02 Isomerism (Theory-01)

ISOMERISM CH-3
1. HOMOLOGOUS SERIES
Organic compounds can be divided into different groups on the basis of similarity in their
structure and properties. The property by which a number of organic compounds form a homologous
series is termed as homology.
The general characteristics of a homologous series are
• All compounds in the series have the same functional group.
• All compounds in the series can be represented by the same general formula and can
be prepared by the general methods of preparation.
• All the homologues show a gradual gradation in their physical and chemical properties.
• Successive members of a homologous series differ by CH 2 group and by a mass of
14 units.
Table 1a: Homologous series of aliphatic organic compounds
Name of the homologous General formula Functional group IUPAC name

series or substituent
Alkanes CnH2n + 2 − (single bond) Alkanes
Alkenes CnH2n = (double bond) Alkenes
Alkynes CnH2n −2  (triple bond) Alkynes
Monohydric alcohols CnH2n + 1 OH −OH Alkanols
Aldehydes CnH2nO −CHO Alkanals
Ketones CnH2nO C=O Alkanones
Monocarboxylic acid CnH2nO2 −COOH Alkanoic acids

Ethers CnH2n + 2 O C−O−C Alkoxy alkanes
Primary amines CnH2n + 1 NH2 −NH2 Alkanamines
Amides CnH2n + 1 CONH2 −CONH2 Alkanamides
Esters CnH2nO2 R − COO − R Alkyl alkanoate

Cyanides CnH2n + 1CN −CN Alkane nitriles
Nitro compounds O Nitroalkanes
CnH2n + 1 NO2 −N
O
Acid chlorides CnH2n + 1 COCl −COCl Alkanoyl chlorides
2. NOMENCLATURE OF ORGANIC COMPOUNDS

Nomenclature implies assigning proper name to a particular organic compound on the basis
of certain standard rules so that the study of these compounds may become systematic.
In the IUPAC system, the name of an organic compound consists of three parts.
(i) Word root (ii) Suffix (iii) Prefix
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ISOMERISM CH-4
WORD ROOT
The word root denotes the number of carbon atoms present in the chain. For example,
Chain length Word root Chain length Word root

C1 Meth C6 Hex
C2 Eth C7 Hept
C3 Prop C8 Oct
C4 But C9 Non
C5 Pent C10 Dec
SUFFIX
The word root is linked to the suffix, which may be primary, secondary or both.
Primary suffix
It indicates the nature of linkages between the carbon atoms. For example,
ane − for single bonded compounds, C−C ;

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

Alcohols −OH −ol
Aldehydes −CHO −al
Ketones C=O −one
Carboxylic acids −COOH −oic acid
Esters −COOR alkyl…..oate
Acid chlorides −COCl −oyl chloride
Acid amides −CONH2 −amide
Nitriles −CN −nitrile
Amines −NH2 −amine
PREFIXES
There are many groups, which are not regarded as functional groups in the IUPAC naming
of the compounds. These are regarded as substituents or side chains. These are represented as
prefixes and are placed before the word root while naming a particular compound. For example,
if a compound contains more than one functional group, then one of the functional group is regarded
as principal functional group and is treated as secondary suffix. The other functional groups are
regarded as substituents and are indicated by prefixes.
ISOMERISM CH-5
Substituent Prefix Substituent Prefix

−CnH2n+1 Alkyl −NH2 Amino
−F Fluoro −NO Nitroso
−Cl Chloro −N=N− Diazo
−Br Bromo −OCH3 Methoxy
−I Iodo −OC2H5 Ethoxy
−NO2 Nitro −OH Hydroxy
Thus, a complete IUPAC name of an organic compound may be represented as

Prefix + Word root + Primary suffix + Secondary suffix.
HOW TO NAME ORGANIC COMPOUNDS USING THE IUPAC RULES

In order to name organic compounds you must first memorize a few basic names. These
names are listed within the discussion of naming alkanes. In general, the base part of the name
reflects the number of carbons in what you have assigned to be the parent chain. The suffix of
the name reflects the type(s) of functional group(s) present on (or within) the parent chain. Other
groups which are attached to the parent chain are called substituents.
2.1 RULES FOR NAMING ALKANES – SATURATED HYDROCARBONS

The name of straight chain saturated hydrocarbons for up to 12 carbon chain are shown
below. The names of the substituents formed by the removal of one hydrogen from the end
of the chain is obtained by changing the suffix –ane to –yl.
Number of Carbons Name

1 methane
2 ethane
3 propane
4 butane
5 pentane
6 hexane
7 heptane
8 octane
9 nonane
10 decane
11 undecane
12 dodecane
ISOMERISM CH-6
There are a few common branched substituents which you should memorize. These are
shown below.
CH3 CH3 CH3 CH3

