Chapter 27

Aniline dissolved in dilute \(\mathrm{HCl}\) is reacted with sodium nitrate at \(0{ }^{\circ} \mathrm{C}\). This solution was added dropwise to a solution containing equimolar mixture of aniline and phenol in dil. HCl. The structure of the major product is:

A compound ' \(\mathrm{X}^{\prime}\) on treatment with \(\mathrm{Br}_{2} / \mathrm{NaOH}\), provided \(\mathrm{C}_{3} \mathrm{H}_{9} \mathrm{~N}\), which gives positive carbylamine test. Compound ' \(X\) ' is :

The most appropriate reagent for conversion of \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{CN}\) into \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{NH}_{2}\) is :(a) \(\mathrm{NaBH}_{4}\) (b) \(\mathrm{CaH}_{2}\)(c) \(\mathrm{LiAlH}_{4}\) (d) \(\mathrm{Na}(\mathrm{CN}) \mathrm{BH}_{3}\)

Conversion of benzene diazonium chloride to chlorobenzene is an example of which of the following reactions?(a) Claisen (b) Friedel-craft (c) Sandmeyer (d) Wurtz

Complete reduction of benzene-diazonium chloride with \(\mathrm{Zn} / \mathrm{HCl}\) gives:Complete reduction of benzene-diazonium chloride with \(\mathrm{Zn} / \mathrm{HCl}\) gives:

Fluorination of an aromatic ring is easily accomplished by treating a diazonium salt with \(\mathrm{HBF}_{4}\). Which of the following conditions is correct about this reaction?(a) \(\mathrm{NaF} / \mathrm{Cu}\) (b) \(\mathrm{Cu}_{2} \mathrm{O} / \mathrm{H}_{2} \mathrm{O}\) (c) Only heat (d) \(\mathrm{NaNO}_{2} / \mathrm{Cu}\)

In the following reaction,$$ \mathrm{CH}_{3} \mathrm{NH}_{2}+\mathrm{CHCl}_{3}+\mathrm{KOH} $$ \(\rightarrow\) Nitrogen containing compound \(+\mathrm{KCl}+\mathrm{H}_{2} \mathrm{O} .\) The nitrogen containing compound is (a) \(\mathrm{CH}_{3}-\mathrm{NH}-\mathrm{CH}_{3}\)(b) \(\mathrm{CH}_{3}-\mathrm{C} \equiv \mathrm{N}\) (c) \(\mathrm{CH}_{3}-\mathrm{N} \equiv \overline{\mathrm{C}}^{+}\) (d) \(\mathrm{CH}_{3}-\overline{\mathrm{N}} \equiv \mathrm{C}^{-}+\mathrm{C}\)

When benzenesulfonic acid and \(p\)-nitrophenol are treated with \(\mathrm{NaHCO}_{3}\), the gases released respectively are(a) \(\mathrm{SO}_{2}, \mathrm{NO}\) (b) \(\mathrm{SO}_{2}, \mathrm{NO}_{2}\) (c) \(\mathrm{CO}_{2}, \mathrm{CO}_{2}\) (d) \(\mathrm{SO}_{2}, \mathrm{CO}_{2}\)

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

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

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

Hinsberg's reagent is:(a) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{COCl}\) (b) \(\mathrm{SOCl}_{2}\) (c) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{SO}_{2} \mathrm{Cl}\) (d) \((\mathrm{COCl})_{2}\)

The formation of cyanohydrin from a ketone is an example of :(a) Electrophilic addition (b) Nucleophilic addition (c) Nucleophilic substitution (d) Electrophilic substiution

Which of the following amines can be prepared by Gabriel phthalimide reaction? \(\quad[\) Main April 8, 2019 (I)](a) \(n\)-butylamine (b) triethylamine (c) \(t\)-butylamine (d) neo-pentylamine

The compound that is most reactive towards electrophilic nitration is(a) toluene (b) benzene (c) benzoic acid (d) nitrobenzene

How would you synthesise 4-methoxyphenol from bromobenzene in NOT more than five steps? State clearly the reagents used in each step and show the structures of the intermediate compounds in your synthetic scheme.

Amongst the three isomers of nitrophenol, the one that is least soluble in water is ...............

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

The products of reaction of alcoholic silver nitrite with ethyl bromide are(a) ethane (b) ethene (c) nitroethane (d) ethyl alcohol (e) ethyl nitrite

Match each of the compounds in Column I with its characteristic reaction(s) in Column II.Column I Column II (A) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CN}\) (p) Reduction with \(\mathrm{Pd}-\mathrm{C} / \mathrm{H}_{2}\) (B) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{OCOCH}_{3}\) (q) Reduction with \(\mathrm{SnCl}_{2} / \mathrm{HCl}\) (C) \(\mathrm{CH}_{3}-\mathrm{CH}=\mathrm{CH}-\mathrm{CH}_{2} \mathrm{OH}\) (r) Development of foul smell on treatment with chloroform and alcoholic KOH (D) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{NH}_{2}\) (s) Reduction with diisobutylaluminium hydride(DIBAL-H) (t) Alkaline hydrolysis

Statement - 1: \(p\)-Nitrophenol is a stronger acid thano-nitrophenol. Statement - 2 : Intramolecular hydrogen bonding makes the o-isomer weaker than the \(p\)-isomer.

