Organic Compounds Containing Nitrogen — JEE Main PYQs

Identify compounds A and E in the following reaction sequence.

[Figure: 1-ethyl-4-nitrobenzene (benzene ring with $\mathrm{C_2H_5}$ and $\mathrm{NO_2}$ para to each other)] $\xrightarrow{\mathrm{Br_2/AlBr_3}}$ A $\xrightarrow[\mathrm{HCl}]{\mathrm{Sn}}$ B $\xrightarrow[\text{273-278 K}]{\mathrm{NaNO_2/HCl}}$ C $\xrightarrow{\mathrm{C_2H_5OH}}$ D $\xrightarrow[\text{(ii) } \mathrm{H_3O^+}]{\text{(i) } \mathrm{KMnO_4/KOH}}$ E

Consider the following reactions sequence

[Figure: 1-methyl-4-nitrobenzene (benzene ring with $\mathrm{NO_2}$ and $\mathrm{H_3C}$ para to each other)] $\xrightarrow[\substack{\text{(ii) } \mathrm{(CH_3CO)_2O} \\ \text{(iii) } \mathrm{Br_2/AlBr_3} \\ \text{(iv) } \mathrm{H_3O^+}}]{\text{(i) } \mathrm{Sn/HCl;\ OH^-}}$ Major Product (P)

When the product (P) is subjected to Carius analysis using $\mathrm{AgNO_3}$, 1.0 g of the product (P) will produce __________ g of the precipitate of AgBr. (Nearest Integer)

(Given : molar mass in g mol$^{-1}$ C : 12, H : 1, O : 16, N : 14, Br : 80, Ag : 108)

Product C of the following reaction sequence will be

[Figure: aniline as starting material]

Aniline $\xrightarrow{\mathrm{Br_2/water}}$ A (Major Product) $\xrightarrow[273-278\ \mathrm{K}]{\mathrm{NaNO_2/HCl}}$ B $\xrightarrow[\text{(ii) } \mathrm{NaNO_2, Cu, \Delta}]{\text{(i) } \mathrm{HBF_4}}$ C

The strongest conjugate acid will result from:

Identify the incorrect statements.

A. [Figure: benzylamine] $\mathrm{C_6H_5CH_2NH_2}$ is a stronger base than [Figure: aniline] $\mathrm{C_6H_5NH_2}$ B. [Figure: 4-methoxyaniline (p-anisidine)] can be synthesized by Gabriel phthalimide synthesis. C. [Figure: 2-phenylacetamide, $\mathrm{C_6H_5CH_2CONH_2}$] $\xrightarrow{\mathrm{Br_2},\ \mathrm{NaOH}}$ primary aromatic amine D. [Figure: 4-nitroaniline] $\xrightarrow[\text{(ii) } \Delta]{\text{(i) } \mathrm{NaNO_2},\ \mathrm{HCl},\ 0^\circ\mathrm{C}}$ product will dissolve in NaOH

Choose the correct answer from the options given below:

Given below are two statements :

Statement I : Heating benzamide with bromine in an ethanolic solution of sodium hydroxide will give benzylamine.

Statement II : Nitration of aniline with $\mathrm{HNO_3/H_2SO_4}$ at 288 K produces m-nitroaniline in higher amount than o-nitroaniline (pH adjusted).

In the light of the above statements, choose the correct answer from the options given below :

Arrange the following compounds according to increasing order of boiling points.

$\mathrm{n\text{-}C_4H_9OH}$ (A), $\mathrm{n\text{-}C_4H_9NH_2}$ (B), $\mathrm{n\text{-}C_4H_{10}}$ (C) and $\mathrm{C_2H_5NHC_2H_5}$ (D).

Consider the following sequence of reactions.

