LECTURE NOTES

ORGANIC CHEMISTRY
TOPIC : IUPAC NOMENCLATURE
AND STRUCTURAL ISOMERISM

Refer sheet : IUPAC NOMENCLATURE AND STRUCTURAL ISOMERISM

JEE Syllabus

Concepts:
Hybridisation of carbon; Sigma and pi-bonds; Shapes of molecules; IUPAC nomenclature of
simple organic compounds (only hydrocarbons, mono-functional and bi-functional compounds);
Structural isomerism.

RESONANCE

page # 1

1. IUPAC NOMENCLATURE
1.1

INTRODUCTION TO ORGANIC COMPOUNDS:Organic compounds are compounds of carbon and hydrogen and the following elements may also be
present: (Halogens, N, S, P, O). There are large no. of organic compounds available and large no of organic
compounds are synthesized every year.The most important reason for large no of organic compounds is the
property of catenation (selflinkage) in carbon.
Element
C
Si
Ge

Bond Energy
CC (strongest bond)
SiSi
GeGe

Decreasing order

Sn
SnSn
Pb
PbPb
Bond energy depends on
(i) Size of atom (Inversely proportional)
(ii) E.N difference along period (Directly)
(iii) Bond order (no. of covalet bonds b/w two atoms) (Directly)

Size : CC>SiSi
E.N Diff : C H < N H < O H < H F
Bond order : C C < C = C < C C

Catenation in carbon: The element carbon has strongest tendency to show catenation or selflinkage due to
(a) its tetravalency so that it can form bonds with many elements as well as carbon itself.
(b) It can form multiple bonds (C = C, C C). Due to its small size, there is efficient colateral overlapping
b/w two Porbitals.

Does not exist

(c) High bond energy of C C bond so that it can form strong bonds in long chains and in cylic compounds.

Hybridised of carbon :
It is of three types and these are sp3, sp2 and sp. These hybridised state in any given structure can be
known by counting bond around the carbon atoms as bond are formed by hybrid orbitals. Thus if there
are four bonds, three bonds and two bonds around the carbon atom then C atom will be in sp3,
sp2 or sp hybridised state respectively.

RESONANCE

page # 2

Few informations regarding these orbitals are summarised as

CC bond
length (A)
CH bond
length (A)

1.54

1.34

1.20

1.10

1.07

1.06

CC bond
energy
(Kcal/mole)

8085

142

200

CH bond
energy
(Kcal/mole)

98.6

106

121

Since the extent of overlap in sideways overlap is low, a carboncarbon bond is always weaker than
a carboncarbon bond. A carboncarbon double bond is, however, stronger than a carboncarbon single
bond since it consists bond and a weak bond. In a similar way, a carboncarbon triple bond is still
stronger than carboncarbon double bond.

Usually following questions are asked for a given organic structure

(i) How many & bonds are present.
(ii) How many type of hybridised carbon atoms are present.
(iii) Which orbitals are used in marked CC bonds.
(iv) Total number of unhybrid orbitals over the C-atom.
Ex.

* CH
* H C
Give the answer of all the four parts for CH2= C

(i) 7 and 3
(ii) sp2 and sp
(iii) for
(sp2 sp)
2
(iv) 6 (as sp hybridised C-atom has one unhybrid orbital and sp hybridised C-atom has two unhybrid
orbitals)
Que.

1.2

Evaluate yourself by answering above four questions for the following structures :

(a)

(b)

(c)

(d)

(e)

(f)

IMPORTANT TERMS:
Saturated compounds:
When all the valencies of an element are satisfied by covalent bonds.
Unsaturated compound:
When a compound contains one or more bonds (C = C, C = N, N = N, C = O or C C, C N, N N)
Molecular Formula (M.F.) :
The molecular formula of a compound indicates the actual number of atoms of each element present in one
molecule.

RESONANCE

page # 3

Structural Formula (S.F.):

It indicates the linkage due to covalent bond between different atoms in a molecule.
(i) Expanded Structural Formula (E.S.F.)
(ii) Condensed Structural Formula (C.S.F.)
(iii) Bondline Structural Formula (B.S.F.)
Ex.

M.F.

C3H8

Ex.
H

Ex.

M.F.

C4H10

E.S.F. H C C C H
H H H

E.S.F. H C C C C H
H H H H

C.S.F. CH3 CH2 CH3

C.S.F. CH3 CH2 CH2 CH3

B.S.F.

B.S.F.

or

B.S.F.

C.S.F.
M.F.

Ex.
CH 3 CH CH 2 CH 3

B.S.F.

M.F.

CH3

C6H12

C5H12

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.

Degree of carbon :
It is defined as the number of carbon atoms attached to a carbon atom.
H
|

Primary (1) carbon

|
H

Secondary (2) carbon :

1

C
|
Tertiary (3) carbon

C
|
Quaternary (4) carbon :

|
3
H

Superprimary :

|
C

(1)

10 5 carbon

Ex.

CH3 CH3
1
2 | 3|
4
5
CH3 C CH CH2 CH3
|
CH3

20 1 carbon
30 1 carbon
40 1 carbon

Ex.

RESONANCE

page # 4

*Degree of hydrogen is same as the degree of carbon to which it is attached.

Type of C C bonds & type of replaceable H-atoms in saturated hydrocarbon.
Note : Total no. of monosubstituted product does not depend upon type of C-atoms but depends upon type
of replaceable H-atoms.
1
1

Ex.

C H3 4

C H3
| 2
3
1
C C H 2 C H C H3
|
|
C H3
C H3
1

Que.

