Chapter 29

Aniline first reacts with acetyl chloride producing compound 'A' ' 'A' reacts with nitric acid/sulphuric acid mixture and produces compound 'B', which hydrolyses to compound ' \(\mathrm{C}^{\prime}\). What is the identity of ' \(\mathrm{C}^{\prime}\) ? (a) acetanilide (b) p-nitroacetanilide (c) p-nitroaniline (d) aniline

Butanenitrile may be prepared by heating (a) propyl alcohol with \(\mathrm{KCN}\) (b) butyl alcohol with KCN (c) butyl chloride with \(\mathrm{KCN}\) (d) propyl chloride with KCN

Benzenediazonium chloride on reaction with phenol in weakly basic medium gives (a) diphenyl ether (b) \(\mathrm{p}\)-hydroxyazobenzene (c) chlorobenzene (d) benzene

Peroxide effect can be checked by the addition of sufficient amount of (a) monophenyl amine (b) diphenyl amine (c) triphenyl amine (d) pentaphenyl amine

Which one of the following compound will react with acetone to give a product having carbon nitrogen double bond? (a) \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~N}\) (b) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHNH}_{2}\) (c) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHC}_{6} \mathrm{H}_{5}\)

Ethyl chloride on heating with \(\mathrm{AgCN}\) forms a compounds X. The functional isomer of \(X\) will be (a) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}\) (b) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NC}\) (c) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{CN}^{2}\) (d) none of these

Identify the correct statement among the following. (a) \(\mathrm{n}, \mathrm{n}\)-dimethylaniline reacts with nitrous acid to give p-nitroso-N,N-dimethyl aniline (b) bromination of p-toluidine produces 3,5 -dibromo, 4-methylaniline (c) aliphatic amines are less basic than ammonia (d) aliphatic primary amines combine with nitrous acid under ice-cold conditions to form stable diazonium salts

Among the following compounds, which will react with acetone to give a product containing \(>\mathrm{C}=\mathrm{N}-?\) 1\. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}\) 2\. \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~N}\) 3\. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHC}_{6} \mathrm{H}_{5}\) 4\. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHNH}_{2}\) (a) 3,4 (b) \(1,3,4\) (c) 1,3 (d) 1,4

Identify C in this series. \(\mathrm{CH}_{3} \mathrm{CN} \stackrel{\mathrm{Na} / \mathrm{C}_{2} \mathrm{H}_{3} \mathrm{OH}}{\longrightarrow} \mathrm{A} \stackrel{\mathrm{HNO}_{2}}{\longrightarrow} \mathrm{B} \stackrel{[\mathrm{O}]}{\longrightarrow} \mathrm{C}\) (a) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{NHOH}\) (b) \(\mathrm{CH}_{3} \mathrm{COOH}\) (c) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CONH}_{2}\) (d) \(\mathrm{CH}_{3} \mathrm{CHO}\)

Benzamide on reaction with \(\mathrm{POCl}_{3}\) gives (a) aniline (b) chlorobenzene (c) benzyl amine (d) benzonitrile

Reaction of RCONH \(_{2}\) with a mixture of \(\mathrm{Br}_{2}\) and \(\mathrm{KOH}\) gives \(\mathrm{RNH}_{2}\) as the main product. The intermediate involved in the reaction are 1\. RCONHBr 2\. \(\mathrm{R}-\mathrm{NHBr}\) 3\. \(\mathrm{R}-\mathrm{N}=\mathrm{C}=\mathrm{O}\) 4\. \(\mathrm{RCONBr}_{2}\) (a) \(1,2,3\) (b) \(1,3,4\) (c) 1,3 (d) 1,2

Among the following, the strongest base is (a) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}\) (b) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2}-\mathrm{NH}_{2}\) (c) \(\mathrm{p}-\mathrm{NO}_{2}-\mathrm{C}_{6} \mathrm{H}_{4} \mathrm{NH}_{2}\) (d) \(\mathrm{m}-\mathrm{NO}_{2}-\mathrm{C}_{6} \mathrm{H}_{4} \mathrm{NH}_{2}\)

