5th Sem B.Sc., Paper-5; Org Chemistry; 1.StereoIsomerism; 8 Hrs.

18-20 Marks Jan 2021

Optical Isomerism Elements of symmetry (Test indicators for

Elements of symmetry chirality)
Plane of symmetry: 2,3-dichrolobutane, tartaric acid,
Center of symmetry: 2,4-dimethyl-1,3-cyclobutanedioic acid, The ultimate test for molecular chirality is to construct
Axis of symmetry: 1,2,3,4-tetramethylcyclobutane.
models of a molecule and its mirror-image and then
Chiral molecules & Achiral molecules (2-chloropropanol, 3-
chloropentane). Chirality, stereogenic center (e.g.: lactic acid, tartaric acid physically see whether the two are superimposible. If
and 2,3-dichlorobutane). not, the molecule is chiral.
Fischer Projection Formulae (lactic acid, 2-chlorobutane, tartaric acid Certain features related to molecular symmetry enable
& 2,3-dichlorobutane). us to recognize whether a molecule is chiral or
Optical isomerism due to free rotation about single bonds:
Enantiomers, optical activity (conditions for optically active compounds); achiral. These are
Absolute configuration of enantiomers (use of +/–, d/l, D/L 1) A plane of Symmetry
notations (e.g.: glyceraldehyde and lactic acid).
Cahn-Ingold-Prelog sequence rules (R & S system) of nomenclature 2) A centre of Symmetry and
with suitable examples. 3) An (alternating) Axis of Symmetry.
Properties of enantiomers.
Meso compounds: Explanation with examples of tartaric acid and 2,3- If a molecule possesses any of these elements of
dichlorobutane. symmetry, it is considered to be symmetric or achiral.
Diastereomers: Explanation with examples of tartaric acid,
2-bromo-3-chlorobutane) & properties. 1) Plane of symmetry (mirror plane): It is a plane,
Relative Configuration of Threo & Erythro nomenclature (using above
examples).
which divides a molecule into two equal halves that
Racemisation: Definition and explanation using lactic acid as an are mirror images of each other.
example. Seeking a plane of symmetry is usually a quick method
Resolution of racemic mixture: definition, explanation of resolution of of deciding whether a molecule is chiral or achiral.
racemic mixture of tartaric acid by chemical method & biochemical
method.
e.g. Meso 2,3-dichorobutane and Meso tartaric acid
Optical isomerism due to restricted rotation about single bonds- contain plane of symmetry, the upper half of the
diphenyl systems: Explanation using 6,6’-dinitrodiphenic acid as an molecule is a mirror image of the lower half.
example. COOH CH3
HO C H Plane of Cl C H
Symmetry
STEREOISOMERISM: Compounds having the HO C H Cl C H
same molecular formula and same structural formula COOH CH3
but differ in the arrangement of atoms or groups in If a molecule has a plane of symmetry, it is achiral
space are called as stereoisomers, and the 2)Center of symmetry: is an imaginary point in the
phenomenon is called Stereoisomerism. molecule. If a line is drawn
CH3 COOH
from an atom or a group to this
Configuration: The arrangement of atoms or groups imaginary point and then H H H H
in space is called Configuration. Hence stereoisomers extended to an equal distance
are also called as Configurational isomers. beyond the point, it meets the COOH CH3
Centre of Symmetry
Stereoisomerism is of two types: mirror image of the atom or
1) Optical isomerism group.
2) Geometrical isomerism. e.g., 2,4-dimethyl-1,3-cyclobutanedioic acid, has a
center of symmetry and therefore optically inactive.
Optical Isomerism: Compounds having the same
molecular formula and same structural formula but 3)Alternating axis of symmetry: This is an axis
differ in the direction of rotating the plane polarized through the centre of the molecule about which if the
light are called optical isomers and the phenomenon molecule is rotated, will lead to the identical position
is known as Optical isomerism. in space more than once in a complete 360º turn.
The property of the compounds rotating the plane e.g.: 1,2,3,4-tetramethylcyclobutane, has 4-fold
polarized light is called optical activity. alternating axes of symmetry. Rotation of form (a)
through 90 about axis AB gives (b) and reflection of
The isomer that rotates the plane of polarized light to (b) gives (a)
the right (clockwise direction) is known as e.g.: Benzene has 6-fold axes of symmetry, and
dextrorotatory (Latin dexter = right) (d)-isomer or requires a 60º rotation to present an identical position.
(+)-isomer, and the one which rotates the plane of A
A

CH3 H H CH3
polarized light to the left (anticlockwise direction) is
Rotated
known as the laevorotatory (Latin laevus = left). (l)- H
H
CH3 CH3 CH3
CH3
H
H
through 90o
isomer or (-)-isomer.
CH3 H H CH3