Mark the type of C-atoms present in the following structure :

(a) (CH3)3CC(CH3)3

(b)

(c) (C2H5)4C (d)

(e)

Ex.

Write the structure of alkane (MM = 72) having 1, 2 and 3 carbon atoms.
CnH2n+2 = 72
CnH2n = 72 2 = 70
12n + 2n = 14n = 70
n = 70/14 = 5
Thus molecular formula is C5H12 and structure will be like

1.3

CLASSIFICATION OF ORGANIC COMPOUNDS :

Ex.

Compounds

(f)

Classification
Unsaturated

Heterocyclic , saturated
Unsaturated

Saturated

Saturated, Alicylic

RESONANCE

page # 5

Aromatic Compound [The Huckel (4n + 2) rule] :

The following three rules are useful in predicting whether a particular compound is aromatic or nonaromatic.
1. Aromatic compounds are cyclic and planar.
2. Each atom in an aromatic ring is sp2 or sp hybridised and has close conjugation.
3. 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,..............

H
Cation

2 e

Cyclopropenium ion

Cation

2 e

Cyclobutenium dication

6 e

Cyclopentadienyl anion

6 e

Cycloheptatrienyl cation (Tropylium cation)

Non-Benzenoid:

+
H

H
H

Anion

..
H
H

+
+

H
H

Benzenoid Aromatic Compounds:

All organic compounds which contain atleast one benzene ring are known as benzenoid aromatic compounds.

Spiro Compounds: One atom shared by two rings

Fused Bicyclic Compounds: Two adjacent atoms shared by two rings

Bridged Bicyclic Compounds:More than two atoms shared by two rings

Isolated Bicyclic Compounds:Two rings directly attached by a sigma bond

1.4

IUPAC NOMENCLATURE OF ORGANIC COMPOUNDS:

General Scheme of Naming:Secondary prefix + Primary prefix + Word root + Primary suffix + Secondary suffix
(1) Word Root : It indicates the no. of carbon atoms present in the main chain (parent chain). It is
represented as Alk.

RESONANCE

page # 6

(2) Primary Suffix:- It indicates the saturation or unsaturation existing in the main chain.
ane single bond (saturated)
ene one = bond
diene If two double bonds
Polyene if plenty of double bond are present.
yne one bond
diyne two bond
(3) Secondary Suffix:- It is used for the principal functional group.
(4) Primary Prefix : Cyclo word is used for alicyclic compounds.
(5) Secondary Prefix : Normal substitutents and junior functional groups are treated as a substituent,
then their name is treated as secondary prefix.
The following substituent groups are always cited in the prefix.
(i) R
Alkyl
(ii) OR
Alkoxy
(iii) X
halo (fluoro, chloro, bromo, iodo)
(iv) NO2
Nitro
(v) N = O
Nitroso
(vi) Junior functional groups.
The prefixes are always written in alphabetical order
The position of substituent group in the main carbon chain is mentioned by writing the number just
before the name of substituent by writing a hyphen ().

1.5

NAMING OF SATURATED HYDROCARBONS

Rules :(Branched and substituted Alkanes)
Selection of parent chain :
(a) Chain with maximum number of C atoms (longest chain).

(b) If number of carbon atoms are same in more than one longest chain then more substituted longest chain
will be the parent chain.

(c) If number of side chain are also same then that will be parent chain having its substituent at lower number.

CCCCCCCC
CCC
C

Numbering :
(a) Numbering is done from that side of the parent chain having it substituent at lower number
(lowest set of locant)

RESONANCE

page # 7

(b) If position of substituent are same from both the end of the parent chain, then numbering is done
from alphbetical order.

* If alphabets are also same then numbering is done from that side of the parent chain having its
substituent of substituent at lower number.

Methylpropane

CH3 CH3
CH3 CH CH CH3

2, 3-Dimethyl butane

CH3
CH3 CH CH3

Ex.

CH3
CH3 C CH3
CH3

Dimethyl propane

2-Methylbutane

C
CCCCC

3-Ethyl-2-methyl hexane

CCC

4, 4-Diethyl heptane

C
CCC
CCCCC
CCC
C

4, 4-Diethyl-2, 5-Dimethyl heptane

CCCCC

3-Ethyl hexane

CCC
CCCCC
CCC

CCC

CCCCC
Cl Br

3-Bromo-2-chloropentane

CCCCC
Br
Cl

2-Bromo-4-chloro pentane

1-Chlorobutane

CH3 CH2 CH2 CH2Cl

4-Bromo-2, 2-dichloro pentane

CCCCCC

5-Bromo-2, 3-dichloro hexane

Cl
CCCCC
Br
Cl

Cl Cl

Br

RESONANCE

page # 8

Rules for writing Radicals :

Alkane

Alkyl

Alkene

Alkenyl

Alkyne

Alkynyl

Benzene

Phenyl
H
CnH2n + 2 CnH2n + 1

Alkyl Radical

H
CnH2n CnH2n 1

Alkenyl Radical

H
CnH2n 2 CnH2n 3

Alkynyl Radical

Phenyl

R (structural formula)
CH3

Name
Methyl

CH3 CH2

Ethyl

CH3
|
(b) CH3 C CH3
|
H

CH3
3
2|
1
H
CH3 C CH2 Isobutyl
|
H

H
CH2 = CH2

CH3
|
CH3 C CH3 Tert butyl
(Tertiary butyl)
|

CH2 = CH
ethenyl

CH3 CH = CH2

Prop 1 enyl
Methylethenyl

Prop 2 enyl
CH3 C CH

CH3 C C
Prop-1-ynyl

CH3 C CH

CH2 C CH
Prop-2-ynyl

RESONANCE

page # 9

Benzene Radical :

1.

