12th Class Chemistry Aldehydes, Ketones and Carboxylic Acids / ऐल्डिहाइड, कीटोन तथा कर्बोक्सिलिक अम्ल

  • question_answer 25)
    Give plausible explanation for each of the following: (i) Cyclohexanone forms cyanohydrin in good yield but2,2,6-tnmethyl cyclohexanone does not. (ii) These are two  groups in semicarbazide. However, only one is involved in the formation of semicarbazones. (iii) During the preparation of esters from a carboxylic acid and analcohol in the presence -of an acid catalyst, the water or the ester should be removed as soon as it is formed. (i) effect due to methyl groups: steric hindrance, make a carbonyl compound less reactive. (ii) Lone pair of electrons involved in conjugation with CO. (iii) Consider the reversible nature of the reaction.  

    Answer:

    (i) In 2,2,6 trimethyl cyclohexanone, three methyl groups arepresents at a-position with respect to the ketonic  group. Therefore, these groups cause steric hindrance during thenucleophilic attack of  ion so cyanohydrin is not formed. Dueto the absence of methyl groups in cyclohexanone, there is nosteric hindrance and cyanohydrin is formed. (ii) Resonance in semicarbazide   Semicarbazide has two amino  groups, out of which one isinvolved in resonance as shown above. Electron-density on this decreases and it does not act as a nucleophile. But the other  group (attached to NH) has lone pair ofelectrons which, are not involved in resonance. So, this pair isavailable for the nucleophilic attack on carbonyl group of aldehydes and/or ketones. (iii) Esterification is a reversible reaction. When the sufficient amount of products is formed, the rate offorward reaction decreases and the reverse reaction begins. Toavoid this condition i.e., in order to shift the equilibrium in forwarddirection, the concentration of products (ester and/or water)should be decreased. (Le-Chatelier's principle). So, water shouldbe removed from time to time.  


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