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24
General Organic
Chemistry
Organic Chemistry
The hydrides of carbon (hydrocarbons) and their derivatives are called
organic compounds. The branch of chemistry which deals with these
compounds is called organic chemistry.
Berzelius (1808) defined organic chemistry as the chemistry of
substances found in living matter and gave the vital force theory.
Synthesis of urea, the first organic compound synthesised in
laboratory, by Wohler, gave death blow to the vital force theory.
D
(NH 4 )2SO4 + 2KCNO ¾¾¾® 2NH 4CNO ¾® NH 2CONH 2
- K 2SO 4 urea
Acetic acid is the first organic compound synthesised from its elements.
Reasons for Large Number of Organic Compounds
(a) Catenation It is the tendency of self combination and is
maximum in carbon. A carbon atom can combine with other carbon
atoms by single, double or triple bonds. Thus, it forms more
compounds than the others.
(b) Tetravalency and small size Carbon being tetravalent, is
capable of bonding with four other C-atoms or some other
monovalent atoms. Carbon can form compound with oxygen,
hydrogen, chlorine, sulphur, nitrogen and phosphorus. These
compounds have specific properties depending upon the nature of
the element or group attached with the carbon.
Furthermore, these compounds are exceptionally stable because of
the small size of carbon.

General Characteristics of Organic Compounds

1. These are the compounds of carbon with H, O, N, S, P, F, Cl, Br and I.
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General Organic Chemistry 335

2. These are generally found in living organisms.
e.g. carbohydrates, proteins etc.
3. These may be gases, liquids or solids.
4. Being covalent in nature, these have low boiling point and
melting point and soluble in organic solvents.
5. These are generally volatile and inflammable.
6. They do not conduct electricity because of the absence of free ions.
7. They posses distinct colour and odour.

Representation of Different Formula

An organic compounds can be represented by the following ways :
1. Complete formula
In it, all the bonds present between any two atoms are shown clearly.
H H H H
½ ½ ½ ½
e.g. H¾ C ¾ C ¾ C ¾ C ¾H
½ ½ ½ ½
H Cl H H
2. Condensed Formula
In it, all the bonds are not shown clearly.
e.g. CH3 CH CH 2CH3 or CH3CH(Cl)CH 2CH3
½
Cl
3. Bond Line Formula
In it, every fold and free terminal represents a carbon and lines
represent the bonds. e.g.
Cl

In such formulae, it is assumed that required number of H-atoms are present,

wherever, they are necessary (to satisfy tetravalency of carbon), e.g.

CH3––C CH––CH2CH3

CH3
CH2 CH––C C–– OH
OH
OH
CH3––CH2––COOH
O
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336 Handbook of Chemistry

Three-dimensional Representation of
Organic Molecule
The three-dimensional (3-D) structure of organic molecule can be
represented on paper by using certain convention, e.g. by using
solid ( ) and dashed ( )wedge formula, the 3-D image of a
molecule from a two-dimensional picture can be perceived. 3-D
representation of methane molecule on paper has been shown below :
dashed wedge
bond in H
(bond away from observer)
the plane
of paper C H
H H solid wedge
(bond towards observer)
wedge-and-dash representation of CH .

Classification of Organic Compounds

Organic Compounds

Open chain or acyclic Closed chain

or aliphatic compounds. or cyclic or ring
e.g. alkane,alkene etc. compounds

Homocyclic or carbocyclic Heterocyclic

O N S
H
Furan Pyrrole Thiophene
(These all are also aromatic.)

Alicyclic Aromatic
e.g.

Cyclopropane Cyclobutane Cyclohexane

Benzenoid Non-benzenoid
O
e.g.
,
e.g.
Benzene Naphthalene
tropolone
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General Organic Chemistry 337

Classification of Carbon Atoms
1. On the Basis of Number of C Attached
(i) Primary carbon atom When carbon atom is attached with
one other carbon atom only, it is called primary or 1° carbon
atom.
(ii) Secondary carbon atom When carbon atom is attached
with two other carbon atoms, it is called secondary or 2°carbon
atom.
(iii) Tertiary carbon atom When carbon atom is attached with
three other carbon atoms, it is called tertiary or 3° carbon atom.
(iv) Quaternary carbon atom When carbon atom is attached
with four other carbon atoms, it is called quaternary or 4° carbon
atom.
Reactivity order of carbon atoms is as follows 3° > 2° > 1°.
1°
CH3
1° 2° ½ 4° 3° 1°
e.g. CH3 ¾ CH 2 ¾ C ¾ CH ¾ CH3
½ ½
CH3 CH3
1° 1°

On the Basis of Position of Functional Group

(i) a-carbon Carbon which is directly attached to the functional
group.
(ii) b-carbon Carbon which is directly attached to the a-carbon.

