Aldehydes, Ketones and Carboxylic Acids appeared 46 times across 3 years — 5.3% of Chemistry.
This question is from Benzil-Benzilic Acid Rearrangement.
The major product (P) in the following reaction is :
Benzil-Benzilic Acid Rearrangement
A.
Benzil-Benzilic Acid Rearrangement
B.
Benzil-Benzilic Acid Rearrangement
C.
Benzil-Benzilic Acid Rearrangement
D.
Benzil-Benzilic Acid Rearrangement
Solution & Explanation
Related Formula
Intramolecular Cannizzaro-type reaction or Benzil-Benzilic acid rearrangement involves nucleophilic attack of hydroxide at a carbonyl group, followed by hydride transfer to the adjacent carbonyl carbon.
Core Logic
Let's analyze the starting compound, phenylglyoxal:
Ph-CO-CHO$$\mathrm{Ph-CO-CHO}$$
The aldehyde carbon (-CHO$-CHO$) is much more electrophilic than the ketone carbon (-CO-$-CO-$) due to less steric hindrance and absence of phenyl group electron donation.
Hydroxide ion (OH^-$\mathrm{OH}^-$) selectively attacks the aldehyde carbonyl carbon, forming a tetrahedral intermediate.
Benzil-Benzilic Acid Rearrangement
Step 1: Hydride Transfer Mechanism
The tetrahedral intermediate collapses, prompting an intramolecular hydride (H^-$H^-$) transfer to the adjacent ketone carbonyl carbon:
In asymmetrical 1,2-dicarbonyl systems with an aldehyde and a ketone, nucleophilic addition occurs preferentially at the more reactive aldehyde carbon. The hydrogen is then transferred as a hydride to the ketone carbon, yielding an α$\alpha$-hydroxy carboxylate salt.
Chapter Mix
Class 12 Chemistry: Aldehydes, Ketones and Carboxylic Acids
More Aldehydes, Ketones and Carboxylic Acids Previous-Year Questions — Page 9
Qjee_main_2024_30_jan_morningPreparation of Aldehydes
This reduction reaction is known as:
The image shows the catalytic hydrogenation of benzoyl chloride to benzaldehyde in the presence of Pd-BaSO4.
The reaction depicts the partial reduction of an acid chloride (benzoyl chloride) to an aldehyde (benzaldehyde) using hydrogen gas in the presence of a poisoned palladium catalyst (Pd supported on BaSO₄$BaSO_4$).
The image shows the catalytic hydrogenation of benzoyl chloride to benzaldehyde in the presence of Pd-BaSO4.
This specific reaction is known as the Rosenmund reduction.
Pattern Recognition
Acid Chloride + H₂, Pd/BaSO₄$H_2, Pd/BaSO_4$arrow$\rightarrow$ Aldehyde is strictly the Rosenmund reduction. The BaSO₄$BaSO_4$ poisons the catalyst to prevent over-reduction to an alcohol.
Chapter Mix
Class 12 Chemistry: Aldehydes, Ketones and Carboxylic Acids
Pathway 1 (Upper): Toluene is treated with Reagent 'A' and acetic anhydride (CH₃CO)₂O$(CH_3CO)_2O$ to form an intermediate (benzylidene diacetate), which on hydrolysis gives benzaldehyde. The reagent used here is Chromic oxide (CrO₃$CrO_3$). Thus, A is CrO₃$CrO_3$.
Pathway 2 (Lower): Toluene is treated with Reagent 'B' in CS₂$CS_2$ to form a chromium complex intermediate, which on hydrolysis yields benzaldehyde. This is the Etard reaction, and the reagent used is Chromyl chloride (CrO₂Cl₂$CrO_2Cl_2$). Thus, B is CrO₂Cl₂$CrO_2Cl_2$.
The image shows the oxidation of toluene to benzaldehyde via two different pathways requiring reagents A and B.
Step 1: Selection
Therefore, A = CrO₃$CrO_3$ and B = CrO₂Cl₂$CrO_2Cl_2$.
Pattern Recognition
Etard reaction always uses Chromyl chloride (CrO₂Cl₂$CrO_2Cl_2$). Oxidation of toluene with acetic anhydride uses Chromic acid (CrO₃$CrO_3$). Both stop the oxidation at the aldehyde stage via intermediate formation.
Chapter Mix
Class 12 Chemistry: Aldehydes, Ketones and Carboxylic Acids
Ethanal (CH₃CHO$CH_3CHO$) reacts with semicarbazide (H₂N-NH-CO-NH₂$H_2N-NH-CO-NH_2$) via nucleophilic addition followed by elimination of water to form a semicarbazone.
Step 1: Product Analysis
The product is Ethanal semicarbazone: CH₃-CH=N-NH-CO-NH₂$CH_3-CH=N-NH-CO-NH_2$.
Counting the nitrogen atoms in this structure:
The imine nitrogen (=N-$=N-$)
The amine nitrogen (-NH-$-NH-$)
The amide nitrogen (-NH₂$-NH_2$)
Total = 3 Nitrogen atoms.
Chapter Mix
Class 12 Chemistry: Aldehydes, Ketones and Carboxylic Acids
Qjee_main_2024_31_jan_eveningPreparation of Aldehydes and Ketones
Identify the name reaction.
The image shows the conversion of benzene to benzaldehyde using CO, HCl, and Anhydrous AlCl3/CuCl.
The reaction of benzene with carbon monoxide (CO$CO$) and hydrogen chloride (HCl$HCl$) in the presence of anhydrous aluminium chloride (AlCl₃$AlCl_3$) and cuprous chloride (CuCl$CuCl$) to give benzaldehyde is known as the Gatterman-Koch reaction.
The image shows the conversion of benzene to benzaldehyde using CO, HCl, and Anhydrous AlCl3/CuCl.
Pattern Recognition
CO + HCl arrow$CO + HCl \rightarrow$ Formyl chloride intermediate (in situ) with Lewis acid arrow$\rightarrow$ formylation of benzene. This is definitively the Gatterman-Koch formylation.
Chapter Mix
Class 12 Chemistry: Aldehydes, Ketones and Carboxylic Acids
Practice past-year questions one chapter at a time. Pick an exam → subject → chapter and get every PYQ for that topic — pulled together from all past papers — with the chapter's key formulas alongside.
.svg)
.svg)
.svg)
.svg)
.svg)
