Basic Organic Chemistry

TABLE OF CONTENTS

CHAPTER TOPIC PAGE

1 CHEMICAL BONDING 2

2 STEREOCHEMISTRY 9

3 ALKANES & ALKYL HALIDES 26

4 ALCOHOLS & ETHERS 35

5 AMINES 43

6 ALKENES 46

7 ALKYNES 51

8 ALDEHYDES & KETONES 54

9 CARBOXYLIC ACIDS & DERIVATIVES 59

10 BENZENE & DERIVATIVES 67

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 Basic Organic Chemistry

CHAPTER 1
CHEMICAL BONDING

The study of the compounds of carbon.

 Organic compounds
is everywhere eg: foods, flavours, fragrances, medicines, toiletries,
cosmetics, clothes, plastic, fibers, glues, fuels and also in our bodies
includes biological molecules, drugs, solvents, dyes
does not include metal salts and materials (inorganic)
does not include materials of large repeating molecules without sequences
(polymers)
 Carbon
Atomic number 6, group 4A element, shares four valences of electrons and
form four strong covalent bonds
Bond to one another through single and multiple bonds. Forming long chains
and rings

CHEMICAL FORMULA IN ORGANIC CHEMISTRY

 An organic compound will contain carbon and hydrogen atoms and possibly
one or more atoms of oxygen, nitrogen, sulfur or phosphorus.

TYPE OF FORMULA

 Three types of chemical formula have energized,

 Empirical formula
 Molecular formula
 Structural formula

Empirical Formula

 Tell us the types of atoms and their numerical ratio in a molecule or the
simplest ratio of atoms in a molecule
 Example:
A molecule of ethane contains carbon and hydrogen atoms in a ratio of 1 to
3 (1:3)
If you are given the empirical formula CH2, its molecular formula could be C2H4,
C3H6 or any multiple CH2
Empirical formula CH2O:-
Formula molecule for formaldehyde (CH2O)
Empirical formula for acetic acid (C2H4O2)
Glucose and fructose (C6H12O6)

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 Basic Organic Chemistry

Molecular Formula

 Tell us the actual number of each type of atom in a molecule

 The molecular formula contains the total number of atoms in the molecule
 Example:
The molecular formula for ethane is C2H6

Structural Formula

 Shows the structure of a molecule, that is the order of attachment of the atoms
 Need to know the structure of a molecule in order to explain or predict the
chemical reaction / reactivity
 The most useful of the different types of formulas
Complete structural formulas
Condensed structural formulas – bonds are not always shown and atoms of the
same type bonded to one another atom are grouped together
Example: CH3CH3

Condensed structural formula of ethane

H H

H C C H

H H

Structural formula of ethane

Example:
 Empirical formula : CHN
 Molecular formula : C2H7N
 Structural formula :

H H H

H C C N

H H
H

 Condensed structural formula : CH3CH2NH2

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 Basic Organic Chemistry

Drawing Chemical Structures

 Chemists use shorthand ways for writing structures

 Condensed structures: C-H and C-C and single bonds aren’t shown but
understood;
If C has 3 H’s bonded to it, write CH3
If C has 2 H’s bonded to it, write CH2; and so on. The compound called 2-
methylbutane, for example, is written as follows:
 Horizontal bonds between carbons aren’t shown in condensed structures, the
CH3, CH2 and CH units are simply but vertical bonds are added for clarity.

Skeletal Structures/Bond-line formula

 Minimum amount of information but unambiguous (clear)

 C’s not shown, assumed to be at each intersection of two lines (bonds) and at
end of each line
 H’s bonded to C’s aren’t shown – whatever number is needed will be there
 All atoms other than C and H are shown

Cyclic Compounds and Polygon Formulas

 Carbon atoms can joined together in rings are well as in chains

 A compound that containing one or more rings is called a cyclic compound
 Cyclic structures usually represented by polygon formulas (another type of
condensed structural formula)
 In polygon formulas, a corner represents a carbon atom along with its
hydrogen; the sides of the polygon represent the bond joining the carbons
 Atoms other than carbon must be indicated in the polygon formula including
multiple bonding

H 2C CH2
H 2C CH2
or
H 2C CH2

H2C CH2
or
H2 C NH N H
H2C CH2

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 Basic Organic Chemistry

ORGANIC REVIEW: FAMILIES OF ORGANIC COMPOUNDS

 Organic compounds can be grouped into families by their common structural

features
 We shall survey the nature of the compounds in a tour of the families in this
course

Functional groups

 Functional group – collection of atoms at a site within a molecule with a

common bonding pattern
 The group reacts in a typical way, generally independent of the rest of the
molecule
 For example, the double bonds in simple and complex alkenes react with
bromine in the same way.

H OH
H
C C
H H

Survey of Functional Groups

 The functional groups affect the reactions, structure, and physical properties of
every compound in which they occur.

Types of Functional Groups: Multiple Carbon – Carbon Bonds

 Alkenes have a C-C double bond.

 Alkynes have a C-C triple bond.
 Arenes have special bonds that are represented as alternating single and
double carbon – carbon bonds in a six membered ring.

C C
C C
C C
C C C C
Alkenes alkynes Arenes (aromatic ring)

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 Basic Organic Chemistry

Functional Groups with Carbon Singly Bonded to an Electronegative Atom

 Alkyl halide : C bonded to halogen (C-X)

 Alcohol : C bonded O of a hydroxyl group (C-OH)
 Ether : Two C’s bonded to the same O (C-O-C)
 Amine : C bonded to N (C-N)

Groups with a Carbon – Oxygen Double Bond (Carbonyl Groups)

 Aldehyde : one hydrogen bonded to C=O

 Ketone : two C’s bonded to the C=O
 Carboxylic acid: OH bonded to the C=O
 Ester : C-O bonded to the C=O
 Amide : C-N bonded to the C=O
 Acid chloride : Cl bonded to the C=O
 Carbonyl C has partial positive charge (δ+)
 Carbonyl O has partial negative charge (δ-)

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 Basic Organic Chemistry

RESONANCE

 Some molecules have structures that cannot be shown with a single

representation.
 The real structure is a hybrid of the different resonance forms.
 Arrows connecting resonance forms are double headed.
 In a resonance form, only the electrons are moved.

 For example, benzene (C6H6) has two resonance forms with alternating
double (1.34 Ao) and single bonds (1.48 Ao). Individual resonance forms
are imaginary structure.

(two individual resonance forms)-imaginary

So what is the real structure of benzene? The real structure of benzene is as

below.

In the resonance hybrid, the real structure, all its C-C bonds equivalent (1.397Ao),
midway between double and single
The resonance hybrid is more stable than any individual resonance form would be.

Resonance Forms

Resonance Forms can be compared using the following criteria, beginning with the
most important:
- Has as many octets as possible.
- Has as many bonds as possible.
- Has the negative charge on the most electronegative atom.
- Has as little charge separation as possible.

Drawing Resonance Forms using the Curved Arrows

 We can imagine that electrons move in pairs to convert from one resonance
form to another
 When drawing resonance forms or structures only electron pi and non-
bonding electrons can moved.
 Atoms will never move.

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 Basic Organic Chemistry

 Those electrons can only move towards the sp and sp2 hybrid atoms but not
sp3.
 A curved arrow shows that a pair of electrons moves from the atom or bond at
the tail of the arrow to the atom or bond at the head of the arrow.

Example 1

The curved arrow indicates that a

lone pair of electrons moves from
the top oxygen atom to become
part of an N=O double bond The new resonance structure has a
double bond here
.. -
:O : :O :
H H
+ +
C N C N

H H -
H :O: H :O:
..

And lone pair of electrons here

Simultaneously 2 electrons from
N=O bond move onto the bottom
oxygen atom to become lone pair

Exercise:
Draw the resonance structure the compound below.

i. iv
.

ii. v.

iii. vi
.

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 Basic Organic Chemistry

CHAPTER 2
STEREOCHEMISTRY

OVERVIEW

Isomers

Constitutional Isomers Stereoisomers

Configurational Conformation
Isomers Isomers

Geometrical Optical
Isomers Isomers

CONSTITUTIONAL ISOMERS

 Different order of connections gives different carbon backbone and/or different

functional groups.
 Isomers that differ in how their atoms are arranged in chains are called
constitutional isomers.
 It is also known as structural isomers
 Compounds other than alkanes can be constitutional isomers of one another.
 However they must have the same molecular formula to be isomers
 Example: Molecular formula C5H10
 Structures of C5H10

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 Basic Organic Chemistry

Type of Constitutional
Isomer Structure
Isomers

Different carbon skeleton

butane
isobutane

O
Different functional groups HO
ethyl alcohol dimethyl ether

Different position of H2N

functional groups H2N
isopropyl amine propyl amine

STEREOISOMERS

 The arrangement of atoms in molecules whose connectivity remains the same

but their arrangement in space is different in each isomer.
 The field of stereochemistry is one of the central parts of organic chemistry and
includes many important topics.
 There are two types of stereoisomerism:

(1) Conformation isomerism

(2) Configurational isomerism

Conformation Isomerism

 Carbon compound with single bond (σ) [sp3 hybridization] can undergo rotation
about that bond with respect to each other.
 The temporary molecular shapes that result from rotation of groups about
single bonds are called conformation of molecules.
 Each possible structure is called a conformer.
 An analysis of energy changes associated with a molecule undergoing rotation
about single bonds is called conformational analysis.

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 Basic Organic Chemistry

Representing Conformations

 Conformers interconvert rapidly and structure is an average of conformers.

 Molecular models are three dimensional (3D) objects that enable us to
visualize conformers.

