CONTENT

CONTENT
CONTENT

TOPIC PAGE No.

1 IUPAC NOMENCLATURE & STRUCTURAL ISOMERISM

1.1 Theory 01-32

1.2 Exercise 33-49

1.3 Answer Key 50-53

2 STRUCTURAL IDENTIFICATION

2.1 Theory 54-71

2.2 Exercise 72-84

2.3 Answer Key 85-86

3 GENERAL ORGANIC CHEMISTRY-I

3.1 Theory 87-96

3.2 Exercise 97-110

3.3 Answer Key 111-112

4 GENERAL ORGANIC CHEMISTRY-II

4.1 Theory 113-129

4.2 Exercise 130-145

4.3 Answer Key 146-147

 IUPAC & Structural Isomerism

IUPAC Nomenclature & Structural Isomerism

Bonding in organic compounds :
Two types of covalent bond exist in organic compounds.
(a) Sigma bond () : The covalent bond formed between 2 atoms by mutual sharing of 1 pair of e– . It is
denoted by (–).
Ex. In CH4 molecule In C2H6 molecule

(b) Multiple bond () : Any other bond with  bond is  bond.
Ex. (i) In ethene molecule (ii) In ethyne molecule

Total  = 5 Total  = 3
= 1 = 2

Illustration 1: Calculate number of  and  bond in following compounds.

(a) HC  CCH=CHCH3 (b) CH2 = C = CHCH3
Solution (a) C–C 4C–H : 6 ; C=C : 1 ; CC : 2 (b) C–C 3C–H : 6 ; C=C : 2

Some important definitions :

(i) Catenation : The property of atoms of an element to link with one another forming chains of identical
atoms is called catenation.
(ii) Homologous series : Homologous series may be defined as a series of similarly constituted compounds
in which the members possess the same functional group, have similar chemical characteristics and have
a regular gradation in their physical properties. The two consecutive members differ in their molecular
formula by CH2.
Structural representation of organic compounds :
There are three ways for representation of organic compounds :
(i) Complete structural formula :- Such a structural formula focuses on the electrons involved in bond
formation. A single dash (–) represents a single bond, double dash (=) is used for double bond and a triple
dash () represents triple bond. Lone- pairs of electrons on heteroatoms (e.g., oxygen, nitrogen, sulphur,
halogens etc.) may or may not be shown.
(ii) Condensed structural formula : Structural formulas can be further abbreviated by omitting some or
all of the dashes representing covalent bonds and by indicating the number of identical groups attached
to an atom by a subscript. The resulting expression of the compound is called a condensed structural
formula.
(iii) Bond line formula :- In this formula , 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.

1
 IUPAC & Structural Isomerism

Illustration 2: Expand each of the following condensed formulas into their complete structural formulas.
(a) CH3CH2 COCH2CH3 (b) CH3CH=CH(CH2 )3CH3

Solution (a) (b)

Illustration 3: For each of the following compounds,write a condensed formula and also their bond-line formula.

(a) HOCH 2 CH2CH2CH(CH3)CH(CH3 )CH3 (b)

Sol. Condensed formula : Bond-line formula :

(a) HO(CH2)3CH(CH3 )CH(CH3 )2

(b) HOCH(CN)2

Degree of Carbon and Hydrogen: There are four types of carbon atoms :
A primary (1°) carbon atom is bonded to one other carbon atom.
A secondary (2°) carbon atom is bonded to two other carbon atoms.
A tertiary (3°) carbon atom is bonded to three other carbon atoms.
A quaternary (4°) carbon atom is bonded to four other carbon atoms.

Degree of hydrogen is decided by the carbon to which hydrogen is attached e.g. hydrogen atom bonded
to primary carbon atom is primary hydrogen.
Ex. o
1 Number of 1o C =5 Number of 1o H = 15
o
CH3
o o
Number of 2o C =1 Number of 2o H = 2
1 3 2 4 1
o o

CH3 CH CH2 C CH3

1
o
1
o(Iso-octane) Number of 3o C =1 Number of 3o H = 1
CH3 CH3
Number of 4o C =1
Note:Carbon of CH4 is known as super primary carbon

2
 Organic Compound
Classification of Organic Compounds:

Open Chain/ Acyclic/ Aliphatic Compound Closed Chain/ Cyclic Compound

3
Saturated Compound Unsaturated Compound Homocyclic Compound Heterocycl ic Compound
Ex. CH 4 , C2H6 , C 4H 10 Ex. H2 C= CH2 , HC CH

Ali cyclic Compound Aromati c Compound Alicyclic Compound Aromatic Compound

Ex. Ex.
Ex.
, , o N
, N
, O

BenzenoidAromatic Compound Non-benzenoid Arom atic Compound

NH2 OH
IUPAC & Structural Isomerism

Ex. Ex. (Cyclopropenyl cation)

, , ,
 IUPAC & Structural Isomerism
Organic compounds and functional groups
Number of known organic compounds is much more than inorganic compounds but, it has been possible to
group them into classes or families based on their structural features. This has given organic chemistry a
logical and systematic shape. Examples are as follows :

Alkanes [general formula CnH2n + 2 where n = 1, 2, 3, ............]

These are open–chain aliphatic saturated hydrocarbon which have no functional groups. These are also
called paraffins.

n = 1  CH4 – Methane n = 2  C2H6 – Ethane

n = 3  CH3CH2CH3 – Propane n = 4  CH3CH2CH2CH3 – Butane

n = 5  CH3CH2CH2CH2CH3 – Pentane n = 10  CH3(CH2)8CH3 – Decane

Alkenes [general formula CnH2n where n = 2, 3, ............]

Alkenes are open chain unsaturated hydrocarbons and having carbon–carbon double bonds (C = C).
These are also called alkylenes or olefins. The first three members are generally named by their common
names.
CH3
|
Ex. CH2 = CH2 CH3 – CH = CH2 CH3 – CH2 – CH = CH2 CH3  C  CH2
ethylene propylene butylene Isobutylene

Alkynes [general formula CnH2n–2 where n = 2, 3, ............]

Unsaturated aliphatic hydrocarbons containing a carbon–carbon triple bond are called alkynes.
The common names of a few simple alkynes are given below.
CHCH – Acetylene
CH3 –CCH – Methyl acetylene
CH3–CH2–CCH – Ethylacetylene
CH3 –CC–CH(CH3 )2 – Methyl isopropyl acetylene

Some names of hydrocarbon groups

(1) Alkyl, Alkenyl & Alkynyl groups
H
Alkane (CnH2n+2) 
 Alk + yl (CnH2n+1)
H
Alkene (CnH2n) 
 Alken + yl (CnH2n–1)
H
Alkyne (CnH2n–2) 
 Alkyn + yl (CnH2n–3)

methane  methyl

– ane  CH   CH3 
–H
Ex.  yl  4


– ane
propane  propyl  C H   C 3H7 
–H
 yl  3 8 
remove H
CH2 = CH2    –CH=CH2 (vinyl group)/ethenyl.

4
 IUPAC & Structural Isomerism
H
HCCH 
 HCC– (Ethynyl)
H
H3 C–CCH 
 H3C–CC– (propynyl)

(2) Normal (n): Radical or hydrocarbon which has straight chain (having only primary and secondary
carbon) and if it has free valency it must be present at either of ends.
C – C – C – C (n butane)
CH3
|
(3) Iso group : A compound having  CH  CH3 group is named as iso.

Ex. CH3  CH  CH3  CH  CH2  CH3  CH  CH2  CH2 – CH3  CH  CH2  CH3
| | | |
CH3 CH3 CH3 CH3

Iso propyl Iso butyl isopentyl Iso pentane

Exception : Isooctane

 CH3 
 
 | 
(4) Neo group : A compound having  CH3  C  CH2  group is named as neo.
 | 
 CH 
 3 
CH3 CH3 CH 3 CH3
| | | |
Ex. CH3  C  CH2 – CH3  C  CH2  CH2 – CH 3  C  CH 3 CH3  C  CH2  CH3
|
| | |
CH3
CH3 CH 3 CH3
Neopentyl Neohexyl Neopentane Neohexane

Illustration 4:
[1o H ]
CH2 CH2 CH3
CH3 CH2 CH3 (propane) (n–propyl)
[ 2 o H ]
CH3 CH CH3


(iso propyl)
 [1o H ]
CH3 CH2 CH2 CH2
CH3 CH2 CH2 CH3 (n–butane) (n–butyl)
[2 o H ]
CH3 CH2 CH CH3


(secondary butyl)
 [1o H]
CH 3 CH  CH 2  (isobutyl)


CH 3
CH 3 CH  CH 3 (isobutane)


CH 3 CH 3
 

 [3o H]
CH 3 C  ( tertiary butyl)
CH 3
CH 3 CH 3
 

 

 [ H]
CH 3 C  CH 3 (neo - pentane)   CH 3  C  CH 2 (neo pentyl)
CH 3 CH 3

5
 IUPAC & Structural Isomerism
Functional group and residue
The characteristic group of atom which decide the physical and chemical properties of an organic molecule
is called functional group.
Functional group is that portion of molecule which is highly reactive and takes part in chemical reactions.
Rest of the molecule is called Residue.
Ex. CH3 CH2CH2CH2 – COOH

Residue Functional Group

IUPAC system of nomenclature

The IUPAC name of any organic compound consists of maximum five parts in the following sequence.
Secondary prefix + Primary prefix + Word root + Primary suffix + Secondary suffix

(1) Word root :

It is the basic unit of the name. It denotes the number of carbon atoms present in the principal chain (the
longest possible continuous chain of carbon atoms including the functional group and based upon the common
names of alkanes) of the organic molecules.

No. of carbon No. of carbon No. of carbon

Word root Word root Word root
atoms in atoms in atoms in
(Alk) (Alk) (Alk)
parent chain parent chain parent chain
1 Meth 9 Non 20 Icos
2 Eth 10 Dec 30 Triacont
3 Prop 11 Undec 40 Tetracont
4 But 12 Dodec 50 Pentacont
5 Pent 13 Tridec 60 Hexacont
6 Hex 14 Tetradec 70 Heptacont
7 Hept 15 Pentadec 80 Octacont
8 Oct 16 Hexadeca 100 Cent & Hect

(2) Primary Suffix.

A primary suffix is always added to the word root to indicate whether the carbon chain is saturated or
unsaturated. The three basic primary suffixes are given below :

Type of carbon chain Primary suffix General name

(a) Saturated – ane Alkane

(b) Unsaturated with one double bond – ene Alkene

(c) Unsaturated with one triple bond – yne Alkyne

If the parent carbon chain contains two, three or more double or triple bonds, numerical prefix such as di
(for two), tri (for three), tetra (for four) etc. are added to the primary suffix. For example,

Type of carbon chain Primary suffix General name

(a) Unsaturated with two double bonds (a) diene Alkadiene

(b) Unsaturated with two triple bonds (a) diyne Alkadiyne

(c) Both double and triple bonds enyne Alkenyne

(3) Secondary suffix :

A secondary suffix is then added to the primary suffix to indicate the nature of the functional group present
in the organic compounds. Secondary suffix of important functional groups are given below in their decreasing
order of seniority.
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 IUPAC & Structural Isomerism
Class Name Suffix Prefix
– oic acid (carboxylic
1. R – COOH Alkanoic Acid Carboxy
acid)
2. R – SO3H Alkane sulphonic Acid – sulphonic acid sulpho
R–C–O–C–R – oic anhydride
3. || || Alkanonic Anhydride (carboxylic ------------
O O anhydride)
alkoxy carbonyl
4. R – COOR Alkyl alkanoate – oate (carboxylate)
or alkanoyl oxy
R–C–X
–oyl halide (carbonyl
5. || Alkanoyl halide halo carbonyl
halide)
O
R – C – NH2
– amide
6. || Alkanamide carbamoyl
(carboxamide)
O
7. R–CN Alkanenitrile – nitrile (carbonitrile) cyano
R–C–H
8. || Alkanal – al (carbaldehyde) formyl / oxo
O
R–C–R
9. || Alkanone – one oxo
O
10. R – OH Alkanol – ol hydroxy
11. R – SH Alkanethiol – thiol mercapto
12. R – NH2 Alkanamine – amine amino

The following examples illustrate the use of word root, primary suffix and secondary suffix in naming of
organic compounds.
Organic compounds Word root Primary suffix Secondary suffix IUPAC name

CH3CH2 OH Eth an(e) ol Ethanol

CH3CH2 CH 2NH2 Prop an(e) amine Propanamine

CH3CH2 CH 2COOH But an(e) oic acid Butanoic acid

CH3CH2 CN Prop an(e) nitrile Propanenitrile

CH2 = CHCHO Prop en(e) al Propenal

HC  CCOOH Prop yn(e) oic acid Propynoic acid

(4) Primary prefix :

A primary prefix is used simply to distinguish cyclic from acyclic compounds.
For example, in case of carbocyclic compounds, (cyclic compounds containing only carbon atoms in the
ring), a primary prefix, cyclo is used immediately before the word root. Thus,
Ex. A primary prefix (cyclo) is used for cyclic for compounds.
CH2 CH2 Cyclo ane
+ but + = Cyclobutane
Ex.
CH2 CH2 Primary pref ix Word root Primary Suff ix IUPAC name
If the prefix cyclo is not used, it simply indicates that the compound is acyclic or open chain.

(5) Secondary prefix :

In IUPAC system of nomenclature, certain groups are not considered as functional groups but are treated
as substituents. These are called secondary prefixes and are added immediately before the word root (or
the primary prefix in case of carbocyclic compounds) in alphabetical order to denote the side chains or
substituent groups. The secondary prefixes for some groups which are always treated as substituent groups
(regardless of the fact whether the organic compound is monofunctional or polyfunctional) are given below:

7
 IUPAC & Structural Isomerism
Substituent group Secondary prefix Substituent group Secondary prefix

–F Fluoro – OCH3 (– OMe) Methoxy

– Cl Chloro – OC2H5(–OEt) Ethoxy

– Br Bromo –R Alkyl

–I Iodo – CH3 (– Me) Methyl

– NO2 Nitro – C2H5 (– Et) Ethyl

– NO Nitroso – CH2CH2CH3(n-Pr) n-Propyl


N N Diazo – CH(CH3)2 (– iPr) Isopropyl

– OR Alkoxy – C(CH3)3 (t-Bu) t-Butyl

Example :
Secondary Primary
Organic compounds Word root IUPAC name
prefix suffix

CH3CH2 – Br Bromo eth ane Bromoethane

CH3 – NO2 Nitro meth ane Nitromethane

C2H5 – OC2H5 Ethoxy eth ane Ethoxyethane

Br
|
4
CH
5 3
Ex. H2C CH2 4-Bromo + cyclo + hex + an (e) + 1-ol
6 2 Primary Word Primary
H2C CH2 Secondary suffix Secondary
prefix prefix root suffix
1CH
|
OH
SO3H
+ cyclo + + +
5 1
2
I
Primary
4 3 prefix
CH3
CH3

OH
2 - Isopropyl - 5 - methylcyclohexanol
CH
CH3 CH3
Here Secondary prefix = 2 - Isopropyl - 5 - methyl
Primary prefix = cyclo
Word root = hex
Primary suffix = an(e)
Secondary suffix = ol

IUPAC nomenclature of branched / complex alkanes

Parent carbon chain selection :
(a) Select the longest continous carbon chain in the molecule.

8
 IUPAC & Structural Isomerism

Longest chain has 7 carbons so word root is "Hept"

(b) When chains of equal lengths are competing for selection then that chain is selected which has more
number of substituents/branches.

longest chain has 7 carbon & 3 substituents

(c) When the number of substituents are same then the substitutents at the nearest positions from the either
end is prefer for parent chain selection.
Ex. Here , 2 choices for longest chain

Chain- (A) 1–2–3–4–5–6–7–8

Chain- (B) 1' –2' –3'–4–5–6–7–8

Chain- (A) & Chain- (B) both have 2 substituents but in chain-B substituent is nearer (at 2nd position) than
in chain-A (at 3rd position). So, chain-B will be preferred.
(d) If the two substituents are found in equivalent positions the lower number is given to the one coming
first in the alphabetical order.
Ex. Here , 2 choices for longest chain

Chain- (A) 1–2–3–4–5–6–7–8–9

Chain- (B) 1' –2' –3'–4'–5'–6'–7'–8'–9'

In both chain-A & chain-B, substituents are at same position (4th). In chain-A substituent is ethyl & in
chain-B, it is methyl. Alphabetically ethyl will be preferred. So, chain-A is selected.
Numbering of the parent carbon chain : Numbering of parent chain always done end to end.
(a) The numbering is done in such a way that the branched carbon atoms(substituent) get the lowest
possible number (lowest set of locant)
(b) If position of substituent are same from both the end of the parent chain, then numbering is done from
alphabetical order.
8 7 6 5 4 3 2 1
C–C–C–C–C–C–C–C
C C–C
Note:
(1) Write the substituents in place of secondary prefix with their appropriate locations in alphabetical order.
(2) If the same substituent occurs more than once in the molecule, the prefix di (for two), tri (for three), etc.
are used to indicate how many times it appears.
(3) Prefixes di, tri, tetra etc. are not considered in deciding alphabetical order for simple substituents but
considered for complex substituents.
(4) Iso & Neo is considered for alphabetical seniority order.
(5) Numbers are separated from each other by commas(,).
(6) Numbers are separated from words by hyphens and there is no break between name of substituents and
word root.

9
 IUPAC & Structural Isomerism

CH3
CH3 CH3 CH3
Ex. (i) (ii) (iii) CH3 C CH3
CH3 CH CH3 CH3 CH CH CH3 CH3
Methylpropane 2, 3-Dimethylbutane 2,2-Dimethylpropane

(iv) 3-Ethyl-2-methyl-4-propylheptane

(v) 3-Ethyl-2,3-dimethyl-4-propylheptane

(vi) 3-Ethyl-2,4-dimethylhexane

IUPAC nomenclature of Alkenes/Alkynes/Alkenyne

Alkenes :
Functional group :
(1) Select the longest carbon chain containing carbon–carbon double bond. This need not be the longest
chain in the compound as a whole. Parent name will be alkene corresponding to number of carbon atoms
in the longest chain.

Ex.

Longest chain has 6 atoms  parent name = hexene

(2) Carbon atoms in the longest chain is numbered from that end in such a way that doubly bonded carbon
atom gets the lowest number. The position of double bond is indicated by the smaller of the numbers
assigned to two carbon atoms of double bond.

The above example can be numbered as,

Position of double bond will be indicated as no. 1,Hence name will be 3–Methyl–3–propylhex–1–ene

Ex. 2,2,5,5-Tetramethylhex-3-ene

10
 IUPAC & Structural Isomerism
Alkynes:
Parent chain selection and numbering of longest chain is exactly same as that for alkenes.

Ex. 4,4–Dimethylpent–1–yne

Alkenyne (containing both double and triple bonds)

Numbering is done in a manner that double and triple bonds get the lowest possible number. If double bond
and triple bond both have same number then double bond is prefer over triple bond.
Ex. HC  C – CH2 – CH = CH2
1 2 3 4 5 (numbering is done from alkyne) (wrong)
5 4 3 2 1 (numbering is done from alkene) (Correct)

Oct-1-en-4-yne

Hepta-3,6-dien-1-yne

IUPAC nomenclature of alicyclic compounds

(1) The names of alicyclic compounds are obtained by adding the prefix "cyclo"

Ex.

Cyclobutane Cyclopentene
(2) The numbering of the carbon atoms in the ring is done in such a way that the substituent which comes first in
the alphabetical order is given the lowest possible number and it does not violate the lowest set of locants rule.
CH3 CH3
3 1
C2H5
4 2 6 2
Ex. 1
5 5 3
CH2CH3
6 4
CH3
1–Ethyl–3–methyl cyclohexane 2–Ethyl–1,4–dimethyl cyclohexane
C2H5 I
3
2 Br
4
CH3
5 1
CH3 6
Cl

3–Ethyl–1,1–dimethyl cyclohexane 2–Bromo–1–chloro–3–iodocyclohexane

(3) When the ring contains more or equal number of carbon atoms than the alkyl group attached to it, then it is
named as a derivative of cycloalkane and the alkyl group is treated as substituent
CH2 – CH2 – CH3

Ex.

Propylcyclopropane

(4) The alkane chain contains greater number of carbon atoms than present in the ring, then the compound is
considered as the derivative of alkane and the ring is designated as substituent.

11
 IUPAC & Structural Isomerism

1 2 3 CH3 – CH2 – CH – CH2 – CH2 – CH3

4

Ex.

2–Cyclopropylbutane 3–Cyclopentylhexane

(5) If ring has unsaturation and side chain is saturated then ring is selected as parent chain.
If side chain has unsaturation and ring is saturated then side chain is selected as parent chain.
If both have unsaturation the chain with maximum unsaturation has selected as parent chain.
If equal unsaturation then longest chain is selected as parent chain.
If unsaturation and number of carbon atoms both are equal then ring is selected as parent chain.
6
5 1 3 2
4
Ex. 4 2 5 1
3 6

1-Ethylcyclohex-1-ene 6-Ethyl-3,3-dimethylcyclohex-1-ene Cyclohexyl ethene

(6) If more than one alicyclic ring is attached to a single chain then the compound is named as a derivative of
alkane and the ring are treated as a substituent group.

Ex. CH2

Dicyclopropylmethane

(7) If a multiple bond and some other substitutents are present in the ring, the numbering is done in such a way
that the multiple bond gets the lowest number
NO2
3
4 2
Ex.
5 1
6
3-Nitrocyclohex-1-ene

(8) If a compound contains an alicyclic ring directly linked to the benzene ring. It is named as a derivative of
benzene.

Ex.
Cyclohexylbenzene
(9) If functional group is present in cyclic compounds then the main chain is taken in which principal functional
lie's, if the principal functional group is present in ring also then main chain will be taken for the maximum
no. of carbon atoms.
OH
1 1 3
2
6
2
Ex.
5 3 OH
4
2-Propylcyclohexan-1-ol 1-Cyclohexylpropan-2-ol 2-Propyl cyclopropan-1-ol

(10) When chain terminating functional group is directly attached with ring then ring is taken as parent chain &
special suffix is used for this functional group.

12
 IUPAC & Structural Isomerism
Functional Group Suffix
CHO Carbaldehyde
COOH Carboxylic Acid
COX Carbonyl halide
COOR Alkyl Carboxylate
CONH2 Carboxamide
CN Carbonitrile

CN CHO

Ex.

Cyclohexanecarbonitrile Cyclohexanecarbaldehyde
O
2
COOC2H5
1

2-Cyclohexyl ethanoic acid Ethyl 2–oxocyclohexane–1–carboxylate

IUPAC nomenclature of compounds containing functional groups

(a) Rules for non chain terminating functional groups
(1) Parent chain : Select the longest possible chain with maximum functional group and maximum unsaturation
without caring whether it also denotes the longest possible chain or not.
4 3 2
Ex. CH3 – CH2 – CH – CH2 – CH3 2-Ethyl butan-1-ol
|
1
CH2OH
(Parent chain contains four rather than five carbon atoms)
(2) Lowest number for the functional group
Numbering is done from that side of the chain which gives lowest locant to the principle functional group
followed by double and triple bonds.
O O
6 5 4 3|| 2 1 1 2 3 4|| 5 6
Ex. CH3 – CH – CH2 – C – CH2 – CH3 CH3 – CH – CH2 – C – CH2 – CH3
| |
CH3 (I) correct CH3 (II) wrong
5-Methyl hexan-3-one
( C = O group gets lowest number 3) ( C = O group gets number 4 which is not lowest)

(3) If a compound contains two or more like groups, the numerical prefixes di, tri, tetra etc. are used

CH2  CH  CH2 CH3 – C – CH2 – C – CH3

Ex. | | | || ||
OH OH OH O O
Propane  1,2,3  triol Pentane-2, 4-dione

(b) Rules for chain terminating functional groups

(1) When a chain terminating functional group such as – CHO, – COOH, – COOR, – CONH2, – COCl,
– C  N etc. is present, it is always given number 1 (one.)

13
 IUPAC & Structural Isomerism

O
4 3 2 ||
Ex. CH3 – CH2 – CH – CH3 CH3 – C  C – CH2 – C – H
| 5 4 3 2 1
1
COOH Pent-3-yn-1-al
2-Methylbutan-1-oic acid

Ex. Write the IUPAC name of

3 4 5
CH3  CH2  CH  CH2  CH  CH3
| | 7
1 2 6
CN  CH2 CH2  CH3

Sol. (i) The longest chain containing functional group is of 7 carbon atoms. Therefore, the word root is hept
& the chain is numbered as shown.
(ii) There is no multiple bond in it. Hence, the primary suffix is ane.
(iii) The functional groups is –CN. Hence, secondary suffix is nitrile
(iv) Moreover, there is a methyl group on carbon 5 and ethyl group on carbon 3.
(v) The IUPAC name is, therefore, 3-Ethyl-5-methylheptanenitrile
(2) The name for benzene as substituent is phenyl. In case the phenyl ring is further substitued, the carbon
atoms of the ring directly attached to the parent chain in such a ways that the substituent on the ring gets
the least possible number. For example

(3) If the organic molecule contains more than one similar complex substitutents, then the numeral prefixes
such as di, tri, tetra etc. are replaced by bis, tris, tetrakis etc. respectively.
Ex.

Ex.

Common name is D.D.T. (Dichloro diphenyl trichloro ethane) & is used as insecticide.

(4) When 3 or more principle functional groups are directly attached with an open chain, then special suffix is
used.

Ex. Pentane- 2,3,4–tricarboxylic acid.

14
 IUPAC & Structural Isomerism

Not true for 3-Carboxymethyl-2,4- dimethylpentanedioic acid

 Anhydride
Functional Group Prefix Suffix IUPAC name

–C –O–C– Oic anhydride Alkanoic anhydride

–
O O or or
carboxylic anhydride alkane carboxylic
anhydride
Heat
(i) R –C –O–H + H –O –C–R –H2 O
R–C –O–C– R
O O O O
Alkanoic anhydride

H –C –O–C– H C –O–C
O O O O
Ex.
Methanoic Anhydride
Cyclopropane carboxylic anhydride
(Unstable)

(ii) Mixed Anhydride: according to alphabetic order

CH3–COOH + C – C –COOH CH3–C –O–C– C2H 5
O O
Ethanoic acid Propanoic acid Ethanoic propanoic anhydride

(iii) Cyclic anhydride:

O O O
C C C
H2C
O O O
H2C C C
C
O O O
Butanedioic anhydrid Cyclohexane-1,2-dicarboxylic anhydride Benzene dicarboxylic anhydride

 ETHERS (R – O – R’):-

Functional Group Prefix Suffix IUPAC name

R – O – R' alkoxy – Alkoxy alkane

(i) Acyclic Ethers:-

(1) C – O – C (2) C – O – C – C (3) C – O – C – C – C
Methoxymethane Methoxyethane 1-Methoxypropane

 In cyclic system, numbering always starts from senior most functional group.
OH OH
–

1 Br Br
–

2 2 1
6 6
(4) (5)
3 3
–

5
–

5
4 O – CH3 4 O–C–C
6-Bromo-5-methoxycyclohex-2-en-1-ol 6-Bromo-5-ethoxycyclohex-3-en-1-ol

15
 IUPAC & Structural Isomerism
(ii) Cyclic Ether: (3-membered Ring)- A hetero cyclic compound
Cl

–
(1) C – C (2) C – C – C (3) C – C – C (4) C – C – C
O O O O
Oxirane or Epoxyethane 1, 3-Epoxypropane 1, 2-Epoxypropane 1-Chloro-2, 3-Epoxypropane

(c) Rules for IUPAC nomenclature of polyfunctional compounds :

(1) When an organic compound contains two or more different functional groups then senior functional
group is selected as the principal functional group while other functional groups are treated as substituents.
(2) Some functional group such as all halo groups (fluoro, bromo, chloro, iodo), nitroso (NO) nitro (– NO2)
and alkoxy (–OR) are always treated as substituent groups.

Ex.

Numbering the principal chain order is

[Principal functional group > Unsaturation > substituents]

Ex.

(3) If more than one same chain terminating group are present then the principal chain is selected including the
functional groups and numbring is done from that side which gives lowest locant to unsaturation and
substituents.
1 2 3 4 5
Ex. (a) HOOC – CH 2 – CH2 – COOH (b) N C C H  C H2  C H2  C N
1 2 3 4 |
CH3
Butane-1, 4-dioic acid 2  Methylpen tanedinitrile
O
(c) CH2CH2–CH2–CH–CH2–C–O–C2H5 Ethyl-3-(3-hydoxy propyl) pent-4-enoate
3 2 1
OH CH=CH2
4 5
Parent chain contains five rather than six carbon atoms.