CH3CH— CH3CH2CH— CH3–C— CH3CHCH2—
CH3
isopropyl sec-butyl tert-butyl isobutyl
Here is a simple list of rules to follow. Some examples are given at the end of the list.
1. Identify the longest carbon chain. This chain is called the parent chain.
2. Identify all of the substituents (groups attached to the parent chain).
3. Number the carbons of the parent chain from the end that gives the substituents the
lowest numbers. When comparing a series of numbers, the series that is the “lowest”
is the one which contains the lowest number at the occasion of the first difference. If
two or more side chains are in equivalent positions, assign the lowest number to the
one which will come first in the name.
4. If the same substituent occurs more than once, the location of each point on which
the substituent occurs is given. In addition, the number of times the substituent group
occurs is indicated by a prefix (di, tri, tetra, etc.).
5. If there are two or more different substituents they are listed in alphabetical order
using the base name (ignore the prefixes). The only prefix which is used when putting
the substituents in alphabetical order is iso as in isopropyl or isobutyl. The prefixes
sec– and tert– are not used in determining alphabetical order except when compared
with each other.
6. If chains of equal length are competing for selection as the parent chain, then the
choice goes in series to :
(a) the chain which has the greatest number of side chains.
(b) the chain whose substituents have the lowest– numbers.
(c) the chain having the greatest number of carbon atoms in the smaller side chain.
(d) the chain having the least branched side chains.
7. A cyclic (ring) hydrocarbon is designated by the prefix cyclo– which appears directly
in front of the base name.
In summary, the name of the compound is written out with the substituents in alphabetical
order followed by the base name (derived from the number of carbons in the parent chain).
Commas are used between numbers and dashes are used between letters and numbers.
There are no spaces in the name.
ISOMERISM CH-7
Here are some examples:
CH3 CH2–CH3 CH3–CH2 CH3

CH3–CH–CH2–CH–CH2–CH3 CH3–CH2–CH2–CH––C–CH2–CH3
CH3
4–Ethyl–2–methylhexane 4–Ethyl–3,3–dimethylheptane
7 6 5 4 3 2 1
CH3––CH2––CH––CH––CH––CH––CH3 CH3
5
CH3 CH2 CH3 CH3 CH
6
CH2 CH2–CH2
7
CH3
2,3,5–Trimethyl–4–propylheptane Methylcyclopropane
(NOT: 2,3–dimethyl–4–sec–butyleptane)
CH3 CH3
6 5 4 3 2 1
CH3–CH–CH2–CH2–CH–CH2–CH–CH2–CH3 CH3–CH2–CH–CH–CH2–CH3
1 2 3 4 5 6 7 8 9
CH–CH3 CH3 CH2
CH2–CH3 CH3
5–Sec–butyl–2, 7–dimethylnonane 3–Ethyl–4–methylhexane
2.2 RULES FOR NAMING ALKENES AND ALKYNES – UNSATURATED HYDROCARBONS

Double bonds in hydrocarbons are indicated by replacing the suffix –ane with –ene. If there
is more than one double bond, the suffix is expanded to include a prefix that indicates the
number of double bonds present (–adiene, –atriene, etc.). Triple bonds are named in a
similar way using the suffix –yne. The position of the multiple bond(s) within the parent chain
is(are) indicated by placing the number(s) of the first carbon of the multiple bond(s) directly
in front of the base name.
Here is an important list of rules to follow:
1. The parent chain is numbered so that the multiple bonds have the lowest numbers
(double and triple bonds have priority over alkyl and halo substituents).
2. When both double and triple bonds are present, numbers as low as possible are
given to double and triple bonds even though this may at times give “–yne” a lower
number than “–ene”. When there is a choice in numbering, the double bonds are
given the lowest number.
3. When both double and triple bonds are present, the –en suffix follows the parent
chain directly and the –yne suffix follows the –en suffix (notice that the ‘e’ is left off, –
en instead of –ene). The location of the double bond(s) is(are) indicated before the
parent name as before, and the location of the triple bond(s) is(are) indicated
between the –en and –yne suffixes.
ISOMERISM CH-8
4. For a branched unsaturated acyclic hydrocarbon, the parent chain is the longest
carbon chain that contains the maximum number of double and triple bonds. If
there are two or more chains competing for selection as the parent chain (chain with
the most multiple bonds), the choice goes to (1) the chain with the greatest number
of carbon atoms, (2) the number of carbon atoms being equal, the chain containing
the maximum number of double bonds.
5. If there is a choice in numbering not previously covered, the parent chain is numbered
to give the substituents the lowest number at the first point of difference.
6 5 4 3 2 1 6 5 4 3 2 1
CH3–CH=CH–CH2–CH=CH2 CHC–CH=CH–CH=CH2
1,4–Hexadiene 1,3–Hexadien–5–yne
CH3
5 4 3 2 1 6 5 4 3 2 1
CH3–CH=CH–CCH CH3–C–CH2–CH2–CH=CH2
CH3
3–Penten–1–yne 5,5–Dimethyl–1–hexene
CH2–CH3
CH2 4
3
6 5 4 3 2 1
CHC–C–C–CH=CH2
1 2
CH2–CH2–CH3
3,4–Dipropyl–1,hexaen–5–yne 1,4,4-Trimethylcyclobutene
2.3 RULES FOR NAMING ALKYL HALIDES

The halogen is treated as a substituent on an alkane chain. The halo–substituent is
considered of equal rank with an alkyl substituent in the numbering of the parent chain. The
halogens are represented as
F fluoro–
Cl chloro–
Br bromo–
I Iodo–
CH3 CH3 Br
1 2 3 4 5 4 3 2 1
CH3–CH–CH–CH2–CH3 CH3–CH–CH–CH3
Cl
3–Chloro–2–methylpentane 2–Bromo–3–methylbutane
ISOMERISM CH-9
2.4 RULES FOR NAMING ALCOHOLS

Alcohols are named by replacing the suffix –ane with –anol. If there is more than one
hydroxyl group (–OH), the suffix is expanded to include a prefix that indicates the number of
hydroxyl groups present (–anediol, –anetriol, etc.). The position of the hydroxyl group(s) on
the parent chain is(are) indicated by placing the number(s) corresponding to the location(s)
on the parent chain directly in front of the base name (same as alkenes).

