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Aldehydes Ketones and Carboxylic Acids question

2015 · Shift 2 · Q19
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Aldehydes Ketones and Carboxylic Acids question

2015 · Shift 2 · Q19

JEE AdvancedChemistryAldehydes Ketones and Carboxylic AcidsMultiple correct+4 / −2
In the following reactions JEE Advanced 2015 Paper 2 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 46 English Compound X is
  1. A
    JEE Advanced 2015 Paper 2 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 46 English Option 1
  2. B
    JEE Advanced 2015 Paper 2 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 46 English Option 2
  3. C
    JEE Advanced 2015 Paper 2 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 46 English Option 3
  4. D
    JEE Advanced 2015 Paper 2 Offline Chemistry - Aldehydes, Ketones and Carboxylic Acids Question 46 English Option 4
View written solutionFree

Correct answer: C

The user wants me to identify compound X in a multi-step reaction sequence.

Step-by-step analysis of the reaction sequence:

  1. Formation of P: Benzene reacts with acetyl chloride (CH3COClCH_3COClCH3​COCl) in the presence of anhydrous AlCl3AlCl_3AlCl3​. This is a Friedel-Crafts Acylation reaction. The electrophile is the acylium ion (CH3C+=OCH_3C^+=OCH3​C+=O), which attacks the benzene ring to form acetophenone. C6H6+CH3COCl→Anhydrous AlCl3C6H5COCH3+HClC_6H_6 + CH_3COCl \xrightarrow{Anhydrous~AlCl_3} C_6H_5COCH_3 + HClC6​H6​+CH3​COClAnhydrous AlCl3​​C6​H5​COCH3​+HCl So, compound P is Acetophenone.

  2. Formation of Q: Compound P (Acetophenone) reacts with methyl magnesium bromide (CH3MgBrCH_3MgBrCH3​MgBr) followed by acidic workup (H3O+H_3O^+H3​O+). This is a Grignard reaction. The nucleophilic methyl group from the Grignard reagent attacks the carbonyl carbon of acetophenone. The subsequent hydrolysis yields a tertiary alcohol. C6H5COCH3→1.CH3MgBr2.H3O+C6H5C(OH)(CH3)2C_6H_5COCH_3 \xrightarrow{1. CH_3MgBr \quad 2. H_3O^+} C_6H_5C(OH)(CH_3)_2C6​H5​COCH3​1.CH3​MgBr2.H3​O+​C6​H5​C(OH)(CH3​)2​ So, compound Q is 2-phenylpropan-2-ol.

  3. Formation of R: Compound Q (2-phenylpropan-2-ol) is heated with concentrated sulfuric acid (H2SO4H_2SO_4H2​SO4​). This is an acid-catalyzed dehydration of an alcohol. A water molecule is eliminated to form an alkene. The reaction proceeds via a stable tertiary benzylic carbocation intermediate. C6H5C(OH)(CH3)2→H2SO4,ΔC6H5C(CH3)=CH2+H2OC_6H_5C(OH)(CH_3)_2 \xrightarrow{H_2SO_4, \Delta} C_6H_5C(CH_3)=CH_2 + H_2OC6​H5​C(OH)(CH3​)2​H2​SO4​,Δ​C6​H5​C(CH3​)=CH2​+H2​O So, compound R is 2-phenylpropene (also known as α\alphaα-methylstyrene).

  4. Formation of S and T: Compound R (2-phenylpropene) undergoes reductive ozonolysis (1.O3,2.Zn/H2O1. O_3, 2. Zn/H_2O1.O3​,2.Zn/H2​O). This reaction cleaves the double bond, and each carbon atom of the double bond is converted into a carbonyl group. C6H5C(CH3)=CH2→1.O32.Zn,H2OC6H5COCH3+HCHOC_6H_5C(CH_3)=CH_2 \xrightarrow{1. O_3 \quad 2. Zn, H_2O} C_6H_5COCH_3 + HCHOC6​H5​C(CH3​)=CH2​1.O3​2.Zn,H2​O​C6​H5​COCH3​+HCHO The products are Acetophenone and Formaldehyde. Given the subsequent reactions involving S, compound S is Acetophenone and compound T is Formaldehyde.

  5. Formation of X: Compound X is formed by the reaction of S (Acetophenone, C6H5COCH3C_6H_5COCH_3C6​H5​COCH3​) with benzaldehyde (Ph−CHOPh-CHOPh−CHO) in the presence of aqueous NaOHNaOHNaOH. This is a base-catalyzed crossed aldol condensation, specifically a Claisen-Schmidt condensation.

    • Enolate formation: The hydroxide ion (OH−OH^-OH−) removes an acidic α\alphaα-proton from acetophenone to form a nucleophilic enolate ion. C6H5−CO−CH3+OH−⇌[C6H5−CO−CˉH2]+H2OC_6H_5-CO-CH_3 + OH^- \rightleftharpoons [C_6H_5-CO-\bar{C}H_2] + H_2OC6​H5​−CO−CH3​+OH−⇌[C6​H5​−CO−CˉH2​]+H2​O
    • Nucleophilic attack: The enolate attacks the electrophilic carbonyl carbon of benzaldehyde (which has no α\alphaα-protons and cannot form an enolate). [C6H5−CO−CˉH2]+C6H5−CHO→C6H5−CO−CH2−CH(O−)−C6H5[C_6H_5-CO-\bar{C}H_2] + C_6H_5-CHO \rightarrow C_6H_5-CO-CH_2-CH(O^-)-C_6H_5[C6​H5​−CO−CˉH2​]+C6​H5​−CHO→C6​H5​−CO−CH2​−CH(O−)−C6​H5​
    • Protonation and Dehydration: The intermediate alkoxide is protonated by water to form a β\betaβ-hydroxy ketone. This aldol addition product readily dehydrates upon heating (or even spontaneously) to form a stable, conjugated α,β\alpha, \betaα,β-unsaturated ketone. The dehydration is highly favorable due to the extended conjugation in the product involving two phenyl rings and a carbonyl group. C6H5−CO−CH2−CH(OH)−C6H5→−H2OC6H5−CO−CH=CH−C6H5C_6H_5-CO-CH_2-CH(OH)-C_6H_5 \xrightarrow{-H_2O} C_6H_5-CO-CH=CH-C_6H_5C6​H5​−CO−CH2​−CH(OH)−C6​H5​−H2​O​C6​H5​−CO−CH=CH−C6​H5​ The final product, compound X, is 1,3-diphenyl-2-propen-1-one, commonly known as Benzalacetophenone or Chalcone.

Conclusion:

Based on the analysis, compound X is Chalcone (C6H5−CO−CH=CH−C6H5C_6H_5-CO-CH=CH-C_6H_5C6​H5​−CO−CH=CH−C6​H5​). Comparing this structure to the given options, it matches the structure in option C.

The provided image for option C is C6H5−C(=O)−CH=CH−C6H5C_6H_5-C(=O)-CH=CH-C_6H_5C6​H5​−C(=O)−CH=CH−C6​H5​, which is the correct structure for Chalcone.

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