CHM 211/212: Organic Chemistry I

Learning Outcomes
At the end of this course, you should be able to:
1.describe and solve problems in chemistry of aromatic compounds;
2.describe the structures of simple sugars, starch and cellulose, peptides and proteins
and show the difference in their conformation structure;
3.describe and solve problems in chemistry of bifunctional compounds;
4.explain the mechanisms of substitution, elimination, addition and rearrangement
reactions;
5.describe stereochemistry and its application;
6.describe condition and pathways of the following organic reactions-Grignard reaction,
Aldol and related reactions; and
7.describe simple alicyclic carbon compounds and their synthesis.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 COURSE CONTENT
Chemistry of aromatic compounds. Structures of simple sugars, starch and
cellulose, peptides and proteins. Chemistry of bifunctional compounds.
Energetics, kinetics, and the investigation of reaction mechanisms.
Mechanisms of substitution, elimination, addition, and rearrangement reactions.
Stereochemistry. Examples of various named organic reactions, e.g., Grignard
reaction, Aldol and related reactions. Simple alicyclic compounds and their
synthesis

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 REACTIONS
A chemical reaction is a process in which one or more substances, known as
reactants, are transformed into one or more substances, called products.
Chemical reactions involve breaking and forming chemical bonds, leading to
changes in the composition and properties of the substance.

Chemical reaction is represented with a chemical equation.

E.g. 2H2(g) + O2(g) 2H2O (l)

The equation indicates that two molecules of hydrogen gas react with one
molecule of oxygen gas to produce two molecules of water (liquid).

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 REACTIONS
Organic reactions fall into four particularly important types.
1.Addition Reactions: Two reactants add together to form a single new product
with no atoms “left over”. The process can be generalized as:
H H H Br
A+B C
+ H Br H C C H
H H H H
Ethylene Bromoethane
(an alkene) (an alkylhalide)

2. Elimination Reactions
A single reactant splits apart into two products. A B + C
H Br
H H
NaOH
H C C H + H Br
H H H H
Bromoethane
Ethylene
(an alkylhalide)
(an alkene)

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 REACTIONS
3. Substitution Reactions
These occur when two reactants exchange partners to give two new products.

A B + C D A C + B D
H H
Light
E.g. H C H + Cl Cl H C Cl + HCl
H H
Methane Chloromethane
(an alkane) (an alkyl halide)

4. Rearrangement Reactions
These occur when a single reactant undergoes a reorganization of bonds and
atoms to yield an isomeric product.

A B

CH3CH2 H Acid H3C H

catalyst
E.g.
H H H CH3
1-Butene 2-Butene

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 HOW ORGANIC REACTIONS OCCUR
An overall description of how a specific reaction occurs is called a Reaction
Mechanism. A reaction mechanism details exactly what takes place at each
stage of a chemical transformation-which bonds are broken, which bonds are
formed, in what order, and the relative rates of each step.

Chemical bond breakage can occur in two ways:

1.electronically symmetrical way where one electron remains with each product
fragment
2.electronically unsymmetrical way where both bonding electrons remain with
one product fragment, leaving the other fragment with an empty orbital.

Symmetrical cleavage is also called a HOMOLYTIC cleavage

Unsymmetrical cleavage is called HETEROLYTIC cleavage or process.

A B A + B Homolytic bond breakage; gives radicals. One electron stays with

each fragment

A B A+ + B- Heterolytic bond breaking (polar); two electrons stay with one

fragment [cation and anion]

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 HOW ORGANIC REACTIONS OCCUR
Conversely, covalent two-electron bond formation can occur in two ways:
Electronically symmetrical (homogenic) way or electronically unsymmetrical
(heterogenic) way.

A + B Homogenic bond making (radical);

A B
one electron from each fragment.
Radical reactions

A + B
Heterogenic bond making (polar); two electrons
A B
from one fragment. Polar reactions.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 RADICAL REACTIONS AND HOW THEY
OCCUR
Rad + A B Rad A + B
Reactant Substitution Product
radical product radical

It involves three steps light

1. Initiation - the initial production of radicals Cl Cl 2 Cl

2. Propagation steps – radicals undergo substitution reactions

a. Cl + H CH3 H Cl + CH3

b. CH3 + Cl Cl Cl 3 + Cl
Cl CH

c. Repeat steps a and b above

3. Termination steps Cl + Cl Cl Cl

Cl + CH3 Cl CH
Cl 3

H3C + CH H3C CH3

3

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 POLAR REACTIONS AND HOW THEY
OCCUR
Polar reactions occur as a result of attractive forces between positive and negative
charges on molecules. Chemists normally indicate the electron pair movement that occurs
during a polar reaction by using curved arrows. A curved arrow indicates where electrons
move as bonds in reactants are broken and bonds in products are formed.

