8.

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES

AND TECHNIQUES
Organic chemistry is the branch of chemistry that deals with carbon compounds. But all carbon
compounds are not considered as organic compounds. (E.g. CO2, CO, metal carbonates, bicarbonates
etc.). So organic chemistry can be defined as the branch of chemistry that deals with
hydrocarbons and their derivatives. Hydrocarbons are the major class of organic compounds and
they contain only carbon and hydrogen atoms. All other organic compounds are formed by replacing
one or more hydrogen atoms of hydrocarbons by other atoms or groups (They are called hydrocarbon
derivatives).
All carbon compounds present in plants and animals are organic compounds. E.g. carbohydrates,
proteins, vitamins, nucleic acids, amino acids, fats and oils, natural polymers etc. Petroleum and coal are
the major source of organic compounds (hydrocarbons).
In ancient times, it was believed that a vital force (living body) is necessary for the production of
an organic compound. But in 1828, Frederic Wohler prepared urea in the laboratory, by heating
ammonium cyanate (NH4CNO). It was the first organic compound prepared in the laboratory.
Heat
NH4CNO → NH2CONH2
Ammonium cyanate Urea
Another scientist Kolbe synthesized acetic acid and Berthelot synthesized methane in the
laboratory. Nowadays about 95% of the organic compounds are synthesized in the laboratory.
Chemistry behind the existence of large number Carbon compounds
Carbon is a unique element and it can form large number of compounds due to the following reasons:
i) Tetravalency of carbon: In all of its compounds, the valency of carbon is four. Carbon has 4
electrons in its valency shell and requires 4 more electrons to complete the octet. So it attains the
octet configuration by forming 4 covalent bonds.
ii) Ability to form single bond and multiple bonds: C can form single bond and multiple bond (double
or triple bond) with itself and also with other elements like oxygen, nitrogen etc. This is possible by
sp3, sp2 or sp hybridisation.
iii) Catenation: Carbon shows catenation. It is the self-linking property of an element to form long
chains and rings.
iv) Isomerism: Carbon compounds can show isomerism. It is the phenomenon in which compounds
having same molecular formula but different structural formula or spatial arrangement of atoms.
Structural representation of organic compounds
An organic compound can be represented by the following ways:
1. Complete structural formula: Here all the bonds between atoms are denoted by dashes (----). A
single dash represents a single bond, a double dash represents a double bond and a triple dash
represents a triple bond. E.g.

2. Condensed stuctural formula: Here the carbon-hydrogen bonds or all the bonds are omitted
except the multiple bonds. It is a simplified representation of an organic compound.
E.g. ethane - CH3CH3, propane - CH3CH2CH3, butane - CH3CH2CH2CH3, ethene - CH2=CH2 etc.
The condensed formula can again simplified as follows:

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 Butane – CH3(CH2)2CH3, Hexane- CH3(CH2)4CH3, Decane – CH3(CH2)8CH3 etc.
3. Bond line representation: It is the simplest form of representation of an organic compound.
Here carbon and hydrogen atoms are not shown and the lines representing carbon-carbon bonds are
drawn in a zig-zag fashion. The only atoms specifically written are oxygen, chlorine, nitrogen etc. The
free terminals denote methyl (–CH3) groups.
E.g. butane:

3-methyl pentane:

Heptanal: H

O
3-Methyl pentanoic acid: OH

O
4. Three-Dimensional Representation (Wedge Representation): Here the structure of an organic
molecule can be represented by using solid ( ) and dashed ( ) wedges. The solid-
wedge is used to indicate a bond projecting out of the plane of paper, towards the observer. The
dashed-wedge indicates the bond projecting out of the plane of the paper and away from the
observer. The broad end of the wedge is always towards the observer. The bonds lying in plane
of the paper are depicted by using a normal line (—).
E.g. methane

Classification of Organic compounds

Organic compounds can be broadly classified into two – Acyclic or open chain compounds and cyclic
or ring compounds.
1. Acyclic or open chain or aliphatic compounds: In these compounds, the carbon atoms are joined
together to form long chains which may be straight chain or branched chain. They are further
classified as saturated compounds and unsaturated compounds. Saturated compounds contain only
carbon – carbon single bonds. But unsaturated compounds contain atleast one carbon – carbon
multiple bond (double or triple bond. Saturated hydrocarbons are called alkanes and unsaturated
hydrocarbons are of two types – alkenes and alkynes.
2. Cyclic or closed chain or ring compounds: In these compounds, the carbon atoms are joined
together to form rings. These rings may be homocyclic or heterocyclic. If the ring contains only
carbon atoms, it is called homocyclic compound and if it contains atoms other than carbon (like O,
N, S etc), it is called heterocyclic compound.

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 Homocyclic compounds are further classified into two – Alicyclic compounds and Aromatic
compounds. Alicyclic compounds contain atleast one carbo-cyclic ring. Alicyclic hydrocarbons are of
three types – cycloalkanes, cycloalkenes and cycloalkynes. Aromatic compounds are some special type
of compounds. These are of two types. Aromatic compounds containing benzene ring are called
benzenoid compounds and those which do not contain benzene ring are called non-benzenoid
compounds. E.g. for a non-benzenoid aromatic compound is tropolone.
Heterocyclic compounds may be alicyclic heterocyclic compounds or aromatic heterocyclic compounds.
The classification of organic compounds can be diagrammatically represented as follows:

