ORGANIC CHEMISTRY –II

5. NITROGEN CONTAINING COMPOUNDS

• NO2 and – ONO are isomeric forms
R – NO2 R – ONO
Nitro alkane Alkyl nitrite
CH3 – NO2 CH3 – ONO
Nitro methane Methyl nitrite
CH3 – CH2 – CH2 – NO2 CH3–CH2–CH2–ONO
1 – Nitro propane Propyl – 1- nitrite
CH3 − CH − CH3 CH3 − CH − CH3
| |
NO ONO
2
2- Nitro propane Propyl – 2-nitrite
• Nitroalkane and alkyl nitrites are functional isomers.
• Naming of Nitro arenes : NO2
NO2
NO2 NO2
NO2

NO2 NO2
m-dinitro benzene P – dinitrobenzene
Nitrobenzene O-dinitro benzene

NO2 CH3 OH
NO2 NO2 NO2
NO2

NO2 NO2
NO2 NO2
2,4, 6 – trinitrotoluene (TNT) 2,4, 6 – trinitrophenol (TNP)
1,3,5-trinitro benzene(TNB)

NITRO BENZENE :
Formula : C6H5 – NO2
O
N
O
Structure :

• Common name : Oil of mirbane

• Preparation : Benzene is heated with the mixture of conc. HNO3 and conc. H4SO4 at about 60°C
to give nitro benzene.
• In the nitration mixture con.HNO3 acts as base
• Con.HNO3 will produce NO2+ on reaction with con. H2SO4.
• If temperature is more than 60°C, dinitro or trinitro benzene may be formed.
NO2

1
 Organic Chemistry – II
con.H2SO 4
+ HO − NO 2 ⎯⎯ ⎯ ⎯⎯→ + H2O
< 60°C

Physical properties :
• It is pale yellow oily liquid
• It has smell of bitter almonds
• It is insoluble in H2O and soluble in organic solvent
• It is high boiling organic solvent
• It is steam volatile
CHEMICAL PROPERTIES :
1) Reduction of nitro group of Nitro benzene :
NH2 + 2H2O

Aniline

6 Zn+HCl (or) H2
(or) Sn + HCl
NHO NO2
Zn+NH4 LiAlH N N
4 8
Phenylhydroxylamin Azo benzene
10 Zn+KO

N N
+ 4H2O
H H
Hydrazobenzene
• Nitro group on complete reduction converts to – NH2 group.
• In the reduction process all others are intermediates.
• NO2 group is highly polar and C – NO2 bond is very strong and it cannot be replaced by groups
like
– OH, – NH2 etc.
2) Reactions of benzene ring of nitro benzene :
• –NO2 group is meta director and ring deactivator. NO2 group withdraws electron density from
benzene and deactivates the benzene of nitrobenzene. It is less reactive than pure benzene towards
electrophilic substitutions
• It undergoes halogenation and nitration only

NO NO NO

Cl2 / Fe Br2 / Fe
HCl + + HBr
C Br
M – chloronitrobenzene M – bromonitrobenzene
Con. HNO3 + Con.
H2SO4
NO

2
NO
 Organic Chemistry – II

Uses of nitrobenzene :
• In the preparation of floor polishes
• As solvent
• As oxidising agent
• In perfumes under the name of oil of mirbane
• In dyes and explosives
AMINES :
• Amines are organic derivatives of NH3.
• In nitrogen fixation, atmospheric nitrogen is reduced to NH3.
• Based on the nature of hydrocarbon part, attached to nitrogen, amines are of two types.
a) Alkyl amines : R – NH2 or R – N <
Nitrogen is attached to sp3 carbon
Ex. CH3 - NH2 , C2H5 – NH2, CH3 – NH – CH3. CH3 − N − C 2H5 ,
|
CH3

b) Aryl amines or Arenamines : Benzene ring is attached to nitrogen through sp2 carbon.
Ex. Ar – N <, C6H5 – NH2 , C6H5– NH – C6H5, C 6H5 − N − C 6H5
|
CH3

• Based on the degree of substitution at nitrogen, amines are of three types.

a) Primary amines: one carbon is attached to nitrogen of amino group.
Ex. R – NH2,CH3 – NH2, C2H5 – NH2, C6H5–NH2
b) Secondary amines : Two carbons are attached to nitrogen of amino group.
Ex. R – NH – R1 , CH3 – NH – CH3,
CH3 – NH – C2H5, CH3 – NH – C6H5
C) Tetriary amines : Three carbons are attached to nitrogen of amino group.
Ex. R − N − R 1 , CH 3 − N − CH 3 , CH3 − N − C 2H5
| | |
R11 CH3 C6H5
NAMING OF AMINES :
COMMON
STRUCTURE IUPAC NAME IUPAC NAME
NAME
CH3 – NH2 Amino methane Methanamine Methyl amine
C2H5– NH2 Amino ethane Ethanamine Ethyl amine
CH3 – CH2 – CH2 – NH2 1-Amino Propane 1 – Propanamine n – propylamine
CH3 − CH − CH3
| 2-Amino Propane 2-Propanamine Isopropyl amine
NH2
CH3 − CH− CH − CH3
| | 3-Amino Butan - 2- ol -- --
OH NH2

