene”.
Nomenclature of Alkenes
IUPAC Naming

Two frequently encountered alkenyl groups are the vinyl group and the allyl
group:
CH2=CH-(vinyl or ethenyl) , CH2=CH-CH2- (allyl or prop-2-en-1-yl).
Example: Give the IUPAC name for the following structures.

Isomerism in Alkenes
Alkenes containing two and three carbon atoms have only one possible structure.
Alkenes containing four or more carbon atoms exhibit isomerism.
In addition to chain isomerism, alkenes show two more types of isomerism:
 Chain isomerism: is due to the difference in the arrangement of the carbon atoms in the
longest continuous carbon chain.
Ex: 1-pentene and 2-methyl-1-butene are chain isomers

 Position isomerism: is due to the difference in the position of the double bondin the
carbon chain.
Ex:
Compounds (a) and (c) represent the position isomers of pentene, (b) and (d) are
position isomers of methylbutene, (a), and (b) or (a) and (d) are the chain isomers,
while all these compounds are the isomers of C5H12.
 Geometrical isomerism: it results from the difference in the relative spatial
arrangement of atoms or groups about the double bond.
Ex: The geometrical isomers of 2-butene are:

Note: alkenes cannot have geometrical isomers if two identical groups are attached to any one of
the carbon atoms linked by a double bond.
Preparation of Alkenes
In the laboratory, alkenes can be prepared by:
 Dehydration of alcohols

 Dehydrohalogenation of alkyl halides with a base (KOH).

Dehydrohalogenation means the removal of hydrogen and a halogen atom.

Example: Write the complete and balanced chemical equations for each of the following
Reactions.

Chemical Properties of Alkenes

They are more reactive than alkanesbecause the weak bond can be used for further reaction.
They undergo several types of reactions:
 
Combustion reaction: Alkenes burn in oxygen with a luminous flame to form carbon
dioxide and water.
General reaction: CnH2n + (3n/2) O2 → nCO2 + nH2O + Heat
 Addition reaction: The addition occurs at the carbon-carbon double bond.
i. Halogenation: When a halogen molecule, X2, (where, X2 = Cl2 or Br2) is added to
alkenes, the product is a dihaloalkane.

If bromine water (bromine in CCl4) is added to alkenes, the reddish-brown colour of Br2 in CCl4
will disappear. So, Br2 in CCl4 is used to detect unsaturation (presence of multiple bonds) in a
compound.
ii. Hydrogenation: The addition of hydrogen molecule to alkenes in the presence of a
nickel or platinum catalyst yields alkanes.

iii. Hydrohalogenation: The addition of hydrogen halide (HCl, HBr or HI) to alkenes
leads to the formation of alkyl halides.
The product of the reaction can be predicted by Markovnikov’s rule; which states that “when an
alkene reacts with a hydrogen halide to give an alkyl halide, the hydrogen adds to the carbon
atom of the double bond that has the greater number of hydrogen atoms, and the halogen to the
carbon that has the fewer number of hydrogen atoms”. “The Rich Get Richer!!”
The same is true when an alkene reacts with water in an addition reaction to form an
alcohol.

Ex:
iv. Addition of water (hydration): When alkenes are hydrated in the presence of an
acid catalyst, they produce alcohols following Markovnikov’s rule.

General reaction:
Oxidation of alkenes: Oxidation of alkenes with cold alkaline potassium permanganate solution
(KMnO4) forms diols (compounds containing two hydroxyl groups).

Alkaline KMnO4 solution is also used as a test for the identification of unsaturation in a
compound. The solution is called Baeyer’s reagent.
In the presence of unsaturated hydrocarbons, the purple colour of solution fades and a
brown precipitate is formed.
v. Polymerization (self-addition) of alkenes: is the union of small molecules called
monomers to form a large molecule called a polymer.

Cycloalkenes
Cycloalkenes are unsaturated cyclic hydrocarbons.They are represented by the general formula
CnH2n–2.
They are isomeric with alkynes.
IUPAC Naming
They are named by adding cyclo as prefix.

Ex:
Alkynes and Their Physical Properties