Classification of Hydrogen Atoms

1°-hydrogen (primary) attached to 1°-carbon.
2°-hydrogen (secondary) attached to 2°-carbon.
3°-hydrogen (tertiary) attached to 3°-carbon.
a-hydrogen(s) Hydrogens which are attached to a-carbon atom.
b-hydrogen(s) Hydrogens which are attached to b-carbon atom.
b a
e.g. CH3 ¾ CH 2 ¾ Cl,
b a
CH3 ¾ CH 2 ¾ COOH
b a
CH3 ¾ CH 2 ¾ CHO
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338 Handbook of Chemistry

Functional Group
The atom, e.g. ¾ Cl, ¾ Br etc., or group of atoms e.g. —COOH, —CHO,
which is responsible for the chemical properties of the molecule, is
called functional group.
Double and triple bonds are also functional groups.
R—OH
R is called alkyl group, it contains only single bond; alkenyl group
contains double bond and alkynyl group contains triple bond.

Homologous Series
The series in which the molecular formula of adjacent members differ
by a ¾ CH 2 unit, is called homologous series and the individual
members are called homologues. e.g. The homologous series of alkene
group is
ü C2H 4
ïC H
ï 3 6
ý difference of ¾ CH 2 unit or 14 unit mass
ï C4H 8
ïþ C5H10
The general characteristics of this series are :
1. All the homologues contain same functional group. That’s why
their chemical properties are almost similar.
2. All the members of a series have same general formula, e.g.
Series General formula

Alkanes C nH n+
Alkenes C nH n
Alkynes C nH n-
Alcohol and ether C nH n+ O
Aldehyde and ketone C nH nO
Acid and ester C nH nO

3. All the members can be prepared by almost similar methods.

4. With increase in the molecular weight of a series, the physical
properties varies gradually.
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General Organic Chemistry 339

Nomenclature of Organic Compounds
Trivial System
It is the oldest system in which names are derived from source or some
property. These are mainly derived from Latin or Greek names. e.g.
acetic acid (acetum = vinegar), oxalic acid (oxalus), malic acid (pyrus
malus), citric acid (citrum), formic acid (obtained from red ant
(formicus)].

IUPAC System
The IUPAC (International Union of Pure and Applied Chemistry)
system, given in 1957, is superior and widely used. IUPAC amends
these rules from time to time. Here, we are following the 1993
recommendations of IUPAC nomenclature. Following rules are used to
write the IUPAC name of an organic compound.

Rule I
Longest chain rule The chain containing the principal functional
group, secondary functional group and multiple bonds as many as
possible is the longest possible chain. In the absence of functional
group, secondary group and multiple bonds, the chain containing the
maximum number of C-atoms will be the longest possible chain. e.g.

C––C––C––C––C––C––C

C
C C Longest chain

Choose the word root from the table given below for the longest
possible chain.
Word Root for Carbon Chain
Chain length Word root Chain length Word root

C Meth- C Hept
C Eth- C Oct
C Prop- C Non
C But- C Dec
C Pent C Undec
C Hex- C Dodec
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340 Handbook of Chemistry

Rule 2
Lowest number rule Numbering is done in such a way so that
1. branching if present gets the lowest number.
2. the sum of numbers of side chain is lowest.
3. principal functional group gets the lowest number.
Select the principal functional group from the preference series :
¾ COOH > ¾ SO3H > ¾ COOR > ¾ COX > ¾ CONH 2 > CN > ¾ NC
> ¾ CHO > C ==O > ¾ OH > ¾ SH
> ¾ NH 2 > ¾ OR > ¾ C ¾ C ¾ > == > ºº > NO2 > X > R

O
Functional group other than the principal functional group are called
substituents.
9 C atom
CH3 CH2 CH2 CH2––CH––CH2 CH2––CH2––COOH Longest
chain
4 C atom CO OH 6 C atom

Rule 3.
Naming the prefixes and suffixes Prefix represents the
substituent and suffix is used for principal functional group.
Primary prefixes are cyclo, bicyclo, di, tri, tetra, tries, tetrakis etc.
Primary suffix are ene, ane, or yne used for double, single and triple
bonds respectively.

