Isomerism Isomerism PDF
Isomerism Isomerism PDF
INTRODUCTION
The word isomerism came from Greek word isomers (isos = equal, meros = a share). Two or more compounds having the
same molecular formula but different chemical and/or physical properties are called isomers and the phenomenon is known
as isomerism.
Isomerism can be broadly divided into two types,
1. Structural isomerism (constitutional isomerism)
2. Stereoisomerism (configurational isomerism)
H3C H3C
CH3 CH3
n-butane Isobutane (2 -methyl propane)
Position Isomerism
Compounds which have the same structure of the carbon chain (carbon length) but differ only in the position of the multiple
(double or triple) bond or the functional group or the substituent group are called position isomers and the phenomenon is
called position isomerism. Example: 1-butene and 2-butene are positional isomers.
H3C H3C
CH2 CH3
1-butene 2-butene
Functional Isomerism
Compounds having the same molecular formula but different functional groups are called functional isomers and the
phenomenon is called functional isomerism. Example:
ISOMERISM BY NKB.CO.IN 2
H3C H3C O
OH CH3
Ethyl alcohol Dimethyl ether
The following classes of organic compounds show functional isomerism among themselves.
(a) Carboxylic acids and esters
O
O O
H3C and CH3
OH
H
acetic acid
methyl formate
(b) Aldehydes and ketones
O O
and H3C
H3C CH3 H
propanone propanal
NH NH
H3C NH CH3 H3C CH3
H3C CH3
Tautomerism
It is the type of isomerism in which two functional isomers exist together in equilibrium. The two forms existing in
equilibrium are called tautomers. It arises due to migration of atomic nuclei from one polyvalent atom to the other
within the same molecule. Example: The compound acetoacetic ester has two tautomersone has keto group and
other has an enol group.
O OH
COOC2 H5 COOC2 H5
H3C H3C
ethyl 3-oxobutanoate ethyl -3-hydroxybut-2-enoate
H3C H H2C H
Generally, keto form is more stable than enol form because of the fact that C=O bond is stronger than C=C bond, but there
are some exceptions to this rule. Example:
OH O
(a)
Effect of solvent: Polar protic solvents such as H2O, CH3OH etc. which form H bonds with the carbonyl group of the keto
form, decrease the enol content. On the other hand, aprotic solvents such as hexane, benzene etc. increases the enol
content. For example, enol form of acetylacetone is available as 76% in ethanol but 92% in benzene.
N N
H3C O H2C O
nitro aci
oxime nitroso
(iv) Imineinamine tautomerism
H3C H2C
N NH2
imine inamine
(ii) Compound should have at least one acidic hydrogen present on -carbon of the molecule. If the above two conditions
are fulfilled, then compound will show tautomerism.
Percentage of enolic contents of some common compounds in decreasing order is given below,
O O
O O O O O O O O O
H5 C6 C6 H5 H3C CH3 H H RO OR H3C CH3 H3C H
[Note: Presence of benzene ring adjacent to carbonyl group increases the enol content due to extended conjugated system
provided by benzene ring.]
(i) In tautomerism, an atom changes its place but resonance involves a change of position of electrons or unshared
electrons.
(ii) Tautomers are different compounds and they can be separated by suitable methods but resonating structures cannot
be separated as they are imaginary structures of the same compounds.
(iii) Tautomers are in dynamic equilibrium but in resonance only one compound exists.
(iv) Resonance in a molecule lowers the energy and thus stabilizes a compound and decreases its reactivity but no such
effects occur in tautomerism.
Geometrical Isomerism
Isomers which possess the same molecular and structural formula but differ in arrangement of atoms or groups in space
around the double bond (or where the rotation is frozen) are known as geometrical isomers and the phenomenon is known
as geometrical isomerism.
Compound will show geometrical isomerism if it fulfils the following two conditions:
(i) The rotation about two adjacent atoms in the molecule should be frozen.
H H H
(a H3C CH3
H3C CH3 (b) H H (c)
)
Frozen rotation about CH3 CH3
Frozen rotation about carbon-
carbon-carbon double Frozen rotation about nitrogen double bond in
bond in alkenes carbon-carbon single oxime and imine
bond in cycloalkanes.
(ii) Both substituents on each carbon should be different about which rotation is frozen.
Types of geometrical isomers. The types of geometrical isomers are,
(i) cistrans isomerism (ii) syn-anti isomerism (iii) EZ isomerism
b b b a
cis form trans form
The isomer in which similar groups are placed on the same side is called cis and the isomer in which the similar groups are
on opposite sides is called trans. Example:
H H H CH3
Geometrical isomerism in nitrogen compounds. Geometrical isomerism due to restricted rotation around > C = N bond.
