Semester- V Core Course -VII Credit-4 Course Code – CH1543

Organic Chemistry- II
 NITRO COMPOUND
• Nitro compounds are organic compounds that contain one or
more nitro (-NO2) functional groups (R-NO2) .
• They are highly explosive especially when the compound
contain more than one nitro group.
Nitro alkanes
• are used as solvent for oils, fats, shellac and cellulose
derivatives.
• They are used for the manufacture of primary amines,
carboxylic acids and their derivatives.
• Nitro alkanes are considered as the derivatives of alkanes in
which one or more hydrogen atoms are replaced by nitro group.
Nitro - Aci tautomerism (shifting of proton)
Primary and secondary nitroalkanes i.e. those containing α–
hydrogen atom, exhibit tautomerism (shifting of proton)

Nitro form is more stable due to resonance stabilisation

 Nitro -Aci tautomerism (shifting of proton)

Preparation of nitro alkanes

In case of higher alkanes
A mixture of different nitroalkanes is obtained which involves
substitution as well as C-C bond fissions.

b) Liquid phase nitration : Alkanes on heating with conc.HNO3

under pressue at 413K gives large no.of polynitro compounds.
(slow reaction)
 3) From salts of α -halogeno carbooylic acids
 When salt of α–halogeno carboxylic acids are boiled with
NaNO2, lower alkanes are formed.

4) From Tertiary amines

Tertiary nitroalkanes are prepared by the oxidation of
ter-alkyl amines with KMnO4
5) From α –nitroalkenes (olefins)
Lower nitroalkanes are prepared by hydrolyzing α-nitroalkenes in
acidic medium( Recent method)
 6) From oximes
Primary and secondary nitroalkanes are obtained by
oxidizing aldoximes and ketoximes in presence of
trifluoroperoxyacetic acid(F3C-COO-OOC-CF3)
 Reactions of nitro alkanes
Nef carbonyl synthesis :

It is the acid hydrolysis (50

50%
% H2SO4) of salt of aci-form of a primary
or a secondary nitro alkanes to yield an aldehydes or a ketones
respectively.
Halogenation
 Nitro compounds as explosives
Explosive decomposition of organo nitro compounds are redox
reactions, wherein both the oxidant (nitro group) and the fuel
(hydrocarbon substituent) are bound within the same molecule.

The explosion process generates heat by forming highly stable

products including molecular nitrogen (N2), carbon dioxide, and
water.

The explosive power of this redox reaction is enhanced because

these stable products are gases at mild temperatures.
Reduction of nitrobenzene under different conditions.
 AMINES
Amines can be considered as derivatives of ammonia obtained
by replacement of one, two or all the three hydrogen atoms
by alkyl and/or aryl groups.

Like ammonia, nitrogen atom of amines is trivalent and carries an

unshared pair of electrons.
Nitrogen in amines are sp3 hybridised and the geometry of amines
is pyramidal.
Each of the three sp3 hybridised orbitals of nitrogen overlap with
orbitals of hydrogen or carbon depending upon the composition of
the amines.
The fourth orbital of nitrogen in all amines contains an unshared
pair of electrons.
 Preparation of Amines

1. Ammonolysis of alkyl halides

The carbon - halogen bond in alkyl or benzyl halides can be easily
cleaved by a nucleophile.
Hence, an alkyl or benzyl halide on reaction with an ethanolic
solution of ammonia undergoes nucleophilic substitution
reaction in which the halogen atom is replaced by an amino (–NH
) group.
This process of cleavage of the C–X bond by ammonia molecule is
known as ammonolysis.
When excess ammonia is used primary amine is obtained as the major
product.
If alkyl halide is used in excess, tertiary amine will be the main product
The order of reactivity of halides with amines is RI > RBr >RCl.
 Preparation of Amines
2) From Nitro Compounds
Nitro compounds are reduced to amines by passing
hydrogen gas in the presence of finely divided nickel,
palladium or platinum and also by reduction with metals
(Sn/Fe) in acidic medium.
Nitroalkanes can also be similarly reduced to the
corresponding alkanamines.
3) Reduction of nitriles (alkyl cyanides )

Nitriles on reduction with lithium aluminium hydride (LiAlH4)

or catalytic hydrogenation produce primary amines.
This reaction is used for ascent of amine series,
i.e., for preparation of amines containing one carbon atom
more than the starting amine.
4
5) From amides

The amides on reduction with lithium

aluminium hydride give amines.
 6) Hoffmann bromamide degradation reaction
Primary amine is prepared by treating an amide with bromine
in an aqueous or ethanolic solution of sodium hydroxide.
7. Schmidt reaction
The Schmidt reaction is an organic reaction in which
an azide reacts with a carbonyl derivative, usually a
aldehyde, ketone, or carboxylic acid, under acidic
conditions to give an amine
8. Gabriel phthalimide synthesis

Gabriel synthesis is used for the preparation of primary

amines.