Phenyl

2.

Benzyl

3.

Benzal

4.

Benzo

5.

Tolyl

CH3
(o, m, p)

Methylene

7.

Alkylidene

8.

- naphthyl

9.

-naphthyl

Systematic Names of Radicals :

Complex Radical :
Ex

5 ( 1,2 Dimethylpropyl) nonane

5 (1,1 Dimethylpropyl) nonane

RESONANCE

page # 10

5 (1 Ethylpropyl) nonane

5 (Dimethylethyl) nonane

Numeral Prefixes :
(1) Following prefixes are considered for alphabetization :
(a) Iso

(b) neo

(c) Di, Tri, Tetra of complex radical are considered for alphabetization
(2) Following are not considered for alphabetization
(a) Di, Tri, Tetra for simple radicals.
(b) Sec, Tert are not considered for alphabetization
(c) Bis , Tris

Retained Names of Alkanes:

(1) Normal (n) : Radical or hydrocarbon which has straight chain and if it has free valency it must be present
at either of ends.
C C C C (n butane)

RESONANCE

page # 11

(2) Iso : Two methyl group at the end of linear chain (unbranched chain)
Isobutane or methyl propane

(ii)

C
C C CC

Isopentane or methylbutane

(iii)

C
C C CCC

Isohexane or 2-methylpentane

(i)

C
C C C

Conditions :-

There should be 4 to 6 carbon atoms only

There should not be any other alkyl group present in the chain.

Ans.

C
C CC CC
C
C
(3) Neo :

Iso-octane (commercial name) in petroleum industry

Q.

IUPAC name is 2, 2, 4-trimethylpentane

There should be 5 to 6 carbon atoms

2, 2-dimethyl
No other substituent.

Ex.

C
C CC
C

Neopentane

C
C C C C Neohexane
C
(4) Secondary : It is applicable only for radical.
Ex.1

(5) Tertiary :

First member

1.6

NAMING OF UNSATURATED COMPOUND (ALKENES AND ALKYNES) :

(A) General formula:- CnH2n and CnH2n 2 respectively
(B) Rules for selection of main chain: Longest carbon chain with a multiple bond.
Longest carbon chain with maximum number of multiple bonds.
If first and second factor are common then chain with lowest locant (multiple bond) is selected as main
chain.
Lowest locant Rule is followed till first point of difference. (Multiple bond prior to substituent).
Alphabetization.
(C) Rules for Numbering: Lowest locant Rule till first point of difference (irrespective of double bond or triple bond).
Then double bond is prefer over triple bond in numbering, naming and longest chain selection, If all the
other factors are common

RESONANCE

page # 12

CH3 CH2 CH = CH2

But-1-ene

CH3 CH = CH CH3

But-2-ene

CH3
CH3 CH CH2 CH = CH2

4-Methylpent-1-ene

Ex.

CH3
|
CH3 CH CH = CH CH3

4-Methylpent-2-ene

5, 5-Dichlorohex-1-ene

(a) C = C C = C

Buta-1,3-diene

(b) C C C C

Butadiyne

(c) C = C C C

Butenyne

Cl
5
4
3
2
1
CH3 C CH2 CH2 CH = CH2
Cl
6

CCCC=CC
1

Hex-4-en-1-yne

Ex.1

3-(2-Methylpropyl) hept-1-ene

Ex.2

4 -(1,1-Dimethylpropyl)-4-ethenylhepta-1,5-diene

Ex.3

3-Ethynylhexa-1, 5-diene

Ex.4

4-Ethenylhept-2-en-5-yne

Ex.5

4-(1, 2-Dimethylbutyl) hept-2-en-5-yne

Ex.6

2, 4-Dimethylpenta-1, 3-diene

Ex.6

2,3-Dimethylhex-1-en-4-yne

RESONANCE

page # 13

1.7

NAMING OF CYCLIC HYDROCARBON (ALICYCLIC COMPOUNDS) :

(A) Main chain selection:
(a) Multiple Bond > No. of carbon atoms > Maximum no. of substituents > Nearest locant > Alphabetization.
(b) If all factors are similar in cyclic and acyclic part, then Cyclic > Acyclic

(B) Numbering:
(a) Lowest Locant

(b) Alphabetization

(C) Naming:
Prefix cyclo is used just before the word root if it constitutes the main chain.
If cyclic part is the main chain then the prefix cyclo is not considered for alphabetical order..
If cyclic part constitutes the side-chain (substituent) then prefix cyclo is considered for alphabetization:-

Cyclopropane

Cyclobutane

Cyclopentane

Cyclohexane

Cycloheptane

Cyclooctane

Methylcyclopropane

Ethylcyclopropane

Propylcyclopropane

1-Cyclopropylbutane

Ex:-

Cl C C

2-Chloroethylcyclopropane

Cl
CCC

Cl
CCC

1-Chloro-3-cyclopropylpropane

Cl

CCC

1-Chloro-2-propylcyclopropane

2
3

Chloroethylcyclopropane

Cl

1-Chloro-1-cyclopropylpropane

Br

C C Cl

2-Bromo-1-chloro-3-fluoro-4-iodocyclohexane

I
Methylethylcyclopropane or isopropylcyclopropane

Cl

Br

2
5

1
6

1-Bromo-2-chloro-4-iodocyclohexane

Br

6
5

1
4

3-Chlorocyclohex-1-ene

Cl

RESONANCE

2
3

5-Bromo-3-chlorocyclohex-1-ene

Cl

page # 14

1.8

FUNCTIONAL GROUP TABLE (Seniority order):

Name

Class

Prefix

1.

