CHM 201: GENERAL ORGANIC CHEMISTRY I

INTRODUCTION
The branch of chemistry dealing with the study of three-dimensional nature (spatial arrangement) of molecules is
known as stereochemistry. The isomers which have same bond connectivity but different arrangement of groups
or atoms in space are termed stereoisomers.

Conformation Analysis: Conformational analysis is the study of the different energy levels associated with the
different conformations of a molecule. Conformations are the different 3-dimensional arrangements that the
molecule can acquire by freely rotating around σ-bonds. One must keep in mind that conformations are not
isomers. Isomers are different molecules. Conformations are simply different structural arrangements of the same
molecule.

Sawhorse Formula
The sawhorse formula indicates the spatial arrangement of all the atoms or groups on two adjacent carbon atoms.
The bond between the adjacent carbon atoms is represented by a diagonal line, usually from lower left to upper
right, the left hand bottom end representing the atom nearest to the observer and the right hand top end the atom
that is farther away. Two of the remaining bonds to the two atoms are drawn vertically and the other four at 1200
angles to these two as shown below

Newman projection
Newman projection represents the spatial arrangement of all the atoms or groups on two adjacent carbon atoms.
Here a molecule is viewed along the axis of a carbon-carbon bond. The carbon atom toward the front is
represented by a dot and the carbon atom toward the rear by a circle. The atoms or groups on the carbon atoms
are shown as being bonded to the dot or circle. For example:

Acyclic Compound: Is one of a group of organic compounds of carbon (C) and hydrogen (H) in which the
carbon atoms have linear, branched chain (open), or both types of structures. Aliphatics, as they are informally
called, can be divided into paraffinic (saturated) and olefinic (unsaturated) chain types. The simplest paraffinic
aliphatic is methane, CH4. The simplest olefinic aliphatic is ethylene, C2H6.

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 CHM 201: GENERAL ORGANIC CHEMISTRY I
CONFORMATIONS OF ACYCLIC SYSTEMS

1. Conformations of ethane: When an ethane molecule rotates about its carbon-carbon single bond, two extreme
conformations can result: the staggered conformation and the eclipsed conformation. An infinite number of
conformations between these two extreme conformations is also possible. These are called skew conformations.
There are various ways to represent the three-dimensional conformations on the paper. Here we will use Newman
projections and Saw horse to discuss the conformations of acyclic compounds.

Saw horse conformations are given below:

Newman projection conformations are given below:

Staggered conformation: A conformation with a 60° dihedral (torsional) angle is known as staggered
conformation. The angle between the atoms attached to the front and the rear carbon atoms is called the torsional
angle.

Eclipsed conformation: A conformation with a 0° torsional angle is known as eclipsed conformation.

The electrons in a carbon-hydrogen bond will repel the electrons in

another carbon-hydrogen bond if the bonds get too close to each other.
This is called torsional or bond opposition strain.

Therefore, the staggered conformation is the most stable conformation

because the carbon-hydrogen bonds are as far away from each other as
possible, i.e., it has least torsional strain. The eclipsed conformation is
the least stable conformation because the carbon hydrogen bonds are
closest.

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2. Conformations of Propane: Similar to ethane, propane also has the following two extreme conformations

However, the torsional strain in propane is a little higher (3.3kcal mol–1) than ethane due to steric hindrance
caused by methyl group in eclipsed conformation. In the eclipsed conformation of propane, van der Waals
repulsion occurs between the methyl group and hydrogen.

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 CHM 201: GENERAL ORGANIC CHEMISTRY I
3. Conformations of Butane: Butane, CH3CH2CH2CH3 can be written as

If we view the molecule of butane through C2–C3 bond, each carbon is seen attached to one methyl group and
two hydrogens. A rotation about C2–C3 bond results in the formation of a number of conformations. The Newman
projections (I-VI) for different conformers of butane, as obtained through 60° rotation around C2 -C3 bond, are
as follows:
Totally staggered or anti-conformation [conformation–I]
In an anti-conformation, the two CH3 groups are farthest from each other and have minimum interaction. Thus,
the anti-form is the most stable conformation.
Totally eclipsed conformation [conformation–IV]
In totally eclipsed conformation, the methyl group on front carbon is exactly in front of methyl group on the rear
carbon. The two bulkier methyl groups are very close to each other and this steric crowding causes Van der
Waals repulsion.
Skew staggered conformation (Conformations III and V)
The staggered conformations in which two methyl groups are not farthest apart but are at an angle of 60°, are
known as Gauche conformations.
Skew eclipsed conformations (Conformations II and VI)
In these conformations, methyl group and hydrogen on adjacent carbon are present exactly in front of each other.