Organic compounds

Acyclic or open chain or Cyclic or ring or

Aliphatic compounds closed chain compounds

Saturated Unsaturated Homocyclic Heterocyclic

compounds compounds compounds compounds

Alicyclic Aromatic Alicyclic Aromatic

Benzenoid Non-benzenoid

Functional groups: Atoms or group of atoms (except hydrogen) which are bonded to
carbon atoms are called functional groups. These groups are responsible for the characteristic
chemical properties of the organic compounds. Some important functional groups, their names and
name of the compounds are listed below:
Functional group Name of the group Name of compound
-OH Hydroxyl group Alcohol
-NH2 Amino group Amine
-X Halo group Halo compound
-CHO Aldehydric (formyl) group Aldehyde
-CO- or >CO Carbonyl (keto) group Ketone
-COOH Carboxyl group Carboxylic acid
-O- Oxy group Ether
-CN Cyano group Nitrile
-NO2 Nitro group Nitro compound

Homologous series: A series or group of organic compounds in which adjacent members

are differed by a –CH2 group is called a homologous series. The members of a homologous
series are called homologues. They contain same functional groups. So they have similar chemical
properties and show gradation in physical properties. They can be prepared by some general methods
of preparation. E.g. for homologous series are alkanes, alkenes, alkynes, alcohols, ethers, carboxylic
acids, aldehydes, ketones, amines, halo compounds etc.
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 Nomenclature of organic compounds
An organic compound has two types of names – Common name and IUPAC name. The common
name is based on the source or some properties. For e.g. citric acid is named so because it is found in
citrus fruits and the acid found in red ant is named formic acid since the Latin word for ant is formica.
IUPAC Nomenclature of organic compounds
A systematic name of an organic compound is generally derived by identifying the parent
hydrocarbon and the functional group(s) attached to it. This name is called IUPAC name. It contains two
parts – word root and suffix or prefix. The word root indicates the number of carbon atoms in the
compound. The word roots for compounds containing 1 -12 carbon atoms are as follows:
No. of C atoms Word root No. of C atoms Word root
C1 Meth- C7 Hept-
C2 Eth- C8 Oct-
C3 Prop- C9 Non-
C4 But- C10 Dec-
C5 Pent- C11 Undec-
C6 Hex- C12 Dodec-

There are two types of suffixes – primary suffix and secondary suffix. Primary suffix indicates saturation
or unsaturation [for alkane the primary suffix is –ane, alkene –ene and for alkyne –yne]. Secondary suffix
indicates the type of functional group. Some functional groups are also indicated as prefixes.

Nomenclature of branched chain alkanes:

A branch (side chain or substituent) is obtained by removing a hydrogen atom from an alkane.
The resulting group is called an alkyl group [alkane – H = alkyl (i.e. word root + yl)]. The names of some
common branches are as follows:
Branch Name
-CH3 Methyl
-CH2-CH3 Ethyl
-CH2-CH2-CH3 n-propyl (normal propyl)
(CH3)2CH- Isopropyl
-CH2-CH2-CH2-CH3 n-butyl
CH3-CH-CH2-CH3 sec-butyl (secondary butyl)
(CH3)2CH-CH2- Isobutyl
(CH3)3C- tert-butyl (tertiary butyl)
(CH3)3C-CH2- Neopentyl

Rules for naming branched chain alkanes:

IUPAC recommenced the following rules for naming a branched chain alkane.
1. Select the longest continuous chain of carbon atoms. This chain is called parent chain or root chain.
If there is more than one such chain, the chain that contains maximum number of branches is
selected as the parent chain. Also identify all the branches or substituents.

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2. Number the carbon atoms of the parent chain in such a way that the branched carbon atoms get
the lowest possible numbers.
3. The names of alkyl groups attached as branches are then prefixed to the name of the parent alkane
and position of the substituents is indicated by the appropriate numbers.
4. If different alkyl groups are present, they are listed in alphabetical order. In alphabetical order, the
prefixes iso- and neo- are considered to be the part of the fundamental name of alkyl group. The
prefixes sec- and tert- are not considered to be the part of the fundamental name.
5. If two or more identical substituent groups are present then their numbers are indicated by prefixes
like di (for 2), tri (for 3), tetra (for 4), penta (for 5) etc and the numbers are separated by commas.
The number and word are separated by a hyphen. (The IUPAC name is written as a single word).
For example:

3-Ethyl-4,4-dimethylheptane

6. If the two substituents are found in equivalent positions, the lower number is given to the one
coming first in the alphabetical listing.
For example:

The above compound is 3-ethyl-6-methyloctane and not 6-ethyl-3-methyloctane.

7. While naming the branched alkyl groups, the carbon atom of the branch that attaches to the root
alkane is numbered 1.
For example:

1,3-dimethyl butyl-

IUPAC nomenclature of compounds containing functional groups

For naming organic compounds containing functional group, the following rules are used:
1. Select the longest continuous chain containing the functional group.
2. Number the carbon atoms in such a way that the carbon to which the functional group is attached
should get the lowest possible number. In the case of functional groups containing carbon atom like
–CHO, -CN, -COOH, -CONH2, -COX. -COOR etc. the numbering should start from the carbon atom of
the functional group. (i.e. carbon atom of these groups should be numbered as 1). (But for ketones,
the functional group –CO- should get the lowest possible number).
3. The name of the functional group is indicated by the following suffix or prefix.