Phthalimide on treatment with ethanolic potassium

hydroxide forms potassium salt of phthalimide which on
heating with alkyl halide followed by alkaline hydrolysis
produces the corresponding primaryamine.

Aromatic primary amines cannot be prepared by this

method because aryl halides do not undergo
nucleophilic substitution with the anion formed by
phthalimide.
THE BASICITY OF AMINES
Amines can act as:
a nucleophile (a Lewis base) because its lone pair none bonding
electrons can form a bond with an electrophile.
a Brønsted-Lowry base because it can accept a proton from a
proton acid.
 The basicity of the amines depends on the ability of the
lone pair none bonding electrons at nitrogen atom to
form bond with an acid.

The more easier the lone pair electrons formed bond

with the acid, will make the amines a stronger base.
Factors That Affect the Basicity of the Amines

1. +I effect ………………… favors basicity

2. Steric hindrance………. decreases basicity

3. Hydrogen bonding or Solvation effects…. favors basicity

When we consider the +I effect alone it will be in the
order
3o>2o>1o>NH3

But due to steric hindrance alkyl group would hinder the

attack of a hydrogen atom, thus decreasing the basicity
of the molecule.
Considering both effects the order of basicity will be
 An amine can abstract a proton from water, giving an
ammonium ion and a hydroxide ion.

These solvation effects increase the electron density on

the amine nitrogen to a greater degree than the inductive
effect of alkyl groups.
The more the hydration energy of the molecule, more is
the stability of the amine.
Experiments have indicated, in terms of hydration
energy, that the tertiary amines are the least stable
followed by the secondary amines followed by the
primary amines.
Decreasing order of extent of H-bonding in water
and order of stability of ions by solvation.
The order of basicity of amines will be as follows
Aromatic Amines:
Aromatic amines are less basic than aliphatic amines
and ammonia.
It is because in aniline or other arylamines, the –NH
group is attached directly to the benzene ring with a –I
effect.
It results in the unshared electron pair on nitrogen atom
to be in conjugation with the benzene ring and thus
making it less available for protonation.
Greater the number of resonating structures, greater is
the stability.
The aniline (with 5 resonence structures) is more stable
than anilinium ion (with only 2 resonance structurs).

Thus aniline is more stable and less basic in nature

In aralkyl amines the electron pair of nitrogen is not
conjugated with the aromatic ring.
Thus they are stronger base than aniline and ammonia.

<

But aralkyl amines are less basic as compared with the alkyl
amines
 Effect of N-alkyl or N-aryl substituent on the basicity of
aryl amine (C6H5- NH2 /Ar- NH2)
When the H atom in Ar- NH2 is replaced by electron
releasing groups (-CH3) its basicity increases

Ar- NH2 < Ar- NH-CH3 < Ar- N-(CH3)2

When the H atom in Ar- NH2 is replaced by electron

withdrawing groups (Ar) its basicity decreases

Ar- NH2 > Ar- NH-Ar > Ar- N-(Ar)2

 Effect of nuclear substituents in aryl amines
In case of substituted aniline, it is observed that electron
releasing groups like –OCH3, –CH3 increase basic
strength ……. whereas
electron withdrawing groups like –NO2, –SO3H, –COOH, -
CHO, & –X (X:halogen) decrease it by a combination of
resonance and inductive effects.
Effect of nuclear substituents in
aryl amines
Electron donating groups will
increase the electron density on
nitrogen making the lone pair more
available for protonation.
Electron withdrawing groups will
decrease the electron density on
nitrogen atom making the lone pair
less available for protonation.
Ortho effect
Anything ortho to the amine
amine, no matter whether it is
electron donating or withdrawing, will decrease the
basicity of the aromatic amine.
This is because of the ortho effect, which is basically
sterics.
sterics
The protonated amine will have a greater steric
interaction with the ortho group, so it will be less stable.

These resonance effects are possible when the

substituent is located at the ortho or para position, but
not at the meta position because cannot do this kind of
resonance at the meta position.
For example: 3-nitroaniline is a stronger base than 4-
nitroaniline due to non-resonance effect lone pair
remains with amine for donation/reaction.
Carbylamine reaction
Aliphatic and aromatic primary amines on heating with
chloroform and ethanolic potassium hydroxide form isocyanides
or carbylamines which are foul smelling substances.
Secondary and tertiary amines do not show this reaction.
This reaction is known as carbylamine reaction or isocyanide test
and is used as a test for primary amines.
Hofmann elimination from quarternary
ammmonium hydroxides

The process of producing tertiary amines and alkenes from

quaternary ammonium is called Hofmann elimination.
This process can also be referred to as exhaustive methylation.
The Hofmann rule states that the major alkene product is the
least substituted and least stable product when it comes to
asymmetrical amines.
Step 1
The ammonium iodide salt is formed from the treatment of the amine
with a beta-hydrogen or quaternary ammonium with excess methyl
iodide

Step 2
The substitution of the iodide ion with the hydroxide ion is achieved
by the reaction between the iodide and silver oxide and the
successive deprotonation of water by the silver oxide ion.
 Step 3
The mixture is heated to facilitate and elimination reaction and
form the required product.

