General Organic Chemistry ( By Jitender sir )

Science of organic chemistry is about two hundred years old. Around the year 1780, chemists
began to distinguish between organic compounds obtained from plants and animals and inorganic
compounds prepared from mineral sources. Berzilius, a Swedish chemist proposed that a ‘vital
force’ was responsible for the formation of organic compounds. However, this notion was
rejected in 1828 when F. Wohler synthesised an organic compound, urea from an inorganic
compound, ammonium cyanate.
NH4CI + KCNO → NH4CNO + KCℓ
𝐇𝐞𝐚𝐭
NH4CNO → NH2CONH2
The pioneering synthesis of acetic acid by Kolbe (1845) and that of methane by Berthelot
(1856) showed conclusively that organic compounds could be synthesised from inorganic sources
in a laboratory.
Electric arc dil.H SO /HgSO
Oxidation
2C+H2 ⎯⎯⎯⎯⎯ → CH  CH ⎯⎯⎯⎯⎯⎯⎯⎯
2 4 4 → CH CHO ⎯⎯⎯⎯⎯
3 → CH3COOH

Q3) Give some examples of alkyl group ?

Ans ) i) CH3- (methyl) ,
ii) C2H5- (ethyl) ,
iii) CH3CH2CH2- (propyl) ,
iv) CH2=CH- (Vinyl),
v) CH2=CH-CH2- (allyl ) ,
vi) CH3CH=CH- (Crotyl )
vii) (CH3)2CH- ( isopropyl )
viii) (CH3)3C- ( tert-Butyl )

2. NOMENCLATURE OF ORGANIC COMPOUNDS

Nomenclature implies assigning proper name to a particular organic compound on the basis of
certain standard rules so that the study of these compounds may become systematic. In the IUPAC system,
the name of an organic compound consists of three parts.
(i) Word root (ii) Suffix (iii) Prefix

2.1 WORD ROOT

The word root denotes the number of carbon atoms present in the chain. For example,

Chain length Word root Chain length Word root

C1 Meth C6 Hex
C2 Eth C7 Hept
C3 Prop C8 Oct
C4 But C9 Non
C5 Pent C10 Dec

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 General Organic Chemistry ( By Jitender sir )
2.2 SUFFIX
The word root is linked to the suffix, which may be primary, secondary or both.

Primary suffix
It indicates the nature of linkages between the carbon atoms. For example,

ane − for single bonded compounds, C−C ;

ene − for double bonded compounds, C=C ;
yne − for triple bonded compounds, CC.
Secondary suffix
It indicates the presence of functional group in the organic compound. For example,

Class of organic compound Functional group Secondary suffix

Alcohols −OH −ol
Aldehydes −CHO −al
Ketones C=O −one
Carboxylic acids −COOH −oic acid
Esters −COOR Alkyl alkanoate
Acid chlorides −COCl −oyl chloride
Acid amides −CONH2 −amide
Nitriles −CN −nitrile
Amines −NH2 −amine
2.3 PREFIXES
There are many groups, which are not regarded as functional groups in the IUPAC naming of the
compounds. These are regarded as substituents or side chains. These are represented as prefixes and are
placed before the word root while naming a particular compound. For example,
if a compound contains more than one functional group, then one of the functional group is regarded as
principal functional group and is treated as secondary suffix. The other functional groups are regarded as
substituents and are indicated by prefixes.

Substituent Prefix Substituent Prefix

−CnH2n+1 Alkyl −NH2 Amino
−F Fluoro −NO Nitroso
−Cl Chloro −N=N− Diazo
−Br Bromo −OCH3 Methoxy
−I Iodo −OC2H5 Ethoxy
−NO2 Nitro −OH Hydroxy

Thus, a complete IUPAC name of an organic compound may be represented as

Prefix + Word root + Primary suffix + Secondary suffix.

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 General Organic Chemistry ( By Jitender sir )
2.4 RULES FOR NAMING OF SATURATED HYDROCARBONS
The following rules are used for naming the branched chain alkanes.
Longest chain rule
Select the longest continuous chain of carbon atoms in the molecule known as parent chain.. If two different
chains of equal length are possible, the chain with maximum number of side chains or alkyl groups is
selected. Eg:
CH3
CH3 CH2
CH2 H3C CH CH2 CH2 CH CH3
CH2 CH2
H3C HC CH2 CH2 CH2 CH3 CH3
4-Methyloctane 3,6-Dimethyloctane

Lowest number rule

Number the carbon atoms in the parent chain as 1, 2, 3… etc. starting from the end which gives lower
number to the carbon atom carrying the substituent.
CH3
H3C CH CH2 CH2 CH2 CH2 CH2 CH3
2-Methyloctane

Lowest set of locants/side chain

When two or more substituents are present, then end of the parent chain, which gives the lowest set of the
locants, is preferred for numbering.
CH3 CH3
H3C CH CH2 CH CH2 CH2 CH2 CH3
2,4-Dimethyloctane

Naming of different substituents

If two or more different substituents or side chains are present in the molecule, they are named in the
alphabetical order along with their appropriate positions. If two different substituents are in equivalent
positions from the two ends of the chain then the numbering of the chain is done in such a way that the
group which comes first in the alphabetical order gets lower number.