R COOH

Alkanoic acid

oic acid (carboxylic acid)

Carboxy

2.

R SO3H

Alkane sulphonic acid

sulphonic acid

sulpho

3.

RCOCR
||
||
O
O

Alkanoic anhydride

anhydride
(carboxylic anhydride)

------------

4.

R COOR

Alkyl alkanoate

alkanoate (carboxylate)

Alkoxy carbonyl

5.

RCX
||
O

Alkanoyl halide

oyl halide (carbonyl halide)

halo carbonyl

R C NH2
||
O

Alkanamide

amide (carboxamide)

Carbamoyl

7.

RCN

Alkanenitrile

nitrile (carbonitrile)

cyano

8.

RCH
||
O

Alkanal

al (carbaldehyde)

formyl / Oxo

Alkanone

one

Oxo / Keto

10. R OH

Alkanol

ol

hydroxy

11. R SH

Alkanethiol

thiol

mercapto

12. R NH2

Alkanamine

amine

amino

6.

9.

1.9

Suffix

RCR
||
O

NAMING OF FUNCTIONAL GROUP CONTAINING COMPOUNDS :

Selection of Main Chain:
Senior F.G. > Max. no. of F.G. (Similar group) > Multiple bond > Max. no. of C atoms > Max. no. of locants
> lowest locant > alphabetization

Numbering (See F.G. + Sub.):

The carbon atom bearing functional group (or C atom of terminal functional group) is given lowest possible
number.
(i) Lowest locant (F.G. > M.B. > substituent > Alphab)

Naming:- General scheme :

The senior most functional group constitutes secondary suffix. Other junior F.G.s are written as prefix in
alphabetical order.
(A)

Rules for non chain terminating functional groups

(SO3H, >CO, OH ,SH, NH2 etc.)
Rule : (1) Parent chain selection :
Select the longest possible chain with maximum functional groups and maximum unsaturation.
4

CH3 CH2 CH CH2 CH3

|
1
CH2OH

RESONANCE

page # 15

Rule : (2) Numbering :

Numbering is done from that side of the chain which gives lowest locant to the principal functional group
followed by double and triple bonds.

3||

CH3 CH CH2 C CH2 CH3

|
CH3
(I) correct
(
(B)

C = O group gets lowest number 3)

4||

CH3 CH CH2 C CH2 CH3

|
CH3
(II) wrong
C = O group gets number 4 which is not lowest)

Rules for chain terminating functional groups :

( CHO, COOH, COOR, CONH2, COCl, C N etc.)
Rule : (1) When a chain terminating principal functional group is present in the carbon chain, it is always
given number 1 (one.)
3

CH3 CH2 CH CH2 CH CH3

|
|
7
1
2
6
CN CH2
CH2 CH3

Rule : (2) If a compound contains two or more like groups, the numerical prefixes di, tri, tetra etc. are
used
CH2 CH CH2
|
|
|
OH OH OH

Rule : (3) The name for benzene as substituent is phenyl. In case the phenyl ring is further substitued,
the carbon atom 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

(C) IUPAC name of polyfunctional compounds :

Rule : (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 groups are treated as substituents.
Rule : (2) Some functional group such as halo groups (fluoro, bromo, chloro, iodo), nitroso (NO) nitro (
NO2) and alkoxy (OR) are always treated as substituent groups.

1.9.1

Sulphonic acid
F.G.

Prefix

SO3H

Sulpho

RESONANCE

Suffix
Sulphonic acid

IUPAC name
Alkanes sulphonic acid

page # 16

(1) CH3 SO3H

Methanesulphonic acid

(2) C C C C C
SO3H

Pentane-2-sulphonic acid

Ex.

SO H
3
(3)

Cyclobutanesulphonic acid
1

(4) HOOC C C C C SO 3H

1.9.2

5-Sulphopentanoic acid

Ketone:Prefix

F.Group

Name

one

Alkanone

Keto or oxo

C=O

Example:-

Suffix

(1) CH3 C CH3

Propanone

O
(2)

Cyclohexanone

O
(3)

Cyclohexane-1, 3, 5-trione

CH2 C CH3

(4)

2-(2-Oxopropyl) cyclohexanone

COOH
(5)

3-(3-Oxobutyl) cyclohexane -1-carboxylic acid

CH2 CH2 C CH3

O

Alcohol:F.Group

Prefix

Suffix

Name

OH

Hydroxy

ol

Alkanol

2-Methyl Propanol

(2) CH 3 CH CH 2 CH 2 CH CH 3
CH 2 OH
CH 2 OH

2, 5-Dimethylhexane-1, 6-diol

(1) CH3 CH CH2 OH

CH3

Example:-

OH

(3)

OH
HO

HO

1.9.3

Cyclohexane-1, 2, 3, 4, 5, 6-hexaol

OH

OH

RESONANCE

page # 17

OH
Cl CH2 CH CH2

CH CH2 CH2 CH2 CH2 OH

(4)

CH3 CH2 CH2

OH
Cl
7-Chloro-5-(3-Chloro-2-hydroxy propyl) octane-1, 6-diol

O
OH

(5)

HO

2, 4, 6-trihydroxy cyclohexane-1, 3, 5-trione

OH

(Glycerol) Propane-1, 2, 3-triol

(1) CH3 SH

Methanethiol

(2)

Butane-2-thiol

(3)

Cyclobutanethiol

(4)

3-Mercaptobutan-2-ol

Thiol:-

Ex.

