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ORGANIC CHEMISTRY
111CHEM-3
for
Health-Science Students

Topics to be Covered:
Chapter 1: Introduction to Organic Chemistry
Chapter 2: Alkanes & cycloalkanes
Chapter 3: Alkenes & dienes
Chapter 4: Alkynes
Chapter 5: Benzene and Aromatic compounds
Chapter 6: Alcohols, Phenols and Ethers
Chapter 7: Aldehydes & Ketones
Chapter 8: Carboxylic acids & Amines

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Aim and Objectives:

The aim of this course is to introduce students to many of the key
concepts of organic chemistry and to provide a core for future
studies in chemistry and allied subjects

 Define organic chemistry.

 Appreciate the uniqueness of carbon in its ability to bond to
other carbon atoms.
 Understand hybridization of carbon in alkanes, alkenes and
alkynes.
 Use IUPAC nomenclature for organic compounds.
 Identify organic molecules as alkanes, alkenes, alkynes,
alcohols, or carboxylic acids.

Evaluation
• Med-term Exam: 25 %
• Home works and Quizzes: 10 %
• Laboratory: 25 %
• Final Exam: 40 %

• Credits 3 (2 Lecture + 1 Lab)

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Chapter 1
What is organic chemistry?
• The chemistry of living things.
• Since the chemistry of living things is based on carbon, the chemistry of carbon
compounds has come to be known as organic chemistry:
 The study of the structure, properties, composition, reactions, and
preparation of carbon-containing compounds.

What makes carbon so special?

• Carbon has 4 valence electrons.
• Carbon makes 4 strong covalent bonds.
• Carbon can bond with any element (H, F, Cl, Br, I, O, N, S, P).
• Carbon can bond with other carbon atoms forming complex
structures, such as long chains, branched chains, and rings.
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1) Compounds composed of only carbon and hydrogen atoms (C, H).

2) Cyclic (with rings) or Acyclic (without rings);
3) Saturated: contains only carbon-carbon single bonds;
4) Unsaturated: contains one or more carbon-carbon double or triple bonds

Chapter 1: Introduction

Atomic Orbitals: Are the space around the nucleus that occupied by electrons.
 The most common orbitals in organic chemistry are: s-orbitals and p-orbitals

(1) s-orbital: spherical orbital

with the nucleus located in
the center.

(2) p-orbital: dumbbell shaped

in which the nucleus is
between the lobes.

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Chapter 1: Introduction
Covalent bond: The forces of attraction between two atoms which are sharing
electrons to obtain a stable outer shell.
There are two types of covalent bond: sigma bond (σ) & pi-bond (π)
(1) sigma bond (σ) : Involves the overlap of two atomic orbitals head-to-head in one
position such as:
(a) two s-orbitals:

(b) one s and one p-orbital:

Chapter 1: Introduction

(c) two p-orbitals

(2) pi-bond (π): Involves the overlap of parallel p-orbitals at both lobes.

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There are three types of Carbon-Carbon Bonds in Organic Compounds:

Each carbon atom can form four bonds, either to other carbon atoms, or to different atoms
(such as H, O, N, S, P, etc.) and sometimes those bonds are multiple bonds (double or triple
bonds)

Chapter 1
 All single bonds are σ bonds;
 All double bonds are made up of one σ bond and one π bond;
 All triple bonds are made up of one σ bond and two π bonds.
There are three types of carbon backbones:

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Hybridization
When carbon atoms form bonds with each other, we describe the
resulting bonds using hybrid orbitals, which are formed by mixing
(hybridizing) the carbon’s atomic orbitals.

What is Hybridization?
Is a mathematical model that helps us to rationalize the bonding
in organic molecules.
 It means Mixing of atomic orbitals to give hybrid orbitals.

There are three types of Hybridization: Sp3, Sp2 & Sp

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Sp3-hybridization:
Electronic Configuration of Carbon atom:6C (ground state)

When carbon atoms bond to 4 other atoms, the 2s orbital and all three 2p orbitals
in the valence shell combine to produce four sp3 hybrid orbitals

All four sp3 orbitals are at the same

energy level, with one electron in
each hybrid orbital. 14

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In order to get as far away from each other as possible, the four sp3 orbitals are
arranged around the central carbon atom, in a tetrahedral shape with bond angles
of 109.5°.

 A functional group is an atom or a group of atoms with characteristic chemical and

physical properties.
 A functional group determines all of the properties of a molecule—its shape, physical
properties, and the type of reactions it undergoes.
 A functional group a way to classify organic compounds into families.
 A functional group a way to name organic compounds.
 There are about 100 functional groups exist, we will focus on about 10.

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Classes and functional groups of organic compounds

Questions: Identify the functional groups in the following molecule.