B B

Form (a) Form ( b)

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Stereochemistry of compounds with ONE

Note: A molecule lacking any of the above stereogenic centre
symmetry elements is likely to be chiral. *
LACTIC ACID: is CH3CHOHCOOH. It contains
To be certain however, we must confirm that the
*
molecule and its mirror image are not superimposible. one asymmetric C. Two enantiomeric forms are given
below in the Fischer Projection Formula (d)-lactic
Chiral carbon: A tetrahedral carbon acid and (l)-lactic acid are enantiomers.
atom, which is attached to four different d
atoms or groups, is called as chiral In this isomers d- or (+)-lactic acid that rotates the
carbon or chirality centre or chiral C* b
a plane of polarized light to the right (clockwise
centre or asymmetric carbon or e direction) and l- or (-)-lactic acid rotates the plane of
stereocentre. Asymmetric carbon atom polarized light to the left (anticlockwise direction)
is indicated by an asterisk (*).
If n is the number of asymmetric carbon atoms in a Racemic Mixture (racemate): (dl)-lactic acid or ()-
molecule, then possible number of stereoisomers are 2n. lactic acid. It is the equimolar mixture of
COOH COOH
The presence of one asymmetric carbon atom (C*) in
the molecule of a simple organic compound causes H OH HO H
molecular dissymmetry, i.e., the molecule cannot be
divided into two equal halves and their mirror images CH 3 CH 3
are non-superimposable. Such molecules are called d-(-) lactic acid l-(-) lactic acid
Chiral Molecules and show optical activity. enantiomers [(d)-form and (l)-form]. e.g. (dl)-lactic
acid or ()-lactic acid. In this the optical rotatory
Chiral Molecule: molecules that are non- powers of two isomers are equal in magnitude but
superimposable on their mirror image are called Chiral opposite in direction. Therefore, racemic mixture of
Molecules lactic acid will not rotate the plane of polarized light at
Achiral Molecule: molecules that are superimposable all and it is said to be optically inactive due to
on their mirror image are called Achiral Molecules External compensation
Cl Cl

CH3 C* CH2OH CH3 CH2 C CH2 CH3

Physical Properties of Lactic acid
Enantiomers m.p.ºC Density Specific
H H Rotation
2-Chloropropanol 3-Chloropentane 1 (+)-lactic acid 26 1.248 +2.24º
Chiral Achiral 2 (-)-lactic acid 26 1.248 -2.24º
Compounds having two or more chirality centers will
stereochemistry of compounds with TWO
be optically active if they do not have
stereogenic centre
1. a plane of symmetry
2. a centre of symmetry. TARTARIC ACID: 2,3-dihydroxybutanedioic acid,
Molecules with more than one chiral centre may or known as tartaric acid. It has two chirality centers that
may not be chiral. e.g. meso tartaric acid it contains are equivalent (have the same four substituents). As a
plane of symmetry, so it is achiral molecule even result, two of its four possible stereoisomers are
though it contains two chiral centres and it is optically identical due to a plane of symmetry, so it has only
inactive. three stereoisomers. Two of these stereoisomers are
enantiomers and the third is an achiral molecule,
Enantiomers: Enantiomers d
Mirror d called a meso compound.
are stereoisomers whose
molecules are non- C* C* Meso isomer: It is a stereoisomer with 2 or more
b b
superimposable mirror a a chirality centers and contains an internal plane of
e e
images of each other. symmetry. It is an achiral molecule and optically
inactive. Its optical inactivity is due to Internal
Enantiomers have same physical and chemical compensation that is positive rotation by the upper
properties (except towards optically active reagents) half the molecule cancels out negative rotation by the
but differ in the direction of rotating the plane lower half the molecule. e.g.
polarised light. meso- tartaric acid, meso-2,3-dichlorobutane