The important class of compounds exhibiting geometrical isomerism due to >C=N bond are (i) oximes (ii) hydrazones and
(iii) semi carbazones.
(i) Oximes: In aldoxime, when hydrogen and hydroxyl group are on the same side, the isomer is known as syn (analogous
to cis) and when these groups are on the opposite sides, the isomer is known as anti ( analogous to trans).
H5 C 6 H H5 C 6 H
N N
OH HO
N N N N
C6 H5 H5 C6 C6 H5
[Note: Certain compounds show geometrical as well as optical isomerism such type of isomerism is known as geometrical
enantiomerism.]
Distinction between cis and trans isomers. Distinction between cis and trans isomers of a compound can be made on
the basis of their physical properties such as melting point, boiling point, solubility, dipole moment etc.
ISOMERISM BY NKB.CO.IN 6
(i) Melting point: In general, the melting point of a trans isomer is higher than that of the corresponding cis isomer. This is
due to the reason that the molecules of a trans isomer are more symmetrical and hence fit more closely in the crystal
lattice as compared to the molecules of a cis isomer.
H H H COOH
Cl Cl Cl H
1.85 0
H H H5 C2 OOC H
2.54 D 2.38 D
(iv) Stability: The trans isomer is more stable than cis isomer due to steric hindrance. Intermolecular reactions occur
easily when reacting groups are close together. Hence, the cis isomer will form cyclic derivatives more readily as
against trans derivatives. But this reaction will take place in only those cis isomers in which the substituents on two
double bonded carbons are capable of intramolecular reaction with each other.
H COOH H
CO
150 C
O
H COOH H CO
Maleic anhydride
H COOH
150 C
No product
HOOC H
Fumaric acid forms anhydride via the formation of maleic acid because at high temperature fumaric acid converts into
maleic acid
Maleic acid Maleic anhydride
Fumaric acid
(v) Action of heat: On strong heating cis and trans isomers are interconvertible. This interconversion takes place as
follows,
a b a b a b a b a b
Ho mo lytic
bond fission
a b a b b a a b b a
(I)
Thus, cis isomer trans isomer.
(vi) Different chemical properties: Syn addition to alkene makes cis form into meso and trans into d and l. Anti addition
makes cis into dl and trans into meso.
Number of geometrical isomer in polyenes. (a) When compound has n double bonds and ending groups of a polyene
are different, the number of geometrical isomers = 2n.
C6H5 CH = CH CH = CH CH = CH CH = CH Cl
Since, the number of double bonds is four and two ends are different, one is C6H5 and other is Cl. Therefore, number of
geometrical isomers = 2n =24 = 16
(b) When the ending groups of polyene are same.
Case I: When number of double bonds is even then the number of geometrical isomers = 2n1 + 2n/21
Cl CH = CH CH = CH CH = CH CH = CH Cl
n = 4, even
No. of geometrical isomers = 2n1 + 2n/21
= 23 + 21 = 10
Case II: When number of double bond is odd then no. of geometrical isomer = 2n1 + 2(n+1)/2 1
C6H5 CH = CH CH = CH CH = CH C6H5
No. of geometrical isomers = 22 + 221 = 6
(E) and (Z) system of nomenclature. The simple cistrans nomenclature is not applicable when there are four different
substituent groups are present on two doubly bonded carbon atoms. In such cases, a more general system of
nomenclature of geometrical isomers has been proposed called the (E) and (Z) system. For naming the compounds by this
method, first the groups of highest priority on each carbon atom are identified by using sequence rules. If the highest
priority groups on two carbon atoms of the double bond are on the same side the configuration is Z (Zusammen in German
means same side) and if they are on opposite sides, the configuration is E (Entgegen in German means opposite). The
group/atom attached to carboncarbon bond is given higher rank, whose atomic weight is higher.
Higher priority
H I H I
Higher priority
Higher priority
Br Cl Cl Br
E bromochloroiodoethene Z bromochloroiodoethene
Exercise: Assign EZ configuration to each of the following:
ISOMERISM BY NKB.CO.IN 8
Br
(a) (b)
H H H3C
H3C
H3C
Br CH3 Cl H
(c) (d)
HO Br D
H3C
Optical Isomerism
Compounds which rotates the plane of polarized light are known as optically active compounds and the phenomenon is
known as optical activity. If a substance rotates the plane of polarized light in clockwise direction then it is dextrorotatory,
(+) form or (d) form. If a substance rotates the plane of polarized light in anti-clockwise direction then it is laevorotatory, (-)
form or ( ) form. (d) form and ( ) form can only be known by the use of polarimeter and not by the configuration of the
compound.
