Organic chemistry

Organic chemistry is defined as the study of structure and properties of carbon compounds

Organic chemistry is studied as a separate discipline for the following reasons

1. Large number of compounds

2. Unique chemical and physical properties

3. Unique character of carbon to bond successively with other carbon atom called
catenation.

Difference between organic and inorganic compounds

Organic compounds In organic compounds

1 Low melting and boiling points High melting and boiling points

2 Less soluble in polar solvents, more highly soluble in polar solvents, less soluble
soluble in non polar solvents in non polar solvents

3 These are flammable compounds These are non flammable

4 Solutions are non conductors of Solutions are good conductors of electricity

electricity

5 These exhibit covalent bonding and These exhibit ionic bonding and isomerism
isomerism to a few compounds

6 chemical Reactions are usually slow chemical Reactions are very fast

Importance of organic compounds

The Importance of organic compounds in everyday life is illustrated by the following

1. Food: - Food materials are solely made of carbon compounds viz. carbohydrates (CHO),

proteins (NH2-CH-COOH), and fats (CH-COO-CH). Even vitamins are organic in nature.
Among beverages alcohol is an organic substance. The changes due to food undergoes in
our body are mainly organic chemical reactions. Metabolism, growth and maintenance of
our body functions involve organic compounds. Some examples include edibles like
milk, bread, sugar or are made of organic materials.
2. Medicine: Medicine is the prime store of organic compounds. Though not all but many
medicines are made of organic substances. Like antibiotics- penicillin, ofloxacin,
chloromphenical, acetaminophen, prozac, anticancer drugs-cisplatin, Carboplatin, anti-
depressant-citalopram sertaline, analgesics-aspirin, dyclopenac sodium, naproxen,
anesthetics-procaine, cocaine etc.
3. Fuels:-Petrochemicals are chemicals derived from crude oil or petroleum. Examples
include gasoline, plastics, detergents, dyes, food additives, natural gas, and medicines.
4. Cosmetics and perfumes:-Whether a fragrance comes from a flower or a lab, the
molecules you smell and enjoy are an example of organic chemistry.
The cosmetic industry is a lucrative sector of organic chemistry. Chemists examine
changes in the skin in response to metabolic and environmental factors, formulate
products to address skin problems and enhance beauty, and analyze how cosmetics
interact with the skin and other products. Examples include Shampoo, gasoline, perfume,
lotion, nail polish remover.
5. Cloths:-cloths we wear such as cotton, silk, wool, nylon, rayon, Dacron are products of
organic compounds.
6. Dyes: - Dyes are the chemical substances that are responsible for turning plain cloth into
the colorful garments that we wear every day. Examples include indigo
carmine, alizarin, fluorescein etc.
 Principles of Purification techniques of organic compounds

Organic compounds extracted from natural sources or synthesized in the laboratory require
purification to study its properties and to determine its structure. Various methods are used for
the purification and are based upon their nature of the compound and the impurity present in it.
The common techniques used are

1) Crystallization

2) Sublimation

3) Distillation

4) Fractional crystallization

5) Distillation under reduced pressure or vacuum distillation

6) Steam distillation

Methods for Purification of Solids

1. Crystallization: - This is one of the most commonly used techniques for the purification
of solid compounds. The separation of compounds is based on the differences in the
solubilities of the compound and the impurities present in a suitable solvent.

In this process, the impure solid substances are dissolved in suitable solvent in which it is
sparingly soluble at room temperature but appreciably soluble at higher temperature. If the
solution is colored then heat with animal charcoal so that which adsorbs colour of the substance.
The solution is filtered and filtrate on cooling deposits crystals of pure compound. Success of the
process depends upon the selection of the solvent. The impurities must be least soluble in
solvent.

2. Sublimation: - certain solids directly convert into vapors when heated without
converting into liquid. These are known as sublimate and the vapors on cooling give back
their solid substances. The purification techniques based on the above principle is known
as sublimation and which is used to separate volatile solid substances from non volatile
solid substances.

The impure substance is placed in a large beaker and is covered with watch glass. On heating
gently, the vapors condense as crystals on the bottom surface of the watch glass. After
sometimes watch glass can be removed and crystals can be separated out.

