5 6145477749600419915

Organic Compounds

Containing Nitrogen
JEE Syllabus
General methods of preparation, properties, reactions and uses. Amines :
Nomenclature, classification, structure, basic character and identification
CHAPTER
6
of primary, secondary and tertiary amines and their basic character.
Diazonium Salts: Importance in synthetic organic chemistry.

NITRO COMPOUNDS THIS CHAPTER

Compound containing NO2 group are termed as nitro compounds. NO2 group INCLUDES
is infact ambident group and is capable of getting attached to the carbon chain  Nitro Compounds
through nitrogen (e.g., RNO2) well as through oxygen (e.g., R–O–N=O alkyl
nitrite).
 Amines
Electronic Structure of NO2 Group :
Nitro alkane have high dipole moment. This suggest that nitro alkanes may be  Cyanides and
represented by following 2 canonical structures : Isocyanides
O O
–
O  Benzene diazonium
+ Chloride (B.D.C.)
R—N R—N R—N
+
O O O
+
(i) (ii) (iii)
The resonance hybrid structure (iii) has both the N–O bond lengths equal, which
is actually found.
General Methods of Preparation

1. By heating an alkyl halide with alcoholic solution of silver nitrite
C2H5Br + AgNO2 

 C2H5NO2 + AgBr
(Some amount of C2H5–ONO is also formed)
2. By direct nitration of hydrocarbons : Nitration of alkanes is difficult in
comparison with that of aromatic hydrocarbons. Alkanes undergo nitration
with fuming HNO3 in the vapour phase at 423-673 K under pressure giving
a mixture of nitroalkanes resulting through cleavage of C—C bonds.
For example,
Fuming
CH 3CH3   CH3 CH2NO 2  CH3 — NO 2
Ethane HNO 3 , 673 K Nitroethane Nitromethane
Lower members can be nitrated by vapour phase nitrations.

This reaction occurs by a free radical mechanism and the ease of substitution
of hydrogens follows the following order.
tertiary > secondary > primary
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(79)
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Organic Compounds Containing Nitrogen JEE/NEET
3. Aromatic nitro compounds are prepared by nitration of aromatic compounds with nitric acid or nitrating
mixture (mixture of conc. HNO3 with conc. H2SO4)
NO2
H2SO4
+HNO3 +H2O
Conc. 333 K
Benzene Nitrobenzene
NO2
Conc.H2SO4
+ Conc. HNO3 m-dinitrobenzene
373K
NO2
NO2
+ Fuming HNO3 + fuming H2SO4 1,3,5–trinitrobenzene

(T.N.B.)
NO2 NO2
Chemical Properties
A. Reactions due to -H-atom
1. Acidity : Due to stablisation of conjugate base formed, primary and secondary nitroalkances having
hydrogen atom on the carbon atom directly attched with –NO2 are weak acidic,
O O
 
CH2—N 
CH2—N
| –H
H O O (Stabilised conjugate base)
Therefore, nitroalkanes having -H show tautomerism.
O O
CH3—N CH2 = N
O OH
Nitro-form Aci-form
(Pseudo acid form) (Nitrolic form) a strong acid
2. Action of halogen :
Cl
CH3NO 2 
2
 CCl3NO 2
NaOH Nitrochloroform ( chloropicrin)
3. Action of nitrous acid :

(a) Primary nitroalkanes react with nitrous acid to form nitrolic acids, which dissolves in sodium hydroxide
giving red solution.
NOH
CH3CH2NO 2 + O = NOH Ch3 – C – No2 + H2O

Nitrolic acid
NOH NONa
CH3 — C — NO2 + NaOH CH3 — C — NO2 + H O

2
Sod. Nitrolate (red)
(80)

(b) Secondary nitroalkanes react with nitrous acid to give colourless crystalline pseudonitroles which
give blue colour in sodium hydroxide solution.
H N=O
R — C — NO2 + HON = O R — C — NO2 + H2O
R R
Pseudonitrol (Blue in NaOH)
(c) Tertiary nitroalkanes do not react with nitrous acid because they do not contain an -hydrogen.
4. Condensation with aldehydes : Primary and secondary nitroparaffins condense with aldehydes in the
presence of alkali forming nitroalcohols.
CH3 CHO  CH3NO 2  CH3CH(OH)CH2NO 2

