.

0 INTRODUCTION

1.1 Historical Background

Organic chemistry is the chemistry of the compounds of carbon, except CO, CO 2, the carbonates,
bicarbonates, and cyanides.

In the early days, chemical compounds were divided into two classes – inorganic and organic –
depending upon where they came from. Inorganic substances came from minerals while organic
substances came from plants or animals; that is, from living organisms. Until the early 19 th century,
chemists believed that a “vital force” in nature was essential for the formation of organic compounds.
This belief was reasonable since a variety of organic compounds had been prepared from a number of
vegetable and animal origin. In 1828, however, Friedrich Wohler, a German chemist, showed that urea
(NH2CONH2), an organic compound formed in the liver, could be synthesized in the laboratory by
heating ammonium cyanate (NH4CNO), an inorganic compound:

NH4CNO NH2CONH2

This and subsequent similar discoveries led to the gradual abandonment of the vital force theory.

The compounds from organic sources had one thing in common – they all contained the element
carbon. And even after it had become clear that these compounds did not have to come from living
sources, it was convenient to retain the name “organic” to describe them.

1.2 Comparison of Properties between Organic and Inorganic Compounds

Property Organic Inorganic

Bond Covalent Ionic
Structural units Molecules Ions
Forces of attraction Intermolecular Interionic
(Van der Waals)
Electrical conductivity Nonconductor Conductor
Flammability Flammable Not flammable
Melting point Low High
Boiling point Low High
Solubility in water insoluble soluble

1.3 Sources of Organic Compounds

1. Natural sources
 Plants Ex: quinine from the bark of cinchona tree; malic acid from
apples; tartaric acid from grapes

 Animals Ex: cholesterol from gallstones; urea from the liver

 Petroleum fractional distillation gasoline, kerosene, lubricating oils,

paraffin, petroleum ether, tar

 Coal destructive distillation coal tar fractional distillation

benzene, naphthalene, phenol

 Natural gas – 50 to 94% methane; ethane; propane

2. Synthetic sources – preparation from organic or inorganic substances

1.4 Classification of Organic Compounds

1. Based on the functional group present in the compound. (A functional group is an atom or a group
of atoms which gives characteristic properties to an organic compound).
Class Functional Group Name

Alkane –C–C– Alkane

Alkene –C=C– Alkene

Alkyne –C≡C– Alkyne

Alkyl Halide –X Halo (chloro, bromo, iodo)

Alcohol – OH Hydroxyl

Ether – OR Alkoxyl

Aldehyde – CHO Formyl

Ketone – CO Carbonyl

Carboxyllic Acid – COOH Carboxyl

Ester – COOR Alkoxy carbonyl

2. Based on the carbon structure of the compound

2.1 Aliphatic or acyclic compounds – those in which the carbon atoms are linked to each other to
form open chains. Open chains are either straight or branched, and they may be saturated (molecules
that contain carbon-carbon single bonds), or unsaturated (molecules that contain carbon-carbon
double or triple bonds).

Ex: CH3 – CH2 – CH2 – CH3 butane

CH2 = CH2 ethene

CH3 – C – OH ethanoic acid

‫װ‬
O

CH3C ≡ CH propyne

CH3 – CH – CH3 2 - chloropropane

‫ו‬
Cl

2.2 Cyclic compounds – those in which the carbon atoms are linked to each other to form one or more
closed chains or cyclic or ring structures.

a. Alicyclic compounds – those that contain a ring of three or more carbon atoms resembling
aliphatic compounds. The typical saturated alicyclic compounds are the cycloalkanes.
Ex: CH2 – CH2 cyclopropane

CH2

CH2 – CH2 cyclobutane

‫ו‬ ‫ו‬
CH2 – CH2
 b. Aromatic compounds – those that contain at least one benzene ring; that is, a ring of six
carbon atoms with alternate single and double bonds.

Ex: Naphthalene CH CH
CH C CH

CH C CH
CH CH
c. Heterocyclic compounds – those that have ring or closed arrangements of carbon and other
atoms such as sulfur, oxygen, and nitrogen with single or multiple bonds.
Ex: Ethylene oxide CH2 – CH2

1.5 Importance of Organic Compounds

1. Biochemistry – The molecules that make life possible, like nucleic acids, carbohydrates,
vitamins, and enzymes, contain carbon; thus, the chemical reactions that take place in living
system, including in our own bodies, are organic reactions.
2. Foods – The three main classes of foodstuffs, carbohydrates, proteins and fats, are organic, and
so are many of our current food additives and preservatives.
3. Fuel – our civilization depends on coal and petroleum for energy
4. Plastics – Common household items are made of plastics, like PVC or polyvinyl chloride (bottles,
food trays, electrical insulation, irrigation pipes) and polyethylene (squeeze bottles, wire
insulation, grocery and trash bags)
5. Natural and synthetic fibers – Materials like cotton, wool, silk, nylon, polyesters, and rayon
provide protection as clothing and enhance aesthetic aspect of society
6. Drugs and medicines – aspirin, decongestants, sedatives, stimulants, contraceptives, fertility
drugs, and antibiotics
7. Cosmetics – soaps, make-ups, perfumes
8. Agriculture – fertilizers, herbicides, and pesticides
9. Paints and dyes