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 Functional Name of Suffix/Prefix IUPAC name
group compound
-OH Alcohol -ol Alkanol
-NH2 Amine -amine Alkanamine
-X Halo compound Halo- Haloalkane
-CHO Aldehyde -al Alkanal
>CO Ketone -one Alkanone
-COOH Carboxylic acid -oic acid Alkanoic acid
-O- Ether Alkoxy- Alkoxyalkane
-CN Nitrile -nitrile Alkanenitrile
-NO2 Nitro Nitro- Nitroalkane
compound
-C=C- Alkene -ene Alkene
-C≡C- Alkyne -yne Alkyne
-COOR Ester -oate Alkyl alkanoate
-CONH2 Acid amide -amide Alkanamide
-COX Acid halide -oyl halide Alkanoyl halide
-SO3H Sulphonic acid -sulphonic Alkanesulphonic
acid acid
In the case of suffixes, the ending –e of the corresponding alkane is replaced. E.g. IUPAC name
of the alcohol CH3-OH is methanol (methane + ol). But for nitriles, the –e of the corresponding
alkane is retained. E.g. IUPAC name of CH3-CH2-CN is propanenitrile.
In the case of alkenes and alkynes, the suffix –ane of the alkane is replaced by –ene and –yne
respectively. (i.e. word root + ene or yne). For naming alkenes or alkynes, the numbering is done in
such a way that the double or triple bond should get the lowest possible number.
Some examples are:
Compound IUPAC Name
CH3-CH2-CH=CH2 But-1-ene OR 1-Butene
CH3-CH=CH-CH3 But-2-ene OR 2-Butene
CH3-CH2-C≡C-CH3 Pent-2-yne OR 2-Pentyne
CH3-CH2-CH2-CH2-CH2-C≡CH Hept-1-yne OR 1-Heptyne
CH3-CH2-OH Ethanol
CH3-CH2-CHOH-CH2-CH2-CH3 Hexan-3-ol OR 3-Hexanol
CH3-CH2-CH2-CHO Butan-1-al or Butanal
HCHO Methanal
CH3-CO-CH3 Propanone
CH3-CO-CH2-CH2-CH3 Pentan-2-one OR 2-Pentanone
CH3-CH2-CH2-CO-CH2-CH2-CH2-CH3 Octan-4-one OR 4-Octanone
HCOOH Methanoic acid
CH3-COOH Ethanoic acid
CH3-CH2-CH2-COOH Butan-1-oic acid OR Butanoic acid

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 CH3-CH2-Cl Chloroethane
CH3-CH2-CHBr-CH3 2-Bromobutane
CH2Cl-CH2-CH2-CH2-CH3 1-Chloropentane
CH3-CH2-CH2-NO2 1-Nitropropane
CH3-CH2-CH2-CN Butanenitrile
CH3-CH2-CH2-CH2-CH2-CN Hexanenitrile
CH3-O-CH3 Methoxymethane
CH3-CH2-O-CH3 Methoxyethane
CH3-CH2-CH2-O-CH2-CH3 1-Ethoxypropane
CH3-CH2-NH2 Ethanamine
CH3-CH2-CH(NH2)-CH3 Butan-2-amine OR 2-Butanamine
CH3-CH2-COOCH3 Methylpropanoate
CH3-CH2-COOCH2-CH3 Ethylpropanoate
CH3-CH2-COCl Propanoylchloride
CH3-CH2-CH2-CH2-COBr Pentanoylbromide
CH3-CH2-CH2-CONH2 Butanamide
CH3-CONH2 Ethanamide

Nomenclature of organic compounds containing more than one functional groups (Poly
functional compounds)
Here one of the functional groups is chosen as the principal functional group and the compound
is named on that basis. The remaining functional groups (called subordinate functional groups) are
named as substituents using the appropriate prefixes. The choice of principal functional group is made
on the basis of order of preference. The decreasing order of priority for some functional groups is
-COOH, –SO3H, -COOR, -COCl, -CONH2, -CN,-CHO, >CO, -OH, -NH2, >C=C<, -C≡C-
The groups like alkyl (–R), phenyl (C6H5-), halogens (F, Cl, Br, I), nitro (–NO2), alkoxy (–OR) etc. are always
prefix substituents.
For example if a compound contains both alcoholic and aldehydic groups, it is named as
hydroxyalkanal, since here aldehydic group is the principal functional group and –OH group is the
subordinate functional group.
The prefix names of some functional groups are as follows:
Functional group Prefix name
-OH Hydroxyl-
-NH2 Amino-
-X Halo-
-CHO Formyl-
>CO Oxo-
-COOH Carboxy-
-O- Alkoxy-
-CN Cyano-
-NO2 Nitro-
-COOR Alkoxy carbonyl-
-CONH2 Carbamoyl-
-COX Halocarbonyl-

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While numbering the carbon chain, the principal functional group should get the lowest possible
number.
Some examples are:
Compound IUPAC Name
CH3-CHOH-CH2-CO-CH3 4-Hydroxy-2-pentanone
CH2Cl-CH2-CHBr- CH2-CH2OH 3-Bromo-5-chloropentan-1-ol or, 3-Bromo-5-chloro-1-pentanol
CH3-CH2-CO-CH2-CH2-CHO 4-Oxohexanal
CH3-CHNH2-CH2-COOH 3-Aminobutanoic acid
CH3-CH2-CHCl-CH2-CO-CH2-COOH 5-Chloro-3-oxo-heptanoic acid

If a compound contains more than one same functional group, their number is indicated by
adding the numeral prefixes di, tri, etc. before the suffix. In such cases the full name of the parent alkane
is written before the suffix. However, the ending – ne of the parent alkane is dropped in the case of
compounds having more than one double or triple bonds.
When both double and triple bonds are present, the double bonds are given the lowest numbers.
Here first give the suffix of the double bond (-ene) and then that of the triple bond (-yne) [the ending –e
of the suffix –ene is avoided].
Examples:
Compound IUPAC Name
CH2OH-CH2OH Ethane-1,2-diol (Ethylene glycol)
CH2OH-CHOH-CH2OH Propane-1,2,3-triol (Glycerol)
CHO-CHO Ethane-1,2-dial (Glyoxal)
COOH-COOH Ethane-1,2-dioic acid (Oxalic acid)
CH3-CO-CH2-CO-CH3 Pentane-2,4-dione
CH2=CH-CH=CH2 1,3-Butadiene or Buta-1,3-diene
CH≡C-CH2-C≡CH 1,4-Pentadiene or Penta-1,4-diene
CH2=CH-CH2-C≡ CH Pent-1-en-4-yne
CH≡C-CH=CH-C=CH2 Hexa-1,3-dien-5-yne
(The names given in the bracket are the common names)
Nomenclature of Substituted Benzene Compounds
For IUPAC nomenclature of substituted benzene compounds, the substituent is placed as prefix to
the word benzene. But common names of some compounds are accepted by IUPAC