Specific rotation. The specific rotation of an optically active substance is defined as the degree of rotation observed
when the plane polarized light is passed through a tube having a path length of 1 decimetre (10 cm) and a concentration of
1 g/mole of the compound at a specified temperature and wavelength. It is denoted by [ ]Dt where t is the temperature and
D is the wavelength of light used.
The specific rotation is calculated as
observed angle of rotation()
Dt =
LC
where, L = length of polarimeter tube
C = conc. of the substance
Chirality and asymmetric carbon. A molecule (or an object) is said to be chiral or dissymmetric, if it is not
superimposable on its mirror image and the property of non-superimposability is called chirality. On the other hand, a
molecule (or an object) which is superimposable on its mirror image is called achiral (non-dissymmetric or unsymmetric).
Example: Alphabet P is chiral and A is achiral.
Mirror Mirror
Thus, for a substance to be optically active, it must be non-superimposable on its minor image.
Chiral carbon atom (chiral centre/stereo centre). Carbon atom bonded to four different atoms or groups is called an
asymmetric carbon atom or a chiral atom. A chiral atom is indicated by an asterisk (*). Example:
OH
H3C C
Chiral atom H
[Note: Isotopes of a particular atom behave as different groups in stereoisomerism.]
D H
35 37
H T Cl Cl
Br D
If a molecule contains only one chiral centre/atom, then the molecule has to be optically active (i.e. non-superimposable on
its mirror image) as it will not contain any element of symmetry. Molecules containing two or more chiral centres may or
may not be chiral (optically active).
It is necessary to distinguish chiral and chiral centre. The word chiral is used for molecule as a whole which is optically
active, whereas chiral centre is for an atom which is attached to form different atoms/groups.
ELEMENTS OF SYMMETRY
The types of elements of symmetry are as follows,
1. Plane of symmetry
2. Centre of symmetry
3. Alternate axis of symmetry
Plane of symmetry. A molecule is said to possess a plane of symmetry if the atoms or groups on one side of the plane
forms the mirror image of those on the other side. In other words, a plane which bisects a molecule/object in two equal
halves.
Plane of symmetry
H3C CH3
H H
CH3 COOH
H H
H H
COOH CH3
Centre of symmetry
H OH
plane of symmetry
H OH
COOH
Although in mesotartaric acid there are two chiral centres, yet the molecule is optically inactive because it contains plane of
symmetry, i.e. presence or absence of symmetries in the molecule can be known by the configuration of the molecule and
not by its structure.
Enantiomers
Optical isomers which are non-superimposable mirror images of each other are called enantiomers. The enantiomers have
identical physical and chemical properties but rotate the plane of polarized light in opposite directions but to some extent.
Mirror
CH3 CH3
H H
HO COOH HOOC OH
Enantiomers of lactic acid
Diastereomers
The stereoisomers which are not mirror images of each other are called diastereomers. The properties of diastereomers
are different from those of enantiomers (which are mirror images of each other). Example: Stereoisomerism in 2, 3-
dibromopentane.
H H
H3C C2 H5
Br Br
n 2
No. of optical isomers possible = 2 = 2 = 4
Mirror Mirror
CH3 CH3 CH3 CH3
H Br Br H H Br Br H
H Br Br H Br H H Br
Meso Compound
An optically inactive compound whose molecule is superimposable on its mirror image inspite of the presence of chiral
carbon atoms is called a meso compound. Example: In Tartaric acid.
HOOC CHOH CHOH COOH
The molecule contains two chiral carbon and the number of optical isomers should be 2n = 22 =4 but number of optical
isomer is reduced to 3 because one molecule has a plane of symmetry.
The stereoisomers of tartaric acid are,
Mirror Mirror
COOH COOH COOH COOH
H OH HO H H OH HO H
HO H H OH H OH HO H
Number of
Number of meso Number of Total number
optical active
S. No. Compounds forms racemic mixture of optical
forms
(m) (a/2) isomers
(a)
The molecule has
1. no symmetry 2n 0 2n1 a+m
Case1:
When compound
(a) 2n1 2n/21 2n1/2 a+m
has even number of
chiral carbon atom
Case2:
When compound 2n1
(b) 2n12(n1)/2 2n1/2
has odd number of
carbon atoms
Example:
(i) H5 C6 CHOH CHOH CHOH CH3
Number of optically active forms = a = 23 = 8
(ii)
HOOC CHOH CHOH COOH
External compensation. If two enantiomers are mixed together in equimolar amount, then the mixture becomes optically
inactive. The rotation caused by one enantiomer is exactly cancelled by other enantiomers and is due to external
compensation. The resulting optically inactive mixture is called racemic mixture. Example: Equimolar amount of d and l
form of tartaric acid.