Amines:F.Group

Prefix

Suffix

Name

NH2

amino

amine

Alkan amine

(a) R NH2

1 = amine

Alkanamine

(b) R N R' 2 = amine

H

N Alkylalkan a min e
(R' )
(R )

(c) R N R' 3 = amine

N, N-Dialkylalkanamine

R'

(d) R N CH3

N-Ethyl-N-methylalkanamine

CH2 CH3

Ex:-

(1) CH3 NH2

Methanamine

(2) C C C C C
NH2

Pentan-3-amine

(3) C C C NH C C

N-Ethylpropan-1-amine

(4) C C C N C

N-Ethyl-N-methylpropan-1-amine

1.9.5

(6) CH2 CH CH2

OH OH OH

1.9.4

C
C

RESONANCE

page # 18

N-Ethylpropan-2-amine

(5) C C C

NH C C

OH
(6) CH2 CH = CH CH CH3
NH CH2 CH3

4-(N-Ethyl amino) pent-2-en-1-ol

1.9.6 ETHERS (R O R):F.Group

Prefix

Suffix

Name

R O R'

alkoxy

Alkoxy alkane

Alkoxy + Alkane

less no.
more no.
of ' C'
of ' C'

Methoxymethane

(2) C O C C

Methoxyethane

(3) C O C C C

1-Methoxypropane

(4) C C C
O
C

2-Methoxypropane

(i) Acyclic Ethers:(1) C O C

(5) C C C O C C

1-Isopropoxypropane
1-(Methylethoxy) propane

OCC

(6)

Ethoxycyclohexane

(7)

Cyclopropoxycyclohexane

Br
OCCC

(8)

3-Bromo-6-chloro-2-propoxycyclohexan-1-ol

OH

Cl
In cyclic system, numbering always starts from senior most functional group.

OH

Br

(9)

6-Bromo-5-methoxycyclohex-2-en-1-ol

O CH3

OH
1

Br

(10)
3

6-Bromo-5-ethoxycyclohex-3-en-1-ol

OCC

RESONANCE

page # 19

(ii) Cyclic Ether :

Hetero cyclic compounds
(1) C C
O

Oxirane or Epoxyethane

(2) C C C
O

1, 3-Epoxypropane

(3) C C C
O

1, 2-Epoxypropane

Cl
(4) C C C
O

1-Chloro-2, 3-Epoxypropane

1.9.7 Hetero atom containing compound :

If hetero atoms are count as a C atom in the parent chain then they are written as
(1) NH Aza
(2) O Oxa
(3) S Thia
(4) Se Selena
Example:-

(1) HOOC CH2 NH CH2 CH3

3-Aza pentanoic acid

H
N

(2)

Aza Cyclo pentane

H
N

(3)

3-Methyl aza cyclo hexane

CH3

Polyethers:(1) C C O C C O C C
1

1, 2-Diethoxyethane
1

10

11

10

11

(2) C C O C C O C C O C C
3, 6, 9-Trioxaundecane
12

13

14

15

(3) C O C C C O C C O C C C O C C
2, 6, 9, 13-Tetraoxapentadecane
2
1
12

3
4

O7

(4)
11

10

1, 4, 7, 10-Tetraoxacyclododecane

1.9.8

Carboxylic acid
F.G.

COOH

Prefix

Suffix

IUPAC name

Oic acid - 'C' of COOH considered

in the parent chain

Alkanoic acid

Carboxylic acid - 'C' of COOH is not

considerd in parent chain

Alkane carboxylic acid

Carboxy

Rule : If first alphabet of sec. suffix is begin from a, i, o, u, y then e of primary suffix will be dropped.

RESONANCE

page # 20

Ex.

(1) HCOOH

Methanoic Acid

(2) CH3 COOH

Ethanoic Acid

(3) C C COOH

Propanoic Acid

(4) C C C COOH

Butanoic Acid

(5) C C C C C C C C
1
COOH

2-propylhexanoic acid

COOH

(6)

Cyclopropanecarboxylic acid

CH2 COOH
(7)

Cyclopropylethanoic acid

COOH
3'
CCC
1'

2'

4-(2-carboxypropyl) cyclohexane-1-carboxylic acid

(8)

COOH
(9) HOOC COOH

Ethanedioic acid

(10) HOOC CH2 COOH

Propanedioic acid

(11) HOOC CH2 CH2 CH2 CH2 COOH

Hexanedioic acid

(12)

Cycloprop-1-ene-1, 2, 3-tricarboxylic acid

1.9.9 Acid halide:F.Group

Prefix

CX

Halo Carbonyl

Suffix

Name

Alkanoyl halide
Oyl-halide
or
or
Carbonylhalide Alkane carbonyl halide

O = C Cl
Example:-

(1)

Benzene carbonyl chloride

(2) CH3 C Cl

Ethanoyl chloride

(3)

Prop-2-enoyl bromide

(4)

6-Methyl hept-4-en-2-ynoyl chloride

RESONANCE

page # 21

Cl
C
(5) CH2 CH2 CH2 CH C Cl
COOH
O

5, 5-Dichlorocarbonylpentanoic acid

COOH

(6)

COOH

3-Chlorocarbonyl cyclopropane-1, 2-dicarboxlic acid

C Cl

O
O

(7)

C CH2 CH CH = CH CH 2 COCl

Cl

5-Methylhept-3-ene-1, 7-dioyl Chloride

CH 3

(8)

4-Bromocarbonyl-2-chlorocarbonyl-5-propanoyloxycycloexane-1-carboxylic acid

1.9.10 Nitrile:-

Example:-

(1) H CN

Methanenitrile

(2) CH3 CN

Ethanenitrile

(3) CH3 CH CH2 CN

CH3

3-Methyl butanenitrile

CN

(4)

