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12.9 : Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives

Aldehydes are more reactive than carboxylic acids and hence, can get over-reduced to alcohol in the presence of strong reducing agents. Therefore, carboxylic acids areinefficient in preparing aldehydes using LAH.

Carboxylic acid derivatives like acid chlorides and esters are more easily reducible than the corresponding acids. The derivatives reduce in the presence of mild reducing agents to give aldehydes. Aldehydes can also be prepared by Rosenmund reduction, that is, the reduction of acid chloride via hydrogenation over a poisoned catalyst. Catalytic poisoning inhibits the over-reduction of aldehydes. A Grignard reagent reduces an acid chloride to tertiary alcohol via a ketone intermediate. The reaction can be stopped at the ketone stage using a milder reducing agent like the Gilman reagent (R2CuLi). Aryl ketones can be prepared by Friedel–Crafts acylationin which acid chloride is treated with benzene and AlCl3.

Another carboxylic acid derivative, an ester, can be reduced to an aldehyde using DIBAL-H at dry ice temperature to give an aldehyde. Ketones cannot be prepared directly from esters because ketones are more reactive than esters and tend to over-reduce to tertiary alcohol.

Tags
AldehydesKetonesCarboxylic AcidsAcid ChloridesEstersReducing AgentsLAHRosenmund ReductionCatalytic PoisoningGrignard ReagentTertiary AlcoholGilman ReagentFriedel Crafts AcylationDIBAL HOver reduction

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12.9 : Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives

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12.1 : Structures of Aldehydes and Ketones

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12.2 : IUPAC Nomenclature of Aldehydes

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12.3 : IUPAC Nomenclature of Ketones

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12.4 : Common Names of Aldehydes and Ketones

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12.5 : IR and UV–Vis Spectroscopy of Aldehydes and Ketones

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12.6 : NMR Spectroscopy and Mass Spectrometry of Aldehydes and Ketones

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12.7 : Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes

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12.8 : Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids

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12.10 : Nucleophilic Addition to the Carbonyl Group: General Mechanism

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12.11 : Aldehydes and Ketones with Water: Hydrate Formation

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12.12 : Aldehydes and Ketones with Alcohols: Hemiacetal Formation

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12.13 : Protecting Groups for Aldehydes and Ketones: Introduction

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12.14 : Acetals and Thioacetals as Protecting Groups for Aldehydes and Ketones

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12.15 : Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

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