based on maharashtra board 2015 syllabus.

1. Compound containing Nitrogen
By Azeem

2. Nitro Compound
General method of preparation-
1. Nitration of alkanes
2. From alkyl halides
3. From salts of α-halogeno carboxylic acid
4. From primary amines
5. From a-nitroalkenes(2methyl nitropropene)
6. From oximes(aldoxime +O in trifluoroperoxy acetic acid)

3. Reaction of nitroalkane
1. Reduction
2. Hydrolysis
3. Halogenation
4. Reaction with nitrous acid
5. Condensation with aldehydes and ketones
Nitro Compound

5. Classification of amines

7. Physical Properties of Amines
• The methylamines (mono-, di-, tri-) and ethylamine
are gases at room temperature , other amines are
liquid at room temperature.
• Amines are irritating to the skin, eyes, and mucous
membranes and are toxic by ingestion.
• Aromatic amines are generally toxic. Amines are
readily absorbed through the skin and affect both
the blood and the nervous system.
• Amines B.P are higher than alkane but not in
alcohol.

8. • Both amine and ammonia are produce basic
aqueous solution.
• Amine and ammonia are weak base due to
accepter of proton.
• NH3 + H2O → NH4 + OH
• Increase mass decrease solubility. Colourless.
Physical Properties of Amines

10. Nomenclature of amines

13. Method of preparation of amines
1. From alkyl halide: by ammonolysis
2. From alkyl halide: Gabriel phthalimide
synthesis(alkylation of phthalimide)
3. From oximes, alkyl cyanides, amides and nitro
compounds: by reduction
(a) From oximes
(b) From alkyl cyanide(alkyl nitriles)
(c) From amides
(d) From nitro compounds
(e) From amides: by hoffman bromamide degradation

14. 1. From alkyl halide: by ammonolysis
H-NH2
100˚C under
pressure

15. 2. From alkyl halide: Gabriel phthalimide
synthesis

16. 3. From oximes, alkyl cyanides,
amides and nitro compounds: by
reduction

17. a. From oximes
• Aldoxime or ketoximes are reduce by
sodium and ethanol to primary amine.
• R- CH= N-OH + 4[H] → R-CH2-NH2 + H2O
• Ketoxime.
• Acetaloxime.

18. b. From alkyl cyanide(alkyl nitriles)
• Alkyl cyanide on reduction by Na and
ethanol give primary amine.
• R-C ≡ N + 4[H] → R-CH2-NH2
• Eg. Acetonitrile and Propanenitrile.

19. c. From amides
4[H]

20. d. From nitro compound
• Nitro compounds are reduced by
tin(Sn) or iron and con HCl to
corresponding primary amines.
• R- NO2 + 6[H] → R- NH2 + 2H2O
• Eg. Nitrobenzene.
• Nitropropane.

21. e. Hoffman bromamide degradation

22. Reaction of Amines
1. Basic nature of amines
2. Action of nitrous acid (1⁰ amine, 2⁰ amine, 3⁰ amine)
3. Acylation of amines
4. Alkylation of amines: Hoffmann's exhaustive
alkylation
5. Hoffmann elimination
6. Hoffmann’s carbylamines test/ isocyanides test
7. Reaction with arylsulphonyl chloride: Hinsberg’s test
8. Electrophilic aromatic substitution
a) Bromination b) Nitration c) sulphonation

23. 1. Basic nature of amines
• R- NH2 + H+X → R-NH3
+X-
ammonium salts
• R-NH3
+X- + NaOH → R-NH2 + NaX + H2O
• This shows that the reaction is reversible.
• C2H5-NH2 + HCl <==> C2H5-NH3
+Cl-
Ethylamine ethyl ammonium chloride
Aqueous solutions amines are basic, and they turn
red litmus paper blue.
R-NH2 + H-O-H  R- NH3
+ + OH-
Weak base strongerbase

24. 2. Action of nitrous acid
• Primary, secondary & tertiary amines react
differently with nitrous acid.
• Since nitrous acid is unstable, it is prepared in
situ(Latin- reaction mixture) at 273K- 278K.
• NaNO2 + HCl → NaCl + HNO2
• Except methyl and ethylamine, all primary amine
give aliphatic diazonium salt.