Nomenclature of aromatic compounds

The aromatic compounds are cyclic compounds which contain one or more benzene type rings. Benzene is
the simplest hydrocarbon of aromatic series which has planar cyclic ring of six carbon atoms having three
double bonds in alternate positions as shown below.
CH
1
HC CH 6 2

HC CH or 5 3
4
CH
(i) Nuclear substituted : The functional group is directly attached to the benzene ring, in the IUPAC
system they are named as derivatives of benzene. The position of the substituents in disubstituted benzenes
are indicated either by prefixes such as o-(ortho) for 1, 2, m-(meta) for 1,3 and p-(para) for 1, 4 position.
However, many of their common names have also been adopted by the IUPAC system.
(ii) Side chain substituted : If functional group is present in the side chain of the benzene ring in the
IUPAC system, these are usually named as phenyl derivatives of the corresponding aliphatic compounds.

16
 IUPAC & Structural Isomerism
The IUPAC and common names of a few important members of each family are given below.

1. Aryl groups :
CH2 CH C

Phenyl (Benzyl) (Benzal) (Benzo)

CH3
CH3 CH3 1
1 1
2
2 2
3
3 4

2 – Tolyl 3 – Tolyl 4 – Tolyl -Naphthyl -Naphthyl

or (o – Tolyl) or (m – Tolyl) or (p – Tolyl)
2. Other aromatic examples

17
 IUPAC & Structural Isomerism

18
 IUPAC & Structural Isomerism

19
 IUPAC & Structural Isomerism

20
 IUPAC & Structural Isomerism

21
 IUPAC & Structural Isomerism

Illustration 5: Write IUPAC name of following aromatic compounds

CH3
|
CH2 – CH – CHO CH2OCH3

(a) (b)

Solution (a) 2-Methyl-3-phenylpropanal (b) Methoxyphenylmethane (Benzyl methyl ether)

Illustration 6: Write the structural formula of :

(a) o-Ethylanisole, (b) p-Nitroaniline,
(c) 2,3-Dibromo-1-phenylpentane (d) 4-Ethyl-1-fluoro-2-nitrobenzene.

Solution (a) (b) (c) (d)

22
 IUPAC & Structural Isomerism
Common and IUPAC Names of Some Organic Compounds

23
 IUPAC & Structural Isomerism

24
 IUPAC & Structural Isomerism

25
 IUPAC & Structural Isomerism
Some important 1993 recommendations for IUPAC nomenclature of organic compounds :
1. Locants (numerals and / or letters) are placed immediately before the part of the name to which they
relate. For example :
CH3CH2CH = CH2 should be named as but-1-ene
CH3CH2CH2OH should be named as propan-1-ol
similarly, a few more examples are given as following :

2. The locant 1 is often omitted when there is no ambiguity. For example.

In all the above examples locant 1 for the functional group is omitted because the position of the functional
group is unambiguous. However, in the following cases the position of the functional group must be mentioned.

Here, we cannot write simply propanol (or propanamine) because there are two propanols ; propan-1-ol
and propan-2-ol.

3. Arrangement of Prefixes
(i) Simple prefixes such as methyl, ethyl, chloro, nitro, hydroxy, etc. are arranged alphabetically.
The prefixes di, tri, etc. are however not considered for comparison.
2 1
Ex. CH2CH2
| |
Cl Br
1-Bromo-2-chloroethane
(ii) The name of a prefix for a substituted substituent is considered to begin with the first letter of its complete
name.

Ex.

for the substituted 1-chloropropyl, 'C' is taken as the first letter.

(iii) When two or more prefixes consist of identical roman letters priority for citation is given to the group which
contains the lowest locant at the first point of difference.
For example,

Here, 1-chloroethyl gets priority over 2-chloroethyl.

26
 IUPAC & Structural Isomerism
Degree of Comopunds :
1. Degree of alcohols, alkyl halids are derived from degree of carbon atom.
2. Amines are ammonia derivatives and their degree depends on the number of alkyl or aryl groups
bonded directly to the nitrogen atom.

Degree of Alcohols (R–OH)

1º 2º 3º
CH3–CH2–OH CH3–CH–CH3 CH3
OH CH3–C–CH3
OH

Degree of Alkyl Halides (R–X)

1º 2º 3º
CH3–CH2–X CH3–CH–CH3 CH3
X CH3–C–CH3
X

Degree of Amines (Ammonia Derivatives)

1º 2º 3º
CH3–CH2–NH2 R–NH–R R–N–R
R
CH3–CH–CH3
NH2
CH3
CH3–C–CH3
NH2
Degree of Amides

1º 2º 3º
O O O
R R
R–C–NH2 R–C–N R–C–N
H R

27
 IUPAC & Structural Isomerism
Structural Isomerism
Definition
When two or more compounds have same molecular formula but they differ in their physical properties or
chemical properties or both then they are called isomers & the phenomena is called isomerism. Isomers are
also sometimes called as isomerides.
Classification of isomerism

Isomerism

Structural or constitutional Stereo or isomerism

isomerism (Same connectivity)
(Different connectivity)

Chain Position Functional Metamerism Tautomerism

isomerism isomerism group isomerism (to be dissucssed
after acid and base)

Double Bond Equivalence (DBE) :

It helps to find number of  bonds in the given compound. It is very helpful in the structural identification
of the compound.

Deficiency of 2H atoms with respect to fully saturated acyclic hydrocarbon is equivalent to One DU.
It is also known as Hydrogen Deficiency Index (HDI) or Degree of Unsaturation (DU) :

–2H
H3 C – H2C – CH3   CH3 – C  CH or CH2 = C = CH2 or
(DU  O)

Note : When open chain compound cyclises, one  bond is used up.

a = Number of Carbon atoms

bcd  b = Number of Hydrogen atoms
DU = (a+1) –  
 2  c = Number of Halogen atoms .
d = Number of Nitrogen atoms
* DU is fractional for the salts.
Note : Total no. of cyclic rings + double bonds will gives us degree of unsaturation.
If DU = 1  One  bond or One ring
If DU = 2  Two  bonds
If DU  4  Benzene or its derivative (In general)
Ex. (i) CH2 = CH2 DU = 1 (ii)     DU = 2

(iii) DU = 4 (iv)       DU = 7
(v) C6H6O DU = 4 (vi) C6H5Cl DU = 4

28
 IUPAC & Structural Isomerism
Some Application of DU :

Alkanes
Alkenes or cycloalkanes
Dienes or Alkynes or cycloalkenes or bicyclo
Aromatic hydrocarbons (In general)
Alcohols or ethers
Aldehydes or ketones or epoxides or ..........
Esters or carboxylic acids or ..........
Amines (1º, 2º & 3º)

Structural isomerism :
When two or more organic compounds have same molecular formula but different structural formula,
(i.e., they differ in connectivity of atoms) then they are called structural isomers and the phenomena is called
structural isomerism
Structural isomers have always different IUPAC name.

(1) Chain isomerism (Skeletal or Nuclear isomerism) :

Chain isomeres have same molecular formula but different number of carbon atoms in principal chain or in
side chain.

1. & are chain isomers

2.
& are chain isome rs

& are chain isome rs

Ex.
3. & are chain isomers

& are chain isomers

No. of alkane isomers as a function of no. of carbon atoms :

no. of
carbon atoms molecular formula no. of isomers
2 C2H6 1

3 C 3H8 1

4 C4 H10 2

5 C 5H12 3

6 C6 H14 5
7 C7 H16 9

8 C 8 H18 15

9 C9 H20 35

10 C10 H22 75

29
 IUPAC & Structural Isomerism
(2) Position isomers(PI):
When two or more organic compounds have same molecular formula but they differ in the position of the
functional group or the substituent, then they are called position isomers & the phenomena is called position
isomerism.
H 3C CH2 CH CH2 (but - 1 - ene ) 
Ex. (1) H3C C H CH CH2 ( but - 2 - ene ) 
position isomers


(2)

(3) C7H7NO2 (3-aromatic position isomers)

NO2 NO2 NO2
CH3
(I) (II) (III)
CH3
CH3

(4) C6H3 (OH)3 (3 aromatic position isomers)

OH OH
OH OH
(I) (II) (III)
OH
OH
(3) Functional isomers (FI):
Compound having same molecular formula but different functional groups in their molecules show functional
isomerism and are called functional isomers.
Formula Functional Isomers
(i) Cn H2n Alkene, Cycloalkane
(ii) Cn H 2n–2 Alkadiene, Alkyne, Cycloalkene etc.

(iii) Cn H 2n +2 O Alcohol, Ether

(iv) C n H2n O Aldehyde, Ketone, Oxirane (epoxy) etc.
(v) Cn H2nO 2 Acid, ester, hydroxy, carbonyl (aldehyde, ketone compounds) etc.
Ex.1 1. CH3–CH2–OH and CH3O–CH3
2. CH3COOH and HCOOCH3
3. Primary, secondary and tertiary amines are functional siomers
4. Aliphatic alcohols and Aromatic alcohols are functional isomers.

Illustration 1: Four structures of C4H11N are given. Established relation between all possible isomeric pairs.
CH3 CH CH2 CH3 CH3 CH CH2 NH2
NH2 CH3
(I ) (II )
CH3
CH3 C N H2 CH 3 CH2 CH2 CH2 NH2
CH3 (IV)
(III)
Solution (I) and (II) are chain isomers (I) and (III) are chain isomers
(I) and (IV) are positional isomers (II) and (III) are positional isomers
(II) and (IV) are chain isomers (III) and (IV) are chain isomers

30
 IUPAC & Structural Isomerism
Illustration 2: Functional isomers of CH 3 C  CH is

(A) CH 2 C  CH 2 (B) (C) (D) Both A and B

Ans. D (Ring cannot have sp carbon unless ring has atleast 8 carbon atoms)

(4) Ring chain isomers(RCI):

Ring-chain isomers develop when
(a) one isomer has open-chain structure while the other has ring structure
(b) both isomers have ring structures but then ring size should be different

Illustration 3:Write all isomers of C4H8 and indicate relationship between them :
C4H8 (DU = 1)

but-1-ene cyclobutane but-2-ene 2-methylcyclopropane 2-methylprop-1-ene

(1) (2) (3) (4) (5)
(1) &(2)  RCI (2) &(3)  RCI (3) &(5)  CI
(1) &(3)  PI (2) &(4)  CI or RCI (4) &(5)  RCI
(1) &(4)  RCI (2) &(5)  RCI
(1) &(5)  CI (3) &(4)  RCI

Illustration 4: Compound CH3 CH2 CH2 C CH and are

(A) Position isomers
(B) Chain isomers
(C) Ring chain isomers
(D) All of these
Ans. C

Illustration 5: 1, 2–Epoxy propane and prop–2–enol (Allyl alcohol) are

(A) Position isomers
(B) Functional isomers
(C) Ring chain isomers
(D) Both B and C
Ans. (D)

(5) Metamerism:
Compound which have same molecular formula same functional group but different nature of alkyl groups
along the polyvalent functional group.
Conditon : 1. Compound should have a polyvalent hetero atom.
2. Chain isomerism is ignored.
This isomerism is common in ethers, secondary amines, esters, anhydrides etc.
Ex. 1. CH3 CH2 O CH2 CH3 & CH3 O CH2 CH2 CH3 are metamers
2. CH3 CH2 NH CH2 CH3 & CH3 NH CH2 CH2 CH3 are metamers.
3. are metamers

4. Let's consider the example of ketones

31
 IUPAC & Structural Isomerism
O
CH3 CH2 C CH2 CH3 (Pentan–3–one)
Diethyl ketone
PI
Metamers
O
CH3 C CH2 CH2 CH3 (Pentan–3–one)
Methyl propyl ketone

On the basis of common name it seems that these are metamers and on the basis of IUPAC nomenclature
these appear to positional isomers, so considering these as positional isomers is more correct.

Illustration 6:
Consider the following isomers
I : CH3 CH2 O CH2 CH3
(Diethyl ether or Ethoxy ethane)
II : CH3 O CH2 CH2 CH3
(Methyl propyl ether or 1-Methoxy propane)
CH3
III : CH3 O CH
CH3
(isopropyl methyl ether or 2-methoxy propane )
Now select correct statments
(A) I and II are metamers (B) I and III are metamers
(C) II and III are postional isomers (D) All are correct
Ans. D

O O
Illustration 7: Compound CH3 CH2 C NH CH2 and CH3 C NH C H2 CH3 are
(I) (II)
(A) Functional isomers (B) Position isomers
(C) Metamers (D) All of these
Ans. C

Illustration 8: Metamer of the compound P is

O
P= C O

O O
(A) C O (B) O C

O
(C) O C (D) All of these

Ans. C

32
 IUPAC Nmenclature and Structural Isomerism

EXERCISE-1
PART- 1: SUBJECTIVE QUESTIONS
Fundamental of Organic Chemistry
001. Write the number of  and  bonds in the following molecules ?

CH3
(a) (b) OH (c) N –CH3

002. Write the number of  and  bonds in the following molecules.

(a) (b) (c)

003. Find the number of 1°, 2° & 3° hydrogen atoms in the following compounds
(a) (b) CH3 –CH2 –CH3 (c) CH 3–CH2 –CH2–CH3

004. Find the number of 1°, 2° & 3° carbon and hydrogen atoms in the following compounds

(a) (b) (c) CH3CH2CHCH2CH3

CH3
005. Expand each the following condensed formulae into their complete structural and bond line formulae :
(a) HOCH 2CH2NH2 (b) CH3(CH2)3OH
(c) CH3 CH2COCH2CH3 (d) CH 3CH=CH(CH2)3CH3
006. Draw formulae for the first four members of each homologous series begining with the following.

(a) H–COOH (b) H–CH=CH2 (c)

007. Classify the following compounds as homocyclic, heterocyclic, alicyclic, aromatic, saturated and
unsaturated.

(a) (b) (c) (d)

008. Indicate the following as 1°, 2° and 3° amines.

CH3
(a) (b) NH (c) N (d) N–CH3

009. Indicate the following as 1°, 2° and 3° alcohol.

OH
(a) OH (b) OH (c) OH (d)

010. Write the common name of the following alkyl groups.

(a) (b) (c) (d) –CH2 –CH3

(e) CH 3–CH2 –CH2 –

33
 IUPAC Nmenclature and Structural Isomerism
IUPAC-Nomenclature of Alkane & Cycloalkane
011. Write IUPAC name of the following compounds :

(a) (b) (c)

012. Write IUPAC name of the following compounds:-

(a) (b)

Me
Me Me
(c) Me (d)
Me
013. Identify the parent chain in the following compounds as ring or side chain.

(a) (b) (c)

(d) (e) (f)

014. Write correct IUPAC name of the following

(a) (b) (c) (d)

(e)

015. Write the correct IUPAC name of the following compounds.

(a)

CH3
|
(b) CH3 — CH2 — CH2 — CH2 — CH2 — CH — C — CH2CH3
| |
CH3 CH2 — CH2 — CH3

(c)

34
 IUPAC Nmenclature and Structural Isomerism
(d)

016. Write structures of the following IUPAC name.

(a) 1, 3-Dicyclopentyl propane (b) 1-Methyl-4-propylcyclohexane
(c) 2-Ethyl-1,1-dimethylcyclopentane
017. Write IUPAC names of the following hydrocarbon (use common naming for hydrocarbon groups.)

(a) (b) (c) (d)

IUPAC-Nomenclature of Alkene, Cycloalkene, Polyenes & Alkyne

018. Write the general formula of alkenes. Give IUPAC names of first three members.
019. Write IUPAC name of the following :
(a) (CH3)3 C – CH = CH2 (b) CH2 = CH – CH = CH2
CH3 CH3

(c) CH3–CH2–CH2–C–CH2–C=CH2 (d)

CH3
020. Draw the bond line structures of the following compounds.
(a) 2-Methylhept-3-ene (b) 2,6-Dimethylhepta-1, 5-diene
021. Write IUPAC name of the following

(a) (b) (c)

022. Draw structure of following IUPAC names.

(a) Hexa-2,4-diyne (b) Pent-3-ene-1-yne (c) Pent-1-en-4-yne (d) Pent-1-en-3-yne
023. Write the IUPAC name of the following

(a) (b)

CH3

(c) (d) CH3 (e)

IUPAC Nomenclature of non-chain terminating functional groups

024. Write the IUPAC names of the following compounds.

(a) (b) (c) (d)

(e) (f) (g) (h)

35
 IUPAC Nmenclature and Structural Isomerism
025. Write the correct IUPAC name of the following compounds.
CH = CH – COCH3 OH OH

(a) (b) CH2 – CH – CH2 – CH3

(c)

026. Draw the structures of each of the followings.

(a) Butan-1-ol (b) Butane-2-thiol
(c) Pentan-2-amine (d) Pentan-2-one
(e) 3-Chloropentan-1-ol (f) Hexan-2,4-dione
027. Write IUPAC names of following ethers :

(a) (b) (c) (d)

IUPAC Nomenclature of chain terminating functional groups

028. Select the parent chain in each of the following molecules.

(a) (b) (c) (d)

(e) (f) (g) (h)

029. Write the structure of the following compounds :

(a) 3-Hydroxypentane-2-sulphonic acid. (b) 3-Chloromethylpentanoic acid
(c) 3-Bromobutanoyl chloride (d) Cyclohexyl ethanoate
(e) Phenyl ethanoate (f) 2-Chloroethyl propanoate
(g) Diethyl pentanedioate
030. Write the structure of the following compounds :
(a) Butanamide (b) N-methylethanamide
(c) Cyclopropanecarboxylic anhydride (d) Cyclopropylbutanoate
031. Write IUPAC Name

O
(a) CH3CH2 – CH – C – OCH3 (b) (c)
– –

CH2
CH3
032. Write IUPAC names of following compounds.

(a) (b) (c) (d)

033. Write IUPAC names of following compounds.

(a) (b) (c) (d)

36
 IUPAC Nmenclature and Structural Isomerism
IUPAC-Nomenclature of Aromatic compounds
034. Write IUPAC name of the following :

OH
CHO
OH
(a) (b) (c) (d)
CH3

035. Write the correct IUPAC name of the following :

(a) (b) (c) (d)

036. Write common & IUPAC name of following structure:

CH3 CH = CH2
CH3
(a) (b) (c) (d)

Structural Isomerism
037. Identify the relationship between the given compounds.

(a) and (b) and

(c) and

038. Identify the relationship between the given compounds.

(a) & (b) & (c) &

(d) &

Number of Structural Isomers

039. Draw all structurally isomeric alkenes with molecular formula C4H8.
040. Draw all structurally isomeric 2º chlorides with molecular formula C5H11Cl.
041. Draw all structurally isomeric benzene containing isomers with molecular formula C7H8O.
042. Draw all structurally isomeric cyclic bromides with molecular formula C4H7Br.
043. The ring chain functional isomer of compound But-2-ene are.

37
 IUPAC Nmenclature and Structural Isomerism
PART- 2: OBJECTIVE QUESTIONS
Fundamental of Organic Chemistry

044. Molecular formula of naphthaquinone is

(A) C12 H8 O2 (B) C11H6 O2 (C) C10 H6 O2 (D) C10H8 O2

045. Number of 10, 20, 30 and 40C present in following compound are respectively

(A) 7, 4, 5 and 1 (B) 7, 3, 4 and 1 (C) 7, 3, 5 and 1 (D) 7, 4, 4, 1

046. How many 1°carbon atom will be present in a simplest hydrocarbon having two 3° and one 2° carbon
atom?
(A) 3 (B) 4 (C) 5 (D) 6
047. How many carbons are present in simplest alkyne having two side chains?
(A) 5 (B) 6 (C) 7 (D) 8
048. Which of the following pairs do not have carbocyclic ring in both compounds?
(A) Pyridine, Benzene (B) Benzene, Cyclohexane
(C) Cyclohexane, Furane (D) Furane, Pyridine
049. Which of the following is not an alicyclic compound ?

(A) (B) (C) N (D)

|
H
050. The saturated heterocyclic compound is :

(A) (B) (C) N (D)

N
.. |
H
051. Which of the following compound is unsaturated hydrocarbon ?

(A) (B) CH3–C  N (C) (D)

052.

Incorrect statement for the above structure :

(A) I & II have CnH2n-2 general formula
(B) I & II have same empirical formula
(C) I & II are homologues
(D) I & II have same molecular formula
053. A substance containing an equal number of primary, secondary and tertiary carbon atoms is:
(A) Mesityl Oxide (B) Mesitylene (C) Maleic acid (D) Malonic acid

38
 IUPAC Nmenclature and Structural Isomerism
IUPAC-Nomenclature of Alkane & Cyclo alkane

054. The correct IUPAC name of the alkane is :

(A) 2-Ethyl-4-methylhexane (B) 5-Ethyl-3-methylhexane

(C) 3,5-Dimethylheptane (D) 3,5-Dimethylhexane
055. The correct structure of 6-Ethyl-2,3,5-trimethylnonane is :

(A) (B)

(C) (D)

056. The correct IUPAC name of the following compound is :

(A) 1-Bromo-1-ethyl-2-fluoro-2-iodo-1-nitroethane.(B) 3-Bromo-4-fluoro-4-iodo-3-nitrobutane.

(C) 2-Bromo-1-fluoro-1-iodo-2-nitrobutane. (D) 1-Fluoro-1-iodo-2-bromo-2-ethyl-2-nitroethane.
057. A student named a certain compound as 2, 3-diethylbutane. Its correct IUPAC names is
(A) 2, 3-Dimethylhexane (B) 3, 4-Dimethylhexane
(C) 2-Ethyl-3-methylpentane (D) 2-Ethylbutane
058. In which of the following compound IUPAC numbering is correct ?

(A) (B) (C) (D)

059. The correct IUPAC name of is :

(A) 1-Cyclopentyl-1, 1-dimethylbutane (B) 2-Cyclopentyl-3-methylpentane

(C) 2-Cyclopentyl-2-methylpentane (D) 1, 1-Dimethyl-1-cyclopentylbutane
IUPAC-Nomenclature of Alkene, Alkyne, Cyclo alkene & polyenes
060. Select the structure with correct numbering in the chain :
(A) (B)

(C) (D)

061. The correct IUPAC name of the compound

(A) 4-Ethylpent-1-ene (B) 2-Ethylpent-4-ene (C) 4-Methylhex-1-ene (D) 3-Methylhex-1-ene
062. The molecular formula of the first member of the family of alkenynes and its name is given by the set
(A) C3H2, Alkene (B) C5H6, Pent-1-en-3-yne
(C) C6H8, Hex-1-en-5-yne (D) C4H4, Butenyne

39
 IUPAC Nmenclature and Structural Isomerism
063. The correct structure of 2-Ethyl-3-methylhexa-1,4-diene :

(A) (B) (C) (D)

064. The correct IUPAC name of the given compound is

(A) 3-Chloro-1-fluoro-1-iodo-4-methoxybut-1-en-3-yne
(B) 4-Methoxy-2-chloro-1-fluoro-1-iodobutenyne
(C) 3-Chloro-4-fluoro-4-iodo-1-methoxybutenyne
(D) 2-Chloro-1-fluoro-1-iodo-4-methoxybutenyne
065. The correct IUPAC name of the compound is –
F I
C

Cl C CH2
CH2 CH2 Br
(A) 4-Bromo-1-chloro-2-fluoroiodomethylbutene
(B) 4-Bromo-2-chloromethyl-1-fluoro-1-iodobut-1-ene
(C) 2-(2-Bromoethyl)-3-chloro-1-fluoro-1-iodoprop-1-ene
(D) 1-Bromo-3-chloromethyl-4-fluoro-4-iodobut-1-ene
066. In which of the following cyclic chain is the main chain ?

(A) (B) (C) (D)

067. IUPAC name of the compound is

(A) 1-Cyclohexyl-3-methylpent-1-ene (B) 3-Methyl-5-cyclohexylpent-1-ene

(C) 1-Cyclohexyl-3-ethylbut-1-ene (D) 1-Cyclohexyl-3,4-dimethylbut-1-ene
068. The correct IUPAC name of the compound

(A) 1-Ethenylcyclohexa-2, 4-diene (B) 5-Ethenylcyclohexa-1, 3-diene

(C) 6-Ethenylcyclohexa-1, 3-diene (D) Cyclohexa-2, 4-dienylethene
IUPAC Nomenclature of non-chain terminating functional groups
069. Which of the following is a correct priority order of functional groups?

(A)

(B) (C)

(D)

40
 IUPAC Nmenclature and Structural Isomerism
070. The IUPAC name of

Br
|
CH3  CH  CH2  CH2  CH2  C  CH3 is :
| |
OH Br

(A) 6, 6-Dibromoheptan-2-ol (B) 2, 2-Dibromoheptan-6-ol

(C) 6, 6-Dibromoheptan-2-al (D) None of these
071. The IUPAC name of the given compound is:

(A) 3,3-Dimethylcyclohexanol (B) 3,3-Dimethyl-1-hydroxy cyclohexane

(C) 1,1-Dimethyl-3-hydroxy cyclohexane (D) 1,1-Dimethylcyclohexan-3-ol
072. The IUPAC name of the compound is :

(A) 4-Ethyl-3-methylnonane-2, 8- diol (B) 6-Ethyl-7-methylnonane-2, 8-diol

(C) 5-Ethyl-1, 6, 7-trimethylheptane-1, 7-diol (D) 4-Ethyl-2-methylnonane-2, 7-diol
073. IUPAC name of the compound CH3  NH  CH  CH2  CH  CH3 is
| |
CH3 CH3
(A) 2-(N-methylamino)-4-methylpentane (B) N-Methyl-4-methylpentan-2-amine
(C) 2-(N-methylamino)-3-isopropylpropane (D) 2-(N-methylamino)-1, 4, 4-trimethylbutane
074. The correct IUPAC name of the compound is :

(A) 3-(1-Methylethenyl)-4-hydroxypentan-2-one
(B) 3-(1-Hydroxyethyl)-4-methylpent-4-en-2-one
(C) 3-(1-Hydroxymethyl)-4-methylenepentan-2-one
(D) 3-(1-Oxoethyl)-4-methylpent-4-en-2-ol.
075. The correct structure of 6-Amino-4-hydroxycylohex-2-ene-1-sulphonic acid.

(A) (B) (C) (D)

IUPAC-Nomenclature of chain terminating Functional groups

076. Which of the following compound is wrongly named ?
(A) CH 3CH 2CH 2CHCOOH ; 2-Chloro pentanoic acid
|
Cl
(B) CH 3C  CCHCOOH ; 2-Methyl hex-3-enoic acid
|
CH 3

41
 IUPAC Nmenclature and Structural Isomerism
(C) CH3CH2CH=CHCOCH3 ; Hex-3-en-2-one
(D) CH 3  CHCH 2CH 2CHO ; 4-Methyl pentanal
|
CH 3
077. The IUPAC name of the following is :
CH3 CH  CH  CH2  CH  CH2COOH
|
NH2
(A) 3-Aminohept-5-enoic acid (B) 5-Aminohex-2-enecarboxylic acid
(C) 3-Aminohept-4-enoic acid (D) 5-Aminohept-2-enoic acid

078. is named as :

(A) 2, 3-Dimethylenebutanal (B) 3-Methyl-2-methylenebut-3-enone

(C) 3-Methyl-2-methylenebut-3-enal (D) 2, 3-Dimethylenebutanone
079. The correct IUPAC name of compound is :

(A) 1-Chloropentane-1, 4-dione (B) 4-Chlorocarbonylbutan-2-one

(C) 4-Oxopentanoyl chloride (D) 3-Oxobutanecarbonyl chloride
080. The correct IUPAC name of following compound is
COOH

OH
CH2NH2
(A) 4-Aminomethyl-3-hydroxycyclohex-5-ene-1-carboxylic acid
(B) 2-Aminomethyl-5-carboxycyclohex-3-en-1-ol
(C) 4-Aminomethyl-5-hydroxycyclohex-2-ene-1-carboxylic acid
(D) 3-Hydroxy-4-aminomethylcyclohex-5-en-1-oic acid
081. IUPAC name of given compound is :

(A) 3- Carbonitrile-3-methyl butanal (B) 3-Formyl-2-methyl propne nitrile

(C) 3-Cyanobutanal (D) 2-Methyl-4-oxobutane nitrile]
082. The correct IUPAC name of following compound is :

(A) Methyl -2-ethylpropanoate (B) Methyl butane-2-carboxylate

(C) Methyl- 2-methylbutanoate (D) Methoxypentanone
083. Ethyl ethanoyloxyethanoate is :

(A) CH2 (B) CH2 (C) CH2 (D) CH2

42
 IUPAC Nmenclature and Structural Isomerism
084. IUPAC name of the compound BrCH2  CH  CO  CH2  CH2 CH3 is
|
CONH2
(A) 2-Bromomethyl-3-oxohexanamide (B) 1-Bromo-2-amido-3-oxohexane
(C) 1-Bromo-2-amido-n-propylketone (D) 3-Bromo-2-proponyl-propanamide

085.

The IUPAC name of the compound is :

(A) Propanoic anhydride (B) Dipropanoic anhydride
(C) Ethoxy propanoic acid (D) 1-Oxopropyl propanoate
086. The IUPAC name of the compound is :

(A) Cyclobutanedioic anhydride (B) Butanedicarboxylic anhydride

(C) Cyclobutanedicarboxylic anhydride (D) Butanedioic anhydride
IUPAC-Nomenclature of Aromatic compounds
087. The IUPAC name of the following compound is :

(A) 5-Bromo-3-hydroxybenzenecarbaldehyde (B) 3-Bromo-5-formylphenol

(C) 3-Bromo-5-hydroxybenzenecarbaldehyde (D) 1-Bromo-3-formyl-5-hydroxybenzene

088. IUPAC name of

(A) 4-Chlorophenyl benzoate. (B) Phenyl-4-chlorobenzenecarboxylate.

(C) Benzyl-4-chlorobenzenecarboxylate. (D) 4-Chloro diphenylcarboxylate.
089. The correct IUPAC name of the compound.

(A) N–Formyl-4-chlorobenzenamine (B) N–Formyl-4-chloroaniline

(C) N–(4-chlorophenyl)methanamide (D) N–(Parachlorophenyl)–N–formylaniline

090. IUPAC name of the compound is

(A) 2-Chlorocarbonyl ethylbenzenecarboxylate (B) 2-Carboxyethylbenzoyl chloride

(C) Ethyl 2-(chlorocarbonyl)benzenecarboxylate (D) Ethyl 1-(chlorocarbonyl)benzenecarboxylate

43
 IUPAC Nmenclature and Structural Isomerism
091. The IUPAC name of the compound is :

(A) 2-Cyano-1-formylbenzene-4-carboxylic acid (B) 3-Cyano-4-formylbenzenecarboxylic acid

(C) 4-Carboxy-2-cyanobenzene-1-carbaldehyde (D) 2-Formyl-5-carboxybenzene-1-carbonitrile
092. The correct IUPAC name of the compound

(A) 2-Phenoxycarbonylbenzenecarboxylic acid (B) Phenyl-2-carboxybenzenecarboxylate

(C) 2-Benzoyloxybenzenecarboxylic acid (D) 2-Benzyloxycarbonylbenzenecarboxylic acid
Structural Isomerism
093. Isomers have essentially identical.
(A) Structural formula (B) Chemical properties (C) Molecular formula (D) Physical properties
094. Compound with same molecular formula but different structural formula are called.
(A) Isomers (B) Isotopes (C) Isobars (D) Isoelectric
095. What is the correct relationship between the following compounds ?
CH3  CH2  CH  CH2  CH3 , CH3  CH2  CH2  CH2  CH2
| |
CH3 CH3
(A) Chain isomers (B) Position isomers (C) Functional isomers (D) Identical
096. What is the relation between 3-Ethylpentane and 3-Methylhexane ?
(A) Chain isomers (B) Position isomers (C) Functional isomers (D) Relation

097.

I II III
Among these, positional isomers are
(A) I and II (B) I and III (C) II and III (D) all of these
098. CH3 – CH2 – NH – CHO ; CH3  CH  CHO
|
NH2

I II
Which type of isomerism is observed between I and II.
(A) Chain isomers (B) Position isomers (C) Functional isomers (D) Metamers
099. Molecular formula C4H10O represent
(A) Two primary alcohol (B) One secondary alcohol
(C) One tertiary alcohol (D) All of these
100. Which amongs the following are not correctly matched ?

(A) & CH2=CH–CH=C=CH–CH=CH2 are ring chain isomers.

44
 IUPAC Nmenclature and Structural Isomerism

(B) & are positional isomers.

(C) & are chain isomers.

(D) & are functional group isomers.

H 3C
101. CH3CH2CH2OCH3 CHOCH3 CH3CH2O CH2CH3
H 3C
I II III
III is the metamer of
(A) I only (B) II only (C) both I and II (D) none of these

Number of Structural Isomers

102. Degree of unsaturation of benzoyl chloride is
(A) 3 (B) 2 (C) 5 (D) 6.
103. How many positional isomers are possible for dimethylcyclohexane ?
(A) 3 (B) 4 (C) 5 (D) 6
104. How many aromatic isomers are possible for trichlorobenzene (C6H3Cl3) ?
(A) 2 (B) 3 (C) 4 (D) 5
105. The number of ether isomers represented by formula C4H10O is (only structural)
(A) 4 (B) 3 (C) 2 (D) 1
106. Total number of 2° amine isomers of C4H11N would be (only structural)
(A) 4 (B) 3 (C) 5 (D) 2
107. How many structural isomers of all the tertiary alcohols with molecular formula C6H14O.
(A) 2 (B) 3 (C) 4 (D) 5
108. The number of structural isomers for C5H10 are :
(A) 8 (B) 6 (C) 9 (D) 10
109. The number of acyclic isomers of C3H5Cl are :
(A) 1 (B) 2 (C) 3 (D) 4
110. The number of cyclic ketones of molecular formula C3H4O are :
(A) 2 (B) 1 (C) 3 (D) 4
111. The number of cyclic isomers of molecular formula C3H4Cl2 are :
(A) 1 (B) 2 (C) 3 (D) 4
112. The number of structural isomers of for C4H9Cl are :
(A) 1 (B) 2 (C) 3 (D) 4

EXERCISE-2
113. Which of the following compounds has wrong IUPAC name: [AIEEE- 2002]
(1) CH3 – CH2 – CH2 – COO – CH2CH3  Ethyl butanoate
(2)  3-Methylbutanal

45
 IUPAC Nmenclature and Structural Isomerism
(3)  2-Methyl-3-butanol

(4)  2-Methyl-3-pentanone

114. The general formula CnH2nO2 could be for open chain [AIEEE- 2003]
(1) diketones (2) carboxylic acids (3) diols (4) dialdehydes.

115. The IUPAC name of the compound is [AIEEE- 2004]

HO

(1) 3, 3-dimethyl-1-hydroxycyclohexane (2) 1, 1-dimethyl-3-hydroxycyclohexane

(3) 3, 3-dimethyl-1-cyclohexanol (4) 1, 1-dimethyl-3-cyclohexanol
116. The IUPAC name of the compound shown below is [AIEEE- 2006]
Cl
|

Br

(1) 2 - Bromo-6-chlorocyclohex-1-ene (2) 6-Bromo-2-chlorocyclohexene

(3) 3-Bromo-1-chlorocyclohex-1-ene (4) 1-Bromo-3-chlorocyclohexene

117. The IUPAC name of is : [AIEEE-2007]

(1) 5, 5-Diethyl-4, 4-dimethylpentane (2) 3-Ethyl-4,4-dimethylheptane
(3) 1, 1-Diethyl-2, 2-dimethylpentane (4) 4, 4-Dimethyl-5, 5-diethylpentane
118. The correct decreasing order of priority for the functional groups of organic compounds in the IUPAC
system of nomenclature is [AIEEE-2008]
(1) –SO3H, –COOH, –CONH2, –CHO (2) –CHO, –COOH, –SO3H, –CONH2
(3) –CONH2, –CHO, –SO3H, –COOH (4) –COOH, –SO3H, –CONH2, –CHO
119. The IUPAC name of neopentane is : [AIEEE-2009]
(1) 2, 2-dimethylpropane (2) 2-methylpropane
(3) 2, 2-dimethylbutane (4) 2-methylbutane
120. Aspirin is known as : [AIEEE 2012]
(1) Acetyl salicylic acid (2) Phenyl salicylate (3) Acetyl salicylate (4) Methyl salicylic acid
121. How many  and  bonds are in the given compound ?
HC  C — CH = CH
2
(1) 3 and 6 bonds (2) 3 and 7 bonds (3) 2 and 7 bonds (4) 4 and 8 bonds
122. How many 2º and 3° carbon atoms are present in the given compound respectively ?

(1) 9 & 4 (2) 10 & 3 (3) 9 & 3 (4) 6 & 1

46
 IUPAC Nmenclature and Structural Isomerism
123. In the organic compound , the pair of hybridised orbitals involved in the formation
of : C 2  C3 bond is :

(1) sp  sp 2 (2) sp  sp 3 (3) sp 2  sp3 (4) sp3  sp3

124. Which of the following is unsaturated hydrocarbon ?

(1) (2) (3) (4)

125. The correct IUPAC name of the following compound is

(1) 4-Ethyl-3,5-dimethylhexane (2) 2,4-Dimethyl-3-ethylhexane

(3) 3-Ethyl-2,4-dimethylhexane (4) 3-sopropyl-4-methylhexane
126. Which is the structure of Pyrrole ?

(1) (2) (3) (4)

N S O N

H
127. Which IUPAC name is incorrect among the following compounds ?
(1) CH3–CH=CH–CH2–Cl 1-Chlorobut-2-ene
(2) HCC–CH2–CH2–Br 1-Bromobut-3-yne
(3) CH3–CH=CH–CH=CH2 Penta-1,3-diene

(4) 4-Bromo-2,2-dichloropentane

128. Which of the following represent incorrect numbering.

(1) (2) (3) (4)

129. The IUPAC name of the compound shown below is

Cl
|

Br

(1) 2 - Bromo-6-chlorocyclohex-1-ene (2) 6-Bromo-2-chlorocyclohexene

(3) 3-Bromo-1-chlorocyclohex-1-ene (4) 1-Bromo-3-chlorocyclohexene
130. The IUPAC name of compound CH3–C(CH3)2 – CH2–CH=CH2 is
(1) 2, 2-Dimethylpent-4-ene (2) 2, 2-Dimethyl-2-pentene
(3) 1,1,1-Trimethylbut-3-ene (4) 4,4-Dimethylpent-1-ene
131. What is the structure of 4-Methylhex-5-en-3-ol.

(1) (2) (3) (4)

47
 IUPAC Nmenclature and Structural Isomerism
132. A compound having straight chain of five carbon atoms has one ketone group and two methyl groups on
different-different carbon atoms. The IUPAC name of the compound is :
(1) 2,4-Dimethyl-3-oxopentane (2) 2,4-Dimethylpentan-3-one
(3) 3,4-Dimethyl-2-oxopentane (4) 3,3-Dimethylpentan-2-one

133. What is the IUPAC name of

(1) 5-Chloro-3-hydroxybenzenecarbonyl chloride. (2) 3-Hydroxy-5-chlorobenzenecarbonyl chloride.

(3) 3-Chloro-5-hydroxybenzenecarbonyl chloride. (4) 1-Chlorocarbonyl-3-chlorobenzen-1-ol
134. The correct IUPAC name of compound is :

COOH
Br

NH2

(1) 3-Amino-6-bromocyclohexane-1-carboxylic acid

(2) 2-Bromo-5-aminocyclohexane-1-carboxylic acid
(3) 5-Amino-2-bromocyclohexane-1-carboxylic acid
(4) 4-Bromo-5-carboxycyclohexanamine

135. The IUPAC name of is :

(1) N-Methyl-N-ethyl ethanamine (2) Diethyl methanamine

(3) N-Ethyl-N-methyl ethanamine (4) Methyl diethyl ethanamine
136. In the given formula G is an unknown group.

What will be the group G, which can change the word root (parent carbon chain length) of above structure?
(1) –CH=CH2 (2) –Cl (3) –CH2–CH2 –CH3 (4) –COOH

137. IUPAC name of is

(1) N-Deutero-N-formylbenzenamine (2) N-Phenylamino-N-deuteromethanal

(3) N-Deutero-N-phenylmethanamide (4) N-Deuterobenzene carboxamide
138. Correct IUPAC name of given ester is:
CH3 – CH– C – O – C 2H5
| ||
Br O
(1) Ethyl 2–bromopropanoate (2) 2–Bromoethylpropanoate
(3) Ethyl 1–bromoethanoate (4) 2–Bromo ethoxyethanecarboxylate
139. Relation between Ethyl benzenecarboxylate and phenyl propanoate is :
(1) Metamers (2) Functional isomers (3) Chain isomers (4) Homologues

48
 IUPAC Nmenclature and Structural Isomerism
140. The correct IUPAC name of the compound :

is :

(1) 4-Methoxy-2-nitrobenzaldehyde (2) 4-Formyl-3-nitro anisole

(3) 4-Methoxy-6-nitrobenzaldehyde (4) 2-Formyl-5-methoxy nitrobenzene
141. Which of the following pair of compounds is not functional isomers ?
OH O
(1) and O (2) and
OH
O O
(3) OH and O (4) and
O O

O
142. and D are related as :
D O
(1) Functional Isomers (2) Position Isomers (3) Chain Isomers (4) Metamers
143. Which of the following is correctly matched.

(1) & chain somer (2) & Identical

(3) & Positional isomer (4) & Metamer

144. Which of the following pairs of structures do not represent isomers ?

(1) & (2) & (3) & (4) &

145. Total number of structural isomers possible from molecular formula C8H18 that contain 7 carbons in the
parent chain are :
(1) 3 (2) 4 (3) 5 (4) 6
146. Total number of position isomers of trimethyl cyclohexane are :
(1) 5 (2) 6 (3) 7 (4) 8
147. How many 1 amines are possible with molecular formula C4H11N (only structural isomers)
(1) 3 (2) 4 (3) 5 (4) 6
148. Hybridisation of carbon atoms present in the smallest ester are :
(1) All sp3 (2) All sp2 (3) sp2 and sp3 (4) sp2 and sp
149. The number of metamers of the compound with molecular formula C5H12O is/are :
(1) 1 (2) 3 (3) 8 (4) 6
150. How many tertiary alcohols is/are possible with molecular formula C5H12O ?
(1) 1 (2) 2 (3) 3 (4) 4
49
 IUPAC Nmenclature and Structural Isomerism

EXERCISE-1
PART-1
001. (a) 19  bonds, 6 bonds (b) 22  bonds (c) 20  bonds
002. (a) 21  bonds, 3 bondsb) 13  bonds, 3 bonds (c) 17  bonds, 2 bonds
003. (a) 1° H  9, 3° H  1 (b) 1°H  6, 2°H  2 (c) 1°H  6, 2°H  4
004. (a) 1° C  1, 1° H  3, 2°C  5, 2°H  10, 3°C  1, 3°H  1
(b) 1° C  2, 1° H  6, 2°C  6, 2°H  12, 3°C  2, 3°H  2
(c) 1° C  3, 1° H  9, 2°C  2, 2°H  4, 3°C  1, 3°H  1

005. (a) H2N–CH2–CH2–OH and

(b) CH3 – CH2 – CH2 – CH2 – OH and

(c) and
(d) CH3 – CH = CH – CH2 – CH2 – CH2 – CH3 and
006. (a) H–COOH, CH3–COOH, CH3–CH2–COOH , CH3–CH2 –CH2–COOH
(b) CH2=CH2, CH3–CH=CH2 , CH3–CH2–CH=CH2, CH3–CH2–CH2–CH = CH2
(c) CH3–CO–CH3, CH3–CO–C2 H5 , C2H5–CO–C2 H5 ,C3 H7 –CO–C2 H5
007. (a) Homocyclic, alicyclic, saturated (b) Homocyclic, aromatic, unsaturated
(c) Heterocyclic, alicyclic, saturated (d) unsaturated.
008. (a) 2° (b) 2° (c) 3° (d) 3°
009. (a) 2° (b) 3° (c) 1° (d) 3°
010. (a) Isopropyl group (b) Secondary–butyl group (c) Tertiary-butyl group (d) Ethyl group
(e) n-propyl group
011. (a) 2-Methyl propane (b) 2, 2-Dimethyl propane (c) 2, 2-Dimethyl butane
012. (a) 5-Ethyl-3-methyloctane (b) 4-Ethyl-3,7-dimethylnonane
(c) 2,2,3-Trimethylpentane (d) 4-Ethyl-2,2,6-trimethylheptane
013. (a) ring (b) side chain (c) ring (d) ring
(e) side chain (f) side chain
014. (a) Propylcyclobutane (b) Propylcyclopropane (c) 1-Cyclopropylbutane
(d)1-Ethyl-2-methylcyclopentane (e) 1-Cyclohexyl-4-cyclopropylbutane
015. (a) 3-Bromo-2-chloro-5-methyloctane
(b) 4-Ethyl-4,5-dimethyldecane
(c) 4-(1,1-Dimethylethyl)-5-(1-methylethyl) octane
(d) 5-(1,2-Dimethylpropyl) nonane

016. (a) (b) (c)

017. (a) sec-Butylcyclohexane (b) tert-Butylcyclohexane

(c) Isopropylcyclohexane (d) Neopentylcyclopentane

50
 IUPAC Nmenclature and Structural Isomerism
018. General formula  CnH2n
H2C = CH2 Ethene
CH3–CH=CH2 Propene
CH3–CH2 –CH=CH2 1-Butene
019. (a) 3,3-Dimethylbut-1-ene (b) Buta-1,3-diene
(c) 2,4,4-Trimethylhept-1-ene (d) But-2-ene

020. (a) (b)

021. (a) 5-Methylhexyne (b) 3-Methylbutyne (c) 4-Methylpent-2-yne

022. (a) (b)

(c) (d)

2
023. (a) (b) 1–(Hex–3–enyl)cyclohex–1–ene
1-cyclobutylethene

(c) (d)

024. (a) 3-Chlorobutan-2-ol

(b) 2-Ethylbut-3-en-1-ol
(c) 5-Aminomethyl-3-ethylheptan-2-ol
(d) 3-Butylpentane-2,4-dione
(e) 5-Oxoheptane-3-sulphonic acid.
(f) 3-(2-Bromoethyl)hexan-2-ol
(g) 2,5-Dichloro-3-ethoxy-4-methoxyhexane
(h) 3-Bromo-4-methylpentane-2-sulphonic acid
025. (a) 4-Cyclohexylbut-3-en-2-one (b) 2-(2-hydroxybutyl) cyclohexan-1-ol
(c) 2-Methoxy-N-methylethan-1-amine
026. (a) CH 3–CH2 –CH2 –CH2–OH (b) CH3–CH(SH)–CH2–CH3
(c) CH 3 –CH(NH2 )–CH2–CH2–CH3 (d) CH3 –CO–CH2 –CH2 –CH3
(e) HO–CH2–CH2 –CH(Cl)–CH2 –CH3 (f) CH 3–CO–CH2 –CO–CH2–CH3
027. (a) Methoxyethane (b) Ethoxyethane
(c) Epoxyethane (d) 1-chloro-2, 3-epoxypropane

51
 IUPAC Nmenclature and Structural Isomerism

028. (a) (b) (c) (d)

(e) (f) (g) (h)

029. (a) CH3–CH(SO3H)–CH(OH)–CH2 –CH3 (b)

(c) (d) (e)

(f) CH3 –CH2 –COOCH2–CH2 –Cl (g)

030. (a) (b)

(c) (d)

031. (a) Methyl-2-ethylbutanoate (b) Ethyl-3-methylpent-4-en-1-oate

(c) 3,3 Dimethyl –2 – (1–methylethyl)butanamide
032. (a) Ethanoic 2-methylpropanoic anhydride (b) Benzenecarboxylic anhydride
(c) Pent-2-enedioic anhydride (d) Cyclohexane-1, 2-dicarboxylic anhydride
033. (a) 2-Methylpropanamide (b) N-Methylpropanamide
(c) N, N-Dimethyl-2-methylpropanamide (d) N-Phenylbenzenecarboxamide
034. (a) Methylbenzene or Toluene (b) Diphenylmethane
(c) 4–Methyl phenol (p–Cresol) (d) 2–Hydroxybenzenecarbaldehyde (Salicylaldehyde)
035. (a) Cyclohexylbenzene (b) 4-Bromo-3, 6-diphenyloctane
(c) 1, 2-Dichloro-4-ethyl-5-nitrobenzene (d) 4-Chloro-1-nitro-2-propylbenzene
036. (a) 1,2–Dimethyl benzene (o–Xylene) (b) Phenylethene (Styrene)
(c) 1-Chloro-1-phenylethane. (d) Isopropylbenzene (Cumene)
037. (a) Chain Isomers (b) Functional isomers (c) Homologs.
038. (a) Chain Isomers (b) Functional isomers (c) Metamers. (d) Position isomers
039. H2C = CH – CH2 – CH3, H3C – CH = CH – CH3, H2 C  C – CH3
|
CH3

040. , ,

041. , , , ,

52
 IUPAC Nmenclature and Structural Isomerism

042. , , ,

043. or

PART-2
044. (C) 045. (C) 046. (B) 047. (B) 048. (D) 049. (D) 050. (C)
051. (D) 052. (C) 053. (B) 054. (C) 055. (A) 056. (C) 057. (B)
058. (C) 059. (C) 060. (D) 061. (C) 062. (D) 063. (C) 064. (D)
065. (B) 066. (B) 067. (A) 068. (B) 069. (B) 070. (A) 071. (A)
072. (A) 073. (B) 074. (B) 075. (B) 076. (B) 077. (A) 078. (C)
079. (C) 080. (C) 081. (D) 082. (C) 083. (D) 084. (A) 085. (A)
086. (D) 087. (C) 088. (B) 089. (C) 090. (C) 091. (B) 092. (A)
093. (C) 094. (A) 095. (A) 096. (A) 097. (A) 098. (C) 099. (D)
100. (B) 101. (C) 102. (C) 103. (B) 104. (B) 105. (B) 106. (B)
107. (B) 108. (D) 109. (C) 110. (B) 111. (B) 112. (D)

EXERCISE-2
113. (3) 114. (2) 115. (3) 116. (3) 117. (2) 118. (4) 119. (1)
120. (1) 121. (2) 122. (1) 123. (3) 124. (4) 125. (4) 126. (1)
127. (2) 128. (2) 129. (3) 130. (4) 131. (2) 132. (2) 133. (3)
134. (3) 135. (3) 136. (4) 137. (3) 138. (1) 139. (1) 140. (1)
141. (4) 142. (1) 143. (2) 144. (4) 145. (1) 146. (2) 147. (2)
148. (3) 149. (4) 150. (1)

53
 Structure Identification & POC

Structure Identification & POC

Introduction:
In this topic we will try to find structure of the given organic compound with the help of characteristic tests
performed by the compound.
Monohalogenation :
It is replacement of one hydrogen by halogen(Cl2, Br2, F2, I2), carried out in sunlight in which a C–
H bond cleaves and a C–X bond is formed.If a molecule has more than one type of H-atoms, then on
monochlorination, it forms a mixture of monochloroisomers and these are structurally position isomers.
So the total no. of positional isomers (structural only) of monochloro compounds is equal to the number
of different types of H-atoms present in the reactant. The different type of H-atoms are also known
as non-identical Hydrogens or non-equivalent Hydrogens or chemically different Hydrogens.
Note : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated by taking X2 and
sunlight, but H-atoms of Benzene ring replaced when X2 is taken with Lewis acid.

Ex. (i) CH4 CH3Cl + HCl (1–Monochloroproduct)

Monochlorination

Cl
–

(ii) + HCl (One Monochloro derivative)

Monochlorination

CH3 CH2Cl
–

(iii) (One Monochloro derivative)

Monochlorination

(iv) CH3 – CH2 – CH2 – CH3 2 Products (structural isomers)

Monochlorination
(v) CH3–CH2–CH2–CH2–CH3 3 Products (structural isomers)
Monochlorination

(vi) 4 Products (structural isomers)

Monochlorination
CH3
–

(vii) 5 Products (structural isomers)

Monochlorination

Catalytic Hydrogenation :
Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room temperature.
All Carbon–Carbon  bonds(C=C, CC) get hydrogenate.
Note : (i) Aromatic  bonds are stable at room temperature but can be hydrogenated at high temperature.
(ii) It can be concluded that the hydrogenation product of an alkene or alkyne or any unsaturated
compound is always a saturated compound.
(iii) The number of mole of H2 consumed by 1 mole of compound is equal to the number of  bonds.
(iv) During catalytic hydrogenation carbon skelton does not change.
Application : This reaction gives an information about molecule that the molecule is saturated or
unsaturated.

54
 Structure Identification & POC
General reaction :
Ni
(a) R – CH = CH – R + H2 
 R – CH2 – CH2 – R
Ni / Pt / Pd
(b) R – C  C – R + 2H2    
 R – CH2 – CH2 – R
H2

R – CH  CH – R H
2
 R – CH2 – CH2 – R
(Not obtained)
2H / Ni
(c) CH2 = CH – CH = CH2  
2

 CH3 – CH2 – CH2 – CH3

CH = CH2 CH2 – CH3

H2 / Ni
–

–
(d)      
room temperature
CH2 – CH3
–

H 2/Ni
(100 – 150ºC)

Ozonolysis :
Ozonolysis reaction is used to determine the position of C=C, CC in a molecule. In this reaction
Alkene, Alkyne and polyalkene on ozonolysis undergo oxidative cleavage. It is of two types.

(i) Reductive ozonolysis

Reagents are : (1) O3 (ozone) (2)H2O/Zn or H2O/(CH3)2S.
The products are carbonyl compounds (aldehydes or ketones).

(ii) Oxidative ozonolysis

Reagents are : (1) O3 (2) H2O or (H2O/H2O2)
The products are ketones and/or acids.

Note : (i) For one double bond or one triple bond, one ozone molecule is used.
(ii) Ozonolysis does not interfere with other functional groups.
(ii) At higher temperature, the aromatic double bonds can also undergo ozonolysis reaction.
General Reaction :
(i) Reductive ozonolysis
(1) O3
R–CH C–R R–CH=O + O=C–R + ZnO + H2O
(2) Zn/H2O
R R
(1) O3
R–CC–H (2) Zn/H2O R–C–C–H + ZnO + H2O
OO

(ii) Oxidative ozonolysis

(1) O3
R–CH C–R (2) H O R–COOH + O=C–R + H2O
2 2

R R
(1) O3
R–CC–H (2) H2O2 R–COOH + HCOOH

(1) O3
Ex. (a) CH2=CH2 CH2=O + CH2=O
(2) Zn/H2O
(1) O3
(b) CH3–CH2–CH=CH2 (2) Zn/H2O
CH3–CH2–CH=O + O=CH2

55
 Structure Identification & POC
(1) O3
(c) CH2=CH–CH2–CH=CH–CH3 CH2=O + O=CH–CH2–CH=O + O=CH–CH3
(2) Zn/H2O

(1) O3
(d) (2) Zn/H2O
2 OHC–CH2–CHO (Propandial)

(1) O3
(e) O=CH–CH2– C –CH2–CH=O + O=CH2
(2) Zn/H2O
O

O3 ()
(f)   or (glyoxal)
Zn, H2O

(i)O3
CH = CH – CH3 + CH3CH=O
(ii)Zn, H2O
–

(g)
2 O=CH–CH=O + O=CH–C–CH=O + CH3CH=O
(ii)Zn, H2O
O

Practical Organic Chemistry (POC) :

Following are the tests which give functional group nature of the organic compound.
Test for acidic or active hydrogen :
When any compound release H2 gas after reaction with sodium or potassium or alkali metals or sodamide
then this reflect the presence of acidic hydrogen.
H atoms which are directly bonded to a O,N,S,X, C (sp hybridised) are active hydrogen atoms.

– + 1
General reaction : Z H + Na  Z Na + 2 H2 

1 1
Ex. (1) R—OH + Na  R— O–Na+ + H  (2) R—SO3H + Na  R—SO3–Na+ + H 
2 2 2 2
1
(3) R—C  CH + Na  R—C  C–Na+ + H  (4) R —CH = CH2 + Na  No reaction.
2 2
1
(5) R —CH2—O —CH3 + Na  No reaction. (6) HCl 
 NaCl  H2 
Na
2
Na 1 Na 1
(7) R  NH2 
 R  NHNa  H2  (8) R  SH 
 RSNa  H2 
2 2
Na 1 Na 1
(9) R  COOH 
 R  COONa  H2  (10) PhOH 
 PhONa  H2 
2 2
Unsaturation test :
(i) ( Br2 + H2O or Br2/CCl4 )Test : Red brown colour.
Red brown colour is decolourised by alkenes and alkynes.
R–CH = CH2  
2 4 Br /CCl

R–C CR  

2 4 Br /CCl

56
 Structure Identification & POC
Note : Benzene gives negative test due to aromaticity.

(ii) Baeyer’s Reagent (Cold dil. 1% alkaline KMnO4 ):Pink/purple solution

Pink or purple colour is decolourised by alkenes and alkynes.

Cold, dil.KMnO4
R–CH = CH2    

Cold, dil.KMnO4
R–C CR    

Note : Benzene gives negative test due to aromaticity.