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In the following examples I & II are mirror images 3 these can not be separated these can be separated by
hence they are enantiomers III and IV are same by physical methods like physical methods like
forms and it is a meso isomer. fractional distillation, fractional distillation,
fractional crystallization etc. fractional crystallization etc.
Diastereomers: are the stereoisomers which are not 4 they have rotation in the they may have rotation in the
mirror images of each other. opposite direction but to same direction but to
different extent. different extent.
Meso and any one of enantiomer are not mirror images
of each other they are Diastereomers D and L notation (Relative Configuration):
I & III or I & IV are NOT mirror images hence they
are diastereomers and also II & III or II & IV are D and L configuration is assigned to the optical
diastereomers isomers by relating the configuration of
Tartaric acid Glyceraldehyde. On the asymmetric carbon atom (C*)
Mirror
COOH COOH COOH COOH of (+)-Glyceraldehyde, –OH group is present on right
HO C H H C OH H C OH HO C H Plane of
side, it is called as D-Glyceraldehyde and in ()-
H C OH HO C H H C OH HO C H Symmetr Glyceraldehyde –OH group is present on left side, it is
y called L-Glyceraldehyde. D and L does not mean
COOH COOH COOH COOH
(+)-tartaric acid (-)-tartaric acid meso-tartaric acid
dextrorotatory and laevorotatory i.e. D and L does
I II III IV not indicate the direction of rotation of plane polarized
Nonsuperimposable Superimposable
light
Enantiomers meso Isomer Mirror Mirror
CHO CHO COOH COOH
2,3-dichlorobutane
Mirror * * * *
H C OH HO C H H C OH HO C H
CH3 CH3 CH3 CH3
CH2OH CH2OH CH3 CH3
Cl C H H C Cl H C Cl Cl C H Plane of
D-glyceraldehyde L-glyceraldehyde D-(-)-Lactic acid L-(+)-Lactic acid
H C Cl Cl C H H C Cl Cl C H Symmetr
-OH on right side -OH on left side -OH on right side -OH on left side
y
CH3 CH3 CH3 CH3
(+)-isomer (-)-(+)-isomer meso-form Fischer extended this system to other monosaccharides. If
I II III IV the chirality centre farthest from, carbonyl group had the
Nonsuperimposable
Enantiomers
Superimposable
meso Isomer
same configuration as D-Glyceraldehyde the
2-bromo-3-chlorobutane: has stereocenters at C2 compound was designated as D-sugar. On the other
and C3 . In general, a molecule with n stereocenters has hand if the chirality centre farthest from, carbonyl group
2n stereoisomers, so there are a total of four had the same configuration as L-Glyceraldehyde the
possibilities for 2-bromo-3-chlorobutane: compound was designated as L-sugar.
Mirror
Mirror
CH3 CH3 CH3 CH3 R-S Configuration (Absolute Configuration):
Br C H H C Br H C Br Br C H
Cahn, Ingold and Prelog suggested a simple
H C Cl Cl C H H C Cl Cl C H procedure to assign a particular configuration for an
CH3 CH3 CH3 CH3 optically active compound in terms of prefixes R and
Enantiomeric Pair Enantiomeric Pair S.
1. Identify the stereogenic center (commonly an sp3 C* with 4
different groups attached)
Diastereomers 2. Assign the priority (using Sequence Rules ) to each group
Each of the four stereoisomers of 2-bromo-3- (high = 1, low = 4) based on the atomic number of the atom
chlorobutane is chiral. There are two pairs of attached to the stereogenic center
enantiomers. Any given molecule has its enantiomer; 3. Position the lowest priority group away as if you were looking
the two other molecules are its diastereomers. along the C-(4) sigma bond. If you are using a model, grasp
the lowest priority group in your fist
Properties (or differences) of 4. For the other 3 groups, determine the direction of high to low
Enantiomers Diastereomers priority (1 to 3)
Enantiomers Diastereomers 5. If this is clockwise, then the it is given R configuration (Latin:
rectus = right)
1 these are stereoisomers that these are stereoisomers that
6. If this is counter clockwise, then it is S (Latin: sinister= left)
have mirror image do not have mirror image
relationship. relationship.
Sequence Priority Rule 1: The higher the atomic
2 have same physical have different physical number of an atom the higher the priority it is
properties. properties.
assigned.

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e.g. for typical non-metals ZX (Z = At. No)

encountered in organic compounds ... 2 2
C 2H5 C 2H5
X= 53I > 35Br > 17Cl > 16S > 15P> 8O > 7N > 6C > 1H 4 4
3 3
Rule 2: If the relative priority of two groups cannot be H H
CH3 H3C
decided by Rule 1, it shall be determined by applying 1
Cl Cl
1
Rule 1 to the next atom or sequence of atoms in the R-Configuration S-Configuration
group 'X'.
e.g. for typing groupings in organic molecules ERYTHRO & THREO Nomenclature
where X is more than one atom The terms Erythro and Threo are generally applied
X = -CH2CH2CH3 > -CH2CH3 > -CH3 > -H only to those molecules which do not have symmetric
i.e. the longer the hydrocarbon carbon chain ends. e.g. 2,3–dibromopentane & 3–chloro–2–butanol.
the higher its priority. When however, the ends are symmetric as e.g. in 2,3–
and a more varied situation where from 1-3 dibromobutane and tartaric acid the terms meso and dl
atoms in the X sequence must be considered are preferred.
.... X =
I > Br > Cl > CH2Br > CH2Cl > CH2-O-CH3 > CH2-O-H > Diastereomers are represented as erythro and
CH2CH2Br > CH2CH2Cl > CH2CH3 > CH3 > H threo in analogy with erythrose and threose. The
diastereomers in which the like (similar) groups are on
Example-1 bromochloroiodomethane the same side of the Ficsher projection is called
Erythro form whereas the diastereomers in which the
2 2
Br Br like (similar) groups are on the opposite side of the
4
3 3
4 Ficsher projection is called Threo form.
H H 2-bromo-3-chlorobutane
Cl Cl
1
I I
1
S-Configuration
CH3 CH3 CH3 CH3
R-Configuration
Bromochloroiodomethane Br C H H C Br H C Br Br C H
Example-2 Lactic acid H C Cl Cl C H H C Cl Cl C H
CH3 CH3 CH3 CH3
2 2
COOH COOH Threo Form Erythro Form
4 4 CH3 CH3 CH3 CH3
3 3
H H
CH3 H3C H C OH HO C H H C OH HO C H
1
HO OH
1 H C Cl Cl C H Cl C H H C Cl
R-Lactic acid L-Lactic acid CH3 CH3 CH3 CH3
Example-3 Glyceraldehyde: Erythro (3-chloro-2-butanol) Threo (3-chloro-2-butanol)