Substituent Prefix Substituent Prefix

—F Fluoro ¾ N == N ¾ diazo
—Cl Chloro ¾ N == O nitroso
—Br Bromo ¾NO nitro

Secondary suffixes are tabulated below :

S. No. Class Formula Prefix Suffix

1. Acid halides O halocarbonyl —oyl halide
½½ —carbonyl halide
¾C ¾ X
2. Alcohols —OH hydroxy —ol
3. Aldehydes —CHO formyl —al
—carbaldehyde
4. Ketones C == O oxo —one
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General Organic Chemistry 341

S. No. Class Formula Prefix Suffix
5. Amides ¾CONH carbamoyl —amide
6. Amine ¾NH amino —amine
7. Carboxylic acid —COOH carboxy —carboxylic acid
8. Ester —COOR oxy carbonyl —alkyl alkanoate
9. Nitriles —CN cyano —nitrile
10. Sulphonic acid —SO —OH sulpho —sulphonic acid

Hence, according to the rules, given above, the IUPAC name of a

compound can be written as
Prefixes + root word + suffixes primary prefix + secondary prefix
+ root word + primary suffix + secondary suffix

e.g. 4 3 2 1 principal functional group

CH3 CH––CH2 CHO (–al)
OH substituent (hydroxy)
4–hydroxybutanal

prefix root suffix

word
If more than two similar functional groups are present, all the groups
are considered as substituent, e.g.
3 2 1
CH 2 ¾ CH ¾ CH 2
½ ½ ½
CN CN CN
propane-1, 2, 3-cyanide
Naming Alicyclic Compounds
For alicyclic compounds, prefix cyclo is used e.g.
1 2
CH3––CH––CH3
1
6 2

5 3
4
cyclohexane 1-(1-methylethyl)
cyclohexane
If the alkyl chain contains a greater number of C-atoms than the ring,
the ring is designated as substituent, e.g.
1 2 3 4
CH2 CH2 CH2 CH3
cyclopropylbutane
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If side chain contains a multiple bond or a functional group, the ring is

treated as a substituent e.g.

3 2 1
CH2––CH––CH2
3-cyclo propylprop-1-ene

Other examples are :

O

1
CH3
6 2
5 3

4 CH2CH3
3-ethyl-2-methylcyclohex-2-en-1-one

Naming Spiro Compounds

Prefix ‘spiro’ is used for the compounds in which one carbon is common
between two rings :
Here, smaller ring is numbered first, e.g.
7 8 1 9 10 1
2
4 2 8 5
O 3
6 5 3 7 4
6
spiro [3.4] octane 6-oxaspiro [4.5] decane

number of atoms in ring

in ascending order

Naming Bicyclo Compounds

Prefix ‘bicyclo’ is used for such compounds, e.g.
1 6
7 2 1
8 3
6 5 2
4
5 4 3
bicyclo [3.2.1] octane bicyclo [2.1.1] hexane

number of atoms in each ring

in descending order

In bicyclo compounds, numbering is done first in larger ring, then in

smaller ring.
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General Organic Chemistry 343

Naming Aromatic Compounds
IUPAC accepted their common trivial names, e.g.
Cl CH3

benzene chlorobenzene toluene

OH NH2 COOH

phenol aniline benzoic acid

CHO CN NO2

benzaldehyde benzonitrile nitrobenzene

Cl CH2CH2CH2Br

Cl Cl
1,4-dichlorobenzene 1-bromo-3-(4-chlorophenyl) propane

Isomerism
The compound having same molecular formula but differ in properties
are known as isomers and the phenomenon is known as isomerism.
There are two main types of isomerism i.e.

1. Structural Isomerism
In this type of isomerism, compounds have same molecular formula
but different structures.
It can further be of following types :
(i) Chain Isomerism
It arises when two or more compounds have similar molecular formula
but different carbon skeletons, e.g. for C5H12. we have
CH3 ¾ CH 2 ¾ CH 2 ¾ CH 2 ¾ CH3
n - pentane
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344 Handbook of Chemistry

CH3
½
CH3 ¾ CH 2 ¾ CH ¾CH3 ; H3C ¾ C ¾ CH3
½ ½
CH3 CH3
iso - pentane neo - pentane