Test for terminal Alkyne(Test due to active hydrogen) :


(i) Tollen’s Reagent (AgNO3 + NH4OH) or {Ag(NH3)2}+ OH
Tollen’s Reagent gives white precipitate (Silver alkynide) with terminal alkyne.
AgNO3 NH4OH
R–C  CH      R–C  CAg + NH4NO3
White precipitate

(ii) Ammonical cuprous chloride (Cu2Cl2 + NH4OH) :

It gives Red precipitate (Cuprous alkynide) with terminal alkyne.
Cu 2Cl 2 NH 4OH
2 R–C  CH     2 R–C  CCu  + 2NH4Cl + 2H2O
Red precipitate

Test for alcohols :

(i) Lucas Reagent (Conc. HCl + anhydrous ZnCl2) :
It gives white turbidity or cloudiness with alcohols (OH groups attached with sp3 carbon).
Lucas Reagent used to distinguish between 1°, 2°, 3° alcohol because 1°, 2°, 3° alcohols react with different
rate.

R–CH2–OH
white turbidity or cloudiness

If white turbidity immediately  3° alcohol

If white turbidity in 5 to 7 min 2° alcohol
If no turbidity or turbidity after 30 min on heating  1° alcohol
* Phenols and enols do not give Lucas test.

(ii) Victor Mayer test :

1° Alcohol
NO2
P+I2 AgNO2 HNO2 base
R–CH–OH
2 R–CH 2–I R–CH–NO
2 2
R–C=N–OH Blood Red colour

57
 Structure Identification & POC

2° Alcohol

3° Alcohol

(iii) Cerric Ammonium Nitrate test :

Alcohols(1°, 2°, 3°) also give characteristic red colour with cerric ammonium nitrate solution.

Test for phenols or enols :

Neutral FeCl3 test :
It form coloured complex (generally violet or green buff colour) with phenol or enol (OH groups attached
with sp2 carbon).
3
  
6 PhOH + FeCl3   PhO  Fe  3HCl + 3H+
 6 
(Coloured complex)

Test for Aldehydes and Ketones :

(i) 2, 4-DNP (2,4–Dinitrophenyl hydrazine) test :
Aldehydes and ketones give yellow–orange precipitate with 2,4–DNP. It is also knwon as Brady’s reagent.
C=O + H2N – NH NO2 C=N – NH NO2
NO2 NO2
2, 4-DNP (yellow–orange precipitate of Hydrazone)

(ii) Sodium bisulphite test:

Aldehydes and less hindered ketones (methyl ketones and some cyclic ketones) give white precipitate with
sodium bisulphite.

OH
C=O + NaHSO3 C
SO3Na
white precipitate

Test for Aldehydes only :


(i) Tollen’s Reagent [AgNO3 + NH4OH or [Ag(NH3)2}+ OH ] : It is mild oxidising agent.
Tollen’s Reagent oxidises aldehyde in carboxylic acid and reduced itself into black precipitate of silver
mirror.
O
AgNO3 NH4OH ||
R–CH = O      R – C – O + Ag 
silver mirror
Note : (i) Ketones do not give this test.
(ii) Formic acid and alkyl formate give this test.

(ii) Fehling’s solution :

It is an alkaline solution of cupric ion complexed with sodium potassium tartarate.
There are two solutions in Fehling solution
Solution (A) : CuSO4 solution and
Solution (B) : Alkaline solution of sodium potassiumtartarate.

58
 Structure Identification & POC
When these two solutions are mixed we get deep blue coloured solution.

CuSO4 + 2NaOH  Cu(OH)2 + Na2SO4

Cu(OH)2 + 

Equal volume of both the solutions are heated with aldehyde to give red brown precipitate of cuprous oxide
(Cu2O) which confirms the presence of aldehyde.
R – CHO + 2CuO  RCOOH + Cu2O (Red ppt)
Blue

RCHO + 2Cu2+ +  RCOO + + 2H2O

(iii) Benedict solution :

It also consists of two solutions.
Solution (A) : CuSO4 solution and
Solution (B) : Alkaline solution of sodium Citrate.
CuSO4 + 2NaOH  Cu(OH)2 + Na2SO4

Cu(OH)2 + 

Aldehyde gives positive test with Benedict solution.

RCH = O + +  +

(iv) Schiff’s reagent :

It is dilute solution of rosaniline hydrochloride whose pink colour has been discharged by passing SO2.
Aldehyde restores pink colour when treated with schiff’s reagent (Magenta solution in H2SO3).
Benzaldehyde does not gives Fehling, Bendict & Schiff's test
* Aromatic aldehydes (Benzaldehyde) do not gives Fehling and Bendict test.

Iodoform Test :
Reagents : I2 + NaOH or NaOI

Acetaldehyde, all methyl ketones & ethyl alcohol give Iodoform test.

(Where R = H, alkyl, aryl group)

59
 Structure Identification & POC
Substrate Products Substrate Products

O
(1) CH C H CHI 3  HCOO  (5) CHI3 

(2) CHI 3  CH 3COO  (6) CHI 3  CH 3CH 2 COO 

(3) CHI 3  HCOO  (7) CHI 3  CH 3CH 2 COO 

(4) CH 3  CH 3COO 

Test for Carboxylic acids :

(i) Sodium bicarbonate test (NaHCO3):
All the acids which are stronger than H2CO3 give CO2 gas with NaHCO3.

HCl + NaHCO3  NaCl + H2CO3

 H2O + CO2 

RSO3H + NaHCO3  RSO3Na + H2CO3

 H2O + CO2 

Note : If electron withdrawing group (NO2) is present at ortho and para position of phenol then it gives
positive test with sodium bicarbonate.
(ii) Litmus test: Acid converts blue litmus into red litmus while base converts red litmus into blue.
(iii) Special test for Acetic acid:
Acetic acid gives blood red precipitate with neutral FeCl3
CH 3COOH 
FeCl3
 (CH 3COO) 3 Fe 
Blood Re d ppt

Note: HCOOH 

conc. H 2SO4

 CO   H 2O
COOH conc. H 2SO4
 
 CO   CO 2  H 2O
COOH
* CO burns with blue flame and CO2 turns lime water milky..
(iv) Test For Amide : Amides give smell of ammonia when heated with alkali.

60
 Structure Identification & POC

(v) Esters are sweet (fruity) smelling liquids.

When react with NaOH & Phenophthalein then pink colour will disappear on heating.

RCOOR’ + NaOH + Phenophthalein (Pink)  R COOH + R’ OH (Colourless solution)
Test for Amines :
(i) NaNO2 + aqueous HCl test:
it is used to distinguish between 1º, 2º and 3º amines and also distinguish between aliphatic and aromatic
primary amines.
1° Aliphatic Amine: R–CH2–NH2 R–CH2–OH + N2 

1° Aromatic Amine : diazonium salt)

2° Amine: R – NH – R (N -Nitroso amine) yellow oily liquid

3° Amine : R3N unstable nitrite

(ii) Carbyl amine test (CHCl3 + KOH)

CHCl3 KOH
R–CH 2 –NH2     R–CH2–N  C + 3KCl + 3H2O
(unpleasent odour of isocyanide)
CHCl3 KOH
Ph – NH2     Ph – N  C

* This test is for 1°Amine and not for 2° and 3° Amines.

(iii) Hofmann mustard oil test

It is a test for 1º amine and aniline. Primary amine reacts with carbon disulphide to form dithioalkyl carbamic
acids which decompose on heating with mercuric chloride (HgCl2) to give alkyl isothiocyanates having
smell like mustard oil .
SH
(a) R – NH2 + S=C=S  R – NH – C 
HgCl2
 R – N = C = S + HgS + 2HCl
|


||

S
Dithioethylcarbamic acid Alkylisothiocyanate


(b) CH3CH2NH2 + S=C=S   
HgCl2
 CH CH –N = C=S + HgS + 2HCl
 3 2
(1º amine) Ethyl isothiocyanate

Similarly aniline gives phenlyisothiocyanate

(i) S=C=S
(c) C6H5NH2 C6H5N=C=S
(ii) HgCl2/
Phenylisothiocyanate

* 2° Amines and 3° Amines do not give this test.

(iv) Hinsberg reagent (C6H5SO2 Cl) :

It is used to distinguish between 1°,2° & 3° amine.

Pyridine Base
1° Amine: R–NH2 + PhSO2Cl R–NH–SO2–Ph Compound is soluble in base.

Pyridine Base
2° Amine: R2NH + PhSO2Cl R2N–SO2–Ph Compound is insoluble in base.

61
 Structure Identification & POC
Pyridine
3° Amine: R3N PhSO2Cl No reaction.

Test of Nitro group : (Mulliken- Barker’s Test)

Nitroalkane & nitrobenzene gives black ppt on reduction with Zn and ammonium chloride followed by
treating with Tollen’s reagent. This is also said to be Mulliken’s test.

(a) R–NO2 R–NHOH Ag 

(b) + Zn + NH4Cl  AgNO NH OH

  
3 
4  

Test for Carbohydrates & Sugars

Molisch test :
This is a general test for carbohydrates. One or two drops of alcoholic solution of -naphthol is added
to 2 ml glucose solution. 1 ml of conc. H2SO4 solution is added carefully along the sides of the test tube.
The formation of a violet ring at the junction of two liquids confirms the presence of a carbohydrate
or sugar.
Test for Amino acids and Proteins
(i) Ninhydrin Test :
This is used to detect the presence of amino acids & proteins.
(ii) Biuret Test (Piotrowski's test):
It is a chemical test used for detecting the presence of peptide bonds. In the presence of peptides, a
copper(II) ion forms violet-colored coordination complexes in an alkaline solution.
(iii) Xanthoproteic test:
Proteins gives yellow color with conc. HNO3.
Detection of Elements:
Detection of Carbon and Hydrogen :
Carbon and hydrogen are detected by heating the compound with copper(II) oxide. Carbon present in
the compound is oxidised to carbon dioxide (tested with lime-water, which develops turbidity) and
hydrogen to water (tested with anhydrous copper sulphate, which turns blue).

C + 2CuO  2Cu + CO2

2H + CuO  Cu + H2O

CO2 + Ca(OH)2  CaCO3 + H2O

5H2O + CuSO4  CuSO4.5H2O
White Blue
Lassaigne’s test : (Detection of N, X and S)
Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by “Lassaigne’s
test”. The elements present in the compound are converted from their covalent form to their ionic form
by fusing the organic compound with sodium metal.
Following reactions take place: C, N, S and X come from organic compound.
Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused mass
by boiling it with distilled water. This extract is known as sodium fusion extract or Lassaigne solution.

Na + C + N  NaCN

2Na + S  Na2S

Na + X  NaX

Na + C + N + S  NaSCN

62
 Structure Identification & POC
(i) Test for Nitrogen :
The sodium fusion extract is boiled with iron(II) sulphate and then acidified with dilute sulphuric acid.
The formation of Prussian blue or green colour confirms the presence of nitrogen. Alternatively FeCl3
and dil. HCl may be added.
6NaCN + FeSO4  Na4[Fe(CN)6]
Na4[Fe(CN)6] + 4Fe3+ 
xH 2O
 Fe4[Fe(CN)6]3. xH2O
Ferric ferrocyanide (Prussian blue)
(ii) Test for Sulphur
(a) The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A black
precipitate of lead sulphide indicates the presence of sulphur.
Na2S + (CH3COO)2Pb  PbS
Black
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour
indicates the presence of sulphur.
Na2S + Na2[Fe(CN)5 NO]  Na4[Fe(CN)5NOS]
Sodium thionitroprusside (Violet/Purple)
(c) In case, nitrogen and sulphur both are present in an organic compound, then sodium thiocyanate is
formed. It gives blood red colour with neutral FeCl3.
Na + C + N + S  NaSCN
FeCl3 + NaSCN  Fe(SCN)3
Blood red
(iii) Test for Halogens :
The sodium fusion extract is acidified with nitric acid and then treated with silver nitrate.
NaX + AgNO3  AgX  (X= Cl, Br, I)

If AgX is white ppt soluble in dilute ammonia then X= Cl

If AgX is white ppt soluble concentrated ammonia then X= Br
If AgX is white ppt insoluble in ammonia then X= I
Note : The sodium fusion extract is first boiled with concentrated nitric acid to decompose cyanide or
sulphide of sodium formed during Lassaigne’s test. These ions would otherwise interfere with silver
nitrate test for halogens.
(iv) Test for Phosphorus :
The compound is heated with an oxidising agent (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.
Na3PO4 + 3HNO3  H3PO4 + 3NaNO3
H3PO4 + 12(NH4)2MoO4 + 21HNO3  (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O
Ammonium Ammonium
molybdate Phosphomolybdate
Quantitative analysis (Estimation of elements):
After the detection of various elements in the organic compound, the next step is the determination of their
percentage composition. The determination of the percentage of various elements is also referred to as
estimation of elements. The different methods employed for the estimation of various elements are
being discussed as follows :
(1) Estimation of Carbon and Hydrogen :
(Liebig’s Method)

63
 Structure Identification & POC
Carbon and hydrogen in the organic compound are estimated together.
Principle :
A known mass of the organic compound is heated with dry copper oxide in an atmosphere of air or oxygen
free from moisture and carbon dioxide. The carbon and hydrogen of the organic compounds are oxidized to
carbon dioxide and water respectively.
C + 2CuO  CO2 + 2Cu
2H + CuO  H2O + Cu
Carbon dioxide produced is collected in potash bulbs (containing KOH) whereas water is absorbed in
calcium chloride tube (containing CaCI2). The respective masses of CO2 and H2O are determined by
difference.
Knowing the masses of CO2 and water vapours formed and the mass of the compound taken, the percentage
of carbon and hydrogen can be calculated.
Calculations :
Let the mass of the organic compound taken = w g
Mass of water formed = x g
(Indicated by increase in the mass of U tube)
Mass of carbon dioxide formed = y g
(Indicated by increase in the mass of potash bulb)
(i) Percentage of Carbon :
44 g of CO2 (G.M.M.) contains carbon = 12 g
12y
y g of CO2 contains carbon = g
44

12y
Now, g of carbon is present in w g of organic compound.
44

12y
 Percentage of carbon in the organic compound = 44  w  100

(ii) Percentage of Hydrogen :

18 g of H2O (G.M.M) contains hydrogen = 2g
2x
x g of H2O contains hydrogen = g
18

2x
Now, g of hydrogen is present in w g of organic compound.
18

2x
 Percentage of hydrogen in the organic compound =  100
18w

12  W
CO2  100 2  WH2O  100
In Short, % C  44  W and %H 
18  Wsubs tan ce
subs tan ce

Que. 0.378 g of an organic acid gave on combustion 0.264 g of carbon dioxide and 0.162 g of water vapour.
Calculate the percentage of C and H.
Ans. Mass of organic compound = 0.378 g
Mass of CO2 formed = 0.264 g
Mass of H2O formed = 0.162 g
(i) Percentage of carbon
44 g of CO2 contains carbon = 12 g

64
 Structure Identification & POC
12
0.264 g of CO2 contains carbon =  0.264 = 0.072 g
44

0.072
Percentage of carbon =  100 = 19.04%
0.378
(ii) Percentage of hydrogen
18 g of H2O contains hydrogen = 2g
2
0.162 g of H2O contains hydrogen =  0.162 = 0.018 g
18

0.018
Percentage of hydrogen =  100 = 4.76%
0.378

(2) Estimation of Nitrogen :

There are two methods in use for the estimation of nitrogen. These are :
(a) Duma’s Method (b) Kjeldahl’s Method.

Duma’s Method : This method is applicable to nitrogenous compounds.

Principle :
A known mass of the organic compound is heated strongly with excess of copper oxide in an atmosphere
of carbon dioxide. The carbon and hydrogen are converted to CO2 and water. Nitrogen is set free as
dinitrogen. If any oxide of nitrogen is produced, it is reduced to dinitrogen by passing over hot reduced
copper spiral. The dinitrogen is collected over the concentrated solution of potassium hydroxide and its
volume is measured at room temperature and atmospheric pressure.
The chemical reaction can be represented as :

Calculations :
Let the mass of the organic compound taken = W g
Volume of moist N2 collected = v cm3
Barometric pressure = P mm
Room temperature = TK
Pressure of water vapours at T K = p mm
Pressure of dry N2 = (P – p) mm
Step I. To reduce the volume of N2 to S.T.P.
V1 = v cm3, V2 = ?
P1 = (P – p), P2 = 760 mm
T1 = T, T2 = 273 K
P1V1 P2 V2
T1
= T
2

P1V1 T2 (P  p)  273

V2 = × =
T1 P2 T  760

65
 Structure Identification & POC
Step II. Calculation of percentage of nitrogen
28 V2
22400 cm3 of N2 at S.T.P. weights = g
22400

28 V2
Now amount of nitrogen present in W g of organic compound = g
22400

28 V2 100
 Percentage of N in organic compound =
22400
× .
W

28  VN 2 (S.T.P.)  100
In Short, %N=
22400  WSubs tan ce

Questions based on Duma’s Method :

Que. 0.25 g of an organic compound gave 30 cm3 of moist dinitrogen at 288 K and 745 mm pressure. Calculate
the percentage of nitrogen. (Aq tension of 288 K = 12.7 mm).
Ans. Mass of the substance = 0.25 g
Volume of moist dinitrogen = 30 cm3
Temperature = 288 K
Pressure = 745 –12.7 = 732.3 mm

Step I. To reduce the volume of N2 at S.T.P.

P1V1 P2 V2
We know , T1
= T2
P2, T2, V2 refer to S.T.P. conditions)
P1V1 T2 732.3  30  273
 V2 =   = 27.4 cm3.
T1 P2 288  760
Step II. Calculation of percentage of nitrogen.
22400 cm3 of dinitrogen at S.T.P. weighs = 28 g
28  274
27.4 cm3 of dinitrogen at S.T.P. weighs =  0.034 g
22400

0.034
Percentage of nitrogen in organic compound =  100 = 13.6.
0.25
Kjeldahl’s Method :
This method is simpler and convenient. It is largely used for the estimation of nitrogen in food, fertilizers
and drugs. The method is however not applicable to compounds containing nitrogen in the ring like pyridine
or quinoline etc, and the compounds, containing nitro (–NO2) and diazo (–N = N–) groups.
Principle :
A known mass of the organic compound is heated with concentrated sulphuric acid. The nitrogen in the
organic compound is quantitatively converted into ammonium sulphate. The resulting liquid is then distilled
with excess of sodium hydroxide solution and the ammonia evolved is passed into a known but excess
volume of the standard acid (HCI or H2SO4). The acid left unused is estimated by titration with some
standard alkali. The amount of acid used against ammonia can thus, be known and from this, the percentage
of nitrogen in the compound can be calculated.
Chemical reactions involved are :

66
 Structure Identification & POC

conc.
C + H+ S CO2 + H2O + SO2
H2SO4
Organic
compound
conc.
N (NH4)2SO4
H2SO4
(NH4)2SO4 + 2NaOH Na2SO4 + 2NH3 + 2H2O

2NH3 + H2SO4 (NH4)2 SO4

Calculation :
Let the mass of organic compound = W g
Volume of standard acid (say HCI) taken = V cm3
Let molarity of acid = M1
Let volume of acid unused be = v1
Let volume of alkali (say NaOH) of molarity M2 used for neutralising unused acid = v2
Chemical equation for titration involved is
NaOH + HCI NaCI + H2O
unused
 According to molarity relation

M2  2 M11 M2  2
 = or 1  M
1 1 1

Volume of acid used by ammonia = (V –v1) cm3

Millimoles of acid used by ammonia = (V –v1) × M1
Milimoles of NH3 formed = Millimoles of acid used up
= (V –v1) × M1

Mass of NH3 formed = Millimoles × 10–3 × Molar mass

= (V –v1) × M1 × 10–3 × 17g
(V – 1 )M1  10 –3  17  14
=
17
Mass of N = a g (say)
a  100
 Percentage of N =
W

1.4  M( acid)  basicity of acid  V( acid used )

In Short %N = WSubs tan ce

1.4  N(acid)  V(acid used)

or = WSubs tan ce

Questions based on Kjeldahl’s Method :

Que. During nitrogen estimation in an organic compounds by Kjeldahl’s method, the ammonia evolved from 0.5
g of the compound neutralised 10 ml, of 1 M H2SO4, What is the % of N in the organic compound ?
Ans. Volume of 1 M H2SO4 used by NH3 = 10 ml,
Millimoles of H2SO4 used = 10× 1 = 10 m. moles

Millimoles of NH3 produced = 2 × millimoles of H2SO4

67
 Structure Identification & POC

= 2 ×10 = 20
(2 mol of NH3 neutralise 1 mol of H2SO4)

Mass of NH3 formed = Moles of NH3 × Molar mass = 20 × 10–3 × 17 g

20  10–3  17  14
Mass of N = = 0.28 g
17

0.28  100
% of N = = 56.0%.
0.5

(3) Carius Method

It is used for the estimation of halogen, sulphur and phosphorus.

Estimation of Halogens : Halogen is estimated as silver halides.

In the process ‘w’ g of organic halide is treated with acidified silver nitrate solution to silver halide which is
washed, dried and weighed. Let ‘a’ g of AgX is obtained.

Atomic mass of X Wt. of AgX

% X = Molecular mass of AgX × Wt. of organic halide × 100

Thus
35.5 Wt. of AgCl
% Cl = 143.5 × Wt. of organic halide × 100

80 Wt. of AgBr
% Br = 188 × Wt. of organic halide × 100

127 Wt. of Ag I
% I– = 235 × Wt. of organic halide × 100

Estimation of Sulphur :
Sulphur is estimated as barium sulphate. In the process ‘w’ g of organic compound having sulphur is taken
in carius tube containing HNO3 where sulphur is finally converted into sulphuric acid. This sulphuric acid is
passed through excess BaCl2 to get BaSO4 which is washed dried & weighed. Let ‘a’ g of BaSO4 is
obtained
Atomic mass of sulphur Wt. of BaSO 4
% S = Molecular mass of BaSO × Wt. of organic compound × 100
4

32 Wt. of BaSO 4
% S = 233 × Wt. of organic compound × 100

Estimation of Phosphorus :
A known mass of the organic compound is heated with fuming nitric acid. The phosphorus present in the
organic compound is oxidised to phosphoric acid (H3PO4). The phosphoric acid, thus formed is treated
with magnesia mixture to get the precipitate of magnesium ammonium phosphate (MgNH4PO4). The
precipitate is separated, dried and ignited to get magnesium pyrophosphate (Mg2P2O7). The chemical
reactions involved are :

68
 Structure Identification & POC

Calculations :
Let the mass of the organic compound = W g

Mass of Mg2P2O7 obtained =xg

Now, 222 g (G.M.M.) of Mg2P2O7 Contains P =62 g

62x
x g of Mg2P2O7 contains P = g
222

62x
Percentage of P in organic compound =  100
222W

62  WMg2P2 O7  100
% of P = 222  WSubs tance

Que. (i) In sulphur estimation, 0.157 g of organic compound gave 0.4813 g of BaSO4. What is the percentage of
sulphur is organic compound ?
(ii) 0.092 g of organic compound on heating is carius tube and susequent ignition gave 0.111 g of Mg2P2O7.
Calculate the percentage of phosphorus in organic compound.

Ans. (i) Mass of BaSO4 = 0.4813 g

mass of organic compound. = 0.157 g
32  WBaSO4  100 32  0.4813  100
% S = 233  W = = 42.10
Subs tance 233  0.157
(ii) Mass of organic compound = 0.092 g
Mass of Mg2P2O7 = 0.111 g
62  WMg2P2 O7  100 62  0.111 100
% of P = 222  WSubs tance
=
222  0.092
= 33.69
8. Separation techniques :
Purification :
Purification means the removal of undersirable impurities associated with a particular organic compound,
i.e. to obtained the organic compound in pure state.

69
 Structure Identification & POC
Methods empolyed for purification of solids

Crystallisation Sublimation
Crystallisation is based on the principles Certain organic substances pass directly from
of solubility of compound (solutes). solute tend to be solid to vapour state on heating and vice-versa
on
more soluble in hot liquid (solvent) than they cooling. This is called sublimation and the process
are in cool liquid. If a saturated hot solution is very useful for separation of substance which
is allowed to cool, the solute is no longer sublime on heating from non volatile substance.
soluble in the solvent and form crystals of
pure compound. Solid is filtered and dried.

Examples : Examples :
(a) Sugar mixed with common salt can be Benzoic acid, naphthalene, anthracene, camphor,
purified with ethanol. indigo, anthraquinone.

(b) Phthallic acid mixed with naphthalene Solid Vapours

can be purified with hot water.

(1) Distillation : It is used to purify liquid on the basis of difference in boiling points.

(a) Simple distillation :

It is applied only for volatile liquids which boil without decomposition at atmospheric
pressure and contains non-volatile impurities. It can also be used for separating liquids having sufficient
difference in their boiling point.
Ex. (i) Benzene (b.pt. 80ºC) and aniline (b.pt. 184ºC)

(ii) Chloroform (b.pt. 61ºC) and aniline (b.pt. 184ºC)

(iii) Ether (b.pt. 35ºC) and toluene (b.pt. 114ºC)

(b) Fractional distillation :
If boiling points of liquids to be separated are closed to each other then fractional distillation is carried out
by using fractionating column.

Ex. (i) Distillation of petroleum, coal tar and crude oil.

(ii) Mixture of methanol (b.pt. 65ºC) and propanone (b.pt. 57ºC).
(iii) Mixture of benzene and toluene.
(c) Vacuum distillation (Distillation under reduced pressure) :
The compounds which decomposes on a temperature below their normal boiling points can not be distilled
at atmospheric pressure. If atmospheric pressure is reduced the liquid will boil earlier than its normal boiling
point.
Ex. (i) Glycerine can be distilled at 180ºC (b.pt. 280ºC) under a pressure 10-12 mm.
(ii) In soap industry, the separation of glycerol from the spent-lye as carried out by this technique.
(d) Steam distillation :
Those compounds which are steam volatile and are sparingly soluble in water can be separated by steam
distillation by passing steam through a heated flask containing the liquid to be distilled. Thus in steam
distillation the liquid gets distilled at a temperature lower than its boiling point and any chances of decomposition
are avoided.

70
 Structure Identification & POC
The proportion of water and liquid in the mixture that distills over is given by the relation
w1 p1  18

w 2 p2  M
where w1 and w2 stand for the masses of water and the organic liquid that distills over;
p1 and p2 represent the vapour pressures of water and the liquid at the distillation temperature and
M is molecular mass of the liquid (molecular mass of water being 18).
Ex. o-, m-, p-chlorotoluenes, o-, p-nitrobenzene.
(2) Solvent Extraction :
The process of separation of organic compound from its aqueous solution by shaking with a suitable
organic solvent is termed solvent extraction. The solvent should be immisible with water and the organic
compound to be separated should be highly soluble in it.
Ex. Benzoic acid can be extracted from water solution by using benzene.
(3) Chromatography :
It is an extremely valuable method for separation, isolation, purification and identification of constituents of
mixture and it is based on the general principle of phase distribution.
This technique is used for the separation of components of a mixture because of the distribution of components
between a liquid as gaseous phase (mobile phase) and a solid phase (stationary phase).
Separation of compounds of mixture takes place as a result of differential adsorption - on adsorption
column. After the separation, the substances are extracted from the adsorbent with suitable solvent which
is called elusion.
Common forms of chromatograph
Type Mobile / Stationary phase Use
Column Liquid / Solid Large scale separation
High performance liquid (HPLC) Liquid / Solid Qualitative and Quantitative analysis
Thin layer (TLC) Liquid / Solid Qualitative analysis
Gas liquid (GLC) Gas / Liquid Qualitative analysis
Paper Liquid / Solid Qualitative and Quantitative analysis of
polar organic and inorganic compounds.

71
 Structure Identification & POC

EXERCISE-1
PART- 1: SUBJECTIVE QUESTIONS
Degree of unsaturation and Hydrogenation :
001. Calculate the DU of following compounds :
(i) C6H6ClBrO (ii) C5H9N
002. How many structural isomeric alkenes on hydrogenation give n-Pentane.
003. On catalytic hydrogenation how many isomeric alkene will give 2-Methyl butane.
004. How many isomeric alkyne on hydrogenation gives 3, 3-Dimethylhexane.
Monochloroination & Ozonolysis
005. A cycloalkane having molecular mass 84 and four secondary carbon atoms will form four monochloro
structure isomers on chlorination. Identify the structure of cycloalkane.
006. Number of monochloro structural isomers of :

Cl / h
(i) Cl / h
2  (ii) 2

007. When Iso-octane is treated with Cl2/h. How many monochloro structural isomers are formed ?
008. Write the product of following reactions :
H3C CH3
| | O3 O3
(a) CH3  C  C  CH3  (b) CH3–CC–CH3 
Zn / H2O H O Zn / 2

CH3
|
(c) CH3–CC–CH3 
O3 / H2O2
  (d) O3 / H2O2
CH3 – C  CH  CH3   

O / Zn O / Zn
009. (i) P(hydrocarbon) H3
O
 + CH2 = O (ii) Q (C6H10) H3
O
 Hexane -1,6-dial
2 2

Write the structure of P and Q.

