CHAPTER 

Organic Compounds
Containing Nitrogen
Introduction, Methods of Preparation and Physical Properties
x Amines: Amines can be considered as the amino derivatives of hydrocarbons or alkyl derivatives
of ammonia. Amines are obtained by replacing one, two or three hydrogen atoms by alkyl and/or aryl groups.
For example, CH3 NH2 , C2 H5 NH2 , C6 H5 NH2 etc.
x Classification of amines:

| |
 NH2 NH N
Pr imary Secondary Tertiary

1o  2o  3 o 
x Structure of amines:
unshared
celectron
pair

— CH2 —

CH3

CH3
108°

Pyramidal shape of trimethylamine

Nitrogen orbitals in amines are sp3 hybridised and the geometry of amines is pyramidal. The fourth orbital
of nitrogen in all amines contains an unshared pair of electrons. Due to the presence of unshared pair of
electrons, the angle C – N – E is less than 109.5q.
x Nomenclature of some alkylamines and arylamines:
Amines Common Names IUPAC name
CH3  CH2  NH2 Ethylamine Ethanamine

CH3  CH2  CH2  NH2 n-Propylamine Propan-1-amine

CH3  C H  CH3 Isopropylamine Propane-2-amine

|
NH2

CH3  N  CH2  CH3 Ethylmethylamine N-Methylethanamine

|
H

CH3  N  CH3 Trimethylamine N,N-Dimethylmethaneamane

|
CH3

NH2 Aniline Aniline or benzenamine

NH2 p-Bromoanaline 4-Bromobenzylamine

Or
4-Bromoaniline

Br
x Preparation of Amines:
¾ By reduction of nitro compounds:
Ni
R  NO2  3H2 
 R  NH2  2H2O
1o a mine
¾ By ammonolysis of alkyl halides:
 
RX RX RX
R  X  NH3  RNH2 
 R2 NH 
 R3 N 
 R4 N X

1o  2o  3 o  Quaternary

ammonium salt
The free amine can be obtained from the ammonium salt by treatment with a strong base:
   
R  N H3 X  NaOH  R  NH2  H2O  Na X
¾ By reduction of nitriles:
Ni
2 H2  R  C  N 
 R  CH2  NH2
Na Hg  / C2H5OH
R  C  N  4  H    R  CH2  NH2
or LiAlH4

1o a mine
 ¾ Gabriel phthalmide synthesis:

O O

C KOH C – +
N—H NK
C C

O O

R—X

O O
– +

C – ONa NaOH(aq) C
R — NH2 + – + N—R
C – ONa C
1° amine
O O
¾ By reduction of amides:
O
||
(i) LiAlH
R  C  NH2 
4  R  CH  NH
2 2
(ii) H2O
¾ By Hoffmann Bromamide degradation reaction:
O
||
R  C  NH2  Br2  4 NaOH 
 R  NH2  Na2CO3  2 NaBr  2 H2O
x Physical properties:
¾ Lower members are combustible gases, members from C3 to C1 are volatile liquids and C12 onwards are
gaseous. Lower aromatic amines are liquids.
¾ Pure amines are colourless, although they develop colour on keeping in air for a long time.
¾ With increase in molecular weight, the boiling point also increases. The order of boiling points of isomeric
amines is, Primary > Secondary > Tertiary.
¾ Lower members of amine are readily soluble in water. They decrease in water and increase in organic
solvents with an increase in molecular weight.

Chemical Reaction of Amines and Diazonium Salts

x Chemical properties:
¾ Reactions due to alkyl group:
  

R  N H2  HX   R  N H3 X  Salt 


NH2
+ –
NH3Cl
+ HCl

Aniline Anilinium chloride

Amines, being basic in nature, react with acids to form salts. When these amine salts are treated with a
base such as NaOH, they regenerate the parent amine.
    