Nomenclatrue of di or polysubstituted benzene

If benzene ring is disubstituted, the position of substituents is indicated by numbering the carbon
atoms of the ring such that the substituents get the lowest possible numbers.
Example – Dibromobenzene

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 In the common system of nomenclature the terms ortho (o), meta (m) and para (p) are used as
prefixes to indicate the relative positions 1,2- 1,3- and 1,4- respectively. So 1,2-dibromobenzene is
named as ortho-dibromobenzene (o-dibromobenzene), 1,3-dibromobenzene as meta-dibromobenzene
(m-dibromobenzene) and 1,4-dibromobenzene as para-dibromobenzene (p-dibromobenzene).
For tri - or higher substituted benzene derivatives, these prefixes cannot be used and the
compounds are named by identifying substituent positions on the ring by following the lowest locant
rule. In some cases, common name of benzene derivatives is taken as the base compound. Substituent
of the base compound is assigned number1 and then the direction of numbering is chosen such that the
next substituent gets the lowest number. The substituents are named in alphabetical order.
Some examples are:

When a benzene ring is attached to an alkane with a functional group, it is considered as substituent,
instead of a parent. The name for benzene as substituent is phenyl (C6H5-, also abbreviated as Ph).
Example:

Isomerism
The phenomenon of existence of two or more compounds having the same molecular
formula but different structural formula or spatial arrangement of atoms is known as
isomerism. Such compounds are called as isomers. Isomers have different physical and chemical
properties. Isomerism can be broadly classified into two –structural isomerism and stereo isomerism.
1. Structural isomerism
Compounds having same molecular formula but different structural formula (arrangement of atoms) are
called structural isomers and the phenomenon is called structural isomerism. There are mainly four
types of structural isomerism:
a) Chain Isomerism: Isomers differ in carbon chain or skeleton are called chain isomers and the
phenomenon is called chain isomerism.
E.g.: Pentane (C5H12)
CH3-CH2-CH2-CH2-CH3 CH3-CH-CH2-CH3 CH3
n-pentane
CH3 CH3 C CH3

isopentane CH3
(2-Methylbutane) neopentane (2,2-Dimethylpropane)
b) Position isomerism: Isomers which differ in the position of the substituent or side chain are
called position isomers and the phenomenon is called position isomerism.
E.g. : Alcohol with molecular formula C4H10O may be 1-butanol or 2-butanol
CH3-CH2-CH2-CH2-OH CH3-CHOH-CH2-CH3
1-Butanol 2-Butanol
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 c) Functional group isomerism: Isomers which differ in the functional group are called functional
group isomers and the phenomenon is called functional group isomerism. This isomerism is
shown by alcohols and ethers and aldehydes and ketones.
E.g. compound with the molecular formula C2H6O may be an alcohol ethanol (CH3-CH2OH) or an
ether methoxy methane (CH3-O-CH3).
d) Metamerism: Isomers which differ in the carbon chain (alkyl groups) around the functional group
are called metamers and the phenomenon is called metamerism. It is commonly shown by
ethers.
E.g.: Ether with molecular formula C5H12O may be methoxybutane (CH3-O-CH2-CH2-CH2-CH3) or
ethoxypropane (CH3-CH2-O-CH2-CH2-CH3).
2. Stereo isomerism
Compounds having same molecular formula but different spatial arrangement of atoms
are called stereoisomers and the phenomenon is called stereoisomerism. They have same atom
to atom bond. There are two types of stereo isomerism – Geometrical isomerism and Optical
isomerism.
The diagrammatic representation of different types of isomerism is:

ORGANIC REACTION MECHANISM - Fundamental Concepts

In an organic reaction, the organic molecule (called substrate) reacts with an attacking reagent to
form one or more intermediates and finally the products.
Substrate + attacking reagent → Intermediate → Products
A sequential account of different steps in which the reactants are converted to products is called
reaction mechanism.
Fission of a covalent bond
A covalent bond can be broken either by homolysis or by heterolysis.
1. Homolysis:
It is a type of bond fission in which each of the bonded atoms gets one of the electrons of the shared
pair. Here the movement of a single electron takes place. The single electron movement is shown by
half – headed arrow or fish hook arrow ( ).

The species formed as a result of homolysis is called free radical. These are species which contain
an odd electron or an unpaired electron.

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 There are three types of free radicals – primary (10), secondary (20) and tertiary
(30). Their stability increases in the order 10 < 20 < 30.

Organic reactions, which take place by homolytic fission are called free radical or homopolar or
nonpolar reactions.
2. Heterolysis:
It is a type of bond fission in which the shared pair of electrons remains with one of the fragments.
After heterolysis, one atom has a sextet of electron and a positive charge and the other atom has
an octet of electron with atleast one lone pair and a negative charge.
For example the bond cleavage in methyl bromide takes place in the following manner.

A species having a carbon atom possessing sextet of electrons and a positive charge is called a
carbocation (carbonium ion). They are of three types – primary, secondary and tertiary.
Carbocations are highly unstable and reactive species. Their stability increases in the
order 10 < 20 < 30. The high stability of tertiary carbocations is due to inductive effect and hyper
conjugation. In carbocations, carbon atom is in sp2 hybridisation and hence they have trigonal planar
(planar triangular) shape.
If the group attached to the carbon atom is less electronegative than C, due to heterolytic
cleavage, a species with C atom containing a shared pair of electrons and negative charge is formed.