010. Write the product of following reactions :

(i) CH3–CC–CH = CH2 

O3 / H2O2
  (ii) 3 
O /H O
2 
2

011. Write the products of the reductive and oxidative ozonolysis of Mesitylene.
Test for acidic hydrogen & Unsaturation
012. How many positions in the following compound will react with sodium metal ?

72
 Structure Identification & POC
013. No. of moles of H2 gas evolved when one mole of the following compound reacts with sodium.

014. Molecular formula C4H6 have two position isomers A and B. Both A and B isomer decolourised the
bromine water. B release H2 gas with sodium metal but isomer A does not release H2 gas. Write
IUPAC name of A and B.
015. An organic compound (X) after hydrogenation gives 2-Methylbutane. Reaction of 'X' with Na metal gives
1
mol of H2 gas. 'X' also gives positive test with Br2 water. Identify the structure of 'X'.
2
Test for Functional groups
016. Write suitable reagent to distiguish the following compounds.
CH2OH OH O–CH3

CH3

017.

Identify the structure of X :

018. A compound X (C5H10O) reacts with 2, 4-DNP but does not give silver mirror test and Iodoform reaction
. The possible structure for X is :

019.

How many –OH group will react with Lucas reagent in above compound.
020. Which of the following does not reduce Tollen's reagent ?
HCHO, HCOOH, CH3CH=O, CH3COOH, PhCHO, Ph-COCH3, CH3COCH3, CH3CONH2
021. Which of the following compounds will not give positive iodoform test.
Acetophenone, Benzophenone, 2-Pentanone, 3-Pentanone, Acetaldehyde,
CH3COCH3 , (CH3)2CHOH, (CH3CH2)2CH-OH, CH3COOH, CH3CONH2 , CH3COOCH3, CH3COCl

022.

Identify the structure of P :

73
 Structure Identification & POC
023. How many position in the following compound will react with 2, 4-Dinitrophenylhydrazine.

024. Which of the following compound will gives positive test with NaHCO3.?

COOH COOH CH=CH–COOH H

OH COOH CH3 — C — COOH
, , , CH3COOH, PhSO3H, PhOH
OH
Salicylic acid Phthalic acid Cinnamic acid
Lactic acid

025. Molecular formula C3H6O2 have two structures A & B. Structure A releases CO2 gas with NaHCO3 but
B does not. Compound B is fruity smelling liquid. Write the structures & IUPAC name of A and B.

2,4-DNP
– ve
026. P Na
– ve
(C2H4O2)
NaHCO3
– ve
Smell
Fruity smell

Identify the structure of P :

Br2 / H 2O
– ve
027. Q
(C2H5NO) NH3
NaHCO3
–ve

Identify the structure of Q :

028. A symmetrical organic compound of C4H11N give yellow oily layer on treatment with HNO2 then find the
structure of the compound.

029.

Identify the structure of amine.

Elements detection
030. When Lassiange extract of Methylamine react with FeSO4/dilute H2SO4 what happend ?
031. Explain the reason for the fusion of an organic compound with metallic sodium for testing nitrogen, sulphur
and halogen.
032. What will happen during lassaigne's test for nitrogen if the compound also contians sulphur?

74
 Structure Identification & POC
PART- 2: OBJECTIVE QUESTIONS
Degree of unsaturation and Hydrogenation :
033. The degree of unsaturation of following compound C8H12O, C3H5N, C4H8O are respectively :
(A) 4,3,2 (B) 3,2,1 (C) 2,1,3 (D) 2,2,3
034. Which of the following hydrocarbons give same product on hydrogenation.
(A) 2-Methyl hex-1-ene & 3-Methyl hex-3-ene
(B) 3-Ethyl hex-1-en-4-yne & 2-Methylhept-2-en-4-yne
(C) 3-Ethylcycloprop-1-ene & 1,2-Dimethylcycloprop-1-ene
(D) 2-Methylbut-2-ene & 3-Methylbut-1-ene
035. Number of moles of hydrogen will required for complete hydrogenation of one mole of following compound
:

(A) 6 (B) 7 (C) 5 (D) 3

036. How many alkenes on catalytic hydrogenation give isopentane as a product (consider only structural
isomers)?
(A) 2 (B) 3 (C) 4 (D) 5
037. If 1 mole H2 is reacted with 1 mole of the following compound.

Which double bond will be hydrogenated most easily+ ?

(A) c (B) b (C) a (D) d
Monochloroination & Ozonolysis
038. Only two isomeric monochloro derivatives are possible for :-
(A) n-Pentane (B) 2,4-Dimethyl pentane
(C) Toluene (D) 2,3-Dimethyl butane
039. The number of possible monochloro derivatives of 2, 2, 3, 3-Tetramethylbutane is -
(A) 2 (B) 3 (C) 4 (D) 1
040. Which of the following alkene gives four monochloro (structural isomer) products after hydrogenation ?
(A) Pent-2-ene (B) 2-Methylbut-2-ene (C) 3-Methylhex-2-ene (D) 2, 3-Dimethylbut-2-ene
041. Which of the following compound will give four monochloro (structural) product on monochlorination.

(A) (B) (C) (D)

042. Identify E in the following sequence of reaction.

H / Ni
E (C6H10) 2  F (C6H12) G (C6H11Cl) (only one isomer)

(A) (B) (C) (D)

75
 Structure Identification & POC

O 3 / Zn
043. X    +

Y..
The IUPAC name of compound Y is :
(A)2-Cyclohexylbutane (B)1-Methylpropylcyclohexane
(C) Butylcyclohexane (D)1-Cyclohexylbutane
044. An alkene give two moles of HCHO, one mole of CO2 and one mole of on ozonolysis.

What is its structure?

(A) (B)

(C) (D)

045. An unknown compound on ozonolysis to give acid C3H6O2 and a ketone C4H8O. From this information,
identifiy structure of unknown compound.
CH3

(A) (CH3)2C = CHCH2 – CH2CH3 (B) CH3CH2 – C = CHCH2CH3

(C) (D) CH3CH2CH2CH = CHCH2CH3
Test for acidic Hydrogen & Unsaturation
046. When one mole of the given compound reacts with sodium metal then how many moles of H2 gas will
release?
NO 2 O
||
OH
(1mole)
||
O
(A) 1 mole (B) 1.5 mole (C) 2 mole (D) 0.5 mole

047.

Compound X is

(A) H3 C–CC–CH3 (B) CH2=CH–CH=CH2 (C) CH3 –CH2 –CCH (D)

048.

Identify X :
(A) CH3 – CH2 – C  C – CH2 – CH3 (B) CH3 – C  C – CH2 – CH2 – CH3

(C) (D)

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 Structure Identification & POC
049. Ammonical AgNO3 gives white ppt after reaction with any compound then this reflects the presence of
(A) One – CHO group (B) One triple bond
(C) A terminal alkyne (D) Compound is unsaturated
050. Which of the following compound gives red ppt with Cu2Cl2 / NH4OH ?
(A) CH3  C  C  CH3 (B) CH3  CH2 – C  CH
(C) CH3 – CH2 – CH  CH2 (D) CH3 – C  C – CH  CH2
051. Identify the hydrocarbon having molecular formula C5H6 which gives white ppt with ammonical AgNO3 ?
(A) (B) (C) (D)

Test for Functional groups

052. The group reagent for the test of alcohols is :
(A) Cerric ammonium nitrate (B) Schiff’s reagent
(C) Molisch’s reagent (D) Bromine water

053.

Identify X :

(A) (B)

(C) (D)

054. Which of the following compounds does not give positive test with neutral FeCl3?

(A) (B) (C) (D)

055. The following two compounds I and II can be distinguished by using reagent

(I) (II)

(a) aq. NaHCO3 (b) Neutral FeCl3

(c) Blue litmus solution (d) Na metal (e) HCl/ZnCl2 anhydrous
(A) a or c (B) b or e (C) d or e (D) c or d
056. Which of the following compound will not react with I2 /OH–.

(A) (B) (C) (D) CH3 – CHO

057. A compound which can give iodoform test, bromine water test, FeCI3 test but not Tollen's test.

(A) (B)

77
 Structure Identification & POC

(C) (D)

058. The compound A gives following reactions.

Its structure can be

(A) (B) OHC – (CH2)2 – CH = CH – COOH

(C) (D)

059. The compound responds to Tollen's reagent is :

(A) CH3 COCH3 (B) CH3CHO (C) CH3CONH2 (D) CH3COOH
060. Which of the following compound does not give yellow ppt when react with NaOI ?

(A) (B)

(C) Ph–CH 2 – C – CH 3 (D)

||
O

061. 2-Pentanone can be distinguished from 3-Pentanone by the reagent

(A) 2, 4- Dinitrophenyl hydrazine (B) Tollen's reagent
(C) I2 and dilute NaOH (D) Fehling solution
062. An oragnic compound X (C4H8O2) gives positive test with NaOH and Phenopthalein. Structure of X will
be :
(A) CH3  CH2  CH2  C  OH (B) CH3  C  C  CH3
|| || ||
O O O

(C) CH3  C  O  C2H5 (D) CH3  C  OCH3

|| ||
O O
063. Which of the following compound will give smell of NH3 with conc. NaOH.
(A) CH3  CH2  C  NH2 (B) CH3  C  CH2  NH2
|| ||
O O

(C) (D) CH3  CH2  C  OH

||
O

78
 Structure Identification & POC
064. Which of the following will not give positive test with CHCl3 / KOH.
(A) CH 3–CH2–NH–CH3 (B) CH 3–CH2 –CH2–NH2

CH3
|
(C) (D) CH3  CH  NH2

065. A positive carbylamine test is given by :

(A) N,N–dimethylaniline (B) 2, 4-dimethylaniline
(C) N-methyl-o-methylaniline (D) N-methylaniline
066. The Hinsberg's method is used for :
(A) preparation of primary amines (B) preparation of secondary amines
(C) preparation of tertiary amines (D) separation of amine mixtures
067. Molisch reagent is used to identify following compound ?
(A) Glucose (B) Raffinose (C) D-oxyribose (D) All of these
068. Which of the following would produce effervescence with sodium bicarbonate?

(A) (B) (C) (D) All of these

069. A compound is heated with zinc dust and ammonium chloride followed by addition of the Tollen's reagent.
Formation of silver mirror indicates the presence of following group

(A) –CHO (B) (C) –NO2 (D) –NH2

070. Which of the following is not used as a test for proteins
(A) Ninhydrn test (B) Xantheproteic test (C) Molisch test (D) Biuret test
Elements detection
071. In the Lassaigne’s test, one of the organic compounds gave red colour with FeCl3. Compound can be :
(A) Na2 S (B) NH2 CSNH2 (C) C6H5Cl (D) NaCN
072. Lassaigne’s test is used in qualitative analysis to detect
(A) Nitrogen (B) Sulphur (C) Chlorine (D) All of these
073. The compound that does not give a blue colour in Lassaigne’s test is
(A) C6H5–NH2 (B) CH3CONH2 (C) NH2–NH2 (D) C6 H5–NO2
074. Nitrogen containing organic compound when fused with sodium metal forms:
(A) NaNO2 (B) NaCN (C) NaNH2 (D) NaNC
075. The sodium extract of an organic compound on acidification with acetic acid and addition of lead acetate
solution gives a black precipitate. The organic compound contains
(A) Nitrogen (B) Halogen (C) Sulphur (D) Phosphorus
076. The Lassaigne’s extract is boiled with conc. HNO3 before testing for halogens. By doing so it :
(A) decomposes Na2S and NaCN, if formed. (B) helps in the precipitation of AgCl.
(C) increases the solubility product of AgCl. (D) increases the concentration of NO3– ions.
077. The sodium extract of an organic compound on boiling with HNO3 and addition of ammonium molybdate
solution gives a yellow precipitate. The compound contains :
(A) N (B) P (C) S (D) Cl
Quantitative analysis (Estimation of elements)
078. In Kjeldahl’s method, nitrogen present in estimated as :
(A) N2 (B) NH3 (C) NO2 (D) None of these

79
 Structure Identification & POC
079. Catalyst used in Kjeldahl’s method for the estimation of nitrogen is :
(A) Sodium (B) Magnesium (C) Mercury (D) Copper

080. 6 g of the organic compound on heating with NaOH gave NH3 which is neutralised by 200 mL of 1NHCl.
Percentage of nitrogen is :
(A) 12% (B) 60% (C) 46.67% (D) 26.67%
081. The dessicants used for absorbing water during Liebig’s method for estimation of carbon and hydrogen
are:
(A) CaCl2 (B) Na2SO4 (C) MgSO4.7H2O (D) Mg(ClO4)2
082. 0.28g of a nitrogenous compound was subjected to Kjeldahl's process to produce 0.17 g of NH3. The
percentage of nitrogen in the organic compound is :
(A) 5 (B) 25 (C) 50 (D) 80
083. In Dumas’ method for estimation of nitrogen, 0.3g of an organic compound gave 50mL of nitrogen collected
at 300K temperature and 715mm pressure. What will be the percentage composition of nitrogen in the
compound. (Aqueous tension at 300K=15 mm)
(A) 22.38% (B) 17.46% (C) 55.11% (D) 82.74%
084. In Carius method of estimation of halogen, 0.15 g of an organic compound gave 0.12 g of AgBr. What is the
percentage of bromine in the compound.
(A) 18% (B) 94% (C) 63% (D) 34%
085. In sulphur estimation, 0.157 g of an organic compound gave 0.4813 g of barium sulphate. What is the
percentage of sulphur in the compound ?
(A) 38.7% (B) 18.5% (C) 42.1% (D) 1.9%
Separation & Purification
086. Aniline is usually purified by
(A) Chromatographic technique (B) Steam distillation
(C) By addition of oxalic acid (D) Fractional crystallisation
087. Steam distillation is applied to those organic compounds which are steam volatile and :
(A) soluble in water (B) insoluble is water
(C) sparingly soluble in water (D) insoluble in all solvents
088. The most satisfactory method for separating sugars is :
(A) fractional distillation (B) vacuum distillation (C) chromatography (D) steam distillation
089. Chromatography technique is used for the separation of :
(A) Small samples of mixtures (B) Plant pigments
(C) Dye stuffs (D) All of the above
090. A mixture of benzene and toluene can be separated by :
(A) Sublimation (B) Distillation (C) Fractional distillation (D) Chromatography
091. In soap industry, the separation of glycerol from the spent-lye is carried out by
(A) Sublimation (B) Fractional distillation
(C) Chromatography (D)Vacuum Distillation
092. A mixture of o-nitrophenol and p-nitrophenol can be separated by :
(A) Sublimation (B) Steam distillation (C) Fractional distillation (D) Chromatography

EXERCISE-2
093. On mixing a certain alkane with chlorine and irradiating it with ultraviolet light, it forms only one
monochloroalkane this alkane could be : [AIEEE 2003]
(1) propane (2) pentane (3) isopentane (4) neopentane.
094. The prussian blue colour obtained during the test of nitrogen by Lassaigne’s test is due to the formation of :
[AIEEE 2004]
(1) Fe4 [Fe(CN)6]3 (2) Na3[Fe(CN)6 ] (3) Fe(CN)3 (4) Na4 (Fe(CN)5NOS]
80
 Structure Identification & POC
095. Of the five isomeric hexanes,the isomer which can give two monochlorinated compounds is ?
[AIEEE 2005]
(1) n–Hexane (2) 2,3-Dimethylbutane (3) 2,2-Dimethylbutane (4) 2-Methylpentane
096. Among the following the one that gives positive iodoform test upon reaction with 2 and NaOH is ?
(1) CH3 CH2CH(OH)CH2 CH3 (2) C6 H5CH2CH2OH
(3) CH3  CH  CH3 (4) PhCHOHCH3
|
CH2  OH
097. In the following sequence of reactions, the alkene affords the compound 'B'
O3 H O
CH3CH = CHCH3  A 2 B compound B is [AIEEE 2008]
Zn
(1) CH3CH3CHO (2) CH3COCH3 (3) CH3CH2 COCH3 (4) CH3CHO
098. Which of the following reagents may be used to distinguish between phenol and benzoic acid ?
[AIEEE 2011]
(1) Aqueous NaOH (2) Tollen's reagent (3) Molisch reagent (4) Neutral FeCl3
099. Silver Mirror test is given by which one of the following compounds? [AIEEE 2011]
(1) Acetaldehyde (2) Acetone (3) Formaldehyde (4) Benzophenone
100. Ozonolysis of an organic compound 'A' produces acetone and propionaldehyde in equimolar mixture. Identify
'A' from the following compounds : [AIEEE 2011]
(1) 1-Pentene (2) 2-Pentene (3) 2-Methyl-2-pentene (4) 2-Methyl-1-pentene
101. Which of the following compounds can be detected by Molisch’s test : [AIEEE 2012]
(1) Nitro compounds (2) Sugars (3) Amines (4) Primary alcohols
102. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of mono
substituted alkyl halide ? [AIEEE 2012]
(1) Tertiary butyl chloride (2) Neopentane
(3) Isohexane (4) Neohexane
103. Iodoform can be prepared from all except : [AIEEE 2012]
(1) Ethyl methyl ketone (2) Isopropyl alcohol
(3) 3–Methyl–2–butanone (4) Isobutyl alcohol
104. Which of the following compound on reductive ozonolysis does not give glyoxal as one of the product.

(1) (2) (3) (4)

105. How many isomeric structural alkene on catalytic hydrogenation gives 3-Methyl hexane.
(1) 3 (2) 4 (3) 5 (4) 6
106. Compound A (C6H12) does not absorb H2 in presence of Ni. It forms two monochloro isomers on photo-
chemical chlorination. Its structure can be :

(1) (2) (3) (4)

107. Which alkyne will give 3-Ethyl heptane on catalytic hydrogenation.

(1) (2) (3) (4)

81
 Structure Identification & POC
108. Compound 'A' gives red precipitate with Cu2Cl2 / NH4OH solution and decolourises bromine water. The
compound 'A' can be :
(1) CH2  CH  C  CH3 (2) CH2  CH  C  H (3) CH3–CCH (4) PhCHO
|| ||
O O
109. An organic compound does not react appreciably with Lucas reagent but give white precipitate with
Tollen’s reagent. Which is the possible structure of compound ?
(1) (2)
OH
(3) (4) CH2=C=CH–CH2–OH
110. Which of the following compounds will give a positive iodoform test ?
(1) Methanol (2) 2,2-Dimethylpropanol
(3) Ethanol (4) Methanal
111. The following two compounds I and II can be distinguished by using reagent

(I) (II)

(a) aq. NaHCO3 (b) Neutral FeCl3 (c) Fehling solution (d) Na metal
(1) a or c (2) b or c (3) c or d (4) b or d
112. Which of the following compound cannot give Iodoform when react with IO–(hypoiodite).
(1) (2)

(3) (4)

113. How many structural isomeric ketones having molecular formula (C5H10O) give iodoform test ?
(1) 1 (2) 2 (3) 3 (4) 4

114. Which of the following statement is incorrect :

(1) Phenol gives positive bromine water test
(2) Aniline gives foul smelling compound on reaction with CHCl3 + KOH
(3) Formic acid gives positive Tollen's test (4) Nitrobenzene gives positive Tollen's test
NH2 CH2–NH2

115. and can be distinguish by

Me
(1) CHCl3 + KOH (2) NaNO2 + HCl followed by -Napthol
(3) CS2 + HgCl2 (4) Na Metal
O3
116. (x) C7H12 Me2S
P+Q
Compound P responds to Tollen’s test and iodoform test but Q does not respond with both the reagents.
Structure of compound (x) is :

(1) (2) (3) (4)

H / Ni Cl / h
117. 2 
 P 2 Q (Total number of monochloro structural products).

(1) 2 (2) 3 (3) 4 (4) 5

82
 Structure Identification & POC
118. Yellow precipitate obtained during the test of halogen by lassaigne’s test is due to the formation of
(1) AgF (2) AgCl (3) AgBr (4) None of these
119. A research scholar get a mixture of three product during an experiment with ammonia. In product I only
one H of ammonia is replaced by ethyl group and in II two H atoms of ammonia are replaced by ethyl
groups and in III all the H-atoms are replaced by ethyl groups . Which test he should use to distinguish or
separate the products :
(1) Carbyl amine test (2) Iodoform test (3) Fehling solution test (4) Hinsberg test
120. How many alcohols give immediate turbidity with Lucas reagent having molecular formula (C5H12O):
(1) 1 (2) 2 (3) 3 (4) 4
121. Which of the following compound can give test with Tollen's reagent and yellow precipitate with iodine in
NaOH ?
(1) CH2=O (2) CH3–CH=O (3) CH3 –CH2 –CH=O (4)

122. Which is incorrect match with respect to the reagent used for lab test ?
(1) Carbohydrates  –Naphthol (Molish reagent)
(2) Nitro ethane  Zn, NH4Cl and AgNO3 (Mulliken Barker test)
(3) Phenol  Anhydrous ZnCl2 + Conc. HCl (Lucas Reagent)
(4) Benzoic acid  NaHCO3
123. How many hydrocarbons having molecular mass 68 can give white precipitate with Tollen's reagent ?
(1) 1 (2) 2 (3) 3 (4) 4
124. On oxidative ozonolysis of 3-Methylhex-3-ene, two products A & B are formed. A gives CO2 gas with
sodium bicarbonate, but B can not. The structures of A & B are respectively :
(1) & CH3–CH2–COOH (2) CH3–CH2 –COOH & CH3–CH2 –CH=O

(3) CH3–CH2–COOH & (4) CH3–CH2–CH2–COOH &

125. and can be differentiated by :

(1) Carbylamine reaction (2) Iodoform test (3) Cold KMnO4 (4) Br2–H2O
126. Test to differentiate between ethanol (CH3CH2OH) and phenol (Ph–OH) is/are :
(1) Litmus test (2) Neutral FeCl3 (3) Sodium metal test (4) All of these
127. Which of the following compound gives azo dye test ?

(1) (2) (3) (4)

128. A compound (P), obtained as an ozonolysis product of (Q) gives brisk effervescence with Na, violet
coloration with neutral FeCl3 and silver mirror with Tollen's reagent. (Q) may be :

(1) (2) (3) (4) All of these

83
 Structure Identification & POC
129. Which of the following reagent can distinguish the given compound I & II ?

&

(1) Na metal (2) NaHCO3 (3) Lucas Reagent (4) 2, 4-D.N.P

131. A compound (P) on reaction with “Q” in basic medium (KOH) gives a bad smelling compound (CH3CH2NC).
Compound Q can be prepare by reaction of acetone with calciumhypochlorite (Ca(OCl)2]. P and Q can
(1) CH3–CH2 –NH2 & CHCl3 (2) CH3–CH2–NO2 & CH3Cl
(3) CH3–CH2–NH–CH3 & COCl2 (4) (CH3–CH2) 3N & Cl2
131. Which of the following can gives Hinsberg test :
(1) CH3 –CH2 –OH (2) CH3–CH2–NO2 (3) CH3–CH2–NH2 (4) CH3—C—NH2
O
132. Identify a reagent from the following list which can easily distinguish between 1-butyne and 2-butyne.
(1) bromine, CCl4 (2) H2/Ni (3) dilute KMnO4 (4) ammonical Cu2Cl2 solution
133. Acetaldehyde and Propyne can be distinguish by :
(i) Tollen’s reagent (ii) I2/NaOH (iii) Lucas reagent (iv) neutral FeCl3
(1) (i) , (ii) & (iii) (2) (ii) & (iii) (3) (i) & (ii) (4) (iii) & (iv)

84
 Structure Identification & POC

ANSWER KEY
EXERCISE-1
PART-1
001. (i) 3 (ii) 2 002. 2 003. 3 004. 3
Cl Cl
Cl
005. Cl / h
2  + + +
Cl
006. (i) 6 (ii) 4 007 . 4
CH3 CH3 O
| | ||
008. (a) CH3 – C  O (b) CH3 – C – C  CH3 (c) CH3–COOH (d) CH3 – C  O + CH3 – C – OH
|| ||
O O

009. P= ; Q=

010. (i) CH3–COOH + HOOC – COOH + HCOOH (ii)

Me O3/Zn, H2O CH3 – C – CHO

O
011 . O3/H2O2
Me Me CH3 – C – COOH
O

012 . 2 013. 2
014. A  CH3 – C  C  CH3 But  2  yne  ; B  CH3  CH2 – C  CH(Butyne)

CH3
|
015 . CH3  CH  C  CH
016. Lucas reagent (HCl/ ZnCl2) or Neutral FeCl3

017.

O
018. 019 . 3
CH3–CH2–C–CH2–CH3

020 . CH3COOH, Ph-COCH3, CH3COCH3, CH3CONH2 .

021. group gives positive iodoform test but acids and acid derivatives do not.

022. 023. 3

85
 Structure Identification & POC
024. Salicylic acid, Phthalic acid, Cinnamic acid, Lactic acid, acetic acid and benzene sulphonic acid.
025. CH3CH2COOH (Propanoic acid)  (A)
CH3COOCH3 (Methyl acetate)  (B) or HCOOC2H5
O
H  C  O  CH3
026 . || 027 . CH3–C–NH2
O
028. CH3CH2 NHCH2CH3 (20 amine)
CH3
029. (3º Amine)
CH3 –N–CH3
030. Prussian blue colour will appear.
031. As the elements present in the organic compounds are in their covalent form, These are fused with sodium
metal to convert them into ionic form (like NaCN, Na2S, NaX).
032. Appearance of blood-red coloration indicates the presense of both sulphur and nitrogen.

PART-2
033. (B) 034. (D) 035. (C) 036. (B) 037. (D) 038. (D) 039. (D)
040. (B) 041. (D) 042. (A) 043. (B) 044. (B) 045. (B) 046. (D)
047. (C) 048. (A) 049. (C) 050. (B) 051. (A) 052. (A) 053. (B)
054. (A) 055. (B) 056. (C) 057. (D) 058. (C) 059. (B) 060. (D)
061. (C) 062. (C) 063. (A) 064. (A) 065. (B) 066. (D) 067. (D)
068. (D) 069. (C) 070. (C) 071. (B) 072. (D) 073. (C) 074. (B)
075. (C) 076. (A) 077. (B) 078. (B) 079. (C) 080. (C) 081. (A)
082. (C) 083. (B) 084. (D) 085. (C) 086. (B) 087. (B) 088. (C)
089. (D) 090. (C) 091. (D) 092. (B)

EXERCISE-2
093. (4) 094. (1) 095. (2) 096. (4)
097. (4) 098. (4) 099. (3,1) 100. (3)
101. (2) 102. (2) 103. (4)
104. (1) 105. (4) 106. (3) 107. (2)
108. (3) 109. (3) 110. (3) 111. (2)
112. (1) 113. (2) 114. (4) 115. (2)
116. (3) 117. (1) 118. (3) 119. (4)
120. (1) 121. (2) 122. (3) 123. (2)
124. (3) 125. (1) 126. (2) 127. (2)
128. (1) 129. (3) 130. (1) 131. (3)
132. (4) 133. (3)

86
 General Organic Chemistry-I

General Organic Chemistry-I

Electronic effects: Electron displacement methods
The effects which arises due to electronic distribution is called electronic effect.

(+H)

Inductive effect
Development of permanent polarity along the carbon chain, due to any group or atom is known as inductive
effect.
If arises due to difference of electronegativity
   
C–C–C–C–X
Electronegativity of X > electronegativity of C
   
C–C–C–C–Y
Electronegativity of Y < electronegativity of C
Features of Inductive effects -
(i) The displacement of electrons takes place due to difference in electronegativity of the two atoms
involved in the covalent bond.
(ii) It can also be defined as polarisation of one bond caused by polarisation of adjacent bond.
(iii) It is also called transmission effect.
(iv) It causes permanent polarisation in molecule, hence it is a permanent effect.
(v) The electrons never leave their original atomic orbital.
(vi) Its magnitude decreases with distance and it is almost negligible after 3rd carbon atom.
(vii) The inductive effect is always operative through  bond, does not involve  bond electron.

Types of inductive effects :

(a) – I Effect : The group which withdraws electron cloud is known as – I group and its effect is called
– I effect. Various groups are listed in their decreasing – I strength as follows.

> – > – > – NO2 > –SO2R > –CN > –CHO > –COR> –COOH> – F > Cl
> – Br > – I > –OR > –SH > –SR > –OH > –CCR > Ar > –CH=CR2

(b) + I effect : The group which release electron cloud is known as + I group and effect is + I effect.
> > – C(CH3)3 > – CH (CH3)2 > – CH2 – CH3 > – CH3 > – D > – H
The hydrogen atom is reference for + I and – I series. The inductive effect of hydrogen is assumed
to be zero.