2.0 Basic Principles and Concepts

2.1 Organic Formulas

1. General formula represents an entire group or series of compounds.

Ex: Alkanes CnH2n + 2 n = number of carbon atoms

Alcohols R – OH R = alkyl group

2. Molecular formula gives the actual number of each kind of atom present in the compound.

Ex: Ethane C2H6

Methane CH4

3. Empirical formula gives the simplest ratio of the atoms present in the compound.

Ex: Ethane CH3

Methane CH4
 1. Structural formula is a graphic representation of the molecular structure, showing all the atoms
and the bonds between them, and the correct valences of each atom in the compound.

Ex: Propane H H H
‫ו‬ ‫ו‬ ‫ו‬
H–C–C–C–H
‫ו‬ ‫ו‬ ‫ו‬
H H H

The structural formulas were based on the structural theory proposed by August Kekule
in1859. This theory postulated that, regardless of the complexity of the organic molecule, each
carbon atom has the normal valence of 4; hydrogen and the halogens, 1; oxygen and sulfur, 2;
nitrogen and phosphorus, 3.

In the following Kekule valence notation, dashes were attached to the symbols to indicate
graphically the valence of each atom.

.
Kekule Valence Notation

1 2 3 4
‫ו‬
H– O= S= –N– −P− –C–
‫ו‬ ‫ו‬ ‫ו‬

Cl – –O– –S– –N= −P= –C=

‫ו‬

Br – N≡ P≡ =C=

I– –C≡

2. Condensed structural formula is a shorthand convention for writing Kekule structural formulas.

Ex: Pentane CH3 –CH2 –CH2 –CH2 –CH3 or CH3CH2CH2CH2CH3

or CH3(CH2)3CH3

2-Butene CH3CH=CHCH3

3. Bond line formula or line angle formula is one in which connections between carbons are
shown but individual carbons and hydrogens are not. The only atoms specifically written in are
those that are neither carbon nor hydrogen bound to carbon.

Ex: Pentane

3 – chloropentane

Cl

2.2 The Carbon Atom

Carbon is the 6th most abundant element in the universe. It is a very special element because it
plays a dominant role in the chemistry of life. Its electron configuration is 1s 2 2s2 2p2. Carbon normally
has four covalent bonds (four electrons to share). This factor allows carbon to form millions of organic
compounds because of its ability to link together by covalent bonding in a variety of ways: in a
continuous open chain, or in a chain with branches, or in chains containing other elements, or even in
ring structures.

CH3CH2CH2CH3 CH3CHCH2CH3 CH3CH2CH2CH2Cl

CH3
2.3 Hybridization of Carbon

When carbon bonds with other atoms, it does not use its pure s and p atomic orbitals; instead, it uses
its sp3, sp2, or sp hybrid orbitals. These hybrid orbitals are formed by the promotion of one 2s electron
to an empty 2p orbital, followed by the combination or mixing of the s and the p orbitals in the 2 nd energy
level of carbon, in a process called hybridization.

1. In sp3 hybridization, there is a mixing of one s orbital and three p orbitals, forming four sp 3
hybrid orbitals. This kind of hybridization occurs when carbon bonds with four other atoms. The
geometry is tetrahedral and the bond angle is 109.5o. The C in CH4 and CH3CH3 is sp3
hybridized.
2. In sp2 hybridization, there is a mixing of one s orbital and two p orbitals, forming three sp 2
hybrid orbitals. This kind of hybridization occurs when carbon bonds with three other atoms. The
geometry is trigonal planar and the bond angle is 120o. The C in CH2 = CH2 is sp2 hybridized.
3. In sp hybridization, there is a mixing of one s orbital and one p orbital, forming two sp hybrid
orbitals. This kind of hybridization occurs when carbon bonds with two other atoms. The
geometry is linear and the bond angle is 180o. The C in HC ≡ CH is sp hybridized.

2.4 Kinds of Carbon and Hydrogen Atoms

1. A primary (1o) carbon atom is a carbon atom attached to one carbon atom. A hydrogen atom
attached to a primary carbon atom is called a primary hydrogen atom. Terminal carbons are
always primary.

2. A secondary (2o) carbon atom is a carbon atom attached to two carbon atoms. A secondary
hydrogen atom is one that is attached to a secondary carbon atom.