 Hydroxy nitropropane
5. Reaction with Grignard reagent :

OH OMgI
RCH = N + CH3MgI CH4 + RCH = N
O O
6. Hydrolysis :
HCl
(a) CH3 CH2NO 2  H2O  CH3 COOH  NH2 OH
(b) Secondary nitroalkanes on hydrolysis produce ketones.
HCl
2R 2 CHNO 2  2 R 2 CO  N2O  H2O
boiling
(c) Tertiary nitroalkanes do not undergo hydrolysis.

7. Halogenation : Primary and secondary nitroparaffins are readily halogenated in alkali solution
(X2 + NaOH or NaOX). The halogen atom enters the -position.
Cl Cl
| |
Cl2  NaOH CH C HNO  CH C NO 2
CH3CH2NO 2    3 2 3
Nitroethane |
(1 nitroparaffin) Cl
8. Reduction : Various reduction stages of nitro group are given below

+2H
— NO 2 +2H
 —
–H2O
 — NHOH +2H
NO    — NH 2
–H O 2
Nitroso 1ºAmine
Reduction in strongly acidic medium

Sn / HCl
CH3 CH2NO 2  6 [H]   CH3 CH2NH2  H2O
OH Ethylamine
(i) Reduction of Nitro benzene in different medium

(a) Acidic Medium
+ –
NO2 NH3Cl NH2
–
Sn|HCl OH
or
Aniline
Fe|HCl
Salt
(81)

(b) Neutral Medium
NO2 NHOH
Zn/NH4Cl
+ZnO
H2O
N-Phenyl hydroxyl amine
(c) Reduction in alkaline medium

Depending upon the nature of the reducing agent, nitro benzene forms different products.
Zn/NaOH N=N
CH3OH [8H] +H2O
Azo benzene
NO2 O
[As2O3+NaOH] N=N
2 +H2O
[6H]
OR Azoxy benzene
Na3AsO3+NaOH
H H
Zn/NaOH (aq.) N–N

[10H] +H2O
Hydrazo benzene
(ii) Selective Reduction (Zinin Reduction)

Reduction of m-dinitrobenzene with ammonium sulphide or sodium poly sulphide reduces only one –NO2
group.
NO2 NO2
(NH4)2S
or m-nitroaniline
Na2Sx
NO2 NH2
9. Electrophilic substituion
NO2 NO2
AlCl3
+ Cl2
Nitrobenzene
Cl
m-Chloro nitrobenzene
NO2 NO2
conc. H2SO4
+ HNO3(conc.)
373 K
NO2
Nitrobenzene
m-Dinitrobenzene
(82)

NO2 NO2
373 K
+ H2SO4(fuming)
SO3H
Nitrobenzene
m-Nitrobenzene sulphonic acid
10. Nucleophilic Aromatic substitution


1 amine act as nucleophile and attacks another molecule of alkyl halide.
Cl Cl Nu Cl Nu Nu
..
+ Nu + Cl
+
N N N NO2
+ O
–
O O O O O
Stablisation of
anion by resonance
CLASIFICATION OF AMINES
H CH3 CH3
—
—
CH3 — N — H CH3 — N — H CH3 — N — CH3

Methylamine Dimethylamine Trimethylamine
(Primary) (Secondary) (Tertiary amine)
General Methods of Preparation

1. By the reaction of an alkyl halide with ammonia (Ammonolysis of alkylhalide) :
OH
C2H5I + HNH2 
 CH3CH2–NH3+I–  CH 3  CH 2  NH 2
1º
The reaction does not give only 1º amine as the product, because now ammine can act as nucleophile and
attacks at other molecule of alkyl halide
–
OH
 (CH3–CH2)2NH2+I– 
C2H5I + H2NC2H5   (CH3 CH2 )2  NH2
2º
–
OH
C 2H5I  HN(C 2H5 )2   (CH3  CH2 )3 N
 (CH3CH2)3NH+I– 
Ethyl iodide Diethylamine 3º

