Single correct option
Benzamide is treated with (aqueous, warm) to give . Compound reacts with at – to give , which on warming with water gives with evolution of a gas. is then heated with and aqueous , followed by acidification, to give the major product . Which statement about is correct?
- A. is 2-hydroxybenzaldehyde, and it is steam volatile because of intramolecular hydrogen bonding
- B. is 4-hydroxybenzaldehyde, and it is steam volatile because of intramolecular hydrogen bonding
- C. is 2-hydroxybenzaldehyde, and it is less volatile than its 4-isomer because of intramolecular hydrogen bonding
- D. is phenyl isocyanide, formed by the carbylamine reaction of
Show answer and solution
Answer: (A) is 2-hydroxybenzaldehyde, and it is steam volatile because of intramolecular hydrogen bonding
Hofmann bromamide degradation: (, aniline; one carbon is lost as carbonate). Diazotisation gives benzenediazonium chloride (); warming with water replaces by , evolving and giving phenol (). Reimer-Tiemann reaction of phenol: 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 is a phenol. Hence option (A) is correct, (B) and (C) misplace the substituent or reverse the volatility argument.
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