Alkanes

What is an Alkane?
Industrial Uses of Alkanes
Alkenes
What is an alkene?
An alkene is an unsaturated hydrocarbon that contains a carbon–carbon double bond such as
ethene or ethylene, propene, butene etc.
Alkenes are represented by the general formula CnH2n. Ethylene for instance is C2H4; propene
is C3H6 etc.
IUPAC NAMING OF ALKENES
▪ IUPAC names of alkenes are formed by changing the ‐ane‐ prefix of the parent alkane to
‐ene‐ Hence, CH2=CH2 is named ethene, and CH3CH=CH2 is named propene.
▪ In higher alkenes, where isomers exist that differ in the location of the double bond, a
numbering system is used as indicated in the next point.
▪ Number the longest carbon chain that contains the double bond in the direction that gives
the carbon atoms of the double bond the lower set of numbers.
▪ Use the number of the first carbon of the double bond to show its location.
Branched or substituted alkenes are named in a manner similar to the alkanes are named. i.e
number the carbon atoms, locate the double bond, locate and name substituent groups, and name
the main (parent) chain.

Note that there is a six‐carbon chain in 2‐ethyl‐3‐methyl‐1‐pentene. However, because the longest chain
that contains the carbon–carbon double bond has only five carbons, the parent hydrocarbon is pentane,
and we name the molecule as a disubstituted 1‐pentene.
▪ Carbon–carbon double bonds take precedence over alkyl groups and halogens in determining the
main carbon chain and the direction in which it is numbered.
▪ Hydroxyl groups, however, outrank the double bond. Compounds that contain both a d ouble
bond and a hydroxyl group use the combined suffix -en-ol to show that both functional groups are
present
Cis-Trans Isomerism in Alkenes
Isomerism is the existence of a compound with the same molecular formular but different
structural or spatial arrangements.
Cis–trans isomerism also known as geometric isomerism occurs in isomers that have the same
order of attachment (connectivity) of their atoms, but a different arrangement of their atoms in
space due to the presence of either a ring or a carbon–carbon double bond.
Conditions for Cis-trans Isomerism
1. The presence of a carbon-carbon double bond. This leads to a restricted rotation about the
double bond due to the presence of the pi bond (or in rings) and this means they don't readily
interconvert.
2. Two different groups must be attached to each carbon of the double bond of the alkene. It
doesn't matter whether the left-hand groups are the same as the right-hand ones or not.

Reactions of Alkenes
Alkenes undergo addition reactions with reagents such as halogens, hydrogen halides and
hydrogens in such a way that the double bond is broken and there is formation of a new bond.
Examples are shown below:
Reaction Mechanisms with Curly Arrows
Curly arrows are used by chemists to represent reaction mechanism and to understand how a
particular chemical reaction works. It shows the movement of a pair of electron. The rules for
using the curly arrows are:
Examples are shown in the hydration and halogenation reactions below:
Hydration reaction

Halogenation reaction

ALKYNES
Hydrocarbons that contain a carbon–carbon triple bond are called alkynes. Alkynes like alkenes
are unsaturated hydrocarbons. The functional group of an alkyne is a carbon–carbon triple bond.
The simplest alkyne is ethyne or acetylene (HC≡CH).
Compounds that have their triple bond at the end of a carbon chain (RC≡CH) monosubstituted,
or terminal, alkynes. Disubstituted alkynes (RC≡CR) are said to have internal triple bonds.
Addition Reactions of Alkynes
The addition reactions of alkynes can be represented by means of simple equation, e.g. reaction
with H2, Br2 and HBr. Alkynes, like alkenes also undergo addition reactions.
1. Hydrogenation reaction of alkyne and hydrogen: this reaction yields an alkane

2. Hydrohalogenation reaction of alkyne with hydrogen halide: this reaction produces

alkenes
 3. Halogenation reaction of alkyne with a halogen: this reaction produces a tetrahaloalkane

Industrial Uses of Alkynes

ALKANOLS
Alkanols belong to a group of organic compounds known as alcohols. They are compounds
composed of the hydroxyl group -OH which serves as their functional group.
The structure of an alkanol is the same as for the parent alkane except that an OH functional
group has substituted for one of the hydrogen atoms. Hence, their general molecular formula is
given as ROH. The first five members is given as:
Isomerism in monohydric alkanols
Monohydric alkanols exhibit four (4) types of isomerism. These are: Positional, functional, chain
and optical isomerism.
Positional isomerism: this occurs in alcohols with three or more carbon atoms due to a different
positioning of the -OH group, i.e. the position of the -OH functional group varies. In other
words, the carbon to which the OH group is attached to is different.
Methods of preparation of monohydric alkanols
There are several methods of preparing alkanols. These include:
1. Preparation from petroleum products by the hydration of ethene
2. Preparation by fermentation
3. Preparation of alcohols by reduction of aldehydes and ketones
4. Preparation by reduction of carboxylic acids and esters
5. Preparation of alcohols from epoxides
Physical properties of alkanols

