3.

5 Isomerism in Organic Molecules

Isomerism

Constitutional
Stereoisomerism
Isomerism

Chain Functional
Positional Geometrical Optical
Group
Isomerism Isomerism Isomerism Isomerism
Isomerism

Same molecular formula but differ in Same molecular formula but

order of attachment of atoms differ arrangement of atoms in
space
Isomerism in Organic Molecules
Constitutional (Structural) Isomerism
i) Chain isomers – differ in carbon skeleton (different carbon
chain). They can be linear or branch. They possess the same
functional group and belong to same homologous series
Isomerism in Organic Molecules
Constitutional Isomerism
ii) Positional isomers - molecules have same carbon
chain and functional groups but differ in the position
of the functional group
Isomerism in Organic Molecules
Constitutional Isomerism
iii) Functional isomers - molecules have different
functional groups, hence their structural formula are
different.
 Isomerism in Organic Molecules
• Some example of functional group isomers
- Alkenes and cycloalkanes (CnH2n)
- Alkynes and cycloalkenes (CnH2n-2)
- Alcohols and ethers (CnH2n+2O)
- Aldehydes and ketones (CnH2nO)
- Carboxylic acids and esters (CnH2nO2)
 Functional isomers
a) Alkene and cycloalkane C4H8 b) Alkyne and cycloalkene C4H6

c) Alcohol and Ether, C2H6O d) Aldehyde and Ketone, C3H6O

Propanal Propanone
e) Carboxylic acid and Ester, C4H8O2

Propanoic acid Ethyl ethanoate 6

 Checkpoint 11
i) Draw any three chain isomers of C7H16

ii) Draw any two positional isomers of C5H12O

iii) Draw any two functional isomers of C5H10O

7
 Isomerism in Organic Molecules
 Rotation about a bond is NOT isomerism
 Isomerism in Organic Molecules
• Stereoisomerism - molecules have same molecular
formula and structural formula but different
orientation of atoms and bond in space within the
molecules

Stereoisomer

Geometrical Optical
 Isomerism in Organic Molecules
Geometrical isomers
 Differ by groups being on the same side (cis-isomer) or opposite
side (trans-isomer) of a rigidity in a molecule
 occurs in the presence of a carbon-carbon double bond in alkene or
carbon-carbon single bond in cyclic compound.

When groups on the doubly bonded carbons are cis, they are on the same side of the double bond
When groups on the doubly bonded carbons are trans, they are on opposite sides

All substituents are All substituents are

on one side on different sides
of  bond of  bond
 Isomerism in Organic Molecules
Condition for geometrical isomerism
Contains at least 1 C=C double bond, or C-C in
cyclic compound
There must be 2 different groups joined to the
carbon on both sides

cis trans No geometrical

isomer
 Isomerism in Organic Molecules
Geometrical isomers

Why –CH3 on same

side is trans?
 Geometrical isomers
HMW HMW HMW
LMW

LMW LMW
LMW HMW

HMW is high molecular weight

LMW is lower molecular weight

This compound named as cis because the This compound named as trans because
propyl group and methyl group are higher the propyl group and methyl group at
molecular weight and at the same side opposite side
 Cycloalkene Nomenclature with cis and trans

How to give a name to the alkenes with more than two substituents

This compound is cis This compound is trans

but the two methyl but the two methyl
groups are trans to each other. groups are cis to each other.
 Checkpoint 15
Tell whether each of the following pairs is isomer or not isomer

a b

d
 Isomerism in Organic Molecules
Optical isomerism
shown by an organic compound which has a stereocentre (chiral carbon atom)
 chiral carbon atom has four different atoms or groups of atoms attached to it.
 Enantiomers are chiral molecules that are mirror images of one another.
Enantiomers are optically active.

Chiral carbon
 Isomerism in Organic Molecules
Optical isomerisms are nonsuperimposable
 Isomerism in Organic Molecules
Superimposable images are not optical isomerism
 Isomerism in Organic Molecules
 Optical isomerism

I
I
I
I
I
I
I
I
 Isomerism in Organic Molecules
 Stereocentre (chiral carbon) in optical isomerism

* *
* *
 Checkpoint 16
Identify the stereocenter present in the
compounds below.
a) c)

b) d)
 Checkpoint 17
Draw the stereoisomer for the following compounds
a) CH3CH2CH(NH2)CH3 and
b) 2-pentene
c) 2-butanol
 3.6 Introduction to Organic Molecules
Reactions
• All chemical reaction involve bond breaking and
bond making.
• Equation of organic reaction is different to general
chemical equation. It consist of starting material/s,
reagent/s, condition/s, and product/s
 3.6 Introduction to Organic Molecules
Reactions
Nucleophile (Nu-)
• is a species which attacks electron-poor carbon atom
of organic molecule, by donating electron-pair to the
atom.
• Nucleophiles are Lewis bases:
– All negative ions, OH-, Br-, I-
– Neutral molecule with lone pairs of electrons, H2O, NH3,
CH3NH2,
– Molecule with electron rich bond (double, triple bond), e.g.
alkene,alkyne, benzene
Introduction to Organic Molecules Reactions

Electrophile (E+)
• is a species (ion or molecule) which attacks electron-
rich site of organic molecules such as double bonds.
• Electrophiles are Lewis acids
– All positive ions, e.g. H3O+
– Electron deficiency species e.g. AlCl3, BF3
– Carbocation .
 Bond fission
• Covalent bond cleavage – during reaction, chemical
bonds have to be broken in order that new
compounds may be formed
• Breaking the chemical bonds is called fission
• Bond breaking or formation can be symmetrical or
unsymmetrical
 Type of bond fission
• Homolytic fission – two shared electrons of the
covalent bonds are split equally.
• The resulting species are known as free radical

• Heterolytic fission – two shared electrons of the

covalent bonds are remain one of the atom
• The resulting species known as ion
Mechanistic arrows in organic reactions
• Curved arrows - indicate breaking and forming of bonds
• A two-headed mechanistic arrow shows the movement of a pair
of electrons.

• Single head arrow shows the movement of a single electron

 Type of Organic Molecules Reactions
 Addition (electrophilic or nucleophilic)– two
reactants added together to form a single product (A
+ B  AB)

Electrophilic addition Nucleophilic addition

 Elimination reactions – single reactant splits into two

products (AB  A + B)
Introduction to Organic Molecules Reactions
 Substitution(nucleophilic,electrophilic or free
radical)– two molecules/atoms exchange parts (AB +
C  AC + B)

 Rearrangement reactions – a molecule undergoes

changes in the way its atoms are connected (A-B-A
 B-A-A)
 Group activity
 Find 3 examples of reaction for each type of organic
reactions.