(ii) Position Isomerism

When two or more compounds have same molecular formula but
different position of functional groups or substituents, they are called
positional isomers and the phenomenon is called position isomerism.
e.g. C3H7Cl
CH3 ¾ CH 2 ¾ CH 2 ¾ Cl, CH3 ¾ CH ¾ CH3
1- chloropropane ½
Cl
2- chloropropane
(iii) Functional Isomerism
It arises when two or more compounds have the same molecular
formula but different functional group. e.g. C3H 6O represents an
aldehyde and a ketone as
O
½½
CH3 ¾ CH 2 ¾ CHO, CH3 ¾ C ¾ CH3
Propanal Propanone
● C2H 6O represents an alcohol and an ether.
·· ··
CH3 ¾ CH 2 ¾ OH, CH3 ¾ O ¾ CH3 etc.
·· ··
ethanol
dimethyl ether
(iv) Metamerism
It arises due to different alkyl groups on either side of the same
functional group in a molecule, e.g.,
·· ··
CH3 ¾ O ¾ C3H7 , C2H5 ¾ O ¾ C2H5
·· ··
1-methoxypropane diethyl ether
(v) Tautomerism
It is a special type of functional isomerism which arises in carbonyl
compounds containing a-H atom. e.g.
O OH
½½ ½
CH3 ¾ C ¾ H j CH 2 ==C ¾ H
keto form enol form
(acetaldehyde)
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General Organic Chemistry 345

O OH
H
a-hydrogen

cyclohexanone enol form

(keto form)

2. Stereoisomerism
The compounds having same molecular formula but different spatial
arrangement of atoms or groups are called stereoisomers and the
phenomenon is called stereoisomerism.
Stereoisomerism is of two types : optical isomerism and geometrical
isomerism.
(i) Optical Isomerism
Compounds having similar physical and chemical properties but differ
only in behaviour towards plane polarised light are called enantiomers
or optical isomers and the phenomenon is known as optical isomerism.
e.g.
CH3 CH3

C––OH HO––C
H H
CH2CH3 H3CH2C
2-butanol
mirror
The isomer which rotate the plane of polarised light towards
right (clockwise) is known as dextrorotatory or d-form while that
which rotates towards left (anticlockwise) is known as laevorotatory
or l-form.
Generally asymmetric or chiral compounds show optical isomerism.
Chiral compounds are those which contain chiral centre i.e. chiral
carbon, the carbon all the four valencies of which are satisfied by four
different groups. Allenes, spiranes and biphenyl compounds, although
have absence of chiral centre, but are asymmetric. That’s why they are
also optically active.
Number of optical active isomers = 2n (where, n = chiral carbon). If two
end are similar number of optical active isomers = 2n - 1 (if n = even)
n -1
and meso form = 2 2 . If n = odd, number of optical active isomers
= 2n - 1 - 2( n - 1)/ 2.
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346 Handbook of Chemistry

Terms Related to Optical Isomerism

(a) Enantiomers The non-superimposable mirror images are called
enantiomers. e.g.
Me Me
H Cl Cl H
H Br Br H
Me Me
(b) Diastereomers The isomers which are non-superimposable and
not related to each other as mirror image, are called
diastereomers.
Me Me
H Cl H Cl
H Br Br H
Me Me
diastereomers

They have different physical and chemical properties.

(c) Meso form The compound in which half part of a molecule is the
mirror image of other half, is called meso form. Generally, a meso
compound have two or more chiral centres and a plane of
symmetry.
It is optically inactive due to internal compensation, thus, it is not
possible to convert it into d and l-form e.g.
COOH
*
H––C––OH
plane of symmetry
H––C––OH
*

COOH
meso compound
(d) Racemic mixture It is a mixture of enantiomers in 1 : 1. It is
optically inactive due to external compensation.

Separation of a racemic mixture into d and l form is called

resolution. It can be done by mechanical method, biochemical
method and chemical method.

(e) Atropisomers These are the isomers that can be

interconvertable by rotation about single bond but for which the
rotation barrier is large enough that they can be separated and do
not convert readily at room temperature.
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General Organic Chemistry 347

(f) Specific rotation It is given by the expression
a observed rotation (degree)
[a ] = =
l´d length ´ density

Nomenclature of Enantiomers
(i) D-L configuration The optical isomer in which H is present
towards left hand side and the other group towards right hand side,
is D-form while in which, H is present towards right and the other
group occupy the left position, is L-form. This system is applicable
mainly for compounds containing one chiral atom.
(ii) Threo-erythro system When the same groups are present at the
same side of the carbon chain, the form is called erythro form. When
the same groups are present on the opposite side of the carbon chain,
the form is called threo form. e.g.
CH3 CH3
H OH H OH
H Cl Cl H
CH3 CH3
erythro form threo form