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Cyclic Compound Closed: Any one of a class of compounds whose molecules contain a number of atoms bonded
together to form a closed chain or ring. Cyclic compounds are also known as “Ring compounds”. As its second
name suggests, cyclic compounds are those kinds of compounds where one or more than one number of atoms
get connected to form a closed ring. It is not mandatory that every ring of these compounds is to be of the same
size.

CONFORMATION OF CYCLOALKANE
Cycloalkanes have sp3 hybridized carbons and thus, they should have a bond angle of 109.5°. The simplest
cycloalkane is cyclopropane.

1. Cyclopropane conformation: Cyclopropane which has a shape of regular triangle with bond angles of 60°.
This reduction in bond angle by 49.5° (from 109.5° to 60°) causes an angle strain in the molecule. The sp3–sp3
overlap in cyclopropane is not as effective as in open chain compounds. The carbon–carbon bonds are bent and
relatively weak which makes the ring less stable. Cyclopropane is a planar molecule and all the six hydrogens are
present in an eclipsed state. Cyclopropane exhibits torsional strain as well as angle strain and these two strains
together cause ring strain in cyclopropane. The Newman projection of cyclopropane is represented as:

2. Cyclobutane conformation: A molecule of cyclobutane adopts a puckered conformation to minimize torsional

strain. If it were planar, there would be eight pairs of C–H eclipsing interactions and the torsional strain would
have been rather high. In a puckered conformation, C–H bonds are in a skew conformation and, therefore, some
torsional strain is still present. On the other hand, cyclobutane still has a relatively high angle strain. Bending of
the ring increases its angle strain. The dihedral angles are 28O and the valency angles are 86O (instead of 90O in a
planar square).
However, the angle strain is not as high as in the case of cyclopropane. As one can see from the example of
cyclobutane, in a cyclic molecule a high angle strain is less destabilizing compared to a high torsional strain.

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3. Cyclopentane conformation: Angles in a regular pentagon are 108O. That is very close to the ideal tetrahedral
angle of 109.5O and, therefore, if cyclopentane were planar it would not exhibit any significant angle strain.
However, in a planar cyclopentane there would be a high degree of torsional strain. All ten of the carbon–hydrogen
bonds would be in eclipsing conformations. This is obvious from the Haworth formula. A Haworth formula
represents the ring as being planar and all the bonds to the substituents are represented as being vertical.

Preferred conformations of cyclopentane are the envelope and the half-chair (also called the ‘‘twist’’ form). In an
envelope conformation four carbon atoms are in the same plane and one is either above or below it. In a half-
chair conformation, three carbon atoms are in a single plain, while two non-adjacent carbon atoms are either
above or below it.
Interconversions of conformations of cyclopentane. Envelope is only a slightly more stable compared to a half-
chair and there is virtually no barrier to intercoversion

4. Conformations of Cyclohexane: Cyclohexane is as stable as its open chain counterpart hexane. Cyclohexane
exists as a puckered or non-planar ring. The twisting about carbon–carbon bond results in the formation of
different conformations of cyclohexane. The four main conformations of cyclohexane are:
(a) Chair conformation (b) Boat conformation (c) Twist conformation (d) Half Chair conformation

a). Chair conformation: This is the most stable conformation of cyclohexane as it is free from torsional strain.
All the twelve hydrogens are in staggered state as evident form Newman projection. The bond angle is nearly
109.5° and thus, it is free from angle strain also.

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b). Boat conformation: Twisting about carbon–carbon single bond of the chair form results in the formation of
boat conformation. Boat conformer is free from angle strain. However, in boat conformation the hydrogens are
in eclipsed state, which causes torsional strain in the molecule. Along with this the hydrogen at C1 and C4 are
close to each other and experience van der Waals repulsion known as flagpole interaction. The torsional strain
and flagpole interaction make boat conformation less stable compared to chair conformation.

c). Twist boat conformation: The boat conformation is flexible and a slight twist about the bond reduces the
torsional as well as flagpole interactions which makes the twist boat conformation a little more stable than the
boat conformation.
d). Half chair conformation: This is the least stable conformation of cyclohexane because carbon atoms at one
end of the ring are planar.

