LO#3:

Isomers
 Learning opportunity outcomes
• Define isomeric molecules and their general properties.
• Distinguish between two major classes of isomers: structural and
stereoisomers.
• Distinguish between three different types of structural isomers: skeletal,
positional and functional isomers.
• Identify the functional groups that form functional isomers of one another.
• Understand the concept of chirality.
• The occurrence and properties of stereoisomers and the different types of
stereoisomers.
• Distinguish between geometrical isomers and enantiomers.
• Identify the difference between cis- and trans- geometrical isomers.
• Compare two compounds and determine whether they are identical to one
another, isomers of one another (which type) or completely different
compounds.
• Draw a set of specific isomers from a given molecular formula.
Introduction

• Isomers  molecules with the same molecular formula (MF) but

different chemical structures.
 Same number of atoms of each element, but have different
arrangements of their atoms in space.
• Isomers do not necessarily share similar properties,

unless they also have the same functional isomers.

• Two forms of isomerism:

constitutional (structural) isomerism

stereoisomerism

SCCH121 LO#3 3
 Skeletal
isomers

Structural or
Positional
Constitutional
Isomers
isomers

Isomers Functional
isomers

Geometrical
Stereoisomers isomers

Optical isomers
3
 Structural isomers
 2 or more organic compounds → same molecular
formulae (MF), but different structures.
 Atoms and functional groups joined in different ways.
 May or may not belong to the same functional group.
 Molecules have different chemical and physical properties.
 Different IUPAC names.

 This group includes:

• skeletal isomerism
• position isomerism
• functional group isomerism
 Structural Isomers
Skeletal isomerism occurs when the way carbon atoms are linked together
is different from compound to compound.

CH3CH2CH2CH2CH3
pentane
2-
2,2-dimethylpropane methylbutane

C5H12
C5H12

C5H12
Structural Isomers
Exercise: Draw all the possible skeletal isomers for the
molecular formula (MF) C6H14 (hint: name each structure to
check if they are different)
C6H14 CnH2n+2 alkane

CH3CH2CH2CH2CH2CH3
hexane 3-
methylpentane

2-methylpentane
2,3-
dimethylbutane
 Structural Isomers
Positional isomerism occurs when the same functional group is in
different positions on the same carbon chain (parent structure).

o-methylphenol p-
m-methylphenol methylphenol
C7 H 8 O
C7 H8 O

C 7 H8 O
Structural Isomers
Exercise: Draw a pair of positional isomers for the following
molecular formulas: C5H10 and C5H11Br. (hint: 1st identify the functionality in the
MF)

C5H10  CnH2n  alkene

isomers
1-pentene

?
isomers
2-pentene
identical

2-pentene
Structural Isomers
Exercise: Draw a pair of positional isomers for the following
molecular formulas: C5H10 and C5H11Br. (hint:
1st identify the functionality in the MF)
C5H11Br  CnH2n+1X  alkyl halide

1-bromopentane
isomers 3-bromopentane

isomers isomers

?
2-bromopentane identical 2-bromopentane
Structural Isomers
Functional isomerism occurs substances have the same
molecular formula but different functional groups.
 Alcohols and ethers CnH2n+2O C 4 H8 O
 Aldehydes and ketones CnH2nO

 Carboxylic acids and esters CnH2nO2

2-butanone butanal
C4H8 O C4 H8 O
 Functional Isomers
Exercise: Draw a pair of functional isomers for the following
molecular formulas: C3H6O2 and C4H10O. (hint: 1st
identify the functionality in the MF)
C3H6O2  CnH2nO2  carboxylic acid + ester

propanoic acid methyl ethanoate

(acetate)

C4H10O  CnH2n+2O  alcohol + ether

2-butanol diethyl
ether
 Stereoisomers
Stereoisomerism
 Same MF, same functional groups and positions, but...
 Different arrangements in space.

 Behave identically in most chemical reactions, except in reactions with

other stereoisomers.
 This group includes:
 Geometrical isomers
• Cis – trans isomers
• E / Z isomers
 Optical isomers
• Enantiomers
• Diasterioisomers
Geometrical isomers
Geometrical isomerism occurs when substances have the same
molecular formula, same functional group, but a different arrangement of
their atoms in space.