(a) Alcohol, amide, carboxylic acid

Q1. (b) Aldehyde, amine, ester
(c) Alcohol, amine, carboxylic acid
(d) Aldehyde, amide, ketone

Q2.
(a) Alcohol, ketone, aldehyde and ether
(b) Amide, ketone, alcohol and carboxylic
(c) Aldehyde, alcohol and ester
(d) Carboxylic acid, ether and aldehyde

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Chemical Formulas
A chemical formula is an expression that states the number and type of atoms
present in a molecule of a substance, and can be represented using:
(1) Molecular formula: which describe the kinds and numbers of each atom in a
molecule.
e.g.: CH4, C3H8, C2H6O

(2) Structural formula: which is an expanded molecular formula showing the

arrangement within the molecule of atoms and of bonds.

There are three types of Structural formulas:

(1) Expanded Structural Formulas:

In this type, all atoms and bonds are shown:

(2) Condensed Structural formulas:

Only specific bonds are shown; it is useful in
reducing the number of C—H bonds that
must be drawn.

(3) Bond-Line formulas:

Bonds are represented by lines; everywhere
two lines meet or a line begins or ends is a C
atom. H’s on C’s are not shown; H’s on other
atoms must be shown.

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Practice:
Q.1: Draw acceptable condensed structures and bond-line formulas associated with the
following expanded structural formulas.

Q.2: Draw an acceptable expanded structure and bond-line formula for the molecule:
CH3CH2CH2OH

Q.3: Draw an acceptable expanded structure and bond-line formula for the molecule:
(CH3)3CCH2CH(CH3)CH3 , CH3CH2CH(CH3)2

Isomerism: Is the phenomenon of the existence of isomers.

 Isomers:
Are different compounds with
the same molecular formula
but have a different structural
formulas.

Structural isomerism: In this type the atoms of the molecule are linked in a different order.
There are three types of structural isomerism: -
(1) Chain isomerism:
Isomers arise because of the possibility
of branching in carbon chains.

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(2) Position isomerism:

In position isomerism, the basic carbon skeleton remains unchanged, but
important groups are move around on that skeleton.

Example: C3H7OH

(3) Functional group isomerism: the isomers that contain different functional
groups are belong to different families of compounds.

Example: C3H6O

aldehyde
ketone

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Chapter 2
Alkanes
 Alkanes are commercially important
as fuels, solvents and oils.

 Are saturated hydrocarbons because they contain the maximum number of

hydrogen atoms that can bond with the number of carbon atoms in the
molecule.
 Are hydrocarbons having only nonpolar C-C and C-H single bonds.
 There are two types of alkanes:
 Acyclic alkanes (have no rings) with a general formula:CnH2n+2.
 Cycloalkanes (have one or more rings) with a general formula: CnH2n. 25

Structure of Alkanes:

 A carbon with four bonded

atoms is:
• sp3 hybridized,
• tetrahedral in shape,
• with 109.5o bond angles.

 Each carbon in the ethane

molecule, is sp3- hybridized and
tetrahedral in shape.
• Bonds arise from the overlap of
orbitals on adjacent atoms.
• Head-to-head overlap of sp3
orbitals produces a σ- bond.

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IUPAC (International Union of Pure and Applied Chemistry)has defined

systematic rules for naming organic compounds.

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Chapter 2

(1) A straight chain alkanes: The name composed of: Prefix ൅ an ൅ e

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Chapter 2
The First 20 Straight-Chain Alkanes

(2) Branched alkanes: Branched chain Unbranched chain

 Step 1: Find the parent chain

Example:
(a) Identify the longest continuous
chain of carbon atoms.

(b) If more than one different chains are of equal length, choose the one with the
greater number of branches as the parent.

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 Step 2: Numbering the carbons of the parent chain

(a) Number the carbon atoms of the
parent chain in the direction that gives
the smaller numbers for the locations of
the branches.

(b) If there is branching equidistant from both

ends of the parent chain, number so the second
branch point has the lowest number.

 Step 3: Substituents :
Identify the substituent groups attached to the parent chain.
CH3- : methyl
Example: CH3-CH2- : ethyl
Br : bromo
Cl : chloro

 Step 4: Write out the name

(a) Write out the name as a single word: Don’t
leave any spaces. Using:
1- hyphens (-) to separate prefixes
2- commas (,) to separate numbers
(b) In the name substituents are listed in
alphabetical order.
(c) If two or more identical substituents are
present use the prefixes below:
Note: these prefixes are not used for
alphabetizing purposes
Examples:

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Examples:

(1) Alkyl group: is an alkane with a hydrogen removed from one bond (an alkane
minus H atom).

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(a) Simple alky groups:

(b) Complex Alkyl groups:

Note:
• Iso- is part of the alkyl group name
and is used for alphabetizing.
• sec- and tert- are not included in the
alphabetical order.

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Examples:

(2) Halogen atoms are named as halo :

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(3) NO2 named nitro.

(4) NH2 named as amino.