Compound \(\mathrm{A}\) on reduction gives \(\mathrm{B}\), which on further reaction with \(\mathrm{CHCl}_{3}\) and alcoholic KOH gives compounds \(\mathrm{C}\), which on further hydrolysis gives aniline. The compound \(\mathrm{A}\) is (a) nitrosobenzene (b) methylamine (c) nitromethane (d) nitrobenzene

\(\mathrm{R}-\mathrm{Cl}+\mathrm{AgCN} \longrightarrow \mathrm{A} \stackrel{\text { reductions }}{\longrightarrow} \mathrm{B}\) A and B respectively are (a) \(\mathrm{RCN}, \mathrm{RCH}_{2} \mathrm{NH}_{2}\) (b) \(\mathrm{RNC}, \mathrm{RNHCH}_{3}\) (c) \(\mathrm{RCN}, \mathrm{RNHCH}_{3}\) (d) \(\mathrm{RNC}, \mathrm{RCH}_{2} \mathrm{NH}_{2}\)

In a set of reactions propionic acid yielded a compound D. \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{COOH} \stackrel{\mathrm{SOCl}_{2}}{\longrightarrow} \mathrm{B} \stackrel{\mathrm{NH}_{3}}{\longrightarrow} \mathrm{C} \stackrel{\mathrm{KOH}}{\mathrm{Br}_{2}} \mathrm{D} \mathrm{D}\) The structure of \(D\) would be (a) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{NHCH}_{3}\) (b) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{NH}_{2}\) (c) \(\mathrm{CH}_{3} \mathrm{CH}_{2}^{2} \mathrm{CH}_{2} \mathrm{NH}_{2}^{3}\) (d) \(\mathrm{CH}_{3} \mathrm{CH}_{2}^{2} \mathrm{CONH}_{2}\)

Among the amines I. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}\) II. \(\mathrm{CH}_{3} \mathrm{NH}_{2}\) III. \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}\) IV. \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~N}\) (a) \(\mathrm{I}<\mathrm{IV}<\mathrm{II}<\mathrm{III}\) (b) \(\mathrm{IV}<\mathrm{III}<\mathrm{II}<\mathrm{I}\) (c) \(\mathrm{I}<\mathrm{II}<\mathrm{III}<\mathrm{IV}\) (d) \(\mathrm{II}<\mathrm{III}<\mathrm{IV}<\mathrm{I}\)

Which of the following is more basic than aniline? (a) p-nitroaniline (b) benzylamine (c) diphenylamine (d) triphenylamine

Identify \(\mathrm{R}\) in the following reaction. \(\mathrm{PhCOOH} \frac{\mathrm{LiAlH}_{4}}{\mathrm{PBr}_{3}} \mathrm{P} \stackrel{\mathrm{KCN}}{\longrightarrow} \mathrm{Q}\) \(\frac{\text { (i) partical hydrolysis }}{\text { (ii) } \mathrm{NaOBr}}=\mathrm{R}\)

Which of the following statements relating to aniline is not true? (a) aniline on Schotten-Baumann reaction gives benzanilide (b) aniline cannot be prepared by the reduction of benzonitrile with \(\mathrm{LiAlH}_{4}\) (c) on heating with concentrated \(\mathrm{H}_{2} \mathrm{SO}_{4}\) at \(180^{\circ} \mathrm{C}\), aniline gives sulphanilic acid (d) aniline liberates nitrogen on treatment with ice cold nitrous acid

Aniline is less basic than (a) 4-nitroaniline (b) 4 -aminobenzaldehyde (c) anilinium hydrochloride (d) dimethyl amine

Identify the product in the following sequence 3,4,5-Tribromoaniline \(\frac{\text { (i) diazotization }}{\text { (ii) } \mathrm{H}_{3} \mathrm{PO}_{2}}\) ? (a) \(3,4,5\)-Tribromobenzene (b) \(3,4,5\)-Tribromonitrobenzene (c) \(2,4,6\)-Tribromobenzene (d) \(1,2,3\)-Tribromobenzene