Such a species carrying a negative charge on carbon atom is called carbanion. They are also
unstable and reactive. Their stability increases in the order : 30 < 20 < 10.
The organic reactions which proceed through heterolytic bond cleavage are called ionic or
heteropolar or polar reactions.
Differences between Homolysis and Heterolysis
Homolytic bond cleavage (Homolysis) Heterolytic bond cleavage (Heterolysis)
It is a type of bond fission in which each of Here, the bond breaks in such a manner that
the bonded atoms gets one of the electrons the shared pair of electrons remains with
of the shared pair. one of the fragments.
Movement of a single electron occurs. Movement of a pair of electrons occurs.
The species formed as a result of homolysis The species formed as a result of
is called free radical. heterolysis, may be carbocations or
carbanions.

Substrate and Reagent

A molecule whose carbon is involved in new bond formation is called substrate and the other molecule or
species is called reagent. When both of the reactants contain carbon atoms, the molecule under
observation is the substrate.
E.g. CH2 = CH2 + Br2 CH2Br – CH2Br
Substrate Reagent Product

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Nucleophiles and Electrophiles
A reagent that brings an electron pair is called a nucleophile (:Nu –) and the reaction
is called nucleophilic reaction. Or, nucleophiles are electron rich species attack at electron
deficient centre. (The word nucleophile means nucleus seeking).
Examples for nucleophiles are OH-, CN-, NO2-, Cl-, Br-, I-, H2O, NH3, R-NH2 etc.
A reagent that takes away an electron pair is called an electrophile (E+) and the
reaction is called electrophilic reaction. Or, electrophiles are electron deficient species
attack at electron rich centre. (The word electrophile means electron seeking).
Examples for electrophiles are carbocations (R+), -CHO, >CO, X+ (halonium ion), NO2+
(nitronium ion), SO2 etc.
Electron displacement effects in covalent bonds
In an organic molecule, the electron displacement may take place either under the influence of an
atom or in the presence of an attacking reagent. The important types of electron displacement effects
are inductive effect, electromeric effect, resonance effect and hyper conjugation.
1. Inductive effect (I effect):
It is a permanent effect arising due to the shifting of sigma electrons through a
carbon chain in presence of an atom or group of atom (having different electronegativity)
attached to a carbon chain. This effect propagates only through C – C σ bonds. This effect decreases
rapidly as the number of C atoms increases.
E.g. 1-chlorobutane CH3 – CH2 – CH2 – CH2 –Cl
Here Cl is more electronegative than C. So the electron pair in the C – Cl bond is shifted towards Cl
and it gets a slight –ve charge (δ-) and C gets a slight +ve charge (δ+). This carbon attracts the electron
density from the second carbon and so the 2nd carbon gets a relatively smaller positive charge (δδ+).

The inductive effect is related to the ability of substituents to either withdraw or donate electron
density to the attached carbon atom. Based on this ability, the substituents can be classified as electron-
withdrawing group (-I effect group) or electron donating groups (+I effect group) relative to hydrogen.
Groups that withdraw (attract) electrons from the carbon chain are said to have -I effect.
Example for such groups are –X (F, Cl, Br, I), nitro (-NO2), cyano (CN-), carboxy (-COOH), ester (-COOR),
aryloxy (-OAr) etc.
Groups which donate (release) electron pairs towards the carbon chain are said to have +I effect.
Example for such groups are alkyl groups like methyl (-CH3), ethyl (-CH2-CH3) etc.
2. Electromeric effect (E effect):
It is defined as the complete transfer of a shared pair of π-electrons to one of the
atoms joined by a multiple bond in presence of an attacking reagent. It is a temporary
effect. It is possible only in compounds containing multiple bonds( alkene or alkyne). This effect
cancels when the attacking reagent is removed from the reaction site. The shifting of the electrons is
shown by a curved arrow (↷).
There are two types of E effects:
a) Positive Electromeric effect (+E effect): Here the pi electrons are transferred to that atom to
which the attacking reagent gets attached.

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 b) Negative Electromeric effect (-E effect): Here the pi electrons of the multiple bonds are
transferred to that atom to which the attacking reagent does not get attached.

When inductive and electromeric effects operate in opposite directions, the electromeric effect
predominates.
Differentiate between Inductive effect and Electromeric effect
Inductive Effect Electromeric Effect
It is the shifting of sigma electrons through It is the complete transfer of the shared pair of π-
a carbon chain in presence of an atom or electrons to one of the atoms joined by a multiple
group of atom attached to a carbon chain. bond in presence of an attacking reagent.
It is a permanent effect. It is a temporary effect.
It propagates only through C – C sigma It is possible only in compounds containing
bonds. multiple bonds.
Partial polarity is developed. Complete polarity is developed.
No attacking reagent is required Takes place only in presence of attacking reagent.

3. Resonance Effect (R effect) or Mesomeric effect (M effect):

It is defined as ‘the polarity (charge) produced in the molecule by the interaction of
two π-bonds or between a π-bond and lone pair of electrons present on an adjacent atom’.
The effect is transmitted through the chain.
There are two types of resonance effect (R effect):
a) Positive Resonance effect (+R effect): Here the transfer of electrons is away from an atom or
substituent group attached to the conjugated system. E.g. + R effect in phenol:

b) Negative Resonance Effect (- R effect): Here the transfer of electrons is towards the atom or
substituent group attached to the conjugated system. E.g. – R effect in nitrobenzene:

The presence of alternate single and double bonds in an open chain or cyclic system is termed as a
conjugated system.
E.g. for +R effect groups: –X (halogen), –OH, –OR, –OCOR, –NH2, –NHR, –NR2, –NHCOR etc.
E.g. for – R effect groups: – COOH, –CHO, >C=O, – CN, –NO2 etc.