 Common names of alkanes make use of prefixes, such as iso-, and neo-.
 The prefix iso- is commonly given to 2-methyl alkanes. In other words, if there is methyl group
located on the second carbon of a carbon chain, we can use the prefix iso-.
 The prefix neo- refers to a substituent whose second-to-last carbon of the chain is
trisubstituted (has three methyl groups attached to it).
 The prefix will be placed in front of the alkane name that indicates the total number of
carbons.
Examples:
 Isobutane which is the same as 2-methylpropane
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Chapter 2
 Isopentane which is the same as 2-methylbutane

 Neopentane which is the same as 2,2-dimethylpropane

Practice:
Q.1: What is the common name of the following compound?

Q.2: 3-ethyl-2,3-dimethylpentane, has how many carbon atoms in its longest continuous
carbon chain?
(a) 2 (b) 3 (c) 4 (d) 5

Q.4: How many carbon atoms are present per molecule in the compound?
5-Ethyl-4-isopropyl-2,3,6-trimethylnonane

(1) Identify the number of carbons in the ring and prefixing the alkane name with
cyclo.

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(3) If the substituent has a greater number of carbons, then use the alkyl chain as the
parent and the cycloalkane as a cycloalkyl- substituent

(4) When dealing with cycloalkanes with more than two substituents, start numbering with
a substituted carbon so that the substituted carbons have the lowest numbers (minimum
sum).

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(5) A carbon with multiple substituents should have a lower

number than a carbon with only one substituent.
(6) When two or more different
substituents are present, number
according to alphabetical order.

(7) Halogen Substituents: are treated exactly like alkyl

groups:

Examples:

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Chapter 2

(1) Alkanes containing up to 4 carbon atoms are gases (used as heating fuels),
pentane to heptadecane (C5 – C17) are liquids (used to make Gasoline, Diesel
and Jet fuels). The higher alkanes from C18 and higher are waxy solids (used as
fuel oil, Lubricating oil and as Paraffin wax).
(2) Alkanes are nonpolar, so they have weak intermolecular forces, low melting
points, and low boiling points.
 Melting points and Boiling points of alkanes increase as the number of
carbons increases (generally, increase with molecular weight), due to
increased surface area.
 Branched chain alkanes have lower boiling points than the straight chain
(generally, branching decrease boiling point).
(3) Solubility: Alkanes and cycloalkanes are insoluble in water.

Chapter 2
Isomerism in Alkanes:
Constitutional (Structural): Example 1: Butane and 2-methylpropane (C4H10) are:
 constitutional isomers (chain isomers);
 different compounds and have different physical and chemical
properties.
 Their boiling points, for example, differ by approximately 11°C.

Example 2:The molecular formula: C5H12

has three structural isomers :

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Chapter 2

Covalent bond can be broken by two ways:

(a) Heterolytic cleavage: Unsymmetrical breaking of bond;
 gives ions; (negatively charged (carbanion) and positively charged (carbocation)

(b) Homolytic cleavage: Symmetrical breaking of bond;

 one electron stays with each atom to form free radicals

Chapter 2

(1) Addition reactions: occur when an unsaturated reactant becomes a saturated

product (the π bond breaks, leaving the σ bond intact).

(2) Elimination reactions: the opposite of addition reactions.

(3) Substitution reactions: occur when an atom (or group) from an added reagent
substitutes for one in the reactant.

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Chapter 2

(1) Halogenation of Alkanes:

 Is a substitution reaction.
 Alkanes react with halogens
to produce alkyl halides.
 The reaction is catalyzed by
light or heat.
(2) Combustion of Alkanes:
 Is the oxidation of alkanes to carbon dioxide and water.
 It is the basis for their use as energy sources of heat and
power:

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Chapter 2
QUESTIONS
Q1. Alkanes whose carbon atoms are joined in rings are called ………………..

Q2. An alkane minus one hydrogen atom is called an …………… group.

Q3. What is the IUPAC name of the following compound?

Q4. What is the structure of 3-ethyl-2,2-dimethylheptane?

Q5. Draw the nine structural isomers of Heptane.

Q6. What is the IUPAC name for each of the following cycloalkanes?

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Chapter 3

Alkenes & Dienes

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Alkenes
Chapter 3

Alkenes contain C, H atoms and single and double bonds (unsaturated hydrocarbons).

 General formula: CnH2n where n = 2,3,..

 It is the same as the molecular formula for a
cycloalkane; therefore, alkenes and cycloalkanes
are structural (functional group) isomers.

Step 1: Number the longest carbon chain that contains the double bond in the direction that
gives the carbon atoms of the double bond the lowest numbers.
Step 2: Indicate the location of the double bond by the number of its first carbon.
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Chapter 3
Step 3: In branched or substituted alkenes the double bond takes priority over other
substituents in an alkene.

Examples:

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Cycloalkenes
Chapter 3

Are cyclic unsaturated hydrocarbons that have one or more carbon—carbon double
bonds.