This happens on a bond with restricted rotation:

 C=C bond in the molecule with 2 points of
difference on each C.
 Cyclic structure with 2/more substituents.

Geo-isomers  different physical properties but similar

Chemical properties.
Cis/trans isomers
Cis/trans isomers  R-chain on either side of the double bond.

2-pentene
Cis-: R-chain on either side of C=C point in same direction.
H on same side of the bond.

cis-2-pentene
(cis same side)

Trans-: R-chain on either side of C=C point in opposite direction.

H on opposite sides of the bond.

trans-2-pentene
(trans opposite)a
Exemple

3-methylcyclohexanol

cis-3-methylcyclohexanol

trans-3-methylcyclohexanol
Geometrical isomers
Exercise: Name the following structures and identify whether
they are cis-, trans-, E- or Z- isomers.

Trans -1-butene

cis-p-methoxyphenol

E-3-methyl-3-octen-4-ol
E/Z-isomers

Cis/trans isomers → R-chain and a H on either side of the double bond.

E/Z isomers → 2/more substituents on the double bond, not

only R-chain.
Z-: substituents of higher priority point in same direction.
E-: substituents of higher priority point in opposite direction.

Priority is assigned according to higher atomic mass of atom

bonded to double bond C.
E/Z-isomers

1-chloro-1-buten-1-ol

E-1-chloro-1-buten-1-ol
(E- opposite sides)

Z-1-chloro-1-buten-1-ol
(Z- same side)
Optical isomers
Optical isomerism, occurs when substances have the same molecular and
structural formulae, but one cannot be superimposed on the other.
Mirror images of one another – like your hands.
Isomers are biologically abundant and important.
Most biological molecules exist as isomers due to complexity (different atoms
and bonds) of molecules.
Nature favours one isomer over another for a specific function.
Enzymes can distinguish between different enantiomers of a compound, and
organisms often prefer one isomer over the other.
Stereoisomers → key role in pharmaceutical drug design.
Enantiomers
Same chemical and physical properties, except that one structure rotates
the plane of polarised light to the right and the other rotates it to the left.
(+) enantiomer  rotates the polarised light clockwise (to
the Right).
(–) enantiomer  rotates the polarised light anti-clockwise
(to the Left).
A 50:50 mixture of (+) and (–) enantiomers is not optically
active. It is called a racemic mixture or racemate.
Optical isomers can occur on an asymmetric C-atom. Asymmetric
carbon atom  bonded to four different groups. Molecules like this are
called enantiomers.

Exhibit chirality. (central C –atom= chiral centre).

The groups can be something hideously complex, or something

comfortably simple like a H or Cl atom.

Remember:
 four groups
 must be different
 Enantiomers

Exercise: Draw 2-hydroxypropanoic acid and

find its chiral centre.

2-hydroxy-propanoic acid
(lactic acid)

 Lactic acid  simple example

of optical isomerism.
 (+) enantiomer of lactic
acid is found in muscle.
 Sour milk contains a
racemic mixture of the two
enantiomers.
Enantiomers
Exercise: Identify the chiral centre in each one of the following molecules (ie. a
C atom with 4 different attachments on it).
Naming of enantiomers

R and S naming (Cahn-Ingold-Prelog role)

• Assignment of Priority.
• Compare the atomic number of the atoms directly attached to the chirality centre.
• The group with the atom of higher atomic number receives higher priority
• After having ranked the four groups attached to the chirality-center, orientate the
molecule such that the lowest ranking group points directly back.
• Look at the 3 substituents left facing you: If the priority of the remaining three
substituents decreases in clockwise direction, it is labelled R (for Rectus, Latin for
right), if it decreases in counterclockwise direction, it is S (for Sinister, Latin for
left).
R or S configuration?
 Diasteroisomers

• Are stereoisomers that are not mirror image of

each other.
• Occur in molecules containing more than one
chiral centres.
• Total number of stereoisomers is 2n
• They may differ in physical properties
(diastereoisomers)
2S,3S; 2R,3R; 2S,3R OR 2R,3S?
 Isomers Quiz on myLMS
Chapter 4.1 – 4.5:
Isomers

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