Resolution
The process by which a racemic mixture can be separated into its (d) and ( ) enantiomers is called resolution.
The racemic mixture can be resolved by following methods namely:
(i) Mechanical separation.
(ii) Biochemical method. Example: Penicillium glaucum added to racemic tartaric acid consumes only (+) tartaric acid
leaving behind (-) tartaric acid.
(iii) Chemical method
NOMENCLATURE
The arrangement of atoms or group of atoms which characterizes a particular stereoisomer is called its configuration.
The two terms which are commonly used to describe the configuration of different stereoisomers are absolute and relative
configuration. By absolute configuration we mean the actual arrangement of atoms or groups of atoms in space of a
particular stereoisomer of a compound.
The relative configuration means the arrangement of atoms or group of atoms in space of stereoisomer of compound
relative to the atoms or group of atoms of another compound chosen as arbitrary standard.
D, L nomenclature or D, L system
Before 1951, there was no method available for determining the absolute configuration of a compound so, the relative
configuration were established with respect to glyceraldehyde chosen as the arbitrary standard. The two enantiomers of
this compound were designated D and L symbols. In this system, all sugars whose Fischer projection formula shows the
OH group on the chiral carbon atom adjacent to the terminal CH2OH group on the right hand belong to the Dseries.
Example:
CHO
CHO H OH
HO H
H OH
H OH
H OH
HO
D(+) Glyceraldehyde CH2 OH
D(+) Glucose
Similarly, if OH is on the left hand side, then the sugar belongs to Lseries.
CHO
CHO HO H
H OH
HO H
HO H
HO H
HO
L(-) Glyceraldehyde CH2 OH
L(-) Glucose
It is important to mention here that there is relation between configuration and sign of rotation.
R, S nomenclature (absolute configuration)
The limitation of the (D, L) system have however been removed by an unambiguous system developed by R.S Cahn, C.K.
Ingold and V. Prelog. This system is called Cahn , Ingold, Prelog system or simply R, S system. R (from Latin rectus means
right) and (from Latin sinister means left). Any chiral carbon atom has either (R) configuration or (S) configuration. The
configuration is assigned by following steps:
Step 1: First a priority sequence is assigned to all groups attached to the carbon atom. The priority can be assigned by,
(i) If four atoms attached to chiral atom are different, priority depends upon atomic number. Atom with highest atomic
number gets highest priority and the one with lowest atomic number is the lowest priority by assigning number 1, 2, 3
and 4.
(ii) If two or more than two isotopes of the same element is present, the isotope of higher mass gets the highest priority.
(iii) If two or more of the atoms directly bonded to the chiral atoms are identical, the atomic numbers of the next atoms are
used for priority assignment. If these atoms also have identical atoms attached to them, priority is determined at first
ISOMERISM BY NKB.CO.IN 14
point of difference along the chain. The atom which has been attached to an atom of highest priority has the higher
priority.
(iv) If a double bond or triple bond is linked to a chiral centre the involved atoms are duplicated or triplicated respectively.
O
O O
N N
N
O
O
OH OH
C C
CH C C H
C C
Step 2: The molecule is then visualized so that the group of lowest priority (4) is directed away from us (i.e. the lowest
priority at the bottom of the plane). If on going from group of highest priority to the second and then to third, i.e.
(1) (2) (3), the eye moves in clockwise direction, then the configuration is specified as R and if in
anti-clockwise direction it is specified as S. Example:
(1) (1)
Br Br
H H
(4)
Cl CH3 H3C Cl (4)
(3) (3)
(2) (2)
(2) (2)
Cl Cl
(1) (1)
H3C Br Br CH3
(3) (3)
H H
Anti -clockwise S Clockwise R
SOLVED EXAMPLES
SECTION A
Sol. CH2 , H C
H3C 3 CH3
(A). , H2C
CH
C CH3 , CH3 ,
H2C
CH3 , CH2 ,
3. The number of isomers for the aromatic compound having molecular formula C7H8O is
(A) 2 (B) 3
(C) 4 (D) 5
, ,
Sol. (D).
Sol. (A). Cl
CH3
Cl2 CH3
H3C h H3C Cl
H3C
H Br H3C Br
H3C Cl H3C Cl
(C) (D)
C C C C
H3C Br H3C Cl
Sol. (B).