3. A tertiary (3o) carbon atom is a carbon atom attached to three carbon atoms. A tertiary hydrogen
atom is a hydrogen atom that is attached to a tertiary carbon.

4. A quaternary (4o) carbon atom is a carbon atom attached to four carbon atoms. There are no
quaternary hydrogen atoms.

Examples: CH3 – CH2 – CH2 – CH3 CH3

‫ו‬
CH3 – CH – CH2 – CH3 CH3 – C – CH2 – CH – CH3
‫ו‬ ‫ו‬
CH3 CH3 CH3

2.5 Homologous Series

Homologous series is a series or group of compounds which all fit the same general formula.
The only difference among individual members is the number of methylene, –CH2, group which they
contain. Compounds in a homologous series have the same functional group. The members of the
series are called homologs. Shown below are the first five members of the alkane and alcohol series.
The same general formula

Alkane Series Alcohol Series

CH4 CH3OH
CH3CH3 CH3CH2OH
CH3CH2CH3 CH3CH2CH2OH
CH3CH2CH2CH3 CH3CH2CH2CH2OH
CH3CH2CH2CH2CH3 CH3CH2CH2CH2CH2OH
CH3CH2CH2CH2CH2CH3 CH3CH2CH2CH2 CH2CH2OH
2.6 Isomers

Isomers are molecules that have the same molecular formulas, but different structural or spatial
arrangement of the atoms within the molecule. The isomers are distinct chemical individuals; therefore,
they have different chemical and physical properties. Isomers are classified into structural or
constitutional isomers and stereoisomers.

1. Structural or constitutional isomers are isomers that differ in the order in which their atoms
are connected. Structural isomers may be further classified into three types.

a. Chain isomers are isomers of molecules whose carbon atoms are connected in
straight chains or branched chains.

Ex: C5H12 CH3CH2CH2CH2CH3 n-pentane

CH3CHCH2CH3 2-methylbutane
‫ו‬
CH3

CH3
‫ו‬
CH3 – C – CH3 2,2-dimethylpropane
‫ו‬
CH3

b. Positional isomers are isomers of molecules having the same functional group but
the functional group is attached to nonequivalent positions in the carbon structure.
Ex: C3H8O CH3CH2CH2OH 1-propanol
CH3CHCH3 2-propanol
‫ו‬
OH

C4H8 CH3CH2CH=CH2 1-butene

CH3CH=CHCH3 2-butene

c. Functional isomers are isomers of molecules having different functional groups.

Ex: C3H6O CH3CH2CHO propanal

CH3COCH3 acetone

C2H6O CH3CH2OH ethanol

CH3OCH3 dimethyl ether

2. Stereoisomers are isomers that have the same molecular formula, same connectivity and
different spatial arrangement of atoms.

To be stereoisomers, molecules must not be identical. The test for identicality is one of
superimposability. A molecule that is not superimposable or not identical with its mirror image
molecule is said to be a chiral molecule and will have a stereoisomer, an enantiomer. A molecule
that is superimposable or identical with its mirror image molecule is said to be achiral and will
have no enantiomer.

How do we predict whether a molecule is chiral or achiral? One, is to use the concept of
stereocenter or chiral center. A chiral center is a carbon atom (or other atoms) which has four
nonidentical atoms or groups directly attached to it. If a molecule has a single chiral center it will
necessarily be chiral. Example is 2-butanol, CH3C*H(OH)CH2CH3. If a molecule has no chiral
center it is achiral. Methyl carbon and methylene carbon are achiral since these groups
automatically have at least two identical hydrogens attached to carbon. Example is butane,
CH3CH2CH2CH3. When there is more than one chiral center, the use of symmetry elements is
 particularly helpful. A molecule that has either a plane of symmetry or a center of symmetry is achiral.
A molecule without a plane of symmetry or center of symmetry is chiral. Example is 1,2-
dimethylcyclobutane.

cis-1,2-dimethylcyclobutane

PS PS

H3C CH3 H3C CH3

H H H H

Original molecule mirror image

__________________________________
Superimposable, with plane of symmetry
Achiral molecule, they are identical

trans-1,2-dimethylcyclobutane

Not PS Not PS

H CH3 H3C H

H3C H H CH3

Original molecule mirror image

__________________________________
Not superimposable, no plane of symmetry
Chiral molecule, they are enantiomers

Stereoisomers are categorized into:

a. Enantiomers – stereoisomers whose molecules are mirror images of each other but are not
superimposable (parts do not coincide when one molecule is placed over another). An
organic molecule that has a single chiral carbon will have two enantiomers. When there are
two or more chiral centers, the molecule will have both enantiomers and diastereomers.

b. Diastereomers – stereoisomers whose molecules are not mirror images of each other and
not superimposable. They have two or more chiral centers. If a pair of molecules contain two
or more chiral centers and at least one – but not all – of the chiral centers are opposite, then
the two molecules are diastereomers.

