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通过O-H原子转移对碳酸的直接脱碳功能化

  • 0Department of Chemistry , The University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599 , United States.

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Reactions of Carboxylic Acids: Introduction 01:41

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Carboxylic acids possess an acidic –COOH functional group. The acidity can be attributed to the resonance stabilization of their conjugate base, wherein the negative charge is delocalized over both oxygen atoms.

The acyl bond is polar because of the high electronegativity of oxygen, making the carbonyl carbon highly reactive and susceptible to nucleophilic attack. Thus, nucleophilic acyl substitution reactions can convert the –COOH to acid derivatives such as acyl halides, esters,...

Loss of Carboxy Group as CO<sub data-lazy-src=

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Carboxylic acids, upon heating, undergo a decarboxylation reaction by releasing carbon dioxide gas. Monocarboxylic acids do not undergo decarboxylation easily. However, a silver salt of carboxylic acid reacts with bromine or iodine under high temperature to release carbon dioxide gas and forms halide with one less carbon. This reaction is called the Hunsdiecker reaction.

Unlike monocarboxylic acids, ꞵ-keto acids bearing a keto group at the β position to the carboxyl group, readily undergo...

Preparation of Carboxylic Acids: Overview 01:31

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There are various methods for the preparation of carboxylic acids. For example, oxidation of primary alcohols or aldehydes using strong oxidizing agents results in a carboxylic acid.  Aldehydes can also be oxidized in the presence of mild oxidizing agents.

Alkyl benzenes, bearing at least one benzylic hydrogen, can be oxidized using KMnO4 or Na2Cr2O7 to yield benzoic acid exclusively. The reaction is carried out under vigorous conditions such as heat and high oxidant concentration. 

When...

Acid Halides to Carboxylic Acids: Hydrolysis 01:01

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Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...

α-Halogenation of Carboxylic Acid Derivatives: Overview 01:14

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Unlike aldehydes and ketones, carboxylic acids do not readily participate in α halogenation reactions via enols or enolate intermediates. However, α-halogenated acids are obtained through other methods. One of the approaches is the Hell–Volhard–Zelinsky (HVZ) reaction, wherein the carboxylic acid is treated with halogen in the presence of PBr3. It involves the conversion of acid to acid halide, which exists in equilibrium with its enol form. The enol attacks the...

Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents 01:13

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Carboxylic acids can be prepared by the carboxylation of Grignard reagents (RMgX). This method is convenient for converting alkyl (primary, secondary or tertiary), vinyl, benzyl, and aryl halides to carboxylic acids with one additional carbon than the starting RMgX.

The carboxylation mechanism involves two steps. In the first step, the nucleophilic attack of the Grignard reagent on the electrophilic site of the carbon dioxide generates the magnesium salt of the carboxylate ion. In the...