Detection of Functional Group

I
n

o
r
g
a
n
i
c

chemistry, functional groups are specific groups (moieties) of atoms or bonds

within molecules that are responsible for the characteristic chemical reactions of
those molecules. The same functional group will undergo the same or similar
chemical reaction(s) regardless of the size of the molecule it is a part of. However,
its relative reactivity can be modified by other functional groups nearby. The
atoms of functional groups are linked to each other and to the rest of the molecule
by covalent bonds. When the group of covalently bound atoms bears a net charge,
the group is referred to more properly as a polyatomic ion or a complex ion. Any
subgroup of atoms of a compound also may be called a radical, and if a covalent
bond is broken homolytically, the resulting fragment radicals are referred as free
radicals.
Combining the names of functional groups with the names of the
parent alkanes generates what is termed a systematic nomenclature for
naming organic compounds. The first carbon atom after the carbon that attaches
to the functional group is called the alpha carbon; the second, beta carbon, the
third, gamma carbon, etc. If there is another functional group at a carbon, it may
be named with the Greek letter, e.g., the gamma-amine in gamma-aminobutanoic
acid is on the third carbon of the carbon chain attached to the carboxylic acid
group.
 Table of common functional groups
The following is a list of common functional groups. In the formulas, the symbols R
and R' usually denote an attached hydrogen, or a hydrocarbon side chain of any
length, but may sometimes refer to any group of atoms.

Hydrocarbon
Functional groups, called hydrocarbyl, that contain only carbon and hydrogen, but
vary in the number and order of double bonds. Each one differs in type (and scope)
of reactivity.

Chemical Structural
Group Formula Prefix Suffix Example
class Formulae

Alkane Alkyl R(CH2)nH alkyl- -ane

Ethane

Alkene Alkenyl R2C=CR2 alkenyl- -ene

Ethylene
(Ethene)

Alkyne Alkynyl RC≡CR' alkynyl- -yne

Acetylene
(Ethyne)

Benzene RC6H5 -
Phenyl phenyl-
derivative RPh benzene
Cumene
(Isopropylbenzene)
There are also a large number of branched or ring alkanes that have specific
names, e.g., tert-butyl, bornyl, cyclohexyl, etc. Hydrocarbons may form charged
structures: positively charged carbocations or negative carbanions. Carbocations
are often named -um. Examples are tropylium and triphenylmethyl cations and
the cyclopentadienyl anion.
Groups containing halogens
Haloalkanes are a class of molecule that is defined by
a carbon–halogen bond. This bond can be relatively
weak (in the case of an iodoalkane) or quite stable (as
in the case of a fluoroalkane). In general, with the
exception of fluorinated compounds, haloalkanes
readily undergo nucleophilic substitution reactions
or elimination reactions. The substitution on the
carbon, the acidity of an adjacent proton, the solvent
conditions, etc. all can influence the outcome of the
reactivity.

Structural
Chemical class Group Formula Prefix Suffix Example
Formula

haloalkane halo RX halo- alkyl halide Chloroethane

(Ethyl chloride)

fluoroalkane fluoro RF fluoro- alkyl fluoride

Fluoromethane
(Methyl fluoride)

chloroalkane chloro RCl chloro- alkyl chloride

Chloromethane
(Methyl chloride)

bromoalkane bromo RBr bromo- alkyl bromide

Bromomethane
(Methyl bromide)

iodoalkane iodo RI iodo- alkyl iodide

Iodomethane
(Methyl iodide)
Groups containing oxygen
Compounds that contain C-O bonds each possess differing reactivity based upon
the location and hybridization of the C-O bond, owing to the electron-withdrawing
effect of sp-hybridized oxygen (carbonyl groups) and the donating effects of sp 2-
hybridized oxygen (alcohol groups).

Chemical Structural
Group Formula Prefix Suffix Example
class Formula

Alcohol Hydroxyl ROH hydroxy- -ol

Methanol

-oyl- (-COR')
Ketone Carbonyl RCOR' or -one
oxo- (=O) Butanone
(Methyl ethyl
ketone)

formyl- (-COH)
Aldehyde Aldehyde RCHO or -al
oxo- (=O)
Acetaldehyde
(Ethanal)

carbonofluoridoyl
-
carbonochloridoyl
Acyl halide Haloformyl RCOX - -oyl halide
carbonobromidoyl Acetyl chloride
- (Ethanoyl
carbonoiodidoyl- chloride)