Let us illustrate enantiomers and diastereomers with some examples.

Example 1: Alanine, CH3C*H(NH2)COOH

H H

C* C*
H3C COOH HOOC CH3
NH2 NH2

(+) Alanine (-) Alanine

 (+) alanine and its mirror image, (-) alanine, are enantiomers.

The (+) alanine means that it rotates the plane of polarization clockwise; (-) alanine rotates
the plane of polarization counterclockwise.

Example 2: 3-bromo-2-butanol, CH3C*H(OH)C*H(Br)CH3

CH3 CH3 CH3 CH3

H - C - OH HO - C - H H - C - OH HO - C - H
Br - C - H H - C - Br H - C - Br Br - C - H
CH3 CH3 CH3 CH3

I II III IV

Enantiomers: I and II, III and IV

Diastereomers: I and III, I and IV, II and III, II and IV

Example 3: 1,2-dichloroethene, CHCl = CHCl

H H H H
C=C C=C
Cl Cl Cl Cl

I II

cis-1,2-dichloroethene, superimposable, with plane of symmetry

H Cl Cl H
C=C C=C
Cl H H Cl

III IV

trans-1,2-dichloroethene, nonsuperimposable, no plane of symmetry

Enantiomers: III and IV
Diastereomers: I and III, I and IV

The terms cis and trans refer to the arrangement in space of two designated atoms or
groups attached to the doubly bonded carbons (designated atoms or groups are those with
higher atomic numbers). When the designated atoms or groups are on the same side of the
double bond, they are said to be cis to each other. When they are on opposite sides, they are
trans to each other. In the given example, the cis isomer has both of its Cl atoms on the same
side of the double bond while the Cl atoms in the trans isomer are on opposite sides of the
double bond.

2.7 Classes of Organic Reactions

The reaction of a given organic compound may involve one of three fundamental classes of reactions.
In some cases, a reaction proceeds spontaneously on mere contact of the reactants, but more
frequently catalysts are required to bring it about.

1. In a substitution reaction, an atom or a group of atoms attached to a carbon is replaced by another

atom or group of atoms.

CH3CH3 + Cl2 uv CH3CH2Cl + HCl

CH3OH + HBr CH3Br + H2O

3. In an addition reaction, an atom or a group of atoms are added to the adjacent carbons of a
 multiple bonded reactant.

CH3CH = CHCH3 + HCl CH3CH2CHCH3

‫ו‬
Cl
Br Br
‫ו‬ ‫ו‬
CH3 C ≡ CH + 2 Br2 CH3 C – CH
‫ו‬ ‫ו‬
Br Br

3. In an elimination reaction, there is an intramolecular loss or removal of an atom or group of atoms

from adjacent carbon atoms of the reactant. This results in the formation of a multiple bond.

CH3CH2OH H2SO4, 170O CH2 = CH2 + H2O

CH3CHCH3 NaOH, EtOH CH3CH = CH2 + NaBr + H2O

‫ו‬
Br

3.0 ALKANES

Alkanes are acyclic saturated hydrocarbons; that is, they consist of carbon and hydrogen atoms
arranged in a structure in which there are only single bonds between carbon atoms. Alkanes are used
as the basis for naming the majority of organic compounds. The general formula for the alkanes is
CnH2n + 2, where n = number of carbon atoms.

3.1 Nomenclature and Structure of Alkanes

The International Union of Pure and Applied Chemistry (IUPAC) is the organization that sets the rules
for the nomenclature of organic compounds. Names that follow IUPAC rules are known as systematic
or IUPAC names.

3.1.1 Open-chain alkanes

The alkanes end with the suffix –ane. The names of the first ten members of the open-chain alkanes
are given below.

Molecular Systematic name

Condensed Structural formula
formula
CH4 CH4 methane
C2H6 CH3CH3 ethane
C3H8 CH3CH2CH3 propane
C4H10 CH3CH2CH2CH3 butane
C5H12 CH3CH2CH2CH2CH3 pentane
C6H14 CH3CH2CH2CH2CH2CH3 hexane
C7H16 CH3CH2CH2CH2CH2CH2CH3 heptane
C8H18 CH3CH2CH2CH2CH2CH2CH2CH3 octane
C9H20 CH3CH2CH2CH2CH2CH2CH2CH2CH3 nonane
C10H22 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 decane