1. The hydroxyl group takes precedence over alkyl groups and halogen substituents, as
well as double bonds, in the numbering of the parent chain.
2. When both double bonds and hydroxyl groups are present, the –en suffix follows the
parent chain directly and the –ol suffix follows the –en suffix (notice that the ‘e’ is left
off, –en instead of –ene). The location of the double bond(s) is (are) indicated before
the parent name as before, and the location of the hydroxyl group(s) is(are) indicated
between the –en and –ol suffixes. Again, the hydroxyl gets priority in the numbering
of the parent chain.
OH OH OH OH
1 2 3 4 5 1 2 3 4 1
CH3–CH–CH–CH2–CH3 CH3–CH–CH–CH3 2
CH3 3
3−Methyl−2−pentanol 2,3−Butanediol 2−Cyclopenten−1−ol
2.5 RULES FOR NAMING ETHERS

The generic IUPAC name of this family is “alkoxy alkane” in which alkane part contains
longer carbon chain in case of unsymmetrical ethers.
CH3−O−CH2−CH3 CH3CH2−O−CH2CH3
Methoxy ethane Ethoxy ethane
1
2
CH3
1 2 3
CH3–O−CH2CH2CH3 CH3–O–CH
3 CH3
1–Methoxy propane 2–Methoxy propane
ISOMERISM CH-10
2.6 RULES FOR NAMING ALDEHYDES

Aldehydes are named by replacing the suffix –ane with –anal. If there is more than one
–CHO group, the suffix is expanded to include a prefix that indicates the number of –CHO
groups present (–anedial –there should not be more than 2 of these groups on the parent
chain as they must occur at the ends). It is not necessary to indicate the position of the
–CHO group because this group will be at the end of the parent chain and its carbon is
automatically assigned as C-1.

1. The carbonyl group takes precedence over alkyl groups and halogen substituents, as
2. When both double bonds and carbonyl groups are present, the –en suffix follows the
parent chain directly and the –al suffix follows the –en suffix (notice that the ‘e’ is left
off, –en instead –ene). The location of the double bond(s) is(are) indicated before the
parent name as before, and the –al suffix follows the –en suffix directly. Remember
it is not necessary to specify the location of the carbonyl group because it will
automatically be the first carbon. Again, the carbonyl gets priority in the numbering of
the parent chain.
3. There are a couple of common names which are acceptable as IUPAC names. They
are shown in the examples in parenthesis.
O
O
Propanal 3–Methylbutanal
O O
H−C−H
Methanal
3–Methyl–3–butenal (Common name: Formaldehyde)
O O
CH3−C−H C−H
Ethanal
(Common name: Acetaldehyde) Benzaldehyde
2.7 RULES FOR NAMING KETONES

Ketones are named by replacing the suffix –ane with –anone. If there is more than one
carbonyl group (C=O), the suffix is expanded to include a prefix that indicates the number of
carbonyl groups present (–anedione, –anetrione, etc.). The position of the carbonyl
group(s) on the parent chain is(are) indicated by placing the number(s) corresponding to the
location (s) on the parent chain directly in front of the base name (same as alkenes).
1. The carbonyl group takes precedence over alkyl groups and halogen substituents, as
2. When both double bonds and carbonyl groups are present, the –en suffix follows the
parent chain directly and –one suffix follows the –en suffix (notice that ‘e’ is left off, –
en instead of –ene). The location of the double bond(s) is(are) indicated before the
ISOMERISM CH-11
parent name as before, and the location of the carbonyl group(s) is (are) indicated
between the –en and –one suffixes. Again, the carbonyl gets priority in the numbering
of the parent chain.
O
O
Propanone 2–Butanone
(Common name: Acetone)
O O O
3–Methyl–3–buten–2–one 2,4–Pentanedione
2.8 RULES FOR NAMING CARBOXYLIC ACIDS