Nitrosoamines \(\left(\mathrm{R}_{2} \mathrm{~N}-\mathrm{N}=\mathrm{O}\right)\) are insoluble in water. On heating them with conc. \(\mathrm{H}_{2} \mathrm{SO}_{4}\). They give secondary amines. The reaction is called (a) Fries reaction (b) Etard reaction (c) Lieberman nitroso reaction (d) Perkin reaction

Arrange the following: I \(\mathrm{CH}_{3} \mathrm{NH}_{2} \quad\) II \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH} \quad \mathrm{III} \mathrm{C}_{6} \mathrm{H}_{3} \mathrm{NH}_{2}\) and IV \(\left(\mathrm{CH}_{3}\right)_{3}^{2} \mathrm{~N}\) in increasing order of basicity in aqueous medium. (a) II \(<\mathrm{I}<\mathrm{IV}<\mathrm{III}\) (b) \(\mathrm{II}<\mathrm{III}<\mathrm{I}<\mathrm{IV}\) (c) \(\mathrm{I}<\mathrm{II}<\mathrm{III}<\mathrm{IV}\) (d) \(\mathrm{III}<\mathrm{IV}<\mathrm{I}<\mathrm{II}\)

Electrolytic reduction of nitrobenzene in strongly acidic medium gives (a) azoxybenzene (b) aniline (c) p-aminophenol (d) phenylhydroxyl amine

The compound that will react most readily with \(\mathrm{NaOH}\) to form methanol is (a) \(\left(\mathrm{CH}_{3}\right)_{4} \mathrm{~N}^{+} \mathrm{I}^{-}\) (b) \(\mathrm{CH}_{3} \mathrm{OCH}_{3}\) (c) \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~S}^{+} \mathrm{I}^{-}\) (d) \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CCl}\)

The correct sequence of reagents used for conversion of aniline into benzylamine is (a) \(\mathrm{NaNO}_{2} / \mathrm{HCl}, \mathrm{CuCN}, \mathrm{Sn} / \mathrm{HCl}\) (b) \(\mathrm{NaNO}_{2} / \mathrm{HCl}, \mathrm{CuCN}, \mathrm{H}_{3} \mathrm{O}^{+}\) (c) \(\mathrm{NaNO}_{2} / \mathrm{HCl}, \mathrm{Cu}^{+} / \mathrm{H}_{3} \mathrm{PO}_{2}, \mathrm{CH}_{3} \mathrm{NH}_{2}\) (d) None

Among the following, the strongest base is (a) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}\) (b) \(\mathrm{p}-\mathrm{NO}_{2}-\mathrm{C}_{6} \mathrm{H}_{4} \mathrm{NH}_{2}\) (c) \(\mathrm{m}-\mathrm{NO}_{2}-\mathrm{C}_{6} \mathrm{H}_{4} \mathrm{NH}_{2}\) (d) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{NH}_{2}\)

When nitrobenzene is treated with \(\mathrm{Br}_{2}\) in presence of \(\mathrm{FeBr}_{3}\), the major product formed is \(\mathrm{m}\)-bromonitrobenzene. The statements which are related to obtain the \(\mathrm{m}\)-isomer are 1\. The electron density on meta carbon is more than at ortho and para positions 2\. the intermediate carbonium ion formed after initial attack of \(\mathrm{Br}^{+}\)at the meta positions is least destabilized 3\. loss of aromaticity when \(\mathrm{Br}^{+}\)attacks at the ortho and para positions and not at m-position 4\. easier loss of \(\mathrm{H}+\) to regain aromaticity from the meta position than from ortho and para positions (a) 1,2 (b) 1,3 (c) \(1,3,4\) (d) 1,4