2 2
CHO CHO Optical activity of biphenyl Derivatives
4 4 Optical activity due to restricted rotation
3 3
H
CH2OH HOH2C
H conformational enantiomorphism
1
HO OH
1
R-Lactic acid L-Lactic acid Conditions for optical activity of biphenyl derivatives
 Neither ring should posses a plane of symmetry
Example-4 -Deutero ethyl bromide
perpendicular to the plane of the other ring .
 Substituents at the ortho-positions must big
2 2
CH3 CH3 enough to prevent free rotation about the carbon-
4 4 carbon bond joining the two rings.
3 3
H H
D D
1
Br Br Optical activity of Biphenyl derivatives: When
1

R-Configuration S-Configuration bulky substituents are present at ortho positions in

biphenyl, the free rotation about carbon-carbon bond
Example-5. sec butyl chloride: joining them is restricted. The two biphenyl rings are
present in plane perpendicular to each other. Neither
ring has a plane of symmetry, as a result of this two
different spatial arrangements are possible

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COOH COOH 2. A suitable microorganism may not available

COOH COOH for the separate of all enantiomers.
2 3 3 2
3 2 ' ' ' 1 2 3
4
1 1' 4 4 1
4
' ' ' 3. Chemical Methods: In this racemic mixture is
6 ' 6
5 6 5
6 5 treated with optically active substance to get a pair of
5
NO2 ' '
' ' NO2 diastereomers. Since diastereomers differ in physical
NO2 NO2
6,6'-Dinitro-2,2’-diphenic acid properties they can be separated by fractional
crystallization. Separated diastereomers are converted
The two isomers are mirror images of each other and back into respective enantiomers by chemical means.
are not superimposable .Therefore properly When (±) tartaric acid is treated with optically active
substituted biphenyl even though they do not contain base (-)B gives a mixture of two salts which are
chiral carbons, exhibit optical isomerism. diastereomers.
e.g.: 6,6'-Dinitro-2,2’-diphenic acid.
(±) A + (-)B (+)A(-)B + (-)A(-)B
If any two substituents are identical then they become
achiral and hence do not exhibits optical activity. Resemic mixture Opt. active Mixture of
of Tartaric acid Base Diastereomeric
RACEMISATION: conversion of an optically active
enantiomer into the optically inactive racemic mixture. (-)B = base like (-)bruicine, (-)quinine, (-)Strychine or
This process involves conversion of half of the d-form (-)cinchonine can be used.
to l-form or vice versa the mixture obtained Diastereomeric salts when treated with dil. HCl,
METHODS: respective enantiomers of tartaric acid are obtained.
H+
1. Autoracemisation: It takes place when an (+)A(-)B (+)A(-)B (+)A + (-)B
optically active enantiomer is kept at room +
H+
temperature for sometime. (-)A (-)B (-)A (-)B (-)A + (-)B
2. By the action of heat: Racemisation takes place mixture of Separated Separated
Diastereomeric salt Salts Enantiomers
when optically active enantiomer is heated. When
(+)–tartaric acid is strongly heated with water it GEOMETRIC ISOMERISM IN ALKENES:
gets converted to a mixture of racemic and
mesotartaric acid. Definition, conditions & explanation e.g.; 2-butene & 1,2-dichloroethene.
Determination of configuration of geometric isomers: cis- & trans- by
3. By the action of chemical reagent: When a 1) Physical methods (melting and boiling points, dipole moments,
foreign substance is added to a solution of an solubility)
2) Spectroscopic methods (UV, IR)
optically active substance it yields racemic mixture 3) chemical methods (cyclisation method: e.g.;-maleic acid to maleic
e.g. Addition of sodium hydroxide to (+)- or (-)– anhydride,
lactic acid leads to the formation of racemic 4) pKa values: Ex Maleic and Fumaric acids).
mixture. E and Z system of nomenclature (Rules with suitable e.g).
GEOMETRIC ISOMERISM IN OXIMES:
RESOLUTION: Process of separating racemic
mixture into its enantiomers is known as resolution. Nomenclature of syn and anti isomers in oximes e.g.;- Benzaldoxime &
Acetophenone oxime.
Simple methods like fractional crystallization
distillation cannot be employed to separate them ALICYCLIC COMPOUNDS: Conformations of four to eight membered
cycloalkanes & disubstituted Cyclohexanes (1,2- ,1,3- & 1,4-
because enantiomers have identical physical and dimethylcyclohexanes as examples).
chemical properties so they are resolved as follows: Bicylic systems: cis & trans- nomenclature & conformations of Decalins
& Norbornane.
1. Mechanical method:
2. Biochemical method: In this method Geometrical or cis-trans isomerism: Compounds
microorganism which are highly specific in their having the same molecular formula and same