[Figure: diazoaminobenzene, $\mathrm{C_6H_5{-}N{=}N{-}NH{-}C_6H_5}$] $\xrightarrow{\text{(i) HCl (ii) Aniline (in excess) (iii) Warm } 40-45^{\circ}\mathrm{C} \text{ (iv) Cool, acetic acid}}$ Yellow Product (X)

The percentage of nitrogen in the yellow product (X) formed is ________ %. (Nearest Integer)

(Given Molar mass in g mol$^{-1}$ H:1, C:12, N:14)

Consider the following organic reaction sequence. Choose the final product (X) from the following (consider the major product in all intermediate reactions)

[Figure: Propanoic acid, $\mathrm{CH_3CH_2COOH}$, as starting material]

$\mathrm{CH_3CH_2COOH} \xrightarrow[\text{(iv) } \mathrm{C_6H_5N_2Cl},\ 0^\circ\mathrm{C}]{\text{(i) } \mathrm{NH_3}/\Delta \quad \text{(ii) } \mathrm{NaOH/Br_2} \quad \text{(iii) } \mathrm{HNO_2/H_2O},\ 0^\circ\mathrm{C}}$ (X) Major Product

The number of compounds from the following which can undergo reaction with $\mathrm{Br_2}$/KOH (alcoholic) to give respective products and these respective products can also be obtained separately by Gabriel phthalimide reaction is :

[Figure: Six amide structures]

1. $\mathrm{C_6H_5{-}CO{-}NH_2}$ (benzamide)
2. $\mathrm{C_6H_5{-}CH_2{-}CO{-}NH_2}$ (2-phenylacetamide)
3. $\mathrm{CH_3{-}CO{-}NH_2}$ (acetamide)
4. $\mathrm{C_6H_{11}{-}CO{-}NHCH_2CH_3}$ (N-ethylcyclohexanecarboxamide)
5. $\mathrm{(CH_3)_3C{-}CO{-}NHCH_3}$ (N-methylpivalamide)
6. $\mathrm{C_6H_{11}{-}CO{-}NH_2}$ (cyclohexanecarboxamide)

Consider the following reaction.

[Figure: 2-(2-oxopiperidin-1-yl)propanal — a piperidin-2-one (six-membered lactam) whose ring N bears the $\mathrm{{-}CH(CH_3){-}CHO}$ group] $\xrightarrow{\text{(i) } \mathrm{NaBH_4}/\text{MeOH; (ii) NaOH(aq.), } \Delta \text{; (iii) } \mathrm{H_3O^+}}$ (P)

The major product (P) formed is :

Which statements are True ?

A. In Hoffmann bromamide degradation, 4 moles of NaOH and 2 moles of $\mathrm{Br_2}$ are consumed per mole of an amide

B. Hoffmann bromamide reaction is not given by alkyl amides.

C. Primary amines can be synthesized by Hoffmann bromamide degradation.

D. Secondary amide on reaction with $\mathrm{Br_2}$ and NaOH will give secondary amine.

E. The by-products of Hoffmann degradation are $\mathrm{Na_2CO_3}$, NaBr and $\mathrm{H_2O}$.

Choose the correct answer from the options given below :

The correct order of basic nature in aqueous solution for the bases $\mathrm{NH_3}$, $\mathrm{H_2N-NH_2}$, $\mathrm{CH_3CH_2NH_2}$, $\mathrm{(CH_3CH_2)_2NH}$ and $\mathrm{(CH_3CH_2)_3N}$ is :

When a concentrated solution of sulphanilic acid and 1-naphthylamine is treated with nitrous acid (273 K) and acidified with acetic acid, the mass (g) of 0.1 mole of product formed is :

(Given molar mass in $\mathrm{g\ mol^{-1}}$ H : 1, C : 12, N : 14, O : 16, S : 32)

Identify [A], [B] and [C], respectively in the following reaction sequence:

$$[\mathrm{A}] \xrightarrow[273-278~\mathrm{K}]{\mathrm{NaNO_2,~HCl}} \mathrm{C_6H_5\overset{+}{N_2}Cl^-} \xrightarrow{\mathrm{KI}} [\mathrm{B}] \xrightarrow[\text{Dry ether}]{2\mathrm{Na}} [\mathrm{C}]$$

[Figure: the intermediate is drawn as benzenediazonium chloride]

In the following reactions, which one is NOT correct?