CH3
CH3 CH2
H3C CH2 CH CH2 CH2 CH2 CH CH2 CH3
3-Ethyl-7-methylnonane
CH3
CH3 CH2
H3C CH CH CH2 CH2 CH2 CH CH2 CH3
CH3
7-Ethyl-2,3-dimethylnonane

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 General Organic Chemistry ( By Jitender sir )
If there happens to be two chains of equal size, then that chain is to be selected which contains more
number of side chains.
H2C CH3
H3C CH2 CH2 CH2 CH2 CH CH2 CH CH2 CH3

CH2
H3C C CH3
H2C CH3

5-( 2-Ethylbutyl)-3,3-dimethyldecane
2.5.RULES FOR NAMING OF CYCLIC HYDROCARBONS
These compounds contain carbon chain skeletons that are closed to form rings. The saturated hydrocarbons
with ring of carbon atoms in the molecule are called cycloalkanes. These have the general formula, CnH2n.
The cyclic compound is named by prefixing cyclo to the name of the corresponding straight chain alkane.
CH3 CH2CH=CH2 CH2CH2CH2CH3
CH2CH3 CH2CH2CH3

Methyl 1-(Cyclopropyl)
Ethyl Propyl 3-(Cyclopropyl) butane
cyclopropane cyclopropane prop-1-ene
cyclopropane

CH3 H3C CH3

Numbering will
1
start alphabatically 1 More branched carbon
2 2 gets lower number
3
3

CH3
1-Methyl-3-propylcyclohexane 3-Ethyl-1,1-dimethylcyclohexane

2.6. RULES FOR COMPOUNDS CONTAINING DOUBLE AND TRIPLE BONDS

For naming compounds containing double and triple bonds, the following rules are followed:
(i) Select the longest continuous chain containing carbon atoms involving the multiple bonds (double
and/or triple). This gives the parent name of the alkene or alkyne.
(ii) While writing the name of the alkene or alkyne, the suffix ‘ane’ of the corresponding alkane is
replaced by ‘ene’ or ‘yne’ respectively.
(iii)The numbering of atoms in the parent chain is done in such a way that the carbon atom carrying the
multiple bonds gets the lowest number.
CH3
(i) H3C CH2 CH2 CH CH CH3 (ii) H3C CH CH2 CH CH CH3
Hex-2-ene 5-Methylhex-2-ene
(iv) If the multiple bonds occur two or more times in the chain, then it is named as diene or diyne, triene
or triyne, etc.
(i) H2C CH CH CH2 (ii) HC C C CH
Buta-1,3-diene Buta-1,3-diyne

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 General Organic Chemistry ( By Jitender sir )
(v) If the compound contains double and triple bond both, the numbering is done from that end which
gives lowest number to either double or triple bond.

(1) H2C CH CH2 C C CH3 (ii) HC C CH2 CH CH CH3

Hex-1-en-4-yne Hex-4-en-1-yne
(vi) If double and triple bond both gets same number, then preference is given to the double bond for
numbering.
H2C CH CH2 CH2 C CH
Hex-1-en-5-yne

2.7 RULES FOR NAMING ORGANIC COMPOUNDS CONTAINING FUNCTIONAL

GROUPS
The rules for naming an organic compound containing functional groups are exactly same as
discussed already for compounds containing multiple bonds. In this case, the preference of lowest
number is given to carbon atom bearing the functional group. The rules are summarized below:
(i) Select the longest continuous chain containing the carbon atom having functional group.
(ii) The numbering of atoms in the parent chain is done in such a way that carbon atom bearing the
functional group gets the lowest number.
(iii)It two or more same functional groups are present, these are indicated by using di, tri, tetra as
prefixed to the name of the functional group.
(iv) If the organic compound contains a functional group, multiple bond, side chain or substituents, the
following order of preference must be followed,
Functional group > Double bond > Triple bond > Side chain.
(v) When an organic compound contains two or more functional groups, one group is regarded as the
principal functional group and the other group is treated as the secondary functional group, which
may be treated as substituent(s). The following order of preference is used for selecting the principal
functional group,
Carboxylic acids > sulphonic acids > acid anhydrides > esters > acid chlorides > amides
> nitriles > aldehydes > ketones > alcohols > amines > ethers > alkenes > alkynes.
2.8 RULES FOR NAMING AROMATIC COMPOUNDS
(i) When the benzene ring is present as one of the substituent in the carbon chain, it is named as phenyl
group.
(ii) Disubstituted, trisubstituted or tetrasubstituted benzenes are named by using the numbers.
(iii)If different groups are attached to the benzene ring, then the principal functional group is fixed as
number 1. The numbering of the chain is done in any direction (clockwise or anticlockwise), which
gives lowest number to the substituents. The substituents are written in the alphabetical order.
Different classes of functional groups including multiple bonded compounds and the suffix or
prefix required to name these compounds are given in the preferential decreasing order in the
following table.