3.1.2 Branched-chain alkanes

Branched-chain alkanes are compounds in which one or more alkyl groups are attached to longer
carbon skeletons as substituents. A substituent is an atom or group of atoms which replaces hydrogen
atom on the parent chain of a hydrocarbon. An alkyl group is an alkane minus one hydrogen. Its name
ends with the suffix –yl. The structure and names of commonly used alkyl groups are:
CH3 - methyl
CH3CH2 - ethyl
CH3CH2CH2 - n-propyl
CH3CH - isopropyl
‫ו‬
CH3
CH3CH2CH2CH2 - n-butyl
 CH3CH2CHCH2 sec-butyl

CH3CHCH2 - isobutyl
CH3

CH3
CH3C - tert-butyl
CH3

The rules to be followed in naming branched alkanes are:

1. Identify the longest continuous carbon chain. The parent alkane corresponds to the name of the
alkane with the same number of carbon atoms in the chain. Groups branching off the longest
chain are treated as substituents.
2. Number the chain consecutively from one end to the other, starting at the end that will give the
lowest numbers to the substituents.
3. Identify each substituent, and the number of the carbon to which it is attached.
4. Name the molecule. The parent alkane is the last part of the name and is preceded by the name
of the substituents and their numerical locations. Use a dash to separate the number from the
name.
5. When two or more different substituents are present, they are listed in alphabetical order in the
name.
6. When two or more substituents are identical, the prefixes di -, tri -, tetra -, etc., are used to
indicate the number of times they appear but are ignored when alphabetizing. Their position
numbers are separated by a comma.

Examples:
CH3CH2CH2CHCH3 2 - methylpentane
‫ו‬
CH3

CH3CH2CHCH2CH2CH3 3 - methylhexane
‫ו‬
CH3

CH3CHCH2CHCH2CH3 4 - ethyl - 2 - methylheptane

‫ו‬ ‫ו‬
CH3 CH2CH2CH3

CH3
‫ו‬
CH3CH2CCH2CH3 3, 3 - dimethylpentane
‫ו‬
CH3
CH3
‫ו‬
CH3CCHCH3 2, 3 - dimethylbutane
‫ו‬
CH3

3.2 Isomerism in Alkanes

Alkanes demonstrate the chain type of structural isomerism. The simplest member of the alkane family
that demonstrates isomerism has the molecular formula C4H10. There are two possible structural
formulas, one in which the four carbons are arranged in an open chain,

CH3CH2CH2CH3 butane

and the other, in a branched chain.

CH3CHCH3 2 - methylpropane
‫ו‬
CH3
 When the number of carbon atoms in a molecular formula increases, the number of possible
isomers increases. Three isomers are possible for C5H12; five for C6H14; nine for C7H16; 18 for C8H18;
and 35 for C9H20.

3.3 Physical Properties of Alkanes

1. The alkanes can exist as gases, liquids, or solids at room temperature. Methane, ethane,
propane, and butane are gases; pentane through hexadecane are liquids; and the homologs
larger than hexadecane are solids.
2. Alkanes are non-polar; thus, they dissolve in nonpolar organic solvents like ether and CCl4, but
they do not dissolve in water, which is a polar solvent.
3. Alkanes have lower densities than water and their density increases as the molecular mass
increases.
4. The boiling point and melting point of unbranched or straight-chain alkanes increase as the
molecular mass or number of carbon atoms or chain length increases. Larger molecules have a
larger surface area which provides greater Van der Waals interactions between adjacent
molecules, thus raising the boiling point.

Ex: CH3CH2CH2CH3 > CH3CH2CH3

5. For isomeric alkanes, boiling point decreases as branching increases. Branched alkanes, being
more compact, have less surface area for Van der Waals interactions. This lowers the boiling
point of branched alkanes.
Ex: CH3
CH3CH2CH2CH2CH3 > CH3CHCH2CH3 > CH3–C – CH3
CH3 CH3
6. For isomeric alkanes, melting point increases as branching increases.
CH3
Ex: CH3 – C – CH3 > CH3CHCH2CH3 > CH3CH2CH2CH2CH3
CH3 CH3
7. When branched isomers have the same number of branches, the isomer with a symmetrical
structure will have higher boiling point but lower melting point than the unsymmetrical structure.

Ex: CH3CH2 - CH - CH2CH3 > BP CH3 - CH - CH2CH2CH3

CH3 < MP CH3
symmetrical unsymmetrical

3.4 Synthesis of Alkanes

The smaller alkanes from C1 to C5 may be obtained in pure form by fractional distillation of petroleum
or natural gas. Above the pentanes, however, the number of isomers becomes so large, and the boiling
point differences between the isomers so small, that it is impractical to isolate pure higher alkanes from
petroleum or natural gas. They are instead prepared synthetically.