Illustration 1: Since – NO2 is – I group it pulls or withdraws electron from cyclohexane ring making it electron
deficient

87
 General Organic Chemistry-I

Illustration 2:
Let us consider effect of COOH & – COO– in carbon chain

(a) (b)
Due to e¯ donating nature of carbon chain has become partially negative but – COOH is – I group
therefore carbon chain has become partially positive.
Illustration 3:
Direction of electron displacements
1. 2. HOOC CH2 CH3 3.

CN

4. 5. 6.

+ + –
7. 8. 9. CH 3 CH CH NO2

Resonance
When two or more structures that differ only in the distribution of electrons can be written for a molecule,
no single Lewis structure is sufficient to describe it's true electron distribution. The true structure is said to
be a resonance hybride of the various Lewis formulas.
The various Lewis formulas called resonating structure/contributing structure/canonical structure, that can
be written for a molecule.
Resonating structures are hypothetical but contribute to the real structure, which is called resonance hybrid.
The resonance hybrid is more stable than any other resonating structures.
Ex. 
CH2 CH CH2 CH CH2 CH
CH CH2
CH CH2 CH CH2
Resonance hybrid

CH2 CH CH2 CH CH2 CH

–
CH CH2
CH CH2 CH CH2

Resonance hybrid

Ex.

The most stable resonating structure contribute maximum to the resonance hybrid and less stable resonating
structure contribute minimum to resonance hybrid.
88
 General Organic Chemistry-I
Conjugation:
A given atom or group is said to be in conjugation with an unsaturated system if:-
(i) It is directly linked to one of the atoms of the multiple bond through a single bond.
(ii) It has π bond, positive charge, negative charge, odd electron or lone pair electrons.
Types of Conjugation :
1. Conjugation between C = C and C = C ( 

2. Conjugation between +ve charge and C = C (  )

3. Conjugation between lone pair and C = C (  )

4. Conjugation between odd electron and C = C (CH2 = CH –  – CH = CH2)

5. Conjugation between negative charge and C = C (  )

The Rules of Resonance :
(i) All the canonical forms (resonating structure) must have proper lewis structure. For instance none of
them may have a carbon atom with five bonds.

(ii) The positions of the nuclei of the atoms must remain the same in all of the structures. Structures 3 is not
a resonance structure of 1 or 2, for example, because in order to form it we would have to move a
hydrogen atoms and this is not permitted :

(iii) All atoms taking part in the delocalisation must lie in a plane so that orbitals overlaping become parallel to
each other.


 i.e. 
 z

(iv) All canonical forms must have the same number of unpaired electron.
Note: 1. The energy of actual molecule is lower than of any form. Therefore delocalisation is a stabilizing
phenomenon.
2. All canonical forms do not contribute equally to the true molecule. The more stable structure is the greater
contributor to its resonance hybrid.
Mesomeric effect (or Resonance effect)
Mesomeric effect is defined as permanent effect of  electron shifting from multiple bond to atom or from
multiple bond to single bond or from lone pair to single bond. This effect mainly operates in conjugated
system of double bond. So that this effect is also known as conjugate effect.

89
 General Organic Chemistry-I

Ex.

Types of Mesomeric effects :

(a) Positive Mesomeric effect (+M effect) :
When the group donates electron to the conjugated system it shows + M effect.
Relative order of +M groups (usually followed) :
– O > –NH2 > –NHR > –NR2 > –OH > –OR > –NHCOR > –OCOR > –Ph > –F > –Cl > –Br > –I

Ex. (I)

(II) .. - +
H2C = CH – CH = CH – NH2 H2C – CH = CH – CH = NH2

(III)

(IV)

(b) Negative Mesomeric effect (–M effect) :

When the group withdraws electron from the conjugated system, it shows – M effect
Relative order of –M groups (usually followed) :

+ –
Ex. (I) (II) H 2C = CH – C N: H 2C – CH = C = .N:.

– + – + . .– – + ..
O – N = .O: O – N – .O:
. O – N = O:
.
(III)
+
Note :
1. When a +M group and –M group are at meta-positions with respect to each other then they are not in
conjugation with each other, but conjugation with benzene ring exists.

etc.

2. +M group increases electron density in benzene ring, called activating group while –M group decreases
electron density in the benzene ring, called deactivating group.
Ex. Write electron density order in the following compound.

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 General Organic Chemistry-I

(a)

(b)

Ans. (a) I > II > III > IV (b ) III > I > II > IV

Comparison of stability of resonating structures:

(i) Structures in which all of the atoms have a complete valence shell of electrons (i.e., the noble gas
structure) are especially stable and make large contributions to the hybrid.

Ex. (II is more stable than I)

(ii) Nonpolar (uncharged) structure are most stable. Charge separation decreases stability. Separating
opposite charges requires energy. Therefore, structures in which opposite charges are separated have
greater energy (lower stability) than those that have no charge separation.
: :

CH2 – CH = Cl +
: :

: :
CH2 = CH – Cl
(I) (II)
(iii) Structures with more covalent bonds are more stable than other structures

(iv) Structure that carry negative charge on a more electronegative atom and positive charge on less
electronegative atom are comparatively more stable.

Ex.  is more stable than )

Resonance Energy:
The P.E. difference between the most stable resonating structure and resonance hybride is called resonace
energy. The stability of molecule is directly proportional to resonance energy.
The difference in energy between the hybrid and the most stable canonical structure is referred as the
resonance energy. (as shown in Fig.)

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 General Organic Chemistry-I
SIR (Steric Inhibition of Resonance):
Restriction in exhibition of resonance due to steric hindrance is known as SIR effect.
In case of 1,2-Disubstituted benzene if the substitutents are bulky then due to steric repulsion (vander wall
repulsion) the group go out of plane with respect to benzene ring.
Due to this change in planarity the conjugation between the substituents on benzene is silightly diminished.
SIR effect  Size of group.
Ex. Arange the following compounds in their decreasing SIR effect order.

(a)

SIR effect order = III > IV > II > I.

(b)

SIR effect order = IV > III > II > I.

Hyperconjugation
It is delocalisation of sigma electron with p-orbital. Also known as –  conjugation or "no bond resonance".
H H
Ex. H–C–CH=CH2 H–C=CH–CH2
H H
1. The electron of the sigma bond between C & H are involved in delocalization.
2. In struclture to right – no bond between C & H due to migration of the sigma bond. Hence Hyperconjugation
is also called as "NO BOND RESONANCE"
3. This figure doesn't indicate the hydrogen is completely detached from the structure but some degree of
ionic character in C–H bond and some single bond character between carbon - carbon double bond.
–H hyperconjugation
The interaction between filled  or p-orbital & adjacent antibonding  orbital is reffered to as "negative
hyperconjugation"
Ex. fluoroethyl anion.
Hyperconjugation may take place in alkenes, alkynes, carbocations, free radicals and benzene nucleus.
The condition for hyperconjugation are as follow -
Necessary Condition :
Presence of at least one hydrogen at saturated carbon which is  with respect to alkenes, alkynes,
carbocations, free radicals and benzene nucleus.
(i) Hyperconjugation in alkenes
Delocalisation of bond electrons in  orbital by hyperconjugation in the case of alkene can be depicted as
in figure. Hypercongugation
H

H
H H

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 General Organic Chemistry-I
(ii) Hyperconjugation in carbocation

H
H

(iii) Hyperconjugation in radical

(iv) Hyperconjugation in toluene

(a) The effect of electron displacement due to this type of resonance is called hyperconjugative effect.
(b) Since canonical forms of this resonance may not contain any bond between H and C so hyperconjugation
is also known as no bond resonance.
(c) These resonating structures only suggest that
* There is some ionic character between C–H bond.
* Carbon-carbon double bond acquires some single bond character.
(d) Number of no bond resonating structures due to hyperconjugation = Number of -hydrogens
(In aliphatic systems)
Number of  hydrogen in the following molecules/ion.

CH3 CH C2H5 
 CH
(i) CH3 CH C2H5 (ii) (iii)
CH3 CH3
H = 5 H=6
H = 6


CH3 CH3
(iv) C C (v)
CH3 CH3 H=6
H = 9
Comparision between electronic effects :

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 General Organic Chemistry-I
Important points :
(i) If any group has more than one  bond in conjugation, then only one  bond will take part in delocalisation.
CH2  CH – C  CH

Out of two  bonds only one  bond will take part in delocalisation.
(ii) If any conjugate position has more than one lone pair then only one lone pair will take part in the
delocalisation.
..
CH 2 = CH – .O. – CH 3

Out of the two lone pair ’s only one will take part in delocalisation.
(iii) If any conjugate position has  bond and any of the positive charge, negative charge, odd electron,
lone pair electrons then only  bond will take part in delocalisation on priority.

.N.

Nitrogen has  bond as well as lone pair, but only  bond of nitrogen will take part in delocalisation.

(d) Electrons of negative charge or lone pair behave as 2 electrons if it is in conjugation to  bond.

; ;

Applications of Electronic effects

(a) Stability of Alkenes : More is the number of hyperconjugative structures more stable is the alkene.
"More alkylated alkenes are more stable".
Stability of alkenes  delocalisation of  electrons
 no. of hyperconjugative structures

H3C CH3 H3C H3C

C=C > C = CH – CH3 > C = CH2
Ex.
H3C CH3 H3C H3C

Ex. > >

Ex. <

(b) Heat of hydrogenation : Greater the number of  hydrogen results greater stability of alkene.
Thus greater extent of hyperconjugation results lower value of heat of hydrogenation
1
Stability of alkenes no. of hyperconjugative structures 
HHydrogenat ion
Ex. CH2 = CH2 > CH3 – CH = CH2 > CH3 – CH = CH – CH3 (  H Hydrogenation )

(c) Bond Length : Bond length is also affected by hyperconjugation

Ex. 

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 General Organic Chemistry-I
(i) Bond length of C(II) – C(III) bond is less than normal C–C bond.
(ii) Bond length of C(II) – C(I) bond is more than normal C=C bond.
(iii) C–H bond is longer than normal C–H bond.
Cl Cl

Ex. C – Cl Bond length  I > II

C
H O
(I) (II)
(d) Stability of reaction intermediates :
(i) Stability of carbocation  + M, +H, + I groups.
(ii) Stability of carbon free radical  + I groups.
(iii) Stability of carbanion  – M, – I groups.
Note: Resonance effect or delocalisation of electrons increases the stability of over all system.
For example carbocation, carbon free radical, carbanion & Alkenes.

(e) Dipole moment : Since hyperconjugation causes the development of charge, it also affects the dipole
moment of the molecule.
Ex. (i) CH2 = CH2 < CH3 – CH = CH2 (Dipole moment)
(ii) H–CH=O < CH3–CH=O < CH3–CH=CH–CH=O (Dipole moment)

–
COO COOH CH3 CH3

(iii) < (iv) < (iv) <

–
COO COOH NO2 NO2 OH OH
=3.93D =4.93D =1.54D =1.57D

(f) Acidic & Basic strength of organic compounds :

(i) Acidity (Ka)  – M, –I groups.
(ii) Basicity (Kb)  + M, +H, +I groups and solvation effect in aqueous solution.

Electromeric effects
It is a temporary effect. The organic compound having a multiple bond ( double or triple bond) show this
effect in the presence of an attacking reagent only. It is defined as the complete transfer of a shared pair of
-electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. It is
represented by E and the shifting on the electrons is shown by a curved arrow. There are two types of
eletromeric effect.
(i) +E effect : In this effect -electron of the multiple bond are transferred to that atom to which the
reagent gets attached.

– CH2 – E
(ii) – E effect : In this effect the -electron of the multiple bond are transferred to that atom to which the

attacking reagent does not get attached + NC

Note : When inductive and electromeric effects operate in opposite directions then the electromeric effect
dominates.

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 General Organic Chemistry-I
Aromatic character [The Huckel 4n + 2 rule]
Definition: Aromatic compounds are characterized by a special stability and that they undergo substitution
reactions more easily than addition reactions.
The following rules are useful in predicting whether a particular compound is aromatic or non–aromatic.
Aromatic compounds are cyclic and planar. Each atom in an aromatic ring is sp2 hybridised. The cyclic 
molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2)  electrons, i.e., 2, 6, 10, 14 ........
 electrons. Where n = an integer 0, 1, 2, 3,..............
Aromatic compounds have characteristic smell, have extra stability and burn with sooty flame.

Comparision between aromatic, anti aromatic and non-aromatic compounds.

Stability of compounds : Aromatic > Non-Aromatic > Anti-Aromatic

(For compounds with same number of atoms.)

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 General Organic Chemistry-I

EXERCISE-1
PART- 1: SUBJECTIVE QUESTIONS
Inductive effect
001. Show the direction of inductive effect in following compounds

(i) (ii) (iii)

(iv) CH3–CH2–CH2– Li (v) CH3 –CH2 –CH2–MgBr (vi)

(vii) (viii) (ix) (x)

Resonance Concepts, Conditions, Resonating Structures & Conjugation

002. Which of the following compounds have delocalized electrons ?
O
||
(P) CH2  CHCCH3 (Q) (R) (S) CH3CH2NHCH = CHCH3
003. Number of  electrons in resonance in the following structure is.

Stability of Resonating Structures and different species

004. In the following sets of resonating structure, label the major and minor contributors towards resonance
hybrid.

(P)  (Q) 

(R)  (S) 

005. Write the stability order of following resonating structures :

I II I II

(P) (Q)

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 General Organic Chemistry-I

(R) (S)

Mesomeric Effect
006. Arrange the following groups in the increasing order of + M :
(i) – I, – Cl, – F, – Br (ii) –NH2, –OH, –O
007. Arrange the following groups in the increasing order of –M :

(i) –NO2, –COOR, –CHO, –CN, –COR (ii) , ,

008. Which of the following groups (attached with benzene ring) show + M effect?

Steric Inhibition of Resonance (SIR Effect)

009. Compare the SIR effect between orthochloro benzoic acid, orthobromobenzoic acid and orthoiodo benzoic
acid.
Hyperconjugation
010. Define hyperconjugation by taking an example of propene.
011. In which molecules or ions hyperconjugation effect is observed and write the number of hyperconjugable
hydrogen atoms.

(A) C6H5 – CH = CH2 (B) CH3 – CH2 – CH = CH2 (C) CH2 = CH2 (D)
CH3 C 2H5 CH3
|  | |
(E ) (F) CH3 — C — C H2 (G) C 2H5 — C  (H) CH3 — C
| | |
CH3 C 2H5 CH3

(I) (J) (K) (L)

Concept of Aromaticity
012. What is aromaticity ?
013. Classify the following as aromatic, antiaromatic and nonaromatic compounds.

(a) (b) (c) (d) (e)

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 General Organic Chemistry-I

(f) (g) (h) (i) (j)

(k) (l) (m)

014. Why cyclooctatetraene is nonplanar.

Applications of electronic effect
015. The correct decreasing order of electron density in aromatic ring of following compounds is :

O O O
|| || ||
C–H O–C–H NH – CH3 C – NH – CH3

(I) (II) (III) (IV)

016. Correct dipole moment order is

(p) (q) (r)

PART- 2: OBJECTIVE QUESTIONS

Inductive effect
017. Inductive effect involves :
(A) Delocalisation of -electrons (B) Partial displacement of -electrons
(C) Delocalisation of -electrons (D) Displacement of lone pair electrons.
018. Select correct statement about I effect?
(A) I effect transfers electrons from one carbon atom to another.
(B) I effect is the polarisation of  bond electrons.
(C) I effect creates net charge in the molecule.
(D) I effect is distance independent.
019. Which of the following group shows +I-effect :
(A) –Br (B) –COOH (C) –OR (D) –COO–

020. Which of the following alkyl group has the maximum +I effect ?
(A) (CH3)2CH– (B) (CH3)3C– (C) CH 3CH2 – (D) CH3 –
021.
I II III
Among these groups, which of the following orders is correct for the magnitude of their I effect?
(A) II > III > I (B) III > II > I (C) I > III > II (D) I > II > III

022.
I II III
Among these groups, which of the following orders is correct for their I effect?
(A) I > II > III (B) II > III > I (C) II > I > III (D) III > I > II

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 General Organic Chemistry-I
023. Decreasing –I effect of given groups is :
(i) –CN (ii) – NO2 (iii) –NH2 (iv) –F
(A) iii > ii > i > iv (B) ii > iii > iv > i (C) iii > ii > iv > i (D) ii > i > iv > iii
024. Which of the following is the strongest -  group :
  
(A) – N (CH3)3 (B) – N H3 (C) – S (CH3)2 (D) – F
Resonance Concepts, Conditions, Resonating Structures & Conjugation
025. Resonance involves
(A) Change in the positions of atoms
(B) Change in the positions of both  and  electrons
(C) Change in the positions of only  electrons
(D) Change in the positions of only  electrons
026. Resonance involves :
(A) Delocalization of –electrons along a conjugated system.
(B) Delocalization of lone pair along a conjugated system.
(C) Delocalization of negative charge along a conjugated system.
(D) All are correct.
027. During delocalization, which statement is incorrect :
(A) Net charge remains same
(B) Number of paired electrons remain same
(C) Number of unpaired electrons remain same
(D) Energy of resonating structures always remains same
028. Resonance structure of the molecule does not have
(A) higher energy than their hybrid structure.
(B) identical arrangement of atoms.
(C) the same number of paired electrons.
(D) always equal contribution to the resonance hybrid.
029. Resonance energy is :
(A) The potential energy difference between most stable resonating structure and resonance hybrid
(B) The potential energy difference between the least stable resonating structure and resonance hybrid.
(C) The potential energy difference between the least stable and most stable resonating structure.
(D) None
030. Which of the following species can not show resonance?

(A) (B) (C) (D)

031. Resonance is not possible in :

(A) (B) (C) CH2 = CH — Cl (D)

032. Which does not have conjugate system ?

(A) CH 2 = CHCl (B) CH 2 = CHCHO (C) CH3CH = CH2 (D)

033. The compound which is not resonance stabilised

(A) CH2=CH–Cl (B) (C) CH2=CH–CH2Cl (D)

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 General Organic Chemistry-I
034 . Delocalization of electrons increases molecular stability because
(A) Inter-electronic repultion decreases
(B) Electrons-electrons repulsion increases
(C) Potential energy of the molecule increases
(D) Potential energy of the molecule remains unaffected
035. Which of the following is not acceptable as resonating structure :

(A) (B) (C) (D) None of these

036. Which of the following pair is not pair of resonating structures?


(A) & (B) & CH2 – CH  O

   
(C) CH2 = CH – O – CH3 & CH2 – CH  O – CH3 (D) CH3 – C  O & CH3 – C  O

037. Which of the following structures are resonance structures ?

(A) & CH3–O–N=O (B) &

(C) (CH3)2CO & (D) CH3 –CH=CH–CH3 & CH3–CH2–CH=CH2

038. Among the given sets, which represents the resonating structure ?

(A) and (B) and

(C) and (D) and

   
039 . CH2 O CH2 O CH2 O
I II III
Which of these structures is practically not a valid canonical structure of formaldehyde ?
(A) I (B) II (C) III (D) none of these
040 .
I II III
Among these compounds the correct order of resonance energy is
(A) I > II > III (B) II > I > III (C) III > I > II (D) I > III > II
041 . Heat of hydrogenation of cyclohexene is -28.6 kcal/mol and that of benzene is –49.8 kcal/mol. Then
resonance energy of benzene will be
(A) 46 kcal/mol (B) 39 kcal/mol (C) 36 kcal/mol (D) 30 kcal/mol

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 General Organic Chemistry-I
Stability of Resonating Structures and different species
042. Which one of the following is least stable resonating structure ?

(A) (B) (C) (D)

043. Which of the following resonating structure is the least contributing structure ?

(A) (B) (C) (D)

044. HNCO (isocyanic acid) has following resonating structures :

HN  C  O  

I
The order of stablity is :
(A) I > III > II (B) I > II > III (C) II > III > I (D) II > I > III
045. The correct stability order of the following resonanating structures is :

(A) (IV) > (I) > (III) > (II) (B) (II) > (IV) > (I) > (III)
(C) (III) > (II) > (IV) > (I) (D) (I) > (IV) > (III) > (II)
046. Which is the most stable resonating structure ?

(A) (B) (C) (D)

 
047. CH2CHOCH3 CH2CHOCH3
I II
On moving from gas phase to water as solvent, the contribution of II in the resonance hybrid
(A) Increases (B) Decreases
(C) Remains constant (D) This question is not valid


048.
 
  
I II III IV V
Among these canonical structures of pyridine, the correct order of stability is
(A) (I = V) > (II = IV) > III (B) (II = IV) > (I = V) > III
(C) (I = V) > III > (II = IV) (D) III > (II = IV) > (I = V)
Mesomeric Effect
049. Which of the following statements is correct about mesomeric effect?
(A) The effect transmitted through  -bonds is called mesomeric effect.
(B) Mesomeric effect operates only when resonance is possible.
(C) All conditions required for resonance to occur are also required for the operation of mesomeric effect.
(D) All of these
050. Which of the following group show +M effect?
(A) –CN (B) –O–NO (C) –CCl3 (D) –CHO

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 General Organic Chemistry-I
051. Which of the following group show –M effect?

(A) –CMe3 (B) (C) (D)

052. Which of the following groups has -M effect?

 CH3  Me
(A) C (B) N Me (C) both (A) and (B) (D) none of these
CH3 Me
053. Which of the following group show +M and –I effect ?
(A) (B) (C) –O (D) –OH

054. Which of the following group show +M > –I effect ?

(A) –F (B) (C) (D) –COOH

055. Which of the following group show –M and –I effect ?

(A) –NO2 (B) –NH2 (C) –OH (D) –F
056. +M and +I both effects are shown by :
(A) (B) (C) (D) – C (CH3)3
057. Which of the following groups has either +M or -M effect, depending upon situation?
(A) CH=CH2 (B) CH=O (C) both (A) and (B) (D) none of these
058. The weakest +M group of the given species is :
(A) – OCH3 (B) – F (C) – I (D) – N (CH3)2
059. OH F Cl
I II III
Which of the following orders is correct for the magnitude of +M effect among these groups?
(A) I > III > II (B) I > II > III (C) III > II > I (D) II > III > I

060. C CH OCH3

I II III
Which of the following orders is correct for the magnitude of +M effect among these groups?
(A) III > I > II (B) II > I > III (C) I > II > III (D) II > III > I
061. OCHCH2 OCHO OH
I II III
Which of the following orders is correct for the magnitude of +M effect among these groups?
(A) I > II > III (B) III > I > II (C) II > I > III (D) I > III > II
Steric Inhibition of Resonance (SIR Effect)
062. Maximum extent of steric inhibition of resonance can be expected in

(A) (B) (C) (D)

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 General Organic Chemistry-I
063. Select the correct statement about this compound.
NO2
3

1 5

NO2 NO2
Br
(A) All three C–N bond length are same.
(B) C1–N and C3–N bonds length are same but shorter than C5–N bond length.
(C) C1–N and C5–N bonds length are same but longer than C3–N bond length.
(D) C1–N and C3–N bonds length are different but both are longer than C5–N bond length.

CH3 CH3 CH3 CH3 CH3 CH3

N N N
CH3 CH3
064 .
CH3 CH3
I II III
Among these compounds, the correct order of ring C-N- bond length is
(A) III > I > II (B) III > II > I (C) I > III > II (D) II > III > I
Hyperconjugation
065. In hyperconjugation there is overlap between :
(A) p- and -orbitals (B) 2-orbitals (C) d-and--orbtial (D) -and p - orbitals
066. Which of the following cannot exhibit hyperconjugation -

(A) CH3 C H2 (B) (C) CH3CH = CH2 (D)

067. Hyperconjugation occurs in


(A) (B) (C) both (A) and (B) (D) none of these

068. Which of the following alkenes will show maximum number of hyperconjugation forms ?

(A) CH2 = CH2 (B) CH3 –CH=CH2 (C) CH3–CH2–CH=CH2 (D)

069. Arrange the stability of following

I II III
(A) I < II < III (B) II < I < III (C) I < III < II (D) II < III < I

070. Hyperconjugation occurs in

 
CHCH3 CH2CH
(A) (B)


(C) CH3 (D) both (A) and (B)
CH3

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 General Organic Chemistry-I
071. Which one of the following has inductive, mesomeric and hyperconjugation effect ?
(A) CH3Cl (B) CH3 – CH = CH2
(C) CH3CH = CH – C – CH3 (D) CH2 = CH – CH = CH2
||
O
072. Which of the following group has the maximum hyperconjugation effect when attached to bezene ring ?
(A) CH3 – (B) CH3 CH2 – (C) (CH3 )2CH– (D) (CH3)3C–
Concept of Aromaticity
073. Aromatic compounds burn with sooty flame because :
(A) They have a ring structure of carbon atoms. (B) They have a relatively high percentage of hydrogen.
(C) They resist reaction with oxygen of air. (D) They have a relatively high percentage of carbon.
074. Which out of the following is aromatic hydrocarbon ?

(A) (B) (C) (D)

075 . Which of the following annulenes is aromatic?

(A) [8]-Annulene (B) [10]-Annulene (C) [12]-Annulene (D) none
076. Identify the aromatic compound ?

(A) (B) (C) (D)

077.

I II
Which of the following orders is correct for the  -electron energy of these two compounds?
(A) I > II (B) II > I (C) I = II (D) Unpredictable

078.

I II
Which of the following orders is correct for the  -electron energy of these two compounds?
(A) I > II (B) II > I (C) I = II (D) Unpredictable

K
079. P, P will be
THF

(A)  2K  (B) 

(C) (D) mixture of (A) and (B)

Applications of electronic effect

080. The decreasing order of electron density on the ring is :

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 General Organic Chemistry-I

(A) III > II > I (B) II > III > I (C) I > III > II (D) III > I > II
081. Which of the following species does not have all C-O bonds of same length?
 
(A) HCOO (B) CO3 (C) CO2 (D) HCOOH
082. Correct dipole moment order is

(p) (q) (r)

(A) p > q > r (B) r > q > p (C) q > r > p (D) p > r > q
083. Arrange following compounds in decreasing order of their dipole moment.

CH3 —CH2—NO2 CH3 —CH2—NH2 CH3—CH2—F CH3—CH2—CN

I II III IV

(A) IV > III >I > II (B) IV > I > III > II (C) I > III > IV > II (D) I > IV > III > II
084. The stability order of alkene in following compounds is :

(I) (II) (III) (IV)

(A) I < II < III < IV (B) II < I < III < IV (C) II < III < I < IV (D) II < IV < I < III

EXERCISE-2
085. In the following benzyl/allyl system
R – CH = CH2 and (R is alkyl group)
Then decreasing order of inductive effect is : [AIEEE-2002]
(1) (CH3)3 C— > (CH3)2CH— > CH3CH2— (2) CH3CH2— > (CH3)2CH— > (CH3)3C—
(3) (CH3)2CH— > CH3CH2— > (CH3)3C— (4) (CH3)3C— > CH3CH2— > (CH3)2CH—
086. Which of the following molecule is least resonance stablised ? [JEE MAIN-2017]

(1) (2) (3) (4)

N O
O
087. Stability of -bond in following alkenes in the increasing order is :
CH3–CH = CH – CH3

(I) (II) (III) (IV)

(1) I < III < IV < II (2) I < II < III < IV (3) IV < III < II < I (4) II < III < IV < I

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 General Organic Chemistry-I
088. Select the correct statement regarding the following compounds :

(I) (II)

(1) II has a greater dipole moment than I (2) Covalent character of II is less than I
(3) I is more soluble in polar solvent than II (4) None of these
089. Which of the following resonating structure of 1-Methoxy-1,3-butadiene is least stable ?
+ +
(1) CH2 – CH = CH – CH = O – CH3 (2) CH2 = CH – CH – CH = O – CH3

+ +
(3) CH2 – CH – CH = CH – O – CH3 (4) CH2 =CH – CH – CH–OCH3
090. Select the correct option related to stability of following structures.

(1) > (2) <

O
||
(3) < (4) > CF3 – C – O

091. The minimum magnitude of heat of hydrogenation per mole of molecule is -

(1) (2) (3) (4)

092. The decreasing order of electron density on the ring is :

(I) (II) (III) (IV)

(1) (II) > (III) > (IV) > (I) (2) (IV) > (I) > (II) > (III)
(3) (IV) > (I) > (III) > (II) (4) (I) > (III) > (IV) > (II)
093. Hyperconjugation observed in

(1) (2) (3) (4)

094. The number of hyperconjugable hydrogen atoms of following species are respectively :


(P) (Q) CH3 CHCH2CH3 (R) C=CHCH3 (S) CH3CH=CHC2H5

(1) 3, 5, 9, 8 (2) 3, 5, 9, 5 (3) 5, 5, 3, 5 (4) 5, 2, 6, 5

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 General Organic Chemistry-I
95. In the following sets of resonating structure, label the major contributors towards resonance hybrid.

