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Aldehydes Ketones and Carboxylic Acids question

2017 · Shift 0 · Q3
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Aldehydes Ketones and Carboxylic Acids question

2017 · Shift 0 · Q3

JEE MainChemistryAldehydes Ketones and Carboxylic AcidsMCQ+4 / −1
The correct sequence of reagents for the following conversion will be : JEE Main 2017 (Offline) Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 231 English
  1. A
    CH3MgBrCH_3MgBrCH3​MgBr, H+H^+H+/ CH3OHCH_3OHCH3​OH, [Ag(NH3)2]+[Ag(NH_3)_2]^+[Ag(NH3​)2​]+OH−OH^-OH−
  2. B
    [Ag(NH3)2]+[Ag(NH_3)_2]^+[Ag(NH3​)2​]+OH−OH^-OH−, CH3MgBrCH_3MgBrCH3​MgBr, H+H^+H+/ CH3OHCH_3OHCH3​OH
  3. C
    [Ag(NH3)2]+[Ag(NH_3)_2]^+[Ag(NH3​)2​]+OH−OH^-OH−, H+H^+H+/ CH3OHCH_3OHCH3​OH, CH3MgBrCH_3MgBrCH3​MgBr
  4. D
    CH3MgBrCH_3MgBrCH3​MgBr, [Ag(NH3)2]+[Ag(NH_3)_2]^+[Ag(NH3​)2​]+OH−OH^-OH−, H+H^+H+/ CH3OHCH_3OHCH3​OH
View written solutionFree

Correct answer: C

To determine the correct sequence, let us identify the role of each reagent.

1. Identify the reagents

  1. Tollen's reagent: [Ag(NH3)2]+OH−[Ag(NH_3)_2]^+OH^-[Ag(NH3​)2​]+OH− This oxidizes an aldehyde to the corresponding carboxylate/carboxylic acid.

  2. Grignard reagent: CH3MgBrCH_3MgBrCH3​MgBr This adds a methyl group to a carbonyl compound. It reacts with aldehydes/ketones, but it is destroyed by acidic proton sources.

  3. Acidic methanol: H+/CH3OHH^+/CH_3OHH+/CH3​OH This is used for esterification of a carboxylic acid to the methyl ester.


2. Logical order of transformation

For such a sequence, the only sensible order is:

  1. Oxidize aldehyde to carboxylic acid using Tollen's reagent.
  2. Convert carboxylic acid to methyl ester using H+/CH3OHH^+/CH_3OHH+/CH3​OH.
  3. React ester with Grignard reagent CH3MgBrCH_3MgBrCH3​MgBr, which ultimately gives a tertiary alcohol after hydrolysis.

Thus the sequence is: [Ag(NH3)2]+OH−→H+/CH3OH→CH3MgBr[Ag(NH_3)_2]^+OH^- \rightarrow H^+/CH_3OH \rightarrow CH_3MgBr[Ag(NH3​)2​]+OH−→H+/CH3​OH→CH3​MgBr


3. Check the options

Option A

CH3MgBr, H+/CH3OH, [Ag(NH3)2]+OH−CH_3MgBr,\ H^+/CH_3OH,\ [Ag(NH_3)_2]^+OH^-CH3​MgBr, H+/CH3​OH, [Ag(NH3​)2​]+OH− Incorrect. Grignard reagent cannot be used first if oxidation and esterification are needed later in this manner.

Option B

[Ag(NH3)2]+OH−, CH3MgBr, H+/CH3OH[Ag(NH_3)_2]^+OH^-,\ CH_3MgBr,\ H^+/CH_3OH[Ag(NH3​)2​]+OH−, CH3​MgBr, H+/CH3​OH Incorrect. After oxidation to acid, Grignard reagent will be quenched by the acidic proton of the carboxylic acid.

Option C

[Ag(NH3)2]+OH−, H+/CH3OH, CH3MgBr[Ag(NH_3)_2]^+OH^-,\ H^+/CH_3OH,\ CH_3MgBr[Ag(NH3​)2​]+OH−, H+/CH3​OH, CH3​MgBr Correct. This is the proper order:

  • aldehyde →\to→ acid
  • acid →\to→ methyl ester
  • ester →\to→ tertiary alcohol via Grignard reaction

Option D

CH3MgBr, [Ag(NH3)2]+OH−, H+/CH3OHCH_3MgBr,\ [Ag(NH_3)_2]^+OH^-,\ H^+/CH_3OHCH3​MgBr, [Ag(NH3​)2​]+OH−, H+/CH3​OH Incorrect. Tollen's reagent is not used after Grignard addition in such a sequence.


4. Final answer

The correct sequence of reagents is: [Ag(NH3)2]+OH−, H+/CH3OH, CH3MgBr\boxed{[Ag(NH_3)_2]^+OH^-,\ H^+/CH_3OH,\ CH_3MgBr}[Ag(NH3​)2​]+OH−, H+/CH3​OH, CH3​MgBr​

So, the correct option is C.

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