1. Hydrogenation of alkenes

Hydrogenation is the addition of H2 to the double bond of an alkene, forming an alkane having the same
carbon skeleton. This method employs metal catalysts such as platinum, palladium, and nickel.

CH3CH = CHCH3 + H2 Pd CH3CH2 – CH2CH3

CH2 = CH2 + H2 Pt CH3 – CH3

2. Hydrolysis of Grignard reagent

Grignard reagent is an organometallic compound in which the carbon is bonded to a metal. It has the
general formula R-Mg-X and the general name alkyl magnesium halide. Hydrolysis means the reaction
between a Grignard reagent and water. It involves the replacement of the MgX by the H in H 2O, forming
an alkane having the same carbon skeleton as the alkyl magnesium halide.
CH3CHCH2MgBr + H2O CH3CHCH3 + Mg(OH)Br
‫ו‬ ‫ו‬
CH3 CH3

3. Reduction of alkyl halides

An alkyl halide has the general formula R - X. Its reduction involves the replacement of the halogen
atom by a hydrogen atom. The hydrogen for the reduction may be obtained by the action of HCl on Zn,
or hydrogen gas and Pt or Pd catalyst may also be used.

CH3I + (H) Zn, HCl CH4 + HI

CH3CH2CHCH3 + H2 Pt CH3CH2CH2CH3 + HCl

‫ו‬
Cl

4. Wurtz synthesis

Wurtz synthesis is the reaction between metallic Na and two alkyl halides in the presence of dry ether,
forming a product where the carbon chain is doubled.

2 CH3I + Na dry ether CH3CH3 + NaI

2 CH3CHCl + Na dry ether CH3CH – CHCH3 + NaCl

‫ו‬ ‫ו‬ ‫ו‬
CH3 CH3 CH3

3.5 Chemical Reactions of Alkanes

Very few chemicals react with the alkanes. This is why they are nicknamed the paraffins, meaning “little
reactivity.” The alkanes are not chemically attacked by water, by strong acids such as H 2SO4 or HCl,
by strong bases like NaOH, by active metals such as Na, by strong oxidizing agents such as KMnO4
or K2Cr2O7 , nor by any of the reducing agents . Among the few reactions of alkanes are combustion
and halogenation.

1. Combustion

Like most other organic compounds, alkanes burn readily in air. This reaction with oxygen is known as
combustion and is quite exothermic. When an alkane is burned with sufficient oxygen, the products are
CO2 and H2O vapor and heat. If insufficient oxygen is present, some CO forms. This is why it is so
dangerous to have an automobile engine running inside a closed garage.

CH3CH2CH3 + 5 O2 3 CO2 + H2O + heat

2. Halogenation (Chlorination or Bromination)

Under the influence of ultraviolet light or at a high temperature (250 – 400oC), alkanes react with Cl2
and Br2 to give the chloro- and bromo- alkanes. This reaction is a substitution reaction which involves
the replacement of an atom of H by an atom of Cl or Br. Fluorine gives too vigorous a reaction while
iodine is too inert to effect such substitutions.

CH3CH3 + Br2 uv CH3CH2Br + HBr

CH4 + Cl2 uv CH3Cl + HCl

CH3CH2CH3 + Cl2 uv CH3CH2CH2Cl + CH3CHClCH3

Br
‫ו‬
CH3CHCH3 + Br2 uv CH3CHCH2Br + CH3 – C – CH3
‫ו‬ ‫ו‬ ‫ו‬
CH3 CH3 CH3
3.6 Uses of some Alkanes

1. Methane and ethane are major components of natural gas, which is used for heating and cooking
purposes and for power utilities.
2. Liquefied propane is used in the propane gas burner or as propellants in aerosol sprays.
3. Liquefied butane is used in cigarette lighters.
4. The alkanes from pentane to octane are highly volatile liquids and good solvents for nonpolar
substances. They are used as fuels in internal combustion engines.
5. Nonane and decane are liquids, and used in diesel and aviation fuels.

3.7 Nomenclature and Structure of Cycloalkanes

Cycloalkanes literally means “cyclic alkanes”. They contain only C-C and C-H bonds but this time the
carbon atoms are joined in a ring. They have the general formula C nH2n. Like their alkane counterparts,
cycloalkanes are saturated and their name with the additional prefix cyclo- is derived from the number
of carbon atoms in the ring. The smallest cycloalkane is cyclopropane. Each cycloalkane is an isomer
of its alkene counterpart; for example, cyclopropane has the same molecular formula (C 3H6) as
propene.

