PHYSICAL AND ORGANIC CHEMISTRY

ISOMERISM

PowerPoint® Slides
by Nazlina

Last Updated:November 11, 2020 1

 Learning Outcomes

• Be able to name write a definition of structural isomerism

and give examples of structural isomers using both full
and skeletal structural formulae
• Be able to identify stereo isomerism,
• Be able to identify configurational isomerism and give
examples using either full and/or skeletal structural formulae of
i. Diastereoisomerism in molecules having double bonds
(geometrical isomerism),
ii. optical isomerism, and
iii. cis- and trans-isomerism in cyclic molecules

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 Isomerism

• Molecules which have the same molecular formula but

different in structures are called isomers.
• Isomers are compounds that have the same numbers and
kinds of atoms but differ in the way the atoms are
arranged.
• Compounds like butane and isobutane, whose atoms are
connected differently, are called constitutional isomers.
• There are other kinds of isomers whose atoms are
connected in the same order.
• The numbers of isomers increases dramatically as the
number of carbon increases.

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 Isomerism (Cont.)

Source: © 2007 Thomson Higher Education

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 Isomerism (Cont.)
Constitutional OR Structural Isomers
• Constitutional isomers are isomers that differ in
their bonding sequence. There are three kinds
of constitutional isomers.

i. Chain Isomers
• Differs in the carbon skeleton
H
H C H
H H H H H H
H C C C C H H C C C H
H H H H H H H
Butane, C4H10 Isobutane, C4H10

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 Isomerism (Cont.)

Constitutional OR Structural Isomers (Cont.)

ii. Positional Isomers
H2C CH CH2CH2CH3 CH3 CH CH CH2CH3
1-Pentene 2-Pentene

iii. Functional Group Isomers

OH
CH3 CH CH3 CH3CH2 O CH3

2-Propanol Ethyl methyl ether

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 Isomerism (Cont.)

Stereoisomers*
‘In stereoisomers the bond structure is the same, but
the geometrical positioning of atoms and functional
groups in space differs. This class includes
enantiomers where different isomers are non-
superimposable mirror-images of each other, and
diastereomers when they are not.
Diastereomerism is again subdivided into
conformational isomerism (conformers) when
isomers can interconvert by chemical bond
rotations and cis-trans isomerism when this is not
possible’.
Source: Isomer. (2009). In Wikipedia, The Free Encyclopedia. Retrieved September 16, 2009, from Wikipedia, The Free Encyclopedia: http://en.wikipedia.org/wiki/Isomer#Isomerism

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 Isomerism (Cont.)

Stereoisomerism
• Isomerism due to differences in the spatial arrangement
of atoms without any differences in connectivity or bond
multiplicity between the isomers*.
• Chiral is an object that is non-superimposable on its
mirror image**.

*Source: Stereoisomerism. (1997). IUPAC Compendium of Chemical Terminology

**Source: Chirality. (2009). In Wikipedia, The Free Encyclopedia. Retrieved September 16, 2009, from Wikipedia, The Free Encyclopedia:
http://en.wikipedia.org/wiki/Chirality_(chemistry)

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 Enantiomers: Compounds that are non
superimposable mirror images. Any molecule that
is chiral must have an enantiomer.

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 Isomerism (Cont.)

Stereoisomerism
• A chiral center is a carbon atom that is bonded to
four different groups (designated as *). A
molecule with a chiral carbon has a mirror image
that is not superimposable, this pair of
compounds are enantiomers.
H H

C* *C
Br CH3 H3C Br
HO OH

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 Isomerism (Cont.)

Stereoisomerism: Enantiomers OR Optical Isomers

• Early attempts to understand and characterize the
structure of enantiomers were based on the rotation of
plane polarized light. Sometimes enantiomers are
called optical isomers.

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 Isomerism (Cont.)

• Diastereoisomers: stereoisomers that are not enantiomers. It

also described as pairs of isomers that have opposite
configurations at one or more (but not all) of the chiral centers
so they are not mirror images of each other.

• Achiral Compounds have superimposable mirror images

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 Isomerism (Cont.)