action are allowed to grow in dilute solution of structural formula but differ in the arrangement of
racemic mixture. The organism selectively atoms or groups about the double bonded carbon
metabolize one enantiomer leaving the other isomer in atoms are called Geometrical isomers and the
the solution in pure form. e.g. Penicillin glaucom phenomenon is called as Geometrical isomerism.
mould when allowed to grow in racemic mixture of
tartaric acid pure (-)-tartaric acid is separated out. Geometrical isomerism arises in alkenes due to the
Advantage: 1. easy to apply restricted rotation of Carbon-Carbon double bond.
2. pure isomer is obtained Conditions for a compound to exhibit Geometrical
Disadvantages: isomerism
1. One enantiomer is completely lost.
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a) Molecule should contain a carbon- a a (c) Melting points: The isomers show the reverse
carbon double bond. trend here. trans- isomers have higher melting
C C
b) Two atoms or groups attached to a b
b
points than the corresponding cis- isomers.
double bonded Carbon atom should Molecules with trans configuration can be closely
be different. (in Fig. a  b) packed in the crystalline state. Therefore more
energy is required to separate them during melting
Nomenclature of Geometrical isomerism: Isomer and hence they have higher melting points
containing similar groups on the same side of the
double bond is called cis isomer (Latin cis= same (d) Solubility: The solubility of the cis- isomer is
side). Isomer containing similar groups on the opposite usually more than that of the trans- isomer.
side of the double bond is called trans isomer (Latin (e) Density: The cis- isomers usually have greater
trans= across). Hence Geometrical isomerism is also densities than the corresponding trans- isomers.
called as cis-trans isomerism.
e.g.: But-2-ene and Butenedioic acid (HOOC-HC=CH- 2. SPECTROSCOPIC METHODS
COOH) [other e.g. (1) 1,2-dichloroethene, (2) Hex-2-ene Geometrical isomers can be distinguished from
(3) Hex-3-ene one another from their characteristic UV, IR and NMR
a a a b spectra.
C C C C
b b b a a) UV-Visible Spectroscopy: The absorption in
cis -isomer trans -isomer compounds containing conjugation is due to the 
i) But-2-ene (2-butene) transitions and that the
H H CH3 H longer is the
wavelength of the H H H
C C C C absorption (λmax) and
H
CH3 CH3 H CH3 larger is the molar
cis-isomer trans-isomer extinction coefficient
( max). It is seen that max =280 nm max =295 nm
ii) Butenedioic acid
H H H COOH the cis- isomer, in max13,500 max,000
C C C C most of the cases has
H
slightly lesser λmax and considerably lesser value than
HOOC COOH HOOC
Maleic acid Fumaric acid that of the trans- isomer. The major contributing factor
cis-isomer trans-isomer for this, is steric inhibition of the resonance. If the
structure of the molecule is such as to prevent
Determination of Configuration of Geometrical planarity, the extent of overlap of the - electrons is
Isomers diminished, resulting in shorter wavelength and lower
molar extinction coefficient.
1. PHYSICAL METHODS
For Example, trans-stilbene molecule is planar and
(a) Dipole moment: cis- isomers have generally therefore, resonance between the double bond and the
greater dipole moments H Cl H Cl phenyl rings (coplanar) is at a maximum. This results
C
than the corresponding C
in higher value of λmax and max; where as in cis-
trans- isomers. In cis- C C stilbene the coplanar arrangement would be extremely
H Cl Cl H
isomers the similar trans-isomer crowded and the two benzene rings must be turned at a
cis-isomer
groups are on the same = 1.85D considerable angle to the plane of the double bond, to
= zero
side of the double bonds avoid repulsion. This results in lesser resonance (
thereby the individual bond moments add up. But lesser λmax and max) and lesser stability of cis-
In trans isomers the similar groups are on the stilbene.
opposite side of the double bonds thereby the
individual bond moments cancel out each other. IR Spectroscopy: Cis- and trans- isomers of type
Example 1,2-dichloroethene RCH=CHR can be distinguished using IR spectra
specifically the C–H bending (deformation)
(b) Boiling points: Generally the cis- isomers have frequencies for the cis- isomer there is a band between
higher boiling points than the corresponding 665-730 cm1, and the trans- isomer there is strong
trans- isomers. This is because the higher dipole band between 960-980 cm1.
moment and higher polarity acts as binding fore
and is responsible for higher b.p.