Eclipsed conformation Staggered conformation

Conformers also can be representing in two dimensional (2D) through:

1. Sawhorse representations

 C-C bonds are at angle to the edge of the page and all C-H bonds are shown.

H
H H H
H
C C C C
H H H H
H H
H

2. Newman projections show how C-C bond would project end-on onto the
paper.
 Bonds to front carbon are lines going to the centre
 Bonds to rear carbon are lines going to the edge of the circle.

H H H
H H
H
H H H H
H H

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 Basic Organic Chemistry

Types of conformation

• Staggered conformation: a conformation about a carbon-carbon single

bond where the atoms on one carbon are as far apart from atoms on the
adjacent carbon (more stable) (θ = 60º)

• Eclipsed conformation: a conformation about a carbon-carbon single

bond where atoms on one carbon are as close as possible to the atoms on
the adjacent carbon (less stable) (θ = 0º)

 Skew conformation (θ = 0º<X<60º)

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 Basic Organic Chemistry

Ethane Conformation

 The most stable conformation of ethane has all six C-H bonds away from each
other is staggered conformation where θ = 60º.
 The least stable conformation has all six C-H bonds as close as possible is
eclipsed conformation where θ = 0º in a Newman projection – energy due to
torsional strain.
 Torsional strain - extra energy present in the eclipsed conformation due to the
slight repulsion between electron clouds in the carbon–hydrogen bonds as they
pass each other relatively in short distances
 The torsional strain between eclipsed and staggered ethane is approximately
12.1 kJ/mol.

12.1 kJ/mol
eclipsed
E
N
E
R
G
Y
0 kJ/mol staggered

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 Basic Organic Chemistry

Conformation of Propane

 Propane (C3H8) torsional barrier around the carbon-carbon bonds 14 kJ/mol.

 Eclipsed conformer of propane has two ethane-type H-H interactions and
interactions between C-H and C-C bond.

CH3 H3C H
H H
H
H H H H
H H

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 Basic Organic Chemistry

Conformations of Butane

CH3 CH2 CH2 CH3

We will look down the C2 - C3 bond.

CH3 start CH3

CH3 H
H
H H H H
H H
SYN (0o) CH3
ANTI (180o)
CH3 CH
CH3 H 3
H
CH3 H
H H
H H H
ECLIPSED (240o)
GAUCHE (60o)
CH3
CH
H
3
CH3 H

H CH3 H H
H H H
finish
o
GAUCHE (300 )
ECLIPSED (120o)

 Anti conformation has two methyl group 180° away from each other
 Rotation around the C2-C3 gives eclipsed conformation
 Staggered conformation with methyl groups 60° apart is gauche
conformation.

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 Basic Organic Chemistry

• Anti conformation provides the lowest energy arrangement

• Gauche conformation position where substituent is closer and intermediate
in energy
• Sterric Strain - the repulsive interaction that occurs when atoms are forced
closer together than their atomic radii allow.

Interaction Cause Energy kj/mol

H-H torsional 4.0
H-CH3 torsional 6.0
CH3-CH3 torsional & sterric 11.0
CH3-CH3 gauche sterric 3.8

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 Basic Organic Chemistry

CONFIGURATIONAL ISOMERISM

 Configurational isomerism can be classified into:

(1) Geometric isomerism

(2) Optical isomerism

Geometric Isomerism

 Results from rigidity in molecules and occurs in only two classes of

compounds; alkenes and cyclic compounds.

Cis – Trans Isomerism in Alkenes

 Groups attached by a double bond cannot rotate around the double bond
without the [sp2 hybridization] pi bond being broken
 Because of rigidity, groups that attached to pi-bonded carbons are fixed in
space relative to one another.
 The presence of a carbon-carbon double can create two possible structures.
Cis isomer – two similar groups on same side of the double bond.
Trans isomer – similar groups on opposite sides
 Each carbon must have two different groups for these isomers to occur.

H H H CH3
C C C C
H3 C CH3 H3 C H
cis-2-Butene trans-2-Butene
mp -139°C, bp 4°C mp -106°C, bp 1°C

 The cis-trans system: configuration is determined by the orientation of atoms of

the main chain

Sequence Rules: The E, Z Designation

 When the carbon double bond is tri– or tetra–substituted, how can we name
the substituents?

A C A C

C C or C C

B D B H

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 Basic Organic Chemistry

Cahn, Ingold, Prelog Rules

• Priority rules
 Each atom bonded to the stereocenter is assigned a priority, based on
atomic number. The higher the atomic number, the higher the priority

(1) (6) (7) (8) (16) (17) (35) (53)

-H -CH3 -NH2 -OH -SH -Cl -Br -I .

Increasing Priority

 If priority cannot be assigned on the basis of the atoms bonded to the

stereocenter, look to the next set of atoms. Priority is assigned at the first
point of difference. (1) (6) (7) (8)
-CH2-H -CH2-CH3 -CH2-NH2 -CH2-OH
Increasing Priority

 Atoms participating in a double or triple bond are considered to be bonded

to an equivalent number of similar atoms by single bonds
The E, Z uses priority rules
• If groups of higher priority are on the same side, configuration is Z
(German, zusammen)
• If groups of higher priority are on opposite sides, configuration is E
(German, entgegen)

higher higher higher lower

C C C C
lower lower lower higher
Z E
(zusammen
Z (zusammen) E (entgegen
(entgegen)
) )

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 Basic Organic Chemistry

• Example: name each alkene and specify its configuration by the E,Z system

(Z)-3,4-dimethyl-2-pentene (E)-2-chloro-2-pentene

H CH 3 Cl H
(a) (b)
C C C C
H3 C CH(CH 3 ) 2 H3 C CH 2 CH 3

ClCH 2 CH 3 Cl H
(c) C C (d) C C
H3 C CH 2 CH 3 Br CH 3

(E)-1-chloro-2,3-dimethyl-2-pentene (Z)-1-bromo-1-chloro-1-propene

cis-trans isomerism in cycloalkanes

 Rotations about C-C bonds in cycloalkanes is limited by the ring structure.

 Rings have two “faces” and substituents are labeled as to their relative facial
positions.
 They are two different 1,2-dimethyl-cyclopropane isomers, one with the two
methyl's on the same side (cis) of the ring and one with the methyl on opposite
sides (trans).

H3C 2 CH3
Br 5 4 H
1 3
3
1 2
H 4 H H CH2CH3

cis-1,3-dimethylcyclobutane trans-1-bromo-3-ethylcyclopentane

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 Basic Organic Chemistry

OPTICAL ISOMERISM

The Reason for Handedness: CHIRALITY

 Molecules that are not superimposable with their mirror images are chiral
(have handedness).
 A plane of symmetry divides an entire molecule into two pieces that are exact
mirror images.
 A molecule with a plane of symmetry is the same as its mirror image and is
said to be achiral.

The mirror image

of a chiral object is
different and will not
superimpose on the Objects which are chiral have a sense of
original object. “handedness” and exist in two forms.

• Mirror image: the reflection of an object in a mirror

• Objects that are not superposable on their mirror images are said to be
chiral, that is, they show handedness
• Objects that are superposable on their mirror images are said to be achiral,
that is, they do not show handedness. An achiral object has at least one
element of symmetry.
• A molecule cannot be chiral if it has a plane of symmetry.
• A plane of symmetry is a plane that cuts through an object in such a way that
one half of the object is an exact mirror image of the other half.
• A molecule that has a plane of symmetry must be identical to its mirror image
and therefore must be nonchiral, or achiral.

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 Basic Organic Chemistry

F The plane of the paper

Cl Cl is a plane of symmetry

Br
F F

Br Cl Cl
Cl Cl Br

Two identical groups render a tetrahedral carbon achiral.

 Center of symmetry: a point so situated that identical components of the

object are located equidistant on opposite sides and equidistant from the point
along any axis passing through the point.
Br H

Cl
Cl

H Br center of
symmetry

Chirality centers

 A point in a molecule where four different groups or atoms) are attached to

carbon is called a chiral or stereogenic or asymmetric center.
 There are two nonsuperimposable ways that 4 different groups (or atoms) can
be attached to one carbon atom.
 A chiral molecule usually has at least one chirality center.
A stereogenic carbon is tetrahedral and has four different groups attached.

stereocenter O
Cl
*
H F * *
Br *

O
Carvone Nootkatone
Spearment oil Grapefruit oil

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 Basic Organic Chemistry

Type of Stereoisomer in Optical Isomerism

 Can be subdivided into two general categorized;

(1) Enantiomers
(2) Distereomers

 Enantiomers are stereoisomers whose molecules are nonsuperposable mirror

images for each other.
 Example:

HO O O OH
C C

C C
HO H H OH
CH 3 H3 C
Lactic acid
OH OH

H3 C C CH 2 OH HOH2 C C CH 3

H H

1,2-propanediol

 Distereomers are stereoisomers whose molecules are not mirror images of

each other.

COOH COOH
H N H2 H 2N C H
C
C C
H OH H OH
CH 3 C H3

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 Basic Organic Chemistry

Fischer projections

 Fischer projection: a two-dimensional representation showing the configuration

of a stereocenter
 horizontal lines represent bonds projecting forward
 vertical lines represent bonds projecting to the rear
 the only atom in the plane of the paper is the stereocenter

COOH COOH
OH
H C
H
OH CH3 CH3
lactic acid

Fisher Projection Steps

1. Orient the stereocenter so that bonds projecting away from you are vertical and
bonds projecting toward you are horizontal
2. Flatten it to two dimensions

OH CH 3 CH 3

C (1) H C OH (2) H OH
H
CH 3
CH 3 CH 2
CH 2 CH 3 CH 2 CH 3
(S)-2-Butanol (S)-2-Butanol
(3-D formula) (Fischer projection)

Naming Enantiomers : R,S convention

• Priority rules (Cahn, Ingold, Prelog)

 Each atom bonded to the stereocenter is assigned a priority, based on
atomic number. The higher the atomic number, the higher the priority

(1) (6) (7) (8) (16) (17) (35) (53)

-H -CH3 -NH2 -OH -SH -Cl -Br -I .