Molecular Structure Name

formula
CH2
C3H6 Cyclopropane
CH2 CH2

CH2 CH2
C4H8 Cyclobutane
CH2 CH2

CH2
C5H10
CH2 CH2 Cyclopentane

CH2 – CH2

CH2
C6H12
CH2 CH2
Cyclohexane
CH2 CH2

CH2

CH2 CH2
C8H16
CH2 CH2
Cyclooctane
CH2 CH2

CH2 CH2

For branched cycloalkanes, the ring is the parent when the ring size (number of carbon atoms) is larger
than the chain; when the ring is smaller than the chain, the chain is the parent; and, when the sizes of
the ring and the chain are the same, the molecule is named either as an alkane or cycloalkane.
Examples:
CH2 CH – CH3 1,2 dimethylcyclobutane

CH2 CH – CH3

CH – CH2CH3 1-ethyl-2-methylcyclopentane

CH2 CH – CH3

CH2 – CH2

CH3CH2CHCH3 2-cyclopropylbutane

CH2CH2CH2CH2CH3 pentylcyclopentane

CH2CH2CHCH2CH3 1-cyclopentyl-3-methylpentane
CH3

3.8 Importance of Cycloalkanes

Life on earth would not be possible without these ring compounds, because the majority of organic
compounds found in nature contain rings in their molecules. Many of these are important medicinal
compounds, pigments or fragrances. Terpenes and steroids are two important classes of natural
products.
In nature, terpenes are widely distributed in essential oils. They are being used as fragrances
and spices in perfume and food industries, respectively. They also find applications as insecticides.
Steroids often exhibit physiological activity. Some of them act as hormones, e.g. as the active
ingredient in the contraceptive pill. Cholesterol is one of the mostly distributed steroids because it is
found in nearly all human and animal tissues. The basic steroidal framework contains three fused
cyclohexane rings and one terminal cyclopentane ring.
 4.0 ALKENES

Alkenes are unsaturated hydrocarbons that are characterized by a double bond between two carbon
atoms. The term unsaturated is applied to alkenes because though each carbon has four bonds, a
carbon involved in a carbon-carbon double bond has fewer than four bonded atoms, the maximum
number possible for carbon. Alkenes can be described as terminal alkenes (when the double bond is
at the end of the chain) and non-terminal or internal alkenes (when the double bond is inside the
chain). The general formula for the alkenes is CnH2n.

4.1 Nomenclature and Structure of Alkenes

In the IUPAC system, alkenes are named by replacing the -ane ending in the name of the
corresponding alkane with -ene.

CH2=CH2 ethene (ethylene)

CH3CH=CH2 propene (propylene)

Starting with butene, a number is used to designate the position of the double bond because of
positional isomerism. The chain is numbered in the direction that gives the lower number to the first
double bonded carbon.

CH3CH2CH=CH2 1-butene
CH3CH=CHCH3 2-butene

CH3CH2CH=CHCH2CH2CH3 3-heptene

Alkenes having two or more double bonds are named by adding the prefixes di, tri, tetra, and so
on before the ending -ene.

CH2=CH-CH=CH2 1,3-butadiene

CH2=CH-CH=CH-CH=CH2 1,3,5-hexatriene

In naming branched alkenes, these IUPAC rules are followed:

1. Select as the parent structure the longest continuous chain that includes the double bond.
2. Number the parent chain from whichever end gives the lower number to the first double bonded
carbon. This rule gives precedence to the location of the double bond over the location of the
substituents on the parent chain.
3. Indicate by numbers the positions of the substituents attached to the parent chain. List the
substituents in alphabetical order.
4. Separate numbers from numbers by a comma, and numbers from names by a dash.

Examples:

CH3 C=CH2 2-methylpropene

CH3
CH3
CH3C-CH2CH=CH2 4, 4-dimethyl-1-pentene
CH3
CH2
CH3CH2-C-CH2CH=CHCH3 2-ethyl-1,4-hexadiene

4.2 Isomerism in Alkenes

Alkenes can exhibit three types of isomerism:

1. Chain isomerism

CH3CH2CH=CH2 CH3-C=CH2
 CH3
1 – butene 2 – methylpropene

2. Positional isomerism

CH3CH2CH=CH2 CH3CH=CHCH3

1 – butene 2 – butene

3. Cis-Trans Stereoisomerism
CH3 CH3 CH3 H
C=C C=C
H H H CH3

cis-2-butene trans-2-butene

Cis-trans stereoisomerism is not possible if an alkene has the same atoms of H at one end of the
double bond. For this reason, only non-terminal alkenes have cis-trans stereoisomers but not
terminal alkenes, since they have identical atoms of hydrogen at one end of the double bond.
CH3CH2 H

C=C two identical atoms

H H
1-butene

4.3 Physical Properties of Alkenes

1. The alkenes can exist as gases, liquids, or solids at room temperature. The first three alkenes
are colorless gases while the next fourteen alkenes are colorless liquids. The rest are colorless
solids.

