ORGANIC CHEMISTRY

20
HIGHER LEVEL
Nucleophilic Substitution Reactions
Nucleophilic Substitution Reactions
Nucleophilic Substitution Reactions
Nucleophilic Substitution Reactions
Nucleophilic Substitution Reactions
Nucleophilic Substitution Reactions
Sample questions
Answers
20.1(part 2): Electrophilic Addition
20.1(part 2): Electrophilic Addition
20.1(part 2): Electrophilic Addition
20.1(part 2): Electrophilic Addition
20.1(part 2): Electrophilic Addition
20.1(part 2): Electrophilic Addition
Answers
Electrophilic Substitution Reactions
Electrophilic Substitution Reactions
Electrophilic Substitution Reactions
Electrophilic Substitution Reactions
Electrophilic Substitution Reactions
Sample questions
Reduction Reactions
Reduction Reactions
Reduction Reactions
Reduction Reactions
Sample Questions
Answers
Synthetic Routes
Synthetic Routes
Synthetic Routes
Synthetic Routes
Synthetic Routes
Synthetic Routes
Synthetic Routes
Synthetic Routes
Synthetic Routes
STEREOCHEMISTRY
 What is stereochemistry?

• The existence of compounds with the same molecular

but different arrangements of atoms in space.
• Types
▪ Conformational isomerism-arises from different
arrangement of atoms in space as a result of rotation
about c-c single bonds.
▪ Configurational isomerism-arises from the arrangement
of atoms in space due to restriction to rotation about
carbon-carbon bonds.
 Conformational isomerism

– Results from rotation of groups on a molecule about C-C

single bonds resulting in three-dimensional shapes
called conformations or conformers.
– Conformational isomers are drawn using the Newman
projection.
– The two most important positions are the eclipsed
conformation and the staggered conformations.

– Eclipsed Staggered
 Interconversion through rotation

The staggered and eclipsed conformations interconvert

by rotation around the C ⎯ C bond.
 CONFORMERS OF CYCLOHEXANE

Two types of conformers; the chair conformer and the boat

conformer. The chair conformer is more stable than the boat
conformer.
Why is the chair conformer more stable?

The boat conformer is less stable because of steric

hindrance caused by the proximity of some hydrogen
atoms.
 CONFIGURATIONAL ISOMERISM

These are compounds that differ from each other due to

arrangement of groups in space caused by restricted
rotation about c-c bonds.

CIS - TRANS ISOMERISM

If similar groups on the doubly bonded carbon are on the
same side of the double bond, it is the cis isomer; if
similar groups are across each other on opposite sides
of the double bond, it is the trans isomer:
CIS - TRANS ISOMERISM IN CYCLIC COMPOUNDS

Cyclic compounds also exhibit cis trans isomerism due to

restriction to rotation about the c-c bonds.

Cis - trans isomerism cannot occur when the groups attached to

the doubly bonded carbons are identical.
 E, Z TERMINOLOGY

In order to use the cis-trans terminology to differentiate

isomers, there are usually two identical groups to
compare.

The E,Z system of nomenclature was devised for

compounds that do not have similar groups attached to the
double bonded carbons such as 1-bromo-2-chloropropene.
 Cahn-Ingold-Prelog rules

In this system priority is given to atoms or groups and the

designation Z or E-isomer given to the isomer depending on
whether the priority groups are on the same side or on
opposite sides across the molecule.

Rules
1. Identify the atom with higher atomic mass directly
attached to the restricted carbons and give it priority.
 E/Z Sample

Br has higher priority. C2H5 has higher prio

 Cahn-Ingold-Prelog rules (continued)

2. For compounds with isotopes of the same elements,

priority should be given to isotopes with higher atomic
masses.

3. Where the same atoms are attached to the doubly bonded

carbons or restricted carbons priority should be given to
the next, and so on. Thus the longer hydrocarbon chain is
given priority.
 Example

• Draw and name, using the E/Z convention, the two

stereoisomers of 3-methylpent-2-ene.

• ANSWER
 OPTICAL ISOMERSIM
• This is the existence of compounds with groups
arranged in space to form non-superimposable
mirror images of each other.
• Optimal isomers have a chiral centre (asymmetric
centre) in which a carbon atom is bonded to four
different groups or atoms.

• Optical isomers are also known as enantiomers.

 Properties of enantiomers.
1. Optical activity: Enantiomers have the same
physical properties except that they rotate plane
polarized light in opposite directions.

2. Reactivity with other chiral molecules.

Enantiomers react the same way with non-chiral
molecules. However, they produce different
products with different chemical and physical
properties when they react with other chiral
molecules.
 Racemic mixture

• A mixture containing equal quantities of

enantiomers is called a racemic mixture. A racemic
mixture is optically inactive.

• When one enantiomer is present in excess of the

other, we say that there is an enantiomeric excess.
 Plane-polarized light

• Optical isomers show a difference in a specific

interaction with light.
• If light is passed through a polarizer, only the light
waves oscillating in a single plane pass through,
while light waves in all other planes are blocked out.
• This is known as plane-polarized light.
– A similar effect is achieved in polarized sunglasses.
 POLARIMETER
• The solution of isomers is placed in a tube through
which plane-polarized light is passed.
• Rotation of the polarization plane occurs and the
light then passes through a second polarizer
known as the analyzer which has been rotated until
the light passes through it.
• This analyzer measures the extent and direction of
rotation.
 Polarimeter
A B

C D
E

A – Light source produces light vibrating in all directions

B – Polarizing filter (polarizer) only allows light that vibrates
in one direction through (plane-polarized)
C – Plane polarize light passes through sample
D – If sample is optically active, the plane polarized light is
rotated in one direction, detro (+) or levo (-)
E – Analyzer – measures the amount of rotation, and gives
direction of rotation.
Factors determining the rotation

The observed rotation depends on:

• The concentration of the sample,

• the length of the sample tube and
• the temperature of the sample.

These must be kept constant in order to be able to

compare the rotation of different enantiomers.
 DIASTEREOMERS

• Diastereomers (diastereoisomers)are optically active

compounds that have more than one carbon bonded to
four different groups however the configuration at one
or more chiral centre is the same.
• Diastereomers do not form mirror images of each other
hence have different physical properties including
optical rotation.
Example
 SEPARATION OF CHIRAL
MOLECULES
• Resolution is the process by which two
enantiomers are separated from a racemic mixture.
– When a racemic mixture is reacted with a single
enantiomer of another chiral compound, the two
components of the mixture, the (+) and (-)
enantiomers react to produce different products.
– These products have different chemical and
physical properties which can be separated easily.
Thank you