H2N – CH2 – CH2 – NH2 1, 2-diamino ethane 1,2 –ethane diamine Ethylenediamine
H2N − CH2 − CH − CH3
| 1, 2 – diamino propane 1,2 – propane diamine --
NH2
CH3 – NH – CH3 N-methyl Amino N- methyl
Dimethyl amine
methane methanamine

3
 Organic Chemistry – II

STRUCTURE IUPAC NAME IUPAC NAME COMMON NAME

CH3 N – methyl
CH3 – NH – CH N- methyl-2- Amino N –methyl 2-
CH3
N – isopropyl
propane propanamine
amine
CH3 − N − CH3 N, N –dimethyl Amino N, N – dimethyl
| Trimethylamine
CH3 methane methanamine
CH3 − N − CH 2 − CH 2 − CH3 N – ethyl – N – methyl N-ethyl , N – methyl Ethyl, Methyl ,
|
C2H5 1–Amino propane 1-propanamine n –propyl amine
C6H5 – NH2 Phenyl amine or
Amino benzene Benzenamine
Aniline
C6H5 – CH2 – CH2 – NH2 2-Phenyl – Amino
2 – phenyl ethanamine --
ethane
NH2
CH3 2 – methyl amino
-- O – toludiene
benzene

CHO

4 – Amino Benzene P – amino benzal

--
carbaldehyde dehyde
NH2

NH2
C2H5
4 – Bromo – 2-ethyl P – bromo –O –
--
Amino benzene ethyl aniline
Br

ISOMERISM IN AMINES :
• Primary, secondary and tertiary amines having same molecular formula are functional isomers.
• Primary amines also exhibit chain and position isomerism.
• Secondary and tertiary amines also exhibit metamerism.
Aniline ( Phenyl amine)
• Aniline was first prepared by unverborden.
• Destructive distillation of indigo gives aniline (Anil = Indigo)
Preparation of aniline :
• In laboratory aniline is prepared by the catalytic hydrogenation or chemical reduction of
nitrobenzene.
• On large scale aniline is prepared by the reduction of nitrobenzene with Fe / H2O and small
amounts of HCl
• Phenol on heating with NH3 in presence of ZnCl2 gives aniline at 300°C.
• Chloro benzene on heating with NH3 in presence of Cu2O gives aniline at 200°C.

4
 Organic Chemistry – II

C6H5 – NO2
C6H5 – NO2 C6H5 – NO2
Fe + H2O H2 |Ni
HCl Sn | HCl

C6H5 – NH2
Cu2O
ZnCl2 200°C
300°C
C6H5 – Cl + NH3
C6H5OH + NH3

Physical properties :
• Freshly prepared aniline is colourless oily liquid with unpleasant smell.
• It is toxic in nature.
• It turns to brown when exposed to air due to oxidation.
• It is denser than H2O, slightly soluble in H2O but readily soluble in organic solvents.
• It is steam volatile and high boiling organic liquid.
• It forms weak hydrogen bonds.
• Extent of hydrogen bonding : NH3> R – NH2 > R2NH > R3N

CHEMICAL PROPERTIES :
I) Reactions of – NH2 group :
1 Basic nature of amines :
• Alkyl groups are electron releasing in nature by means of +ve inductive effect alkyl groups
attached to nitrogen increases electron density on nitrogen and increases basic nature of amines.
• Thus electron releasing groups like alkyl groups increases the basic nature due to +ve inductive
effect and electron with drawing groups like – Cl, –F, – NO2, – C6H5 decreases the basic nature
due to – ve inductive effect.
Ex. R – NH2 > Ar – NH2
H – NH2 > Cl – NH2
R – NH2 > H – NH2
R – NH2 > H – NH2 > Ar – NH2
• Due to electron with drawing nature of C6H5 – group aniline is weak base and almost neutral to
litmus paper. But aniline form salts with acids. These anilinium salts are acidic and then can be
decomposed by basic substances like Na2CO3. NaHCO3 and produces effervescence.
• If more hydrogens are present on nitrogen, it forms more number of hydrogen bonds and the basic
nature is more.
• Due to stearic crowding of bulky alkyl groups, tertiary amine is less basic than those of secondary
and primary amines.
• In view of all the three effects, the observed basic nature is
R2 – NH>R–NH2>R3N>NH3>C6H5 – NH2 (R = CH3)
2. Alkylation : Aniline reacts with excess CH3 – Cl to give secondary amine, tertiary amine and
quaternary salt.