In the Hofmann bromamide degradation reaction, the number of moles of \(\mathrm{NaOH}\) and \(\mathrm{Br}_{2}\) used per mole of amine produced are :(a) Two moles of \(\mathrm{NaOH}\) and two moles of \(\mathrm{Br}_{2}\). (b) Four moles of \(\mathrm{NaOH}\) and one mole of \(\mathrm{Br}_{2}\). (c) One mole of \(\mathrm{NaOH}\) and one mole of \(\mathrm{Br}_{2}\). (d) Four moles of \(\mathrm{NaOH}\) and two moles of \(\mathrm{Br}_{2}\).

The test to distinguish primary, secondary and tertiary amines is :(a) Sandmeyer's reaction (b) Carbylamine reaction (c) Mustard oil test (d) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{SO}_{2} \mathrm{Cl}\)

On heating an aliphatic primary amine with chloroform and ethanolic potassium hydroxide, the organic compound formed is:(a) an alkanol (b) an alkanediol (c) an alkyl cyanide (d) an alkyl isocyanide

The final product formed when methyl amine is treated with \(\mathrm{NaNO}_{2}\) and \(\mathrm{HCl}\) is:(a) Diazomethane (b) Methylalcohol (c) Methylcyanide (d) Nitromethane

Show with equations how the following compounds are prepared (equations need not be balanced):(i) 4 -nitrobenzaldehyde from benzene. (ii) \(p\)-bromonitrobenzene from benzene in two steps. (iii) toluene to \(m\)-nitrobenzoic acid?

A compound with molecular mass 180 is acylated with \(\mathrm{CH}_{3} \mathrm{COCl}\) to get a compound with molecular mass 390 . The number of amino groups present per molecule of the former compound is :(a) 2 (b) 5 (c) 4 (d) 6

The order of basicity of amines in gaseous state is :(a) \(1^{\circ}>2^{\circ}>3^{\circ}>\mathrm{NH}_{3}\) (b) \(3^{\circ}>2^{\circ}>\mathrm{NH}_{3}>1^{\circ}\) (c) \(3^{\circ}>2^{\circ}>1^{\circ}>\mathrm{NH}_{3}\) (d) \(\mathrm{NH}_{2}>1^{\circ}>2^{\circ}>3^{\circ}\)

\(\frac{\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}}{\mathrm{DMF}, \Delta}(\mathrm{A}) \frac{\text { i) } \mathrm{NaNO}_{2} / \mathrm{HCl}}{0^{\circ}-5^{\circ} \mathrm{C}}{\longrightarrow}(\mathrm{B}) .\) (B) is: ii) \(\mathrm{H}_{2} / \mathrm{Ni}\)

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

In the reaction \(p\)-chlorotoluene with \(\mathrm{KNH}_{2}\) in liq. \(\mathrm{NH}_{3}\),the major product is:(a) \(o\)-toluidine (b) \(m\)-toluidine (c) \(p\)-toluidine (d) \(p\)-chloroaniline.

Amongst the following, the most basic compound is :(a) Benzylamine (b) Aniline (c) Acetanilide (d) \(p\)-Nitroaniline

Carbylamine test is performed in alcoholic \(\mathrm{KOH}\) by heating a mixture of :(a) chloroform and silver powder (b) trihalogenatedmethane and a primary amine (c) an alkyl halide and a primary amine (d) an alkyl cyanide and a primary amine

Acetamide is treated separately with the following reagents. Which one of these would give methylamine?(a) \(\mathrm{PCl}_{5}\) (b) \(\mathrm{NaOH}+\mathrm{Br}_{2}\) (c) soda lime(d) hot conc. \(\mathrm{H}_{2} \mathrm{SO}_{4}\)

The compound which on reaction with aqueous nitrous acid at low temperature produces an oily nitrosoamine is(a) methylamine (b) ethylamine (c) diethylamine (d) triethylamine

Consider the reaction sequence from \(\mathbf{P}\) to \(\mathbf{Q}\) shown below. The overall yield of the major product \(\mathbf{Q}\) from \(\mathbf{P}\) is \(75 \%\). What is the amount in grams of \(\mathbf{Q}\) obtained from \(9.3 \mathrm{~mL}\) of \(\mathbf{P} ?\) (Use density of \(\mathbf{P}=1.00 \mathrm{~g}\) \(\mathrm{mL}^{-1} ;\) Molar mass of \(\mathrm{C}=12.0, \mathrm{H}=1.0, \mathrm{O}=16.0\) and \(\mathrm{N}=14.0 \mathrm{~g} \mathrm{~mol}^{-}\) ')

In an acidic medium, ................. behaves as the strongest base. (nitrobenzene, aniline, phenol)