Carboxylic acids are named by counting the number of carbons in the longest continuous
chain including the carboxyl group and by replacing the suffix –ane of the corresponding
alkane with –anoic acid. If there are two –COOH groups, the suffix is expanded to include
a prefix that indicates the number of –COOH groups present (–anedioic acid – there should
not be more than 2 of these groups on the parent chain as they must occur at the ends). It
is not necessary to indicate the position of the –COOH group because this group will be at
the end of the parent chain and its carbon is automatically assigned as C–1.
1. The carboxyl group takes precedence over alkyl groups and halogen substituents, as
2. If the carboxyl group is attached to a ring, the parent ring is named and the suffix
–carboxylic acid is added.
3. When both double bonds and carboxyl groups are present, the –en suffix follows the
parent chain directly and the –oic acid suffix follows the –en suffix (notice that the ‘e’
is left off, –en instead of –ene). The location of the double bond(s) is(are) indicated
before the parent name as before, and the –oic acid suffix follows the –en suffix
directly. Remember it is not necessary to specify the location of the carboxyl group
because it will automatically be the first carbon. Again, the carboxyl gets priority in
the numbering of the parent chain.
4. There are several common names that are acceptable as IUPAC names. They are
shown in the examples in the parenthesis.
ISOMERISM CH-12
O O
H−C−OH CH3−C−OH
Methanoic acid Ethanoic acid
(Common name: Formic acid) (Common name: Acetic acid)
O O
C−OH
HO
3–Methylpentanoic acid Benzoic acid
OH O O O
HO−C−C−OH HO
COOH
2−Hydroxybenzoic acid Ethanedioic acid 3–Butenoic acid
(Common name: Salicyclic acid) (Common name : Oxalic acid)
2.9 RULES FOR NAMING ESTERS

Systematic names of esters are based on the name of the corresponding carboxylic acid.
Remember esters look like this:
O
R–C––O––R
acyl group alkyl group
The alkyl group is named like a substituent using the –yl ending. This is followed by a space.
The acyl portion of the name (what is left over) is named by replacing the –ic acid suffix of
the corresponding carboxylic acid with –ate.
O O O
CH3CH2−C−OCH3 C−OCH2CH3 CH3−C−OC(CH3)3

Methyl propanoate Ethyl benzoate Tert–butyl acetate
or
Tert−butylethanoate
2.10 RULES FOR NAMING AMINES

Primary amines (R−NH2) are named as alkanamine. If the compound contain double bond
along with amino group, then it is named alkanamine. Alkyl and halo substituents are named
as prefix in alphabetical order.
ISOMERISM CH-13
For example,
CH3CH2–NH2 CH3–CH2–CH2−NH2
Ethanamine Propanamine
Cl
3 2 1 4 3 2 1
CH2=CH−CH2−NH2 CH3–CH–CH2–CH−NH2
CH3
2–Propenamine 1−Chloro−3−methylbutanamine
Secondary amines (R2NH) and tertiary amines (R3N) are named as N−alkyl alkanamine and
N,N−dialkyl alkanamine.
CH3CH2–NH−CH3 CH3CH2CH2−NH−CH2CH3
N−Methylethanamine N−Ethylpropanamine
CH3CH2−N−CH3 CH3CH2CH2–N−CH2CH3
CH3 CH3
N,N−Dimethylethanamine N−Ethyl−N−methylpropanamine
2.11 RULES FOR NAMING ORGANIC COMPOUNDS CONTAINING ONE OR MORE

FUNCTIONAL GROUPS
The rules for naming an organic compound containing functional groups are exactly same
as discussed already for compounds containing double and triple bonds. In this case, the
preference of lowest number is given to carbon atom bearing the functional group. The rules
are summarized below:
(i) Select the longest continuous chain containing the carbon atom having functional group(s).
(ii) The numbering of atoms in the parent chain is done in such a way that carbon atom bearing
the functional group gets the lowest number.
(iii) It two or more same functional groups are present, these are indicated by using di, tri, tetra
as prefixed to the name of the functional group.
(iv) If the organic compound contains a functional group, multiple bonds, side chain or
substituents, the following order of preference must be followed,
Functional group > Double bond > Triple bond > Side chain.
(v) When an organic compound contains two or more functional groups, one group is regarded
as the principal functional group and the other group is treated as the secondary functional
group, which may be treated as substituent(s). The following order of preference is used for
selecting the principal functional group,
Carboxylic acids > sulphonic acids > acid anhydrides > esters > acid chlorides > amides
> nitriles > aldehydes > ketones > alcohols > amines > imines > ethers >
alkenes > alkynes.
ISOMERISM CH-14
Different classes of functional groups including multiple bonded compounds and the suffix
or prefix required to name these compounds are given in the preferential decreasing order
in the following table.
Functional group or
Class of compounds Suffix Prefix
substituent
1. Carboxylic acids C=O Carboxylic acid/oic acid carboxy

HO
O
2. Sulphonic acids −S−OH Sulphonic acid sulfo
O
O O
3. Acid anhydrides oic anhydride ⎯
C−O−C
C=O (R) … carboxylate

4. Esters alkoxy carbonyl
RO /(R)…oate
C=O Carbonyl halide/oyl

5. Acid halides halo carbonyl
X halide
6. Amides C=O Carboxamide/amide carbamoyl

NH2
7. Cyanides −CN Carbonitrile/nitrile cyano
8. Aldehydes C=O Carbaldehyde/al formyl/oxo

H
9. Ketones C=O one keto/oxo
10. Alcohols −OH ol hydroxy
11. Amines −NH2 amine amino
12. Imines =NH imine imino
13. Ethers C−O−C ⎯ alkoxy
14. Alkenes = (double bond) ene ⎯
15. Alkynes  (triple bond) yne ⎯
For those functionalities, which have two prefixes and/or suffixes, the first one is used when
carbon atom of the functional group is not a part of the longest continuous chain and the second
one is used, when carbon atom is counted in the longest chain.
ISOMERISM CH-15
2.12 RULES FOR NAMING AROMATIC COMPOUNDS