O OH
8. N N
H
(A) (B)
Sol. (B).
H3C H CH3
CH3
(A) optical isomerism (B) geometrical isomerism
(C) optical and geometrical isomerism (D) tautomerism
Sol. (C). It contains chiral centre as well as different groups about the double bond.
Sol. (D).
H3C H
H
H3C
H3C
11. The following compound can exhibit COOH
Sol. (D).
H3C CH3
NO 2 COOH
(C) (D) (CH3)2CHCOOH
NO 2 NO 2
Br Me H Me Me H Br H
OH Et Et OH Et Me OH Et
Me Me OH Me
(I) (II) (III (IV)
(A) I and II ) (B) II and III
(C) I and IV (D) I and III
Sol. (D).
is
Br
(A) 2 (B) 3
(C) 1 (D) 4
ISOMERISM BY NKB.CO.IN 18
Sol. (A). Br
Br
16. Out of the following compounds, which one would have a zero dipole moment?
(A) 1, 1-dichloroethylene (B) cis-1, 2-dichloroethylene
(C) trans-1, 2-dichloroethylene (D) None of the above [IIT 1987]
Sol. (C).
17. Which of the following hydrocarbon has the lowest dipole moment?
H3C CH3
(A) (B) H3C CH3
H H
CH2 CH
(C) H3 C (D)
H2C [IIT2002]
(A) (B) O O
OH
O O
(C) (D)
O O
(A) 1, 2, 3 (B) 1, 3, 4
(C) 1, 2, 4 (D) 1, 2, 3, 4 [IIT 1998]
Sol. (B).
Sol. (D).
Sol. (A).
22. Which of the following have asymmetric carbon atoms?
1. ClCH2 CH2 Br 2. CH3 CHCl2
3. CH3 CH DCl 4. CH2 Br CHOH CH3
(A) 1, 2, 3 (B) 1, 3, 4
(C) 2, 3 (D) 3, 4 [IIT 1989]
Sol. (D).
Sol. (A).
Sol. (C).
25. The number of possible enantiomeric pairs that can be produced during monochlorination of 2-methyl butane is
(A) 2 (B) 3
(C) 4 (D) 1 [IIT 1997]
Sol. (D).
H OH H OH H OH
is
H OH H OH HO H
COOH COOCH3 COOCH3
(A) (B) (C)
(A) A and B are identical (B) A and B are diastereomers
(C) A and C are enantiomers (D) A and B are enantiomers [IIT 1997]
27. How many optically active stereoisomers are possible for Butane -2,3-diol?
(A) 1 (B) 2
(C) 3 (D) 4 [IIT 1997]
Sol. (C).
28. The optically active tartaric acid is named as D (+) tartaric acid because it has a positive
(A) optical rotation and is derived from D - glucose
(B) pH in an organic solvent
(C) optical rotation and is derived from D (+) glyceraldehyde
(D) optical rotation only when substituted by deuterium [IIT 1999]
Sol. (C).
30. An enantiomerically pure acid is treated with racemic mixture of an alcohol having one chiral carbon. The ester formed
will be
(A) optically active mixture (B) pure enantiomer
(C) meso compound (D) racemic mixture [IIT-2003]
Sol. (D).
Fill in the Blanks
O O
H
6. Geometrical isomerism is due to rotation of bond.
(restricted, double)
7. cannot be resolved into d and l form.
(meso form)
8. E and Z system of naming geometrical isomers is based on rules.
(sequence)
9. Fisher projection is a representation of the three dimensional structure.
(planar)
10. Amongst the three isomer of nitrophenol, the one that is least soluble in water is .
(o-nitrophenol)
Short Answer Type Questions
Prob.1. Write all possible structural isomers of the compound with molecular formula C4H10O.
Prob.2. Write structural formula of all the isomeric alcohols having the molecular formula C4H10O.
CH3
Sol. (A) H3C OH (B) OH
H3C
CH3 CH3
Prob.3. Write all possible isomers of the compound having molecular formula C3H8O.
CH3
CH3
Sol. (A) H3C (B) H3C O
OH
OH
(C) H3C
Prob.4. How many isomers are possible with the formula C2ClBrFI?
Br I Br F F Br F I
(Z) (E) (Z) (E)
Cl F Cl Br
I Br I F
(Z) (E)
Prob.5. Identify the pairs of enantiomers and diastereomers from the following compounds I, II and III.