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 General Organic Chemistry ( By Jitender sir )
Functional Group Naming Prefix/ As alkyl Example

RCOOH Alkan + oic acid carboxy CH3COOH

Carboxylic acid Ethanoic acid

Always come Alkyl alkan+oate Alkoxycarbonyl CH3COOC2H5

first as alkyl Ethyl ethanoate
O
R - C - O-R' CH3COOC6H5
Ester Phenyl ethanoate

RCOCℓ Alkan+oyl chloride Chlorocarbonyl CH3COCI

Ethaoyl chloride
Acid chloride

RCONH2 Alkan+amide Carbamoyl CH3CONH2

Acid amide Ethanamide

RCN Alkane+nitrile Cyano CH3CH2CH2CN

Alkane nitrile Butane nitrile

RCHO Alkan+al Formyl CH3CH2CHO

Aldehyde Propanal

O Alkan+one Keto or oxo CH3COCH3

Propanone
R - C - R'
Ketone
R-CH2-OH Alkan+ol Hydroxy CH3CH2CH2CH2CH2OH
Alcohol Pentan-1-ol

R-NH2 Alkan+amine Amino CH3CH2CH2NH2

Amine
Propanamine

R-O-R’ Alkoxy alkane Alkoxy CH3CH2-O-CH3

Ether Methoxy ethane

*Those functional group are above black line their carbon is taken as first carbon for numbering

Double bond and Triple bond are more prefer over halogens(F,Cl,Br and I) and NO2 groups.

CH2=CH-CH2-Br name is 3-Bromopro-1-ene

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 General Organic Chemistry ( By Jitender sir )

I. Acyclic or open chain compounds

These compounds are also called as aliphatic compounds and consist of straight or branched chain
compounds, for example: Ethane , isobutane etc.
II Cyclic or closed chain or ring compounds
(a) Alicyclic compounds
Alicyclic (aliphatic cyclic) compounds contain carbon atoms joined in the form of a ring (homocyclic).

Sometimes atoms other than carbon are also present in the ring (heterocylic). These exhibit some of the
properties similar to those of aliphatic compounds.eg: Tetrahydrofuran
(b) Aromatic compounds: These include benzene and other related ring compounds (benzenoid). Like
alicyclic compounds, aromatic comounds may also have hetero atom in the ring. Such compounds are called
hetrocyclic aromatic compounds. Some of the examples of various types of aromatic compounds are:

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 General Organic Chemistry ( By Jitender sir )
Some More Example for practice:
1. H3C CH2 CH2 CH2 CH CH2 CH2 CH2 CH2 CH3
CH2
H3C C CH3
CH3
5-(2,2-dimethylpropyl)decane

2. H3C CH2 CH2 CH2 CH CH2 CH2 CH2 CH2 CH3

CH2
H3C C CH3
CH3
5-(2,2-dimethylpropyl)decane
H3C CH3
CH 4. COOH

3. H3C CH2 CH2 CH CH CH2 CH2 CH2 CH2 CH3

CH
H3C CH2 CH3 OHC OCH3
5-Formyl-3-methoxycyclohex-1-ene
5-sec-Butyl-4-isopropyldecane carboxylic acid

Cl NO2
NO2 OCH3
4. 5. 6. Cl
Cl
NO2
CH3
1-Chloro-2,4dinitrobenzene CH3
2-chloro-4-nitrotoluene 2-Chloro-4-methyl Anisole
H3C CH2 CH3

7. H3C CH2 CH C CH2 CH2 CH3

CH3
3-Ethyl-4,4-dimethylheptane

CH3 COOH NO2 COCH3

8. 9. 10. 11.
Benzne carboxylic acid Nitrobenzene 1-Phenylethanone
Methyl benzene ( Benzoic acid) ( Acetophenone)
( Toluene)
CHO COOH CHO OH

12. 13. 14. 15.

Cyclohexanecarbaldehyde Phenol
Benzene carbaldehyde Cyclohexanecarboxylic acid
(Benzaldehyde)

NH2 Br OCH3 N=N-Cl

16. 17. 18. 19.