The substances which sublime can be purified by this method provided the impurities present
does not sublime. Camphor, naphthalene and anthracene are purified by sublimation.
Fractional crystallization: -

Fractional crystallization is a method of separating a mixture of soluble solids by

dissolving them in a suitable solvent and then lowering the temperature slowly. The least
soluble component will crystallize out first, leaving the other components in the solution.
By controlling the temperature, it is sometimes possible to remove each component in turn.

If the impure substance is a mixture of substances A and B which are soluble in the
same solvent but the rate of solubility is different, then the less soluble (suppose A) will
crystallizes out first from a saturated solution. It may be contaminated with a little of B. the
mother liquor on further concentration gives crystals of B. this process is repeated several times
to get pure sample of A and B. This is known as fractional crystallization. It involves
separation of two or more substances present in the impure sample by fractions at various stages
of crystallization.

Thus fractional crystallization can be defined as a process of separating less soluble

substances from a more soluble one from the same solution.

Methods for Purification of Liquids

Distillation: -

This important method is used to separate the volatile liquids from non volatile liquids
which are having sufficient difference in their boiling point (greater than 100 0C).liquids
having different boiling points vaporize at different temperatures. The one which has low
boiling point vaporize first and then the one which has high boiling point vaporizes. The
vapors are collected separately and are cooled to get liquids.

Ex: - chloroform (B.P 334K) and aniline (434K) are easily separated by the distillation technique
where chloroform having low boiling point vaporize first and then aniline will vaporize.

The apparatus used for this distillation is shown in diagram. The liquid mixture is taken in a
round bottom flask fitted with a thermometer and condenser at the side tube. A suitable vessel is
attached to the lower end of the condenser to receive the condensed liquid. On boiling the liquid
mixture, the vapors of the lower boiling component are formed first which is indicated by rise in
temperature recorded by the thermometer which soon becomes constant. The vapors are
condensed by using a condenser and the liquid is collected in a receiver. The vapors of higher
boiling component form later which can be collected separately. To prevent it is necessary to
place few bits of porcelain.
Distillation under reduced pressure or vacuum distillation: -

This method is used to purify liquids having very high boiling points, but decompose before
their boiling point is reached. Such liquids can be purified by distillation under reduced
pressure much below than their boiling points.

e.g., glycerol decomposes at 2980C but can be distilled at 12mm pressure when it is boiled at
1800C.thus glycerol can be separated from spent lye in soap industry.

These types of liquids are made to boil at a temperature lower than the normal boiling points by
reducing the pressure on their surface. A liquid boils at a temperature at which its vapor pressure
is equal to the atmospheric pressure or external pressure. The pressure can be reduced using a
vacuum pump or suction pump.
Steam distillation: -

many substances are insoluble in water, but steam volatile in nature, having high
molecular weight and high vapour pressure are purified by steam distillation provided the
impurities present are not steam volatile.

e.g., o-hydroxy acetophenone and p-hydroxy acetophenone are separated by this method and
also used for the recovery of various essential oils from plants and flowers.

The impure mixture along with the some water is taken in a round bottom flask which is
connected to steam generator at one side and the condenser at the other side. The flask is
adjusted in a slanting position so that no droplets of the mixture splash into the condenser on
boiling and bubbling of the steam.

The mixture in the flask is heated and a current of steam is passed into it. Steam picks up the
volatile substances from the mixture and passes into the condenser which can be collected using
collector. The distillate contains water and compound can be separated by separating funnel.
Fundamental concepts in organic reaction

In a chemical reaction, the substrate reacts with an appropriate attacking reagents and leads to the
product through formation of intermediates.

Substrate + reagent products

Substrate: - The species or molecule which undergoes attack by other chemical species in a
reaction is called a substrate.

Reagent: - The species or a molecule which attacks the substrate.

Mechanism of a reaction: - The stepwise study of formation of products showing the breaking
and making of bonds is known as mechanism.

Most of the attacking reagent either carries a positive charge or negative charge. The positively
charged species attacks the region of high electron density in the substrate molecule. On the
other hand, a negatively charged reagent attacks the region of low electron density in the
substrate molecule.

Electrophiles and nucleophiles

Electrophiles (electron loving): - electron deficient species are called as electrophiles. All
positive charged species like H+, NO2+, +CH3 are the examples of electrophiles.
An electrophile is the same thing as a Lewis acid as they accept electron pairs.

Nucleophiles: - electron rich species are called as nucleophiles. All negative charged species like
Cl-, OH-, -CH3, -CN, -SH etc are examples for nucleophiles.