Increasing Priority

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 Basic Organic Chemistry

 If priority cannot be assigned on the basis of the atoms bonded to the

stereocenter, look to the next set of atoms. Priority is assigned at the first
point of difference.

(1) (6) (7) (8)

-CH2-H -CH2-CH3 -CH2-NH2 -CH2-OH
Increasing Priority

 Atoms participating in a double or triple bond are considered to be bonded

to an equivalent number of similar atoms by single bonds

Steps in Naming Enantiomers

1. Locate the stereocenter

2. Assign a priority to each substituent from 1 (highest) to 4 (lowest)
3. Orient the molecule so that the group of lowest priority (4) is directed away
from you
4. Read the three groups projecting toward you in order from highest (1) to lowest
priority (3)
5. If reading is clockwise, configuration is R (from the Latin rectus). If it is
counterclockwise, configuration is S (from the Latin sinister).

1 2 2
clockwise
1 counter
clockwise
C C
4 4
3 3
view with
substituent
of lowest
priority in R S
back
(rectus) (sinister)

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 Basic Organic Chemistry

MESO COMPOUND

 Meso compound: an achiral compound possessing two or more stereocenters.

 Example: Stereoisomer of tartaric acid

COOH COOH
H C OH HO H
C
A:
C C
HO H H OH
COOH COOH
2R, 3R 2S, 3S

COOH COOH
H C OH HO H
B: C
C C
H OH HO H
COOH COOH

2R, 3S 2S, 3R

 2R, 3S and 2S, 3R are identical due to existence a plane of symmetry

perpendicular to C-C.
 One meso compound (B) and a pair of enantiomers (A).
 Meso compounds are achiral by virtue of a symmetry plane, but contain a
stereogenic center.

plane of symmmetry mirror

Cl Cl Cl Cl

H3C CH3 H3C CH3

H H H H

PROPERTIES OF STEREOISOMERS

 Enantiomers have identical physical (except for ) and chemical properties.

 Diastereomers are different compounds and have different physical and
chemical properties.
 Meso-tartaric acid, for example, has different physical and chemical
properties from its enantiomers.

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 Basic Organic Chemistry

CHAPTER 3
ALKANES AND ALKYL HALIDES

 Alkanes: hydrocarbons in which all the carbon-carbon bonds are single bond.
 General formula: CnH2n+2
 Cycloalkanes: alkanes in which all or some of carbon atoms are arranged in a
ring.
 General formula: CnH2n
 Source: Petroleum - involved in refining / distillation of petroleum based on
volatility of compound, petroleum catalytic cracking (thermal cracking)

SHAPES OF ALKANES

 Tetrahedral orientation and sp3 hybridization

 Straight chain in 2 dimension (2D)
 Zigzagged in 3 dimension (3D)
 Branched – chain alkanes - Rotation of carbon-carbon (C > 3) single bond
produce rearrangements to less straight chain; neoalkane and isoalkanes
Example: isobutane, neopentane

isobutane neopentane

 Unbranched or normal alkanes – each carbon atom within the chain is

bonded to no more than two other carbon atoms; n-alkanes.
Example: n-butane

n-butane

 Constitutional isomers – two compounds have their atoms connected in a

different order (same molecular formula and different structures)
Example: butane, isobutane
Different physical properties (boiling point, densities etc)

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 Basic Organic Chemistry

HOMOLOG SERIES OF ALKANE AND ALKYL GROUPS

M.F Name B.P(oC) Phy. State Solubility

CH4 Methane -161.6
C2H6 Ethane - 88.6
C3H8 Propane - 42.1
C4H10 Butane - 0.5
C5H12 Pentane 36.1
C6H14 Hexane 68.7
C7H16 Heptane 98.4
C8H18 Octane 125.7
C9H20 Nonane 150.8
C10H22 Decane 174.0

Alkyl

 Alkyl group: remove one H from an alkanes (a part of structure)

 The alkyl groups have names that end in; …yl
Example: methane  methyl
 Type of alkyl group:

ALKANE GROUP ALKYL TYPE

methyl (-CH3)
Methane
methylene (-CH2)
n-propyl
Propane
isopropyl
n-butyl
sec-butyl
Butane
isobutyl
tert-butyl

CH3CH2CH2 CH3CHCH3
n-propyl isopropyl

CH3

CH3CH2CH2CH2 CH3CHCH2
n-butyl isobutyl

CH3
CH3CH2CHCH3
CH3CCH3

sec-butyl
tert-butyl

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 Basic Organic Chemistry

IUPAC SYSTEM OF NOMENCLATURE (ALKANES GROUP)

The numenclature of organic compounds (alkane/other organic compounds ),

normally follow the IUPAC System.

Prefix + Parents + Suffix (PPS)

Prefix – what and where are the substituents?
Parents – how many carbon atoms present / longest carbon chain?
Suffix – what is/ are the functional group/ family present?

STEP 1

 Determine the number of carbon in the longest continuous carbon chain.

The longest continuous chain may not always be obvious way formula is
written

STEP 2

 Number the longest chain beginning with the end of the chain nearer to
the substituent.

STEP 3

 Use the number obtained by application of step 2 to assign the location

of substituent group. Put the parent name in last place and precede by the
assign’s number of substituent group. Number separated with hyphen.

STEP 4

 If 2 or more substituents present, give each substituent a number

corresponding to its location on the longest chain.

STEP 5

 If 2 substituents are present on the same carbon atom, use that number
twice.

STEP 6

 If 2 or more substituents are identical, indicate by the use of prefixes di-,

tri, tetra- make each or every substituent has a number and commas to
separated number.

*STEP 7

 When 2 chains of equal length compete for selection as parent chain,

choose the chain with the greater of substituent.

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 Basic Organic Chemistry

*STEP 8

 If branching occurs at an equal distance from either end of the longest chain,
choose the name that gives the lower number at the first point of different.
* 2 rules maybe required occasionally.

*STEP 9
 First letter of prefixes di, tri, terta, t-butyl, sec-butyl are not counted in the
arrangement of IUPAC name but first letter of isopropyl and cyclobutyl are
counted.

Examples

1. 2. 3.

NOMENCLATURE OF CYCLOALKANES

 Cycloalkanes with one ring are named by attaching the prefix cyclo
 Straight-forward naming for only one substitution (alkylcycloalkanes)
 If ≥2 substituents, beginning with the substituent in alphabetical and number in
direction (lowest number possible)
 If single ring system attached to greater single chain; compound is named
cycloalkylalkanes

Exercise:

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 Basic Organic Chemistry

PHYSICAL PROPERTIES OF ALKANES AND CYCLOALKANES

 Each alkane differs from preceding alkanes by one CH2 group.

 Compound series where member differs from next member by constant unit;
homologous series (Member of homologous series – homologs)
 <C4 (gases) C5-C17 (liquid) >C18 (solid).
 Boiling point
 Increase with increasing molecular weight
 Branched alkanes provide lower boiling point.(Van der Waals force)
(Example: Hexane (68.7°C) compared to 2-methylpentane (60.3°C)
 Unbranched alkanes provide higher molecular size and surface area,
then Van der Waals force increase. Thus, more energy required to
separate molecule from boiling point.(Branched alkanes or compact
molecule provide lower surface area – lower van der Waals force)
Melting point
 Unbranched alkanes – not smooth increase in melting point with
increasing molecular weight
 Branched alkanes – unpredictable
 Cycloalkanes – higher melting point than open-chain counterparts.
 Density
 The least dense of all groups of organic compounds (< 1.00 gmL-1).
 Solubility
 Insoluble in water (low polarity and inability to form hydrogen bond)
 Dissolve in solvent with low polarity.

REACTION OF ALKANES

 Halogenation Reaction

Heat or light
R-H + X2 R-X + HX (X = Cl or Br)

SYNTHESIS OF ALKANES AND CYCLOALKANES

Hydrogenation Of Alkenes And Alkynes

 Alkenes and alkynes react with H2 in the presence of metal catalyst (Pd, Ni and
Pt) and in solvent (EtOH)
 1 mole H2 for alkenes and 2 molar H2 needed for alkynes.

H2, Ni
C=C C–C
2 H2, Ni
C≡C C–C

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 Basic Organic Chemistry

Reduction Of Alkyl Halides

 Reduction of alkyl halides are carried out through:

i. Reduction by lithium aluminium hydride

R-X LiAlH4 R-H

C9H19CH2Br LiAlH4 C9H19CH3

ALKYL HALIDES

 The halogen atom (F,Cl,Br,I) is attached to an sp3-hybridized carbon.

 The carbon-halogen bond of alkyl halides is polarized – halogen more
electronegatives than carbon.(C-F – highly polar and C-I lower polarity)
 Alkyl halides are used as solvents for non-polar compound.
 Compound in which a halogen atom is bonded to an sp2-hybridized carbon are
called; vinylic halides or phenyl halides.

NOMENCLATURE OF ALKYL HALIDES

 Alkanes bearing halogen substituents are named as haloalkanes (IUPAC

system).
 If the parent chain has both alkyl group and halogen, number the chain from
the nearer the substituent.
 If 2 substituents are in equal distance, number the chain from the end nearer
that has alphabetical precedence.