Cyclopropane-1, 2, 3-tricarbonitrile

CN

CN

CN

(5)

Benzene carbonitrile

(7)

CH2 CH CH2
CN CN CN

Propane-1,2,3-tricarbonitrile

RESONANCE

3-Cyano propanoic acid

CH2 CH2 COOH

CN

(6)

page # 22

1.9.11 Isocyanide :-

F.Group

Prefix

Suffix

Name

NC

Isocyano

Isocyanide

Alkyl Isocyanide

Example:-

(1) CH3 N C

Methyl isocyanide

(2) CH3 CH2 N C

Ethyl isocyanide

NC

(3)

Phenyl isocyanide

1.9.12 Aldehyde:Prefix

F.Group

Name

Formyl or oxo al or carbaldehyde Alkanal or Alkane

Carbaldehyde

CH = O

Example:-

Suffix

(1) HCHO

Methanal

(2) CH3 CH2 CH = O

Propanal

(3) CCl3 CH2 CH2 CH2 CH = O

5, 5, 5-Trichloro pentanal

CH = O
(4)

Cyclohexane carbaldehyde

CH = O

(5)

Benzaldehyde/Benzene carbaldehyde

CH CH
Ph

CH = O

2-Chloromethyl-3, 3-diphenyl propanal

Ph
(6)

CH2Cl

CH = O
(7)

Benzene-1, 3-dicarbaldehyde

CH = O
(8) HOOC CH2 CH2 CH2 CH = O

(9) HOOC CH2 CH CH2 COOH

CH2 CH = O

5-Oxopentanoic acid
3-(2-Oxoethyl) pentane-1, 5-dioic acid

COOC2H5

(10)

Ethyl 3-(3-oxopropyl) cyclohexane-1- carboxylate

CH2 CH2 CH = O

RESONANCE

page # 23

3-(N-Phenyl amino) pentanal

(11) OHC CH2 CH CH2 CH3

NH Ph

(Glyceraldehyde) 2, 3-Dihydroxy propanal

(12) CHO
CH OH
CH2 OH
(13) OHC CH2 C CH3

3-Oxobutanal

1.9.13 Anhydride

(a) R C O H + H O C R

Heat
H2O

R C O C R
O

Alkanoic anhydride
(b) Mixed Anhydride (according to alphabet)
CH3 COOH +
Ethanoic
acid

CH3 CH2 COOH

Pr opanoic
Acid

CH3 C O C C2H5
O

Ethanoic propanoic anhydride

Ex.

(1)

H C O C H
O

(2)

C
C
CCCOCCC
O

Methanoic Anhydride
(unstable )

2-Methylpropanoic anhydride

(3)

Butanedioic anhydride

(4) C C C C O C C C C
||
||
O
O

Butanoic anhydride

O
||
C
O

(5)

Cyclohexane-1, 2-dicarboxylic anhydride

C
||
O

(6)

COC
O

RESONANCE

Cyclopropane carboxylic anhydride

O
page # 24

(7)

Benzene dicarboxylic anhydride (Phthalic anhydride)

1.9.14 Ester :
F.group

Prefix

Suffix

Name

C OR

Alkoxy Carbonyl

Oate

Alkyl....alkanoate

or
(Ester)

or

Alkanoyloxy

or

carboxylate

Alkyl.....Alkanecarboxylate

H2 O R C O R'

R C O H + H O R'
O
O

Example:-

(1) H C O CH3

Methyl methanoate

(2) C C C O C C C

Propyl propanoate

(3) C C O C C C C

Ethyl butanoate

C
(4) C C C O C H

Isobutyl methanoate

O
3

(5) C O C C C COOH

3-(Methoxycarbonyl)propanoic acid

O
(6) C C O C C COOH

3-(Ethanoyloxy)propanoic acid

(7)

2-(Methoxycarbonyl)-4-(Propanoyloxy) cyclohexan-1-carboxylic acid

O

(8)

Cyclopropyl benzene carboxylate

O

(9)

O C CH2 CH3

Methyl-3-propanoyloxy cyclohexane carboxylate

O=C
OCH3

RESONANCE

page # 25

1.9.15 Amide:F.Group

Prefix

Suffix

Name

C NH2

Carbamoyl

amide
or
Carboxamide

Alkanamide
or
Alkane Carboxamide

Example:-

(1) H C NH2

Methanamide (Formamide)

(2) CH3 C NH2

Ethanamide (Acetamide)

(3) CH3 C NH CH3

N-methylethanamide

(4) CH3 C N C C C

N-butyl-N-propylethanamide

C
C
C
C

O = C NH2
(5)

Benzene carboxamide

O = C NH2

(6)

Benzene-1, 3-dicarboxamide

C NH2
O

COOH
(7)

3-Carbamoyl cyclohexane-1- carboxylic acid

C NH2

O
C NH CH3
(8) CH2

N, N-Dimethyl propane-1, 3-diamide

C NH CH3
O

AROMATIC COMPOUNDS:

CH3
(1)

Methylbenzene (Toluene)

CH3

1.10

CH3

(2)

RESONANCE

(Ortho) 1, 2-Dimethylbenzene (Ortho-xylene)

page # 26

CH3
(3)

(Meta) 1, 3-Dimethylbenzene (Meta-xylene)

CH3

CH3

(4)

(Para) 1, 4-Dimethylbenzene (Para-xylene)

CH3

Q.

Write structures of the following

CC
(i) Metadiethylbenzene

CC

CC
(ii) 1-ethyl-4-isopropylbenzene

CCC
(iii) Orthodiethenylbenzene

C=C
C=C

Trialkyl Substituted Benzene:

If all the three substituents are similar, then only 3 trisubstituted benzene derivative are possible.