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 4. Hyper conjugation:
It is a permanent effect. In this effect the σ electrons of C—H bond of the alkyl
group enter into partial conjugation with the unsaturated system or with the unshared p
orbital. i.e. the σ electrons of C –H bonds get delocalised.
E.g. Ethyl cation (CH3-CH2+)

Hyper conjugation stabilizes the carbocation because electron density from the adjacent σ bond
helps in dispersing the positive charge. In general, the greater the number of alkyl groups attached to
a positively charged carbon atom, the greater is the hyper conjugation interaction and stabilization
of the cation.
Thus the relative stability of carbocations is in the order: (CH3)3C+ > (CH3)2CH+ > CH3-CH2+ > CH3+.
Here tertiary carbocation has 9, isopropyl has 6, ethyl carbocation has 3 and methyl carbocation
has zero hyper conjugative structures.
Hyper conjugation is also called no-bond resonance and it is also possible in alkenes and alkyl arenes.
Types of Organic reactions
Organic reactions can be classified into the following categories:
i. Substitution reactions
ii. Addition reactions
iii. Elimination reactions
iv. Rearrangement reactions
PURIFICATION OF ORGANIC COMPOUNDS
An organic compound may contain impurities and is essential to purify it. Various methods used
for the purification of organic compounds are based on the nature of the compound and the impurity
present in it.
The common techniques used for purification are as follows:
i. Sublimation
ii. Crystallisation
iii. Distillation
iv. Differential extraction and
v. Chromatography
1. Sublimation
It is the process of conversion of a solid substance directly to vapour by heating. It is used to
separate sublimable compounds from non-sublimable impurities.
In this method, the substance is placed in a sublimation apparatus and heated under vacuum.
Under this reduced pressure, the solid sublimes and condenses as a purified compound on a cooled
surface. The impurities left behind on the apparatus.
This method is used for the purification of naphthalene, iodine, camphor etc.
2. Crystallisation
This is one of the most commonly used techniques for the purification of solid organic compounds.
It is based on the difference in the solubilities of the compound and the impurities in a suitable
solvent. The impure compound is dissolved in a solvent in which it is sparingly soluble at room
temperature but appreciably soluble at higher temperature. The solution is concentrated to get a
nearly saturated solution. On cooling the solution, pure compound crystallises out and is removed by

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filtration. If the compound is highly soluble in one solvent and very little soluble in another solvent,
crystallisation can be satisfactorily carried out in a mixture of these solvents.
3. Distillation
This method is used to separate (i) volatile liquids from non-volatile impurities and (ii) the
liquids having sufficient difference in their boiling points. The principle of this method is that
liquids having different boiling points vapourise at different temperatures. The vapours are cooled
and the liquids so formed are collected separately.
In this method, the liquid mixture is taken in a round bottom flask and heated carefully. On boiling,
the vapours of lower boiling liquid are formed first. The vapours are condensed by using a condenser
and the liquid is collected in a receiver. The vapours of higher boiling liquid form later and it can be
collected separately. Chloroform (b.p 334 K) and aniline (b.p. 457 K) are separated by this technique.
There are different types of distillation methods. They are:
a) Fractional distillation:
Fractional distillation is used to separate two or more liquids that are miscible. It is a special type
of distillation designed to separate a mixture of two or more liquids that have different boiling
points. The process involves heating the mixture and partial condensation of the vapours along a
fractionating column. The column is set up such that components with lower boiling points pass
through the column and are collected earlier than components with higher boiling points. Repeated
vaporization and condensation result in the separation of the components of the mixture. The
efficiency of fractional distillation depends on the use of the fractionating column. The fractionating
column is packed with glass beads. It provides a large surface area for vaporization and condensation
of the liquid mixture.
Ethanol and water mixture, crude oil, toluene and cyclohexane etc. are separated by this method.
b) Distillation under reduced pressure:
This method is used to purify liquids having very high boiling points and those, which
decompose at or below their boiling points. Such liquids are made to boil at a temperature lower
than their normal boiling points by reducing the pressure on their surface. The pressure is
reduced with the help of a water pump or vacuum pump. Glycerol can be separated from spent-lye
in soap industry by using this technique.
c) Steam Distillation:
This technique is applied to separate substances which are steam volatile and are immiscible
with water. In steam distillation, steam from a steam generator is passed through a heated flask
containing the liquid to be distilled. The mixture of steam and the volatile organic compound is
condensed and collected. The compound is later separated from water using a separating funnel.
Aniline – water mixture is separated by this method.
4. Differential Extraction
When an organic compound is present in an aqueous medium, it is separated by shaking it with
an organic solvent in which it is more soluble than in water. The organic solvent and the aqueous
solution should be immiscible with each other. So they form two distinct layers which can be
separated by separating funnel. The organic solvent is later removed by distillation or by evaporation
to get back the compound.
5. Chromatography
This method is used to separate mixtures into their components, to purify compounds and
to test the purity of compounds. Here the mixture to be separated is passed through a stationary
phase, which may be a solid or a liquid. A pure solvent (sometimes a mixture of solvents or a gas) is
allowed to move slowly over the stationary phase. The moving phase is called the mobile phase. The