Aniline Bromobenzene Anisole ( Methoxybenzene) Benzene diazonium chloride
Aminobenzene or Benzenamine

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 General Organic Chemistry ( By Jitender sir )
For those functionalities, which have two prefixes and/or suffixes, the first one is used when carbon atom
of the functional group is not a part of the longest continuous chain and the second one is used, when
carbon atom is counted in the longest chain.
Let us see the application of these IUPAC rules to some organic compounds.
C 2H 5
1
2
(i) 3
1−Ethyl−4−methylcyclohaxane
4

CH3

O
(ii) CH3CH2CH2−C−CH2Cl 1−chloropentan−2−one
5 4 3 2 1

(iii) (CH3)3C-OH 2-Methyl propan-2-ol

OHC-CH2CH2-CH−CH2-CHO
(iv) CH2CHO 3−(Formylmethyl)hexanedial

4 3 2 1
OHC-CH2CH2CH−CH2CHO
(v) Butane−1,2,4−tricarbaldehyde
CHO

COOH
(vi) HOOC- CH2-CH-CH2-COOH Propane-1,2,3-tricarboxylic acid

NCCH2CH2CH2CH−CH2CH2CN
(vii) Hexane−1,3,6−tricarbonitrile
CN

O
(ix) CH3−C−CH2CH2CH2CO2H 5−Oxohexanoic acid
6 5 4 3 2 1

O O
(x) CH3CH2−C−CH2−C−CH3 Hexane−2,4−dione
6 4 2 5 3 1

(xi) CH2=CHCH2CH(OH)CH3 Pent−4−en−2−ol

NO2 OH
3 1
2 2
(xii) 3−Nitrocyclohexene (xiv) Cyclohex−2−en−1−ol
1 3

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 General Organic Chemistry ( By Jitender sir )

Check your knowledge

CN O OCH3 NH2
i) CH3-CH-CH2-C-CH2-COOH (ii) OHC-CH2-CH-CH2-CH-COOC2H5
5-Cyano-3-oxohexanoic acid Ethyl-2-amino-5-formyl-4-methoxypentanoate

OH Br
iii) NC-CH2-CH2-CH2-CHO (iv) CH3-CH-CH=CH-CH-COCI
2-Bromo-5-hydroxyhex-3-enoyl chloride
4-Formylbutanenitrile

COCI C2H5 C2H5 COOH

v) CH3-CH=CH-CH-CH2-CH-COOH (vi) CH3-CH-CH2-CH-CH2-CH3
2-Ethyl-4(chlorocarbonyl)hept-5-enoic acid 2-Ethyl-4-methylhexanoic acid

CH2-COOH O O
(vii) (viii)

2-Cyclohexyl ethanoic acid 3-Methylpentane-2,4-dione

COOC2H5
O
(ix) CH3-CH2-CH2-C-O- (x)

EthylBenzoate
Phenylbutanoate

CH=CH2 CHO
(xi) (xii)
CH2=CH-CH2-CH-CH2-CH=CH2 HOOC-CH2-CH-CH2-COOH
4-Ethenylhepta-1,6-diene 3-Formylpentane-1,5-dioic acid
OH
C2H5 Br
CH-CH2-COOH
CH3-CH-CH2-CH-CH2-CH2-CH=CH2 (xiv)

5-Bromo-7-methylnon-1-ene
3-Hydroxy-3-phenylpropanoic acid

(xv) H2C CH3

H3C CH2 CH2 CH2 CH2 CH CH2 CH CH2 CH3

CH2
H3C C CH3
5-( 2-Ethylbutyl)-3,3-dimethyldecane
H2C CH3

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 General Organic Chemistry ( By Jitender sir )

ISOMERISM IN ORGANIC COMPOUNDS

Compounds with same molecular formula but different structural formula so different physical and
chemical properties.
1. Structural isomerism (constitutional isomerism) (2) Stereo isomerism
STRUCTURAL ISOMERISM
The structural isomers have the same molecular formula but different structural formulae. The
structural isomers usually show different physical and chemical properties. The structural
isomerism is further divided into:
(a) Chain isomerism (b) Positional isomerism (c) Functional isomerism
(d) Metamerism (e)Tautomerism

CHAIN ISOMERISM
The chain isomers have same molecular formula but different types of chains ( or different number of
carbon atoms in a chain ) i.e., linear and branched. e.g. Threechain isomers possible with the
molecular formula, C5H12

CH3 CH3
CH3-CH2CH2CH2CH3 CH3-CH-CH2-CH3 CH3- C- CH3
CH3
n-Pentane 2-Methylbutane 2,2-Dimethylpropane

POSITIONAL ISOMERISM
Compound which have same molecular formula but different positions of side chains, substituents,
functional groups, double bonds, triple bonds etc., on the parent chain. e.g.
C3H7Cl. These isomers arise due to difference in the position of the chloro group on the main chain.

2) but-1-ene and but-2-ene the position of double is different but they have same molecular formula,
C4H8.

3) The functional group, -OH is at different positions on the main chain of the following alcohols. They
have the same molecular formula, C3H7OH.

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 General Organic Chemistry ( By Jitender sir )

FUNCTIONAL ISOMERISM
The functional isomers have the same molecular formula but possess different functional groups.
The functional isomers show different physical as well as chemical properties. e.g.
1) Ether is the functional isomer of alcohol. Both have the same molecular formula, C2H6O. However
they have different functional groups.

2) aldehyde is a functional isomer of ketone.

3) Carboxylic acid and ester are also functional isomers.

METAMERISM :
The metamerism arises when different alkyl groups are attached around the functional group. E.g.