Exercise:

1. 2. 3.

CLASSIFICATION OF ALKYL HALIDE

Primary alkyl halide Secondary alkyl halide Tertiary alkyl halide

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 Basic Organic Chemistry

PHYSICAL PROPERTIES OF ORGANIC HALIDES

 Solubility: alkyl halide has low solubility in water.

 Dichloromethane (methylene chloride, CH2Cl2), trichloromethane (chloroform,
CHCl3) and tetrachloromethane (carbon tetrachloride, CCl4) used as solvents
for non-polar compound
 Cumulative toxicity and carcinogenic
 Boiling point:
Increase with increasing of molecular weight
F < Cl < Br < I
If compound with same halogen atom, increments of atoms in chain increase
the boiling point.

Compound Phase
Iodomethane (bp 42°C) Liquid
Bromoethane (bp 38°C) Liquid
Chloroethane (bp 13°C) Gas

 Density: correspond to the molecular weight.

F < Cl < Br < I

REACTION OF ALKYL HALIDES

Reduction Of Alkyl Halides

LiAlH4
i. C9H19CH2Br C9H19CH3
n-decane bromide n-decane

Zn, CH3COOH
ii. C16H33I C16H34
H H
Mg, (CH3)2CHOH
iii. H
Cl

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 Basic Organic Chemistry

SYNTHESIS OF ALKYL HALIDES

Halogenation Of Alkenes

Addition of Hydrogen Halides to Alkenes

 Reaction are controlled by Markonikov rule;

In the addition of HX to an alkene, the hydrogen atom adds to the carbon atom of the
double bond that already has the greater number of hydrogen atoms.

CH3 CH CH2 + HBr CH3 CH CH3

propene
Br
2-bromopropane

Addition of Halogen to Alkenes

CH3 CH CH2 + Br2 CH3 CH CH2

propene
Br Br
1,2-dibromopropane
 Reaction will produce vicinal alkyl halides

Allylic Halogenation

 Alkenes can be directly halogenated in the allylic position.

 High temperature and lower concentration of halogen used to prevent reaction
at double bond.
Cl

400OC
+ Cl2 + HCl

 Karl Zieglar (1942) introduce; A reagent is more specific than Br2 for allylic and
benzylic halogenation, N-bromosuccinimide (NBS).

O
(NBS)
N Br Br O
H H
O N H
+
hv CCl4
O
Conversion Of Alcohol To Alkyl 3-bromocyclohexene
Halides

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 Basic Organic Chemistry

 Alcohol react with a variety of reagents to yield alkyl halides

 The most commonly used reagent are:

Hydrogen Halides (HCl, HBr, HI)

 Only tertiary alcohol actively reaction with hydrogen halide. Reactivity followed
tertiary > secondary > primary alcohol

HX
R-OH R-X + H2O (X = Cl, Br or I)
H2SO4

H3C OH H3C Cl

HCl (gas)
+ H2O
ether

1-methylcyclohexanol 1-chloro-1-methylcyclohexane

Phosphorus Tribromide (PBr3)

 Secondary and primary alkyl halide can be synthesized with PBr3

OH Br
PBr3
3CH3CH2CHCH3 3CH3CH2CHCH3 + P(OH)3
Ether, 35 C 0

2-butanol 2-bromobutane

Thionyl chloride (SOCl2)

 Alkyl halides from secondary and primary alcohol are synthesized from SOCl2

OH Cl
O O
SOCl2
pyridine

benzoin decyl chloride

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 Basic Organic Chemistry

CHAPTER 4
ALCOHOLS & ETHERS
 Alcohol: Compound that have hydroxyl group bonded to saturated, sp 3
hybridized, carbon atom.
 Phenol: compound that have hydroxyl groups bonded to aromatic rings.
 Application: MeOH (methanol) starting material for production of
formaldehyde, acetic acid, gasoline additive (MTBE). 2-phenylethanol main
component of rose oil fragrance.

IUPAC NOMENCLATURE OF ALCOHOL

 Alcohol are classified as primary (1°), secondary (2°) or tertiary (3°) depending
on the number of organic groups bonded to the hydroxyl-bearing carbon.

H H R

R C OH R C OH R C OH

H R R
primary alcohol secondary alcohol tertiary alcohol

STEP 1: Select the longest carbon chain containing the hydroxyl group and derive
the parent name by replacing -e ending of the corresponding alkanes with –ol.

STEP 2: Number the alkane chain beginning at the end nearer the hydroxyl group.

STEP 3: Number the substituent according to their position on the chain, and write
the name listing the substituents in alphabetical order.

HO H
4
OH 1
2 2 1
3
3 5 6 3
2 4
1 7 4
OH
CH3 HO H
3-methyl-2-heptanol cis-1,4-cyclohexanediol 3-phenyl-2-butanol

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 Basic Organic Chemistry

PROPERTIES OF ALCOHOL

 (Methanol and Ethanol) – liquid; (Butanol – Decanol) – (conc. liquid); Branched

alcohol – solid; Phenol – solid in room temperature
 Boiling point
 Elevated boiling point compared to other hydrocarbon
 Form hydrogen bond in liquid state – a positively polarized –OH hydrogen
atom from one molecule is attracted to lone pair of electrons on a negatively
polarized oxygen atom from another molecule, strong force hold that
molecules together
 Intermolecular attractions must be overcome for a molecule to break free
from the liquid and enter vapor state – boiling point is raise.
hydrogen bond interaction
R
 
O H R
H O


Molecular Boiling point

Compound
weight at 1 atm (°C)
Methanol CH3OH 65
Methane CH4 -88.6
Ethanol CH3CH2OH 78.5
Ethane CH3CH3 -44.5
Phenol C6H5OH 182
Toluene C6H5CH3 110.6
 For alcohol and isomer compound, (compact and bulky molecules) provide
lower surface (lower hydrogen bond interaction) and boiling point decrease
with increasing of alkyl branch.
 Straight chain alcohol provides high surface area, increase hydrogen bond
interaction.

 Solubility of alcohol
 Hydroxyl group (OH-) – hydrophilic
 Hydrocarbon – hydrophobic
 Solubility of alcohol decrease with increasing of carbon atom (highly
hydrophobic)
 Branched alcohol provides higher solubility compared unbranched alcohol;
branch alkyl – compact of hydrophobic group.

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 Basic Organic Chemistry

REACTION OF ALCOHOL

OXIDATION OF ALCOHOL

 Oxidation of 1° and 2° alcohol → aldehydes and ketones.

 3° alcohol – no reaction

Collins reagent or Cu metal

 Collins reagent or Cu metal (moderate oxidation reagent)

 Oxidation of 1° and 2° alcohol with moderate oxidation reagent yielded
an aldehydes and ketones

O
Cu or CrO3 in pyridine
CH3CH2OH CH3CH
ethanol ethanal

Chromic acid reagent

 Chromic acid – strong oxidation reagent (reaction between potassium

dichromate and sulfuric acid).

K2Cr2O7 + H2SO4 H2Cr2O7 + K2SO4

 Oxidation of 1° and 2° alcohol with strong oxidation reagent yielded an

carboxylic acids and ketones

H2Cr2O7
CH3CH2CH2OH CH3CH2COOH + Cr3+
acetone, 25 C 0

1-propanol propanoic acid

REDUCTION OF ALCOHOL
TsCl LiAlH4
ROH ROTs R-H
pyridine
O
TsCl = tosyl chloride
Cl S CH3

OH OTs
LiAlH4
+ TsCl
pyridine
C.
cyclohexanol cyclohexane

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 Basic Organic Chemistry

CARBON-HYDROXYL (C-OH) BOND BREAKING

HCl or PCl3
Conversion of alcohol into alkyl halides RCl

HBr or PBr3
ROH RBr

HI or PI3 RI

Reaction with hydrochloric acid (Lucas reagent)- “refer PRACTICAL”

ROH + HCl/H2O ZnCl2

RCl

Reaction with thionyl chloride, SOCl2

ROH + SOCl2 RCl + SO2 + HCl

Reaction with phosphorus trichloride, PX3

3ROH + PX3 3RX + H3PO3

PX3 = PCl3, PBr3 or PI3

DEHYDRATION

Alcohol into alkenes

H OH

H+
C C C C + H2O

CH3CHCH3
H+
CH3CH=CH2 + H2O
*Zaitsev Rule OH propene
2-propanol

Alcohol into ether

 Dehydration of 2 molecules of alcohols in the presence of strong acid

(high quantity) at 140°C yielded symmetry ether.
H2SO4, 140°C
2CH3CH2OH CH3CH2OCH2CH3 + H2O

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 Basic Organic Chemistry

SYNTHESIS OF ALCOHOL

ALCOHOL FROM ALKENES

Hydration of alkenes

 Addition of water in the presence of acid as catalyst (Markonikov rules).

H OH

H+
C C + H2O C C

H+
CH3CH=CH2 + H2O CH3CHCH3
propene
OH
2-propanol

Hydroboration – Oxidation alkenes

 Hydroboration / oxidation yields the product of anti-Markonikov rule.