2. Alkenes are non-polar; thus, they dissolve in nonpolar organic solvents like ether and CCl4, but
they do not dissolve in water, which is a polar solvent.

3. Intermolecular forces are Van der Waals forces, which increase as molecular mass increases.

4. Boiling point, melting point, and density of alkenes increase as the molecular mass or chain
length increases.
Ex: 5-decene > 3-nonene > 1-heptene

5. Isomeric alkenes have similar boiling points.

Ex: 1-butene (- 6.5 oC) and 2-methylpropene (-7 oC)

6. Alkenes are less dense than water.

7. Terminal alkenes have lower boiling points than their corresponding alkanes.
Ex: CH3CH2CH=CH2 < CH3CH2CH2CH3

8. Cis-isomers have higher boiling points than trans-isomers.

Ex: CH3 CH3 CH3 H

C=C C=C
H H H CH3

cis-2-butene trans-2-butene
9. Trans-isomers have higher melting points than cis-isomers.

Ex: CH3 H CH3 CH2CH3

C=C C=C
H CH2CH3 H H

trans-2-pentene > cis-2-pentene

4.4 Synthesis of Alkenes

An alkene is formed by elimination reaction, which involves removal of atoms or groups from two
adjacent carbon atoms. The two important methods of synthesizing alkenes in the laboratory are
dehydrohalogenation of alkyl halides and dehydration of alcohols.

1. Dehydrohalogenation of Alkyl Halides, RX

Dehydrohalogenation is the removal of H-X from an alkyl halide. The reaction is carried out by heating
the alkyl halide with a strong base such as KOH, NaOH, and NaOCH2CH3 in aqueous ethyl alcohol as
solvent (the base is soluble in water while the alkyl halide is soluble in alcohol).

CH3CH2CH2I NaOH, EtOH CH3CH = CH2 + NaI + H2O

Δ EtOH
EtOH
CH3CHCH3 NaOCH2CH3, EtOH CH3CH=CH2 + EtOH + NaBr
Δ
Br

2. Dehydration of Alcohols, ROH

Dehydration is the removal of H-OH from an alcohol. This reaction requires the presence of an acid
catalyst such as H2SO4 and H3PO4, and the application of heat.

CH3CH2OH H2SO4, Δ CH2 = CH2 + H2O

Predominant Product in Dehydrohalogenation and Dehydration

Dehydrohalogenation and dehydration often yield a mixture of isomeric alkenes; however, only
one isomer generally predominates. To predict the predominant product, we apply the rule formulated
by the Russian chemist Alexander Saytzeff. This rule, known as Saytzeff rule, states that: “In
dehydrohalogenation and dehydration, the double bond of the alkene is formed predominantly towards
the carbon atom having fewer hydrogen atoms.”
KOH, EtOH
CH3CH2CHCH3 CH3CH=CHCH3 + CH3CH2CH=CH2
|
Br 81% 19%

CH3 CH3 CH3

H2SO4
CH3-C-CH2CH3 CH3-C=CHCH3 + CH2=C-CH2CH3

OH 90% 10%
4.5 Chemical Reactions of Alkenes

Alkenes are highly reactive and react principally by addition reactions, where the reagent adds across
the carbon-carbon double bond of the alkene to yield a saturated product. The addition reactions of
alkenes are:

1. Hydrogenation

Hydrogenation is the addition of hydrogen to the double bond of an alkene at elevated temperatures,
under high pressure, and in the presence of a catalyst (Pt, Pd, Rh, or Ni) to form the corresponding
alkane.
Ni
CH3CH=CH2 + H2 CH3CH2CH3

2. Halogen addition

This reaction involves the addition of CI2 or Br2 (I2 is too unreactive) to the alkene, forming a vicinal
dihalide (a compound that contains a halogen atom on adjacent carbons). The reaction is carried out
at room temperature or below in a variety of solvents, including CHCl3, CCI4, and HAc.

CH2=CH2 + CI2 CHCl3 CH2CI−CH2CI

3. Hydrohalogenation
Hydrohalogenation is the addition of gaseous hydrogen halide, HX, to an alkene, forming an alkyl
halide. The aqueous solutions of hydrogen halides are not used in order to avoid the addition of water
to the alkene which will form an alcohol. The order of reactivity of HX is HI > HBr > HCI. HI is the
strongest acid and thus reacts fastest with the alkenes.

In symmetrical alkenes of the type RCH=CHR, only one product is formed.

CH2=CH2 + HI CH3CH2I

CH3CH=CHCH3 + HBr CH3CH2–CHBrCH3

For unsymmetrical alkenes of the type RCH=CH 2, two isomeric products may be formed.

CH3CH = CH2 + HCl CH3CH–CH3 + CH3CH2–CH2CI

CI
predominant
product