In the reaction given below, the product \(Y\) is \(\mathrm{C}_{6} \mathrm{H}_{6} \stackrel{\mathrm{HNO}_{3}}{\mathrm{H}_{2} \mathrm{SO}_{4}}-\mathrm{X} \frac{\mathrm{Cl}_{2}}{\mathrm{FeCl}_{3}}-\mathrm{Y}\) (a) 4 -nitrochlorobenzene (b) 3 -nitrochlorobenzene (c) 1 -nitrochlorobenzene (d) none of the above

p-nitrotoluene on further nitration gives

\(\mathrm{p}\) - Nitroaniline is obtained by (a) 1,4 dinitrobenzene \(\stackrel{\mathrm{NH}_{4} \mathrm{HS}}{\longrightarrow}\) (b) Benzene sulphonic acid \(\stackrel{\mathrm{HNO}_{3} / \mathrm{H}_{2} \mathrm{SO}_{4}}{\longrightarrow}\) (c) Aniline \(\frac{\text { 1. Acetylation 2. } \mathrm{HNO}_{3} / \mathrm{H}_{2} \mathrm{SO}_{4}}{\text { 3. aq. } \mathrm{NaOH}, \Delta}\) (d) Aniline \(\frac{1 . \mathrm{HNO}_{j} / \mathrm{H}_{2} \mathrm{SO}_{4}}{2 . \mathrm{aq} \cdot \mathrm{NaOH}}\)

Match the following: List I List II (Compound) \(\quad\) (Nature) 1\. Acetamide (i) Acidic 2\. Phthalimide (ii) Basic 3\. Benzonitrile (iii) Nautral 4\. Grignard reagent The correct matching is: \(\begin{array}{lll}1 & 2 & 3\end{array}\) 4 (a) (iii) (i) (i) (iii) (b) (iii) (i) (iii) (ii) (c) (i) (ii) (ii) (iii) (d) (ii) (iii) (i) (ii)

Match the following (a) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{CO}-\mathrm{NH}_{2}\) (p) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{O}-\) \(\mathrm{Br}_{2} / \mathrm{KOH}\) \(\mathrm{C}(\mathrm{O})-\mathrm{CH}_{3}\) (b) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{COOH}+\) (q) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{NCO}\) \(\mathrm{HN}_{3} \frac{\text { conc. } \mathrm{H}_{2} \mathrm{SO}_{4}}{\text { heat }}\) (c) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{C}(\mathrm{O})-\mathrm{NH}_{2}\) (r) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{NH}_{2}\) \(\frac{\text { (i) } \mathrm{LiAlH}_{4}}{\text { (ii) } \mathrm{H}_{2} \mathrm{O}}\) (d) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{C}(\mathrm{O})-\mathrm{CH}_{3}\) (s) \(\mathrm{R}-\mathrm{CH}_{2}-\mathrm{CH}_{2}\)

Match the following (p) Saytzeff's elimination (q) \(\mathrm{OH}^{-}, \Delta\) (r) Hoffmann's elimination/ reaction (s) Nitrene (t) Alkyl isocyanate

Piperidine is subjected to exhaustive methylation and the quaternary iodide is heated with moist \(\mathrm{Ag}_{2} \mathrm{O}\) and the number of double bonds present in the product formed is/are

Of the following the number of compounds which answer Fehling's test is Glucose, \(\alpha\)-hydroxyl ketone, glyoxal, p-chlorobenzaldehyde, glyoxalic acid, succinaldehyde.

The number of \(\mathrm{N}-\mathrm{CH}_{2}-\mathrm{N}\) bonds in urotropine is

The \(\mathrm{pK}\) of the carboxyl group in valine, \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CH}\) \(\mathrm{CH} \mathrm{NH}_{2} \mathrm{COOH}\) is \(2.31\) and \(\mathrm{pK}_{a}\) for the amino group of the acid is \(9.69 .\) The isoelectric point of the valine is

The total number of isomers which are primary amines with a molecular formula \(\mathrm{C}_{4} \mathrm{H}_{7} \mathrm{~N}\), having no \(\mathrm{C} \equiv \mathrm{C}\) bond is

On heating benzyl amine with chloroform and ethanolic KOH, the product obtained is (a) benzyl alcohol (b) benzaldehyde (c) benzonitrile (d) benzyl isocyanide