R N H3 X  O H 
 R N H 2  H2 O  X
Amine base parent
Salts amine
Amine salts are soluble in water but insoluble in organic compounds like ether. This reaction helps in
separating the amines from the non basic organic compounds insoluble in water.
The reaction of amines with mineral acids to form ammonium salts shows that these are basic in nature.
The order of basic strength in case of methyl Substituted amines and ethyl substituted amines in aqueous
solution is as follows:
C2 H5 2 NH  C2 H5 3 N  C2 H5 NH2  NH3
CH3 2 NH  CH3 NH2  CH3 3 N  NH3
The –NH2 group is attached directly to the benzene ring in aryl amines, which 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.
In case of substituted aniline, it is observed that electron releasing groups increase basic strength whereas
electron withdrawing groups decrease it.
Alkylation:

 CH3 CH2  Br  
CH3  CH2 3 N 
 HBr
 CH3  CH2 4 N Br
Tetraethyl
ammonium bromide
Acylation:
Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters by
nucleophillic substitution reaction. This reaction is known acylation.

Benzoylation:

Carbylamine reaction: Secondary and tertiary amines do not give this reaction. This reaction is used as
a test for primary amines.
Heat
R  NH2  CHCl3  3 KOH  R  NC  3 KCl  3 H2O
–
C
+
NH N
2

CHCl3
KOH

Reaction with nitrous acid:

   
NaNO2  HCl H2O
R  NH2  HNO2    R  N2 Cl    ROH  N2  HCl
 
1o amine
R2 NH  HNO2 
 R2 N  N  O  H2O
2o amine N-Nitrosamine
No Reaction

 
NaNO  2 HCl
C6 H5  NH2 
2  C6 H5  N2 Cl NaCl  2 H2O
273 278 k
Arom
matic Benzenediazonium
amine chloride

Secondary and tertiary amines react with nitrous acid in a different manner.
Reaction with arylsulphonyl chloride:
O O

S Cl + H – N – C2H5 S N – C2H5 + HCl

O H O H
N-Ethylbenzenesulphonamide
(soluble in alkali)
O O

S Cl + H – N – C2H5 S N – C2H5 + HCl

O C2H5 O C2H5
N, N-Diethylbenzenesulphonamide
Tertiary amines do not react with benzenesulphonyl chloride and therefore, benzenesulphonyl chloride is
used to differentiate between primary, secondary and tertiary amines.
Bromination:
Aniline reacts with bromine water at room temperature to give a white precipitate of 2, 4, 6-tribromoanaline.
NH2 NH2

Br Br
Br2/H2O + 3 HBr
+ 3Br2

Aniline
Br
2, 4, 6- Tribromoaniline
Nitration:
Direct nitration of aniline yields nitro derivatives.
NH2 NH2 NH2 NH2

NO2
HNO3, H2SO4, 288K
+ +
NO2

NO2
(47%) (2%)
(51%)
 Preparation of monosubstituted aniline derivative by acetylation of group:
NH2 NHCOCH3 NHCOCH3 NH2

–
(CH2CO)2O HNO3, H2SO4, 288K OH or H+
Pyridine

Acetanilide
NO2 NO2
p-Nitroacetanilide p-Nitroaniline
Sulphonation:
.. + - +
NH2 N H 2 HSO4 NH2 NH2

H2SO4 453–473 K

–
Anilinium SO3H SO3
hydrogensulphate Sulphanilic acid Zwitter ion
Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with
aluminium chloride.
Ammonolysis:
Alkyl halide reacts with ammonia to form primary amine. The reaction of ammonia with alkyl halide is
known as ammonolysis.