Carbonate (alkoxycarbonyl)o alkyl carbo

Carbonate ROCOOR Triphosgene
ester xy- nate
(bis(trichloromet
hyl) carbonate)

carboxy- -oate Sodium acetate

Carboxylate Carboxylate RCOO−
(Sodium
ethanoate)
Carboxylic
Carboxyl RCOOH carboxy- -oic acid
acid
Acetic acid
(Ethanoic acid)

alkanoyloxy-
alkyl
Ester Ester RCOOR' or Ethyl butyrate
alkanoate
alkoxycarbonyl (Ethyl butanoate)

Methoxy Methoxy ROCH3 methoxy-

Hydroperox Hydroperox alkyl hydro

ROOH hydroperoxy-
ide y peroxide tert-Butyl
hydroperoxide

alkyl peroxi
Peroxide Peroxy ROOR peroxy-
de Di-tert-butyl
peroxide

Ether Ether ROR' alkoxy- alkyl ether Diethyl ether

(Ethoxyethane)

-al
RCH(OR')
Hemiacetal Hemiacetal alkoxy -ol alkyl hemia
(OH)
cetal

-one
RC(ORʺ)
Hemiketal Hemiketal alkoxy -ol alkyl hemik
(OH)R'
etal
-al
RCH(OR')
Acetal Acetal dialkoxy- dialkyl acet
(OR")
al

Ketal (or Ac Ketal (or Ac RC(ORʺ) -one

dialkoxy-
etal) etal) (OR‴)R' dialkyl ketal

RC(OR')
Orthoester Orthoester trialkoxy-
(ORʺ)(OR‴)

1,2-
Methylenedi
Heterocycle PhOCOPh methylenedioxy- -dioxole Methylenedioxyb
oxy
enzene
(1,3-
Benzodioxole)
tetraalkylort
Orthocarbo Orthocarbo C(OR)(OR')
tetralkoxy- hocarbonat
nate ester nate ester (ORʺ)(OR″)
e
Groups containing nitrogen
Compounds that contain nitrogen in this category may contain C-O bonds, such as
in the case of amides.

Chemic Structural
Group Formula Prefix Suffix Example
al class Formula

carboxami
do-
Carboxam
Amide RCONR2 or -amide
ide
carbamoyl Acetamide
- (Ethanamide)

Primary
RNH2 amino- -amine
amine Methylamine
(Methanamine)

Secondary
R2NH amino- -amine
amine
Dimethylamine
Amines

Tertiary
R3N amino- -amine
amine
Trimethylamine

4°
ammoniu R4N+ ammonio- -ammonium
m ion
Choline

Imine
Primary RC(=NH
imino- -imine
ketimine )R'

Secondary imino- -imine

ketimine
 Primary RC(=NH
imino- -imine
aldimine )H Ethanimine

Secondary RC(=NR
imino- -imine
aldimine ')H

(RCO)2N
Imide Imide imido- -imide
R'
Succinimide
(Pyrrolidine-2,5-
dione)

Azide Azide RN3 azido- alkyl azide

Phenyl azide
(Azidobenzene)

Azo
Azo Methyl orange
compou RN2R' azo- -diazene
(Diimide) (p-
nd
dimethylamino-
azobenzenesulfoni
c acid)

alkyl cyanat
Cyanate ROCN cyanato-
e
Cyanat Methyl cyanate
es

Isocyanat isocyanato alkyl isocya

RNCO
e - nate
Methyl isocyanate
 nitrooxy-, alkyl nitrate
Nitrate Nitrate RONO2 Amyl nitrate
nitroxy-
(1-
nitrooxypentane)
alkanenitril
e
Nitrile RCN cyano-
alkyl cyanid Benzonitrile
e (Phenyl cyanide)
Nitrile
alkaneisonit
rile
Isonitrile RNC isocyano-
alkyl isocya
Methyl isocyanide
nide

Nitrosoox nitrosooxy
Nitrite RONO alkyl nitrite
y - Isoamyl nitrite
(3-methyl-1-
nitrosooxybutane)

Nitro
compou Nitro RNO2 nitro-
nd Nitromethane

Nitroso
nitroso-
compou Nitroso RNO
(Nitrosyl-)
nd Nitrosobenzene

RCH=N
Oxime Oxime Oxime
OH Acetone oxime
(2-Propanone
oxime)

4-pyridyl
(pyridin-
4-yl)
Pyridin
e 3-pyridyl
Pyridyl RC5H4N (pyridin- -pyridine
derivati
ve 3-yl) Nicotine
2-pyridyl
(pyridin-
2-yl)
 Tests for the functional groups
Tests for Unsaturation

There are two tests for determining unsaturation in an organic compound.