(iii) R-S system This system was proposed by Cahn, Ingold and
Prelog. In this system, configuration R is given to the isomer in which
sequence of groups is clockwise and S is given to the isomer in which
sequence of groups is anticlockwise.
Priority sequence is decided by following rules :
1. Priority is given to the atom having high atomic number, e.g. in
Cl, Br and F, the priority order is Br > Cl > F.
2. In case of group of atoms, priority is decided by the atomic
number of first atom. e.g. in —COOH, —OH and ¾ NH 2 priority
order is
¾ OH > ¾ NH 2 > ¾ COOH
3. If the first atom of the group of atoms is same, the priority is
decided by second atom of the group, e.g. among —COOH,
¾ CH 2OH and—CHO, priority order is
¾ COOH > ¾ CHO > ¾ CH 2OH
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348 Handbook of Chemistry

4. When a multiple bond is present in a group, the atom at the end

of the multiple bond is like as if it is equal to equivalent number
of single bond, e.g.

––C––C––
C C is equivalent to
––C C––

N C

Similarly, –C N is equivalent to ––C––N––

N C
1
OH 1

Interconversion
e.g. 4 H––C––CH3 4 3
3
NH2
2
2
3

2 1 Clockwise;
R configuration

Priority order OH > NH2 > CH3 > H

3 4
H3C H 4

2 1 3 1 Clockwise;
R configuration
H 2
H

(ii) Geometrical Isomerism

The isomers having same molecular formula but different spatial
arrangement of atoms about the double bond are known as geometrical
isomers and this phenomenon is called geometrical isomerism, e.g.

H 3C CH3 H 3C H
C C C C
H H H CH3
cis-2-butene trans-2-butene
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General Organic Chemistry 349

For exhibiting geometrical isomerism, the essential conditions are :
1. The compound must contain at least one double bond.
2. The groups present at the double bonded carbon atoms, must be
different. However, one similar group should be present at the
adjacent double bonded carbon atoms.
Number of geometrical isomers (if two ends are not similar = 2n
where, n = number of double bonds).
Types of Geometrical Isomers
(a) Cis-trans isomers In cis-isomer, similar groups are present on
the same side of the double bond and in trans-isomer, similar
groups are present on the opposite side of the double bond. e.g.
H3C CH3 H3C H
C ==C C ==C
H H H CH3
cis- form trans- form
Cycloalkanes also exhibit cis-trans isomerism.
H 3C CH3 H 3C H

H H H CH3
cis-form trans-form
OH OH OH

OH OH OH
cis trans cis
(b) Syn-anti isomers compounds containing C ==N bond (as in
aldoxime), N ==N bond (as in H 2N 2O) exhibit this type of isomerism.
e.g.
H3C H H3C H
C C

N N
OH HO
syn anti

(c) E-Z isomers In E-isomer, bulkier (heavier) groups are present

on the opposite side of the double bond and in Z-isomer, heavier
groups are present on the same side of the double bond. E is
entgegen means opposite and Z is Zusammen means together, e.g.
H Cl
C C
Cl Br
bulkier bulkier
Z isomer Z-3-hexene
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Fission of a Covalent Bond

1. Homolytic Fission
In this, one of the electrons of the shared pair in a covalent bond goes
with each of the bonded atoms. The neutral chemical species thus
formed, is called free radical. Generally, homolytic fission takes place
in non-polar, covalent molecules in the presence of sunlight or high
temperature.
Sunlight
A ¾ B ¾¾® A· + B ·
1
424 3
free radicals

Cl2 — ¾® 2Cl·
Sunlight
e.g.
Free radicals are highly reactive, neutral and electron deficient species.
2. Heterolytic Fission
In this, the bond breaks in such a fashion that the shared pair of
electrons goes with one of the fragments.
more electronegative

A ¾ B ¾® A+ + B-
electrophile nucleophile
less electronegative

or A ¾ B ¾® A- + B+
nucleophile electrophile
Carbon bearing a positive charge is called carbocation and carbon
bearing negative charge is called carbanion.

Heterolytic fission generally takes place in polar covalent molecules

but in non-polar molecules, it takes place in the presence of catalyst
like AlCl3 (anhy.), FeCl3(anhy.) etc.

Attacking Reagents
These are of two types :

1. Electrophiles or Electrophilic Reagents

These are electron deficient species i.e. behave as Lewis acids. The
following species behave as electrophiles :
(i) All non-metal cations and metal cations which have vacant
d-orbitals. e.g. Cl+ , NO+2 , CH3CO+ etc.
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General Organic Chemistry 351

(ii) Lewis acids (incomplete octet), e.g. BF3 , ZnCl2 (anhydrous),
FeCl3 (anhydrous), AlCl3 (anhydrous), ··CH 2 etc.
(iii) Non-metal (acidic) oxides e.g. CO2 , SO2 etc.