B2H6 H2O2, OH-

C C C C C C

H B H OH
H H

H2O2, OH-
CH3CH=CH2 + B2H6 CH3CH2CH2OH
propene propanol
Hydroxylation of alkenes

KMnO4, OH-
C C C C

OH OH
alkene diol

CH3CH=CH2 KMnO4, OH-

CH3CH2CH2 + MnO2

OH OH
propene 1,2-propanediol

REDUCTION OF CARBONYL COMPOUND

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 Basic Organic Chemistry

Hydrogenation aldehydes and ketones (Non-Selective)

 Hydrogenations of aldehydes or ketones are carried out in the presence

of Ni, Pt or Pd as a catalyst.
 Hydrogenations of aldehydes → primary alcohol
 Hydrogenations of ketones → secondary alcohol

O
+ H2 Pt
CH3CH CH3CH2OH
ethanal ethanol

=O + H2 Ni
OH

cyclohexano ne cyclohexanol

Reduction of acid carboxylic and ester (Non-Selective)

 Reducing agent: LiAlH4

 Reduction of acid carboxylic and ester → primary alcohol

O
=

=
CH2COCH3 LiAlH4 CH2CH2OH
O HO
H3O+

Reduction of acid carboxylic and ester (Selective)

 Reducing agent: NaBH4

O O
=

= CH2COCH3 NaBH4 CH2COCH3

O HO
CH3OH
H

NaBH4
CH3CH=CHCH2C=O CH3CH=CHCH2CH2OH
H2O
3-pentenal 3-penten -1-ol

ETHERS

40
 Basic Organic Chemistry

 Ethers: substance that has 2 organic groups bonded to the same

oxygen atoms, R-O-R.
 Application: diethyl ether (anesthetic solvent), aromatic ether
(perfumery), vanillin (vanillin pea)

IUPAC NOMENCLATURE OF ETHERS

 Simple ethers with no other functional groups are named by identifying

the two organic substituents and adding the word ether:

O C H3
H3 C O
C
C H2 C H3
H3 C C H3

tert-butyl methyl ether ethyl phenyl ether

 If other functional groups are present, the ether part is considered an

alkoxy substituent. Example:
CH3

O C CH3
CH3O OCH3
CH3

p-dimethoxybenzene 4-tert-butoxycyclohexene

PROPERTIES OF ETHERS

 Ether nearly the same geometry with water.

 R-O-R bonds have approximately tetrahedral bond angle (112° in
dimethyl ether) and the oxygen atom is sp3 hibridized.
 Boiling point: higher than comparable alkanes but lower than alcohol
(no hydrogen bond formation among ether).
 Solubility: ~ with solubility of alcohol (formation of H bond between
ether and water).

REACTION OF ETHERS

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 Basic Organic Chemistry

 Ethers are unreactive to many reagents use (oxidation or reduction

agent, base) in organic chemistry and play a role as good solvent.

ACID CLEAVAGE

 Ethers are cleaved by strong acid

HX (X = Br or I)
R'-O-R R'-X + R-X
HBr
CH3-O-CH2CH3 CH3-Br + CH3CH2-Br

SYNTESIS OF ETHERS

DEHYDRATION OF ALCOHOL (symmetrical ether)

 Involves 2 molecules of alcohol

 Reaction is carried out at 140°C in the presence of concentrated acid
as a catalyst (H2SO4 or H3PO4).
 If temperature >140°C, reaction → alkenes.

H+
R OH + HO R R-O-R + H2O
140°C

H2SO4
CH3CH2OCH2CH3 + H2O
140°C
CH3CH2OH
H2SO4
CH2=CH2 + H2O
180°C

WILLIAMSON ETHER SYNTHESIS (symmetrical & unsymmetrical ether)

 The best method for the preparation either symmetrical or

unsymmetrical ethers.
 Method involves between alkyl halides and sodium alkoxides (R-ONa)
 Sodium alkoxides, prepared by reaction of an alcohol with strong base
such as sodium hydride.
 Sodium alkoxide reacts with alkyl halides to produce ether

ROH + NaH RO-Na+ + H2

R-X + Na+ - OR' R - O - R' + NaX

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 Basic Organic Chemistry

CHAPTER 5
AMINE

 Organic derivatives of ammonia with one or more alkyl or aryl groups

bonded to nitrogen atom
 Uses as defense system, drug and medicine

Classes of Amines
 Primary (1): Has one alkyl group bonded to the nitrogen (RNH2).
 Secondary (2): Has two alkyl groups bonded to the nitrogen (R2NH).
 Tertiary (3): Has three alkyl groups bonded to the nitrogen (R3N).
 Quaternary (4): Has four alkyl groups bonded to the nitrogen and the
nitrogen bears a positive charge(R4N+).

Classify the following amines into primary, secondary or tertiary.

H

NH2 N
N

NH2 NH2

IUPAC Names

 Name is based on longest carbon chain.

 -e of alkane is replaced with -amine.
 Substituents on nitrogen have N- prefix.

NH2 N N

propylamine ethylmethylamine triethylamine

propanamine N-methylethanamine N,N-diethylethanamine

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 Basic Organic Chemistry

PHYSICAL PROPERTIES

Boiling Points

 N—H less polar than O—H.

 Weaker hydrogen bonds, so amines will have a lower boiling point than the
corresponding alcohol.
 Tertiary amines cannot hydrogen-bond, so they have lower boiling points
than primary and secondary amines.

Basicity of Amines
 Lone pair of electrons on nitrogen can accept a proton from an acid.
 Aqueous solutions are basic to litmus.
 Alkyl amines are usually stronger bases than ammonia.

REACTION OF AMINE

Reaction of Amines with Carbonyl Compounds

Hofmann Elimination

 A quaternary ammonium salt has a good leaving group-a neutral amine.

 Heating the hydroxide salt produces the least substituted alkene
 Regioselectivity of the Hofmann Elimination

 The least substituted product is the major product of the reaction—Hofmann product.

44
 Basic Organic Chemistry

SYNTHESIS OF AMINE

SYNTHESIS OF AMINES BY ACYLATION–REDUCTION

i) 1° amine

 Acylation of the starting amine by an acid chloride gives an amide with no

tendency toward overacylation.
 Reduction of the amide by LiAlH4 gives the corresponding amine.

ii) 2° amine

 Acylation–reduction converts a primary amine to a secondary amine.

 LiAlH4, followed by hydrolysis, can easily reduce the intermediate amide to
the amine.

iii) 3°amine

 Acylation–reduction converts a secondary amine to a tertiary amine.

 Reduction of the intermediate amide is accomplished with LiAlH4.

B. REDUCTION OF NITRILES

 Nitrile (CN) is a good SN2 nucleophile.

 Reduction with H2 or LiAlH4 converts the nitrile into a primary amine.

45
 Basic Organic Chemistry

CHAPTER 6
ALKENES

COMPOUND ALKENES ALKYNES

Type of Bonding Carbon-carbon double bond Carbon-carbon triple bond.
General Formula CnH2n CnH2n-2
Application Ethylene/propylene (simplest Acetylene (starting material
alkenes)  acetaldehyde, acetic
acid).

IUPAC SYSTEM OF NOMENCLATURE (ALKENES GROUP)

STEP 1
 Name the parent hydrocarbon. Find the longest carbon chain containing
double bond, using suffix -ene.

STEP 2
 Number the carbon atoms in the chain. Begin with nearer double bond
(Lowest possible number).

STEP 3
 Write the full name. Number the substituents according to their positions in
the chain, list alphabetically. If more than one double bond, indicate position
and suffixes diene, triene.
 Cycloalkenes; number the compound begin with double bond as C1 and C2.
The substituent as low number as possible

CH3CH=CH2 CH3CH=CHCH3
(propylene)
propene 2-butene 4-methyl-1-pentene

CH3 Br

CH3CH2

3-methylcyclohexane 3-bromo - 4-ethylcyclobutene 1,4-cyclohexadiene

 Several common names are often used and recognized by IUPAC.

H2C H2C CH H2C CH CH2

methylene group vinyl group allyl group

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 Basic Organic Chemistry

CIS-TRANS ISOMERISM IN ALKENES

 Lack of rotation around the carbon-carbon double bond (sp2 hybridization)

H3C CH3 H CH3

C C C C
H H H3C H

cis-2-butene trans-2-butene
E-Z System

 A set of sequence rules to assign priorities to the substituent groups on the

double bond carbons.
 If higher-priority groups on each carbon are same side, Z (zusammen –
together).
 If the higher-priority groups are on opposite side, E (entgegen – opposite).
 Priority of each substituent follow Cahn Ingold Prelog (CIP) system.

O H

H3C C H C CH2
OH
C C
C C
H3C CH3
H CH2OH

(Z)-2-hydroxymethyl-2-butenoic acid (E)-3-methyl-1,3-pentadiene

PHYSICAL PROPERTIES OF ALKENES

 Boiling point – Increase with increasing molecular weight. Branched alkenes

provide lower boiling point compared to straight chain alkenes.
 Density ~ 0.6 – 0.7 gcm-3 range.
 Solubility and polarity – non-polar, insoluble in water with soluble in non-
polar solvent eg. Hexane.
Alkenes provide higher polarity compared to alkanes due the presence of π (pi)
bonding (polarisable).

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 Basic Organic Chemistry

REACTION OF ALKENES

ADDITION REACTION

i) Addition of Hydrogen to Alkenes

 Alkenes react with 1 mol of hydrogen in the presence of Platinum

catalyst.
Pt
+ H2

1-hexene n-hexane

ii) Addition of Halogens to Alkenes (Halogenation)

 Alkenes react with halogen to yield 1,2-dihalides (vicinal halide)

Cl
Cl
+ Cl2 CCl4

1-pentene 1,2-dichloropentane
iii) With HX

 Addition of HX, where X=Cl, Br or I

 Markovnikov regiochemistry is observed: H adds to the less highly
substituted carbon (more hydrogen atom), and X adds to the more
highly subsitituted carbon (less hydrogen atom).
 Symmetrical alkenes  1 product obtained
 Unsymmetrical alkenes  2 product obtained
Br

+ HBr
2-butene (symmetrical alkene)
2-bromobutane (100%)

Br

+ HBr 2-bromopropane (91%)

propene (unsymmetrical alkene)

Br

1-bromopropane (9%)

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 Basic Organic Chemistry

iv)

+ H2 SO4 OSO3H
1-pe n tene sec-pentyl hydrogen sulfate

iv) With H2O (Hydration)

 Alkenes react with water in the presence of acid (catalyst) yield an

alcohol by following Markovnikov rules.
 Hydroboration/oxidation of alkenes yield the product of anti-Markonikov
rule.