Reactions of monohydric alkanols

The following are some of the reactions alkanols can take part in:
a. Reaction with active metals (alkoxide formation)
b. Reaction with alkanoic acids (esterification)
c. Dehydration reaction
d. Oxidation reaction
e. Addition/elimination reaction
Therefore, depending on the reaction conditions, alkenes or ethers can be prepared by the
dehydration of alkanols.
2. Esterification reaction: Acid-catalyzed condensation reaction of alkanols and carboxylic acid
yields esters and water. This is known as Fischer-esterification reaction.

3. Alkoxide formation: Alkanols react with active metals such as Li, Na, Mg, K and other active
metals to produce a salt and a hydrogen gas as shown below:

The salt of an alkanol in IUPAC nomenclature is called a metal alkanoate (traditional name is a
metal alkoxide)
4. Oxidation reaction: the oxidation of an alkanol yields a carbonyl compound. The resulting
carbonyl can be an aldehyde, ketone or carboxylic acid, but this is largely dependent on the
alkanol and the oxidizing agent.
Oxidation of primary alkanol gives aldehyde or carboxylic acid:

Oxidation of secondary alkanols produces ketones:

Tertiary alkanols however, are not oxidized. This is because the carbon that bears the -OH group
does not have a hydrogen atom attached but is instead bonded to other carbon atoms.

Mechanism of the dehydration of alkanols

Primary alcohols react by the following two step mechanism, in which step 2 is the rate
determining step:

Classification of alkanols
Alkanols can either be monohydric or polyhydric. In between these two, there could be a
dihydric or trihydric alkanols depending on the number of hydroxyl groups attached. Generally,
alkanols are classified according to the number of alkyl or aryl groups attached to the carbon that
bears the -OH group as:
Industrial Uses of Alkanols
Methanol and ethanol are the two most important. While methanol is largely manufactured from
petroleum feedstock, ethanol is obtained from ethene or by fermentation of sugar and starch.
Both have many uses in industry. There are several uses of alcohols. Some are listed below:
HALOALKANES
Haloalkane (or alkyl halide or halogenoalkane) is any compound containing a halogen atom
covalently bonded to an Sp3 hybridized carbon atom. The general formula for an alkyl halide is
R-X, where X may be F, Cl, Br or I.
They are structurally related to the alkanes through the replacement of one or more hydrogen
replaced by a halogen atom (fluorine, chlorine, bromine or iodine).
Classification of haloalkanes
Haloalkanes fall into different classes depending on how the halogen atom is positioned on the
chain of carbon atoms. There are some chemical differences between the various types:
1. Primary haloalkanes: In a primary (1o) haloalkane, the carbon which carries the halogen
atom is only attached to one other alkyl group. Some examples of primary haloalkanes.

Notice that it doesn’t matter how complicated the attached alkyl group is. In each case, there is
only one linkage to an alkyl group from the -CH2 group holding the halogen.
2. Secondary haloalkanes: In a secondary haloalkane, the carbon with the halogen attached
is joined directly to two other alkyl groups, which may be the same or different.
Examples are:

3. Tertiary haloalkanes: In a tertiary (3o) haloalkane, the carbon atom holding the halogen is
directly attached to three (3) alkyl groups, which may be any combination of same or
different. Examples are:
IUPAC Naming of Haloalkanes