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Cis- isomer also shows a O O

H H R H H C H C
strong carbon=carbon double C OH O
C C C C C
bond stretching frequency H + H+
around 1620-1680 cm1 (due R R H R
H
C
C
OH
H
C
O
C
to significant dipole cis-isomer trans-isomer
O O Inramolecular
H bond
moment) where as trans- isomer does not show Maleic acid Maleate anion
stretching of double bond because it possesses a centre This is stabilized by intermolecular hydrogen bonding,
of symmetry and zero dipole movement. which is possible due to the proximity of the two
carboxyl groups (in the cis- isomer). Because the
conjugate base (the maleate anion) is more stable than
3. CHEMICAL METHODS: the parent acid (maleic acid). Maleic acid easily
ionizes to (maleate anion). This explains its low pka
Cyclisation Method: This method is based on the value. Such stabilisation is not possible in fumerate
observation that because of the proximity (nearness) of anion because its carboxyl groups are too far from
the COOH groups, the cis- isomers readily undergo each other
elimination reaction to give a cyclic compound, while E- Z - SYSTEM OF NOMENCLATURE.
the trans- isomers do not undergo such cyclisation
readily or do so under drastic conditions. The Cahn-Ingold-Prelog Priority Rules are used for
naming both geometric isomers (e.g. E- or Z-alkenes)
For example, maleic a cis readily eliminates a and configurational isomers (e.g. R- or S- for
molecule of water and is converted into its anhydride, enantiomers and diastereomers). The rules are based
by heating it to a temperature slightly above its melting on atomic number.
point. Fumaric acid (trans-) does not form an Assign the priority (High = 1, Low = 2) to each atom
anhydride under similar conditions. Therefore, in or group on each double bonded C atom using Priority
maleic acid the two carboxyl acid groups must be on Rules
the same side as they react readily, i.e., it is a cis- 1. Determine the relative position of the 2 Higher
isomer. priority groups
O O 2. If they are on the same side of the double bond
H C H O
C OH
C
230ºC
H
C then it is a Z-alkene (German; Zusammen =
140ºC C OH
O C together)
C -H2 O C -H2 O
C
OH HO C 3. If they are on opposite sides of the double bond
H H C
C H then it is an E-alkene (German; Entgegen =
O O O
Maleic acid Maleic anhydride Fumaric acid opposite)
High Priority High Priority High Priority Low Priority
But in the case of fumaric acid the distance between group group group group
the two carboxylic acid groups is grater thus
C C C C
preventing the formation of the anhydride, i.e., fumaric
acid is a trans- isomer. However, if fumaric acid is Low Priority Low Priority Low Priority High Priority
group group group group
heated to a higher temperature (275º-300ºC), it forms
maleic anhydride but not fumaric anhydride as Z-isomer E-isomer

expected. This is because at higher temperature Examples

isomerization occurs along with dehydration. The 1 Cl 1 Cl H
Cl 1 2
anhydride obtained from fumaric acid gives maleic C C C C
acid on treatment with water and not fumaric acid. 2 H H 2 2 H Cl 1

Z-isomer E-isomer
4. pKa values: Larger the pKa value, weaker is the acid. 1,2-dichloroethne
smaller the pKa value, stronger is the acid. Maleic acid and 1 HOOC COOH 1 1 H COOH 1
fumaric acid are Dicarboxylic acids, and so have two
C C C C
pKa values each. These are:
2 H H 2
2 HOOC H 2
Maleic acid Fumaric acid
pka1 pka2 Z-isomer E-isomer
Maleic acid 1.82 6.59
Fumaric acid 3.0 4.52 1 Br I 1 1 Br F 2
C C C C
This cis- isomer (maleic acid) is a much stronger acid
2 Cl F 2 2 Cl I 1
for the first ionization, but is weaker for the second.
Z-isomer E-isomer
When one proton is removed from maleic acid, the
maleate anion is formed. 1-bromo-1-chloro-2-fluoro-2-iodoethene

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GEOMETRICAL ISOMERISM IN OXIMES R = R’.)