Nucleophiles are Lewis base as it donates pair of electron.

Organic reactions usually involve breaking of covalent bond this is known as bond fission. This
bond fission takes place in two ways

Homolytic fission or cleavage: the symmetrical cleavage of a covalent bond resulting in the
formation of a neutral species containing unpaired electron is called homolysis or homolytic
fission.

Heterolytic fission or cleavage: - the unsymmetrical cleavage of covalent bond in which shared
pair of electron remains with one of the fragment is called heterolytic fission or heterolysis.

Reaction intermediates

The unstable species formed between the reactants and products due to the cleavage of covalent
bond are called reaction intermediates.

The important reaction intermediates are carbocation, carbanion, carbon free radicals and
carbenes.
Carbocation

A carbocation is that molecule in which the carbon atom acquires a positive charge.

Carbocations are classified into three categories:

Primary carbocation: The positively charged carbon atom is attached to only one alkyl group.
This is also called 1O carbocation.

Secondary carbocation: The positively charged carbon atom is attached to two alkyl groups.
This is also called 2O carbocation.

Tertiary carbocation: The positively charged carbon atom is attached to three alkyl groups.
This is also called 3O carbocation.

Structure: alkyl carbocations are sp2 hybridized, planar systems at the cationic C centre. The p-
orbital that is not utilized in the hybrids is empty and is often shown bearing the positive charge
since it represents the orbital available to accept electrons.

Stability: 
The general stability order of simple alkyl carbocations is: (most stable) 3o > 2o > 1o > methyl
(least stable) 
This is because alkyl groups are weakly electron donating due to hyper conjugation and
inductive effects. Resonance effects and inductive effect can further stabilize carbocations,
therefore 3O carbocations are more stable than 2O carbocation which in turn more stable than
primary carbocations and which is more stable than methyl carbocation. Thus electron donating
group stabilize the carbocation whereas electron withdrawing group destabilize the carbocation.

Carbanions

The carbon atoms containing negatively charge are called carbanion. They are formed by
heterolytic fission.

Structure: Carbanions have three groups attached to each other and a lone pair of electrons
which gives it its negative charge (similar to the ammonia molecule where the central N has 3 H
and a lone pair of electrons). So its geometry is pyramidal (tetrahedral but since there is no
fourth group again it’s like a tetrahedral with head cut off) and the carbon atom is sp3
hybridized.

Carbanions are also stable in polar solution (electrostatic stabilization).

Stability: 
The general stability order of simple alkyl carboanion is
Here electron donating groups makes the carbanion less stable and electron withdrawing groups
will stabilize the carbanion by partial removal of electrons. Thus a methyl carbanion is more
stable than primary carbanion which in turn is more stable than secondary, which in turn is more
stable than tertiary carbanion.

Carbon free radical

The neutral species containing an odd electron formed due to homolytic cleavage of a
covalent bond is called a free radical.

Structure: The alkyl free radicals are planar in shape and use sp2 hybrid orbitals to form three
sigma bonds. Thus electrically neutral and have one unpaired electron. The free radicals can
combine with one another to form larger free radical.

Stability: 
The general stability order of simple alkyl carbon free radical is
This is because alkyl groups are weakly electron donating due to hyper conjugation and
inductive effects. Resonance effects and inductive effect can further stabilize carbocations,
therefore 3O carbocations are more stable than 2O carbocation which in turn more stable than
primary carbocations and which is more stable than methyl carbocation. Thus electron donating
group stabilize the carbocation whereas electron withdrawing group destabilize the carbocation.

Carbenes
Carbenes are divalent, neutral species having a carbon atom with two bonds and two non
bonding electrons. These carbenes are highly reactive and short lived and never exist as stable
species. These act as a strong electrophile. Examples are methylene (:CH2) and
dichlorocarbene (:CCl2)

There are two forms of carbene (methylene):

Triplet carbenes - have two unpaired electrons that are both the electrons are in parallel spins.
These are paramagnetic in nature and they have linear shape due to sp hybridization.

Singlet carbenes - Singlet carbenes are spin-paired that is they have anti parallel spins. Singlet
carbenes are diamagnetic in nature and they have trigonal planar structure due to sp2
hybridization.

Triplet carbene is more stable than singlet carbene due to parallel spins.