(i) When the benzene ring is present as one of the substituent in the carbon chain, it is named
as phenyl group.
(ii) Disubstituted, trisubstituted or tetrasubstituted benzenes are named by using the numbers.
(iii) If different groups are attached to the benzene ring, then the principal functional group is
fixed as number 1. The numbering of the chain is done in any direction (clockwise or
anticlockwise), which gives lowest number to the substituents. The substituents are written
in the alphabetical order.
Let us see the application of these IUPAC rules to some organic compounds.
(i) (HOCH2CH2O)2CH−CO2H Bis(2−hydroxyethoxy)ethanoic acid
C2H5
1
2
(ii) 3
1−Ethyl−4−methylcyclohaxane
4
CH3
F F
CH3CH−CH CH2CH3
(iii) CH3(CH2)4CH2CHCH2CH(CH2)3CH3 7−(1,2−Difluoropropyl)−5−ethyltridecane
CO2H
1
(iv) 2 4−Oxo−1,2,3,4−tetrahydronaphthalene
4
3 −1−carboxylic acid
O
O
(v) CH3CH2CH2−C−CH2Cl 1−chloropentan−2−one
5 4 3 2 1
(vi) 1,2−Didehydrobenzene
2 1
(vii) CH3CH2−O−CH2CH2Cl 1−Chloro−2−ethoxyethane
(viii) OHCCH2CH2CH−CH2CHO 3−(Formylmethyl)hexanedial
CH2CHO
4 3 2 1
(ix) OHCCH2CH2CH−CH2CHO Butane−1,2,4−tricarbaldehyde
CHO
(x) CH3CH2CH−OCH2CH3 1,1−Diethoxypropane
OCH2CH3
(xi) HO2CCH2CH2CH−CH2CH2CO2H Pentane−1,3,5−tricarboxylic acid.
CO2H
ISOMERISM CH-16
(xii) NCCH2CH2CH2CH−CH2CH2CN Hexane−1,3,6−tricarbonitrile

CN
O
3 2
1
(xiii) OHC 4 CO2H 4−Formyl−2−oxocyclohexane−1−carboxylic acid
(xiv) CH3CS−O−COCH2CH3 Propionic thioethanoic anhydride
(xv) CONH2 Cyclohexanecarboxamide
O
(xvi) CH3−C−CH2CH2CH2CO2H 5−Oxohexanoic acid
6 5 4 3 2 1
O O
(xvii) CH3CH2−C−CH2−C−CH3 Hexane−2,4−dione
6 4 5 3 2 1
(xviii) CH2=CHCH2CH(OH)CH3 Pent−4−en−2−ol

NO2
3
2
(xix) 3−Nitrocyclohexene
1
OH
1
2
(xx) Cyclohex−2−en−1−ol
3
3. ISOMERISM
The existence of different compounds having same molecular formula but different
physical and chemical properties is called isomerism. If the difference in properties is due to
difference in their structural formulae, it is called structural isomerism. And if the difference in
properties is due to the arrangement of atoms or group of atoms in space, it is called stereo
isomerism. The different compounds are named as isomers.
Isomerism is broadly divided into two types,
(i) Structural isomerism and (ii) Stereoisomerism
3.1 STRUCTURAL ISOMERISM

Two or more compounds with the same molecular formula, which differ in the
arrangement of atoms within the molecule are called structural isomers and the phenomenon
is called structural isomerism. There are different types of structural isomerism.
ISOMERISM CH-17
3.1.1 CHAIN ISOMERISM

The chain isomers have same molecular formula but they differ in the length of carbon chain
(straight or branched). Compounds with four or more carbon atoms can show this kind of isomerism.
For example,
(a) C4H10 has two chain isomers.

CH3CH2CH2CH3 CH3−CH−CH3
(n−Butane)
CH3
2−Methyl propane
(isobutane)
(b) C5H12 has three chain isomers.

CH3
CH3CH2CH2CH2CH3 CH3−CH−CH2CH3 CH3−C−CH3
n−pentane
CH3 CH3
2−Methyl butane 2,2−Dimethyl propane
(isopentane) (neopentane)
(c) C4H9OH has two chain isomers.

CH3CH2CH2CH2OH CH3−CH−CH2OH
Butan−1−ol CH3
(n−Butyl alcohol) 2−Methyl propan−1−ol
(Iso−butyl alcohol)
(d) C4H8 has two chain isomers.

CH3CH2CH=CH2 CH3−C=CH2
But−1−ene CH3
(Butylene)
2−Methyl propene
(Iso−butylene)
3.1.2 POSITION ISOMERISM

The position isomers have same molecular formula but differs in the position of either
substituent or functional group on the same carbon skeleton. For example,
(a) The molecular formula C4H8 has two position isomers.

CH3CH2CH=CH2 CH3CH=CHCH3
But−1−ene But−2−ene
(Butylene) (Dimethyl ethylene)
(b) The molecular formula C4H6 has two position isomers.