Oximes are compounds obtained by the condensation
reaction of aldehydes and ketones with hydroxylamine.
(H2N-OH) ALICYCLIC COMPOUNDS
H H Conformations of 4 to 8 membered cycloalkanes
C O + H2 N-OH C N-OH + H2O
Cyclobutane: 4 carbon atoms in cyclobutane are not
R R
Aldehyde Aldehyde oxime coplanar, instead the ring typically adopts a folded or
"puckered" conformation
Oximes of aldehydes (except formaldehyde) are found
• Angle strain due to compression
to exhibit geometrical isomerism, depending upon
• Torsional strain partially relieved by ring-puckering
whether the H & OH groups are arranged on the same
•
side or opposite side of C=N. example, benzaldoxime
exist in two stereomeric forms which are not mirror
images of each other (diastereomers).

Nomenclature of Oximes: In oxime chemistry, the

terms syn and anti are used instead of cis and trans. Cyclopentane:
The syn form is one in which both the hydrogen atom • If planar, angles would be 108°, but all
and the hydroxyl groups are on the same side; when hydrogens would be eclipsed.
the groups are on the opposite side, the designation is • Puckered conformer reduces torsional strain.
anti. •
H OH H
C N C N
H5 C6 H5C6
OH
Syn-Benzaldoxime Anti-Benzaldoxime
The E–Z system of nomenclature is also applied to
oximes. Thus the syn-benzaldoxime is given the Geometrical Isomerism in Disubstituted
designation E & the anti-benzaldoxime is designated Cyclohexanes.
as Z. In Cycloalkanes, cyclic structure prevents the rotation
about C-C single bond thus gives rise to geometric
In ketoximes the prefix indicates the spatial isomers. when substituents present on two carbon
relationship between the first group named and the atoms of the ring. The compound with similar groups
hydroxyl group. on the same side of the ring is known as cis-
isomer and the compound with two similar groups on
the opposite sides of the ring known as the trans-
isomer. The

The cis- and trans- isomers of dimethyl

cyclohexanes are shown below. In these structures, the
cis- isomer has two methyl groups on the same side of
the ring and in the trans- isomer, the two methyl
groups are on the opposite side of the ring.
CH3 CH3
CH3 CH3 CH3 CH3

CH3 CH3
cis-isomer trans-isomer cis-isomer trans-isomer

The group with the higher priority (C6H5) is taken as a 1,3-dimethyl cyclohexane 1,4-dimethyl cyclohexane
being cis- (same side) with respect to OH in anti-
benzaldoxime and hence is designated as Z-isom CONFORMATIONS OF CYCLOHEXANE
No such geometrical isomerism is possible in
symmetrical ketoximes (derived from simple ketones Two important conformations of cyclohexane are:
(i) Chair conformation ii) Boat conformation
The two benzaldoxime isolated were found to differ in melting points
 or syn-benzaldoxine has a melting point of 35ºC whereas the β or
anti form has a melting point of 130º C.

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Chair conformation. It is the most stable and hence (b) In trans-1,2-dimethylcyclohexane H CH3
the most preferred conformation of, cyclohexane. In two chair conformations are possible
this conformation, the electron pairs forming carbon- with unequal energies. One conformation CH3 H
carbon bonds (bond pairs) are exactly staggered. The in which, two methyl groups are in axial
bond angles are tetrahedral. Also there is no steric (a, a) positions is energetically not favoured because
interference of dipole, dipole interactions between the of 1,3-diaxial Interactions (Gauche). And the
non-bonded atoms. Hence, this conformation has other, two methyl groups are in equatorial positions
minimum energy it is free of strain as well as torsional (e,e) is energetically favoured because of no such
strains. Interactions. So it is more stable.
Cyclohexane exists in two
chair combinations (I and II) CH3
which are undergoing rapid CH3
interconversion at room I II CH3
temperature. a
a CH3 diequatorial
diaxial
Because of the mobility of the e
e a Less Stable More Stable
chair conformation, one chair e
form is readily converted into e a e 2) 1,3-Dimethyl cyclohexane
e
the other chair form and in a
doing so all axial (a) and a (a) In cis-1,3-dimethyl cyclohexane CH3
equatorial (e) bonds in the a = axial Bond e = equatorial Bond two chair conformations are possible CH3
first become ‘e’ and ‘a’ bonds, respectively in the with unequal energies. One
second. conformation in which, two methyl
groups are in axial positions (a,a) is
Mono Substituted Cyclohexane. When a hydrogen atom in cyclohexane energetically not favoured because of two Gauche
is replaced by a bulky group (alkyl group), then it leads to crowding. The Interactions and methyl-methyl group interaction.
crowding especially steric repulsion And the other, two methyl groups are in equatorial
takes place among positions (e,e) is energetically favoured because of no
H
atoms or groups which H H
are located on the axial 5
H Gauche Interactions. So it is more stable.
H CH3
bonds on the same side . 1 CH3
CH3 1
of the molecule. The 3 CH3
non-bonded interactions 3
H3C
between such axial axial Form 5%
More Crowded
equatorial Form 95%
3
1
Less Crowded di-axial Form
atoms or groups which Less Stable More Stable
di-equitorial Form
result from this crowding 2 "regular" Gauche interactions (0 Gauche interactions
is known as 1,3-diaxial interactions. + CH3-CH3 interaction