Stereoisomerism: Diastereoisomers
• Tartaric acid shows diastereisomeric properties.

(2S,3S)-tartaric acid (2R,3R)-tartaric acid (2R,3S)-tartaric acid

• The first two molecules, are clearly enantiomers of each other since
they are mirror images. The third molecule is different yet the same
atoms are bonded to each other. It is also very clearly not a mirror
image of either of the first two. Thus, as a non-superimposible, non-
mirror image with the same arrangement of atoms, (2R,3S)-tartaric
acid is a diasteromer of the first two molecules.
Source: Stereochemistry. (2009). In OrganicChemistry.22web.net. Retrieved September 16, 2009, from OrganicChemistry.22web.net :
http://www.organicchemistry.22web.net/stereochemistry.html

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 Isomerism (Cont.)

Stereoisomers for Achiral Molecules: Cis-Trans Isomers

• Isomers that differ only in how atoms are oriented in space.

Source: Dimethylcyclopropane. (2008). In Terzach. Retrieved September 16, 2009, from Terzach: http://terzach.pbworks.com/Dimethylcyclopropane

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 Isomerism (Cont.)

Stereoisomers for Achiral Molecules: Cis-Trans Isomers

(Cont.)
• Alicyclic compounds also display cis-trans isomerism.
Example cis-trans isomers (also called geometric
isomers) due to a ring structure is1,2-
dichlorocyclohexane.

cis-1,2-dichlorocyclohexane trans-1,2-dichlorocyclohexane

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 Isomerism (Cont.)

Stereoisomers for Achiral Molecules: Cis-Trans Isomers

(Cont.)
• Open ring compounds also display cis-trans isomerism. 2-
Butene shows geometric isomeric structures.

cis-2-Butene trans-2-Butene
• The molecules are clearly distinct; they clearly have the
same arrangement of atoms structurally; and they clearly
are not mirror images. Thus, these molecules are
diastereomers.
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 Isomerism (Cont.)

Sequence Rules: The E,Z Designation

• Neither compound is clearly
“cis” or “trans”
Substituents on C1 are
different than those on C2
We need to define
“similarity” in a precise way
to distinguish the two
stereoisomers
• Cis, trans nomenclature only
works for disubstituted double
bonds
*Source: Isomer. (2009). In Wikipedia, The Free Encyclopedia. Retrieved September 16, 2009, from Wikipedia, The Free
Encyclopedia: http://en.wikipedia.org/wiki/Isomer

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 E,Z Nomenclature

 Priority rules of Cahn,

Ingold, and Prelog
 Compare where higher
priority group is with
respect to bond and
designate as prefix
 E -entgegen, opposite
sides
 Z - zusammen,
together on the same
side

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 Ranking Priorities: Cahn-Ingold-Prelog
Rules
• Must rank atoms that are connected at comparison point
• Higher atomic number gets higher priority
• Br > Cl > O > N > C > H

In this case,The higher

priority groups are
opposite:
(E )-2-bromo-2-chloro-
propene

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 Extended Comparison

• If atomic numbers are the same, compare at next

connection point at same distance
• Compare until something has higher atomic number
• Do not combine – always compare

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1. Rank the groups (or atom) that are bonded to the asymmetric
carbon and draw an arrow with the highest priority to the lowest
priority
Cl
(R)-3-chlorohexane
CH3CH2 CH2CH2CH3

H
2. If the lowest priority is on a horizontal bond, the naming is
opposite to the direction of the arrow
CH3

H OH (S)-2-butanol

CH2CH3
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3. The arrow can go from group 1 to 2, passing group 4, but not
group 3
CO2H
(S)-lactic acid
H CH3

OH

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 References
• IUPAC. Compendium of Chemical Terminology, 2nd ed. (the
"Gold Book"). Compiled by A. D. McNaught and A. Wilkinson.
Blackwell Scientific Publications, Oxford (1997).
• Solomons, T. W. Graham and Fryhle, Craig B. (2004). Organic
Chemistry. 8th Edition. John Wiley & Sons, Inc.

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