H+
CH3 CH=CH2 + H2 O CH3CHCH3
propene
OH
2-propanol

B 2 H6
CH3CH=CH2 CH3CH2 CH2OH
H2O2, OH-
propene 1-propanol

OXIDATION OF ALKENES: HYDROXYLATION AND CLEAVAGE

Alkene Cleavage

 Moderate oxidation reagent will cleave C=C bonds and produce 2

fragment
 Ozone, O3 – passing a stream of oxygen through high voltage electrical
discharge react with alkene at low temperature  cyclic intermediate,
malozonide  ozonide  aldehydes and ketones.

CH3 O
1. O3
C O + CH3CCH3
2. Zn, H3O+
CH3

isopropylidenecyclohexane cyclohexanone acetone

CH3
1. O3 H
+ O=C
2. Zn, H3O+ C=O
H3C CH3
2-methyl- 2-butene
acetaldehyde acetone

49
 Basic Organic Chemistry

 Strong oxidation reagent such as KMnO4 at high temperature cleave

C=C bond to yield ketones and carboxylic acid.

HO CH3
KMnO4
C=O + O=C

H3C CH3
2-methyl- 2-butene
acetic acid acetone

SYNTHESIS OF ALKENES

 There are 2 most common alkenes forming elimination reactions :

1. Dehydration (the loss of water from an alcohol)
2. Dehydrohalogenation (the loss of HX from an alkyl halides)

Dehydration Reaction

 Reaction is carried out by treatment of an alcohol with strong acid,

H2SO4, H3PO4.
 Products yield follow Zaitsev rule (more highly substituted alkenes
product predominates.
CH3 CH3
OH H2SO4, H2O
+ H2O
THF, 50°C

1-methylcyclohexanol 1-methylcyclohexene

Dehydrohalogenation Reaction

 Reaction occurs by reaction of an alkyl halide with strong base such as

potassium hydroxide (Saytzeff products)

H
Br H
KOH
+ KBr + H2O
CH3CH2OH
H H
H

bromocyclohexane cyclohexene

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 Basic Organic Chemistry

CHAPTER 7
ALKYNES

 Contain carbon-carbon triple bond.

 Also called acetylenes because they are derivatives of acetylene, the simplest
alkynes
 Terminal alkyne – triple bond is located at the end of a carbon chain
 Internal alkyne – triple bond is located somewhere other than the end of the
carbon chain

IUPAC SYSTEM OF NOMENCLATURE (ALKYNES GROUP)

 The suffix –yne is used, and the position of triple bond is indicated by giving the
number of the first alkyne carbon in the chain. Numbering the main chain begin
at the end nearer the triple bond (as low number as possible).
 Compound with more than one triple bond are called diynes, triynes.

REACTION OF ALKYNES

ADDITION REACTION

Addition of Hydrogen Halides, HX

 Electrophile undergo addition reactions with alkynes as with alkenes

 Excess of HX leads to give a dihalide product.
 The regiochemistry of addition follows Markovnikov’s rule: Halogen adds to
the more highly substituted side of the alkyne bond, and hydrogen adds to the
less highly substituted side.

Br
HBr HBr
CH3COOH
H
1-hexyne Br Br
2-bromo-1-hexene 2,2-dibromohexane

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 Basic Organic Chemistry

Addition of Halogen, X2

 Bromine and chlorine also add to alkynes to give addition products.

Br Br
Br
Br2 Br2
CH2Cl2 CH2Cl2
Br Br
1-hexyne Br
1,2-dibromo-1-hexene 1,1,2,2-tetrabromohexane

Addition Of Alkynes With Hydrogen

 Alkynes react with excess hydrogen in the presence of Platinum yield alkanes.
 Meanwhile, alkynes react with hydrogen and Lindler catalyst (Paladium treat
with BaSO4 with quinoline) yield alkenes.
Pt
+ 2H2

1-hexyne hexane

Pd / BaSO4
+ 2H2
N
MeOH
1-hexyne hexene

Hydration of Alkynes

 Alkynes can be hydrated by either of 2 methods

i. Addition of water catalyzed by mercury (II) ion yield the Markovnikov products
(direct addition).

H2O, H2SO4
HgSO4
OH O
1-hexyne
an enol 2-hexanone

ii. Addition of water by a hydroboration / oxidation yields the non-Markovnikov

product (indirect addition).

BH2 O
BH3 H2O2 CH
BH2 H2O, pH 8
1-hexyne
hexanal

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 Basic Organic Chemistry

OXIDATIVE CLEAVAGE OF ALKYNES

 Alkynes are cleaved by reaction with powerful oxidizing agent such ozone, O 3
or KMnO4.
 The products obtained from cleavage of an internal alkyne are carboxylic
acids; from a terminal alkyne, CO2 is formed as one product.

O O
KMnO4 or O3
internal alkyne R C C R'
RCOH + R'COH

O
KMnO4 or O3
terminal alkyne R C C H
RCOH + CO2

SYNTHESIS OF ALKYNES

Alkylation of Acetylide Anions

 Acetylide anions (strong nucleophile) react with an alkyl halide to substitute for
the halogen and yield new alkyne product (SN2).

H H

H C C Na+ + H C Br H C C C H + NaBr

H H

1. NaNH2, NH3
2. CH3CH2CH2CH2Br, THF
1-hexyne 5-decyne

Elimination Reactions of Dihalides

 Treatment of a 1,2-dihaloalkane (vicinal dihalide) with excess strong base such

as KOH or NaNH2 results in a twofold elimination of HX and formation of
alkyne.

Br
Br
2 KOH
200°C
2,3-dibromopentane 2-pentyne

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 Basic Organic Chemistry

CHAPTER 8
ALDEHYDES AND KETONES
 Aldehydes: Compounds that have a carbonyl group (C=O), bonded one side
to a carbon and the other side to a hydrogen.
 Ketones: compounds that have a carbonyl group which situated between two
carbon atoms.
 Application: formaldehyde (resin and protective coating);citral (flavor
compound), camphor (medicine), cyclohexanone (starting material  nilon).

IUPAC SYSTEM OF NOMENCLATURE

ALDEHYDES

 Aldehydes are named substitutively by replacing the final –e of the name of

the corresponding alkane with –al.
 Aldehydes group must be at an end of the chain of carbon atoms; No need
to indicate its position (Position 1).
 Aldehydes in which -CHO group is attached to a ring system are named by
adding the suffix carbaldehydyde.

O O
O H
H H
H O Cl
Propanal 5-chloropentanal Benzenecarbaldehyde Cyclohexanecarbaldehyde
(propionaldehyde) (benzaldehyde)

KETONES

 Aliphatic ketones are named substitutively by replacing the final –e of the name
of the corresponding alkane with –one.
 Gives the carbonyl carbon atom the lowest number.
 Common functional group for ketones – separately naming the groups attached
to the carbonyl group and adding word ketone as a separate word.

O
O O CH3
H3C O
Butanone Pent-4-en-2-one Acetone Benzophenone
(ethyl methyl ketone) (allyl methyl ketone) (propanone) (diphenyl ketone)

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 Basic Organic Chemistry

PHYSICAL PROPERTIES

Boiling Point
 Carbonyl group – polar group (provides higher boiling points than hydrocarbon
of the same molecular weight)
 Lower boiling points (provides dipole moment; between their molecules
weaker than hydrogen bonds) than corresponding alcohols.

 O C 
Dipole-dipole moment
 C O

Molecular Boiling point

Compound
weight (°C)
Butane 58 -0.5
Propanal 58 49.0
Acetone 58 56.1
1-propanol 60 97.2

Solubility
 Carbonyl oxygen atom allows molecules of aldehydes and ketones to form
strong hydrogen bonds to the molecules of water.
 Low molecular weight aldehydes and ketones – appreciable solubilites in
water.
H
O
H H H
O
hydrogen bond O
C
H3C CH3

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 Basic Organic Chemistry

REACTION OF ALDEHYDES AND KETONES

ADDITION

Addition of Metal Hydride: Alcohol Formation

 Aldehydes and ketones react with metal hydride to yield alcohol

 Example of metal hydride: LiAlH4 (non-selective) or NaBH4 (selective)

OXIDATION OF ALDEHYDES

 Aldehyde reacts with oxidation agent, KMnO4 or chromic acid to yield

carboxylic acid.

O O
[O]
R-CH R-C-OH

aldehyde carboxylic acid

Tollen test, Chromic acid test, Iodoform test – “refer PRACTICAL”

DEOXYGENATION OF ALDEHYDES AND KETONES

 Deoxygenation of aldehydes and ketones –replacement of oxygen atom

(carbonyl group) with two hydrogen atoms [reduction of carbonyl into
methylene group]
 Deoxygenation of aldehydes and ketones are carried out through 2
types of reactions :

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 Basic Organic Chemistry

Clemensen Reduction

 Carbonyl compound react with zinc-amalgam (Zn react with Hg and

hydrochloric acid) to yield an alkane.