ISOMERISM BY NKB.CO.IN 22
H OH HO H HO H
HO H H OH HO H
CH3 CH3 CH3
(I) (III) (II)
Prob.6. What is the relation between following pairs of structure, indicate whether they are identical or enantiomers?
(a) O O
and
OH OH
(b) H H
and
Prob.7. What do you think about the following compounds optically active or not? Support your answer.
Cl CH3 CH3
(a) (b)
C HO H
Cl H
HO H
CH3
H CH3
Cl
(c) (d)
C
Cl H
Sol. (a) It is optically inactive due to presence of two chlorine in same carbon.
(b) It has two chiral carbon atoms but due to plane of symmetry it is optically inactive.
(c) It has two chiral carbon and dont have any plane of symmetry, so it is optically active.
(d) There is no chiral carbon but the molecule is chiral (an allene), so it is optically active.
Prob.8. Calculate total number of optically active isomers of the compound COOH(CHOH)2COOH
Sol. When the molecule can be divided into two equal halves (i.e. has symmetry), number of asymmetric carbon atoms
is even, then
Number of optically active isomers, a = 2n 1
Number of meso forms, m = 2(n/2)1
Total number of optical isomers = a + m
Where n = number of chiral carbon atoms
Here n = 2 a = 2 , m = 1
Total optical isomers = 2+1=3
Prob.9. How many total stereoisomers are possible for butane -2, 3-diol and how many of them are optically active?
2, 3- dihydroxybutane
CH3 CH3 CH3
H OH H OH HO H
H OH HO H H OH
Prob.10.Write down the structures of the stereoisomers formed when cis 2 butene is reacted with bromine.
[IIT-JEE-1995]
Sol. The addition of bromine to cis 2-butene involves anti-addition and thus racemic 2, 3-dirbromo butane is formed.
CH3 CH3
H3C CH3
H Br Br Br
Br2 anti
addition
H H Br H H Br
2-butene (cis) CH3 CH3
ISOMERISM BY NKB.CO.IN 24
Sol. False
7. The arrangement in space of the atoms or groups that characterizes a stereoisomer is called its configuration.
Sol. True
8. Diastereomers have different physical properties and similar but not identical chemical properties.
Sol. True
Sol. True
Sol. True
SECTION B
Subjective Problems
O
O
(b) H COOH
HOOC H
H3C
O O
or
O
CH3
O
O O
Prob.3. What are the possible types of compounds that can have a molecular formula C3H6O?
Sol. O
II O
C2 H5 - CHO, CH3 - C- CH3 , CH 2 = CH - CH 2 - OH, CH 2 = CH - O - CH3 , CH3 etc.
Prob.4. Write the structure of a tautomeric isomer for each of the following compound:
HO O HO
(a) (b)
H2C CH2
H
N O
(c)
HO OH O O O
Sol. (a) (b)
H3C CH2
ISOMERISM BY NKB.CO.IN 26
N OH
(c)
CH3
2-methylbut-2-ene H3C
(c) CH3
Sol. (a) E (b) Not possible (c) Z (d) E (e) Not possible
Prob.6. C4H8 can have so many isomers. Write their structures. What are different tests to make distinction between them?
CH3CH CH3COH
+ alkaline KMnO4
CH3CH CH3COH
cis 2-butene H
Meso-isomer
H
CH3CH CH3COH
+ alkaline KMnO4
HCCH3 HOCCH3
trans 2-butene H
d-and l-butane-2,3-diol
O O OH O O OH
Prob.7.
Sol. O O O OH OH O
(I) (II)
(II) will be favoured because it is more stable due to extended conjugation than (I).
Prob.8. For each of the following addition, predict the regiochemistry of each adduct and determine whether the product
mixture is optically active. If not, determine whether the inactivity results from the absence of chiral centre; the
formation of equal amounts of enantiomers or formation of a meso compound.
CH3
(a)
DCI
(b)
HBr
CH3
+
(c)
DO
3 (d)
Br2
CH3
Cl
Br
Sol. (a) (b)
D
chiral
a chiral
CH3
OD
Br
(c) (d) and enantiomer
H
D
chiral Br
(racemic)
Prob.9. For each of the following reactions, predict whether the desired stereochemistry and regiochemistry can be
attained with the acid-catalysed hydration, hydroboration-oxidation, or not at all.
ISOMERISM BY NKB.CO.IN 28
CH3 OH CH3
CH3
CH3
(a) (b)
OH
CH3 H3C H3C
(c) (d) CH2
H3C H3C OH
OH
(i) (ii) HO OH
C 6 H5 H
Prob.13. In the following compounds, identify those that are optically active and meso compound.