[Figure: each option shows benzenediazonium chloride ($\mathrm{C_6H_5\overset{+}{N_2}Cl^-}$) converted to a product]

The sequence from the following that would result in giving predominantly 3, 4, 5-Tribromoaniline is :

X g of nitrobenzene on nitration gave 4.2 g of m-dinitrobenzene. X = __________ g. (nearest integer)

[Given : molar mass (in $\mathrm{g\ mol^{-1}}$) C : 12, H : 1, O : 16, N : 14]

The correct order of basicity for the following molecules is :

[Figure: three cyclic amide structures — (P) N-methylpiperidin-2-one (six-membered saturated lactam with N–Me); (Q) N-methyl-5,6-dihydropyridin-2(1H)-one (six-membered lactam with N–Me and a C=C conjugated with the C=O); (R) a bridged bicyclic lactam (1-azabicyclo[2.2.2]octan-2-one type) in which the nitrogen lone pair cannot conjugate with the C=O]

Which of the following amine (s) show (s) positive carbylamine test?

A. [Figure: aniline — $\mathrm{C_6H_5NH_2}$] B. $\mathrm{(CH_3)_2NH}$ C. $\mathrm{CH_3NH_2}$ D. $\mathrm{(CH_3)_3N}$ E. [Figure: N-methylaniline — $\mathrm{C_6H_5NH(CH_3)}$]

Choose the correct answer from the options given below:

The descending order of basicity of following amines is :

(A) aniline ($\mathrm{C_6H_5NH_2}$)

(B) 4-methoxyaniline ($\mathrm{4\text{-}MeO\text{-}C_6H_4NH_2}$)

(C) 4-nitroaniline ($\mathrm{4\text{-}O_2N\text{-}C_6H_4NH_2}$)

(D) $\mathrm{CH_3NH_2}$

(E) $\mathrm{(CH_3)_2NH}$

Choose the correct answer from the options given below :

$$\mathrm{A \xrightarrow[(ii)\ H_3O^+]{(i)\ NaOH} B \xrightarrow[(ii)\ H_2SO_4,\ \Delta]{(i)\ EtOH} C}$$

'A' shows positive Lassaign's test for N and its molar mass is 121.

'B' gives effervescence with aq $\mathrm{NaHCO_3}$.

'C' gives fruity smell.

Identify A, B and C from the following.

The products formed in the following reaction sequence are :

[Figure: benzene ring with $\mathrm{NO_2}$ group (nitrobenzene)]

$$\mathrm{C_6H_5NO_2} \xrightarrow{\text{(i) } \mathrm{Br_2}, \text{ AcOH; (ii) Sn, HCl; (iii) } \mathrm{NaNO_2}, \text{ HCl, 273 K; (iv) } \mathrm{C_2H_5OH}} \mathrm{A} + \mathrm{B}$$

Consider the following sequence of reactions :

[Figure: benzene ring with $\mathrm{NO_2}$ group (nitrobenzene)]

$$\mathrm{C_6H_5NO_2} \xrightarrow{\text{(i) Sn + HCl; (ii) } \mathrm{NaNO_2}, \text{ HCl, } 0°\mathrm{C}\text{; (iii) } \mathrm{Cu_2Cl_2}\text{; (iv) Na, Ether}} \mathrm{A}\ (\text{Product})$$

Molar mass of the product (A) formed is ________ $\mathrm{g\ mol^{-1}}$.

Match the compounds (List-I) with the appropriate catalyst/reagents (List-II) for their reduction into corresponding amines :

List-I (Compound)	List-II (Catalyst/Reagent)
(A) $\mathrm{R{-}\overset{\displaystyle O}{\overset{\|}{C}}{-}NH_2}$	(I) NaOH (aqueous)
(B) [Structure: nitrobenzene, $\mathrm{C_6H_5{-}NO_2}$]	(II) $\mathrm{H_2/Ni}$
(C) $\mathrm{R{-}C{\equiv}N}$	(III) $\mathrm{LiAlH_4,\ H_2O}$
(D) [Structure: N-alkyl phthalimide, N–R]	(IV) $\mathrm{Sn,\ HCl}$

Choose the correct answer from the options given below :

Which among the following react with Hinsberg's reagent?