2) The metamerism is also possible in amines as shown below.

TAUTOMERISM :
Tautomerism refers to the dynamic equilibrium between two compounds with same molecular formula ,
migration of hydrogen takes place from 1st positon to 3rd position .

It is very important to note that the tautomers are not the resonance structures of same compound.

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 General Organic Chemistry ( By Jitender sir )
STEREOISOMERISM IN ORGANIC COMPOUNDS
The isomerism which arises due to different spatial arrangements of atoms or groups is called stereo
isomerism. It is broadly divided into:
1. Geometrical isomerism 2. Optical isomerism 3. Conformational isomerism
The stereo isomers have same structural formula i.e., same connectivity order between atoms. However
the atoms or groups are arranged differently in space.

GEOMETRICAL ISOMERISM
The geometrical isomerism arises when atoms or groups are arranged differently in space due to
restricted rotation of a bond or bonds in a molecule. e.g.
There are two necessary conditions for a compound to possess geometrical isomerism:
(i) It must contain a carbon-carbon double bond in the molecule.
(ii) Two unlike atoms or groups must be linked to each doubly bonded carbon atoms.
➢ Terminal alkenes ( Alk-1-ene) never shows geometrical isomerism. Eg: Prop-1-ene, But-1-ene.
Cis-isomer Trans- isomer
1. HC CH HC H
3 3 3
C C C C
H H H CH3
2. similar groups are present on the same side Similar group are present diagonally to each other
of the double bond. of the double bond.
3. Possess high boiling point Possess low boiling point
4. Possess low melting point Possess high melting point
5. Less stability due to steric hindrance More stable due to lack of steric hindrance
6. Polar in nature Nonpolar in nature
7. Dipole moment = 0
Dipole moment = 0

Electrophiles Nucleophiles
a) Electron loving species a) Nucleus loving species
b) all positively charged species b) AII negative charged species
eg: H+, CI+, CH3+, NO2+ etc. eg: OH─, CN─, CI─ etc.
c) all Lewis acid. eg: BF3, AICI3 etc. c) all Lewis base. eg: NH3, H2O, ROH etc.
e) Electron deficient e) Electron rich

Electron withdrawing group (following –Inductive effect)

NO2 > CN > CHO > COOH > CONH2 > F > Cl > Br > I > OH > OR > C6H5
EWG: responsible for INCREASE in acidic nature
Electron donating group (following + Inductive effect )
All alkyls and alkoxy are good electron donating group, larger the size of alkyl group higher is the
EDG Eg :
H < D < CH3─ < C2H5 ─ < (CH3)2CH─ < (CH3)3C─ etc
EDG: responsible for DECREASE in acidic nature.

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 General Organic Chemistry ( By Jitender sir )

Inductive Effect
The polarization of a σ bond due to electron withdrawing or electron donating effect of
adjacent groups or atoms is called inductive effect.

Salient features of inductive effect:

* It arises due to electronegativity difference between two atoms forming a sigma bond.
* It is transmitted through the sigma bonds.
* The magnitude of inductive effect decreases while moving away from the groups causing it.
* It is a permanent effect.
* It influences the chemical and physical properties of compounds. ( acidic , basic and reactivity )

TYPES OF INDUCTIVE EFFECT

The inductive effect is divided into two types:
1) Negative inductive effect (-I effect): (Increase the acidic strength of molecule)
The ( EWG) electron withdrawing groups or atoms when attach to any Carbon atom of any
compound/ molecule then these group will create a effect which is known as negative inductive effect.
It is indicated by ─ I. Examples of groups in the decreasing order of their ─ I effect:
NO2 > CN > CHO > COOH > CONH2 > F > Cl > Br > I > OH > OR > C6H5

2) Positive inductive effect (+I effect): (decrease the acidic strength of molecule)
The ( EDG) electron donating groups or atoms when attach to any carbon atom of any compound /
molecule then these group create a effect which is known as positive inductive effect and it is denoted
by +I. examples of groups in the decreasing order of their +I effect.
(CH3)3 C─ > (CH3)2CH─ > CH2CH3 ─ > CH3─ > D > H

Arrange the following compound according to their acidic strength?

i) CH3COOH < Cl-CH2COOH
ii) Cl-CH2COOH < O2N-CH2COOH
iii) NO2CH2COOH < Cl3C-COOH
iv) F-CH2CH2CH2COOH < CH3CHFCH2COOH < CH3CH2CHFCOOH
v) 3oAlcohol < 2oAlcohol < 1oAlcohol
vi)

(vii) Basic Strength : R-NH2 < R2-NH < R3N

Q. In which C–C bond of CH3CH2CH2Br, the inductive effect is expected to be the least?
Ans) Magnitude of inductive effect diminishes as the number of intervening bonds increases. Hence, the
effect is least in the bond between carbon-3 and hydrogen.

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 General Organic Chemistry ( By Jitender sir )

Q) Why alkyl groups are showing positive inductive effect?