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components of the mixture get gradually separated from one another.
Based on the principle involved, there are mainly two types of chromatography:
(a) Adsorption chromatography, and
(b) Partition chromatography
a) Adsorption Chromatography: Adsorption chromatography is based on the fact that different
compounds are adsorbed on an adsorbent in different degrees. Commonly used adsorbents are
silica gel and alumina. Here a mobile phase is allowed to move over a stationary phase (adsorbent).
Based on the adsorbing power, the components of the mixture are adsorbed at different places over
the stationary phase. Following are two main types of chromatographic techniques based on the
principle of differential adsorption.
i) Column chromatography, and
ii) Thin layer chromatography.
i) Column Chromatography:
It involves the separation of a mixture over a column of adsorbent (stationary phase) packed in a
glass tube. The column is fitted with a stopcock at its lower end. The mixture to be separated is
passed through the column. Based on the adsorbing power, the components are adsorbed at
different places over the column. The most readily adsorbed substances are retained near the top
and others come down to various distances in the column. Then an appropriate eluant (mobile
phase) is allowed to flow down the column slowly. [Eluant is a solvent or a mixture of solvents used
to move the compounds through the column]. Thus the different components can be collected
separately.
ii) Thin Layer Chromatography (TLC):
It is another type of adsorption chromatography. It involves the separation of substances of a
mixture over a thin layer of an adsorbent coated on a glass plate. A thin layer of an adsorbent like
silica gel or alumina is coated over a glass plate of suitable size. The plate is known as thin layer
chromatography plate or chromaplate.
The solution of the mixture to be separated is applied as a small spot, 2 cm above one end of the
TLC plate. The glass plate is then placed in a closed jar containing the eluant. As the eluant rises up
the plate, the components of the mixture move up along with the eluant to different distances
depending on their degree of adsorption and separation takes place. The relative adsorption of each
component of the mixture is expressed in terms of its retardation factor (Rf value).
Rf = Distance moved by the substance from base line (x)
Distance moved by the solvent from base line (y)
The spots of coloured compounds are visible on TLC plate due to their original colour. The spots of
colourless compounds can be detected by putting the plate under ultraviolet light.
b) Partition Chromatography:
It is based on continuous differential partitioning of components of a mixture between stationary
and mobile phases. Paper chromatography is a type of partition chromatography.
In paper chromatography, a special quality paper known as chromatography paper is used.
Chromatography paper contains water trapped in it, which acts as the stationary phase. A strip of
chromatography paper, spotted at the base with the solution of the mixture, is suspended in a
suitable solvent or a mixture of solvents. This solvent acts as the mobile phase. The solvent rises up
the paper by capillary action and flows over the spot. The paper selectively retains different
components according to their differing partition in the two phases. The paper strip is known as a
chromatogram. The spots of the separated coloured compounds are visible at different heights from
the position of initial spot on the chromatogram. These spots can be visible by u.v. light or by
spraying suitable reagents.

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 QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS
An organic compound mainly contains carbon and hydrogen. Some compounds may also contain
oxygen, nitrogen, sulphur, halogens and phosphorus.
Detection of Carbon and Hydrogen
Organic compound is heated with copper (II) oxide [CuO]. Carbon present in the compound is oxidised
to carbon dioxide and hydrogen to water. CO2 can be tested by passing through lime-water, which turns
milky and water can be tested with anhydrous copper sulphate, which turns blue.
C + 2CuO Δ → 2Cu + CO2
2H + CuO Δ → Cu + H2O
CO2 + Ca(OH)2 → CaCO3↓ + H2O
Detection of Nitrogen, Sulphur and Halogens – Lassaigne’s Test
Nitrogen, sulphur and halogens present in an organic compound are detected by “Lassaigne’s
test”. Here the organic compound is fused with metallic sodium in a fusion tube. It is then plunged
into distilled water taken in a china dish. The solution is boiled and filtered. The filtrate is known
as sodium fusion extract.
Principle: In an organic compound, nitrogen, sulphur and halogen atoms are present in covalent form.
By heating with metallic sodium, these elements are converted to ionic form as follows:
Na + C + N Δ → NaCN
2Na + S Δ → Na2S
Na + X Δ → Na X (X = Cl, Br or I)
For the detection of the elements, the following tests are done:
No. Experiment Observation Inference

1. To one part of sodium fusion extract add Blue or green Presence of

freshly prepared ferrous sulphate colouration or nitrogen
(FeSO4) solution. Heated to boiling, precipitate (ppt)
cooled and acidified with dil. H2SO4.

2. A little of the sodium fusion extract is White ppt soluble in Presence of

acidified with dil. HNO3 and then silver ammonium hydroxide Chlorine
nitrate (AgNO3) is added. (NH4OH)

Pale yellow ppt slightly Presence of

soluble in NH4OH Bromine

Yellow ppt insoluble in Presence of

NH4OH Iodine

3. To a little of the sodium fusion extract, Violet colouration Presence of

add sodium nitroprusside solution sulphur

Test for Phosphorus

The organic compound is heated with an oxidising agent like sodium peroxide. The phosphorus
present in the compound is oxidised to phosphate. The solution is boiled with nitric acid and then
treated with ammonium molybdate. A yellow colouration or precipitate indicates the presence of
phosphorus.
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 QUANTITATIVE ANALYSIS OF ORGANIC COMPOUNDS
The percentage composition of elements present in an organic compound is determined by the
following methods:
1. Estimation of Carbon and Hydrogen
Carbon and hydrogen are estimated by Liebig’s combustion method. In this method, a known mass of
an organic compound is burnt in the presence of excess of oxygen and copper(II) oxide. Then carbon is
oxidised to CO2 and hydrogen is oxidised to H2O.
CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O
The water so produced is absorbed in a weighed U-tube containing anhydrous calcium chloride and
carbon dioxide is absorbed in another U-tube containing concentrated solution of potassium hydroxide.
These tubes are connected in series. The increase in masses of calcium chloride and potassium
hydroxide gives the amounts of water and carbon dioxide from which the percentages of carbon and
hydrogen are calculated.
Calculations:
Let the mass of organic compound be w g, mass of water and carbon dioxide produced be m1 and m2 g
respectively.
2 x 𝑚 x 100
Percentage of hydrogen = 181x w %
12 x 𝑚2 x 100
Percentage of carbon = %
44 x w

2. Estimation of Nitrogen
There are two methods for estimation of nitrogen: (i) Dumas method and (ii) Kjeldahl’s method.
i) Dumas method:
Here the organic compound is heated with copper oxide in an atmosphere of carbon dioxide so that
free nitrogen, carbon dioxide and water are produced.
CxHyNz + (2x + y/2) CuO → x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
This mixture of gases is collected over an aqueous solution of potassium hydroxide which absorbs
carbon dioxide. Nitrogen is collected in the upper part of the graduated tube.