In methyl cyclohexane two chair conformations are possible. One in High energy Less stable Ligh energy Mess stable
which, methyl group is in axial position and in the other, in equatorial (b) In trans-1,3-dimethylcyclohexane CH
position. The axial hydrogens on C3 and C5 approach axial methyl group two chair conformations are possible
3

on C1 rather closely. Thus, axial methyl group is more crowded due to 1,3-
diaxial interactions compared to equatorial methyl. with equal energies. In both
The axial Me on C1 is in a Gauche relationship with C3 and C5 of the ring. conformations, one methyl group is in CH 3
When it is in an anti relationship, i.e. equatorial, no steric strain is axial positions and the other methyl
observed. group is in equatorial position. (a, e) or (e, a). Since
Hence equatorial conformations is more stable than axial
conformations
same interactions are there in both conformations with
equal energies, both have equal stabilities.
CH3
Conformations of Disubstituted Cyclohexane
1
1) 1,2-Dimethyl cyclohexane: CH CH 3 3
CH3
3
(a) In cis-1,2-dimethylcyclohexane two
CH3 1
chair conformations are possible with H H 3
a,e Form CH3 e,a Form
equal energies. In both
conformations, one methyl group is in axial positions 3) 1,4-Dimethylcyclohexane:
and the other methyl group is in equatorial position.
(a,e) or (e,a). Since same interactions are there in both (a) In cis-1,4-dimethyl cyclohexane CH3 CH3
conformations with equal energies, both have equal two chair conformations are possible
stabilities. with equal energies. In both
CH3 conformations, one methyl group is in axial positions
CH3
and the other methyl group is in equatorial position. (a,
CH3
CH3 e) or (e, a). Since same interactions are there in both
a, e Form e, a Form
conformations with equal energies, both have equal
Same Stability stabilities.

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CH3 CH3 H

1 4

H3C CH3
4 1

a,e Form e,a Form H

(b) In trans-1,4-dimethyl cyclohexane CH 3 trans-decalin
two chair conformations are possible
Norbornane, bicyclo[2.2.1]heptane, is another
with unequal energies. One
CH bicyclic molecule, consisting of a six carbon ring
conformation in which, two methyl 3
whose opposite sides are held together by a bridging
groups are in axial positions (a,a) is energetically less
methylene (CH2) group. Norbornane rings show up in
favoured because of two Gauche Interactions and
a lot of interesting molecules, such as camphor.
methyl-methyl group interaction and has a higher
energy level than the di-equatorial conformation by 3.6
k.cal/mole. So it is less stable. And the other, two
methyl groups are in equatorial positions (e,e) is
energetically favoured because of no Gauche
Interactions. So it is more stable
CH3
4 Conformations & stability
1
CH3 CH3
4
1
Extra Information
CH3
di-equatorial Form
Dimethyl cyclohexane Chair conformations
di-axial Form
2 "regular" Gauche interactions (0 Gauche interactions stability
+ CH3-CH3 interaction
1 cis-1,2- a, e e, a
High energy Less stable Less energy More stable
2 trans-1,2- a, a e, e
BICYCLIC ALKANES 3 cis-1,3- a, a e, e
Bicyclic or polycyclic compounds are molecules that
4 trans-1,3- a, e e, a
contain two or more rings that are joined together. The
most common are fused rings, where two atoms and 5 cis-1,4- a, e e, a
the bond between them are shared. When more than 6 trans-1,4- a, a e, e
two atoms are shared, the result is a bridged system,
so-called because the shared atoms form a "bridge".
Fused Rings Bridged Rings
H2
C
H2 H H2 H
C C C
H2C C CH2
H2C CH2
H2C C CH2 C
C C C H C
H2 H H2 H2 H2
Decalin Norbornane
Decalin: has 4 carbons in each of two chains and
none in the third. Therefore, decalin is
bicyclo[4.4.0]decane. Notice that the numbers are
enclosed in square brackets after the prefix “bicyclo”
and before the name of the hydrocarbon.

Conformations: Ring fusion can occur either in a

cis- or trans- fashion. The cis-isomer can interconvert
between two double-chair forms (which are
enantiomers).
H
H
H H

cis-decalin
However, the trans-isomer only has one possible rigid
double-chair form. Substitutents may be therefore be
forced to be axial.

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