5
 Organic Chemistry – II
To continue the alkylation , HCl produced is neutralised by basic casrsenate salt.
3. Acylation : Anilie on acylation with acetyl group, acetanilide is formed.
Acetylating agents are CH3COCl, (CH3CO)2O, CH3COOC2H5
Reactivity of acetylating agents : CH3COCl > (CH3CO)2O >> CH3COOC2H5
4. Benzoylation : (Schoten – Baumen Reaction ) :
Aniline reacts with benzoyl chloride to form benzanilide or N- phenyl benzamide.
5. Sulphonylation : Aniline reacts with benzene sulphonyl chloride to give N – phenyl benzene
sulphonamide.
6. Condensation with benzaldehyde : Aniline condenses with benzaldehyde in presence of conc.
H2SO4 to give benzilidene aniline or Schiff’s base.
7. Carbyl amine reaction : Aliphatic or aromatic primary amines react with chloroform and alcoholic
potash to give isocyanide having foul smell.
8. Diazotisation : HNO2 is formed from NaNO2 and HCl. Aniline reacts with HNO2 / NaNO2 + HCl
at 0°C to form benzene diazonium chloride. These diazonium salts are useful in the synthesis of
many important organic compounds.
Only aromatic primary amines give these diazonium salts.

C6H5–N(CH3)3+

CH3Cl

C6H5–N(CH3)2
–HCl
C6H5NH3+Cl– CH3Cl

C6H5–NH–CH3
HCl C6H5–
–HCl Pyridine
CH3Cl CH3COCl

HNO2+HCl
C6H5– C6H5 – C6H5COCl
C6H5–NH–
0°– 5°C
–HCl
CHCl3+KOH
C6H5SO2Cl
C6H5CHO
–HCl
C6H5–NH–
C6H5–NC + 3KCl +
C6H5–N=CH–C6H5 +

II. Reactions of benzene ring of aniline :

••
• N H2 - group attached to benzene ring will activate the benzene ring towards electrophilic
substitutions by it’s electron releasing nature.
••
• N H2 - group is O, P –director and substitution occurs at ortho and parapositions.
1) Bromination : Aniline reacts with Br2 instantaneously to give a white precipitate of 2, 4, 6 –
tribromo aniline.
2) Sulphonation : Aniline on heating with fuming sulphuric acid gives sulphanilic acid. The
intermediate is anilinium hydrogen sulphate.

6
 Organic Chemistry – II
3) Nitration : Aniline is first acylated to protect – NH2 group form getting oxidised. Then
acetanilide is nitrated and subsequently hydrolysed to give 90% yield of para nitro aniline.

NH2
Br Br + 3HBr

Br

0 – 5°C 3Br2
••
N H2

CH3COCl H2SO4
NH3+HSO4–
H3C-COHN 180–200°C

conc.HNO3 NH2
Δ
H3C-COHN Δ

+
SO3 N H3
NH2 NO2
H2O

SO3–
NO2
(90%)

• Uses of Aniline :
• In the preparation of acetanilide, Sulphanilic acid, sulpha drugs, azodyes etc.
• In the preparation of Schiff’s bases which are used as antioxidants in rubber industry.
In the preparation of diazonium chloride which is used as starting material in the synthesis of many
important compounds

7
 Organic Chemistry – II
IDENTIFICATION OF 1o , 2o and 3o AMINES
• HINSBERG’S TEST : (Action of benzene sulphonyl chloride)
10 amine: N-alkylbenzene sulphonamide is formed, which is soluble in alkali
RNH 2 + ClSO2 . C6 H 5 → RNH .SO2C6 H 5 + HCl
20 amine: N,N-dialkyl benzene sulphonamide is formed,which is insoluble in alkali
R2 NH + Cl.SO2 .C6 H 5 → R2 N .SO2 .C6 H 5
30 amine: No characteristic change
• HOFMANN MUSTARD OIL REACTION (REACTION WITH CS 2 FOLLOWED BY HgCl2 )
10 AMINE:Black precipitate is formed due to the formation of HgS
RNH 2 + CS2 → RNH
C =S ⎯⎯⎯ → HgS + RNCS + 2HCl
HgCl2

HS

20 AMINE:No precipitate is observed

no precipitate
0
3 AMINE:No reaction

• OXIDATION BY KMnO4
10 AMINE:Aldehydes and ketones are formed
(O) H+ / H 2O
R.CH 2 .NH 2 ⎯⎯→ R.CHNH ⎯⎯⎯⎯ → R − CHO + NH 3
+
R2CHNH 2 ⎯⎯→
(O )
R2C = NH ⎯⎯⎯⎯
H / H 2O
→ R2CO + NH 3
20 AMINE:Tetraalkyl hydrazine is formed R2 NH ⎯⎯→
(O )
R2 N − NR2
0
3 amine: No reaction
• ACTION OF CARO’S ACID ( H 2 SO5 )
10 amine:Aldoxime and hydroxamic acid are produced
RCH 2 NH 2 ⎯⎯→
(O )
RCH=NOH aldoxime