C 2H5I  N(C 2H5 )3  (C 2H5 ) 4 NI¯
Tetraethyl ammonium iodide
( quaternary salt )
Note : Arylamines cannot be prepared by this method. Aryl amine i.e., aniline is however prepared by
reacting chlorobenzene with NH3
Cl NH2
475 K
2 + 2NH3 + Cu2O 2 + Cu2Cl2 + H2O
60 atm
Chlorobenzene Aniline
(83)

2. By the reduction of nitro compounds :
Raney Ni
CH3 CH2NO 2  3H2  or
 CH3 CH2NH2  2H2O

Nitroethane Ethylamine
Pd - C
Raney Ni
C 6H5NO 2  3H2    C 6H5NH2  2H2O
or
Nitrobenzene Aniline
Pd - C
with above reactions only 1º –amine can be formed.

3. By the reduction of alkyl nitriles (or cyanides) and isonitriles (isocyanides) :
2 Raney Ni / H
CH3 C  N    
  CH3CH2NH2
Acetonitrile LiAlH4 or Na / C 2H5OH Ethylamine
Raney Ni / H2
CH3NC    CH3NHCH3
Or LiAlH4 2º amine
4. By the reduction of amides :

LiAlH /ether
CH3 CONH2  4  CH3 CH2NH2
Acetamide Ethylamine
5. By the reduction of oximes :

Na/C H OH
CH3 CH  NOH  4[H]  2 
5
 CH3CH2NH2  H2O
Acetaldoxi me Ethyl amine
6. By rearrangement reactions
(a) By Hofmann bromamide reaction : This is one of the most convenient method for the preparation of
primary amines. It involves action of halogen (bromine or chlorine) and alkali (NaOH or KOH) on 1° amides
to form amines with one carbon atom less. In this reaction molecular rearrangement takes place, in
which alkyl group migrated over to N–atom.
CH3 CONH2  Br2  4KOH  CH3NH2  2KBr  K 2CO 3  2H2 O
C 6H5CONH 2  Br2  4KOH  C 6H5NH 2  K 2 CO3  2KBr  2H2 O

Benzamide Aniline
Conc .
(b) Schmidt reaction : RCOOH + HN3   R–NH2 + CO2 + N2 + H2O
H2SO 4
(c) Curtius reaction : 

RCOCI + HN3  R–NH2 + HCI + CO2 + N2
7. By Gabriel phthalimide reaction : This is a very convenient method for the preparation of pure aliphatic
primary amines. Phthalimide is first of all treated with KOH to form potassium phthalimide which on heating
with alkyl halide gives N-alkyl phthalimide. The latter is hydrolysed or hydrozinolysed to give primary amines.
CO CO COOH
RX H2O
NK NR + RNH2
CO CO COOH
Pot. phthalimide Pot. phthalimide
O
H2N – NH2 NH
+ R–NH2
NH
O
Aromatic amines cannot be prepared from this reaction.
(84)

8. Secondary amines can be prepared by the hydrolysis of p-nitroso-dialkyl aniline with boiling alkali:
NH2 N(CH3)2 N(CH3)2 OH
2CH3I HONO NaOH

+ (CH3)2NH
Aniline Dimethylaniline
NO NO
p-Nitroso p-Nitroso Dimethylamine
dimethylaniline phenol
9. Tertiary amines are prepared by the decomposition of tetra-alkyl ammonium hydroxide :
(C 2H5 ) 4 NI¯  AgOH  (C 2H5 )4 N OH¯  AgI

Tatraethyl ammonium Tatraethyl ammonium
iodide hydroxide
heat
(C 2H5 ) 4 N OH¯  (C2H5 )3 N  C 2H4  H2 O
Triethyl amine
However, tetramethyl ammonium hydroxide also decomposes to give tertiary amine but in a different way.
heat
(CH3 ) 4 N OH¯   (CH3 )3 N  CH3 OH
Chemical Properties
Nitrogen atom of all the three types of amines has a lone pair of electrons which is responsible for most of the
reactions of amines.
A. Reactions given by primary, secondary and tertiary amines :
1. Basic character : The basic character of amines is due to the presence of unshared electron pair
on nitrogen atom which accepts proton; the readiness with which the lone pair of electrons is
available for co-ordination with a proton determine the relative basic strength of amines.
H N H R N H R N R
H H H
Ammonia Primary amine Secondary amine
Like ammonia, amines dissolve in water to form alkylammonium ion and hydroxide ion.
+
RNH2 + H2O RNH3 + OH–
Aliphatic amines are stronger bases than ammonia and aryl amines. [RNH2 > NH3 > C6H5NH2]
:NH NH2 NH2 :NH2