Naming cycloalkenes:

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Chapter 3

Is similar to naming alkenes, except that you number the ring so that the
double bond is between C1 and C2.
Examples:

4-ethyl-1-methylcyclohexene

Alkenyl groups: Chapter 3

The names of the following alkenyl groups are used in IUPAC nomenclature of
cycloalkenes and cycloalkanes:
Examples:

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Structure of Alkenes Chapter 3

 A carbon with three bonded atoms is sp2-hybridized, trigonal,

and has approximately 120o bond angles.
sp2 hybridization:
 a 2s orbital is ‘mixed’ with two of
the 2p orbitals to form three
hybridized sp2 orbitals of equal
energy.
 A single 2p orbital is left over.
Structure of ethene (C2H4)

 Each Sp2 hybridized carbon forms three σ

bonds using three Sp2 hybridized orbitals.
 The remaining 2p orbital overlaps with a
parallel p-orbital of the adjacent atom to
form a pi (π) bond and complete the double
bond. 53

Chapter 3
Geometrical isomerism in Di-substituted alkenes

• Geometrical isomerism is an example

of stereoisomerism
• Found in some, but not all, alkenes
• Get two forms....

Examples:

(a) CH3-CH=CH-CH3 (b) BrCH=CHCl :

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Chapter 3
(c) CH3CH2CH=CHCH3 : (d) cis-trans isomers of 3-Hexene:

Problem: Which of these compounds exhibit geometric isomerism?

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Chapter 3
Reactions of Alkenes
(A) Electrophilic addition reactions:
(1) Hydrohalogenation of Alkenes:

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Chapter 3

Bromine (Br2) and chlorine (Cl2) add rapidly to alkenes to yield 1,2-dihalides (vicinal dihalides).

(3) Addition of Water to Alkenes:

 Hydration of alkene; A method for the preparation of alcohols (ethanol manufacture).
 Dilute aqueous solution of sulfuric or phosphoric is used to catalyze the hydration.

Chapter 3
(B) Hydrogenation of Alkenes:
Addition of hydrogen to alkenes in the presence of a metal catalyst (platinum, palladium, or
nickel).
Example:

Margarine is a synthetic product that mimics the taste and texture of

butter.
Margarine is composed mainly of partially hydrogenated vegetable oils
formed by adding hydrogen to the double bonds in the carbon chain
derived from unsaturated fatty acids.
This increases the melting point of the oil, thus giving it a semi-solid
consistency that more closely resembles butter.

Unsaturated oils with C - C double bonds are healthier than saturated fats with no double bonds.
Why does the food industry hydrogenate oils? The reasons relate to texture and shelf life.

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Glycol formation (Bayer's test): Alkenes can easily be oxidized by alkaline solution
of potassium permanganate (KMnO4) to give glycols:

 This reaction is used as a test of unsaturation: The purple color of KMnO4

disappears and a cloudy brown color appears due to precipitation of MnO2

Chapter 3
Types and Stability of Carbocation
A carbocation: is molecule in which a carbon atom bears three bonds and a positive charge.

Types of carbocations:
(1) Alkylic carbocations: in which an alkylic carbon bears the positive charge.

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Chapter 3
(2) Allylic carbocations: in which an allylic carbon bears the positive charge.
(Allylic: means next to a carbon-carbon double bond).

(3) Benzylic carbocations: in which a carbon attached to a benzene ring bears the
positive charge.

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Chapter 3
Stability of carbocations:
The stability of carbocations increases as the number of alkyl groups on the
positively-charged carbon atom increases.
The order of carbocation stability is :

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Chapter 3

Problem 1:

Problem 2:

Problem 3: Arrange the following carbocations in order of decreasing stability

(a) (b) (c) (d)

Solution: a = d > b = c

Chapter 3
The rule for predicting the predominant product:
Markovnikov's rule:
(In addition of HX to alkenes, H bonds to the carbon with more hydrogens and the
X bonds to the carbon with fewer hydrogens)
Example 1:

Example 2:

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Chapter 3

 In case if both carbon atoms of the double bond have the same number of hydrogens
or alkyl groups a mixture of addition products results:

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Chapter 3

Dienes: Are alkenes containing two double bonds, the suffix is diene.
Dienes are classified into three classes:
(1) Conjugated Dienes: In which
the double bonds and single
bonds are alternative (double –
single – double – single ….)
(2) Non-conjugated Dienes
(Isolated Dienes): In which the
double bonds are separated
from each other.

(3) Cumulated Dienes: In which

the double bonds are not
separated from each other.

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Addition Reactions of Conjugated Dienes:

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Chapter 3
Practice:
Q1. Draw the structure for each compound.
a. 2-methyl-2-pentene b. 2,3-dimethyl-1-butene
c. 1-Methylcyclohexene d. 5-Methyl-1-hexene
Q2. Complete the following reactions

Q4. What is the IUPAC name for each of the following compounds?