Hydrogen bonding plays a central role in the following phenomena(a) Ice floats in water (b) Higher Lewis basicity of primary amines than tertiary amines in aqueous solutions (c) Formic acid is more acidic than acetic acid (d) Dimerisation of acetic acid in benzene

A positive carbylamine test is given by(a) \(\mathrm{N}, \mathrm{N}-\) dimethylaniline (b) 2,4 -dimethylaniline (c) N-methyl-o-methylaniline (d) \(p\)-methylbenzylamine

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

\(p\)-Chloroaniline and anilinium hydrochloride can be distinguished by(a) Sandmeyer reaction (b) \(\mathrm{NaHCO}_{3}\) (c) \(\mathrm{AgNO}_{3}\) (d) Carbylamine test

Statement-1 : In strongly acidic solutions, aniline becomes more reactive towards electrophilic reagents. Statement-2 : The amino group being completely protonated in strongly acidic solution, the lone pair of electrons on the nitrogen isno longer available for resonance. [2001S] (a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1. (b) Statement- 1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (c) Statement- 1 is True, Statement- 2 is False (d) Statement-1 is False, Statement-2 is True

There is a solution of \(p\)-hydroxybenzoic acid and \(p\)-aminobenzoic acid. Discuss one method by which we can separate them and also write down the confirmatory tests of the functional groups present.

Compound \(A\left(\mathrm{C}_{8} \mathrm{H}_{8} \mathrm{O}\right)\) on treatment with \(\mathrm{NH}_{2} \mathrm{OH} . \mathrm{HCl}\) gives \(B\) and \(C\). \(B\) and \(C\) rearrange to give \(D\) and \(E\), respectively, on treatment with acid \(B, C, D\) and \(E\) are all isomers of molecular formula \(\left(\mathrm{C}_{8} \mathrm{H}_{9} \mathrm{NO}\right)\). When \(D\) is boiled with alcoholic \(\mathrm{KOH}\) an oil \(\mathrm{F}\left(\mathrm{C}_{6} \mathrm{H}_{7} \mathrm{~N}\right)\) separates out. \(\mathrm{F}\) reacts rapidly with \(\mathrm{CH}_{3} \mathrm{COCI}\) to give back \(D .\) On the other hand, \(E\)on boiling with alkali followed by acidification gives a white solid \(G\) \(\left(\mathrm{C}_{7} \mathrm{H}_{6} \mathrm{O}_{2}\right)\). Identify \(A\)-G. \(\quad\) [1999 - 7 Marks]

Complete the following with appropriate structures:(i) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{NH}_{2} \stackrel{\left(\mathrm{CH}_{3} \mathrm{CO}\right)_{2} \mathrm{O}, \text { heat }}{\longrightarrow} 2\) products (ii) \(\mathrm{CH}_{3} \mathrm{CONHC}_{6} \mathrm{H}_{5} \stackrel{\mathrm{Br}_{2}, \mathrm{Fe}}{\longrightarrow} 2\) products (iii) \(\triangle \mathrm{NH}_{2}+\langle 0\rangle-\mathrm{COCl}\) base \(?\) Nc1ccccc1N

Give reasons for the following : (i) Dimethylamine is a stronger base than trimethylamine [19 (ii) Cyclohexylamine is a stronger base than aniline.

Acetophenone on reaction with hydroxylamine hydrochloride can produce two isomeric oximes. Write structures of the oximes.

Write the structure of the foul-smelling compound obtained when aniline is treated with chloroform in the presence of \(\mathrm{KOH}\).

A basic, volatile nitrogen compound gave a foul smelling gas when treated with chloroform and alcoholic potash. A \(0.295 \mathrm{~g}\) sample of the substance. dissolved in aq. HCl and treated with \(\mathrm{NaNO}_{2}\) solution at \(0^{\circ} \mathrm{C}\), liberated a colorless, odourless gas whose volume corresponded to \(112 \mathrm{~mL}\) at STP. After the evolution of the gas was complete, the aqueous solution was distilled to give an organic liquid which did not contain nitrogen and which on warming with alkali and iodine gave a yellow precipitate. Identify the original substance. Assume that it contains one \(\mathrm{N}\) atom per molecule.

A mixture of two aromatic compounds \(A\) and \(B\) was separated by dissolving a chloroform followed by extraction with aqueous \(\mathrm{KOH}\) solution. The organic layer containing compound \(A\), when heated with alcoholic solution of \(\mathrm{KOH}\) produced a compound \(\mathrm{C}\left(\mathrm{C}_{7} \mathrm{H}_{5} \mathrm{~N}\right)\) associated with an unpleasant odour. The alkaline aqueous layer on the other hand, when heated with chloroform and then acidified gave a mixture of two isomeric compounds \(D\) and \(E\) of molecular formula \(\mathrm{C}_{7} \mathrm{H}_{6} \mathrm{O}_{2}\). Identify the compounds \(A, B, C, D, E\) and write their structures.