C
1, 2, 4-Trimethyl benzene
(Unsymmetrical Trimethyl benzene)

C
1, 2, 3-Trimethyl benzene
(Vicinal Trimethyl benzene)

C
C
1, 3, 5-Trimethyl benzene
(Symmetrical Trimethyl benzene)

Examples :
Isopropylbenzene (Cumene)

1.

CC
C

2.

1-Chloro-4-methyl-2-nitrobenzene

NO2

Cl
C=C

3.

Phenylethene (Double bond > Phenyl) (Common name : Styrene)

CC=C

4.

3-Phenylprop-1-ene (Allylbenzene)

CH = CH CH3

5.

1-Phenylprop-1-ene

RESONANCE

page # 27

COOH

6.

Benzene carboxylic acid (Benzoic acid)

COC

7.

Benzene carboxylic anhydride (Benzoic anhydride)

SO3H

8.

Benzene sulphonic acid

C O C2H5

9.

Ethyl benzene carboxylate (Ethyl Benzoate)

O C CH3

10.

Phenyl ethanoate

C Cl

11.

Benzene carbonyl chloride ( Benzoyl chloride)

NH C CH3

12.

N-Phenylethanamide

C NH CH3

13.

N-Methylbenzene carboxamide

CN

14.

Benzene carbonitrile (Benzonitrile popular)

CH = O

15.

Benzene carbaldehyde (Benzaldehyde popular)

O

16.

Diphenyl ketone (Benzophenone)

17.

CH3

Methyl phenyl ketone (Acetophenone)

OH

18.

Phenol

OH

19.

CH3

RESONANCE

Methylphenol [o-Cresol, m-cresol, p-cresol]

page # 28

OH
OH

20.

o-Hydroxyphenol (Catechol)

OH
m-Hydroxyphenol (Resorcinol)

21.

OH

OH

22.

p-Hydroxyphenol (Quinol)(Hydroquinone)

OH

NH2

23.

Benzenamine (Aniline)

SH

24.

Benzenethiol

O
O C CH3
O
25.

1.11

2-Ethanoyloxy (Acetoxy) benzene -1-carboxylic acid (Aspirin)

COH

Calculation of Degree of Unsaturation (DU):-

(a) It is the hydrogen deficiency index (HDI) or Double Bond Equivalence (DBE)

2H
(b) H3 C H2C CH3
(DU O)

2H
CH3 C CH or CH2 = C = CH2 or

That means Deficieny of 2H is equivalent to 1 DU

(c)

(i) 1DU = Presence of 1 Double Bond or Presence of 1 Ring closure

(ii) 2DU = Presence of 2 Double bond or 1 Triple bond or two ring closure or 1 double bond + 1 ring.

(d)

G.F.

D.U.

(i) CxHy

y
(x + 1)
2

(ii) CxHyOz

yo

(x + 1)
2

(iii) CxHyXs

ys

(x + 1)
2

(iv) CxHyNw

yw

(x + 1)
2

(v) CxHyOzXsNw

ys w

(x + 1)
2

RESONANCE

page # 29

Ex

Calculate DU of following compounds

(a) C6H6O

DU = 4

(b) C6H5Cl

DU = 4

(c) C6Br6

DU = 4

(d) C5H11OCl

DU = 0

(e) C9H12N2

DU = 5

(f) C6N6

DU = 10

(g) C10H8SO5 N4Cl2

e.g.
M.F.

DU = 8
DU

S.F.

H
1.

C4H6

CC=C=C

H
H

H H
CCCC
CCCC
C=CC=C

CH2
C

2.

C2H2Cl2

=1

Total isomers = 3

3. C7H6O (Aromatic)

=5

4. C7H8 (Aromatic)

=4

Note : In case of the aromatic Compounds minimum DU = 4. That means at least 1 Benzene ring is
present

RESONANCE

page # 30

2. ISOMERISM
Isomers:
Compounds with same general formula or molecular formula but different physical and chemical property.
Ex:-

CH3 CH2 OH and CH3 O CH3

Ex:-

CH3COOH and HCOOCH3

Difference between isomers and homologs:-

Structural isomers:
When two or more number of organic compounds have same molecular formula but different structural
formula these are called structural isomers.Structural isomers are also known as Skeletal isomers,
Linkage isomers & Constitutional isomers.

Stereo isomers:
When two or more compounds have same Molecular Formual (M.F.) and same Structural Formula (S.F.) but
have different stereochemical formula (S.C.F.), these are called stereoisomers.

RESONANCE

page # 31

2.1 Chain isomers :

They have different size of main carbon chain and / or side alkyl chain
(i) The two chain isomers should have same nature of F.G./multiple bonds/substituents (except R group)
(ii) The position of F.G./M.B./substituent (locants) is not. considered here.
Ex:-

Alkanes:(a) C1 C3
(b) C4H10

chain isomers not possible

H3C CH2 CH2 CH3 and CH3

(c) C5H12

CH3 CH2 CH2 CH2 CH3 , CH3 CH2

(d) C6H14

(i) CH3 CH2 CH2 CH2 CH2 CH3, (ii) CH3 CH CH2
(iii) CH3 CH2

CH3

CH2 CH3, (iv) CH3

(v) CH3 CH2

CH3 ,

CH3

CH3
CH3,

CH3,

CH3

(i) and (ii) Chain isomers

(i) and (iii) Chain isomers
(i), (iv) Chain isomers
(i), (v) Chain isomers
(ii), (v) Chain isomers
(ii), (iii) Position isomers
(iv), (v) Position isomers

Ex.

and

shows which types of isomerism ?