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Chapter 4

Alkynes

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Chapter 4

Alkynes:
Are hydrocarbons with one or more CC bond.
The triple bond in alkynes have one  and two  bonds between two C atoms.
Ethyne (acetylene) is a reactive alkyne: HCCH.
When acetylene is burned in the presence of oxygen the temperature is about
3200 K.

Acetylene
gas welding
& cutting.

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Chapter 4
Nomenclature of Alkynes
Alkynes are named in the same way as alkenes with the suffix -yne replacing the -ene for
alkenes.

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Chapter 4
Classification of Alkynes:

 Disubstituted alkynes, R-CΞC-R, are called internal alkynes.

 Monosubstituted alkynes, R-CΞC-H, are called terminal alkynes.

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Chapter 4

A carbon with two bonded atoms is:

 sp-hybridized, linear in shape, and has 180o bond angles.

The 2s orbital and one of the

three 2p orbitals are ‘mixed’ to
form two hybridized sp orbitals,
that are directed opposite to one
another on a straight line.
The two remaining 2p-orbitals
overlap with 2p-orbitals on the
adjacent carbon atom to form
two pi-bonds and complete the
triple bond.

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Chapter 4

Orbital Picture of Acetylene C2H2

1
pZ pZ
 
sp sp  sp
Hs C
py py
C sp Hs
2

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Chapter 4
Reactions of Alkynes
(1) Electrophilic Addition:
(a) Addition of HX to Alkynes:
Alkynes react with HCl or HBr to form geminal
dihalides (both halogen atoms are added to the
same carbon). Both additions are following
Markovnikov’s rule.

Example:

(b) Addition of Bromine and Chlorine to Alkynes (X2):

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Chapter 4
(2) Reduction of Alkynes: (hydrogenation)
Alkynes react with hydrogen gas in the presence of a metal catalyst
(Pt: Platinum or Pd: Palladium or Ni: Nickel).

(3) Alkyne Acidity: (Formation of acetylide anions)

Hydrogen atoms of the terminal alkynes (H-C≡C-; acidic), can be replaced by certain
metals to form salts known as acetylides when reacted with strong base like
sodium amide, NaNH2 :

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Chapter 4
(4) Alkylation of acetylide anions:
The acetylide anion can react with an alkyl halide to yield a new alkyne product.

Example: Synthesis of Octane from 1-Pentyne:

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Chapter 5
Aromatic compounds:
The term aromatic is used to describe benzene like molecules (in structure and chemical
behavior).
Many aromatic
compounds are
common in nature
and in medicine:

Characteristics of Aromatic Compounds:

• non-polar,
• insoluble in water,
• volatile, and flammable.
• toxic. Benzene itself is implicated as a cancer causing chemical.
• they tend to react by substitution rather than by addition.
• fulfill the aromaticity requirements. 80

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Chapter 5
To be classified as aromatic, a compound must have:
(1) Cyclic structure.
(2) Planar structure.
(3) Completely conjugated compound (no atoms in the ring can be sp3 hybridized instead
all atoms must be sp2 hybridized).
(4) Fulfill Hückel’s rule
Hückel’s Rule
 If the compound has 4n + 2  electrons, it is aromatic.
 If the compound has 4n electrons, it is antiaromatic.

Hückel’s rule, based on calculations: Example: Benzene

A planar cyclic molecule with alternating  It is a planar cyclic molecule with

double and single bonds has aromatic
stability if it has 4n+ 2  electrons (n is 0,
1, 2, 3, 4).
alternating double and single bonds,
 it has 6  electrons, therefore 4n+2 =
6, where: n = 1,
 benzene is aromatic

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Considering aromaticity, a compound can be classified in one of three ways:

1. Aromatic — A cyclic, planar, completely conjugated with 4n + 2  electrons.
2. Antiaromatic — A cyclic, planar, completely conjugated with 4n  electrons.
3. Nonaromatic — A compound that lacks one or more of requirements for aromaticity.

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Chapter 5
Q. Which of these is aromatic?

Q. Is this compound aromatic or antiaromatic?

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Chapter 5
Q. Indicate which of the following are aromatic and antiaromatic?

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Chapter 5
Nomenclature of Benzene Derivatives
1. Mono-substituted benzene: name the substituent and add the word benzene.
No number is needed .

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Chapter 5
2. The substituent and the benzene ring taken together may form a commonly
accepted parent name (11 compounds).

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Chapter 5
3. A hydrocarbon with a saturated chain and a benzene ring is named by choosing the
larger structural unit as the parent

4. Di-substituted Benzenes: there are three different ways that two groups can be
attached to a benzene ring, so a prefix—ortho, meta, or para—can be used to designate
the relative position of the two substituents.

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Chapter 5

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Chapter 5
7. For polysubstituents (three or more) on a benzene ring:
1. Number to give the lowest possible numbers around the ring (minimum sum).
2. Alphabetize the substituent names.
3. The substituent that comprises the common name if any, is located at C1

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Chapter 5
8. Phenyl and Benzyl groups:
 Phenyl group: used when the benzene ring is
named as substituent (C6H5-), (often abbreviated
Ph).