1. Bromine Test

In this test, the orange-red colour of bromine solution disappears when it is

added to an unsaturated organic compound (unsaturated hydrocarbon).

2. Baeyer’s Test (Alkaline KMnO4 Test)

In this test, pink colour of KMnO4 disappears, when alkaline KMnO4 is

added to an unsaturated hydrocarbon. The disappearance of pink colour
may take place with or without the formation of brown precipitate of MnO2.
Tests for Alcoholic Group

Alcohols are compounds in which the hydroxyl group (-OH) is linked to

aliphatic carbon chain or in the side chain of an organic compound.
Depending upon the number of hydroxyl group, alcohols are classified as
mono (contain only one –OH group), di (contain two –OH groups) and
trihydric (contains three –OH groups).

Alcohols are further classified as primary (1°), secondary (2°) and tertiary
(3°) according to the –OH group is attached to the primary, secondary and
tertiary carbon atoms respectively.

The alcoholic group can be detected by the following tests:

1. Sodium metal test

Alcohols react with active metals like sodium and liberate hydrogen gas
that can be observed in the form of effervescence.
2. Ester test

Alcohols react with carboxylic acids to form fruity smelling compounds

called esters. The reaction between alcohol and carboxylic acid is called
esterification and is catalysed by an acid such as concentrated sulphuric
acid.

3. Ceric ammonium nitrate test

Alcohols reacts with ceric ammonium nitrate to form a red coloured alkoxy
cerium (IV) compound.
4. Acetyl chloride test

Alcohols react with acetyl chloride to form esters and gives out hydrogen
chloride gas. The hydrogen chloride formed gives white fumes of
ammonium chloride with ammonium hydroxide.

5. Iodoform test

This test is given by acetaldehyde, all methyl ketones and all alcohols
containing CH3-CH-OH group. When alcohol is warmed with sodium
hydroxide solution and iodine, a yellow precipitate of iodoform is formed.

Tests for Phenolic group

Phenols are compounds containing a hydroxyl group attached to an

aromatic ring. The simplest phenol is C6H5OH that is solid in winter and
liquid in summer. Phenols are generally colourless but are coloured when it
comes in contact with air due to oxidation. Other examples of phenols are:
o-cresol, m-cresol, p-cresol, quinol, catechol, resorcinol etc.
The phenolic group can be detected by the following tests:

1. Litmus test

Phenol is a weak acid, it gives red colour with litmus paper. The
dissociation of phenol in water is represented as follows:

2. Ferric chloride test

Phenol reacts with ferric ions to form violet coloured complex.

3. Liebermann’s test

When phenol is treated with sodium nitrite in the presence of concentrated

sulphuric acid, deep blue or green colour is produced. The blue or green
colour changes to red or brown colour on treatment with water. The red
colour is due to the formation of indophenol. The red colour again changes
to blue or green by the addition of strong alkali. The blue or green colour is
due to the formation of indophenols anion.

4. Phthalein Dye test

Phenol on heating with phthaleic anhydride in the presence of sulphuric

acid produces phenolphthalein, which is colourless. Phenolphthalein gives
pink colour on treating with alkali.

Tests for Aldehydic and Ketonic Groups

Aldehydes and Ketones are compounds containing carbonyl group.

Carbonyl group consisting of a carbon atom bonded to oxygen atom by a
double bond.

In Aldehydes the carbonyl carbon is attached to atleast one hydrogen atom

and to a carbon containing group (aliphatic or aromatic radical).
Formaldehyde is an exception, in which carbonyl group is attached to two
hydrogen atoms.
But in ketones the carbonyl carbon is attached to two aliphatic or aromatic
groups.

Carbonyl groups in aldehydes and ketones are identified by the

following tests:

1. 2,4-dinitrophenyl hydrazine test (2,4-DNP test)

2,4-dinitrophenyl hydrazine can be used to qualitatively detect the carbonyl

group of an eldehyde or ketone. A positive result is indicated by the
formation of an yellow or orange-red precipitate of 2,4-dinitrophenyl
hydrazone.

2. Sodium bisulphite test

Most aldehydes and ketones give bisulphate addition product with sodium
bisulphate, which is white crystalline in nature.
Note: Acetone phenone and benzophenone do not give this test.