The stability order of different conformations of cyclohexane is:

Chair conformation >> twist boat conformation > boat conformation > half chair conformation

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Axial and equatorial hydrogens in chair conformation
In the chair conformation of cyclohexane, all the twelve hydrogens are not equivalent. The chair conformation
has two types of hydrogens, axial (a) and equatorial (e).
Six hydrogens are present perpendicular to the plane of the ring and are termed as axial hydrogens while the
remaining six hydrogens project out sideways, along the plane of the ring and are termed as equatorial hydrogens.

It’s important to know that cyclohexane undergoes a conformation change called flipping as a result of ring
flipping the up carbon becomes down carbon and axial bond become equatorial bond.

Chair conformation is more stable that boat conformation Using Newman projection to prove it

Chair
Staggered

Eclipsed
Boat

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GEOMETRICAL (CIS-TRANS) ISOMERISM
The isomerism which arises due to restricted (frozen) rotation about a bond in a molecule is known as geometrical
or cis-trans isomerism. Compounds having restricted rotation about a bond exhibit geometrical isomerism if they
are suitably substituted.
Geometrical (cis-trans) isomerism is exhibited by a variety of compounds which may be classified as follows:
a. Compounds containing a double bond; C=C, C=N, N=N.
b. Compounds containing cyclic structure; homocyclic, heterocyclic and fused-ring, ring systems.
c. Compounds having restricted rotation about a single bond due to steric hindrance; some biphenyls.
Some examples:
carbon-carbon double bond - as in 1,2-dichloroethene

In one, the two chlorine atoms are locked on opposite sides of the double bond. This is known as the trans isomer.
(trans: from latin meaning "across" - as in transatlantic).
In the other, the two chlorine atoms are locked on the same side of the double bond. This is known as the cis
isomer. (cis: from latin meaning "on this side")

The most likely example of geometric isomerism you will meet at an introductory level is but-2-ene. In one case,
the CH3 groups are on opposite sides of the double bond, and in the other case they are on the same side.

Cis-and Trans- isomerism in disubstitute cyclohexanes

Disubstitued cyclohexanes exhibit cis–trans isomerism due to restricted rotation in cyclic system. There are three
possible disubstituted cyclohexanes:
a) 1,2-disubstituted cyclohexanes
b) 1,3-disubstituted cyclohexanes
c) 1,4-disubstituted cyclohexanes

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Representing cis- and trans- isomers in chair conformation

In chair conformations, the two substituents may occupy (e,e), (e,a), (a,e), and (a,a) conformation. The
substituents may be attached through an axial or an equatorial bond. The equatorial and axial bonds may point in
upward or downward direction. Example:

Different chair conformations possible for 1,2-dimethylcyclohexane are:

Different chair conformations possible for 1,3-dimethylcyclohexane are:

E–Z system
The alkenes of the type abC==Cxy exhibit geometrical isomerism but they cannot be classified as cis- or trans-
isomers, as all the substituents attached to olefinic carbons are different. The configuration about any carbon–
carbon double bond is specified using E–Z system
a. The atoms or groups attached to each olefinic carbon are given priority as per sequence rules.
b. If higher priority groups are present on same sides across the double bond, the geometrical isomer is said
to have Z-configuration [German: Zusammen— sameside].
c. If higher priority groups are present on opposite sides across the double bond, the geometrical isomer is
said to have E-configuration [German: Entegegen —opposite side].

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All geometrical isomers (including cis- and trans-) are designated by E–Z system.

OPTICAL ISOMERISM

Plane Polarized Light – Ordinary light ray vibrate in all possible directions perpendicular to the direction of
propagation. When ordinary light is passed through a nicol prism the vibration of ray are adjusted in a single
phase only. The light whose vibration occurs only in one plane is called plane polarized light. The apparatus
which bring polarization in the light is called polarimeter.

Optical Activity – Some substances have the property to rotate plane polarized light to the left or to the right.
These substances are termed as optically active substance and this property is called Optical activity. The
substance which rotate the polarized light to the right is called dextrorotatory or D – form and the substance which
rotate the plane polarized light to the left is called laevorotatory or L – form. D – form is also indicated by (+)
sign and L – form is also indicated by (–) sign.

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Optical Isomerism (Enantiomerism)

Isomers which are nonsuperimposable mirror images of each other are called enantiomers and the isomerism
exhibited by them is known as enantiomerism. Enantiomers are also called mirror-image isomers, enantiomorphs
or optical antipodes.