NH2
I II IV V
III
We have observed that aniline is a resonance hybrid of five structures (I to V) while the protonated
aniline (anilinium ion) is a resonance hybrid of only two structures.
(85)

2. Arylalkylamines
Arylalkylamines are stronger bases than arylamines (e.g., aniline), but slightly weaker than the
alkylamines.
Alkylamines  Arylalkylamines  Arylamines
(e.g., CH3NH2 ) (e.g., C6H5CH2NH2 ) (e.g., C6H5NH2 )
Effect of substituents on the nitrogen atom of the group :

(a) The replacement of hydrogen atom of an amino group by an electron-releasing substituent
(e.g., methyl group) increases the basic character.
NH2 H — N — CH3 H3C — N — H3C
< <
Aniline N-Methylaniline N, N-Dimethylaniline
(b) On the other hand, replacement of hydrogen atom(s) of the amino group by electron-withdrawing
phenyl group(s) decreases the basic character.
NH2 H—N— —H—N—
> >
Aniline Diphenylamine Triphenylamine
(i) Reaction of water :
NH3  H2O  NH4OH NH4  OH¯

Ammonia Ammonium
hydroxide
CH3NH2  H2O  CH3NH3OH

Methyl amine Methyl amm.
CH3NH3  OH¯
(Pri.) hydroxide
(CH3 )2NH  H2O  (CH3 )2NH2 OH (CH3 )2 NH2  OH¯

Dimethyl amine Dimethyl amm.
(Sec.) hydroxide
(ii) Reaction with inorganic acids :


C 2H5NH2  HCl  C 2H5NH3 Cl –
Ethyl amine Ethylamine hydrochlor ide
2(C2H5 )2 NH  H2SO 4  [(C2H5 )2 NH2 ] 2.SO 4

Diethyl amine Diethylamine hydrogen sulphate
3. Alkylation :

1. CH I 1. CH I CH I
CH3NH2  
3
–
 (CH3 )2 NH  
3
–
3
 (CH3 )3 N   (CH3 )4 NI–
Methyl amine 2. OH Dimethyl amine 2. OH Trimethyl amine Tetramethylammine.
(primary amine) (sec. amine) (ter. amine) iodide
+ –
NH2 NHCH3 N(CH3)2 N (CH3)3I
1. CH3I 1. CH3I CH3I
– –
2. OH 2. OH
Anline N-Methylaniline N, N-Dimethylaniline Trimethylanilinium iodide
Hence, this reaction may be used for distinguishing the three types of amines.
(86)

4. Dealkylation :
heat
(CH3 )3 N.HCl  (CH3 )2 NH  CH3Cl
Trimethyl amine Dimethyl amine
hydrochlor ide
heat
(CH3 )2 NH.HCl  CH3NH2  CH3Cl
Dimethyl amine Methyl amine
hydrochlor ide
heat
CH3NH2 .HCl  CH3Cl  NH3
Methyl amine Methylchlo ride
hydrochlor ide
5. Reaction with nitrous acid : Different types of amines form different products with nitrous acid
(NaNO2 + HCl).
(i) An ice cold solution of a primary aromatic amine in hydrochloric acid reacts with an ice-cold
aqueous solution of sodium nitrite, forming water-soluble compound known as diazonium
salt.
NaNO 2  HCl  HNO 2  NaCl

C6H5 NH2 .HCl  HONO  C6H5 N  NC l  H2O
0 – 5C
Aniline hydrochlor ide Benzenedia zonium
chloride
Aliphatic primary amines react with cold nitrous acid to give alcohols or sometimes alkenes
with the quantitative evolution of nitrogen gas (test for aliphatic primary amines).
HONO / HCl H2O

