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JEE Advanced 2023 Paper 2 · Chemistry · Carbonyl Compounds, Carboxylic Acids and Amines · medium

Benzamide is treated with Br2/NaOH (aqueous, warm) to give A. Compound A reacts with NaNO2/HCl at 273–278 K to give B, which on warming with water…

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Benzamide is treated with Br2/NaOH\mathrm{Br_2/NaOH} (aqueous, warm) to give A\mathbf{A}. Compound A\mathbf{A} reacts with NaNO2/HCl\mathrm{NaNO_2/HCl} at 273273–278 K278\ \mathrm{K} to give B\mathbf{B}, which on warming with water gives C\mathbf{C} with evolution of a gas. C\mathbf{C} is then heated with CHCl3\mathrm{CHCl_3} and aqueous NaOH\mathrm{NaOH}, followed by acidification, to give the major product D\mathbf{D}. Which statement about D\mathbf{D} is correct?
  1. A. D\mathbf{D} is 2-hydroxybenzaldehyde, and it is steam volatile because of intramolecular hydrogen bonding
  2. B. D\mathbf{D} is 4-hydroxybenzaldehyde, and it is steam volatile because of intramolecular hydrogen bonding
  3. C. D\mathbf{D} is 2-hydroxybenzaldehyde, and it is less volatile than its 4-isomer because of intramolecular hydrogen bonding
  4. D. D\mathbf{D} is phenyl isocyanide, formed by the carbylamine reaction of C\mathbf{C}
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Answer: (A) D\mathbf{D} is 2-hydroxybenzaldehyde, and it is steam volatile because of intramolecular hydrogen bonding

Hofmann bromamide degradation: C6H5CONH2→Br2/NaOHC6H5NH2\mathrm{C_6H_5CONH_2\xrightarrow{Br_2/NaOH}C_6H_5NH_2} (A\mathbf{A}, aniline; one carbon is lost as carbonate). Diazotisation gives benzenediazonium chloride (B\mathbf{B}); warming with water replaces N2+\mathrm{N_2^+} by OH\mathrm{OH}, evolving N2\mathrm{N_2} and giving phenol (C\mathbf{C}). Reimer-Tiemann reaction of phenol: CHCl3/NaOH\mathrm{CHCl_3/NaOH} generates dichlorocarbene, which attacks the phenoxide ion mainly at the ortho position, so the major product is 2-hydroxybenzaldehyde (salicylaldehyde), with 4-hydroxybenzaldehyde minor. Salicylaldehyde has an intramolecular O-H...O=C hydrogen bond, so molecules do not associate with one another and it is more volatile and steam volatile; the 4-isomer is intermolecularly associated. The carbylamine reaction needs a primary amine, but C\mathbf{C} is a phenol. Hence option (A) is correct, (B) and (C) misplace the substituent or reverse the volatility argument.
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