Ethers

Ethers are a class of organic compounds that mostly contain an ether group wherein
the oxygen atom is bonded to two alkyl or aryl groups. The word Ether has been derived
from the Latin word ‘aether’ which means ‘to ignite’. At room temperature and under a
high-pressure, ethers are usually flammable. The general formula of ether is given as R-
O-R, R-O-R’, R-O-Ar or Ar-O-Ar where R represents an alkyl group and Ar represents
an aryl group

Examples Of Ethers

Below we have given a few ethers examples.

1. CH3 – O – CH3 (Dimethyl ether)

2. (CH3)2CH – O – CH(CH3)2 (Diisopropyl ether)

3. Cyclic ethers such as

C6H5 – O – C6H5 (Diphenyl ether)

Physical Properties of Ethers

Dimethyl ether and ethyl methyl ether are both gases at room temperature. Other lower
homologues are colourless, pleasant smelling, volatile liquids with a typical ether smell.

1) Dipole moment: C-O-C bond angle is not 180°, dipole moments of the two C-O
bonds do not cancel each other, and thus ethers possess a small net dipole moment.

2) Boiling point: The boiling points of ether molecules are comparable to that of
alkanes but they are very low compared to that of alcohols of comparable molecular
mass. This is because of the presence of hydrogen bonding in alcohol.

3) Solubility: The solubility of ethers with water resembles those of alcohols of

comparable molecular mass. Ether molecules are soluble in water. This is because of
the fact that like alcohol, oxygen atoms of ether can also form hydrogen bonds with a
water molecule. Also, solubility decreases with an increase in carbon atoms. This is
because the relative increase in hydrocarbon content of the molecule decreases the
tendency of H-bond formation.
4) Polarity: Ether is less polar than esters, alcohols or amines because of the oxygen
atom that is unable to participate in hydrogen bonding due to the presence of bulky alkyl
groups on both sides of the oxygen atom. but ether is more polar than alkenes.

5) Hybridization: In ethers, the oxygen atom is sp3 hybridized with a bond angle of
109.50.

Classification of Ethers

Ethers can be classified into two broad categories based on the substituent group
attached to its oxygen atom: symmetrical ethers and asymmetrical (or unsymmetrical)
ethers.

Symmetrical ethers are those ethers where two identical groups are attached to the
oxygen atom

Example:

CH3 – CH2 – O – CH2 – CH3 (Diethyl ether)

Asymmetrical ethers are those where two different groups are attached to the oxygen
atom.

Example:

CH3 – O – CH2 – CH3 (Ethyl methyl ether)

Their structure is similar to that of the structure of the alcohol. Interestingly, the
structures of both ether and alcohol are similar to the structure of water molecules. This
is because, in alcohol, one hydrogen atom of a water molecule is replaced by an alkyl
group, and in the case of ethers both hydrogen atoms of water molecules are replaced
by an alkyl or aryl group.

Note: Ether does not possess a hydroxyl group, unlike alcohols and phenols.

Nomenclature of Ethers

Ethers are named simply by the names of two alkyl/aryl groups bonded to oxygen and
add the word ‘ether’. Those alkyl groups are listed in alphabetical order.
For example, t-butyl methyl ether, ethyl methyl ether

If only one alkyl/aryl group is shown in the name of a particular ether, it implies two
identical groups, as in ethyl ether for diethyl ether. Naming for ethers adopted by IUPAC
uses a more complex group as the root name, with the oxygen atom and the smaller
group named as an alkoxy substituent. Thus, in IUPAC systems, ethers are alkoxy
alkanes.

Example: ethoxyethane (diethyl ether), methoxy ethane (methyl ethyl ether), 2-methoxy-
2-methylpropane (methyl tert-butyl ether), phenoxy benzene (diphenyl ether).

This IUPAC nomenclature is very useful for naming compounds with additional
functional groups because these functional groups can be described by the root name.

Rules for Naming the Ether Using IUPAC Name

Rule 1: Select the longest carbon chain as the base chain and give the base name.

Rule 2: Change the name of the other hydrocarbon group ends with ‘yl’ change into
‘oxy’.

Example: Methyl becomes methoxy and ethyl becomes an ethoxy group.