Acylation
Aliphatic and aromatic primary and secondary amines react with acid
chlorides, anhydrides and esters by nucleophilic substitution reaction.
This reaction is known as acylation.
In this reaction the replacement of hydrogen atom of –NH2 or >N–H
group by the acyl group will take place.
The products obtained by acylation reaction are known as amides.
The reaction is carried out in the presence of a base stronger than the
amine, like pyridine, which removes HCl so formed
 Reaction with nitrous acid
 Nitrous acid is unstable and must be prepared in the reaction solution by mixing
sodium nitrite with acid.

Primary aliphatic amines react with nitrous acid to form

aliphatic diazonium salts which being unstable, liberate
nitrogen gas quantitatively and alcohols.
Quantitative evolution of nitrogen is used in estimation of
amino acids and proteins.
Reaction with nitrous acid
Aromatic amines react with nitrous acid at low temperatures (273-
278 K) to form diazonium salts, a very important class of
compounds used for synthesis of a variety of aromatic compounds
Reaction with nitrous acid

Secondary aliphatic and aromatic amines form nitrosoamine

(yellow oils) with nitrous acid.
Reaction with nitrous acid
 A tertiary aliphatic amines react with HNO2 will produce
ammonium salts which is readly soluble in cold water

R3N + HNO2 → [R3NH] NO2 (aq)

+ -
Reaction with nitrous acid
Electrophilic substitution reactions of aniline
Ortho- and para-positions to the –NH group become centres of
high electron density. Thus –NH group is ortho and para
directing and a powerful activating group.
 Electrophilic substitution reactions of aniline
(a) Bromination: Aniline reacts with bromine water at room
temperature to give a white precipitate of 2,4,6-tribromoaniline.

Due to their very high reactivity in aromatic amines substitution

tends to occur at ortho- and para-positions.
To prepare monosubstituted aniline derivative the activating effect
of –NH2 group be controlled
 Electrophilic substitution reactions of aniline
This can be done by protecting the –NH2 group by acetylation with
acetic anhydride, then carrying out the desired substitution
followed by hydrolysis of the substituted amide to the substituted
amine.

The lone pair of electrons on nitrogen of acetanilide interacts with

oxygen atom due to resonance and hence is less available for
donation to benzene ring by resonance…. thus reducing the activity.
Electrophilic substitution reactions of aniline
(b) Nitration:
In the strongly acidic medium, aniline is protonated to form the
anilinium ion which is meta directing.
That is why besides the ortho and para derivatives, significant
amount of meta derivative is also formed.
 Electrophilic substitution reactions of aniline

However, by protecting the –NH2 group by acetylation reaction with

acetic anhydride, the nitration reaction can be controlled and the
p-nitro derivative can be obtained as the major product.
 Electrophilic substitution reactions of aniline
(c) Sulphonation: Aniline reacts with concentrated sulphuric acid to
form anilinium hydrogensulphate which on heating with sulphuric
acid at 453-473K produces p-aminobenzene sulphonic acid,
commonly known as sulphanilic acid, as the major product.
 Benzidine rearrangement
Treatment of this hydrazine with mineral acids (HCl or H2SO4) (in
aqueous or ethanolic medium)induces a rearrangement reaction to
4,4'-benzidine.

Mechanism
Hinsberg’s test to identify and separate the mixture of amines
Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as
Hinsberg’s reagent, reacts with primary and secondary amines to
form sulphonamides.
Primary, secondary & tertiary amines can be identified &
distinguished by Hinsberg’s test.
In this test, the amines are allowed to react with Hinsberg’s
reagent, benzene sulphonyl chloride (C6 H5 SO2 Cl).
The three types of amines react differently to Hinsberg’s reagent.
Therefore, they can be easily identified using Hinsberg’s reagent.
Hinsberg’s test to identify and separate the mixture of amines

(a) The reaction of benzenesulphonyl chloride with primary amine

yields N-ethylbenzenesulphonyl amide.

The hydrogen attached to nitrogen in sulphonamide is strongly acidic

due to the presence of strong electron withdrawing sulphonyl group.
Hence, it is soluble in alkali.
Hinsberg’s test to identify and separate the mixture of amines

(b) In the reaction with secondary amine, N,N-

diethylbenzenesulphonamide is formed.

Since N, N-diethylbenzene sulphonamide does not contain any

hydrogen atom attached to nitrogen atom, it is not acidic and hence
insoluble in alkali.

(c) Tertiary amines do not react with benzenesulphonyl chloride.

Hinsberg’s test to identify and separate the mixture of amines

10 amine --- soluble salt (B)

20 amine --- insoluble salt (C)
30 amine --- No reaction (A)
Benzoylation Reaction
 DIAZONIUM SALTS
Diazonium salts are a group of organic compounds sharing a
common functional group R-N2+ X- where R can be any organic
residue such as alkyl or aryl and X is an organic or inorganic anion
such as halogen.
The N2+ group is called diazonium group.

Primary aromatic amines form arenediazonium salts which are

stable for a short time in solution at low temperatures (273-278 K).
The stability of arenediazonium ion is explained on the basis of
resonance.
The conversion of primary aromatic amines into diazonium salts is
known as diazotisation.

Due to its instability, the diazonium salt is not generally stored and
is used immediately after its preparation.

The reactions of diazonium salts can be broadly divided into two

categories
(A) reactions involving displacement of nitrogen…….. and
(B) reactions involving retention of diazo group.
A. Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted by
other groups such as Cl–, Br–, I–, CN– and OH– which displace
nitrogen from the aromatic ring.
The nitrogen formed escapes from the reaction mixture as a gas.

1. Replacement by halide or cyanide ion:

The Cl–, Br – and CN– nucleophiles can easily be introduced in the
benzene ring in the presence of Cu(I) ion. This reaction is called
Sandmeyer reaction.
Alternatively, chlorine or bromine can also be introduced in the
benzene ring by treating the diazonium salt solution with
corresponding halogen acid in the presence of copper powder.
This is referred as Gatterman reaction.

2. Replacement by iodide ion: Iodine is not easily introduced into

the benzene ring directly, but, when the diazonium salt solution is
treated with potassium iodide, iodobenzene is formed.
3. Replacement by fluoride ion:
When arenediazonium chloride is treated with fluoroboric acid,
arene diazonium fluoroborate is precipitated which on heating
decomposes to yield aryl fluoride.

4. Replacement by H: (Schimann Reaction or Baltz-Schimann

Reaction)
Certain mild reducing agents like hypophosphorous acid (phosphinic
acid) or ethanol reduce diazonium salts to arenes and themselves
get oxidised to phosphorous acid and ethanal, respectively.
5. Replacement by hydroxyl group:
If the temperature of the diazonium salt solution is allowed to rise
upto 283 K, the salt gets hydrolysed to phenol.

6. Replacement by –NO2 group:

When diazonium fluoroborate is heated with aqueous sodium
nitrite solution in the presence of copper, the diazonium group is
replaced by –NO2 group.
 Replacement by a thiol group
Diazonium salts can be converted to thiols in a two-step
procedure. Treatment of benzenediazonium chloride
with potassium ethylxanthate followed by hydrolysis of the
intermediate xanthate ester gives thiophenol:

Replacement by an aryl group

The aryl group can be coupled to another using arenediazonium
salts. For example, treatment of benzenediazonium chloride with
benzene (an aromatic compound) in the presence of sodium
hydroxide gives diphenyl:
 Meerwein reaction
Benzenediazonium chloride reacts with compounds
containing activated double bonds to produce phenylated
products. The reaction is called the Meerwein arylation:
 B. Reactions involving retention of diazo group
coupling reactions
The azo products obtained have an extended conjugate system
having both the aromatic rings joined through the –N=N– bond.
These compounds are often coloured and are used as dyes. Benzene
diazonium chloride reacts with phenol in which the phenol molecule
at its para position is coupled with the diazonium salt to form p-
hydroxyazobenzene.
This type of reaction is known as coupling reaction.
This is an example of electrophilic substitution reaction.
 Synthetic applications of diazonium chloride
From the above reactions, it is clear that the diazonium salts are
very good intermediates for the introduction of –F, –Cl, –Br, –I, –CN,
–OH,–NO2 groups into the aromatic ring.
Aryl fluorides and iodides cannot be prepared by direct
halogenation.
The cyano group cannot be introduced by nucleophilic
substitution of chlorine in chlorobenzene but cyanobenzene can
be easily obtained from diazonium salt.
Thus, the replacement of diazo group by other groups is helpful
in preparing those substituted aromatic compounds which
cannot be prepared by direct substitution in benzene or
substituted benzene.
Preparation and synthetic applications of
diazomethane???????