Ans.

Chain Isomers

Q.

Write chain isomers of N-alkanamine (1) containing 4 carbon atoms ?

Ans.

C C C C NH2,

2.2

Positional isomers:

C
C C C NH2

They have different position of locants Functional group (F.G.) or Multiple Bond (M.B.) or substituents in
the same skeleton of C-atoms.
Nature of F.G. or M.B. should not change.
The skeleton of C-atom should not change.
(1) C C C C C ,

CC C CC

(2) C = C C C ,

CC=CC

(3) C C C C C ,

CCCCC

(4) C C C C ,
OH

C C C C OH

Ex.

RESONANCE

page # 32

Write all Positional isomers of Dichlorobenzene ?

Cl

Cl

Cl

Q.

Cl

Q.

,
Cl

Cl Cl

Ans.

,
Cl

Write all Positional isomers of Dichlorocyclobutane ?

Cl Cl
,

Cl

Ans.

Cl Cl

Cl

Write all Positional isomers of Dichlorocyclopentane ?

Cl

Cl Cl

Cl

Q.

Cl

Write all Positional isomers of Dichlorocyclopropane ?

Cl

Q.

Ans.

Cl

Ans.

Cl

(iii) C C C C C C

CC

(ii) C C C C C C,

(i) C C C C C C

Ex.

(i), (ii) Chain

(ii), (iii) Position
(i), (iii) Chain
C6H12 (Cycloalkanes):-

Ex.

(2)

(3)

(1)

(4)

(10)

Ans.

(3) and (4) Positional isomer

(3) and (6) Positional isomer
(4) and (6) Positional isomer
(5) and (10) Positional isomer
(All are chain isomers of 1)
Remaining are chain isomers

2.3

Functional isomers:

(6)

CC

(9)

CCC

(5)

C
CC

(7)

(11)

(8)

CC

They have different nature of functional group (F.G.). The chain and positional isomerism is ignored (not
considered).
Compound
Functional isomer
CCCC
CCC=C

RESONANCE

Nil
(Ring-chain isomers are Functional isomers)

page # 33

Ex.

Compound

Isomer Functional

Remarks

(1)

CCCC

(a) C = C C = C Alkadiene

(a), (b) are not functional isomers

Alkyne

(b)

Cycloalkene

among themselve

(c)

Bicyclo

C C C OH
Alcohol

CCOC
Ethers

(3)

C C CH = O

C C C

Aldehydes

O
Ketones

C C COOH

C C OC

Carboxylic acids

O
Esters

C C C NH2

..
(a) C C NH C

1 amine

2 amine

CCCN
Cyanide
(Propanenitrile)

C C NC
Isocyanide
(Ethane isocyanide)

(4)

(5)

(6)

..
(b) C N C
C
3 amine

(2)

1, 2, 3 amines are functional isomers

Important point:- Following compounds dont exist at room temperature therefore not consider as a structure
isomer
(ii) C C OH

(iii) C OH

(i) C = C OH

(v) C O C = C

(vi) Any peroxy compound

(iv) C OH

OH

OR

OH

Q.

Write acyclic isomers of C5H12O

Ans.

(i) C C C C C OH,

C C C C C,
OH

C
C C C C OH,

C
C C C OH,
C

C
C C C OH
C

(7 alcohols)

C C C C O C,

C C C O C,

C C C O C,

C C C O C C,

C
C
C COCC

C
C C O C,
C

G.F.
CnH2n + 3N

n
(1) 3

M.F.
C3H9N

2 Amine (R NH R)

3 Amine R N R
R
M.F.
C2H5N

C
C C C C OH,

C C C C C,
OH

1 Amine (R NH2)
G.F.
CnH2n + 1N
2

n
(1) 2

1 Amine
(1) C = C NH2
Ethenamine

2 Amine
3 Amine
CC=N
CN=C
Ethanimine
N-Methylene methanamine
(Unstable at room temperature)
H2C CH2 Azine
N
H

Q.

(6 ethers).

RESONANCE

page # 34

Q.

G.F.
CnH2n 1N

n
2

M.F.
C2H3N

Ans.

Cyanides and isocyanides

H3 C C N

CH2 = C = NH

HC C NH2

H3 C N

2.4

Metamers:
When two isomers have same functional group (containing a hetero atom O, N, S) but have different nature
of alkyl or aryl (aromatic radical) group attached to hetero atom, then these are called metamers.

Conditions:
(a) Same functional group
(b) Chain or position isomerism is not considered.
(c) >C = O (keto) group does not show metamerism
Following functional groups show metamerism
Ethers

(b) R NH R

2 Amines

(c) R N R
R''

3 Amines

(d) R S R

Thioethers

(e) R C O R

Esters

(f) R C O C R Anhydrides

(a) R O R

O
(g) R S O R

Sulphonate esters

O
Q.

How many esters are possible for C3H6O2 ?

Ans.

C C O C H and C C O C are metamers

||
||
O
O

Q.

3 Amines of M.F. C5H13N (All metamers)

C C NC

OC

OCC

Q.

CCC NC

CC NCC

Ans.

and

Show which type of isomerism ?

Q.

Acyclic compound (A) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (A).

Ans.

C C
C C C C C8H18
C C

Q.

Cyclic compound (P) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (P).

Metamerism

Ans.

Ans.

or

Ans.

Compound X is an ether. It has 12 1 H atoms. It has 2 types of H-atoms and 3 types of C-atoms. Write it
Structural formula ?

CH3
H3C O C CH3

Q.

CH3

RESONANCE

page # 35