O
Zn(Hg)
CH3(CH2)5-CH CH3(CH2)5-CH3
HCl, H2O
heptanal heptane

O
Zn(Hg)
HCl, H2O
cyclohexanone cyclohexane

Wolff-Kishner Reduction

 Aldehyde or ketone reacts with hydrazine, NH2NH2 to give hydrazone. Heating

of hydrazone with base reagent, KOH produces alkane.

O N-NH2

+ H2N-NH2 KOH

175oC
hydrazon

SYNTHESIS OF ALDEHYDES AND KETONES

OXIDATION OF ALCOHOL

Aldehydes

 Oxidation of primary alcohol with moderate oxidation agent, Cu or Collins

reagent (CrO3 in pyridine)
O
CH3CH2CH2OH Cu or CrO3 in pyridine CH2CH3CH
propanol propanal
Ketones

 Oxidation of secondary alcohol in the presence of oxidation agent produces

H2Cr2O7
OH =O

cyclohexanol cyclohexanon

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 Basic Organic Chemistry

ALKENE CLEAVAGE

 Ozone, O3 – passing a stream of oxygen through high voltage electrical

discharge react with alkene at low temperature  cyclic intermediate,
malozonide  ozonide  aldehydes and ketones.

CH3 O
1. O3
C O + CH3CCH3
2. Zn, H3O+
CH3

isopropylidenecyclohexane cyclohexanone acetone

CH3
1. O3 H
+ O=C
2. Zn, H3O+ C=O
H3C CH3
2-methyl- 2-butene
acetaldehyde acetone

HYDRATION OF ALKYNES

 Aldehydes or ketones are synthesized through 2 main methods:

1. Addition of water catalyzed by mercury (II) ion yield the Markovnikov
products (direct addition).

H2O, H2SO4
HgSO4
OH O
1-hexyne
an enol 2-hexanone
2. Addition of water by a hydroboration / oxidation yields the non-Markovnikov
product (indirect addition).

BH2 O
BH3 H2O2 CH
BH2 H2O, pH 8
1-hexyne
hexanal

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 Basic Organic Chemistry

CHAPTER 9
CARBOXYLIC ACIDS AND DERIVATIVES
 Carboxylic acid: organic acid with functional group of COOH [carbonyl group,
C=O and hydroxyl, OH].

Natural
Carbon Structural Formula IUPAC Name Name
Sources
1 HCO2H Metanoic acid Formic acid Ant
2 CH3CO2H Ethanoic acid Asetic acid Vinegar
3 CH3CH2CO2H Propanoic acid Propionic acid Milk
4 CH3(CH2)2 CO2H Butanoic acid Butiric acid Butter
5 CH3(CH2)3 CO2H Pentanoic acid Valeric acid Valerion root
6 CH3(CH2)4 CO2H Hexanoic acid Caproic acid Goat

IUPAC SYSTEM OF NOMENCLATURE

 Common name: substitution numbering use Greek alphabetical: α,β,γ and δ.

OH
O O
 OH
   
C C C C Br
C COOH
6 5 4 3 2 1
2-bromopropanoic acid 2,3-dimethylpentanoic acid
bromopropionic acid)  -dimethylvaleric acid)

 Carboxylic acids that are derived from open chain alkanes are systematically
named by replacing the terminal –e of the corresponding alkanes name with –
oic acid.
 The carbonyl carbon atom is numbered C1 in this system .
O

O HO O
OH O
OH OH
O OH
4-methylpentanoic acid 3-ethyl-6-methyloctanedioic acid 3-pentenoic acid 3-phenyl-2-butenoic acid

 Alternatively, COOH group bonded to a ring are named using the suffix –
carboxylic acid.
 The COOH carbon is attached to C1 and is not itself numbered in this system.
Br O
O HO HO OH
HO
HO O O O
3-bromocyclohexanecarboxylic acid 1-cyclopentenecarboxylic acid cyclopentanoic acid oxalic acid

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 Basic Organic Chemistry

PHYSICAL PROPERTIES

Boiling Point
 Carboxylic acid provides highest boiling point among organic compound
(alcohol, aldehyde, ketone)
O O
OH HO

acetic acid 1-propanol acetone

Molecular weight : 60 60 58
Boiling point (°C ) : 118 79 56

 High boiling properties of carboxylic due to presence of dimmer formation

between two carboxylic acids through hydrogen bond.

R O H O
C
C
O H O R

Figure 1: Dimmer formation

Solubility
 Carboxylic acid also provides highest solubility among organic compound
(functional group).
 Solubility of compound due to hydrogen bond interaction.

O H O
R C OH O H
H

H H

H O

hydrogen bond interaction

Acidity
 Weak acid with incomplete dissociation but provides highest acidity among
organic compound (functional group).
 Carboxylic acids dissociate slightly in dilute aqueous solution to gives H3O+
and carboxylate anions, RCO2-.

O O
OH + H2O O- + H3O+
R R

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 Basic Organic Chemistry

 Carboxylic acid provides higher acidity compared to alcohol: Carboxylate anion

delocalized over two equivalent oxygen atoms in contrast; alkoxide ion
negative charge is localized on a single electronegative atom.

R OH + H2O R O- + H3O+

O -
O O
OH + H2O O - O- + H3O+
R R R

REACTION OF CARBOXYLIC ACID

REDUCTION TO PRIMARY ALCOHOL

 Reduction of carboxylic acid in the presence of reduction agent to yield

primary alcohol.
LiAlH4 or BH3
CH3CH2COOH CH3CH2CH2OH
H3O+
propanoic acid 1-propanol

NUCLEOPHILIC SUBSTITUTION

 Substitution of carboxylic acid (OH –functional group) with nucleophile

yield carboxylic acid derivatives.

O O

R-C-OH + Nu R-C-Nu + OH-

O O O O O O

R-C-OH R-C-X R-C-OR' R-C-NR2 R-C-O C-R'

carboxylic acid acid halide ester amide acid anhydride

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 Basic Organic Chemistry

SYNTHESIS OF CARBOXYLIC ACID

OXIDATION OF ALKENES AND ALKYNES

 KMnO4 at high temperature cleave C=C bond to yield ketones and

carboxylic acid.
 Meanwhile, alkynes are cleaved by ozone, O3 or KMnO4 to yield
carboxylic acids (internal alkynes)

O O
KMnO4 or O3
internal alkyne R C C R'
RCOH + R'COH
H R
O O
KMnO4
alkene C C
RCOH + RCR"
R R"

OXIDATION OF PRIMARY ALCOHOL OR ALDEHYDE

 Oxidation of primary alcohol or aldehyde with KMnO4 or chromic acid yield

carboxylic acid
O O
[O] [O]
R-CH2OH R-CH R-C-OH

primary alcohol aldehyde carboxylic acid

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 Basic Organic Chemistry

CARBOXYLIC ACID DERIVATIVES

ACYL HALIDES OR ACID HALIDES (R-COX)

 Acid halides are named by identifying first acyl group then the halide.
 Acyl group derived from carboxylic acid name by replacing the –ic acid ending
with –yl or the –carboxylic acid ending with –carbonyl.

O O
Cl
O Cl Cl
acetyl chloride benzoyl chloride cyclohexanecarbonyl chloride
(from acetic acid) (from benzoic acid) (from cyclohexanecarboxylic acid)

REACTION OF ACYL HALIDES

Reduction reaction

 Strong reduction agent (LiAlH4) reacts with acid chloride to yield primary
alcohol.
O
H2O
R-C-Cl + LiAlH4 RCH2OH

SYNTHESIS OF ACYL HALIDES

 Reaction of carboxylic acid with thionyl chloride or phosphorus trichloride or

phosphorous pentachloride yield acid halides.
O O
R-C-OH + SOCl2 R-C-Cl + SO2 + HCl

O O
R-C-OH + PCl3 R-C-Cl + P(OH)3
O O
R-C-OH + PCl5 R-C-Cl + POCl3 + HCl

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 Basic Organic Chemistry

ESTERS (R-CO2R’)

 Esters are named by first identifying the alkyl group attached to oxygen and
then the carboxylic acid, with the –ic acid ending replaced by –ate.
O
O
O O
O O
ethyl acetate diethyl malonate
(ethyl ester of acetic acid) (methyl ester of malonic acid)

REACTION OF ESTERS

Substitution Reaction

 An ester is hydrolyzed, either by aqueous base or aqueous acid to yield

carboxylic acid or carboxylate salt and alcohol.

O O
H+
R-C-OR' + H2O R-C-OH + R'OH

O O
NaOH
R-C-OR' + H2O R-C-ONa + R'OH
Reduction reaction

 LiAlH4 convert esters into primary alcohol

O
LiAlH4
R-C-OR' RCH2OH + R'OH
H2O
 Moderate reduction agent, diisobutylaluminium hydride, DIBAH converts ester
into aldehyde.
O O
DIBAH
R-C-OR' R-C-H + R'OH
H2O

SYNTHESIS OF ESTERS

 Ester are prepared through reaction between alcohol with carboxylic acid
(reversible and in the presence proton (H+)) or acid halide or acid anhydride.
O O
R-C-OH + R'OH R-C-OR' + H2O

O O
R-C-Cl + R'OH R-C-OR' + HCl
O O O
R-C-O-C-R + R'OH R-C-OR' + RCOOH

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 Basic Organic Chemistry

AMIDES (R-CONH2)

 Amides with an unsubstituted –NH2 group are named by replacing the –oic
acid or ic acid ending with –amide; or replacing the –carboxylic acid ending
with –carboxamide.
 If Nitrogen atom is further substituted, the compound is named by identifying
substituent groups (preceded letter N)and parent name

O O H2N
NH2 NH2
O
acetamide hexanamide cyclopentanecarboxamide
(from acetic acid) (from hexanoic acid) (from cyclopentanecarboxylic acid)

O
O
HN N

N-methylpropanamide N,N-diethylcyclohexanecarboxamide

REACTION OF AMIDES

Reduction reaction

 Reduction of amide with LiAlH4 yield amine.