Gabriel Phthalimide Synthesis: In Gabriel phthalimide synthesis, phthalimide reacts with alcoholic
KOH to get potassium phthalimide which reacts with alkyl halide to form N-alkyl phthalimide which on
basic hydrolysis gives primary amine and phthalic acid.
O O O

C KOH
C –+ R–X
C
N—H NK N—R
C C C

O O O
Phthalimide N-Alkyphthalimide
Friedel-Crafts reaction: Aniline does not undergo Friedel-Crafts reaction as it forms a salt with AlCl3
which is a Lewis acid.
x Diazonium salts:
  
¾ General formula: R N2 X , where R stands for an aryl group and X ion may be for halides
¾ Stability of diazonium salts: Primary aliphatic amines are highly unstable alkyldiazonium salts.
Arenediazonium salts, made up of primary aromatic amines are more stable than alkyl diazonium salts
due to the dispersal of the positive charge over the benzene ring.
  y  y  y
:

N  N: N  N: N  N: N  N:

 y



¾ Preparation of diazonium salts:

NH2 N2+ Cl -

0° – 5°C + NaCl + 2H2O

+ NaNO2 + 2HCl

Benzene diazonium
¾ Chemical properties:
Reactions involving displacement of nitrogen:
Replacement by halide or cyanide ion-
CuCl/HCl
ArCl + N2
+– CuBr/HBr
ArN2X ArBr + N2
CuCN/KCN
ArCN + N2
Sandmeyer reaction
Cu/HCl
+– ArCl + N2 + CuX
ArN2X Cu/HBr
ArBr + N2 + CuX
Gatterman’s reaction
Replacement by iodide ion-
 
Ar N2 Cl  KI 
 ArI  KCI  N2
Benzene Iodobenzene
diazonium
chloride
Replacement by fluoride ion-
   
Ar N2 Cl  HBF4 
 Ar N2 BF4

 

Ar N2 BF4  Ar  F  BF3  N2
Replacement by H-
 
Ar N2 Cl H3 PO2  H2O 
 ArH  N2  H3 PO3  HCl
 
Ar N2 Cl CH3CH2OH 
 ArH  N2  CH3CHO  HCl
Replacement by hydroxyl group-
 

Ar N2 Cl H2O  ArOH  N2  HCl
Phenol
Replacement by –NO2 group-
+ - + -
N2 C l N2 B F 4 NO2

NaNO2
+ N2 + NaBF4
+ HBF4 Cu, D
Fluroboric
acid
 Reactions involving retention of diazo group:
Coupling reaction: The reaction of diazonium salts with phenols and aromatic amines to form azo
compounds with the general formula, Ar – N = N Ar is known as coupling reaction.
+ – –
OH –
N NCl + H OH N=N OH + Cl + H2O

p-Hydroxyazobenzene (orange dye)

+ – –
OH –
N NCl + H NH2 N=N NH2 + Cl + H2O

p-Aminoazobenzene (yellow dye)

¾ Importance of Diazonium salts: They are very good intermediates for the introduction of –F, –Cl, Br, –
I, – CN, – OH, – NO2 groups into aromatic ring. Cyanobenzene can be prepared from diazonium salts.
x Synthesis of organic compounds from diazonium salts:
 
CH CH OH
C6 H5 N 2 Cl 
3 2  C6 H6
 
H O
C6 H5 N 2 Cl 
2  C H OH
6 5

 
HBF
C6 H5 N 2 Cl 
4 C H F
6 5

 
C H / NaOH
C6 H5 N 2 Cl 
6 6
 C6 H5C6 H5

 
C H NH / acid
C6 H5 N 2 Cl 
6 5 2


x Identification of primary, secondary and tertiary amines:

Test Primary amine Secondary amine Tertiary amine
Reaction with nitrous Gives alcohol with Gives only nitrosoamine Forms nitrite in cold
acid. effervescence of N2 gas. which gives Liebermann’s soluble in water and
nitrosoamine test. on heating gives
nitrosoamine.
Recation with benzene Gives N-alkyl benzene- Gives N, N-dialkyl benzene No reaction.
sulphonyl chloride sulphonamide which is sulphonamide which is
(Hiesenberg’s reagent). soluble in alkali. insoluble in alkali.
Carbylamine test: Forms carbylamines or No reaction. No reaction.
Reaction with isocyanide (RNC) with
chloroform and characteristic unpleasant
alcoholic KOH. odour.
Hoffman’s Mustard oil Forms N-substituted No reaction. No reaction.
reaction: Recation with isotiocyanate with
CS2 and HgCl2. characteristic unpleasant
smell of mustard oil.
 EXERCISE
1. C3H9N represents 11. When aniline reacts with NaNO2 and dil. HCl
(a) Primary amine (b) Secondary amine at 0° – 5° C, the product formed is
(c) Tertiary amine (d) All of these (a) Nitroaniline
2. Triaminobenzene is a (b) Benzene diazonium chloride
(a) 2° amine (b) 3° amine (c) Benzene
(c) 1° amine (d) Quarternary salt (d) Trinitroaniline
3. Which of the following is not a nitro-derivative. 12. CH3 Br  KCN (alc) 
 X 
Reduction
Na  C H OH
Y
2 5
(a) C6H5NO2 (b) CH3CH2ONO What is Y in the series?
O (a) CH3CN (b) C2H5CN
(c) CH3 CH – N (d) C6H4(OH)NO2 (c) C2H5NH2 (d) CH3NH2
13. Which of the following compound is expected to
O be most basic
CH3
4. Number of isomeric primary amines obtained (a) Aniline (b) Methylamine
from C4H11N are (c) Hydroxylamine (d) Ethylamine
(a) 3 (b) 4 14. Aniline when treated with HNO2 and HCl at 0°C
(c) 5 (d) 6 gives.
5. The molecular formula of benzonitrile is (a) Phenol (b) Nitrobenzene
(a) C6H5CN (b) C6H5NC (c) A diazo compound (d) None of these
15. Ethyl amine undergoes oxidation in the presence
(c) C6H5CNO (d) C6H5NCO
of KMnO4 to form
6. Amides may be converted into amines by reaction
(a) An acid (b) An alcohol
named after
(c) An aldehyde (d) A nitrogen oxide
(a) Parkin (b) Claisen
16. Reaction of primary amines with aldehyde yields.
(c) Hoffmann (d) Kolbe
Na C H OH
(a) Amides (b) Aldimines
7. CH3C  N  4[H] 
2 5 
 CH3CH2 NH2 (c) Nitriles (d) Nitro compounds
Re duction
The compound ‘X’ is 17. Nitrobenzene on nitration gives
(a) CH3CONH2 (b) CH3CH2NH2 (a) o-dinitrobenzene
(c) C2H6 (d) CH3NHCH3 (b) p-dinitrobenzene
8. Reduction of nitroalkanes yields (c) m-dinitrobenzene
(a) Acid (b) Alcohol (d) o-and p-nitrobenzene
(c) Amine (d) Diozo compounds 18. When primary amines are treated with HCl. the
Product obtained is
9. When methyl iodide is heated with ammonia,
the product obtained is (a) An Alcohol (b) A cyanide
(a) Methylamine (c) An amide (d) Ammonium salt
(b) Dimethylamine 19. Which of the following do not react with HNO2
(c) Trimethylamine (a) Primary nitroalkanes
(d) A mixture of the above three amines (b) Secondary nitroalkanes
10. Identify ‘B’ in the reaction (c) Tertiary nitroalkanes
PO 4H (d) All of these
Acetamide 
2 5
 A 
B
 20. The product of mustard oil reaction is
(a) CH3NH2 (a) Alkyl isothiocyanate
(b) CH3CH2NH2 (b) Dithio carbonamide
(c) CH3CN (c) Dithio ethylacetate
(d) CH3COONH4 (d) Thioether
21. The maximum number of –NO2 groups that can 23. When methyl cyanide is hydrolysed in presence
be introduced by nitration in benzene is usually of alkali, the product is
(a) 4 (b) 2 (a) Acetamide (b) Methane
(c) 3 (d) 6 (c) CO2 + H2O (d) Acetic acid
22. Primary nitro compounds when reacts with HNO2 24. Methyl amine reacts with HNO2 giving
forms crystalline solids which on treatment with (a) CH3O – N = O (b) CH3–O–CH3
NaOH gives
(c) CH3OH (d) (a) and (b) both
(a) Red solution (b) Blue solution
(c) White precipitate (d) Yellow colouration