Three forms of lactic acid are known, of which two are optically active and the third one is optically inactive.
1. (+)-LacticAcid: Rotate the PPLto the right (clockwise) and is dextrorotatory
2. (-)-Lactic Acid: Rotate the PPL to the left (anti-clockwise) and is levorotatory.
3. (±)-Lactic Acid: Does not rotate PPL and is optically inactive because it is a racemic mixture of (+) and
(-) forms

Asymmetric Carbon or Chiral carbon: A carbon atom which is attached to four different atoms or groups is
called asymmetric carbon atoms or chiral carbon.

Chiral molecule: A chiral molecule is one that cannot be superimposed on its mirror image. It rotate the PPL
Diastereomers: Diastereomers are stereoisomers that are not mirror images of each other. For a molecule to have
a diastereomer, it must contain more than on chiral center.
Enantiomers: Mirror images of each other are enantiomers
Plane of Symmetry: A plane which cut an object into two equal halves is called plane of symmetry.

Tartaric acid has plane of symmetry.

An object lacking a plane of symmetry is called dissymmetry or chiral dissymmetry.
A dissymmetric object can’t be superimposable on its mirror image.

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Meso compounds: Compounds that contain a chiral center but is achiral because of plane of symmetry

Optically active: Compounds having the ability to rotate the Plane Polarize Light (PPL)
Racemic mixture: A racemic mixture is a 50:50 mixture of two enantiomers. Racemic mixture do not rotate PPL
and is optically inactive.
There are two necessary conditions for optical isomerism.
1. The molecule must have an asymmetric carbon.
2. The mirror image of the molecule must be non – superimposable.

Lactic acid has an asymmetric carbon atom and its mirror image is non superimposable i.e. mirror image
represents different optical isomer. Therefore lactic acid shows the phenomenon of optical isomerism.

D/L Nomenclature
According to this nomenclature if in glyceraldehyde molecule the –OH group on right and –H on left, the –CHO
and –CH2OH groups being on top and bottom, respectively the molecule is designated as (+) Glyceraldehyde and
it was arbitrary given the configuration symbol D. The mirror image of this compound (-) glyceraldehyde was
given the configuration L.

RECEMIC MODIFICATION AND RESOLUTION

Racemic mixture
A mixture containing equal amounts of a pair of enantiomers is termed as racemic mixture (also called racemic
modification). A racemic mixture is optically inactive. As the enantiomers exhibit same specific rotation in
opposite directions, the specific rotation values of two isomers cancel each other, resulting in zero optical activity.
The separation of a racemic mixture into its two optically active compounds (+ and – isomers) is known as
Resolution. For example, (+) lactic acid and (–) lactic acid.
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Resolution or Resolution of racemic mixture – The process of separation of a racemic mixture into two ‘D’ and
‘L’ form is called Resolution. The separation of ‘D’ and ‘L’ form of a racemic mixture is very difficult because
they have identical physical and chemical properties.
The following methods can be used for the separation of ‘D’ and ‘L’ form.
1. Mechanical Separation – If the ‘D’ and ‘L’ form of a compound exist in well-defined crystalline form the
separation can be done by hand picking with the help of magnifying lens. eg. D and L forms of sodium
ammonium tartrate can be separated by this method but this method has very limited applications.
2. Biochemical Separation – In this method the resolution is done by the use of microorganism when certain
bacteria are added to a solution of a racemic mixture, they decompose one of the optically active form
rapidly than the other. This process is very slow and only small amount of material can be separated.
3. Chemical Seperation – This is the best method of resolution. In this method the racemic mixture is
combine with another optically active compound and the resulting product differ in properties particularly
in solubility in various solvent. By fractional crystallization from a suitable solvent, they can be separated.

Racemization: The conversion of an optically active compound (+)- or (-)- into racemic mixture (±) is known as
Racemization. Racemization can be accomplished by the means of heat, light or by the conversion of an optically
active isomers into an optically inactive intermediate which then reverts to the racemic mixture. The conversion
of either of the optically active lactic acids into a racemic mixture by heating its aqueous solution may proceed
through an enol intermediate.

According to Pasteur, if a solution of (+)-tartaric acid is heated for some time at 165°C, it loses its optical activity
forming the racemic mixture and meso acid

This is due to the fact that tartaric acid having two asymmetric carbon atoms may undergo inversion of H and OH
only about one carbon or both, yielding meso or racemic form, respectively.

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