 Benzyl group: (the phenyl methyl group) is

the seven carbon unit consisting of
benzene ring and methylene (-CH2-).

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Chapter 5
Practice

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Chapter 5

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Chapter 5
Electrophilic Aromatic Substitution Reactions
 Is the characteristic reaction of benzene and
its derivatives.
 In these reactions, hydrogen on the benzene
ring is replaced by an electrophile.

ሺ1ሻ Halogenation of Benzene:

Benzene reacts with bromine (Bromination) and chlorine (Chlorination) in the
presence of Lewis acids.
Electrophile

Cl+

Br+
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Chapter 5
ሺ2ሻ Nitration of Benzene:
Benzene reacts with a mixture of concentrated nitric acid and concentrated sulfuric acid.

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Chapter 5
ሺ3ሻ Sulfonation of Benzene:
Benzene reacts with fuming sulfuric acid at room temperature to produce
benzenesulfonic acid.

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Chapter 5
ሺ4ሻ Friedel–Crafts Alkylation:
Reaction of benzene with an alkyl halide in the presence of a Lewis acid to produce
alkylbenzenes (Ar-R).

ሺ5ሻ Friedel–Crafts Acylation:

Reaction of benzene with an acyl halide in the presence of a Lewis acid (AlCl3,
FeBr3, etc.) to produce aryl ketone.

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Chapter 5
Effects of the Substituents on the benzene ring
A substituent already present on a benzene ring can affect the reactivity of the ring toward
electrophilic substitution and the orientation that the incoming group takes when it replaces
a hydrogen atom on the ring.
Substituents are classified into three classes:
(1) Electron-Donating Groups: speed-up the reaction (make the
ring more reactive than benzene) and direct new groups to
ortho-, para-positions.

(2) Electron-Withdrawing Groups: slow-down the reaction (make

the ring less reactive than benzene) and direct new groups to
the meta-position.

(3) Halogens: direct new groups to ortho-, para- positions but

they slow down the reaction, they are electron-withdrawing
groups (make the ring less reactive than benzene).
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Chapter 5
Examples:
(1) Methyl group is electron-donating group, activating group and ortho–para director.
 Toluene reacts faster than benzene in all electrophilic substitutions:

(2) Nitro group is an electron withdrawing group, very strong deactivating and a meta
director. Nitrobenzene undergoes nitration at a rate only 10-4 times that of benzene.

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Examples: Chapter 5

99

Chapter 5
Examples for other Aromatic Compounds

Aromatic Heterocycles:

Aromatic Polycyclic

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101

Chapter 6

Alcohols, Phenols
&
Ethers

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Chapter 6

General formula: &Q+Q 2+

 Alcohol contain -OH group bonded to an sp3

hybridized carbon.

 Since the -O-H bond is polar, alcohols are soluble in water.

103

Example: Give the IUPAC name of the following alcohol:

The IUPAC name is 5-methyl-3-hexanol

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Common names are often used for simple alcohols. To assign a common name:
Name all the carbon atoms of the molecule as a single alkyl group.
 Name all the carbon atoms of the molecule
as a single alkyl group.
 Add the word alcohol, separating the
words with a space.

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Chapter 6
Naming cyclic alcohols
When OH is bonded to a ring, the ring is numbered beginning with the OH.
• Because the functional group is at C1, the 1 is usually omitted from the name.
• The ring is then numbered to give the next substituent the lowest number.

Q. What is the IUPAC name of the following cyclic alcohol?

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Chapter 6
Glycols
• Compounds with two hydroxyl groups are called diols.
• Compounds with three hydroxyl groups are called triols
and so forth.
• 1, 2 diols (vicinal diols) are called glycols.

 Common names for glycols: use the name of the alkene from which they were
made.

107

Isomerism in Alcohols:
• Alcohols with three or more carbon
atoms display positional isomerism.
• The number of the carbon to which the
OH is attached is written before the –ol.

Alcohols are classified into three groups:

Based on the degree of substitution of the carbon to which the hydroxyl group is
directly attached

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Chapter 6
Physical Properties of Alcohols:
(1) Boiling points: Hydrogen bonding causes the boiling points of alcohols to be higher
than those compounds of similar molecular weight in other functional groups.
(2) Solubility: Because of hydrogen bonding, low molecular weight alcohols are water
soluble.
 Small alcohols are miscible in water, but solubility decreases as the size of the
alkyl group increases.

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Chapter 6

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Chapter 6
Reactions of Alcohols
(1) Dehydration of Alcohols:
Dehydration (elimination of H2O), is a 
elimination reaction in which the elements of
OH and H are removed from the  and  carbon
atoms respectively. It requires strong acids such
as sulfuric acid and forms alkenes.