A+ + B-

This curved arrow shows that electrons are moving from B- (electron-rich) to A + (electron-
poor)
Nucleophile
electron-rich

A+ + B- A B

Electrophile The electrons that moved

electron-poor from B- end up here in
the new bond

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 REACTION RATES AND EQUILIBRIA
All chemical reactions can be written as equilibrium processes. The position of a chemical
equilibrium is expressed by an equation in which K eq, the equilibrium constant, is equal to
the product concentrations multiplied together, divided by the starting material
concentrations multiplied together.
aA + bB cC + dD

The equilibrium constant tells which side of the reaction arrow is energetically favoured.
If Keq is bigger than 1, then the product concentrations [C] c[D]d are larger than the reactant
concentrations [A]a[B]b, and the reaction proceeds as written from left to right.
Conversely, if Keq is smaller than 1, the reaction does not take place as written.

For reaction H2C=CH2 + HBr CH3CH2Br

= 7.5x107

Since Keq is relatively large, the reaction proceeds in the direction written and 99.999997%
of all ethylene molecules are converted into bromoethane molecules.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 REACTION RATES AND EQUILIBRIA
The direction in which a reaction proceeds, that is have a fabourable equilibrium constant,
that is, proceed as written, the energy level of the products must be lower than the energy
level of the starting materials. In other words, when that reaction proceeds, energy must
be given off.
The total amount of energy change during a reaction is called the standard Gibbs free-
energy change, Go.
Go ( is difference) is the difference between the free energy of the products and the free
energy of the starting materials. For a favourable reaction, Go has a negative value.

Go.and Keq measure whether or not a reaction is favoured, therefore, they are related

Go = -RT lnKeq or Keq = e-Go/RT

R is gas constant = 1.986 cal/degree.mol [8.309 J/degree.mol]; e = 2.718, the base of

natural logarithm.

Go is attributable to the combination of an enthalpy factor, Ho, and an entropy factor, So
Go = Ho + TSo

The o (enthalpy term) is called the heat of reaction and is a measure of the change in total
bonding energy during a reaction. If o is negative, then the bonds in the product are
stronger than the bonds in the starting material, heat is evolved; reaction is EXOTHERMIC.
CHM 212 Organic Chemistry II Charles C. Orji, Ph.D
 REACTION RATES AND EQUILIBRIA
If o is positive, then reaction is termed ENDOTHERMIC. The bonds in the product are
weaker than the bonds in the starting material.
So is the entropy term. It is a measure of the change in the amount of molecular disorder or
freedom of motion caused by a reaction.

E.g. A B+C

There is more freedom of movement (disorder) in the products than in the reactant because
one molecule has split into two. So has a positive value.

For a reaction of the type A + B C, So is negative.

The thermodynamic quantities that go into making up an equilibrium are limited.

Equilibrium constant tells the position of equilibrium, or how much product is formed.
Equilibrium constant does NOT tell the RATE of reaction, or how fast equilibrium is
established. A reaction may be extremely slow even when it has favourable equilibrium
constants.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

DESCRIBING A REACTION: ENERGY DIAGRAMS AND TRANSITION STATES

In order for a reaction to proceed, reactant molecules must collide, and reorganization of
atoms and bonds must occur.
Consider addition reaction of HBr with ethylene:

H H H H
H Br Br
H C C H C C Br
H H H H
Carbocation

As the reaction proceeds, ethylene and HBr must approach each other, the ethylene pi
bond and H-Br bond must break, a new carbon-hydrogen bond must form in the first step,
and a new carbon-bromine bond must form in the second step.

Reaction energy diagrams are used to graphically depict energy changes that occur during
a reaction.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

DESCRIBING A REACTION: ENERGY DIAGRAMS AND TRANSITION STATES

At the beginning of the reaction, ethylene and HBr have the total amount of energy
indicated by the reactant level on the left side of the diagram. As the two molecules crowd
together and reaction commences, their electron crowds repel each other causing the
energy level to rise. If the collision has occurred with sufficient force and proper orientation,
the reactants continue to approach each other despite the rising repulsion until the new
carbon-hydrogen bond starts to form. At some point, a structure of maximum energy is
reached. This structure of maximum energy is called the TRANSITION STATE.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

DESCRIBING A REACTION: ENERGY DIAGRAMS AND TRANSITION STATES

a. A fast exothermic reaction

(c) (d) b. A slow exothermic reaction
c. A fast exothermic reaction
d. A slow exothermic reaction

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 DESCRIBING A REACTION: INTERMEDIATES

Recall again the reaction of ethylene and HBr:

H H H H
H Br Br
H C C H C C Br
H H H H
Carbocation

The carbocation, which is formed

briefly during the course of the
multistep reaction, is called a
reaction intermediate. As soon
as the intermediate is formed in
the first step by reaction of
ethylene and H+, it reacts further
with bromide ion in a second step
to give the final product.

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D

 DESCRIBING A REACTION: INTERMEDIATES

Each step in a multistep step process can be considered separately. Each step
has its own G# (rate) and its own Go (energy change). The overall Go of the
reaction, however, is the energy difference between initial reactants (far left) and
final product (far right).

CHM 212 Organic Chemistry II Charles C. Orji, Ph.D