Calculations:
Let the mass of organic compound = w g
Volume of nitrogen collected = V1 mL
Room temperature = T1 K
Volume of nitrogen at STP = P1V1 x 273 = V mL
760 × T1
Where P1 and V1 are the pressure and volume of nitrogen gas.
P1= Atmospheric pressure – Aqueous tension

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We know that 22400 mL N2 at STP weighs 28 g.
Therefore, V mL N2 at STP weighs = 28 x V g
22400
Percentage of nitrogen = 28 x V x 100 %
22400 x w
ii) Kjeldahl’s method:
Here the organic compound containing nitrogen is heated with concentrated sulphuric
acid. Nitrogen in the compound gets converted to ammonium sulphate. The resulting acidic
mixture is then heated with excess of sodium hydroxide. The liberated ammonia gas is
absorbed in an excess of standard solution of sulphuric acid. The amount of ammonia
produced is determined by estimating the amount of sulphuric acid consumed in the
reaction. It is done by estimating unreacted sulphuric acid left after the absorption of
ammonia by titrating it with standard alkali solution. The difference between the initial
amount of acid taken and that left after the reaction gives the amount of acid reacted
with ammonia.
NaOH
Organic compound + H2SO4 → (NH4)2SO4 → Na2SO4 + NH3 + H2O
2NH3 + H2SO4 → (NH4)2SO4
Calculations:
Let the mass of organic compound taken = w g
Volume of H2SO4 of molarity M, taken = V mL
Volume of NaOH of molarity M, used for titration of excess of H2SO4 = V1 mL
V1mL of NaOH of molarity M = V1/2 mL of H2SO4 of molarity M
Volume of H2SO4 of molarity M unused = (V - V1/2) mL = y mL
y mL of H2SO4 of molarity M = 2y mL of NH3 solution of molarity M.
1000 mL of 1 M NH3 solution contains 17g NH3 or 14 g of N
14 x M x 2y
2y mL of NH3 solution of molarity M contains gN
1000
14 x M x 2y x 100
Percentage of N = %
1000 x w
Note: Kjeldahl’s method is not applicable to compounds containing nitrogen in nitro and azo groups and
nitrogen present in the ring (e.g. pyridine) as nitrogen of these compounds does not change to
ammonium sulphate under these conditions.

3. Estimation of halogens (Carius method):

Here a known mass of an organic compound is heated with fuming nitric acid in the presence of silver
nitrate contained in a hard glass tube known as Carius tube, in a furnace. Carbon and hydrogen present
in the compound are oxidised to carbon dioxide and water. The halogen present forms the
corresponding silver halide (AgX). It is filtered, washed, dried and weighed.
Calculations:
Let the mass of organic compound taken = w g
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of halogen
Atomic mass of halogen x m1
Mass of halogen in m1g of AgX = g
Molar mass of AgX
Atomic mass of halogen x m1 𝑥 100
Percentage of halogen = %
Molar mass of AgX x w

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 4. Estimation of Sulphur (Carius method):
A known mass of an organic compound is heated in a Carius tube with sodium peroxide or
fuming nitric acid. Sulphur present in the compound is oxidised to sulphuric acid. It is precipitated as
barium sulphate by adding excess of barium chloride solution. The precipitate is filtered, washed, dried
and weighed. The percentage of sulphur can be calculated from the mass of barium sulphate (BaSO4).
Calculations:
Let the mass of organic compound taken = w g and the mass of barium sulphate formed = m1 g
1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
32 x m1
m1 g BaSO4 contains g sulphur
233
32 x m1 𝑥 100
Percentage of sulphur = %
233 x w
5. Estimation of Phosphorus
A known mass of an organic compound is heated with fuming nitric acid. Phosphorus present in the
compound is oxidised to phosphoric acid. It is precipitated as ammonium phosphomolybdate
[(NH4)3PO4.12MoO3] by adding ammonia and ammonium molybdate.
Calculations:
Let the mass of organic compound taken = w g and mass of ammonium phosphomolydate = m1g
Molar mass of (NH4)3PO4.12MoO3 = 1877 g
31 x m1 𝑥 100
Percentage of phosphorus = %
1877 x w

6. Estimation of Oxygen
The percentage of oxygen in an organic compound is usually found by difference between the total
percentage composition (100) and the sum of the percentages of all other elements.
i.e. percentage of oxygen = 100 – sum of the percentage of all the other elements.

Q1) On complete combustion, 0.246g of an organic compound gave 0.198g of CO2

and 0.1014g of H2O. Determine the percentage composition of carbon and
hydrogen in the compound.
Ans: Mass of organic compound (m) = 0.246 g
Mass of CO2 formed (m1) = 0.198 g
12 x 𝑚2 x 100 12 x 0.198 x 100
Percentage of carbon = % = % = 21.95%
44 x w 44 x 0.246
Mass of water formed (m2) = 0.1014 g
2 x 𝑚1 x 100 2 x 0.1014 x 100
Percentage of hydrogen = % = % = 4.58 %
18 x w 18 x 0.246
Q2) In the Carius method of estimation of halogen, 0.15g of an organic
compound gave 0.12g of AgBr. Find the percentage of Br in the compound.
Ans: Mass of organic compound (m) = 0.15 g
Mass of AgBr formed (m1) = 0.12 g
Atomic mass of Br = 80
Molar mass of AgBr = 108+ 80 = 188 g/mol
Atomic mass of Br x m1 𝑥 100 80 x 0.12 x 100
Percentage of Br = %= % = 34.04 %
Molar mass of AgBr x w 188 x 0.15
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