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Department of Chemical & Physical Sciences

Faculty of Natural Sciences
NMD Campus
CHE21M4
ORGANIC CHEMISTRY

Foreword

Organic Chemistry is a set of concepts and key facts interconnected to build the
foundation of this science. This course is a logical continuation of the First Year Organic
Chemistry course and is intended to give you a deeper understanding of Organic
Chemistry. New basic concepts and facts that are closely interrelated to CHE1201 will be
presented and you are encouraged to familiarise yourselves with all the notions you have
learnt last year. Attending all classes is highly recommanded.
You are invited to read the notes carefully and complement them by reading organic
chemistry textbooks in the library. The list of textbooks given below is just indicative and
not exhaustive. You are welcome to come to my office (Room 304-A) to ask questions on
any aspect of the course.

Selected Reference Books:

- Advanced Organic Chemistry Part A & B by Fancis A. Carey & Richards J.
Sundberg.
- Organic Chemistry by McMurry. Internation Student 6th Edition.Thompson.
- Organic Chemistry by K. Peter C. Vollhardt. W.H. Freeman & Co
- Stereochemistry of Organic compounds. Principles and Applications by
D.Nasipuri. John Wiley & Sons
- Various internet resources.
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Introduction, Revision:

Chapter One
ACIDS AND BASES.

1. Brønsted-Lowry definition

A Brønsted-Lowry acid is a substance that donates a proton; a Brønsted-Lowry base

is a substance that accepts a proton;
Example:

HCl H O H O H Cl
Acid Conjugate
Base base
H H
Conjugate acid
In general:
H A B A H B
Acid Base conjugate Conjugate
base acid
Example:
O O
H H
C C O
H C H O H H C H H
O O
base
acid Conjugate
H H Conjugate acid
base
Water can act either as an acid or a base, depending on the circumstances: with HCl,
water acts as a base that accepts a proton to give the hydronium ion, H3O+. When
reacted with amide ion, -NH2, water becomes an acid which donates a proton to give
ammonia and hydroxide ion, -OH.

2. Acid and Base Strength

Strong acids, like HCl, react almost completely with water; weak acids such acetic
acid (CH3CO2H) react only slightly.
The strength of an acid is described by its equilibrium constant:
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H A H2O A H3O

H3O A
Keq
HA H2O
In dilute aqueous solutions normally used for measuring acidity, the concentration of
water [H2O], remains nearly constant at approximately 55.6 M. Thus the following
expression can be derived:
H3 O A
Ka Keq H2O Ka acidity constant
HA
The higher the value of Ka, the stronger the acid, and the more dissociated.
Acid strengths are normally expressed in pKa:
pKa -log Ka
The stronger the acid, the smaller the pKa value.

3. Predicting Acid-Base Reactions from pKa values

The proton will always go from the stronger acid to the stronger base: an acid will
donate its proton to the conjugate base of any acid that has a higher pKa, and the
conjugate base of an acid will remove a proton from an acid that has a lower pKa.
Example:
CH3CO2H + -
OH CH3CO2- + H2O
pKa = 4.76 pKa = 15.75
Another way to correctly predict acid-base reactivity is to remember that the products
of an acid-base reaction must be more stable than the reactants, so that the products
do not react back to the reactants. Water is a weaker acid than acetic acid; -OH will
hold a proton more tightly than the acetate ion does.

CH3CO2H + -
OH H2O + CH3CO2-
stronger acid stronger base weaker acid weaker base

4. Organic Acids and Organic Bases

Organic acids are compounds containing hydrogen atoms bonded to oxygen

atoms (like in methanol, CH3O-H or acetic acid, CH3COO-H) and those
hydrogen atoms bonded to a carbon atom next to a C=O double bond (like in
acetone).
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O
H H O H H
C
C C O C C
C O H H
H H
H H
H H Acetic acid H
Acetone H
Methanol pKa=4.76
pKa=15.54 pKa= 19.3

Why are these molecules acidic? Because the loss of a proton results in the
formation of a conjugate base that is relatively stabilized:

H H
this anion is stabilized by
- H+ C O having a negative charge on
C O H
H a highly electronegative atom.
H H
H

H O H O H O

C C O - H+ C C O C C O
H H H
H H this anion is stabilized by H
H
having a negative charge on
a highly electronegative atom
and by resonance.