Answer Keys
1. (d) 2. (c) 3. (b) 4. (b) 5. (a) 6. (c) 7. (b) 8. (c) 9. (d) 10. (b)
11. (b) 12. (c) 13. (d) 14. (c) 15. (c) 16. (b) 17. (c) 18. (d) 19. (c) 20. (a)
21. (c) 22. (a) 23. (d) 24. (d)

Solutions
1. C3H9N can form all the 3 amines. Na C H OH
7. CH3C  N  4[H] 
2 5 
 CH3CH2 NH2
Re duction
CH3CH2CH2–NH2,
CH3  CH2  NO2  6  H  
Sn / HCl
1° amine 8.
Nitro ethane
CH3–CH2–NH–CH3, CH3  CH2  NH2  2H2O
2° amine Ethyl amine
e

CH3  N  CH3
| CH3 
NH
3
 CH3 NH2 
3

CH I
CH3 9. 
Methyl amine
3 amine
CH3 2 NH 
CH3I
 CH3 3 N
2. Dimethyl amine Trimethyl amine

P O
10. CH3 CONH2 
2 5
 CH3 CN 
4H
 CH3 CH2 NH2
+ –

3. CH3CH2–O–N = O is a nitrite derivative, hence 11.

it is not a nitro derivative.
4. Four 1° amines are possible
Na / C H OH
CH 3 CH 2 CH 2 CH 2 NH 2 , (CH 3 ) 2 CHCH 2 NH 2 , 12. CH3 Br 
alc. KCN
 CH3CN 2 5
reduction
 CH3CH2 NH2
CH3CH(NH2) CH2CH3, (CH3)3 CNH2 [x] Ethyl amine

5. The molecular formula of benzonitrile of phenyl 13. Due to +ve I.E. of alkyl group, N-atom of amines
cyanide is C6H5CN. acquires partial –ve charge thus electron pair is
6. Hofmann’s bromamide reaction easily donated.
H O
CH3  CO  NH2  Br2  4KOH 
2
 14.
Acetamide
CN3 NH2  K 2 CO3  2KBr  2H2 O
Methyl amine
 KMnO H O
15. CH3CH2  NH2 
4  CH CH  NH 
3 
 CH3  CHO
Ethylamine
O 
3
Aldimine Acetaldehyde

16. R – CH2 – NH2 + O = CH – R oR – CH2 – N = CH – R + H2O

1° amine aldehyde Aldimine
NO2 NO2

17. Conc. H2SO4

+ HNO3 NO2
Conc.
Nitrobenzene m-dinitrobenzene

–NO2 group is meta directed group.

18. CH3 – CH2 – NH2 + HCl oCH3CH2 – NH3+Cl–
Ethyl ammonium chloride
Amines are basic in nature they reacts with acid to form salt.
19. Tertiary nitroalkanes do not react with HNO2 because in tertiary nitroalkanes D – H atom is absent.
20. Mustard oil reaction
HgCl
CH3  CH2  NH2  CS2 
2  CH  CH  N  C  S  H S
3 2 2
Ethyl amine Ethyl issothiocyanate

NO2

Nitration
21.
NO2 NO2
1, 3, 5-trinitrobenzene
3-nitro group can be introduced.
HNO
22. R  CH2  NO2 
2

 R  C NO2 
NaOH
 R  C NO2
1 nitro  
N  OH N O Na
Nitrolic acid (Blood red)

23. CH3 – C {N + 2H2O o CH3COOH + NH3

Methyl cyanide Acetic acid
24. CH3NH2 + 2HNO2 oCH3 – O – N = O + N2 + 2H2O

2CH3NH2 + 2HNO2 oCH3 – O – CH3 + 2N2 + 3H2O