2. Nucleophiles or Nucleophilic Reagents

These are electron rich species i.e. behave as Lewis bases.
These attack at electron deficient area.
The following species behave as nucleophiles :
(i) All anions e.g. Cl- , NH -2 , OH - etc.
·· ··
(ii) Lewis bases e.g. ··NH3 , H 2O, R ¾ O ¾ R, R ¾ OH etc.
·· ··

(iii) Benzene, alkenes etc.

Nucleophilicity order is
H - > CH3- > NH -2 > RO- > OH -
In case of same nucleophilic site, nucleophilicity parallels basicity i.e.
as the basicity increases, nucleophilicity also increases.

If nucleophilic sites (or attacking atoms) are different nucleophilicity

varies inversely with electronegativity.

3. Ambiphiles
These species behave like both electrophiles as well as nucleophiles.
Organic compounds containing a multiple bond between carbon and a
more electronegative atom can act as ambiphiles. e.g.
d-
H d+ ·· d+ d-
C ==O·· ; CH3 ¾ C ººN ··
··
H

electrophile nucleophile electrophile nucleophile

Reaction Intermediates
These are formed as a intermediate during the course of a reaction.
These are short lived and highly reactive.
Free radicals, carbocations, carbanions, carbenes and nitrenes are
important reactions intermediates.
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352 Handbook of Chemistry

1. Free Radicals
These are the product of homolysis and contain an odd electron. These
are highly reactive planar species with sp2-hybridisation.
Their order of stability is
· · ·
(C6H5 )3C > (C6H5 )2 CH > C6H5CH 2
· ·
> CH 2 ==CH ¾ CH 2 > 3° > 2° > 1° > CH 2 ==CH

2. Carbocations
These are the product of heterolysis and contain a carbon bearing
positive charge. These are electron deficient species. Carbocations
contain six electrons in the valence shell.
These are also planar chemical species, i.e. sp2-hybridised with an
empty p-orbital.
empty p-orbital
s
s
s C

The stability order of carbocations is :

+ + +
(C6H5 )3 C+ > (C6H5 )2CH > (CH3 )3C > C6H5CH 2 > 2°
+ + +
> CH 2 ==CH ¾ CH 2 > 1° > C6H5 > CH 2 ==CH

3. Carbanions
These are also the product of heterolysis and contain a carbon
bearing negative charge and 8 electrons in its valence shell.
s
These have pyramidal shape with sp3 -hybridised carbon s C s
(having one lone pair)
The order of stability of carbanions is
- - -
(C6H5 )3 C- > (C6H5 )2CH > C6H5CH 2 > CH 2 ==CH ¾ CH 2
-
> CH3 > 1° > 2° > 3° carbanions

4. Carbenes
These are divalent carbon species having two non-bonding electrons
along with two bond pairs.
These are obtained by photolysis or pyrolysis, e.g.
hn
CH 2 ==C ==O ¾¾® ··CH 2 + ··C ==O
ketene or D
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These being electron deficient behave as Lewis acids. These are of two
types :
(i) Singlet carbene In it, the C-atom is sp2-hybridised. The
unhybridised orbitals contain no electrons and a hybridised orbital
contains two electrons :
empty
s 2
s C sp -hybridised with 2 unbonded electrons
s

Singlet carbene has bent structure and is less stable than triplet
carbene.
The order of stability of singlet carbenes is
·· ·· ·· ··
CH 2 > CF2 > C Cl2 > C Br2

(ii) Triplet carbene In it, the central C-atom is sp-hybridised. The

unhybridised orbitals contain 1 electron each.
unhybridised orbitals with 1 electron

s C s

Triplet carbene has linear geometry.

5. Nitrene
These are neutral monovalent nitrogen species in which N atom has
two unshared pair of electrons with a mono valent atom or group
attached.
These are obtained by thermolysis of azides and as reactive as
carbenes.
These are of two types : singlet nitrene and triplet nitrene

Y Y
N N
Z Z
Singlet Nitrene Triplet Nitrene
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354 Handbook of Chemistry

6. Arynes
2
It contains a formal carbon-carbon triple bond in sp
aromatic molecule.
The additional bond is formed between two sp2
neighbouring C-atoms by sideways overlapping of two
sp2-orbitals. The new bond lies along with side of the ring and has little
interaction with the p electron cloud lying above and below the ring.
The sideways overlapping is weak and thus, makes the benzene more
reactive.