(P) (Q)

(R) (S)

(1)  (2)  (3)  (4) 

96. In which of the following C = C bond length is minimum :

(1) (2) C=CH2 (3) CH2 = CH – N (4)

97. Which of the following compound is non aromatic :

(1) (2) (3) (4)

98. Which compound has least e– density in benzene ring

(1) (2) (3) (4)

99. The order of heat of hydrogenation in following compound is :

(I) (II) (III) (IV)

(1) I < II < IV < III (2) III < IV < II < I (3) II < III < I < IV (4) II < IV < I < III
100. Resonance stabilized cation is :

(1) (2) (3) (4)

101. In HCOO–, the two carbon-oxygen bonds are found to be of equal length. What is the reason for this ?
(1) The anion is obtained by the removal of a proton from the acid molecule.
(2) Electronic orbitals of carbon atoms are hybridised.
(3) The C=O bond is weaker than C–O bond.
(4) The anion HCOO– has two equally stable resonating structures.
102. Compare C–N bond length in the following :

(1) I > II > III (2) I > III > II (3) III > II > I (4) III > I > II
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 General Organic Chemistry-I
103. Which of the following is false for order of –I effect :
(1) –F > –Cl > –Br > –I (2) –C  CH > –CH = CH2 > –CH2 – CH3
(3) –CCN > –C–OH (4) –Ph > –C  CH
O

104.

which resonating structure is least stable

(1) x (2) y (3) z (4) All are equivalent
105. The aromatic compound would be

(1) (2) (3) (4)

106.

Squaric acid dianion has :

(1) 4-identical resonating structure (2) C–C bond length is equal to C–O bond length
(3) 3 nonidentical resonating structure (4) Localised negative charged on oxygen

107. Which of the following benzene ring has greater electron density than

(1) (2) (3) (4)

108. Compare C–N bond length in the following

correct order is

(1) I > II > III (2) I > III > II (3) III > II > I (4) III > I > II
109. Among the following aromatic compound is

(1) (2) (3) (4)

110. :

(1) Resonating structures (2) Tautomers

(3) Geometrical isomers (4) Optical isomers
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 General Organic Chemistry-I
111. Which is not stable at room temperature ?

(1) (2) (3) (4)

112. Correct order of stability of following alkenes is

(1) I > II > III (2) I > III > II (3) III > II > I (4) III > I > II
113. All the carbon-carbon bond lengths are equal in

(1) CH2=CH–CH2–CH3 (2) (3) CH3–CH=CH–CH3 (4) CH2=CH–CH=CH2

114. The kind of delocalization involving sigma bond orbitals is called

(1) Inductive effect (2) Hyperconjugation effect
(3) Electromeric effect (4) Mesomeric effect
115. The molecule having largest dipole moment among the following is:
(1) CHI3 (2) CH4 (3) CHCI3 (4) CCI4

116. in C1–H, C2–H and C3–H the homolytic bond dissociation energy order is :

(1) C2–H > C3–H > C1–H (2) C2–H > C3–H > C1–H
(3) C2–H > C3–H > C1–H (4) C3–H > C2–H > C1–H

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 General Organic Chemistry-I

ANSWER KEY
EXERCISE-1
PART-1

001. (i) (ii) (iii)

(iv) CH3 CH2 CH2 Li (v) CH3 CH2 CH2 MgBr (vi)

(vii) (viii) CH3 COOH (ix) (x)

002. (P), (R), (S)

003. 8
004. (P) I – minor II – major
(Q) I – minor II – major
(R) I – minor II – major
(S) I – minor II – major

005. (P) I > II ; (Q) II > I ; (R) I > II ; (S) II > I

006. (i) +m : – I < – Br < – Cl < – F (ii) +m : –OH < –NH2 <

007. (i) –m : –COOR < –COR < CHO < CN < NO2 (ii) –m : < <

O
||
O — S — OH

008.

have + M group.
009. SIR effect increases with the size of ortho group. The order of SIR effect is o-iodo benzoic acid > o-bromo
benzoic acid > o-chloro benzoic acid.
010. It is delocalisation of sigma electron with p-orbital. It may take place in alkenes, alkynes, carbocations, free
radicals, alkelyl benzene.
Necessary Condition : Presence of at least one hydrogen at saturated carbon which is  with respect to
alkene, alkynes, carbocation, free radical, benzene nucleus.

Propene 

011. (A) 0 (B) 2 (C) 0 (D) No hyperconjugation

(E ) 0 (F) 0 (G) 6 (H) 9
(I) 3 (J) 10 (K) 0 (L) 10

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 General Organic Chemistry-I
012. Those molecules are aromatic which have very high resonance energy. Only those molecules has sufficiently
high amount of resonance energy to become aromatic which
(a) are cyclic
(b) are planar
(c) contains (4n +2) number of  -electrons in ring.
(d) must have cyclic resonance between (4n + 2) number of -electrons
Where n = 0,1,2,3,4 ..........
013. Aromatic: (a), (b), (c), (d), (e), (f), (h), (l)
Antiaromatic : (g), (i), (j), (m)
Nonaromatic : (k)

014. Cyclooctatetraene is nonplanar to avoid its anti aromaticity and it becomes tub-shaped structure.

015. (III) > (II) > (IV) > (I)

+m group increases electron density and – m group decreases electron density in aromatic ring.
016. p>q>r

PART-2
017. (B) 018. (B) 019. (D) 020. (B) 021. (C) 022. (A) 023. (D)
024. (A) 025. (C) 026. (D) 027. (D) 028. (D) 029. (A) 030. (A)
031. (A) 032. (C) 033. (C) 034. (A) 035. (B) 036. (A) 037. (B)
038. (B) 039. (C) 040. (B) 041. (C) 042. (C) 043. (B) 044. (A)
045. (D) 046. (B) 047. (A) 048. (A) 049. (D) 050. (B) 051. (D)
052. (A) 053. (D) 054. (B) 055. (A) 056. (C) 057. (A) 058. (C)
059. (B) 060. (A) 061. (B) 062. (C) 063. (C) 064. (A) 065. (D)
066. (D) 067. (D) 068. (B) 069. (C) 070. (D) 071. (C) 072. (A)
073. (D) 074. (C) 075. (D) 076. (B) 077. (B) 078. (A) 079. (A)
080. (A) 081. (D) 082. (B) 083. (D) 084. (A)

EXERCISE-2
085. (1) 086. (2) 087. (1) 088. (3) 089. (4) 090. (3) 091. (4)
092. (3) 093. (4) 094. (2) 95. (3) 96. (2) 97. (1) 98. (3)
99. (2) 100. (3) 101. (4) 102. (1) 103. (4) 104. (3) 105. (3)
106. (1) 107. (3) 108. (1) 109. (3) 110. (1) 111. (3) 112. (3)
113. (2) 114. (2) 115. (3) 116. (4)

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 General Organic Chemistry-II

General Organic Chemistry-II

Applications of electronic effects :
Reaction Intermediates
Breaking of old bonds and formation of new bonds is called as Reaction.
During the course of an organic reaction some reactive, shortlived, highly energetic, unstable species are
formed, which are called as reaction intermediates.
Reaction intermediates generally formed after bond breaking and before bond formation.
A covalent bond can get cleaved either by :
(i) Heterolytic cleavage (ii) Homolytic cleavage.

Homolytic fission of Covalent Bonds :

The bond may break in such a way that each fragment takes away one of the electrons of the bond. This
process called homolysis, produces fragments with unpaired electrons called radicals.

Heterolytic fission of Covalent Bonds :

The bond may break in such a way that one fragment takes away both electrons of the bond, leaving the
other fragment with an empty orbital. This kind of cleavage called heterolysis, produces charged fragments
or ions.

Heterolysis of a bond normally requires that the bond be polarised.

Polarisation of a bond usually result from different electronegatives of the atoms joined by the bond. The
greater the difference in electronegativity, the greater the polarisation. In the given instance, atom B is more
electronegative than A.
(1) Carbocation :
A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation or
cabonium ion.
Hybridisation : Carbocation may be sp2 & sp hybridised
Hybridisation Example
sp2 , , ,

sp H2C = , HC 
Carbocations are electron deficient. They have only six electrons in their valence shell, and because of this,
carbocations act as Lewis acids. Most of the carbocations are short-lived and highly reactive, they occur
as intermediates in some organic reactions. Carbocations react with Lewis bases or ions that can donate
the electron pair, that they need to achieve a stable octet of electrons (i.e., the electronic configuration of
a noble gas):
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 General Organic Chemistry-II

Because carbocations are electron seeking reagents, chemists call them electrophiles. All Lewis acids, including
protons, are electrophiles. By accepting an electron pair, a proton achieves the valence shell configuration of
helium; carbocations achieve the valence shell configuration of Neon.

Stability : Carbocations are stabilised by

(i) + M effect (ii) delocalisation of charge (iii) Hyperconjugation (iv) + I effect
General stability order :
> > > >

> > >

Illustration: 1 > >

t-Butyl carbocation has +I effect of three Me–groups and also Hyperconjugation effect which makes it most
stable.

Illustration: 2 (i) < CH3 < CH3 CH3 < (CH3)3

CH 3
(ii) CH3 – > CH3 – CH2 – CH2 – > – > CH3 C –
CH 3
(due to resultant of inductive effect and hyperconjugation)

Illustration: 3 > >

In Benzyl cation, Extensive Resonance is seen which stabilises .

In Ethyl carbocation + I and Hyperconjugation of Me – group stabilizes carbocation.
In vinyl carbocation stability decreases rapidly since carbon of (CH2) is sp2 hybridized which is slightly
more electronegative hence acts as – I group which increases (+) charge density.

Rearrangement of carbocation :
Whenever an Intermediate carbocation is formed in reaction it may rearranges.
Only those carbocation will rearrange which can produce more stable species. It can be done either by
(i) Shifting of H, alkyl, aryl, bond (1, 2 shifting)
(ii) Ring expansion (more strained ring to less strained ring)
(iii) Ring contraction

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 General Organic Chemistry-II
(i) Shifting of H, alkyl, aryl, (1, 2 shift)

1,2 H
(A) 

Shifting

1,2 Me 
(B)  
Shifting

1,2 Ph 
(C)  
Shifting

+
CH2
–

1,2 Bond
(ii) Ring expansion :  
Shifting

1,2 Bond
(iii) Ring contraction :  
Shifting

Note: Cyclopropylmethyl cation: In solvolysis of simple primary cylcopropylmethyl systems the rate is enhanced
because of the participation by the  –bonds of the rings. The ion that forms initially is an unarranged
cyclopropylmethyl cation that is symmetrically stabilized, that is, both the 2, 3 and 2, 4  –bonds help
stabilize the positive charge. Cyclopropyl group stabilizes on adjacent positive charge even better than a
phenyl group.

3

2 1


4 ~ 48% ~ 47%
 ~ 5%

This special stability, which increases with each additional cyclopropyl group, is a result of conjugation
between the bend orbitals of the cyclopropyl rings's and the vacant P-orbital of cationic carbon.

Illustration: 4. Rearrange (if applicable) the following carbocations into more stable form :-
CH3
+
(a) CH3 – CH2 – CH2 (b) (c) CH3 – C – CH – CH3
+
CH3

CH3 CH3
–

––

(d) (e) CH3 (f)

+ +

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 General Organic Chemistry-II

+ 1,2 H
Sol. (a) CH3 – CH2 – CH2 Shifting
  +
CH3– CH – CH3

1,2 H
(b) 

Shifting

CH3
CH3 +
1,2 Me 
(c) CH3 – C – CH – CH3   CH3– C – CH – CH 3
+ Shifting
CH3
CH3
CH3
–

1,2 H
(d) 

+ Shifting

CH3
––

1,2 Me 
(e) CH3  
Shifting
+

1,2 Bond
(f)  
Shifting

(2) Free Radicals :

Homolysis of covalent bond results into free radical intermediates possess the unpaired electrons.

It is generated in presence of Sunlight, Peroxides or High temperature

hv
or 

Free Radical : An uncharged intermediate which has three bond pair and an unpaired electron on carbon.
Note : (i) It is Neutral species with odd e¯
(ii) It is paramagnetic in nature due to odd e¯
(iii) No rearrangement is observed generally.
(iv) Carbon atom having odd electron is in sp2 hybridised state
(v) Any reaction if it is carried out in the presence of sunlight, peroxide or high temperature it generally
proceeds via free radical intermediate.
Stability of free radical : It is stabilised by resonance, hyperconjugation and + I groups.
  
(i) (H3C)3C > H3 C – C H – CH3  H3 C – C H2  C H3 (Stability order)

(ii) < CH3 – < CH3 – – CH3 < CH3 – (Stability order)

(iii) CH3 – > CH3 – CH2 – > > (Stability order)

(due to resultant of inductive effect and hyperconjugation, both operates in same direction)
  
(iv) (C 6H5 )3 C > (C 6H5 )2 C H > C 6H5 – C H2 > CH2  CH – C– CH3 (Stability order)
|
CH3

(3) Carbanion :
A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.
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 General Organic Chemistry-II
Hybridisation : Hybridisation of carbanion may be sp3, sp2 & sp.
Hybridisation Example

sp3 , CH3– , , ,

sp2 H2C= , CH2=CH– ,

sp HC 

Stability of carbanion : Carbanions are stabilised by electron withdrawing effect as

(i) – I effect (ii) – m effect (iii) Delocalisation of charge
Carbanions are Lewis bases. In their reactions they seek a proton or some other positive centre to which
they can donate their electron pair and thereby neutralize their negative charge.

Example of stability order :

(a) CH3 CH 3 CH2 > CH 3 CH2 CH3 > CH3 C CH3

CH3
(b) CH C > >
.. .. ..
CH2
(c) > >


  ••
(d) CH2  CH  CH2 < C 6H5 – C H2 < (C 6H5 )3 C
Rearrangement : Generally carbanions do not undergo rearrangement.

Carbocation

(4) Carbenes (Divalent Carbon intermediates) :

There is a group of intermediates in which carbon forms only two bonds. These neutral divalent carbon
species are called carbenes. They are electron deficient species hence electrophile.
Methods of preparation of carbene :
CHCl3 + : CCl2 CH2I2 + Zn : CH2

CH2N2 N2  + : CH2 CH2 = C = O : CH2 + CO

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 General Organic Chemistry-II

Types of carbene Singlet Triplet

Shape Bent Linear

2
Hybridisation sp sp
Nature of reaction stereospecific None
State Excited state Ground state
Magnetic Diamagnetic Paramagnetic
Nature Paired electrons Diradical

(5) Nitrenes :
The nitrogen analog of carbenes are nitrenes. They are very much reactive since in them octet of N is
incomplete. In nitrenes only one valencies of N are satisfied.

(6) Benzyne :
The benzene ring has one extra C – C  bond in benzyne

Clearly, we can see that the newly formed  bond cannot enter in resonance with other  orbitals of ring.
since it is in perpendicular plane.
It is also important to note that hybridisation of each carbon involved in 'Benzynic bond' is sp2 since the
overlap between these sp2 hybrid orbitals is not so much effective.

ACID BASE CONCEPT

Acids
(a) Arhenius acid : An acid is a substance that can donate (or loose) a proton in H2O.
(b) The Bronsted - Lowry definition of acids and bases
An acid is a substance that can donate (or loose) a proton, and a base is a substance that can accept a proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :

Hydrogen chloride, a very strong acid, transfers its proton to water. Water acts as a base and accepts the
proton. The products that result from this reaction are a hydronium ion (H3O+) and a chloride ion (Cl–).
The molecule or ion that forms when an acid loses its proton is called the conjugate base of that acid. (The
chloride ion is the conjugate base of HCl). The molecule or ion that is formed when a base accepts a
proton is called the conjugate acid of that base.
(c) The Lewis definition of acids and bases
Lewis proposed that acids are electron pair acceptors and bases are electron pair donors.

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 General Organic Chemistry-II
(d) Acid dissociation constant (Ka) :
RCOOH + H2O RCOO– + H3O+
[RCOO  ] [H3O  ]
Keq =
[RCOOH] [H2O]

[RCOO ] [H3O ]
Ka =
[RCOOH]
pKa = – log Ka

Relative acidity of hydrocarbons :

Being most electronegative the sp hybridised carbon atom of ethyne polarizes its C–H bond to the greatest
extent causing its H to be most positive therefore ethyne is most acidic hydrocarbon.
HC  CH > H2C = CH2 > H3C – CH3
Acidity of Phenols :
The phenoxide ion is more stabilised by resonance than the unionised phenol.
Groups which are – I, – M increases acidic character of phenol because effectively dispersing the negative
charge of phenoxide ion. Alternatively + I and + M groups decreases acid strength.

Illustration: 4

Ans. Acid strength order : I > II > IV > V > III

Sol. Step-1. III will be least acidic as it has no dispersion of negative charge (No delocalisation of negative
charge).
Step-2. since –I, –M group will increase acid strength, Nitrophenol will be most acidic followed by phenol,
Step-3. Amongst cresol and methoxyphenol, methoxyphenol has +M effect of – OCH3 which increases e–
density hence decrease acidic strength

Illustration: 5

Ans. Acid strengh order : I > III > II > IV

Sol. Step-1 : Notice that CH3 have + I effect so all methylphenols (cresols) are less acidic than phenol (I).
Step-2 : Now amongst cresols p- and o-CH3 are increasing the e– density due to their hyper conjugation but
ortho isomer has viable + I effect also, which will help in destabilising phenoxide ion therefore o- is least
acidic. Since at meta position only + I works it as least e– density amongst the cresol.

Illustration: 6

Ans. Acid strength order : II > IV > III > I

Sol. Step-1 : In nitrophenols – I effect of NO2 will help to increase acidic strength hence phenol is least acidic
amongst all nitrophenols

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 General Organic Chemistry-II
Step-2 : Only – I effect is applicable in meta nitrophenol it will be number three. Now – o, – p have both –
I and – M effect of NO2 group over OH and in this particular case para isomer is more acidic than ortho
since

H is trapped by NO2 group.

Table : pKa values of some phenols and Ethanol. (Ref. NCERT)

Com pound Form ula pK a
o-Nitrophenol o–O 2N–C6 H4 –OH 7.2
m-Nitrophenol m–O 2 N–C 6H 4–OH 8.3
p-Nitrophenol p–O 2N–C6 H4 –OH 7.1
Phenol C 6H 5–OH 10
o-Cresol o–CH 3–C 6H 4–OH 10.2
m-Cresol m–CH 3–C6 H4 –OH 10.1
p-Cresol p–CH 3–C 6H 4–OH 10.2
Ethanol C 2H 5OH 15.9

From the above data, you will note that phenol is million times more acidic than ethanol.
Acidity of carboxylic acids :
Conjugate base of carboxylic acid exists as two equivalent cannonical structures (A) and (B). This ion is
resonance stablised and resonance hybrid structure is (C).

Electron withdrawing group (–M, –I effect) increases acidic nature.

Electron releasing group (+M, +I effect) decreases acidic nature.
Examples.
(a) F–CH2–COOH > Cl–CH2COOH > Br–CH2COOH > I–CH2COOH
Cl Cl
(b) Cl – C – COOH > Cl – CH – COOH > Cl–CH2COOH > CH3COOH
Cl
(c) HCOOH > CH3COOH > CH3–CH2–COOH

COOH COOH CH2 – COOH

(d) > CH2 >
COOH COOH CH2 – COOH
The effect of the following groups in increasing acidicty order is [Ref. NCERT]
Ph < I < Br < Cl < F < CN < NO2 < CF3
Thus, the following acids are arranged in order of decreasing acidity (based on pKa values) :
CF3 COOH > CCl3COOH > CHCl2 COOH > NO2CH2 COOH > NC – CH2COOH > FCH2COOH >
ClCH2COOH > BrCH2COOH > HCOOH > ClCH2CH2COOH > C6H5COOH > C6H5CH2COOH > CH3COOH
> CH3CH2COOH

Comparison between two geometrical isomers :

Maleic acid :

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 General Organic Chemistry-II

Fumaric acid :

Now K 1m > K1f

Since the conjugate base is stabilised by intramolecular H bonding.
But K2f > K2m Since in maleate ion, after donation of H two –COO groups faces each other and makes
system unstable. In fumarate ion this repulsion is minimised.
Acidic strength of substituted benzoic acids :
Formic acid is more acidic than benzoic acid while phenyl acetic acid is more acidic than acetic acid.
HCOOH > PhCOOH > >
O O
Electron withdrawing group attached to benzene ring will increase the acidic strength while electron releasing
group decreases acidic strength.
If electron donating group present at para position than it is always less acidic than benzoic acid.

> > > >

Also it is less acidic then meta substituted benzoic acid.

> >

On the other hand if e– withdrawing group is present at meta position then it is more acidic than benzoic
acid.

> > > >

Ortho effect of benzoic acid:

It is common observation that generally ortho substituted benzoic acids are more acidic as compared to their
isomers and benzoic acids itself. This is called ortho effect (which is combined effect of steric hindrance,
crowding & electronic effect) in benzoic acid. However exceptions are seen.

Ex. (a) > > >

(b) > > >

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 General Organic Chemistry-II
COOH COOH

(c) > > >

NO2
NO2

(d) > > > >

(e) > > >

(f) >

exerts –M with benzene nucleus

OH OH OH
NO2 NO2 NO2

(g) > ON > ON NO2

2 2

NO2 NO2 NO2

(picric acid)

Bases
(a) Arhenius base : Base is a substance that can donate (or loose) OH– ions in H2O.
(b) The Bronsted : Lowry definition of acids and bases
An acid is a substance that can donate (or loose) a proton, and a base is a substance that can accept a proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :

(c) The Lewis definition of acids and bases

Lewis proposed that acids are electron pair acceptors and bases are electron pair donors. For example
aluminiumchloride, reacts with ammonia in the same way that a proton donor does. Using curved arrows to
show the donation of the electron pair of ammonia (the Lewis base), we have the following examples:

Cl¯ + H –

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 General Organic Chemistry-II

(d) Basicity (Kb) :

[NH4  ] [OH ]
Kb = [NH3 ]
pKb = – log Kb
Basicity order in periodic table :
(1) Basic strength decreases down the group,
(2) Basic strength decreases along the period because electron negativity increases so electron donor
tendency decreases.
Aliphatic bases :
(1) On the basis of + I effect basic strength of amines should be 3º > 2º > 1º > NH3
But this order is applicable only when the amines are in gaseous state or in case of non-polar aprotic
solvent.
(2) Basic strength of nitrogeneous compound depends upon the hybridised state of nitrogen
R–CH2 –CH2 –NH2 > R –CH2 –CH = NH > R–CH = CH–NH2 > R–CN
   
3
sp (localised) sp (localised)
2 2
sp (delocalised) sp

(3) More electronegative atom (–I group) will decrease the basic strength
CH3–CH2–CH2–NH2 > CH2=CH–CH2–NH2 > H–CC–CH2–NH2
(4) Cyclic amines are more basic than acyclic amines of same nature

>

(5) Amidines are more basic in nature because their conjugate acid are more stable due to resonance.

 
 
H

Nitrogen (X) is more basic than nitrogen (Y).

Basic Strength of Aromatic Amines and substituted Anilines :
(a) Aniline :
Lone pair of aniline lies in conjugation with a multiple bond, it resides in ‘2p’ atomic orbital, so that it can get
resonance stabilisation and hence, basic strength decreases. So, Aniline is a weaker base than NH3

(b) Pyridine (C5H5N) : 6-electrons, aromatic

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 General Organic Chemistry-II
 
H H


–


–
N: N


H  
S.F.:- A.O. Diagram: 2
sp hybrid orbital

–
(localised lone pair)

–
H H

Lone pair of N in pyridine is localised so it is more basic than aniline.

(c) Pyrrole (C4H5N:) : 6- electrons, aromatic

 
 (lone pair in 2p A.O.)
••N–H  N–H
S.F. :- (sp2) A.O. Diagram:- 
—
Complete delocalisation of e

Lone pair of N in pyrrole is delocalised in the aromaticity so it is very less basic than aniline.

> >


N
–

N
:NH2
–

H
H H H

+ +
N ––– sp (4e )
3
–
N
–

NH3
–

–
–

H H H
Aromatic Aromatic Non-aromatic
(d) Substituted Anilines :
Electron releasing groups (ERG) +M, HC, + increases the Kb and
Electron withdrawing groups (EWG) –M, – decreases the Kb
Steric effect of ortho-substituent in Aniline (ortho effect) :
H
–

H2N: +
H–N–H
–

G
–

H G
–

 (conjugate acid)

–

(i) Ortho-substituted anilines are mostly weaker bases than aniline itself.
(ii) Ortho-substituent causes steric hinderance to solvation in the product (conjugate acid i.e. cation).
(iii) The small groups like –NH2 or –OH do not experience (SIR) due to small size.
Ex. (a) G = (–M, –); NO2

NH2
–

(Aniline > m > p > o).

(b) G = (–); CCl3

NH2 NH2 NH2 NH2
–
–

–
–

CCl3
–

(Aniline > p > m > o).

–

CCl3
–

CCl3

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 General Organic Chemistry-II
Only (–) decides the order.

(c) G = (– > + M); Cl

NH2 NH2 NH2 NH2

–
–

–
Cl
–
(Aniline > p > m > o)

–
Cl

–
Cl
Only (–) decides the order.
(d) G = (+, HC); If R = –CH3 (Toluidines)

NH2 NH2 NH2

–

–
–
–

CH3

–
+m CH3
+w
HC  more do min ating
(e) G = (+M > –);

Kb order : p > Aniline > o > m

General basicity order :

Solvent Effect in bases :

The trend is not regular in the aqueous state as evident by their pKb values given in Table.
Na m e of a m ine pK b Na m e of a m ine pKb

Methanamine 3.38 N,N-Diethylethanamine 3.25

N-Metheylmethanamine 3.27 Phenylmethanamine 4.70

N, N-Dimethylmethanamine 4.22 Aniline 9.38

Ethanamine 3..29 N-M ethylaniline 9.30

N-Ethylethanamine 3.00 N,N-Dimethylaniline 8.92

Table : pKb Values of Amines in Aqueous Phase (Ref. NCERT)

In the aqueous phase, the substituted ammonium cations get stabilised not only by electron releasing effect
of the alkyl group (+I) but also by solvation with water molecules. The greater the size of the ion (Alkyl
groups are hydrophobic and inhibits H bonding and solvation.), lesser will be the solvation and the less
stabilised is the ion. The order of solvation of ions are as follows:

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 General Organic Chemistry-II

R H OH2
+| R
| |
N +
R N H OH2

|
| |
|
R H OH2 R

20 30
Greater is the stability of the substituted ammonium cation, stronger should be the corresponding amine as
a base.
On the basis of above two sequences, we can say that the basic strength of amines is the combined effect of
inductive effect, steric hindrance and solvation.
R2NH > RNH2 > R3N > NH3 (if R = CH3) ......... (1)
R2NH > R3NH > RNH2 > NH3 (if R = C2H5) ..........(2)
Reactions of Bases :
(i) Nature of aqueous solution : Amines combine with water to form alkyl ammonium hydroxides. This gives
hydroxide ions in solution, thus the aqueous solution of amines is basic in nature.

RNH2 + HOH R N H3 OH– [RNH3]+ + OH–
1º Amine

R2NH + HOH R 2 NH2 OH– [R2NH2]+ + OH–
2º Amine
The aqueous solution of amines behave like NH4OH and gives the precipitate of ferric hydroxide with ferric
chloride.
3RNH3OH + FeCl3  Fe(OH)3 + 3RNH3Cl
Brown ppt.
(ii) Aliphatic and aromatic amines form salt because of their basic nature:
 –
RNH2 + H2O  R N H 3 O H
Alkylammoniumhydroxide
 –
RNH2 + HCl  R N H 3 C I
Alkylammoniumchloride

RNH2 + H2SO4  ( R N H3 )2 SO4–2
Similarly we get
 –
C6H5NH2 + H2O  C6H5 N H 3 O H
Aniliniumhydroxide
 –
C6H5NH2 + HCl  C 6 H5 N H3 C I or C6H5NH2 : HCl
Aniliniumchloride Anilinehydrochloride
Salts of amines are ionic compounds and hence water soluble.

