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Question of 87

Q.(a) Complete the reaction: HCHO + C6H5CHO --50% NaOH--> [2 marks]

(b) Write a note on: Clemmensen reduction [2 marks]
(c) Carry out the following conversion: Ethanoic acid -> 2-Hydroxyethanoic acid [1 mark] OR
(a) An organic compound A with molecular formula C4H8O gives a red-orange precipitate on reaction with 2,4-DNP. Compound A does not reduce Tollens' reagent, but gives a yellow iodoform precipitate on reaction with I2 and NaOH. Compound A reacts with NaBH4 to give compound B, which on reaction with concentrated H2SO4 undergoes dehydration to give compound C. Ozonolysis of C gives two molecules of ethanal. Identify A, B and C, and write the possible reactions. [3 marks]
(b) Distinguish, with the help of a chemical test, between formaldehyde and formic acid. [1 mark]
(c) Give an example of the benzoin condensation reaction. [1 mark]
Tripura TbseHigher Secondary (+2 Stage) Examination 2023Subjective· 5mImportance★★★★★
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(a) Formaldehyde and benzaldehyde, both lacking alpha-H, undergo a CROSSED Cannizzaro reaction in 50% NaOH - formaldehyde is always the one oxidized (it is the better hydride donor), while benzaldehyde is reduced. (b) Clemmensen reduction converts C=O directly to CH2 using zinc amalgam and concentrated HCl. (c) Ethanoic acid is converted to glycolic acid via alpha-halogenation (HVZ reaction) followed by hydrolysis.

(a) HCHO + C6H5CHO --(50% NaOH)-->

Both formaldehyde and benzaldehyde have NO alpha-hydrogen, so neither can undergo an aldol reaction; instead, in the presence of concentrated (50%) NaOH, they undergo a CROSSED CANNIZZARO REACTION - an intermolecular disproportionation where one molecule is oxidized (to the carboxylate) and the other is reduced (to the alcohol). Formaldehyde, being a much better hydride donor (less hindered, more electrophilic carbonyl), is ALWAYS the one that gets oxidized in a crossed Cannizzaro with an aromatic aldehyde, while the aromatic aldehyde is reduced:

HCHO + C6H5CHO + NaOH --> HCOONa (sodium formate) + C6H5CH2OH (benzyl alcohol)

(b) Clemmensen reduction:

This is a method for reducing the carbonyl group (C=O) of an aldehyde or ketone directly and completely to a methylene group (-CH2-), using zinc amalgam [Zn(Hg)] and concentrated hydrochloric acid:

C=O --(Zn(Hg), conc. HCl)--> >CH2

It is particularly useful for reducing carbonyl compounds that are STABLE to acidic conditions (for base-sensitive substrates, the analogous Wolff-Kishner reduction, using NH2NH2/KOH, is used instead).

(c) Ethanoic acid -> 2-Hydroxyethanoic acid (glycolic acid): …

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