CH3CH2CCH CH3CCHCH3
But−1−yne But−2−yne
(Crotonylene) (Dimethyl acetylene)
ISOMERISM CH-18
(c) The molecular formula C4H9Cl has two position isomers.
CH3CH2CH2CH2−Cl CH3CH2−CH−CH3
1−Chlorobutane
Cl
2−Chlorobutane
(d) The molecular formula C6H6O3N has three position isomers.
OH OH OH
NO2
NO2
ortho−nitrophenol NO2
meta−nitrophenol
(1, 2−substitution) (1, 3−substitution) para−nitrophenol
(1, 4−substitution)
3.1.3 FUNCTIONAL GROUP ISOMERISM

The isomers having same molecular formula but different functional groups in the molecule
are called functional isomers. The following classes of organic compounds show functional
isomerism among themselves.
(a) Alcohols and ethers are functional group isomers.
CH3CH2OH and CH3−O−CH3

Ethanol Methoxy methane
(Ethyl alcohol) (Dimethyl ether)
(Functional group −OH) (Functional group−O−)
(b) Aldehydes and ketones are functional isomers. They are also functionally isomeric to
unsaturated ethers, unsaturated alcohols, cyclic ethers and cyclic alcohols.
O
CH3CH2CH2−C=O CH3CH2−C−CH3 CH2=CH−O−CH2CH3, CH2=CH−CH2CH2OH
H Butanone
Butanal (Functional group C=O)
(butyraldehyde) O OH
(Functional group−CHO)
(c) Carboxylic acids and esters also share functional group isomerism.
O O
CH3−C−OH H−C−OCH3
Ethanoic acid Methyl methanoate
(d) Dienes, allenes and alkynes are functional isomers.
CH2=CH−CH=CH2 CH2=C=CH−CH3 CH3CH2CCH

Buta−1, 3−diene Buta−1, 2−diene (An allene) But−1−yne
ISOMERISM CH-19
(e) Nitro alkanes and alkyl nitrites are functional group isomers.
CH3CH2−NO2 CH3CH2−ONO
Nitroethane Ethyl nitrite
(f) 1°, 2° and 3° amines share functional group isomerism.
CH3
CH3CH2CH2NH2 CH3CH2−NH−CH3
Propan−1−amine N−methyl ethanamine CH3−N−CH3
(1° amine) (2° amine) N, N−Dimethyl methanamine
(3° amine)
(g) Cyanides and isocyanides are functional group isomers.

CH3−CN CH3−N C
Ethane nitrile Methyl isocyanide
(h) Aromatic alcohols, phenols and ethers are also functional isomers.
CH2OH OCH3 OH
CH3
Benzyl alcohol Anisole o−Cresol
DEGREE OF UNSATURATION
Deficiency of two hydrogen atoms in a molecule is a result of either a pi−bond or a ring in the
structure of that molecule. The sum of pi−bonds and rings in the structure of a compound
collectively is called degree of unsaturation or double bond equivalents in that
compound. The most general type of formula for any organic species is (C aHbNcOd).
If the compound contains other atoms also, the tetravalent atoms are replaced by carbon,
monovalent atoms are replaced by hydrogen, divalent atoms are replaced by oxygen and
trivalent atoms are replaced by nitrogen. Then all oxygen and all nitrogen atoms are removed
from the formula. However, for the removal of each N atom, one H atom is also removed
from the molecular formula. If the molecular species is charged, H + are added or removed
to neutralise the charge. As a result of all these operations, we will get a hydrocarbon. Now
this concluded hydrocarbon is compared with saturated alkane containing same number of
carbon atoms to determine the degree of unsaturation or double bond equivalents.
Example 1: C12H16N2OCl2
C12H16N2OCl2 will give C12H18N2O after replacing Cl atoms by H atoms and C 12H16 after
removing O and N. Corresponding saturated alkane should be C 12H26.
26 − 16
Double bond equivalents = =5
2
ISOMERISM CH-20
Example 2: C13H10BrNS
C13H10BrNS will give C13H11NO after replacing Br by H and S by O atoms. Removal of
O and N gives us C13H10. The corresponding saturated alkane will be C 13H28.
28 − 10
Double bond equivalents = = 9.
2
Example 3: C3H8N+
C3H8N+ will give C3H7N after losing one H+ ion. Removal of N gives us C3H6.
The corresponding saturated alkane will be C 3H8.
8−6
Double bond equivalents = = 1.
2
Example 4: C 5 H5−
C 5 H5− will give C5H6 after adding one H+ ion. The corresponding saturated alkane will be
12 − 6
C5H12. Double bond equivalents = = 3.
2
Catalytic hydrogenation (hydrogenation using H 2 in presence of Ni or Pd at room
temperature) data is used to distinguish between the unsaturation due to a −bond or unsaturation
due to a ring. Compounds having unsaturation due to −bonds absorb 1 mole of H 2 for each mole
of a −bond while compounds having unsaturation due to rings do not absorb any hydrogen at room
temperature.
But compounds like cyclopropane and cyclobutane do absorb 1 mole of H 2 at 120°C and
200°C respectively because these rings are highly strained and in order to get relieve from strain,
they do get cleaved by H2 at elevated temperatures. Cyclopentane and higher rings to not absorb
any H2 at the experimental temperatures (200−300°C) as such rings are quite stable.
Ni at
+ H2 120°C
CH3−CH2−CH3
Ni at
+ H2 200°C
CH3−CH2−CH2−CH3
3.1.4 METAMERISM
Compounds having same molecular formula but different number of carbon atoms
(or alkyl groups) on either side of the multivalent functional group (i.e. –O−,−S−,−NH−, –CO− etc.)
are called metamers and the phenomena is called metamerism. Metamerism occurs among the
members of the same family. For example,
CH3
(a) CH3CH2COCH2CH3 is a metamer of CH3COCH2CH2CH3 and CH3−CO−CH
Pentan−3−one Pentan−2−one CH3
3−methyl butanone
The first two compounds are also related as position isomers as the position of C=O in the
two isomers is different.
ISOMERISM CH-21
1
2 CH3
(b) CH3CH2O−CH2CH3 is a metamer of CH3−O−CH2CH2CH3 and CH3−O−CH 3
Ethoxy ethane 1−Methoxy propane
CH3
(Diethyl ether) (Methyl n−propyl ether) 2−methoxy propane
CH3
(c) CH3CH2−NH−CH2CH3 is a metamer of CH3−NH−CH2CH2CH3 and CH3−NH−CH
Diethyl amine (Methyl n−propyl amine) CH3
Methyl isopropyl amine
Draw all possible metamers of CH3CH2−N−CH2CH2CH3.