O
1) LiAlH4
R-C-NHR' R-CH2NHR'
2) H2O

Hoffman Rearrangement reaction

 Amide react with alkaline lipohalyte solution to yield amine (loss of 1 carbon)
 Alkaline lipohalyte solution is prepared from bromine or chlorine with NaOH.

O
Br2 / NaOH
R-C-NHR' R-NHR'
SYNTHESIS OF AMIDES

 The lowest reactive among carboxylic derivatives

 Amides are derived from reaction of acid chloride or acid anhydride with
amines
O O
R-C-Cl + R'NH2 R-C-NHR' + HCl

O O O
R-C-O-C-R + R'NH2 R-C-NHR' + RCOOH

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 Basic Organic Chemistry

ACID ANHYDRIDES (R-CO2CO-R’)

 Symmetrical anhydrides of unsubstituted monocarboxylic acids and cyclic

anhydrides of dicarboxylic acids are named by replacing the word acid with
anhydrides.

O O O

O O O
acetic anhydride benzoic anhydride

 Unsymmetrical anhydrides are named by citing 2 acids alphabetically.

O O

O
acetic propionic anhydride

REACTION OF ACID ANHYDRIDES

Nucleophilic Substitution reaction

 The chemistry of acid anhydrides (less reactive) is similar to that of acid

chlorides.
 Acid anhydrides react with water to form acids, with alcohol to form esters,
with amines to form amides.
O
H2O
R-C-OH + RCOOH

O O O
R'OH
R-C-O-C-R' R-C-OR' + RCOOH

O
R'NH2
R-C-NHR' + RCOOH

SYNTHESIS OF ACID ANHYDRIDES

 Reaction between sodium carboxylate salt with acid chloride yield acid
anhydride.
O O O O
R-C-O-Na+ + Cl-C-R' R-C-O-C-R' + NaCl

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 Basic Organic Chemistry

CHAPTER 10
BENZENE AND DERIVATIVES

 Michael Faraday – separated compound at 80°C through combustion of

organic compound.
 Compound also can be synthesized by direct heating of benzoic acid (benzyn
 benzoin  benzene)
 Chemical analysis indicate that compound have empirical formula, CH,
molecular weight, 78
 Also known as aromatic compound (including derivatives)
 Sources:
 Coal (complex mixture) with thermal breakdown (1000°C)
 Petroleum (large alkanes) passed through catalyst about 500°C under
high pressure.

IUPAC NOMENCLATURE OF AROMATIC COMPOUND

MONOSUBSTITUTION

 Monosubstituted benzene is systematically named in the same manner as

other hydrocarbon, with –benzene as the parent name.

Br NO2 CH2CH2CH3

bromobenzene nitrobenzene propylbenzene

 However monosubstituted benzene also have common name which widely

used. O O O
H OH

benzaldehyde benzoic acid styrene acetophenone

 Alkyl-substituted benzenes, sometimes referred to as arenes, are named in

different ways depending on the size of alkyl group (six of fewer carbons).
 If the alkyl substituent is larger than ring (more than six carbons), the
compound is named as a phenyl-substituted alkanes.
 Phenyl group abbreviation – Ph or Φ (Greek phi) or used for –C6H5.

O
OH
OH

3-phenylpentane 2-phenylethanol 3-phenylpropanoic acid

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 Basic Organic Chemistry

DISUBSTITUTION

 Common name for disubstituted benzenes are named using one of prefix
ortho- (o), meta- (m) or para- (p).
 An ortho-disubstituted benzene has its two substituents in a 1, 2
relationship on the ring.
 A meta-disubstituted benzene has its two substituents in a 1, 3
relationship.
 A para-disubstituted benzene has its substitutents in a 1, 4 relationship.

 However, according to IUPAC, nomenclature of disubstituted benzene is

through numbering system and arranged in alphabetical order.
Cl Cl Cl

Cl Cl
Cl
1,3-dichlorobenzene 1,4-dichlorobenzene
1,2-dichlorobenzene (p-dichlorobenzene)
(o-dichlorobenzene) (m-dichlorobenzene)

Cl
Br F

I
NO2
1-bromo-2-ethylbenzene 1-chloro-3-nitrobenzene 1-fluoro-4-iodobenzene

 Common name for monosubstitution of benzene also can play a role as a

parent names.
 Some disubstituted benzene also have their own common name.

O
OH
OH

(p-cresol) (m-toluic acid) (o-xylene)

4-methylphenol 3-methylbe nzoic acid 1,2-dimethylbenzene

POLISUBSTITUTION

 Benzene with more than two substituents are named by numbering the position
of each substituent so that the lowest possible numbers are used.

Cl Br
NO2 OH

Br O2N Br

4-bromo-1,2-dimethylbenzene 2-chloro-1,4-dinitrobenzene 2,6-dibromophenol

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 Basic Organic Chemistry

PHYSICAL PROPERTIES

THE KEKULÉ STRUCTURE OF BENZENE

 Proposed by Friedrich Kekulé with 1,2,5-cyclohexatriene structure in a ring and
are bonded to each other by alternating single and double bond, and one
hydrogen atom is attached to each carbon atom.
 Resonance theory: 2 or more Lewis structure can be written for a molecule that
differs only in position of their electron; none of the structures will be in
complete accord with the compound’s chemical and physical properties.

STABILITY
H2
Pt H = 28.6 kcal/mol

2H2
Pt H = 57.6 kcal/mol

3H2
Pt H = 85.8 kcal/mol

3H2
H = 49.6 kcal/mol
Pt
 The above results clear that benzene is much more stable than the
hypothetical 1,3,5-cyclohexatriene.
 The energy difference between of hydrogenation of 1,3,5-cyclohexatriene and
benzene is called resonance energy.

HÜCKEL’s RULE: THE 4n + 2 π ELECTRON RULE

 A molecule is aromatic only if it has a planar, monocyclic system of conjugation
and contains a total of 4n + 2 π electron, where n is an integer (n=0,1,2….)
 In other words, molecules with 2,6,10,14,18 π electrons possess high possibility
to be an aromatic compound.
 However, the existence of anti-aromatic properties for molecules with 2,
6,10,14,18 π occur while the absence of delocalization π electrons in cyclic
system.

BOILING POINT
 Related with dipole moment with ortho substitution provides highest boiling
point. Meanwhile para substitution (symmetrical compound- no dipole
moment). Cl Cl Cl
Cl

Cl
Cl
o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene
b.p. 181°C b.p. 173°C b.p. 170°C

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 Basic Organic Chemistry

REACTION OF BENZENE

 5 main electrophile aromatic substitution which are;

1. Aromatic Halogenation
2. Aromatic Nitration
3. Friedel-Crafts Alkylation
4. Friedel-Crafts Acylation
5. Aromatic Sulfonation

1. Aromatic Halogenation
H X

H2SO4 or FeX3
+ X2 + HX

halobenzene
2. Aromatic Nitration

H NO2

H2SO4
+ HNO3 + 2H2O

nitrobenzene

3. Friedel-Crafts Alkylation
H CH3

AlCl3
+ CH3Cl + HCl

toluene
4. Friedel-Crafts Acylation

H O CH3
O
AlCl3
+ H3C Cl + HCl

acetophenone
5. Aromatic Sulfonation

H
SO3H
H2SO4
+ SO3

benzenesulfonic
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 Basic Organic Chemistry

SUBSTITUENT EFFECTS IN SUBSTITUTED AROMATIC RINGS

 Some substituents active in the ring, making it more reactive than benzene,
and some deactive the ring, making it less reactive than benzene.
 Substituents affect the orientation of the reaction – 3 possible disubstituted
products – ortho, -meta and para are usually not formed in equal amount.
 Substituent can be classified into 2 group:
i. ortho- and para- directing activators
ii. meta- directing deactivators

Ortho- and Para- Directing Meta-Directing

Deactivator increase
Activator increase

-COR
-NH2, -NHR, -NR2 -CO2R
-OH -SO3H
-OR -CHO
-NHCOR -CO2H
-C6H5 -CN
-R -NO2
X (deactivator) -NR2+

 Reactivity and orientation in electrophilic aromatic substitution are controlled by

interplay of inductive effects and resonance effects.

 Inductive effect is the donation of electrons through a sigma, σ bond due to

electronegativity and the polarity of bonds in functional groups. (ortho- and
para- directing).

 Resonance effect is the withdrawal of electrons through a π bond due to the

overlap of a p orbital on the substituents with a p orbital on the aromatic ring.
(meta- directing).

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 Basic Organic Chemistry

HALOGENATION OF ALKYLBENZENE SIDE CHAINS

 Side chain bromination at the benzylic position occurs when alkylbenzene is

treated with N-bromosuccinimide (NBS).
O

N Br Br
CH2CH2CH3 CHCH2CH3
O
CCl4

 Free radical also occurs between alkylbenzene side chain with halogen in the
presence heat or light (hv).

CH3 CH2Cl
+ Cl2 hv

OXIDATION OF ALKYLBENZENE SIDE CHAINS

 Benzene ring is inert to strong oxidizing agents such as KMnO4 and chromic
acid reagent.
 Alkyl side chains react readily with oxidizing agents and are converted into
carbonyl group –COOH (Benzoic acid)

KMnO4
CH3 COOH

KMnO4
CH2CH3 COOH

KMnO4
H3C CH2CH3 HOOC COOH

72