A. $\mathrm{C_6H_5{-}NH_2}$ (aniline)

B. $\mathrm{C_6H_5{-}N(CH_3)_2}$ (N,N-dimethylaniline)

C. $\mathrm{CH_3{-}NH_2}$

D. $\mathrm{N(CH_3)_3}$

E. $\mathrm{(C_6H_5)_2NH}$ (diphenylamine)

Choose the correct answer from the options given below:

Consider the following sequence of reactions to produce major product (A)

[Figure: 3-nitrotoluene (benzene ring with $\mathrm{CH_3}$ group and $\mathrm{NO_2}$ at the meta position)]

$$\xrightarrow{\substack{\text{i) } \mathrm{Br_2},\ \mathrm{Fe} \\ \text{ii) } \mathrm{Sn}, \mathrm{HCl} \\ \text{iii) } \mathrm{NaNO_2}, \mathrm{HCl}, 273\,\mathrm{K} \\ \text{iv) } \mathrm{H_3PO_2}, \mathrm{H_2O}}} \text{(A) Major Product}$$

Molar mass of product (A) is _____ g mol$^{-1}$.

(Given molar mass in g mol$^{-1}$ of C : 12, H: 1, O :16, Br : 80, N : 14, P :31)

Consider the following sequence of reactions.

[Figure: reaction scheme] 4-ethoxyaniline (p-ethoxyaniline) $\xrightarrow[\text{0-5}^{\circ}\text{C}]{\text{(i) NaNO}_2,\ \text{HCl}}$ (A, the diazonium salt) $\xrightarrow[\text{(ii) dil. HCl}]{\text{(i) phenol, NaOH}}$ (B) (Molecular formula $\mathrm{C_{14}H_{14}N_2O_2}$) $\xrightarrow[\text{(ii) } \mathrm{H_3CCH_2Br}]{\text{(i) NaOH}}$ (C) (Molecular formula $\mathrm{C_{16}H_{18}N_2O_2}$)

Total number of $sp^3$ hybridised carbon atoms in the major product C formed is ________.

For reaction

[Figure: aniline (benzene ring with $\mathrm{-NH_2}$) $\rightarrow$ 2-bromoaniline (benzene ring with $\mathrm{-NH_2}$ and an ortho $\mathrm{-Br}$), labelled (Major)]

The correct order of set of reagents for the above conversion is :

[Stem unrecoverable: the PDF pages carrying this question's stem are corrupted in both the English and Hindi copies. The options indicate a five-statement (A-E) multiple-select question. Option texts below are recovered from the Hindi copy.]

Consider the following sequence of reactions:

[Figure: benzene ring with Cl substituent (Chlorobenzene)]

$$\text{Chlorobenzene} \xrightarrow[\substack{\text{ii) } \mathrm{CO_2, H_3O^+} \\ \text{iii) } \mathrm{NH_3},\ \Delta}]{\text{i) Mg, dry ether}} \mathrm{A} \xrightarrow{\mathrm{Br_2,\ NaOH}} \mathrm{B}$$

11.25 mg of chlorobenzene will produce ---- $\mathrm{x}10^{-1}$ mg of product B.

(Consider the reactions result in complete conversion.)

[Given molar mass of C, H, O, N and Cl as 12, 1, 16, 14 and 35.5 $\mathrm{g\ mol^{-1}}$ respectively]

The product B formed in the following reaction sequence is :

$$\text{4-methyl-(prop-1-en-1-yl)benzene} \xrightarrow[\text{(Major)}]{\mathrm{HCl}} (A) \xrightarrow[\text{(Major)}]{\mathrm{AgCN}} (B)$$

[Figure: reactant is 1-(prop-1-en-1-yl)-4-methylbenzene, i.e. p-tolyl–CH=CH–CH$_3$]

Identify correct statements :

(A) Primary amines do not give diazonium salts when treated with $\mathrm{NaNO_2}$ in acidic condition. (B) Aliphatic and aromatic primary amines on heating with $\mathrm{CHCl_3}$ and ethanolic KOH form carbylamines. (C) Secondary and tertiary amines also give carbylamine test. (D) Benzenesulfonyl chloride is known as Hinsberg's reagent. (E) Tertiary amines reacts with benzenesulfonyl chloride very easily.