Rule 3: Alkoxy name is placed with a locator number in front of the base chain name.

Example:

1. CH3 – O – CH2 – CH2 – CH2 – CH3 (1 – Methoxybutane)

2. CH3 – CH (CH3) – CH2 – O – CH2 – CH3 ( 1- Ethoxy – 2- methylpropane)

Ether Chemical Reactions

Of all the functional groups, ethers are the least reactive ones. Ether bonds are quite
stable towards bases, oxidizing agents and reducing agents. But on the other hand,
ethers undergo cleavage by reaction with acids. The prominent chemical reactions of
ethers are as follows;

Cleavage of C-o Bonds in Ethers

Cleavage of C-O bonds in ether takes place in excess hydrogen halide (which are
acidic) under extreme conditions like in concentrated acids (usually HBr and HI) and
high temperatures.

For example, the reaction of dialkyl ether produces, initially, an alkyl halide and alcohol.
This alcohol further reacts with halide to form a second mole of alkyl halide and water.

Reactivity of RX: HI>HBr>HCl

It is known that the oxygen atom of ether is basic, similar to the oxygen atom of alcohol.
Thus, the initial reaction between ether and halide produces a protonated ether. The
nucleophilic attack of halide ion on this protonated ether leads to cleavage of C-O bond.

Methods of Preparation of Ethers:

1. Preparation of Ethers by Dehydration of Alcohols
In the presence of protic acids (like sulphuric acid) alcohols undergo dehydration to
produce ethers at 413 K (i. e 140 0C). This is an ideal method of preparation through
primary
alcohols.
This method is applicable for symmetrical ethers.

2. Preparations of Ethers by Williamson Synthesis

Williamson synthesis is versatile method for the preparation of symmetrical and
asymmetrical ethers in laboratories. In this method, an alkyl halide is reacted with
sodium alkoxide which leads to the formation of ether. The reaction generally follows
the SN 2 mechanism for primary alcohol.

alkoxides are strong bases and they can react with alkyl halides leading to elimination
reactions. Williamson synthesis gives higher yield in the case of primary alkyl halides. In
the case of secondary alkyl halides, elimination competes with substitution. Formation
of only elimination products is observed in tertiary alkyl halide

Uses of Ether

 Dimethyl ether is used as a refrigerant and as a solvent at low temperatures.

 Diethyl ether is a common ingredient in anaesthesia used in surgeries.
 Ether is used along with petrol as a motor fuel.
 Diethyl ether is a common solvent for oils, gums, resins, etc.
 Phenyl ether can be used as a heat transfer medium because of its high boiling
point.

Nitriles

Nitriles are the organic compounds in organic chemistry which are also called Cyano
Compounds. This class of organic compounds contain cyanide as the functional group
with the formula −C ≡ N. Inorganic compounds with -CN group are called cyanides.

Some compounds of nitriles are mainly manufactured by heating up carboxylic acids

with the ammonia compound in presence of some catalysts. This is a process which is
employed in the preparation of nitriles from oils and fats. These products are being used
as the softening agents in substances such as synthetic rubbers, textiles, plastics and
also in the making of amines. Nitrile compounds are also formed by the process of
heating amides with the phosphorous pentoxide. They can also be reduced to primary
amines by reacting lithium aluminium hydride or getting it hydrolyzed to carboxylic acids
in presence of acid or base.

Properties

The chemical and physical properties of nitriles are given below-

 Nitriles are colourless solids or liquids with unique odours.

 They have boiling points measuring between 82-118 °C.
 Nitriles exhibit strong dipole-dipole movements and also the Van der Waals
forces of dispersion between the molecules.
 They also show high polarity and electronegativity.
 These are said to be highly soluble in water, and the solubility decreases as the
chain length increases.

Reactions

Nitrile undergoes a various set of reactions as shown below-

1. Hydrolysis- The hydrolysis of nitriles in the presence of an acid or a base

produces carboxamides and carboxylic acids efficiently.

2. Reduction- Nitriles are reduced to primary and tertiary amines by treating them
with lithium aluminium hydride. The reduction process occurs in the presence of
some catalysts.

3. Alkylation- The alkylation of nitrile compounds leads to the formation of nitrile

anions.
The other reactions are nucleophilic addition reactions, Friedel–Crafts acylation, etc.