Inductive Effect
It is just like shifting of shared pair of electrons in polar covalent
molecules. If shared pair is more shifted towards the more
electronegative atom, the less electronegative atom acquires slight
positive charge and more electronegative atom acquires partial
negative charge, e.g.
+d -d
CH3 ®¾ Cl
It is a permanent effect and propagates through carbon chain. Atoms
or groups having greater electron affinity than hydrogen, are said to
have electron attracting or negative inductive effect ( - I ) while that
having, smaller electron affinity than hydrogen are said to have
electron releasing or positive inductive effect ( + I ). e.g.
+ dd +d -d
CH3 ®¾ CH 2 ®¾ Cl
+ ddd + dd +d -d
CH3 ®¾ CH 2 ®¾ CH 2 ®¾ Cl
1°alkyl halide
Here, Cl has - I effect and alkyl group has + I effect.
Order of groups producing - I effect is
+
R3N > NO2 > CN > SO3H > CHO > CO > COOH > F >
Cl > Br > I > OH > OR > NH 2 > C6H5 > H
Order of groups producing + I effect is
O- > ¾ COO- > 3° alkyl group > 2° alkyl group
> 1° alkyl group > CH3 > H
Applications of Inductive Effect
1. Presence of groups showing + I effect increases the stability of
carbocation while presence of groups showing - I effect
decreases their stability.
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General Organic Chemistry 355

2. Strength of acid increases with the attachment of group showing
- I effect and decreases with the attachment of group showing
+ I effect.
3. Presence of + I effect showing groups increases the basic
strength of amines.
4. Reactivity of carbonyl compound is increased by - I effect
showing groups.
5. Reactivity of alkyl halides towards SN 1 is increased by
+ I showing groups.

Electromeric Effect
It is defined as the polarity produced in a multiple bonded compound
as a reagent approaches it. In the presence of attacking reagent, the
two p electrons are completely transferred to any of the one atom. This
effect is temporary.
This may be of + E type (when displacement of electron pair is away
from the atom or group) or of - E type (when the displacement is
towards the atom or group). e.g.
H H Reagent H H
C C Å – C+–––C
H H [E Nu ] H H
E+
Reagent
C O C––O–
[E+Nu–]
Nu–

Hyperconjugation
It involves delocalisation of s electron of a C—H bond of an alkyl group
attached directly to an atom of unsaturated system or to an atom with
an unshared p-orbital.
H
H+
–
CH2––CH CH2 CH2 CH––CH2

This effect is also called no bond resonance or Baker Nathan

effect.

Applications of Hyperconjugation
(i) Stability of alkenes More the number of a-hydrogen atoms,
more stable is the alkene.
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356 Handbook of Chemistry

a
CH3 a a
a CH3 a CH3 a a
H3C––C C > CH3CH C > CH3––CH CH––CH3
CH3 CH3
a a

(ii) Stability of carbocation Greater the number of alkyl groups

attached to a positively charged carbon atom, the greater is the
stability.
+ + +
(CH3 )3 C+ > (CH3 )2 CH > CH3 ¾ CH 2 > CH3

Resonance Effect
When all the properties of a molecule cannot be shown by a single
structure and two or more structures are required to show all the
properties of that molecule, then the structures are called resonating
structures or canonical forms and the molecule is referred as
resonance hybrid. This phenomenon is called resonance.
In resonance,
1. The arrangement of atoms must be identical in all the formulae.
2. The energy content of all the canonical forms must be nearly
same.
3. Each canonical form must have the same number of unpaired
electrons.
It involves delocalisation of p electrons. This effect may be of + R type
or - R type.

Positive Resonance Effect ( +R )

Electron donating groups with respect to conjugate system show
+R effect. Central atom of functional groups should be more
electronegative than the surrounding atoms or groups to show
+ R effect. e.g. halogens, —OH, —OR, —OCOR, —NH 2,—NHCOR etc.
– + + +
NH2 NH2 NH2 NH2
– –

Electron donating groups producing, + R effect are ortho and para

directing. They activate the benzene ring towards the electrophilic
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General Organic Chemistry 357

substitution reactions except halogens. Halogens slightly deactivate
the benzene ring towards the electrophilic substitution reaction. More
the E.D.G, more is the basic nature.