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Chapter 6
(2) Oxidation of Alcohols:
(a) Primary alcohols: can be oxidized by an excess oxidizing agent like aqueous H2CrO4 or
aqueous solution of acidified potassium dichromate (VI) to give carboxylic acids:

(b) Secondary alcohols: can be oxidized to ketones using either aqueous H2CrO4 or aqueous
solution of acidified potassium dichromate (VI):

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(c) Tertiary alcohols: are resistant to oxidation due to the lack of hydrogen atoms on the
carbon atom to which the hydroxyl group is attached.

 Notice:
Chromium is reduced from the +6 oxidation state in H2CrO4 which is orange to the +3
with green color. This test can distinguish 1° and 2° alcohols from 3° alcohols.
113

Phenols
Chapter 6

Are compounds that have a hydroxyl group attached

directly to a carbon of benzene ring. Phenols are mostly
crystalline substances, with limited solubility in water,
they often have a characteristic smell.

IUPAC Nomenclature of Phenols:

 Phenols are named according to the rules for a substituted benzene ring, the parent
name is phenol.
 Numbering of the ring begins with the hydroxyl group.

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Chapter 6

Relative Acidities of Alcohols and Phenols:

(1) The polar O-H bond of alcohols makes them weak acids.
(2) Phenols are more acidic than alcohols and this is the characteristic property
that distinguishes them.
(3) Phenols will react with the base sodium hydroxide but alcohols will not.

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Chapter 6
Ethers
Are compounds having two alkyl or aryl groups bonded to an oxygen atom, as in the formula:

(R ൌ alkyl, Ar ൌ aromatic)

IUPAC Nomenclature of Ethers:

(1) The ether functional group does not have a
characteristic IUPAC nomenclature suffix, the name is
based on the longest carbon chain connected to the
ether oxygen. The other alkyl group is named as an
alkoxy group.
(2) The hydrocarbon groups may be alkyl, alkenyl,
vinyl, alkynyl, or aryl. 116

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Examples: Chapter 6

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Chapter 6
Common names of ethers:
Ethers are named using the names of the two alkyl groups followed by ether.

Isomerism:
Alcohols and ethers are functional group isomers.

Example: The formula C2H6O has

two functional isomers:
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Chapter 6
Q. Draw all the possible isomers (positional & functional) for each of the following
molecular formulas:
(a) C3H8O (b) C4H10O

119

Chapter 7

Aldehydes & Ketones

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Chapter 7

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Chapter 7

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Chapter 7

123

Common names:
 The first four aldehydes have common names:
 The simplest ketone is acetone.
 Others are named by expressing the two alkyl or aryl groups bonded to the
carbonyl group as separate words followed by the word ketone.

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 The IUPAC system retains the common names acetophenone, and

benzophenone.

125

Chapter 7

Example: Write structural formulas for all ketones with the molecular formula C6H12O and
give each its IUPAC name?

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Chapter 7
Reactions of Aldehydes and Ketones:
(1) Addition of Carbon Nucleophile:
 Addition of a carbon nucleophile (Grignard reagent) is the most
important type of carbonyl addition reaction because a new carbon-
carbon bond is formed in the process.
 Grignard reagents add to formaldehyde, aldehydes, and ketones to
give primary, secondary, and tertiary alcohols.

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Chapter 7

(c) Addition to a Ketone:

Treatment of a Grignard reagent with a ketone followed by protonation in aqueous acid
gives a 3˚alcohol.

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Chapter 7
(2) Oxidation:
(a) Oxidation of Aldehydes:
 Aldehydes are easily oxidized to carboxylic acids using a variety of reagents, including
chromic acid, silver salts, ...
Example: Oxidation of hexanal by
chromic acid to give hexanoic acid.

Aldehydes are also oxidized to carboxylic acids by Tollens’ reagent, a form of

Ag(I), which reduced to metallic silver. If this reaction is carried out properly,
silver precipitates as a smooth, mirror like deposit.

(b) Oxidation of Ketones:

 Ketones are not easily oxidized, requiring strong oxidizing agents as well as heat.
 Ketones undergo oxidative cleavage, via their enol form, when treated with potassium
dichromate, potassium permanganate, and other strong oxidants at higher temperatures
and higher concentrations of acid or base.
 The C - C double bond of the enol is cleaved to form two carboxyl or ketone groups.

Chapter 7

Example:
oxidation of cyclohexanone to
hexanedioic acid (adipic acid).

(4) Reduction
 Aldehydes are reduced to primary alcohols, and Ketones are reduced to secondary alcohols.

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Chapter 7

(b) Catalytic Reduction:

 The carbonyl group of an aldehyde or a ketone is reduced to a hydroxyl group by
hydrogen in the presence of a metal catalyst, (platinum or nickel).
 Reductions are generally carried out at temperatures from 25 to 100°C and at pressures
of hydrogen from 1 to 5 atm.

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Chapter 7

133

Chapter 8

Carboxylic Acids
&
Amines

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Chapter 8
Carboxylic Acids
Are compounds that contain the carboxyl group. They form important derivatives,
including esters, amides, anhydrides, and acid halides.

