Write short notes on the following:
(i) Carbylamine reaction (il) Diazotisation (iii) ‘Hofmann's bromamide reaction
(iv) Coupling reaction (v) Ammonolysis (vi) Acetylation
(vii) Gabriel phthalimide synthesis
(i) Carbylamine reaction: Both aliphatic and aromatic primary amines when warmed with chloroform and an alcoholic solution of KOH, produces isocyanides or carbylamines which have very unpleasant odours. This reaction is called carbylamine reaction.
(ii)Diazotisation: The process of conversion of a primary aromatic amino compound into a diazonium salt, is known as diazotisation. This process is carried out by adding an aqueous solution of sodium nitrite to a solution of primary aromatic amine (e.g., aniline) in excess of HCl at a temperature below 5 °C.
(iii)Hoffmann's bromamide reaction: When an amide is treated with bromine in alkali solution, it is converted to a primary amine that has one carbon atom less than the starting amide. This reaction is known as Hoffinann's bromamide degradation reaction.
(iv) Coupling reaction: In this reaction, arene diazonium salt reacts with aromatic amino compound (in acidic medium) or a phenol (in alkaline medium) to form brightly coloured azo compounds. The reaction generally takes place at para position to the hydroxy or amino group. If para position is blocked, it occurs at ortho position and if both ortho and para positions are occupied, than no coupling takes place.
(v) Ammonolysis: It is a process of replacement of either halogen atom in alkyl halides (or aryl halides) or hydroxyl group in alcohols (or phenols) by amino group. The reagent used for ammonolysis is alcoholic ammonia. Generally, a mixture of primary, secondary and tertiary amine is formed.
(vi) Acetylation: The process of introducing an acetyl (CH3CO-) group into molecule using acetyl chloride or acetic anhydride is called acetylation.
(vii) Gabriel phthalimide synthesis: It is a method of preparation of pure aliphatic and aralkyl primary amines. Phthalimide on treatment with ethanolic KOH gives potassium phathalimide which on heating with a suitable alkyl Or aralkyl halides gives N-substituted phthalimides, which on hydrolysis with dil HCI or with alkali give primary amines.
Describe a method for the identification of primary, secondary and tertiary amines. Also write chemical equations of the reactions involved.
Why is benzene diazonium chloride not stored and is used immediately after its preparation?
Under which of the following reaction conditions, aniline gives p-nitro derivative as the major product?
(a) Acetyl chloride/pyridine followed by reaction with cone. H2SO4 + cone.
(b) Acetic anhydride/pyridine followed by cone. H2SO4 + cone. HNO3
(c) Dil. HCl followed by reaction with cone. H2SO4 + cone. HNO3
(d) Reaction with cone. HNO3 + cone. H2S04
Which of the following reactions belong to electrophilic aromatic substitution?
(a) Bromination of acetanilide
(b) Coupling reaction of aryldiazonium salts
(c) Diazotisation of aniline
(d) Acylation of aniline
Complete the following acid-base reactions and name the products:
(i) CH3CH2CH2NH2+HCl ——–>
(ii) (C2H5)3 N+HCl ——–>
Assertion (A): N, N-diethylbenzene sulphonamide is insoluble in alkalf. Reason (R): Sulphonyl group attached to nitrogen atom is strong electron withdrawing group.
Predict the product of reaction of aniline with bromine in non-polar solvent such as CS2.
Account for the following
(i)pKb of aniline is more than that of methylamine
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv)Although amino group is o and p – directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v)Aniline does not undergo Friedel-Crafts reaction.
(vi)Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii)Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Give plausible explanation for each of the following:
(i) Why are amines less acidic than alcohols of comparable molecular masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic amines?
Reduction of nitrobenzene by which of the following reagents give aniline?
(a) Sn/HCl (b) Fe/HCl (c) H2-Pd (d) Sn/NH4OH
How wjll you convert:
(i) Ethanoic acid into methanamine (ii) Hexanenitrile into 1-aminopentane
(iii) Methanol to ethanoic acid. (iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid (vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine (viii) Propanoic acid into ethanoic acid?
The best reagent for converting 2-phenylpro-panamide into-2-phenyl- propanamine is .
(a) excess H2
(b) Br2 in aqueous NaOH
(c) iodine in the presence of red phosphorus
(d) LiAlH4 in ether
A solution contains 1 g mol each of p-toluene diazonium chloride and p-nitrophenyl diazonium chloride. To this 1 g mol of alkaline solution of phenol is added. Predict the major product. Explain your answer.
Write chemical reaction of aniline with benzoyl chloride and write the name of the product obtained.
The reagents that can be used to convert benzene diazonium chloride to benzene are
(a) SnCl2/HCl (b) CH3CH2OH
(c) H3PO2 (d) LiAlH4
The best reagent for converting-2-phenylpro-panamide into 1-phenylethana- mine is .
(a) excess H2/Pt (b) NaOH /Br2
(c) NaBH4/methanol (d) LiAlH4/ether
A colourless substance 'A' (C6H7N) is sparingly soluble in water and gives a water soluble compound 'B' on treating with mineral acid. On reacting with CHCl3 and alcoholic potash 'A' produces an obnoxious smell due to the formation of compound 'C'. Reaction of 'A' with benzenesulphonyl chloride gives compound 'D' which is soluble in alkali. With NaNO2 and HCl, 'A' forms compound 'E' which reacts with phenol in alkaline medium to give an orange dye 'F’ Identify compounds 'A' to 'F’
Assertion (A): Only a small amount of HCl is required in the reduction of nitro compounds with iron scrap and HCl in the presence of steam.
Reason (R): FeCl2 formed gets hydrolysed to release HCl during the reaction.
Write IUPAC names of the following compounds and classify them into primary, secondary and tertiary amines.
(i) (CH3)2 CHNH2 (ii) CH3(CH2)2NH2 (iii) CH3NHCH(CH3)2
(iv) (CH3)3 CNH2 (v) C6H5NHCH3(vi) (CH3CH2)2NCH3
(vii)m-BrC6H4NH2
Which of the following species are involved in the carbylamine test?
(a) R-NC (b) CHCl3 (c) COCl2 (d) NaN02 + HCl
A primary amine, RNH2 can be reacted with CH3-X to get secondary amine, R NHCH3 but the only disadvantage is that 3 ° amine and quaternary ammonium salts are also obtained as side products. Can you suggest a method where RNH2 forms only 2 ° amine?
Write following conversions:
(i) nitrobenzene –> acetanilide
(ii) acetanilide –> p-nitroaniline
Assertion (A): Hofmann's bromamide reaction is given by primary amines. Reason (R): Primary amines are more basic than secondary amines.
Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid.
The correct IUPAC name for CH2 = CHCH2NHCH3 is
(a) allylmethylamine (b) 2-amino-4-pentene
(c) 4-aminopent-l-ene . (d) N-methylprop-2-en-l-amine.
Which of the following cannot be prepared by Sandmeyer's reaction?
(a) Chlorobenzene (b) Bromobenzene
(c) Iodobenzene (d) Fluorobenzene