Negative Resonance Effect ( -R )

Electron withdrawing groups with respect to conjugate system show
- R effect. Central atom of functional groups should be less
electronegative than surrounding atoms or groups to show -R effect.
e.g. halogens, — COOH, — COOR, — CHO,— CN,—NO 2 etc.

H––C O H––C––O– H––C––O– H––C––O–

+ +

+
Electron withdrawing group (E.W.G.) producing - R effect are meta
directing. They deactivate the benzene ring towards the electrophilic
substitution reaction. More the E.W.G, more is the acidic nature.

Stability of Canonical Forms

It can be judged by the following rules :
1. Non-polar structure is more stable than the polar structure.
2. Among polar structures, structure with maximum number of
covalent bonds is most stable.
3. The structure with maximum charge separation is more stable.
4. Structure with positive charge on more electropositive element
and negative charge on more electronegative element is more
stable.

Resonance Energy
Number of p bonds µ contributing structures µ resonance energy µ
stability.
In benzene, resonance energy is 36 kcal/mol.

Relation Between Resonance and Bond order

Total number of bonds betwen two atoms
Bond order =
Total number of resonating structures

2+1
e.g. BO = = 1.5
2
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358 Handbook of Chemistry

Types of Organic Reactions

Reactions are of following types :

1. Addition Reactions
These reactions are given by unsaturated compounds or compounds
containing multiple bonds.
In these reactions, the reagent adds to the substrate molecule.
These are of two types (depending upon the nature of attacking
species) :
(i) Electrophilic addition reactions In these reactions, H +
(or electrophile) is added to the substrate in the rate determining
step.
These reactions are given by alkenes and alkynes. e.g.
X
+ –
X
C C + H+ C—C C— C

H H

(ii) Nucleophilic addition reactions In these reactions,

nucleophile is added to the substrate in the rate determining step.
These reactions are given by carbonyl compounds. e.g.

O– H
+ OH
C O + CN – C C
CN CN
nucleophile

2. Substitution Reactions
In these reactions, one atom or group of atoms, called the leaving
group, is substituted by a nucleophile or an electrophile. On this basis
these reactions are of two types :
(i) Electrophilic substitution reactions When leaving group is
replaced by an electrophile, the reaction is called electrophilic
substitution reaction.
NO2
+ NO2+
Electrophile

(ii) Nucleophilic substitution reactions In these reactions,

nucleophiles are the attacking species.
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General Organic Chemistry 359

These are of two types :

(a) SN 1 (Nucleophilic substitution unimolecular) reaction is
a two step process, e.g.
R ¾ X ¾® R + + X -
R+ + OH - ¾® ROH
nucleophile
For such reaction, rate = k [R - X ]
The reactivity of alkyl halides towards SN 1 reaction is
3° > 2° > 1° alkyl halide.
(b) S N 2 (Nucleophilic substitution bimolecular) reaction
is a single step process e.g.
d- d-
OH - + R ¾ X ¾® H OK RK X ¾® R ¾ OH + X -
nucleophile
For such reactions, rate = k [RX ] [OH - ]
These reactions involve inversion of configuration.
For such reactions the order of reactivity of alkyl halide is
1° > 2° > 3°

3. Elimination Reactions
In these reactions, two groups from the same or adjacent atoms are
lost and electron deficient or unsaturated compound is formed.
These can be of two types :
(i) a-elimination In it, both the groups are eliminated from the
same carbon atom. Such reactions are rare. e.g.
-
CHCl3 ¾® ··CCl3 ¾® ·CCl
· 2
carbene

(ii) b-elimination Here, the groups are eliminated from the adjacent
carbon atoms. These can further be E1 or E2 reactions .e.g.

H3C Nu H3C CH3 H3C CH3

H3C CH3 H3C + C==C
–Nu –H
H CH3 H CH3 H3C CH3
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360 Handbook of Chemistry

4. Rearrangement Reactions
Reactions involving the migration of an atom or a group from one atom
to another within the same molecule are called rearrangement
reactions.
e.g. Hofmann bromamide reaction involving the conversion of 1°
amides to 1° amines on treatment with Br2 in the presence of KOH.
O O
Br2 /KOH OH–
R––C––NH2 R––C––N––Br
(rearrangement) –H2O
1° amide
H
O

R––C––N–––Br
–Br–

O
KOH rearrangement
R––NH2 O C N––R R––C––N
+ Alkyl isocyanate

K2CO3 Acylnitrene

This reaction involves the migration of alkyl group, R from C to N to

form alkyl isocyanate.