General formula:
 For an aliphatic carboxylic acid is RCOOH
 For an aromatic carboxylic acid is ArCOOH

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Chapter 8

(1) The name is derived from that of the longest carbon chain that contains the
carboxyl group by dropping the final -e from the name of the parent alkane and
adding the suffix -oic followed by the word acid.

(2) The chain is numbered beginning with the carbon of the carboxyl group.
Because the carboxyl carbon is understood to be carbon 1, there is no need to give
it a number.
Examples:

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Chapter 8
(3) A carboxylic acid containing a carboxyl group bonded to a cycloalkane ring is named by
giving the name of the ring and adding the suffix -carboxylic acid. The atoms of the ring are
numbered beginning with the carbon bearing the -COOH group.

(4) Dicarboxylic acids are named by adding the suffix -dioic acid to the name of the
carbon chain that contains both carboxyl groups.

137

(5) Many aliphatic carboxylic acids are named according to their source or for some
characteristic property.

Some Aliphatic Carboxylic Acids

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Chapter 8

(1) Acidity: Carboxylic acids are weak acids. They react with bases like NaOH and KOH to
form water-soluble salts.

(2) Esterification: (Fischer Esterification)

 Esters can be prepared by treating a carboxylic acid with an alcohol in the presence of
an acid catalyst, (H2SO4).
 An example of Fischer
esterification is the treatment
of acetic acid with ethanol in
the presence of concentrated
sulfuric acid, which gives
ethyl acetate and water.
139

Amines
Chapter 8

Amines are widely distributed in nature in the form of amino acids and proteins,
which are found in all higher animal forms, and in alkaloids, which are found in
most plants. Some of these substances are fundamental building blocks of
animal tissue, and other biologically important substances, including many
vitamins, antibiotics, and other drugs, contain amino groups, -NR2.

Structure and Classification:

 Amines are derivatives of ammonia in which one or more hydrogen atoms
have been replaced by alkyl or aryl groups.
 Amines are classified as primary, secondary, or tertiary, depending on the
number of carbon atoms bonded directly to nitrogen
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Chapter 8

 Amines are further divided into aliphatic and aromatic amines. In an aliphatic
amine, all carbons bonded to nitrogen are derived from alkyl groups; in an
aromatic amine, one or more of the groups bonded to nitrogen are aryl groups.

141

Chapter 8

 An amine in which the nitrogen atom is part of a ring is classified as a

heterocyclic amine. When the nitrogen is part of an aromatic ring, the amine is
classified as a heterocyclic aromatic amine

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Chapter 8
Nomenclature:
(1) Systematic names (IUPAC) for aliphatic amines: The suffix -e of the parent
alkane is dropped and is replaced with -amine

(2) For heterocyclic aromatic amines, their common names have been retained in
the IUPAC system.

143

Chapter 8
(4) Common names for most aliphatic amines are derived by listing the alkyl groups bonded
to nitrogen atom in alphabetical order in one word ending in the suffix -amine; that is,
they are named as alkylamines.

Physical Properties:
 Amines are basic compounds.
 Amines are polar compounds, and both primary and secondary amines form hydrogen
bonds. An N-H --- N hydrogen bond is weaker than an O-H --- O hydrogen bond. Because
hydrogen bonding is stronger in methanol than in methylamine, methanol has the higher
boiling point.
 All classes of amines form hydrogen bonds with water and are more soluble in water than
hydrocarbons of comparable molecular weight. Most low-molecular weight amines are
completely soluble in water. Amines of higher molecular weight are moderately soluble or
are insoluble.
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145

Some Medically Important Amines:

Amines are largely used in pharmaceutical industry. Morphine is used as
analgesics (pain killers). Novocaine, Amphetamine and Methamphetamine are
used as anesthetic (pain blockers), stimulate the central nervous system:

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Chapter 8
Reactions of Amines:
(1) Reactions with Acids:
Amines react with strong acids to form water-soluble salts.

(2) Reaction with Nitrous acid

Nitrous acid, HNO2, is an unstable compound that is prepared by adding sulfuric or
hydrochloric acid to an aqueous solution of sodium nitrite, NaNO2.
Nitrous acid is a weak acid undergoes reaction with amines in different ways,
depending on whether the amine is primary, secondary, or tertiary and whether
it is aliphatic or aromatic.
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Chapter 8
(a) Secondary Aliphatic and Aromatic Amines:
Secondary amines, whether aliphatic
or aromatic, undergo reaction with
nitrous acid to give N-
nitrosamines.
(b) Primary Aromatic Amines:
Primary aromatic amines react with nitrous acid to form arenediazonium salts, and when an
arenediazonium salt is treated with an appropriate reagent, nitrogen is lost and replaced
with another atom or functional group.
Example: Aromatic amines
can be converted to
phenols by first forming
the arenediazonium salt in
aqueous sulfuric acid and
then heating the solution.
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