When the carbon chain bears both a halogen and an alkyl substituent, the two substituents are
considered of equal rank, and the chain is numbered so as to give the lower number to the
substituent nearer the end of the chain.
Physical Properties of Haloalkanes
1. They resemble the parent alkane in being colourless, relatively odourless and
hydrophobic.
2. The melting and boiling points of chloro-, bromo-, and iodoalkanes are higher than the
analogous alkanes.
3. As branching in alkyl halides increases, the boiling point decreases.
4. Since they contain a fewer C-H bond, hydrocarbons are less flammable than alkanes, and
some are used in fire extinguisher.
5. They are better solvents than the corresponding alkanes because of their increased
polarity.
6. They are slightly soluble in water but tend to readily dissolve in organic solvents.
 7. Many volatile halogen compounds are sweet in smell
8. Lower members are gases due to less molecular weight, while higher members are liquids
or solids.
Methods of Preparation of Haloalkanes
There are different methods of preparation of haloalkanes. Some of these important methods are:
1. Preparation by conversion of alcohols to alkyl halides using suitable reagents (e.g. thionyl
chloride, concentrated halogen acids)
2. Preparation from alkenes following the Markovnikov’s rule
3. Preparation by free radical halogenation of alkanes.
Reactions of Haloalkanes
The following are the typical reactions of haloalkanes: reaction with alkali, reaction with
potassium cyanate, reaction with ammonium and reaction with magnesium metal.
a. Reaction with aqueous alkali
This reaction converts alkyl halides to alcohols using water or hydroxide as the nucleophile in a
simple nucleophilic reaction.
Depending on the conditions used and the type of haloalkane, there are two sorts of reactions that
can take place; a substitution reaction or elimination reaction. These two reactions produce
different products.
A substitution reaction produces an alcohol as seen below:

An elimination reaction produces an alkene:

b. Reaction with alcoholic potassium cyanide (KCN)

This reaction of haloalkanes is a useful way of lengthening carbon atoms. Haloalkanes react with
alcoholic KCN to form alkyl cyanides (or alkanenitriles) in a process called nucleophilic
substitution reaction. E.g 1-bromopropane reacts to produce butane nitriles as seen below:

The bromine (or other halogen) in the halogenoalkane is replaced by a -CN group, hence a
substitution reaction. Secondary and tertiary haloalkanes also react similarly but varies in
mechanism.
 c. Reaction with alcoholic ammonia:
Reaction of haloalkanes with alcoholic ammonia occurs in a 2 stage process to produce amines.
A primary amine is formed first, but the reaction proceeds further to give the secondary amine,
which further continues to form tertiary amine.

d. Reaction with magnesium metal:

Haloalkanes react with magnesium metal in dry ether to form alkyl-magnesium halides, known
as Grignard reagent. Haloalkanes are useful in the synthesis of organometallics such as
Grignard’s reagent and Reformatski’s reagent. An example of a Grignard reagent is
CH3CH2MgBr.

ALDEHYDES
An aldehyde is a carbonyl group (a C=O) bonded to a hydrogen atom. It has a functional group
with the structure -CHO, and the general formula is written as R-CHO (where R represents an
alkyl group, except in the case of methanal where it represents H).
The simplest aldehydes are methanal, ethanal, propanal, etc

Note: when writing formula for aldehydes, it is written as -CHO and not as -COH (an alcohol).
Summary of Aldehyde Nomenclature
1. Aldehydes take their name from their parent alkane chains. The -e from the end of the
alkane is removed and replaced with -al.
2. The aldehyde functional group is given the #1 numbering location, and this number is not
included in the name.
 3. For the common name of aldehydes, start with the common parent chain name and add
the suffix – aldehyde. Subsequent positions are shown with Greek letters.

E.g.

Preparation of aldehydes
Aldehydes have been prepared by different methods, but in the industry, it is commonly prepared
by the oxidation of alcohols. Primary alcohols are oxidized to aldehydes, while secondary
alcohols are oxidized to ketones.
An example is the oxidation of methanol to produce formaldehyde, a starting material for the
production of plastics.

Uses of aldehydes
1. Formaldehyde is used as a preservative, embalming, making polymeric products, etc.
2. Acrolein, an aldehyde is used in the manufacture of plastics, adhesives, polish, making paper,
chemical weapon, etc.
3. Acetaldehyde is used in acetic acid manufacture, carbohydrtates metabolism, perfume
production, etc.
4. Benzaldehyde is used a s a flavoring agent, in tyre and rubber manufacturing, auto repairs, etc.

KETONES
A ketone is a carbonyl group bonded to two carbon atoms. The following general formulas, in
which R represents an alkyl group, and Ar represents an aryl group, is used to represent ketones:

Examples of ketones are acetones, propanone, butanone (or ethylmethylketone).

Methods of preparation of ketones

Reactions of Ketones
The reactions of ketones are: condensation reaction, oxidation reaction and nucleophilic addition
reaction.
Uses of Ketones
1. The most common ketone, acetone, is an excellent solvent for a number of plastics and
synthetic fibers, and as paint remover and thinner
2. It is used in chemical peeling and for acne treatments
3. Methyl ethyl ketone (MEK), chemically butanone is a common solvent, used in the
production of textiles, varnishes, plastics, paraffin wax, etc.
4. MEK is also used as a welding agent for plastics due to its dissolving properties.
5. Cyclohexanone, an important ketone, is used in the production of nylon.