20 AMINE:Dialkyl hydroxyl amine is produced

R2 NH ⎯⎯→
(O )
R2 NOH
0
3 amine:Tertiary amine oxide is formed
R3 N ⎯⎯
O
→ [ R3 N → O ]

• CARBYLAMINE TEST : (Amine + CHCl3 + alc.KOH)

10 AMINE:Foul smell is observed due to the formation of RNC (isocyanide)

8
 Organic Chemistry – II
20 AMINE:No reaction
30 AMINE:No reaction
• REACTION WITH NITROUS ACID ) (NaNO2 + HCl
10 AMINE:Alcohols are formed with the liberation N 2 of gas . With CH 3 NH 2 , it produces
methyl nitrite with the liberation of N 2 gas
20 AMINE:Yellow coloured oily layered nitrosoamines are produced. This test is called
Liberman’s reaction
30 AMINE:Nitrite salts are produced, which are soluble in water

DIAZONIUM SALTS :
+
General formula of diazonium salts is R N 2 X − . Here R is alkyl or aryl group and X − may be Cl −
, Br − , HSO4− , BF4− etc.
Primary aliphatic amines form highly unstable alkyl diazonium salts. Primary aromatic amines
form arene diazonium salts which are stable for a short time in solution at low temperature (273-
278K). The stability of arene diazonium ion is because of resonance.
+
N 2+ group ( N ≡ N ) is called diazonium group.

PREPARATION OF DIAZONIUM SALTS :

0 − 50 C
C6 H 5 NH 2 + NaNO 2 + 2HCl ⎯⎯⎯ →
C6 H 5 N 2 Cl + NaCl + 2H 2 O

PROPERTIES OF BENZENE DIAZONIUM CHLORIDE :

• It is colourless crystalline solid
• It is highly soluble in water.
• It is stable at 0oC, but on warming it reacts with water
• In dry state it easily decomposes, but in the form of benzene diazonium fluoroborate, it is water
insoluble and stable at room temperature.

CHEMICAL PROPERTIES :
As diazonium group is a good leaving group, it may be substituted by Cl − , Br − , I − , CN − , OH − etc.

SANDMEYER’S REACTION :

GATTERMAN’S REACTION :

9
 Organic Chemistry – II

More yield is observed in Sandmeyer’s reaction than in Gatterman’s reaction. In these reactions,
nucleophile has been introduced into benzene ring.

REPLACEMENT BY I − :
+
Ar N 2 Cl − + KI → ArI + KCl + N 2

REPLACEMENT F− :
+
Ar N 2 Cl − + HBF4 → Ar N 2+ BF4− → ArF + BF3 + N 2
fluoboric acid
REPLACEMENT BY ‘H’
+
Ar N 2 Cl − + H 3 PO2 + H 2O → ArH + N 2 + H 3 PO3 + HCl
hypophosphorous acid
+
Ar N 2 Cl − + C2 H 5OH → ArH + N 2 + CH 3CHO + HCl
REPLACEMENT BY OH − GROUP :
+
Ar N 2 Cl − + H 2O ⎯⎯⎯
283 K
→ ArOH + N 2 + HCl
REPLACEMENT BY NO2−
NaNO2 / Cu , Δ
ArN 2+ Cl − + HBF4 ⎯⎯⎯⎯⎯ → Ar − NO2 + N 2 + NaBF4

IMPORTANCE OF DIAZONIUM SALTS IN SYNTHESIS OF AROMATIC COMPOUNDS

• Diazonium salts are intermediates in the preparation of variety of aromatic compounds including
dyes.
• Substituted arenes are easily prepared through diazonium salts.
• Fluorides and iodides can not be prepared by direct reaction of halogen.
• Cyano group cannot be introduced by nucleophilic substitution of chlorine in chlorobenzene but
cyanobenzene can be easily obtained from diazonium salt.
(AZODEYES) COUPLING REACTIONS :
Benzene diazonium chloride reacts with phenol, aniline etc in which these compounds attach to
the diazonium ion through their para positions giving azo products. These reactions are
electrophilic substitution reaction.

N 2 Cl OH

−
+ ⎯⎯⎯
OH
→ N=N OH + Cl− + H 2 O

P-hydroxy azobenzene
(orange dye)

10
 Organic Chemistry – II

N 2 Cl NH 2

−
+ ⎯⎯⎯
OH
→ N=N NH 2 + Cl − + H 2 O

P-amino azobenzene
(yellow dye)
The azo products have extended conjugate system with aromatic ring and -N=N-. Therefore, these
compounds are coloured and used as dyes.

11