Reactions of Acids with salts :

(1) NaX + HY  NaY + HX
Salt of Weak acid Strong Acid

Remark : A stronger acid displaces the weaker acid from weak acid metal salt. The weaker acid is
released out as a gas or liquid or precipitates out as a solid. The weaker acid cannot displace the stronger
acid from the salt.
1. 2 NaCl + H2SO4  Na2SO4 + 2HCl

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 General Organic Chemistry-II
2. Na2SO4 + 2HCl  No reaction
3. CH3COONa + CH3SO3H  CH3COOH + CH3SO3Na (feasible)
4. CH3COONa + PhOH  PhONa + CH3COOH (not feasible)
Tautomerism
Definition :
Tautomerism is a phenomenon by which a single compound exists in two or more readily interconvertible
structures that differ in the relative positions of at least one atomic nucleus, generally hydrogen.
These two isomers remain in dynamic equilibrium and can be isolated also give different lab test.
Conditions :
1. Usually present in the following functional groups

2. Basic need for its existence is attachment of these groups with the sp3 hybridised C-atom having atleast
one hydrogen atom as –

To get tautomer of above structures -hydrogen atom is shifting to more electronegative atom attached to
double bond (i.e. hydrogen atom from 1st atom to 3rd atom) and double bond is developed between 1,2-
atom from 2,3-atom. This can be represented as :

These two forms (remain in equilibrium) are called tautomers of each other. The interconvertibility of
tautomers is a chemical reaction which involves making and breaking of bonds.
O OH
|| |
Ex. (a) CH3  C  CH3 CH2  C  CH3 (b)
( I) (II)

(c) (d)

Keto-enol Tautomerisation :
(A) Base-catalyzed enolization :


 


Protonation of the carbanion by water on the -carbon gives back the carbonyl compound. Protonation on
oxygen gives the enol. Notice that the enolate ion is the conjugate base of both the carbonyl compound and
the enol.

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 General Organic Chemistry-II
(B) Acid-catalyzed enolization :
Involves the conjugate acid of the carbonyl compound. Recall that this ion has carbocation characteristics.
Loss of the proton from oxygen gives back the starting carbonyl compound; loss of the proton from the -
carbon gives the enol. Notice that an enol and its carbonyl isomer have the same conjugate acid.


 


% Enol content in the carbonyl compounds :

(a) For monocarbonyl, % Enol is very less
(b) Enol content increases with increase in the stability of enol by resonance, hyperconjugation, hydrogen
bonding etc.

Decreasing order of enol content for above carbonyl compounds is : 3 > 2 > 1.
(c) For a carbonyl compound having active methylene group percentage of enol content will be more
because enolic form has intramolecular H-bonding and also it will be stabilised by resonance.

(d) If active methylene group is more acidic then enol content will be more.
O O
For example in acetyl acetone enolic content is 75–76% while it is 7–8% in acetoacetic
ester because ester group shows less electron withdrawing nature than keto group.
(e) Percentage of enol content is more in non-polar media while % of keto form is more in polar media.

Racemisation and D-exchange :

Exchange of -hydrogen from deuterium as well as racemization at the -carbon are catalyzed not only by
bases but also by acids due to the phenomenon of tautomerisation.

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 General Organic Chemistry-II

1. (D-exchange)

2.

3.

Other examples of Tautomers

(a) Imine-Enamine system :
R 2CH – CR = NR
Imine
Among these two tautomers, enamines are stable only when there is no hydrogen on the nitrogen, otherwise
the imine form predominates.
(b) Nitroso-oxime system :
Like primary and secondary nitro compounds, primary and secondary nitroso compounds also exhibit
tautomerism with their more stable isonitroso or oxime form.
NO
|
; CH3 – CH – CH3 CH3 – C – CH3
||
2-Nitrosopropane
NOH
Acetoneoxime
(c) Nitro-Acinitro system :
The acidic nature of the nitro compounds gives rise to the belief that the nitro compounds exist in two forms,
a more stable or normal nitro form and the less stable acinitro form.
R – CH2 R – CH
| ||
N N
O O HO O
Nitroform Acinitroform

The stability of the nitro form is more as compared to the acinitro form because it is stabilised by resonance.
O OH
C6H5 – CH2 – N C 6H 5 – CH = N
Nitroform O Acinitroform O
(d) Lactam-Lactim system :

O OH
O || |
O
C C
N ; NH N
O N
| OH SO2 SO2
H

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 General Organic Chemistry-II

EXERCISE-1
PART- 1: SUBJECTIVE QUESTIONS
Carbocations

001.

Hybridization of the positively charged C-atom of this cation is

002. Arrange the following carbocations in decreasing order of their stability :
(I) (II) (III) (IV)
   
(P) CH3 —CH2 — CH 2 CH3 — CH — CH2 CH3 — CH — CH2 CH3 — CH — CH2
| | |
F Br Cl

(Q)

(R)

003. Which of the following carbocation is more stable and why ?

(I) (II)

004. Draw the structures of P and Q.

Carbon free radicals

005. Rank the following free radicals in increasing order of their stability and give appropriate reasons.

006. Arrange the following free radicals in decreasing order of stability :

 
CH3 – CH2 CH3
I IV

Carbanions
007. Arrange the following in decreasing order of stability

(a) (b)
1 2 3

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 General Organic Chemistry-II
008. Arrange the following in decreasing order of stability
..
.. CH3

–
(a) .. ..

–
CH3
1 2 3 4

.. ..
(b) (c) CCl3 CF3
1 2

Acidic Strength
009. Which ‘H’ atom is most acidic in the following compounds.

O O
(I) (II) (III)

010. Arrange the following in decreasing order of acidity

011. The given compound X = . is a strong acid. Justify this statement.

Basic Strength
012. Compare the basic strength of the following compounds:
HO– C 2H5 – NH 2 – F–
(I) (II) (III) (IV)
013. Compare the basic strength of the following compounds :

(a) PhNH 2 Ph2 NH Ph3 N

(b)


N
–

N
:NH2
–

H
(c) Ph–CH2 –NH–CH3

014. Which of the following group is most basic in the given compounds :

015. Which of the following is a stronger base ? Give reason to justify your answer.

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 General Organic Chemistry-II
Feasible Reactions of Acids and Bases
016. Which of the follwing reactions is/are feasible ?
(a) CH3COOH + HCOONa  (b) HC  C – Na + H2O 

(c) +  (d) + 

017. Which of the following reaction is feasible ?

(a)

(b) +  NH3 +

(c) +  +


N H2 CH2 NH CH2

(d) NH2  C  NH2 + CH3  C  NH2  NH2  C  NH2 + CH3  C  NH3

018. Which of the following acids (given below) react with NaHCO3 and liberate CO2(g) ?

CCl3–COOH CH 3 –CH2 –OH HCl

Tautomerism
019. Which of the following compounds can exhibit tautomerism ?

CH3
– –

(A) CH3 – C – C – H (B) Ph – C – CH3 (C) (D)

CH3 O O

O O
O
(E) (F) (G) (H)
O

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 General Organic Chemistry-II
020. Write the tautomers of the following compounds :

(P) (Q) CH3 – CH = NH (R) (S)

021. Monocarbonyl compounds have very small percentage enol form at equilibrium. Explain.

PART- 2: OBJECTIVE QUESTIONS

Carbocations
022. The most unstable carbocation is :
   
(A) CH3 C H2 (B) Cl – CH2 – C H2 (C) C H2 – CHO (D) C H2 – O – CH3

023. Which of the following shows the correct order of decreasing stability ?

(A) > > > CH3 – C H2


(B) > > > CH3 – C H2


(C) > > > CH3 – C H2


(D) > > CH3 – C H2 >

024. The most stable carbocation is :

(A) (B) (C) (D)

025. Which of the following is the rearranged more stable carbocation of the given species ?
CH3
| 
CH3 – C – C H  CH3 
|
CH3
CH3 CH3 CH3 CH3
CH3 |
| |  | | 
(A) CH3 – C – C H – CH3 (B) CH3 – C – C H2 – C H2 (C) CH3– C — CH – CH3 (D) CH3 – CH – CH  C H2
| |  |
CH3 CH3 CH3

  
026.

I II III
Which of the following orders is correct for the stability of these carbocations?
(A) I > II > III (B) III > II > I (C) II > I > III (D) II > III > I

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 General Organic Chemistry-II
027. Most stable rearranged form of given carbocations is :

(A) (B) (C) (D)

028. Which of the following in the rearranged more stable carbocation of the given species?

(A) (B)

(C) (D)

Carbon free radicals

029. Among the following, the paramagnetic species is :
(A) Free radical (B) Carbonium ion (C) Carbanion (D) All the three
030. The stability of given free radicals in decreasing order is :
  
(i) CH3– C H2 (ii) CH3– C H –CH3 (iii) (iv) C H3

(A) iii > iv > i > ii (B) i > ii > iii > iv (C) iii > ii > iv > i (D) iii > ii > i > iv
031. Which of the following is the correct order of stability of free radicals?
(A) Benzyl > allyl > 2º > 1º (B) Allyl > benzyl > 2º > 1º
(C) Allyl > 2º > 1º >benzyl (D) Benzyl > 2º > 1º > allyl
032. Most stable radical among the following is :

(A) (B) (C) (D)

033. Arrange the following radicals in decreasing order of their stability.

(I) (II)

(III) (IV)
(A) IV > I > III > II (B) IV > III > II > I (C) I > II > III > IV (D) IV > III > I > II

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 General Organic Chemistry-II
034. Least stable radical among the following is :

(A) (B) (C) (D)

Carbanions
035. Which of the following is the least stable carbanion ?
(A) (B) (C) (D)
036. The most stable anion is :

(A) (B) (C) (D)

037. In which of the following pairs of carbanion the first one is more stable than second.
(A) , (B) ,

(C) , (D) ,

038. Arrange the following carbanions in decreasing order of stability :

I II III IV
(A) III > I > IV > I (B) III > II > I > IV (C) I > III > II > IV (D) III > I > II > IV
039. The most stable anion is :

(A) (B) (C) (D)

040. Arrange the following carbanions in increasing order of stability :

(A) III > IV > I > II (B) I > III > IV > II (C) I > II > III > IV (D) I > IV > III > II
Acidic Strength
041. Among the following compounds, the strongest acid is :
(A) HC  CH (B) C6H6 (C) C2H6 (D) CH3OH
042. Which of the following is not correct decreasing Ka order.
(A) CH4 > NH3 > H2O > HF (B) CH3–OH > CH3–NH2 > CH3–F > CH3–CH3
(C) HI > HBr > HCl > HF (D) PhOH > H2O > C2H5OH > CH3–CCH

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 General Organic Chemistry-II
043. Which of the following acid has the smallest dissociation constant ?
(A) (B) O2N–CH2 –CH2–COOH

(C) Cl–CH2 –CH2–COOH (D) NC–CH2–CH2 –COOH

044. Find the strongest acid among the following compounds is :
(A) HOOC–(CH2)2 –COOH (B) H3N –(CH2)2 –COOH
(C) F–(CH2 )2 –COOH (D) CH3–(CH2 )2 –COOH
045. Which of the following option shows the correct order of decreasing acidity :
(A) PhCO2 H > PhSO3 H > PhCH2 OH > PhOH
(B) PhSO3H > PhOH > PhCH2OH > PhCO2 H
(C) PhCO2H > PhOH > PhCH2OH > PhSO3 H
(D) PhSO3H > PhCO2H > PhOH > PhCH2OH

046. Arrange increasing order of acidic strength of following dibasic acids :

(I) Oxalic acid, (II) Succinic acid, (III) Malonic acid, (IV) Adipic acid
(A) III < II < I < IV (B) II < III > I > IV (C) I > III > II > IV (D) II > I > III < IV

Acidic strength of Phenol

047.

I II III
Arrange above phenol in increasing order of pKa value :
(A) I < II < III (B) III < I < II (C) III < II < I (D) I < III < II
048. Give the acidic strength order for given compounds :

I: II : III : IV :

(A) II > III > I > IV (B) II > IV > III > I (C) III > I > II > IV (D) IV > III > I > II
Acidic Strength of Aromatic carboxylic Acid
049. Order of Ka of following acids is :
O O O
C C – OH C – OH
OH

O2N CH3O
I II III

(A) I > II > III (B) II > I > III (C) I > III > II (D) III > I > II
050. Arrange the following compounds in increasing order of their acidic strength.
COOH COOH OH

CH3 Cl
II III IV
(A) IV < II < I < III (B) I < II < III < IV (C) IV < II < III < I (D) I < III < II < IV

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 General Organic Chemistry-II
051. Find the order of Ka of following compounds :
COOH COOH COOH COOH
NO2
(I) (II) (III) (IV) (V)
NO2
NO2
(A) I < II < III < IV < V (B) IV < I < III < II < V
(C) III < II < I < IV < V (D) II < I < III < IV < V
Basic Strength
052. The correct basic strength order of following anions is :

(A) > > > > >

(B) > > > > >

(C) > > > > >

(D) > > > > >

053. Which of the following shows the correct order of decreasing basicity in gas phase ?
(A) (CH3)3N > (CH3 )2NH > CH3NH2 > NH3
(B) (CH3)2NH > (CH3)3N > CH3 NH2 > NH3
(C) (CH3)2NH > CH3NH2 > (CH3 )3N > NH3
(D) (CH3)2NH > CH3 NH2 > NH3 > (CH3)3 N
054. Find the order of basic strength. (if R = Me) ?
(I) R4 N  OH¯ (II) R3N (III) R2NH (IV) RNH2
(A) I > III > IV > II (B) IV > III > I > II (C) II > IV > III > I (D) II > IV > I > III
055. Which of the following cannot be a base ?

(A) (B) CH3  C  NH2 (C) (D)

O
056. Select the basic strength order of following molecules ?

(I) Piperidine (II) Pyridine (III) Morpholine (IV) Pyrrole

(A) (IV) > (I) > (III) > (IV) (B) (III) > (I) > (IV) > (II)
(C) (II) > (I) > (III) > (IV) (D) (I) > (III) > (II) > (IV)
057. Arrange the following in increasing order of pKa value ?

(I) (II) (III)

(A) II < I < III (B) III < I < II (C) III < II < I (D) II < III < I

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 General Organic Chemistry-II
058. Select the decreasing order of relative basic strengths of following species :

(I) (II) (III) (IV)

(A) II > IV > I > III (B) III > I > IV > II (C) III > IV > I > II (D) II > I > IV > III
059. Select the basic strength order of following molecule :

(A) II > III > IV > I (B) II > IV > III > I (C) IV > II > III > I (D) IV > III > I > II

Feasible Reactions of Acids and Bases

060. Which of the following reactions is not possible?
 
OH O OH OH2

(A)  
+ H2O + H 3O (B) + H2O + OH

(C) Both (A) and (B) (D) None of these

061. 1 Mole of CH COONa

     
3
 


The products will be :

(A) + CH3COOH (B) + CH3COOH

(C) + CH3COOH (D) Reaction is not feasible

062. Which of the following reactions is not feasible ?

(A) + NaHCO3  + H2O + CO2

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 General Organic Chemistry-II

(B) + NaHCO3  + H2O + CO2

(C) + NaHCO3  + H2O + CO2

(D) +  +

063. Which of the following will accept H+ from NH4+ ion.

(A) (B) (C) (D) CH3 –CH2 –NH2

064. Product

(A) (B) (C) (D)

Tautomerism
065. Which of the following statements is true about tautomerism / tautomers?
(A) Tautomers can not be separated as they exist in dynamic equilibrium.
(B) Tautomers are not constitutional isomers
(C) Both isomers are present in equal proportion.
(D) Tautomerism can take place in presence or absence of a catalyst.
066. Keto-enol tautomerism is not observe in :
O O
(A) (B)
O O O
(C) (D)

067. The enolic form of acetone contains :

(A) 9  bonds, 1  bond and 2 lone pairs (B) 8  bond, 2  bond and 2 lone pairs
(C) 10  bond, 1  bond and 1 lone pair (D) 9  bond, 2  bond and 1 lone pair

068. Molecule can be enolised by which hydrogen ?

(A) y–H (B) z–H (C) both (D) None of these

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O
069. O Ph
Ph
I II
Which among these can exhibit tautomerism?
(A) I only (B) II only (C) both I and II (D) none of these
070. Which among the following compound will give maximum enol content in solution :
O O O O
(A) (B) CH3 – C – CH2 – C – CH3
O O
(C) CH 3 – C – CH 2 – CH 2 – CH 3 (D) CH 3 – C – CH 2 – COOC 2H 5
071. Arrange the following in decreasing order of percentage enol content.

(I) (II) (III) (IV)

(A) I > II > III > IV (B) II > I > III > IV (C) II > III > I > IV (D) III > II > IV > I

EXERCISE-2
072. The correct order of increasing basic nature for the bases NH3, CH3NH2 and (CH3)2NH is:
[AIEEE-2003]
(1) CH3NH2 < NH3 < (CH3)2NH (2) (CH3)2NH < NH3 < CH3NH2
(3) NH3 < CH3NH2 < (CH3)2NH (4) CH3NH2 < (CH3)2NH < NH3
073. Which of the following is the strongest base? [AIEEE-2004]

(1) (2) (3) (4)

074. Consider the acidity of the carboxylic acids: [AIEEE-2004]

(i) PhCOOH (ii) o-NO2 C6H4 COOH (iii) p-NO2C6H4COOH (iv) m-NO2C6H4COOH
(1) i > ii > iii > iv (2) ii > iii > iv > i (3) iii > ii > iv > i (4) ii > iv > iii > i
075. Among the following acid which has the lowest pKa value ? [AIEEE-2005]
(1) CH3 CH2COOH (2) (CH3 )2CH–COOH (3) HCOOH (4) CH3COOH
076. Amongst the following the most basic compound is [AIEEE-2005]
(1) p-Nitroaniline (2) Acetanilide (3) Aniline (4) Benzylamine
077. The increasing order of stability of the following free radicals is : [AIEEE-2006]
(1) (CH3)2 H < (CH3)3 < (C6H5)2 H < (C6H5)3
(2) (C6H5)2 < (C6H5)2 H < (CH3)3 < (CH3)2 H
(3) (C6H5)2 H < (C6H5)3 H < (CH3)3 < (CH3)2 H
(4) (CH3)2 H < (CH3)3 < (C6H5)3 < (C6H5)2 H
078. The correct order of increasing acid strength of the compounds. [AIEEE-2006]
Me
(a) CH 3CO2 H (b) MeOCH2CO2 H (c) CF3 CO2 H (d) CO2H is
Me
(1) b < d < a < c (2) d < a < c < b (3) d < a < b < c (4) a < d < c < b

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079. Which one of the following is the strongest base in aqueous solution? [AIEEE-2007]
(1) Dimethylamine (2) Methylamine (3) Trimethylamine (4) Aniline

080. Arrange the carbanions, (CH3)3C, CCl3, (CH3)2 CH, C6H5 CH2 in order of their decreasing stability :
[AIEEE-2009]
(1) (CH3)2 CH > CCl3 > C6H5 CH2 > (CH3)3 C (2) CCl3 > C6H5 CH2 > (CH3)2 CH > (CH3)3 C
(3) (CH3)3 C > (CH3)2 CH > C6H5 CH2 > CCl3 (4) C6H5 CH2 > CCl3 > (CH3)3 C > (CH3)2 CH
081. The correct order of increasing basicity of the given conjugate bases (R = CH3) is :
[AIEEE-2010]
(1) RCO O  HC  C  R  N H2 (2) R  HC  C  RCO O  N H2

(3) RCO O  N H2  HC  C  R (4) RCO O  HC  C  N H2  R

082. The strongest acid amongst the following compounds is : [AIEEE-2011]

(1) CH3COOH (2) HCOOH
(3) CH3CH2 CH(Cl)CO2 H (4) ClCH2 CH2CH2COOH
083. Identify the compound that exhibits tautomerism. [AIEEE-2011]
(1) 2-Butene (2) Lactic acid (3) 2-Pentanone (4) Phenol
084. The correct order of acid strength of the following compounds: [AIEEE-2011]
(A) Phenol (B) p-Cresol (C) m-Nitrophenol (D) p-Nitrophenol
is :
(1) D > C > A > B (2) B > D > A > C (3) A > B > D > C (4) C > B > A > D
085. Arrange the following compounds in order of decreasing acidity : [JEE(Main)-2013]

; ; ;

(1) II > IV > I > III (2) I > II > III > IV (3) III > I > II > IV (4) IV > III > I > II
086. The order of stability of the following carbocations : [JEE(Main)-2013]

; ; is :

(1) III > II > I (2) II > III > I (3) I > II > III (4) III > I > II
087. Considering the basic strength of amines in aqueous solution, which one has the smallest pKb value ?
(1) (CH3)2NH (2) CH3NH2 (3) (CH3)3N (4) C6H5NH2
088. The increasing order of basicity of following compounds is
(a) NH2 (b) NH

NH2
(c) (d) NHCH3
NH
(1) a < b < c < d (2) b < a < c < d (3) b < a < d < c (4) d < b < a < c

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089. Which of the following would produce effervesence with sodium bicarbonate ?

(1) (2) (3) (4) All of these

090. Select correct statement from the following :

(1) is more basic than (2) is more acidic than

(3) HCCH is more acidic than NH3 (4) is more stable than

091. Arrange the following compounds in order of decreasing acidity.

(i) (ii) (iii) (iv)

(1) (i) > (ii) > (iii) > (iv) (2) (iii) > (i) > (ii) > (iv)
(3) (iv) > (iii) > (i) > (ii) (4) (ii) > (iv) > (i) > (iii)
092. The order of decreasing basicity in the four halide ions is :
(1) I– > Br– > CI– > F– (2) CI– > Br– > I– > F– (3) F– > Cl– > Br– > I– (4) CI– > F– > Br– > I–
093. Correct order of acidic strength :

(1) (iv) > (i) > (ii) > (iii) (2) (iv) > (iii) > (ii) > (i)
(3) (iv) > (ii) > (iii) > (i) (4) (ii) > (iv) > (i) > (iii)
094. The correct order of acidity for the following compound is
(1) Benzoic acid > phenol > p-nitrobenzoic acid > m-nitrobenzoic acid.
(2) phenol > p-nitrobenzoic acid > m-nitrobenzoic acid > benzoic acid.
(3) p-nitrobenzoic acid > m-nitrobenzoic acid > benzoic acid > phenol.
(4) m-nitrobenzoic acid > p-nitrobenzoic acid > benzoic acid > phenol.
095. Which of the following is the most stablized carbocation ?

(1) (2)

(3) (4)

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096. Which one among the following is the least basic :

(1) (2) (3) (4)

097. Which is most basic in aqueous solution ?
(1) CH3NH2 (2) (CH3)2NH (3) (CH3)3 N (4) Ph–NH2
098. Stability order of given anions is :

(1) I > III > II (2) I > II > III (3) III > II > I (4) III > I > II

099. Which is less basic than benzyl CH2 carbanion?

CH2 CH2

(1) (2) (3) (4)

NO2 OCH3
100. The correct order of decreasing acid strength of trichloroacetic acid (A), trifluoroacetic acid (B), acetic
acid (C) and formic acid (D) is :
(1) B > A > D > C (2) B > D > C > A (3) A > B > C > D (4) A > C > B > D
101. Base strength is in the order of
–
(i) CH3CH2 (ii) and (iii)
(1) (ii) > (i) > (iii) (2) (iii) > (iii) > (i) (3) (i) > (iii) > (ii) (4) (i) > (ii) > (iii)
102. The order of stability of following carbocation :


; ;

(1) II > III > I (2) I > II > III (3) III > I > II (4) III > II > I
103. The most stable carbocation is :

(1) (2) (3) (4)

104. Pyridine is less basic than triethylamine because :

(1) Pyridine has aromatic character (2) Nitrogen in pyridine is sp2 hybridised
(3) Pyridine is a cyclic system (4) In pyridine, lone pair of nitrogen is delocalised
105. Which of the following phenol has lowest pKa ?

(1) (2) (3) (4)

106. Which is most basic among the followings ?

(1) Ph-NH2 (2) NH3 (3) CH3–NH2 (4) C2H5–CN

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107. Assertion : The pKa of acetic acid is lower than that of phenol.
Reason : Phenoxide ion is more resonance stabilised.
(1) If both assertion and reason are true and reason is a correct explanation of assertion.
(2) If both assertion and reason are true but reason is not a correct explanation of assertion.
(3) If assertion is true but reason is false.
(4) If assertion and reason both are false.
108. The order of stability of the following tautomeric compounds is :
OH O O O OH O
| || || || | ||
CH2 = C – CH2 – C – CH3 CH3 – C – CH2
– C –CH3 CH3 – C –
– CH – C – CH3

I II III
(1) III > II > I (2) II > I > III (3) II > III > I (4) I > II > III
109. The feasible reaction is :
(1) CH3COOH + NaCl  (2) C6H5COOH + KBr 

(3) + KHSO4  (4) + 

110. In which of following carbocation rearrangement take place with change carbon skeleton :

(1) (2) (3) (4)

111. Observe the following reaction sequence.

H–CCNa + CH3OH

HCCH + CH3ONa

CH3OH + CH3COONa

CH3SO3Na + CH3COOH
Which is correct acidic strength order :
(1) HC  CH > CH3COOH > CH3SO3H (2) CH3SO3H > CH3COOH > HC  CH
(3) CH3SO3H > HC  CH > CH3COOH (4) CH3COOH > CH3SO3H > HC  CH
112. Identify the most stable carbocation among the following :

(1) (2) (3) (4)

113. Select the most basic compound.

(1) (2) (3) (4)

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114. Among the following compounds having highest enol content.
(1) CH3COOCH3 (2) CH3COCH3 (3) (4)

115. Which is more basic than hydroxide (OH–) ion ?

(1) CH3–NH2 (2) CH3 –CH2–O– (3) F– (4) Ph–NH2
116. Give the stability order of following radicals :

(I) (II) (III) (IV)

(1) III > IV > II > I (2) IV > III > II > I (3) I > II > III > IV (4) IV > II > III > I
117. The most stable carbanion among the following is

(1) (2) (3) (4)

118. Which of the following is the most stable carbocation

(1) (2) (3) (4)

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ANSWER KEY
EXERCISE-1
PART- 1
001. sp2
002. (P) I > III > IV > II (Q) IV > III > II > I (R) III > II > IV > I
003. (II) is more stable carbocation due to extented conjugation

004. (P) = ; (Q) =

005. Stability order : I < II < III < IV

IV is most stable being 3º and delocalised but III is 2º and delocalised.
006. III > II > I > IV
007. (a) 1 > 2 > 3 (b) 1 > 2 > 3
008. (a) 2 > 1 > 3 > 4 ; (b) 1 > 2 > 3 ; (c) 1 > 2
009. I - a, II - b, III - c, (acidic strength  stability of conjugate base)
010. III > I > II (acidic strength  stability of conjugate base) In III conjugate base is highly stabilised by
intra molecular H-bonding.

011. etc.

Its conjugate base (anion) is resonance stabilised like anion of carboxylic acid.
012. II > III > I > IV
013. (a) PhNH 2 > Ph2 NH > Ph3 N

(b) > >



N
–

N
:NH2
–

H
(c) Ph–CH2 –NH–CH 3 > >

014. 2
015. I is less basic than II because, in compound (I) the lone pair of electrons is involved in resonance but not in II.
016. (a) Not feasible (b) Feasible (c) Not feasible (d) Not feasible
017. (c) Strong base accept H+ ions so this reaction is feasible.
018. (i, iii, iv, v, vi, vii)
019. B, C, E, G, H
OH
|
020. (P) CH3  C  CH2 (Q) CH2 = CH – NH2 (R) (S)

021. In Monocarbonyl Keto form is more stable due to greater strength of the carbon-oxygen double bond as
compared to the carbon carbon double bond.

PART- 2
022. (C) 023. (B) 024. (B) 025. (C) 026. (D) 027. (D) 028. (B)
029. (A) 030. (D) 031. (A) 032. (C) 033. (B) 034. (C) 035. (C)
036. (A) 037. (B) 038. (D) 039. (B) 040. (D) 041. (D) 042. (A)
043. (C) 044. (B) 045. (D) 046. (C) 047. (C) 048. (C) 049. (C)

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 General Organic Chemistry-II
050. (A) 051. (D) 052. (C) 053. (A) 054. (A) 055. (D) 056. (D)
057. (A) 058. (D) 059. (D) 060. (A) 061. (B) 062. (C) 063. (D)
064. (C) 065. (D) 066. (A) 067. (A) 068. (B) 069. (D) 070. (A)
071. (A)

EXERCISE-2
072. (3) 073. (4) 074. (2) 075. (3) 076. (4) 077. (1) 078. (3)
079. (1) 080. (2) 081. (4) 082. (3) 083. (3) 084. (1) 085. (3)
086. (4) 087. (1) 088. (3) 089. (4) 090. (3) 091. (2) 092. (3)
093. (3) 094. (3) 095. (3) 096. (4) 097. (2) 098. (1) 099. (2)
100. (1) 101. (4) 102. (3) 103. (4) 104. (2) 105. (4) 106. (3)
107. (3) 108. (1) 109. (4) 110. (1) 111. (2) 112. (3) 113. (3)
114. (3) 115. (2) 116. (2) 117. (4) 118. (3)

*
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