Though the C-H bond is practically considered as non-polar, there is partial positive charge on hydrogen
atom and partial negative charge on carbon atom. Therefore, each hydrogen atom acts as electron
donating group. This cumulative donation turns the alkyl moiety into an electron donating group.

Q)What do you mean by Electromeric effect ?

Ans) It is defined as the complete transfer of a shared pair of π-electrons to one of the atoms joined by a
multiple bond on the demand of an attacking reagent. The effect is annulled as soon as the attacking
reagent is removed from the domain of the reaction.
Positive Eelctromeric Effect (+E effect): (Electrophilic addition in alkene / alkyne)
In this effect the π−electrons of the multiple bond (C to C as in alkene and alkynes) are transferred to
that atom to which the reagent gets attached.e.g.
CH3 H
CH3 H CH3 + − H
C=C + H+ ⎯→ C−C + H+ ⎯→ H−C−C−H
H H H H +
H
Isopropyl carbonium ion
(+ E effect)
Negative Electromeric Effect (–E effect): (Nucleophilic addition in aldehyde / ketones)
In this effect the π - electrons of the multiple bond are transferred to more electronegative atom
( O,N,S) joined by multiple bonds

C = O + CN− ⎯→ C−O− (−E effect)

CN

In an organic reaction, the organic molecule reacts with an appropriate attacking reagent and
leads to the formation of one or more intermediate(s) and finally product(s) is called substrate.
The general reaction is depicted as follows:
Attacking Reagent
Organic molecule Intermediate Product (s) + By Product
( Substrate)
Eg: CH3-CH2-Br + aq. KOH CH3-CH2-OH + KBr
H
H H H
- -
HO + H C Br
HO C Br
HO C H + Br

H H weaker
H nucleophile
Bromomethane Methanol
(dextrorotary) (leavorotatory)

A sequential account of each step, describing details of electron movement, energetics during
bond cleavage and bond formation, and the rates of transformation of reactants into products
(kinetics) is referred to as reaction mechanism.

Attacking Reagent → Electrophile Nucleophile Free radical

Substrate intermediate → Carbanion Carbocation Free radical

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 General Organic Chemistry ( By Jitender sir )
Any Substrate to Reaction Intermediate created by:
(i) Heterolytic cleavage, (ii) Homolytic cleavage.
(i) Heterolytic cleavage:
(a) the bond breaks in such a fashion that the shared pair of electrons remains with one of the
fragments. Eg: Carbocation
Carbocation:
These are the species having trivalent carbon bearing positive
charge and surrounded by six electrons.
Types and Stability Order of carbocation:
CH3 H
CH3
CH3-C > CH3-C > CH3-C
CH3 H H

( 3o) (2 o) (1 o)
(b) The heterolytic cleavage can also give a species in which carbon gets the shared pair of electrons.
Such a carbon species carrying a negative charge on carbon atom is called carbanion.
Carbanion: Sp3
These are the species having trivalent carbon atom bearing negative
charge and surrounded by octet of electrons.
CH3 H
Stability Order : CH3
CH3-C < CH3-C < CH3-C
CH3 H H

( 3o) (2o) (1o)

homolytic cleavage
One of the electrons of the shared pair in a covalent bond goes with each of the bonded atoms. Thus,
in homolytic cleavage, the movement of a single electron takes place instead of an electron pair. The
single electron movement is shown by ‘half-headed’ curved arrow. Such cleavage results
in the formation of neutral species (atom or group) which contains an unpaired electron. These species
are called free radicals.

Free radicals
Trivalent carbon carry six bonded electron and a
unshared electron
❖ stability of free radicals increases with
increase in the number of alkyl groups.
Thus the stability of different free radicals is:

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 General Organic Chemistry ( By Jitender sir )
Problem 12.11 Using curved-arrow notation, show the formation of reactive intermediates when the
following covalent bonds undergo heterolytic cleavage.
(a) CH3–SCH3 (b) CH3–CN (c) CH3–Cu
Ans: (a) CH3 SCH3 CH3 + SCH3

Question 12.16: For the following bond cleavages, use curved-arrows to show the
electron flow and classify each as homolysis or heterolysis. Identify reactive intermediate
produced as free radical, carbocation and carbanion.
(a) CH3O OCH3 CH3O + OCH3 ( Homolytic cleavage / intermediate is Free radical)

(b) C =O + OH C =O + H2O ( Heterolytic cleavage / intermediate is carbanion)

(c) + Br ( Heterolytic cleavage / intermediate is carbocation)

Br

(d) E
( Heterolytic cleavage / intermediate is carbocation
+ E

RESONANCE EFFECT OR MESOMERIC EFFECT

The resonance effect is defined as ‘the polarity 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.
Positive resonance or mesomeric effect (+M or +R):

In this effect, the transfer of electrons is away from an atom or substituent group attached to
the conjugated system. This electron displacement makes certain positions in the molecule of
high electron densities. These groups are having by +M or +R effect in aromatic compounds.
e.g. -OH, -OR, -NH2, etc.
❖ ( +Ve resonance responsible for ortho / para directing of aromatic compounds)

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 General Organic Chemistry ( By Jitender sir )
Negative resonance or mesomeric effect :( -R or -M effect)

H O H O− H O− O− H O
H
C C C C C
 

This effect is observed when the transfer of electrons is towards the atom or substituent
group attached to the conjugated system are denoted by -M or -R. The electron density on
rest of the molecular entity is decreased due to this effect.e.g. -NO2, -C≡N, -COOH etc.
❖ -ve resonance responsible for meta directing of aromatic compounds.