CH3CH2NH2   [CH3CH2N  NCl¯]  CH3CH2OH  N2
273  278 K Ethanediaz onium chloride
(ii) Secondary amines (aliphatic as well as aromatic) react with nitrous acid to form N-nitrosoamines.
(CH3 )2 NH  HONO  (CH3 )2 N — N  O  H2O

Dimethylam ine NNitrosodimethylamine
Nitrosoamines are water-insoluble yellow oils and when warmed with a crystal of phenol and a
few drops of conc. H2SO4 produce a green solution which turns blue on adding alkali. This
reaciton is known as Libermann’s nitroso reaction and may be used as a test for secondary
amines.
(iii) Aliphatic tertiary amines dissolves in cold nitrous acid to form unstable nitrites which decompose
on warming to give nitrosoamine and alcohol.

heat
(CH3 )3 N  HNO2  (CH3 )3 NH N O2   (CH3 )3 N.NO  CH3OH
Trimethyl amine Trimethylammoniumnitrite NNitrosodimethylamine
N(CH3)2 N(CH3)2
+ HONO + H2O + NaCl

N, N-Dimethylaniline
NO
p-Nitroso-N, N-Dimethylaniline
(87)

B. Reactions given only by primary and secondary amines :

1. Acylation : (Reaction with acetyl chloride) : Primary and secondary amines react with acid chlorides
and acid anhydrides to form acyl derivatives or substituted amides.
CH3NH2  ClCOCH3  CH3NHCOCH3  HCl

Acetyl methyl amine
(NMethylacet amide)
(CH3 )2 NH  ClCOCH3  (CH3 )2 NCOCH3  HCl

Acetyl dimethyl amine
(N, N Dimethyl acetamide)
Like alkyl amines, aryl amines react with acid chlorides and acid anhydrides to form aryl substituted
amides commonly called anilides. The reaction is best carried out in the presence of a base like pyridine.
Br
C2H5NH2 + CH3MgBr CH4 + Mg
NHC2H5
Br
C2H6 + Mg
(C2H5)2NH + C2H5MgBr
N(C2H5)2
C. Reactions given only by primary amines :

1. Carbylamine reaction :
C2H5NH2  CHCl3  3KOH  C2H5NC  3KCl  3H2O

Ethylamine Ethyl isocyanide
C6H5NH2  CHCl3  3KOH  C6H5NC  3KCl  3H2O

Aniline Phenyl isocyanide
2. Hofmann’s mustard oil reaction :
NHCH3
CH3NH2 + S = C = S S=C
SH
N–Methyl dithiocarbamic acid
HgCl2
CH3N = C = S + HgS + 2HCl

Methyl isothiocyanate Black ppt.
(Mustard oil like smell)
HgCl2
C6H5NH2  S  C  S   C6H5N  C  S  H2S  2HCl
Aniline Phenyl isothiocyanate
3. Reaction with aldehydes and ketones : Primary amines react with carbonyl group to form anils or
schiff’s bases
C 2H5NH2  CH3CHO  C 2H5N  CH.CH3  H2O

Ethylidene thylamine
(88)

D. Reactions of the benzene nucleus :

1. Electrophilic substitution reaction :
(i) Halogenation :
NH2 NH2
Br Br
+ Br2 (water)
Aniline
Br
2, 4, 6-Tribromoaniline
(ii) Nitration : Nitration reactions are never performed directly as they get connected to p-benzoquinone
hence they are first acetylated and then nitrated.
NH2 NHCOCH3 NH2

