TH41645A - The process for carbonylation of allyl butenol or butenyl ester of carboxylic acid. - Google Patents

Abstract

DC60 (04/11/42) A process for the carbonylation of allylic butenol or butenyl esters of carboxylic acids (e.g., 3-acetoxybutene-1 and mixtures thereof) in anhydrous carboxylic acid solvents and the production of unsaturated beta-gamma carboxylic anhydrides (3-pentenoic acid anhydrides) using rhodium-supported catalysts (e.g., dicarbonyl acetyl acetonate rhodium (I)) supported by metal hydrides (e.g., dicarbonyl acetyl acetonate rhodium (I) or similar). Such a process is particularly useful in the production of unsaturated beta-gamma carboxylic anhydrides. Without the support of a reverse reaction that produces butadiene and carboxylic acids, processes for the carbonylation of allyl butenol or butenyl esters of carboxylic acids (e.g., 3-acetoxybutene-1 and mixtures of these) in anhydrous carboxylic acid solvents and the production of unsaturated beta-gamma carboxylic anhydrides (3-pentinoid acid anhydrides) using rhodium-supported catalysts (e.g., dicarbonyl acetyl acetonate rhodium (I)) supported by metal hydrides (e.g., dicarbonyl acetyl acetonate rhodium (I) or similar) are particularly useful for the production of unsaturated beta-gamma carboxylic anhydrides without the support of a reverse reaction that produces butadiene and carboxylic acids.

Claims (4)

1. The process for carbonylation of allylic butenol or butenyl esters of carboxylic acid and production of unsaturated beta-gamma carboxylic acid anhydride consists of the steps of (a) reaction of allylic butenol or butenyl esters of carboxylic acid with carbon monoxide in the presence of a rhodium-containing catalyst and iodide metal promoter in a C1-C20 carboxylic acid solvent under anhydrous conditions and (b) recovery of the unsaturated beta-gamma carboxylic acid anhydride. 2. The process of claim 1 in which the aforementioned allyl butenyl ester is selected from a group consisting of crotyl acetate, acetoxybutene-1 and a mixture of these compounds and an unsaturated beta-gamma carboxylic acid anhydride, namely 3-pentenoic acid anhydride. 3. The process of claim 2 in which the aforementioned metal halide promoter is selected from a group comprising CoI2, BI3, AII3, GaI3, GeI3, SnI4, LaI3, TiI4, ZrI4, crI3, MnI2, ZnI2 and HgI2. 4. The process of claim 3 in which the promoter of the metal halide is cobalt iodide.