Question 15 Marks
i. Write the structure of main products when aniline reacts with the following reagents :
a. $Br _2$ water
b. HCl
c. $\left( CH _3 CO \right)_2 O /$ pyridine
ii. Arrange the following in the increasing order of their boiling point:$C _2 H _5 NH _2, C _2 H _5 OH ,\left( CH _3\right)_3 N$
iii. Give a simple chemical test to distinguish between the following pair of compounds : $\left( CH _3\right)_2 NH$ and $\left( CH _3\right)_3 N$.
a. $Br _2$ water
b. HCl
c. $\left( CH _3 CO \right)_2 O /$ pyridine
ii. Arrange the following in the increasing order of their boiling point:$C _2 H _5 NH _2, C _2 H _5 OH ,\left( CH _3\right)_3 N$
iii. Give a simple chemical test to distinguish between the following pair of compounds : $\left( CH _3\right)_2 NH$ and $\left( CH _3\right)_3 N$.
Answer

ii. Increasing order of boiling point $\left( CH _3\right)_3 N< C _2 H _5 NH _2< C _2 H _5 OH$ Alcohols have a higher boiling point as compared to that of amines because oxygen being more electronegative forms stronger hydrogen bond as compared to that of nitrogen. In tertiary amine, there is no hydrogen bond formation due to the absence of H -atoms and hence, has the lowest boiling point.
iii. $\left( CH _3\right)_2 NH$ and $\left( CH _3\right)_3 N$ are secondary and tertiary amines respectively. These are distinguished by Hinsberg's reagent which gives sulphonamide with secondary amines and no reaction with tertiary amines. $\left( CH _3\right)_2 NH$ reacts with benzene sulphonyl chloride to give N, N-dimethyl benzene sulphonamide, which is insoluble in alkali. The reaction is as follows:

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ii. Increasing order of boiling point $\left( CH _3\right)_3 N< C _2 H _5 NH _2< C _2 H _5 OH$ Alcohols have a higher boiling point as compared to that of amines because oxygen being more electronegative forms stronger hydrogen bond as compared to that of nitrogen. In tertiary amine, there is no hydrogen bond formation due to the absence of H -atoms and hence, has the lowest boiling point.
iii. $\left( CH _3\right)_2 NH$ and $\left( CH _3\right)_3 N$ are secondary and tertiary amines respectively. These are distinguished by Hinsberg's reagent which gives sulphonamide with secondary amines and no reaction with tertiary amines. $\left( CH _3\right)_2 NH$ reacts with benzene sulphonyl chloride to give N, N-dimethyl benzene sulphonamide, which is insoluble in alkali. The reaction is as follows:










