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Aldehydes Ketones and Carboxylic Acids question

2009 · Shift 1 · Q18
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Aldehydes Ketones and Carboxylic Acids question

2009 · Shift 1 · Q18

JEE AdvancedChemistryAldehydes Ketones and Carboxylic AcidsMCQ+3 / −1
A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBrMeMgBrMeMgBr followed by dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoes intramolecular aldol reaction to give predominantly S. IIT-JEE 2009 Paper 1 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 20 English ComprehensionThe structure of the product S is
  1. A
    IIT-JEE 2009 Paper 1 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 20 English Option 1
  2. B
    IIT-JEE 2009 Paper 1 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 20 English Option 2
  3. C
    IIT-JEE 2009 Paper 1 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 20 English Option 3
  4. D
    IIT-JEE 2009 Paper 1 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 20 English Option 4
View written solutionFree

Correct answer: B

  1. Identify carbonyl compound PPP from iodoform test

A compound gives positive iodoform test if it contains either:

  • a methyl ketone group, RCOCH3RCOCH_3RCOCH3​, or
  • an alcohol oxidizable to it.

Since PPP is itself a carbonyl compound, the relevant possibility is that PPP is a methyl ketone: P=RCOCH3P = RCOCH_3P=RCOCH3​

  1. Reaction with MeMgBrMeMgBrMeMgBr followed by dehydration

Methylmagnesium bromide adds a methyl group to the carbonyl carbon of the ketone: RCOCH3→MeMgBrR−C(OH)(CH3)2RCOCH_3 \xrightarrow{MeMgBr} R-C(OH)(CH_3)_2RCOCH3​MeMgBr​R−C(OH)(CH3​)2​

On dehydration, this tertiary alcohol gives an alkene QQQ. The most natural alkene formed is: Q=R−C(CH3)=CH2Q = R-C(CH_3)=CH_2Q=R−C(CH3​)=CH2​

So QQQ is an alkene having one end as =CH2=CH_2=CH2​ and the other alkene carbon attached to RRR and CH3CH_3CH3​.

  1. Ozonolysis of QQQ

For an alkene of type R−C(CH3)=CH2R-C(CH_3)=CH_2R−C(CH3​)=CH2​ ozonolysis cleaves the double bond to give:

  • formaldehyde from the terminal CH2CH_2CH2​
  • a carbonyl compound from the substituted carbon: RCOCH3RCOCH_3RCOCH3​

But the question says ozonolysis gives a dicarbonyl compound RRR (single molecule containing two carbonyl groups), which then undergoes intramolecular aldol reaction.

Therefore, the group RRR in P=RCOCH3P=RCOCH_3P=RCOCH3​ must itself contain another carbonyl in such a way that after ozonolysis, the product is a diketone/keto-aldehyde capable of cyclization.

The suitable starting methyl ketone is: P=CH3CO(CH2)3CHOP = CH_3CO(CH_2)_3CHOP=CH3​CO(CH2​)3​CHO

This is a carbonyl compound and contains the methyl ketone unit, so it gives iodoform test.

  1. Addition of MeMgBrMeMgBrMeMgBr and dehydration

For P=CH3CO(CH2)3CHOP = CH_3CO(CH_2)_3CHOP=CH3​CO(CH2​)3​CHO MeMgBrMeMgBrMeMgBr attacks the ketone carbonyl preferentially to give: CH3C(OH)(CH3)(CH2)3CHOCH_3C(OH)(CH_3)(CH_2)_3CHOCH3​C(OH)(CH3​)(CH2​)3​CHO

Dehydration gives: Q=CH2=C(CH3)(CH2)3CHOQ = CH_2=C(CH_3)(CH_2)_3CHOQ=CH2​=C(CH3​)(CH2​)3​CHO

  1. Ozonolysis of QQQ

Cleavage of CH2=C(CH3)(CH2)3CHOCH_2=C(CH_3)(CH_2)_3CHOCH2​=C(CH3​)(CH2​)3​CHO gives:

  • HCHOHCHOHCHO from terminal CH2CH_2CH2​
  • and the substituted carbon becomes a carbonyl: CH3CO(CH2)3CHOCH_3CO(CH_2)_3CHOCH3​CO(CH2​)3​CHO

Thus the dicarbonyl compound obtained is: R=CH3CO(CH2)3CHOR = CH_3CO(CH_2)_3CHOR=CH3​CO(CH2​)3​CHO which is a keto-aldehyde.

  1. Intramolecular aldol reaction of RRR

Now consider: R=CH3COCH2CH2CH2CHOR = CH_3COCH_2CH_2CH_2CHOR=CH3​COCH2​CH2​CH2​CHO

The enolate forms at the methyl ketone side, and intramolecular attack occurs on the aldehyde carbonyl. This gives the most favorable six-membered ring.

Cyclization leads to a β-hydroxy ketone, which under aldol conditions predominantly dehydrates to the conjugated product SSS:

S=3-methylcyclohex-2-en-1-oneS = \text{3-methylcyclohex-2-en-1-one}S=3-methylcyclohex-2-en-1-one

This is the standard predominant product from intramolecular aldol condensation of CH3CO(CH2)3CHOCH_3CO(CH_2)_3CHOCH3​CO(CH2​)3​CHO

  1. Match with options

Hence the correct structure is the option corresponding to: 3-methylcyclohex-2-en-1-one\boxed{\text{3-methylcyclohex-2-en-1-one}}3-methylcyclohex-2-en-1-one​

So the correct option is: B\boxed{B}B​

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