Differentiating tests for aldehydes

The major difference between aldehydes and ketones is that an aldehyde

is readily oxidised to carboxylic acid whereas ketones cannot be oxidised
easily. This difference forms the basis of the tests for distinguishing
aldehydes and ketones.

The following are the tests for aldehydes but not for ketones:

1. Schiff’s Test

Aldehydes give pink or magenta colour with Schiff’s reagent.

Note: With benzaldehyde the pink colour developes slowly.

2. Tollen’s Test

Tollen’s reagent is ammoniacal silver nitrate. Aldehydes react with Tollen’s

reagent to form elemental silver, accumulated onto the inner surface of the
reaction vessel, producing silver mirror on the inner surface of the vessel.

3. Fehling’s Test

This is an important test to distinguish aldehydes from ketones. The

reagents used in this test are Fehling’s solution A and Fehling’s solution B.
Fehling’s solution A is an aqueous solution of copper sulphate and
Fehling’s solution B is a clear solution of sodium potassium tartrate
(Rochelle salt) and strong alkali (usually NaOH).

The final Fehling’s solution is obtained by mixing equal volmes of both

Fehling’s solution A and Fehling’s solution B that has a deep blue colour. In
Fehling’s solution, copper (II) ions form a complex with tartrate ions in
alkali. Aldehydes reduces the Cu(II) ions in the fehling’s solution to red
precipitate of cuprous oxide(copper (I) oxide).

Note: Benzaldehyde may or may not give this test as the reaction is very
slowly.
Differentiating tests for Ketones

The following tests are given by ketones but not by aldehydes:

1. m-dinitrobenzene Test

Ketones react with m-dinitrobenzene to give a violet colouration.

2. Sodium nitroprusside Test

The anion of the keton formed by a alkali reacts with nitroprusside ion to
form a red coloured complex.

Tests for Carboxylic group

Carboxylic acids are organic compounds containing carboxyl functional

group. It is of two types aliphatic and aromatic. Aliphatic acids are soluble
in water where as aromatic acids are sparingly soluble in water. Formic
acid and acetic acid are the simplest aliphatic acid and benzoic acid is the
simplest aromatic acid. Formic acid and acetic acid are liquids. Carboxylic
acids such as benzoic acid, oxalic acid, phthalic acid, tartaric acid etc are
colourless crystalline solids.

The following tests can be used to identify carboxylic acids:

1. Litmus Test

Carboxylic acid turns blue litmus red. The hydroxyl group in carboxylic is far
more acidic than that in alcohol. The dissociation of carboxylic acid is
represented as:

2. Sodium Hydrogen Carbonate Test

Carboxylic acids reacts with sodium hydrogen carbonate to produce carbon

dioxide gas which can be seen in the form of a brisk effervescence.

3. Ester Test

Carboxylic acid reacts with alcohol in presence of conc. sulphuric acid to

form ester that is identified by the presence of a fruity smell.
Tests for Amines

Amines are derivatives of ammonia in which one or more hydrogen atoms

are replaced by alkyl or aryl groups.

When one of the three hydrogen atoms is replaced by alkyl or aryl group,
primary amine is formed. It is generally represented as RNH2.

When two of the three hydrogen atoms are replaced by alkyl or aryl group,
secondary anime is formed. It is generally represented as R2NH.

When all the three hydrogen atoms are replaced by alkyl or aryl
substituents, tertiary amine is formed. It is generally represented as R3N.
1. Solubility Test

Amines are basic in nature and dissolves in mineral acids.

2. Litmus Test

Amines are basic in nature and turns red litmus blue.

3. Carbylamines Test

When primary amine is treated with alcoholic potassium hydroxide and

chloroform, an offensive smelling isocyanide is formed.

4. Azo-Dye Test

This test is given by aromatic primary amines. Aromatic primary amines

react with nitrous acid to form diazonium salts. These diazonium salts
undergo coupling reaction with β-naphthol to form orange coloured azo
dye.
Distinguishing tests for Primary, Secondary and Tertiary Amines

1. Nitrous acid Test

Primary aliphatic amines react with nitrous acid to produce nitrogen gas
which is seen as bubbles.

Secondary amines react with nitrous acid to form a yellow oily

nitrosoamine.

Tertiary amines react with nitrous acid to form soluble nitrite salts.

2. Hinsberg Test

The reactions of primary, secondary and tertiary amines are as follows.