Resonance energy: Difference in energy between the actual structure and the lowest
energy resonance structure is called the resonance stabilization energy or simply the
resonance energy

Q. Give the resonance in (i) nitromethane (ii) Acetate ion?

What do you mean by Hyperconjugation effect or No bond resonance?

Ans) The delocalization of σ-electrons or lone pair of electrons into adjacent π-orbital
or p-orbital is called hyperconjugation.
H H H H H H H H
H C C=C H C=C C H C=C C H C=C C
H H H H H H H H H H HH
It occurs due to overlapping of σ-bonding orbital or the orbital containing a lone pair with
adjacent π-orbital or p-orbital.

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 General Organic Chemistry ( By Jitender sir )
Conditions for hyperconjugation:
* There must be an α-hydrogen should present with sp2 hybrid carbon or other atoms.

CONSEQUENCES & APPLICATIONS OF HYPERCONJUGATION

1) Stability of alkenes:
those alkenes carry more number of alpha hydrogens they are more stable.
For example, 2-butene is more stable than 1-butene. This is because in 2-butene, there are
six alpha hydrogens involved in hyperconjugation whereas there are only two alpha
hydrogens involved in case
The increasing order of stability of alkenes with increases in the number of methyl groups on
the double bond is depicted below.

From the above diagram, it can be seen clearly that the electron density on benzene ring is
increased especially at ortho and para positions. Since the hyperconjugation overpowers the
inductive effect

Q13) Why (CH3)3C+ is more stable thanCH3CH2+ andCH3+ is the least stable cation.
Ans) Hyperconjugation interaction in (CH3)3C+ is greater than inCH3 CH2+ as the(CH3)3C+ has
nine C-H bonds. InCH3+ , vacant p orbital is perpendicular to the plane in which C-H bonds lie;
hence cannot overlap with it. Thus, CH3+ lacks hyper conjugative stability.

Q. Why O2NCH2CH2O– is expected to be more stable than CH3CH2O─ . Explain?

Answer: NO2 group is an electron-withdrawing group. Hence, it shows –I effect. By withdrawing the
electrons toward it, the NO2 group decreases the negative charge on the compound, thereby stabilizing it.
On the other hand, ethyl group is an electron-releasing group. Hence, the ethyl group shows +I effect.
This increases the negative charge on the compound, thereby destabilizing it.

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 General Organic Chemistry ( By Jitender sir )
Types of reaction
(A) Nucleophilic substitution:
𝐴𝑞𝑢𝑒𝑜𝑢 𝑠 𝐾𝑂𝐻
(i) CH3 − CH2 − X → CH3 − CH2 − OH + KX Where X= Cℓ , Br , I

CH 4 + Br2 ⎯⎯
hv
→ CH 3 -Br + HBr
(B)Free radical substitution:
Methane Bromomethane
(C) Addition reaction:
OH
+
(i) H3C CH CH2 + H+-OH
- H H3C CH CH3
prop-1-ene propan-2-ol
Br

(ii) H3C CH CH2 + H+-Br

- H+ H3C CH CH3
prop-1-ene 2-Bromopropane
(D) Elimination reaction:
β α
(i) CH3 -CH2 - X ⎯⎯⎯→
alc.KOH
CH2 =CH2 + H2O + KBr (X=Cl,Br,I)
Haloalkane Ethene
Br
alc. KOH
(ii) H3C CH2 CH CH3 H3C CH CH CH3 + H3C CH2 CH CH2

2-bromobutane Saytzeff `s But-2-ene But-1-ene

rule (80% stable) (20%stable)
OH
Conc. H2SO4 / 443K H3C CH CH2
(iii) H3C CH CH3 + H2O
Dehydration prop-1-ene
propan-2-ol

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 General Organic Chemistry ( By Jitender sir )
Check your knowledge
1. Write the structural formula of:
(a) o-Ethylanisole, (b) p-Nitroaniline, (c) 2,3 - Dibromo -1 - phenylpentane,
(d) 4-Ethyl-1-fluoro-2-nitrobenzene.
2. For each of the following compounds, write a condensed formula and their bond-line formula.
(a) HOCH2CH2CH2CH(CH3)CH(CH3)CH3
OH
(b)
N C- CH-C N