A substance forms zwitter ion. It can have functional groups [2002] (a) \(-\mathrm{NH}_{2},-\mathrm{COOH}\) (b) \(-\mathrm{NH}_{2},-\mathrm{SO}_{3} \mathrm{H}\) (c) both (d) none of these

In an organic compound of molar mass is \(108 \mathrm{~g} \mathrm{~mol}^{-1}\). \(\mathrm{C}, \mathrm{H}\) and \(\mathrm{N}\) atoms are present in \(9: 1: 35\) by weight in it. Molecular formula can be (a) \(\mathrm{C}_{6} \mathrm{H}_{8} \mathrm{~N}_{2}\) (b) \(\mathrm{C}_{7} \mathrm{H}_{10} \mathrm{~N}\) (c) \(\mathrm{C}_{5} \mathrm{H}_{6} \mathrm{~N}_{3}\) (d) \(\mathrm{C}_{4} \mathrm{H}_{18} \mathrm{~N}_{3}\)

When a primary amine reacts with chloroform in ethanolic KOH, the product formed is (a) an aldehyde (b) an alcohol (c) a cyanide (d) an isocyanide

Ethyl isocyanide on hydrolysis in acidic medium generates \([\mathbf{2 0 0 3}]\) (a) ethylamine salt and methanoic acid (b) propanoic acid and ammonium salt (c) ethanoic acid and ammonium salt (d) methylamine salt and ethanoic acid

The correct order of increasing basic nature for the bases \(\mathrm{NH}_{3}, \mathrm{CH}_{3} \mathrm{NH}_{2}\), and \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}\) is \([\mathbf{2 0 0 3}]\) (a) \(\mathrm{NH}_{3}<\mathrm{CH}_{3} \mathrm{NH}_{2}<\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}\) (b) \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}<\mathrm{NH}_{3}<\mathrm{CH}_{3} \mathrm{NH}_{2}\) (c) \(\mathrm{CH}_{3} \mathrm{NH}_{2}<\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}<\mathrm{NH}_{3}\) (d) \(\mathrm{CH}_{3} \mathrm{NH}_{2}<\mathrm{NH}_{3}<\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}\)

Amongst the following, the most basic compound is [2004] (a) benzylamine (b) aniline (c) acetanilide (d) p-nitroaniline

Which one of the following methods is neither meant for the synthesis nor for separation of amines? \([\mathbf{2 0 0 5}]\) (a) Hinsberg method (b) Hoffmann method (c) Wurtz reaction (d) Curtius reaction

An organic compound having molecular mass 60 is found to contain \(\mathrm{C}=20 \%, \mathrm{H}=6.67 \%\) and \(\mathrm{N}=\) \(46.67 \%\) while rest is oxygen. On heating, it gives \(\mathrm{NH}_{3}\) along with a solid residue. The solid residue gives violet colour with alkaline copper sulphate solution. The compound is \([2005]\) (a) \(\mathrm{CH}_{3} \mathrm{NCO}\) (b) \(\mathrm{CH}_{3} \mathrm{CONH}_{2}\) (c) \(\left(\mathrm{NH}_{2}\right)_{2} \mathrm{CO}\) (d) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CONH}_{2}\)

Which of the following is the strongest base in Aqueous solution? (a) Trimethylamine (b) Aniline (c) Dimethylamine (d) Methyl amine

\(\mathrm{CH}_{3}-\mathrm{CH}_{2}-\mathrm{NH}_{2}+\mathrm{CHCl}_{3}+3 \mathrm{KOH}\) \(\mathrm{A}+\mathrm{B}+3 \mathrm{H}_{2} \mathrm{O}\) Here compound \(\mathrm{A}\) and \(\mathrm{B}\) are respectively? (a) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{CN}\) and \(3 \mathrm{KCl}\) (b) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CONH}_{2}\) and \(\mathrm{KCl}\) (c) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NC}\) and \(3 \mathrm{KCl}\) (d) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NC}\) and \(\mathrm{K}_{2} \mathrm{CO}_{3}\)