+
(i) (CH3CO)2O H2O/H
(ii) HNO3/H2SO4
+ CH3COOH
heat
Aniline
NO2 NO2
p-Nitroacetanilide p-Nitroaniline
(iii) Sulphonation :
NH2 NHSO3H NH2
453 K 453 K
+H2SO4 (fuming)
–H2O 3 hours
Aniline Salt
SO3H
Sulphanilic acid
2. Coupling reaction :
+
N  NCl + H2N 313 K
(
HCl)
  N = N.NH
Weak acidic medium
Benzenediazonium Aniline Diazoaminobenzene
chloride (yellow dye)
N=N NH2
p-Aminoazobenzene
(brilliant orange red dye)
3. Oxidation : Arylamines, unlike alkyl amines, are very susceptible to oxidation. This is because of the
presence of high electron density on the ring of arylamines due to which electron removal (oxidation)
becomes very easy. Thus arylamines (e.g., aniline) darken in colour even on standing in air at room
temperature. More intense colour is obtained by stronger oxidising agents e.g.,
Oxidising agent Colour
Bleaching powder Violet
K2Cr2O7 + conc. H2SO4 Blue
K2Cr2O7 + CuSO4 + dil. H2SO4 Black
Na2Cr2O7
NH2 O O
H2SO4
Aniline p-Benzoquinone (Oxidised product)
(89)

CYANIDES AND ISOCYANIDES

Cyanides and isocyanides, the two series of isomeric compounds, are derivatives of hydrogen cyanide (hydrocyanic
acid or prussic acid) which exists in the following two tautomeric forms.
H—CN H—N C
General methods of preparation of Nitriles and Isonitriles :
1. From alkyl halides :
CH3 Cl  KCN  CH3 CN  KCl

Chloromethane Ethanenitrile
2. From arenediazonium salts :
+
N  NCl CN
CuCN
+ KCN or Cu powder + N2 + KCl
Benzene diazonium chloride Benzonitrile
3. From primary amines : Alkyl and aryl carbylamines are prepared by carbylamine reaction
(heating of primary amine with chloroform and alcoholic potash).

CH3 CH2NH2  CHCl3  3KOH(alc.)  CH3 CH2N  C  3KCl  3H2O
Ethyl amin e Ethyl isonitrile
C 6H5NH2  CHCl3  3KOH(alc.)  C 6H5NC  3KCl  3H2O

Aniline Phenyl isonitrile
Chemical Properties
The two important chemical reactions of nitriles and isonitriles are hydrolysis and reduction.
1. Hydrolysis :
O
+ – + –
H or OH H or OH
R—CN R — C — NH2 RCOOH + NH3
(+H2O) +H2O
Isonitriles, on the other hand, are hydrolysed by dilute acids but not by alkalies to form a primary
amine and formic acid.
O
+ +
H H
R — N = C + H2O R — NH — C — H R — NH2 + HCOOH
(+ H2O) (+ H2O)
Alkyl isonitrile
1° Amine Methanoic acid
Note : Complete hydrolysis is done using dilute acids while partial hydrolysis is done using conc. acids.
(90)

2. Reduction : Nitriles are fully reduced to primary amines by sodium and alcohol (Mendius reaction), lithium
aluminium hydride or hydrogen in presence of Ni or Pt (catalytic reduction).
Na / C2H5OH
R — C  N + 4[H] or   RCH NH
LiAlH 2 2 4
Na|C2H5OH
R — NC    R — NH — CH
or LiAlH 3
4
R — C  N + 2H2 Pt or Ni
  RCH2NH2
Stephen’s reduction : Partial reduction of nitrile with stannous chloride in presence of hydrochloric acid to
form imine hydrochloride (Stephens reduction) is also possible. The imine hydrochloride may be decomposed
easily with boiling water forming aldehyde as the final product.
SnCl2 + 2HCl  SnCl4 + 2H
ether
CH3 — C  N + 2[H] + HCl 290 K
CH3CH = NH.HCl
Acetaldimine hydrochloride
boiling
water
CH3CHO + NH4Cl
Ethanal
3. Reaction with Grignard reagents :
R R
H OH +
ether H
R — C  N + RMgX R—C N MgX R—CO
H2
o
Reaction may not stop at ketonic stage. May be ketone further is attacked by Grignard reagent to give 3
alcohol.
4. Addition reaction :
 
CH3  N  C :  Cl2  CH3  N  CCI2
Methyliminocarbonyl chloride
 
CH3  N  C :  S  CH3  N  C  S
Methyl isonitrile Methyl isothiocyanate
5. Rearrangement :

Δ
R N  C  R C  N
Isonitrile Nitrile
(91)

DIAZONIUM SALT
NH2
1. Preparation of benzene diazonium chloride 0–5ºC N2Cl

+ NaNO2 + HCl + NaCl + H2O
2. Properties of Benzene Diazonium Chloride (B.D.C.)