3. Write IUPAC names of the following compounds:

(i) (CH3)3CCH2C(CH3)3 (ii) (CH3)2C(C2H5)2 (iii) tetra – tert-butylmethane
4. Which bond is more polar in the following pairs of molecules: (a) H3C-H, H3C-Br
(b) H3C-NH2, H3C-OH (c) H3C-OH, H3C-SH
Solution: (a) C–Br, since Br is more electronegative than H, (b) C–O, (c) C–O
5. Draw the resonance structure of (i) Nitromethane (ii) Acetate ion( CH3COO-).
6. What are hybridisation states of each carbon atom in the following compounds?
CH2=C=O, CH3CH=CH2, (CH3)2CO, CH2=CHCN, C6H6
7. Indicate the σ- and π- bonds in the following molecules :
C6H6, C6H12, CH2Cl2, CH2=C=CH2, CH3NO2, HCONHCH3
8. Write bond line formulas for: Isopropyl alcohol, 2,3-Dimethylbutanal, Heptan-4-one.
9. Which of the following represents the correct IUPAC name for the compounds concerned?
(a) 2,2-Dimethylpentane or 2-Dimethylpentane (b) 2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane
(c) 2-Chloro-4-methylpentane or 4-Chloro-2-methylpentane (d) But-3-yn-1-ol or But-4-ol-1-yne.
10. Draw formulas for the first five members of each homologous series beginning
with the following compounds. (a) H–COOH (b) CH3COCH3 (c) H–CH=CH2
11. Give condensed and bond line structural formulas and identify the functional group(s) present, if
any, for :
(a) 2,2,4-Trimethylpentane (b) 2-Hydroxy-1,2,3-propanetricarboxylic acid (c) Hexanedial
12. Classify the following reactions in one of the reaction type studied in this unit.
a) CH 3CH2Br + HS− → CH3 CH2 SH →Nucleophilic substitution
b) (CH3)2 C = CH2 + HCl → (CH3)2C(Cl )CH3 → Addition reaction
c) CH 3CH2 Br + HO− → CH2= CH2 + H2O → Elimination reaction

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 General Organic Chemistry ( By Jitender sir )
Worksheet for self-practice:
CN O OCH3 NH2
(1) CH3-CH-CH2-C-CH2-COOH (2) OHC-CH2-CH-CH2-CH-COOC2H5

OH Br
(3) NC-CH2-CH2-CH2-CHO (4) CH3-CH-CH=CH-CH-COCI

COCI C2H5 C2H5 COOH

(5) CH3-CH=CH-CH-CH2-CH-COOH (6) CH3-CH-CH2-CH-CH2-CH3

CH=CH2 CHO
(7) (8)
CH2=CH-CH2-CH-CH2-CH=CH2 HOOC-CH2-CH-CH2-COOH

OH
C2H5 Br
CH-CH2-COOH
(9) CH3-CH-CH2-CH-CH2-CH2-CH=CH2 (10)

H2C CH3

(11) H3C CH2 CH2 CH2 CH2 CH CH2 CH CH2 CH3

CH2
H3C C CH3
H2C CH3

(12) Br-CH2-CH=CH2 (13) HO-CH2-(CH2)3-CH2-CO-CH3

OCH3
Cl
(14) OHC-CH2-CN (15)

CH3
NH2
(16) CH3 O
(17) CH3-CH=CH-C-CH2-COOC2H5

C2H5

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 General Organic Chemistry ( By Jitender sir )
Academic window
S.No. Question Details Marks
1. Identify the type of organic reaction mechanism in each case: 1
a. R-X + OH- → R-OH + X-
b. Bromoethane to ethene
2. How many primary carbons are there in the following hydrocarbon? 1

3. Write bond line formula for Tert-butyl cyclopentane.

4. Explain the following. 2
a. (CH3) 3C+ is more stable than CH3CH2+ and CH3+
b. Chloro ethanoic acid is stronger than ethanoic acid.
5. a) Name the chain isomers of C5H12 which has a tertiary hydrogen atom. 2
b) Why is sp hybrid orbital more electronegative than sp2 or sp3 hybridized orbitals?
6. Draw the two geometrical isomers of, but – 2 – en – 1, 4 dioic acid. Which of these will 2
have higher dipole moment?
7. Write the resonance structures of- (a) CH3NO2 (b) CH3COO- 2
8. Draw the orbital diagram showing hyperconjugation in ethyl cation. 3
9. Write structural formulae of the following compounds 3
(a) 3 – Hexenoic acid (b) 4 – Nitropent - 1 – yne (c) 2 – Formylbut – 3 - enenitrile
10. What is resonance? Draw the resonating structures for the following molecules showing 3
electron shift using curved arrow notation. a) Phenol b) Benzyl carbocation.
11. Identify the type of isomerism exhibited by the following compounds. 3
a)Butane b) Pentene c) C3H6O
12. Draw resonance structures for NO2+ and find the structure with lowest energy? 3
What are the different types of reaction intermediates formed by homolytic and heterolytic
fission of a covalent bond? Explain with examples.
13. 3

14. 5

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