Br Br
(a) (b)
Br Br
OH OH Et OH
(c) H H (d) H H
Me Me OH Et
H3C H3C Ph H
H OH O H5 C2
( ) ( )
Ph H
COOH C2 H5 Ph
( ) ( ) H3C CH3
(Racemic mixture) O
H H
O H5 C2
() ( )
The bonds attached to the chiral carbon in both the molecules are not broken during the esterification reaction. (+)
acid reacts with (+) alcohol to give an (++) ester while () acid reacts with (+) alcohol to give (+ ) ester. These
two esters are diastereoisomers.
Prob.15. The structure of D-Glucose is as follows:
CHO
(a) Draw the structure of L-Glucose.
H OH (b) Give the reaction of L-Glucose with Tollens reagent.
HO H
H OH
H OH
HO
Sol. -
O O
CHO
H OH H OH
HO H
HO H
Ag( NH3 ) 2
H OH H OH
HO H HO H
HO HO
L-Glucose
ISOMERISM BY NKB.CO.IN 30
ASSIGNMENT PROBLEMS
SECTION A
1. The maximum number of cyclic isomers possible for the compound having molecular formula C4H8O is
(A) 8 (B) 6
(C) 7 (D) 5
O O
(C) (D)
O O
H3C OCH3 H
(C) (D )
O O NH
(A) C (B)
N
HO
HO
(C) O (D) O
HO
(C) O O (D)
O O
7. O O O
8. CH3CHOHCHClBr have
(A) 2 optical isomers (B) 2 geometrical isomers
(C) 4 optical isomers (D) none of the above
13. The total number of isomeric optically active monochloro isopentane is:
(A) two (B) three
(C) four (D) one
14. Isopentane, (CH3)2CH.CH2.CH3 can form four isomeric monochloro derivatives. How many of these are optically active?
(A) 1 (B) 2
(C) 3 (D) 4
15. Each of the following compound is expected to be optically active except
H
(B) H3 C CH CH CH CHO
(A) HO COOH
OH
CH3
(C) methyl-2-methyl propanoate (D) methyl-2-chloro propanoate
ISOMERISM BY NKB.CO.IN 32
16. Configurations:
Me COOEt
H Br H Br
Br H and Br H
COOEt Me
I II
(A) represent same compound
(B) represent two different molecules which are mirror-images of one another
(C) represent two different molecules which are diastereomeric pair
(D) represent two different molecules whose equimolecular mixture will be racemic
17. A compound contains two dissimilar asymmetric carbon atoms. The numbers of possible stereoisomers are
(A) 2 (B) 3
(C) 4 (D) 5
(A) C (B) C
H H H H
H H
H3C H3C
(C) (D)
H3C H3C
CH3 CH3
H Cl Cl
(A) Cl H (B) H H
Br H Br H
H H
(C) H Br
(D) H Br
Br Br
Fill in the Blanks
10. An organic compound with molecular formula C2H5NO contains doubly linked atoms, it shows . and
......................isomerism.
1. Write the structural formula of all the isomers having molecular formula C5H12.
3. Explain that enol form of acetoacetic ester is said to be more volatile than keto form.
7. Why does 2-butene exhibit cistrans isomerism but 2-butyne does not?
H COOH HOOC H
10. What is the relation between the members of the following pairs of structures? Are they identical, structural isomers,
geometrical isomers or resonance contributors?
ISOMERISM BY NKB.CO.IN 34
H H3C
N N
(a)
H3C CH3 H CH3
-
O O
(b)
-
H3C O H3C O
8. A molecule containing only one chiral centre always exhibit optical activity.
Subjective Problems
3. Write the structure of a tautomeric isomer for each of the following compound:
O
H3C O
(a) CH3 (b)
H3C H
O
(c) O
H3C CH3
hexa-1,4-diene
(b)
Stilbene
(c)
Stilbene
5. O O
O O
(I) (II)
enol percentage, I > II
ISOMERISM BY NKB.CO.IN 36
Enol form of I is more stabilized due to resonance, hence have higher percentage than enol form of II at equilibrium.
In enol form there are greater numbers of resonating structures and hydrogen bonding also exists, so enol form is more
stable than keto form.
7. In each of the following molecules, indicate the presence of a centre of chirality with an asterisk (*).
Br Br
Cl
(a) (b)
CH3
H Cl
(c) (d) H H
Br Br
CH3
Cl
(e)
H3C
CH3
8. For each of the following pairs of structures, identify the relation between them. Are they enantiomers, diastereomers,
geometrical isomers or same structures?