Uses

Nitrile finds its uses in various medical and industrial applications of which some are
listed below-

 Nitriles are used in the manufacture of nitrile gloves, seals, and hoses as they
exhibit resistance to chemicals.
 They are used as an antidiabetic drug.
 They are utilized in the applications of oil-resistant substances and also for low-
temperature uses
They are also employed in automotive systems, hydraulic hoses and also in aircraft
systems.

CARBOXYLIC ACID AND DERIVATIVES

Compounds containing the carboxyl group are distinctly acidic and are called carboxylic
acid.

They have general formula Cn H2nO2 Carboxylic acid derivatives are compounds with
functional
groups that can be converted to carboxylic acids by a simple acidic or basic hydrolysis.

CLASSIFICATION OF CARBOXYLIC ACIDS

NOMENCLATURE OF CARBOXYLIC ACIDS

The IUPAC system of nomenclature assigns a characteristic suffix to these classes. The
ending “e” is removed from the name of the parent chain and is replaced –”oic” acid.

IUPAC name of simple carboxylic acid

AMINES

There many organic nitrogen containing compounds, among which is amines.Organic

nitrogen compounds are: Amines RNH2 , Amide RCONH2 , Imine R’R C=NR’’ , Nitrile
RC≡N. Generally amines are derivatives of ammonia in which one or more hydrogen
atom(s) have been replaced by alkyl or aryl(phenyl) group

NH3 Ammonia, RNH2 primary , RR’NH secondary, and RR’R’’NH tertiary which are all
amines

Primary amine is formed when one hydrogen atom of ammonia is replaced by alkyl or
aryl group e.g. methylamine, ethylamine, propylamine, phenylamine (alanine)
• Secondary amine is formed when two hydrogen atoms of ammonia are replaced by
alkyl or aryl group e.g. diethylamine, dipropylamine, diphenylamine, ethylmethylamine,
methylpropylamine
• Tertiary amine is formed when all (3) hydrogen atoms of ammonia are replaced by
alkyl
or aryl group e.g. trimethylamine, triethylamine, tripropylamine, triphenylamine,
ethylmethylpropylamine.
• When all the alkyl or phenyl groups are the same in secondary and tertiary amines,
such amines are called simple amines but when they are not the same they are called
mixed amines.
• Examples of simple amines are diethylamine, dipropylamine, diphenylamine,
trimethylamine, triethylamine, tripropylamine, triphenylamine
• Examples of mixed amines are ethylmethylamine, methylpropylamine,
Ethylmethylpropylamine