Choose the correct answer from the options given below :

X g of ethylamine is subjected to reaction with $\mathrm{NaNO_2/HCl}$ followed by water; evolved dinitrogen gas which occupied 2.24 L volume at STP. X is ________ $\times 10^{-1}$ g.

From 6.55 g of aniline, the maximum amount of acetanilide that can be prepared will be ________ $\times 10^{-1}$ g.

Phthalimide is made to undergo following sequence of reactions.

$$\text{Phthalimide} \xrightarrow{\text{(i) KOH (ii) Benzylchloride}} \text{'P'}$$

Total number of $\pi$ bonds present in product 'P' is/are ________.

9.3 g of pure aniline is treated with bromine water at room temperature to give a white precipitate of the product 'P'. The mass of product 'P' obtaind is 26.4 g. The percentage yield is ________ %.

X g of ethanamine was subjected to reaction with $\mathrm{NaNO_2/HCl}$ followed by hydrolysis to liberate $\mathrm{N_2}$ and HCl. The HCl generated was completely neutralised by 0.2 moles of NaOH. X is ________ g.

9.3 g of pure aniline upon diazotisation followed by coupling with phenol gives an orange dye. The mass of orange dye produced (assume 100% yield/conversion) is _________ g. (nearest integer)

Identify the product (A) in the following reaction.

[Figure: benzene ring with $\mathrm{NH_2}$ group (aniline)] $\xrightarrow{\substack{\text{(i) } \mathrm{NaNO_2 + HCl} \\ \text{(ii) } \mathrm{Cu_2Cl_2} \\ \text{(iii) } \mathrm{NaOH},\ 623\ \mathrm{K},\ 300\ \mathrm{atm} \\ \text{(iv) } \mathrm{H^+}}}$ (A)

An amine (X) is prepared by ammonolysis of benzyl chloride. On adding p-toluenesulphonyl chloride to it the solution remains clear. Molar mass of the amine (X) formed is ________ $\mathrm{g\ mol^{-1}}$.

(Given molar mass in $\mathrm{gmol^{-1}}$ C : 12, H : 1, O : 16, N : 14)

If 279 g of aniline is reacted with one equivalent of benzenediazonium chloride, the maximum amount of aniline yellow formed will be _______ g. (nearest integer)

(consider complete conversion).

Number of amine compounds from the following giving solids which are soluble in NaOH upon reaction with Hinsberg's reagent is ________.

[Figure: eleven structures — (1) aniline $\mathrm{C_6H_5NH_2}$; (2) benzamide $\mathrm{C_6H_5CONH_2}$; (3) semicarbazide $\mathrm{H_2N{-}NH{-}CO{-}NH_2}$; (4) N-methylaniline $\mathrm{C_6H_5{-}NH{-}CH_3}$; (5) phenyl–NH– attached to a six-membered diene ring bearing NH2 (N-phenyl diamine structure); (6) urea $\mathrm{H_2N{-}CO{-}NH_2}$; (7) 2-methoxyaniline (benzene ring with NH2 and OCH3 on adjacent carbons); (8) propan-1-amine $\mathrm{CH_3CH_2CH_2NH_2}$; (9) triethylamine $\mathrm{(C_2H_5)_3N}$; (10) tertiary amine — N bearing ethyl, methyl and cyclohexylmethyl groups; (11) cyclohexylamine]

Given below are two statements :

Statement (I) : All the following compounds react with p-toluenesulfonyl chloride.

$\mathrm{C_6H_5NH_2}$ $\quad$ $\mathrm{(C_6H_5)_2NH}$ $\quad$ $\mathrm{(C_6H_5)_3N}$

Statement (II) : Their products in the above reaction are soluble is aqueous NaOH.