CH3 H3C
(a) (b) H H HO OH
HO OH H H
CH3 H3C
H3C CH3
(c) HO H H OH (d)
H OH HO H H3C CH3 H3C CH3
H3C CH3
CH3 H3C
(e) (f)
H3C CH3
H3C CH3 H3C CH3
H3C
H2C
CH3
10. C4H8O2 (A) reacts with Na but does not give colour with neutral FeCl3. (A) by iodoform test is converted into iodoform
and sodium salt of dibasic acid (B). (B) can decolourize KMnO4 and gives white ppt. with CaCl2 solution in acetic acid.
Identify (A) and (B) write all isomers of A.
11. Optically active 2-iodobutane on treatment with NaI in acetone gives a product which does not show optical activity.
Explain briefly.
12. Explain that -methyl acetyl acetone undergoes enolization to a smaller extent than acetyl acetone.
14. How many asymmetric carbon atoms are created during the complete reduction of benzyl, (PhCOCOPh) with LiAlH4?
Also write the number of possible stereoisomers of the product.
15. C4H8 has 4 isomers, A, B, C and D. A, B, C decolourizes Br2 water but D doest not. A give optically inactive meso form,
while B forms optically inactive mixture in equal amounts. Identify A, B, C and D.
ISOMERISM BY NKB.CO.IN 38
SECTION A
1. CH3
H3C
H3C CH3 , CH3 , H3C CH3
pentane CH3 CH3
isopentane neopentane
3. Due to intramolecular H-bonding in enolic form which reduce the intermolecular association and lowers the boiling
point.
4. (i) E (ii) Z
5. COOH COOH
H OH HO H
CH3 CH3
It shows optical isomerism
In lactic acid number of chiral carbon = 1
Total number of optical isomers = 21 = 2
C=C=C
H
H3C
Thick bonds represent the bonds coming towards the viewer while the thinner represent the bonds going away from the
viewer. Thus, mirror image of this compound is not superimposable.
H
H CH3 H3C
C=C=C C=C=C
H H
CH3
H3C
Thus, compound is optically active and one is (+) isomer and other is () isomer. They are not interconvertible because
of restricted rotation about a double bond.
7. 2-butene has two dissimilar groups attached to each unsaturated carbon, 2-butyne is linear so it cannot have
geometrical isomer.
9. (i) S (ii) R
1. True
2. False, inorganic molecule can also show optical activity.
3. False
4. False, 2 chiral atoms.
5. False, e.g. allenes.
6. False
7. True
8. True
9. True
10. False, only two but has three configurations (d, l and meso form)
Subjective Problems
O
O
H3C CH3 O
1. (a) (i) (ii)
O H3C CH3
ISOMERISM BY NKB.CO.IN 40
O O O O CH3
CH3
(iii) (iv)
H H CH3
H H3C H
(iii)
H3C CH3
CH3 CH3
2. (a) (i) OH (ii) OH
H2C H3C
CH3
(iii) OH (iv)
OH
(b) OH
CH2
H3C OH
3. (a) OH (b)
H3C CH3
(c) None
4. (a) E at C4
(b) E
(c) Z
5. COOH COOH
HO C H H C H
CH3 CH3
Non-superimposable
Hence enantiomers
H H H H H Cl Cl H
6. (a)
Cl Cl Cl Cl Cl H H Cl
Same structure enantiomers
Cl Cl
H H
(b) H H
Cl Cl
No chiral centre
Br
Cl
7. (a) Achiral (b)
H Cl
Br Br
Cl
(e) CH3
H3C
8. (a) Identical, (b) Same structure, (c) enantiomer, (d) Structural, (e) same structure, (f) geometrical (Z,Z) and
(Z,E), (g) geometrical (Z.Z) and (E,E), (h) cis and trans (Z and E) at C3, (i) diastereomers,
(j) diastereomers, (k) diastereomers and (l) enantiomers.
9. (a) H Br Br H H Br (b)
CH3 CH3 CH3
OH O
O Na O
10. A = B=
O Na
CaCl2
ACOH
CaC2 O4
white ppt.
CH3 CH3 OH
11. The breaking and reforming of C I bonds occur. This results into two enantiomers, which forms racemic mixture and
does not show optical activity due to external compensation.
CH3 CH3 CH3
(I) I
H I H I I H
(II) I
12. H
O O O O
Enolization (smaller
due to higher strain)
H COOH H COOH
14. O O OH OH
The reaction is
LiAlH 4
Ph Ph
Ph Ph
Ph H
Two asymmetric carbons are created on complete reduction of benzil. Therefore, these stereoisomers are meso, d and
l.