IUPAC NOMENCLATURE OF AMINES

• Amines are known as amino group (containing –NH2).
• Amines are named as alkylamine
• Primary amines’ name result from naming the alkyl group bonded to the amino
group (–NH2) and adding the suffix “-amine”. The entire name is written as one
word e.g. CH3–NH2 Methylamine, C4H7–NH2 Butylamine
• Secondary and tertiary amine names are obtained by listing the alkyl groups
alphabetically and when two or more identical alkyl groups are present, the
prefixes “ di, tri” are used e.g.
• C2H5NHCH3 Ethylmethylamine
• C2H5NHC2H5 Diethylamine
• C2H5N(CH3)C3H7 Ethylmethylamine
• CH3NH(C6H5) Methylphenylamine
PREPARATION OF AMINES
Ammonolysis of Alkylhalides: This is reaction between alkylhalides and ammonia.
All classes of amines can be prepared by this method
RX + NH3 RNH2 + HX (primary amine)
RX + RNH2 R2NH + HX (secondary amine)
RX + R2NH R3N + HX (tertiary amine)
RX + R3N R4N+ x- (quaternary ammonium salt)
The order of reactivity of alkylhalide (RX) is RI>RBr>RCl
PHYSICAL PROPERTIES OF AMINES
 Lower aliphatic amines (methylamine and ethylamine) are gases at ordinary
temperature and pressure and are highly soluble in water
 Higher members are liquids, then solids, their solubility falling off with increasing
molecular weight• Amines have higher boiling points than alkanes of similar molecular
weight but
lower boiling points than alcohol due to their C-N bond being more polar than
C-C bond but less polar than C-OH bond
• Primary and secondary amines can form intermolecular hydrogen bonds because
they serve as both hydrogen bond donors and acceptors but tertiary amines have
no hydrogen atoms bonded to the nitrogen atom and therefore are not hydrogen
bond donor. Hence tertiary amines have lower boiling points than primary and
secondary amines of comparable molecular weight.
• Lower alkylamines have notorious “fishy ammonia smells” – a smell rather like
bad fish; indeed, a decaying fish produces various amines
• Aromatic amines are liquids or solids with high boiling points and they have
similar smell like bad fish and are soluble in organic solvents but almost insoluble
in water.
• Aniline is markedly toxic by absorption through the skin.
General Chemical Reactions of Amines
Basic Character of Amine
• All primary amines are bases, undergoing reactions of the general type:
RNH2 + HA RN+H3 + A-
• Simpler alkylamines are only a little stronger as bases than ammonia. The lower
members of the series are highly soluble in water, presumably like ammonia on account
of hydrogen bonding and their solutions are markedly alkaline e.g.
C2H5NH2 + H2O C2H5N+H3 + OH-
• Amine with acids form well defined crystalline salts
C2H5NH2 + HCl C2H5N+H3 + Cl-
Ethylamine and other volatile amines show the characteristics “white cloud” with
hydrogen chloride (or any other acid in the vapour state as ammonia itself)
USES OF AMINES
• Amines are used in the manufacturing of many pharmaceuticals (Mepacrine- an
antimalarial drug)
• Primary aromatic amines are used to make azo dyes
• They are used in production of plastics. 1,6-diaminohexane (H2N(CH2)6NH2) is
used in manufacture of nylon 6,6. Other amines are used in the production of
isocyanates for polyurethane plastics
• They are used as inhibitors in preventing the deterioration of rubber through
oxidation by atmospheric oxygen
Aldehydes and Ketones
Aldehydes are compounds of the general formula HCHO; ketones are compounds of
the general
formula RR'CO. The groups R and R' may be aliphatic or aromatic.
Both aldehydes and ketones contain the carbonyl group, C O, and are often referred to
collectively as carbonyl compounds. It is the carbonyl group that largely determines the
chemistry of aldehydes and ketones.
This difference in structure affects their properties in two ways:
(a) aldehydes are quite easily oxidized, whereas ketones are oxidized only with
difficulty;
(b|) aldehydes are usually more reactive than ketones toward nucteophilic addition, the
characteristic reaction ot carbonyl compounds.
Nomenclature
The common names of aldehydes are derived from the names of the corresponding
carboxyiic
acids by replacing -ic add by -aldehyde. The IUPAC names of aldehydes follow the
usual
pattern. The longest chain carrying the CHO group is considered the parent structure
and is
named by replacing the -e of the corresponding alkane by -al. The position of a
substituent
is indicated by a number, the carbonyl carbon always being considered as C-l. Here, as
with the
carboxylic acids, we notice that C-2 of the IUPAC name corresponds to alpha of the
common
name

The simplest aliphatic ketone has the common name of acetone. For most other
aliphatic
ketones we name the two groups that are attached to carbonyl carbon, and follow these
names
by the word ketone. A ketone in which the carbonyl group is attached to a benzene ring
is
named as a -phenone, as illustrated below.
According to the IUPAC system, the longest chain carrying the carbonyl group is
considered
the parent structure, and is named by replacing the -e of the corresponding alkane with
-one.
The positions of various groups are indicated by numbers, the carbonyl carbon being
given the
lowest possible number.

Physical properties
1-The polar carbonyl group makes aldehydes and ketones polar compounds.
2- they have higher Boiling pOlliU lliaa aon-pulai compounds or comparable
molecular weignt.
3- they are not d&pable Of intcrmoiecular hydrogen bonding since they conten
hydrogen
bonded bfaiy to carbon; as a result they have lower boiling points than comparable
alcohols or
carboxylic acids.
4-The lower aldehydes and ketones are appreciably soluble in water, presumably
because of
hydrogen bonding between solute and solvent molecules; borderline solubility is
reached at
about five carbons .
5-Aldehydes and ketones are soluble in the usual organic solvents