CH2CH3
3.1.5 TAUTOMERISM
It is a special type of functional isomerism in which an −hydrogen atom is shifted from one
position (atom−1) to another (atom−3). This shift is referred as 1,3−shift. Such shifts are
common between a carbonyl compound containing an −hydrogen atom and its enol form.
R R
R−C−C−R
1 2 R−C=C−R
1 2
3 3
H O H−O
Keto form Enol form
H = (C−H + C−C + C=O) − (C=C + C−O + O−H) = 359 − 347 = 12 kcal/mol.

Thus, generally keto form is more stable than enol form by 12 kcal. So, in most cases, the
equilibrium lies towards the left.
The term tautomerism is used for isomers that are fairly readily interconvertible and that differ
from each other only (a) in electron distribution and (b) in the position of a relatively mobile
atom or group, The mobile atom is generally hydrogen and the phenomenon is then called
as prototropy.
Both acids and bases catalyse such interconversions. Possible limiting mechanisms are
those (a) in which proton removal and proton acceptance (from the solvent) are separate
operations and a carbanion intermediate is involved. i.e. an intermolecular pathway and
(b) in which one and the same proton is transferred intramolecularly.
B: H H
R2C−CH=Y
ROH
(a) R2C−CH=Y R2C=CH−Y (Intermolecular)
−BH −RO−
R2C=CH−Y
Carbanion
intermediate
ISOMERISM CH-22
 H
H H
(b) R2C−CH=Y R2C Y R2C=CH−Y (Intramolecular)
CH
Transition state
Mostly the keto form is more stable than enol form but in certain cases, enol form can become
the predominant form. The enol form is predominant in following cases:
1. Molecules in which the enolic double bond is in conjugation with another double bond/phenyl
ring. In such cases, sometimes intramolecular hydrogen bonding also stabilizes the enol.
R R
C−C−R C=C−R
H O H−O
Keto form Enol form
(Cross−conjugation)
CH
CH3−C−CH2−C−OEt CH3−C C−OEt
O O O O
H
Keto form Enol form
(Cross−conjugation and
intramolecular hydrogen bonding)
CH
CH3−C−CH2−C−CH3 CH3−C C−CH3
O O O O
H
Keto form Enol form
(Cross−conjugation and intramolecular
hydrogen bonding)
2. Molecules, which contain two bulky aryl groups.

Me
Ar Ar
C−C−H C=C−H where Ar = Me
Ar Ar
H O H−O Me
Keto form (5%) Enol form (95%)
In the keto form of 2,2−dimesitylethanal, the Ar−C−Ar bond angle is 109°, whereby the bulky
aryl groups experience greater steric repulsion. This steric repulsion eases off when the keto
form transforms to enol form, where the Ar−C−Ar bond angle widens to 120°.
3. When the enol is aromatic stabilized.
O OH
H
H
Keto form Enol form
ISOMERISM CH-23
The extent of enolization is also affected by the solvent, concentration and temperature.
Thus, acetoacetic ester has an enol content of 0.4% in water and 19.8% in toluene. This is
because water reduces the enol content by hydrogen bonding with the carbonyl group,
making this group less available for intramolecular hydrogen bonding. The effectiveness of
intramolecular hydrogen−bonding in stabilizing the enol, with respect to the keto form is seen
on varying the solvent and particularly on transfer to a hydroxylic solvent with
MeCOCH2COMe.
Solvent % Enol Thus, the proportion of enol in the non−polar solvent

(hexane) is the same as in the gas phase and higher than in
Gas phase 92
the liquid itself, the latter acting as a polar auto−solvent. The
Hexane 92 proportion drops again in the more polar MeCN and more
Liquid 76 dramatically in water. What is happening is the increasing
relative stabilization of the keto form by solvation, this being
MeCN 58 particularly marked in water where intermolecular hydrogen
H2 O 15 bonding of the keto form’s C=O groups can now take place
as an alternative to its enolization.
Also, the enol content of pentan−2,4−dione (CH3COCH2COCH3) is found to be 95% and 45%
at 27.5° and 275°C respectively.
When a strong base is added to a solution of a ketone with −hydrogen atom, both the enol
and keto form can lose a proton. The resulting anion is same in both the cases as they differ
only in the placement of electrons. They are not tautomers but canonical forms.
R R
C−C−R C=C−R
R R
H O H−O
+H+ −H +H+ −H
+ +
R .. R
C−C−R C=C−R
R R
O O
(Carbanion) (Enolate ion)
Other types of tautomerism