O O
H H
C - H+
C C
H H
H H
5. Lewis Definition
O
H H H
H
C C
C C C C
H H
H H H H
this anion is stabilized by
having a negative charge on
a highly electronegative atom
and by resonance.

Lewis definition is broader and covers more facts than Brønsted-Lowry’s.

A Lewis acid is a substance that accepts an electron pair, and a Lewis base is
substance that donates an electron pair.
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Filled Vacant
orbital orbital

B .. A B A
Lewis Base Lewis Acid
Examples:

..O

..
Cl-
..
Cl H H H O H
- +
Hydrogen H H
Chloride Water Hydronium ion
(a Lewis Acid) (a Lewis Base)
Cl CH3 Cl CH3
Cl Al ..N CH3 Cl Al N CH3
Cl CH3 Cl CH3
Aluminum Trimethylamine
trichloride (a Lewis Base)
(a Lewis Acid)
Note that in both reactions above, the electrons flow from the electron-rich Lewis
base to the electron-poor Lewis acid as shown by the arrows.

Exercices:

1. Classify the following acids by their decreasing acid strength (starting from the
strongest to the weakest):

a) HCOOH, CH3COOH, CH3CH2COOH, CH3CH2CH2COOH

Answer:
pKa
HCOOH 3.75
CH3COOH 4.76
CH3CH2COOH 4.87
CH3CH2CH2COOH 4.82

The acids can be strengthened by pulling charge away from the -COO- end. You
can do this by attaching electronegative atoms like chlorine to the chain.
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b) CH3COOH, CH2ClCOOH, CHCl2COOH, CCl3COOH.

pKa
CH3COOH 4.76
CH2ClCOOH 2.86
CHCl2COOH 1.29
CCl3COOH 0.65

c) CH2FCOOH, CH2ClCOOH, CH2BrCOOH, CH2ICOOH.

pKa
CH2FCOOH 2.66
CH2ClCOOH 2.86
CH2BrCOOH 2.90
CH2ICOOH 3.17

2. Show the most acidic hydrogen atoms in the following molecules:

CH3-OH, CH3CO2H, CH3CO2CH3, CH3CO2CH2CH3, CH3COCH2CH3

3. Which one is the stronger base among the following molecules:

NH3, CH3NH2, (CH3)2NH, (CH3)3N
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Chapter Two:

Reactions in Organic Chemistry

1. Addition Reaction: occurs when 2 reactants add together to form a single new
product with no atoms “left over”. The new product is larger than the reactants.
H H Br
H H H
C C + H Br H C C H C C H
H H H
Ethene H H H
Bromoethane
If the alkene is unsymmetrical, the product will be determined by the
Markovnikov’s rule: the proton will become attached to the carbon atom with the
fewer alkyl substituents and the halide ion (Br-) becomes attached to the carbon
with more alkyl substituents.

CH3CH2 H
CH3CH2 H
C C + H Br Br C C H
H H
H H
1-Butene 2-Bromobutane

Watch this animation on Electrophilic additions video:

http://www.youtube.com/watch?v=YnD42ZTPdFU

2. Rearrangement Reaction: where a single reactant undergoes a reorganisation of

bonds and atoms to yield an isomeric product.
CH3CH2 H CH3 H
Acid catalyst
C C C C
H 1-Butene H H 2-Butene CH3

3. E limination Reaction: is the opposite of addition reactions where a single product

splits into two products.
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H Br
H H
Base H Br
H C C H C C +
H H
H H Ethene
Bromoethane
H OH H H
H2SO4
H C C H C C + H OH
H H
H H

When the starting material (alcohol or alkyl halide) is secondary or tertiary, the
reaction proceeds by the preferential removal of the β-hydrogen atom from the
carbon that has the smallest number of hydrogen atoms (Saytsev’s rule):
H
H
H3C H H H3C C H
Base
H C C H C C H

Br H H H

4. Substitution Reaction: where 2 reactants exchange parts to give 2 new products. It

is a reaction in which an atom (or group of atoms) in a molecule is replaced by
another atom (or group of atoms).
Here again, the reaction can be polar (electrophilic or nucleophilic) or non polar
(radical).
H H
light
H C H + Cl Cl H C Cl + H Cl

H H
Methane Chloromethane
Neutral (radical) substitution