In the light of the above statements, choose the correct answer from the options given below :

Correct order of basic strength of Pyrrole, Pyridine and Piperidine is :

[Figure: structures of pyrrole (five-membered aromatic ring with N-H), pyridine (six-membered aromatic ring with N) and piperidine (saturated six-membered ring with N-H)]

Given below are two statements :

Statement (I) : Aminobenzene and aniline are same organic compounds.

Statement (II) : Aminobenzene and aniline are different organic compounds.

In the light of the above statements, choose the most appropriate answer from the options given below :

Given below are two statements :

Statement (I) : The $\mathrm{NH_2}$ group in Aniline is ortho and para directing and a powerful activating group.

Statement (II) : Aniline does not undergo Friedel-Craft's reaction (alkylation and acylation).

In the light of the above statements, choose the most appropriate answer from the options given below :

Number of compounds which give reaction with Hinsberg's reagent is ________.

[Figure: eleven structures — benzenediazonium chloride $\mathrm{C_6H_5N_2^+Cl^-}$; N-benzoylbenzamide (dibenzimide) $\mathrm{(C_6H_5CO)_2NH}$; aniline $\mathrm{C_6H_5NH_2}$; N-phenylpiperidine; N-methylbenzylamine $\mathrm{C_6H_5CH_2NHCH_3}$; trimethylamine $\mathrm{(CH_3)_3N}$; ethane-1,2-diamine $\mathrm{H_2NCH_2CH_2NH_2}$; piperidine; pyridine; propan-1-amine $\mathrm{CH_3CH_2CH_2NH_2}$; urea $\mathrm{H_2N{-}CO{-}NH_2}$]

Which of the following is strongest Bronsted base ?

The arenium ion which is not involved in the bromination of Aniline is ________.

The final product A, formed in the following multistep reaction sequence is :

$$\mathrm{C_6H_5Br} \xrightarrow{\substack{\text{(i) Mg, ether then } \mathrm{CO_2},\ \mathrm{H^+} \\ \text{(ii) } \mathrm{NH_3},\ \Delta \\ \text{(iii) } \mathrm{Br_2},\ \mathrm{NaOH}}} A$$

Following is a confirmatory test for aromatic primary amines. Identify reagent (A) and (B).

$$\mathrm{C_6H_5NH_2 \xrightarrow{(A)} C_6H_5\overset{\oplus}{N_2}\overset{\ominus}{Cl} \xrightarrow[\text{NaOH}]{(B)} \text{Scarlet red dye}}$$

The products A and B formed in the following reaction scheme are respectively

[Figure: benzene $\xrightarrow[\text{ii) Sn / HCl}]{\text{i) con. } \mathrm{HNO_3}/\text{Con. } \mathrm{H_2SO_4},\ 323-333\ \mathrm{K}}$ A $\xrightarrow[\text{ii) Phenol}]{\text{i) } \mathrm{NaNO_2},\ \mathrm{HCl},\ 273-278\ \mathrm{K}}$ B]

Given below are two statements :

Statement I : Aniline reacts with con. $\mathrm{H_2SO_4}$, followed by heating at 453 - 473 K gives p-aminobenzene sulphonic acid, which gives blood red colour in the 'Lassaigne's test'.

Statement II : In Friedel - Craft's alkylation and acylation reactions, aniline forms salt with the $\mathrm{AlCl_3}$ catalyst. Due to this, nitrogen of aniline aquires a positive charge and acts as deactivating group.

In the light of the above statements, choose the correct answer from the options given below :

The azo-dye ($Y$) formed in the following reactions is

Sulphanilic acid + $\mathrm{NaNO_2}$ + $\mathrm{CH_3COOH}$ → X.

$$\mathrm{X} + \text{naphthalen-1-amine} \longrightarrow \mathrm{Y}$$

[Figure: X reacting with 1-aminonaphthalene (naphthalene with $\mathrm{NH_2}$ at position 1)]

A compound ($x$) with molar mass $108\ \mathrm{g\ mol^{-1}}$ undergoes acetylation to give product with molar mass $192\ \mathrm{g\ mol^{-1}}$. The number of amino groups in the compund ($x$) is _______.