25. • Primary amine: (HNO2) eg. Aniline
R – NH2 + NaNO2 + 2HCl → [ R- N2
+Cl-] + NaCl + 2H2O
Alkyl diazonium chloride
• Secondary amine: (HNO2)eg. diethylamine
R2 – NH + NaNO2 + HCl → R2N-N=O + NaCl + 2H2O
N- nitroso dialkylamine
• Tertiary amine: (HNO2)eg. triethylamine
R3 – N + NaNO2 + HCl → [ R3- NH]+NO2
- + NaCl
trialkyl ammonium nitrate
2. Action of nitrous acid

26. 3. Acylation of amines
• Amine react with acyl chloride in presence of
pyridine.
• R- NH2 + X-CO-R  R- NH – CO –R + HX
• Eg. Ethylamine
• Silimalary reaction in acetic anhydride,
• R- NH2 + (CH3- CO-)2OR-NH-CO-CH3 + CH3- COOH
Amines ethanoic anhydride alkyl acetamide
• Eg. Aniline

27. 4. Alkylation of amines: Hoffmann's
exhaustive alkylation
• R- NH2  R2NH  R3N  R4N+X-
» 2⁰ amine 3⁰ tetraalkyl ammonium halide
• Eg. Methylamine
• Eg. Dimethanamine
• Eg. N,N- dimethyl aniline
RXRX RX

28. 5. Hoffmann elimination
• Tetra alkyl ammonium halide on heating with moist
Ag2O form tetra-alkyl ammonium hydroxides.
• This is deliquescent crystalline solid and basic in
nature.
(of a solid) tending to absorb moisture from the air and
dissolve in it.
• On heating undergo β-elimination to form alkene,
tertiary amine and water.
• C2H5N-(CH3)3
+I- + AgOH  C2H5-N+(CH3)3OH- + AgI
Ethyltrimethyl ammonium iodide
• C2H5-N+(CH3)3OH-  CH2=CH2 + (CH3)3N + H2O
Ethyltrimethyl ammonium hydroxide

29. 6. Hoffmann’s carbylamines test/
isocyanides test
• R-NH2 + CHCl3 + 3KOH → R- NC + 3KCl + 3H2O
• Eg. Ethylamine
• and aniline.

30. 7. Reaction with arylsulphonyl
chloride: Hinsberg’s test

31. 8. Electrophilic aromatic substitution
• Bromination

32. Bromination

33. Nitration

34. Nitration
• Aniline on acetylation on heating 298K.

35. Sulphonation

36. Preparation of Diazonium Salt’s

37. Reaction of Diazonium salts
A. Reaction involving replacement of diazonium
group
1. Replacement by –Cl, -Br, -CN: sandmeyer rxn
2. Gettermann reaction: replacement by –Cl, Br:
3. Balz- Schiemann: Replacement by –F.–I,-H, -
OH, -NO2
B. Reactions involving retention of diazonium
Group: Coupling reaction

38. Replacement by –Cl, -Br, -CN:
sandmeyer rxn
Cl

39. 2. Gatterman reactions
diazonium groups are replaced with Cl or Br by
treating the diazonium salt solution with
halogen acid in the presence of copper powder.

40. 3. Replacement of –I
• Diazonium group may be replaced by iodine
by treatment with potassium iodide.

41. 4. The Schiemann reaction
the diazonium group is replaced by hydrogen after treatment
with mild reducing agents such as hypophosphorous acid (or)
ethanol.

42. 5. Replacement of -OH

43. Azo coupling Reaction
Benzendiazonium chloride + phenol give p-
hydroxyazobenzene.

44. Importance of Diazonium salts
• Arene diazonium salts are intermediates to
introduce –F, -Cl, -Br, -I, -CN, -H, -OH, NO2
groups in aromatic ring.
• Azo comounds are strongly coloured(red,
yellow, orange, blue) and used as dyes.