(i) Phenol−Keto tautomerism:
O OH
H
H
Cyclohexadienone Phenol
In this case, enol form is more stable than keto form because of the aromatic stabilization.
ISOMERISM CH-24
(ii) Nitroso−Oxime tautomerism:

R R
C−N C=N
R R
H O OH
Nitroso form Oxime form
This equilibrium lies far to the right and as a rule nitroso compounds are stable only when
there is no −hydrogen atom.
(iii) Nitro−Aci tautomerism:

Aliphatic nitro compounds are in equilibrium with the aci forms.
R O R  O R  O
C−N C−N C=N
R 
O R O R OH
H H
Nitro form Aci form
The nitro form is much more stable than the aci form because nitro group has resonance.
Aci form of nitro compounds is also called nitronic acids.
(iv) Imine−Enamine tautomerism / cyanide−enimine tautomerism:
R R
C−C−R
R R C=C−R
H N−R NH−R
Imine form Enamine form
Imine form predominates generally. Enamines are stable only when there is no hydrogen
atom attached to nitrogen.
R R
C−C C=C
R R
H N N−H
Cyano form Enimine form
Which of the following compound shows tautomerism and also draw their tautomer?
(a) CH3CHO (b) CH3COCH3 (c) CH3COCH2CH3 (d) C6H5CHO
(e) C6H5COCH3 (f) C6H5COC6H5 (g) O O (h) O

02 Isomerism (Theory-01)

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ISOMERISM CH-3

Table 1a: Homologous series of aliphatic organic compounds

Name of the homologous General formula Functional group IUPAC name

Monocarboxylic acid CnH2nO2 −COOH Alkanoic acids

Amides CnH2n + 1 CONH2 −CONH2 Alkanamides

Esters CnH2nO2 R − COO − R Alkyl alkanoate

2. NOMENCLATURE OF ORGANIC COMPOUNDS

Chain length Word root Chain length Word root

ane − for single bonded compounds, C−C ;

Class of organic compound Functional group Secondary suffix

Substituent Prefix Substituent Prefix

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

HOW TO NAME ORGANIC COMPOUNDS USING THE IUPAC RULES

2.1 RULES FOR NAMING ALKANES – SATURATED HYDROCARBONS

Number of Carbons Name

CH3 CH3 CH3 CH3

Here are some examples:

CH3 CH2–CH3 CH3–CH2 CH3

2.2 RULES FOR NAMING ALKENES AND ALKYNES – UNSATURATED HYDROCARBONS

Here is an important list of rules to follow:

Here are some examples:

2.3 RULES FOR NAMING ALKYL HALIDES

Here are some examples:

2.4 RULES FOR NAMING ALCOHOLS

Here is an important list of rules to follow:

Here are some examples:

2.5 RULES FOR NAMING ETHERS

2.6 RULES FOR NAMING ALDEHYDES

Here is an important list of rules to follow:

2.7 RULES FOR NAMING KETONES

2.8 RULES FOR NAMING CARBOXYLIC ACIDS

Here is an important list of rules to follow:

2.9 RULES FOR NAMING ESTERS

acyl group alkyl group

Here are some examples:

CH3CH2−C−OCH3 C−OCH2CH3 CH3−C−OC(CH3)3

2.10 RULES FOR NAMING AMINES

2.11 RULES FOR NAMING ORGANIC COMPOUNDS CONTAINING ONE OR MORE

1. Carboxylic acids C=O Carboxylic acid/oic acid carboxy

C=O (R) … carboxylate

C=O Carbonyl halide/oyl

6. Amides C=O Carboxamide/amide carbamoyl

7. Cyanides −CN Carbonitrile/nitrile cyano

8. Aldehydes C=O Carbaldehyde/al formyl/oxo

9. Ketones C=O one keto/oxo

10. Alcohols −OH ol hydroxy

11. Amines −NH2 amine amino

12. Imines =NH imine imino

13. Ethers C−O−C ⎯ alkoxy

14. Alkenes = (double bond) ene ⎯

15. Alkynes  (triple bond) yne ⎯

2.12 RULES FOR NAMING AROMATIC COMPOUNDS

(xii) NCCH2CH2CH2CH−CH2CH2CN Hexane−1,3,6−tricarbonitrile

(xiv) CH3CS−O−COCH2CH3 Propionic thioethanoic anhydride

(xv) CONH2 Cyclohexanecarboxamide

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

Isomerism is broadly divided into two types,

(i) Structural isomerism and (ii) Stereoisomerism

3.1 STRUCTURAL ISOMERISM

3.1.1 CHAIN ISOMERISM

(a) C4H10 has two chain isomers.

(b) C5H12 has three chain isomers.

(c) C4H9OH has two chain isomers.