A. Substitution Reaction :
Benzene diazonium chloride is used for prepration of several organic compounds.
C2H5OH
+ N2 + HCl + CH3CHO
OR Na2SnO2
H3PO3 + H2O
+
+ N2 + HCl + H3PO3
Cu
Cl
HCl
+ N2 + HCl
Cu2Br2 OR Cu
N2Cl Br
HBr
+ N2 + HCl
Cu2Br2 OR Cu
OR CN
+
NNCl NaCN
+ N2 + NaCl
+ CuCN
OH
H2O
H2SO4
I
KI
+ N2 + KCl
F
HBF4
+ N2 + BF3 + HCl
NHNH2
(i) Na2SO3H3O + 373K
+ NaCl + H2O
(ii) NaOH
C6H6
biphenyl
NaOH
(92)

B. Coupling Reaction :
Condensation of diazonium salt with electron rich aromatic compounds like phenols and amines to form
azodyes.
OH
— N=N OH
OH
p-Hydroxy azobenzene
(orange dye)
NH2
N2Cl +
N=N NH2
H
p-Amino azobenzene
OH
N=N
OH
Phenylazo--naphthol
(Red dye)

(93)

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Organic Compounds

NITRO COMPOUNDS THIS CHAPTER

General Methods of Preparation

Lower members can be nitrated by vapour phase nitrations.

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+ Fuming HNO3 + fuming H2SO4 1,3,5–trinitrobenzene

Therefore, nitroalkanes having -H show tautomerism.

3. Action of nitrous acid :

CH3CH2NO 2 + O = NOH Ch3 – C – No2 + H2O

CH3 — C — NO2 + NaOH CH3 — C — NO2 + H O

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R — C — NO2 + HON = O R — C — NO2 + H2O

CH3 CHO  CH3NO 2  CH3CH(OH)CH2NO 2

5. Reaction with Grignard reagent :

(c) Tertiary nitroalkanes do not undergo hydrolysis.

8. Reduction : Various reduction stages of nitro group are given below

Reduction in strongly acidic medium

(i) Reduction of Nitro benzene in different medium

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(b) Neutral Medium

N-Phenyl hydroxyl amine

(c) Reduction in alkaline medium

Zn/NaOH (aq.) N–N

(ii) Selective Reduction (Zinin Reduction)

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10. Nucleophilic Aromatic substitution

CH3 — N — H CH3 — N — H CH3 — N — CH3

General Methods of Preparation

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2. By the reduction of nitro compounds :

with above reactions only 1º –amine can be formed.

4. By the reduction of amides :

5. By the reduction of oximes :

CH3 CONH2  Br2  4KOH  CH3NH2  2KBr  K 2CO 3  2H2 O

C 6H5CONH 2  Br2  4KOH  C 6H5NH 2  K 2 CO3  2KBr  2H2 O

(c) Curtius reaction : 

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NH2 N(CH3)2 N(CH3)2 OH

2CH3I HONO NaOH

9. Tertiary amines are prepared by the decomposition of tetra-alkyl ammonium hydroxide :

(C 2H5 ) 4 NI¯  AgOH  (C 2H5 )4 N OH¯  AgI

:NH NH2 NH2 :NH2

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Effect of substituents on the nitrogen atom of the group :

NH2 H — N — CH3 H3C — N — H3C

Aniline N-Methylaniline N, N-Dimethylaniline

NH2 H—N— —H—N—

Aniline Diphenylamine Triphenylamine

(i) Reaction of water :

NH3  H2O  NH4OH NH4  OH¯

CH3NH2  H2O  CH3NH3OH

(CH3 )2NH  H2O  (CH3 )2NH2 OH (CH3 )2 NH2  OH¯

(ii) Reaction with inorganic acids :

2(C2H5 )2 NH  H2SO 4  [(C2H5 )2 NH2 ] 2.SO 4

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NaNO 2  HCl  HNO 2  NaCl

HONO / HCl H2O

(CH3 )2 NH  HONO  (CH3 )2 N — N  O  H2O