TH41644A - The process of preparing unsaturated beta-gamma esters. - Google Patents

Abstract

DC60 (04/11/42) The carbonylation process of allyl butenyl ethers (e.g., methylcrotyl ether, 3-methoxybutene-1 and mixtures of these, or mixtures of butadiene and alcohol (e.g., methanol), and the production of unsaturated beta-gamma-carboxylic acid esters (e.g., methyl-3-pentinoate) using rhodium-containing catalysts (e.g., rhodium(I) dicarbonylacetylate or similar) supported by iodide-containing compounds (e.g., HI, AII3, SnI4, TiI4, CrI3 and CoI2 or similar) is particularly useful for the production of difunctional monomers and intermediates in adipic acid synthesis. The following representative reaction shows butadiene in the presence of methanol under reaction conditions with a catalyst providing an intermediate. 3-methoxybutene-1 (an isomer relating to methylcrotyl ether), which is subsequently combined with carbon monoxide to produce methylphentinoate, is shown as the total carbonyl (chemical formula). The carbonylation process of allyl butenyl ethers (e.g., methylcrotyl ether, 3-methoxybutene-1 and mixtures of these, or mixtures of butadiene and alcohol (e.g., methanol)) and the production of unsaturated beta-gamma-carboxylic acid esters (e.g., methyl-3-phentinoate) using rhodium-containing catalysts (e.g., rhodium(I) dicarbonylacetylate or similar) supported by iodide-containing compounds (e.g., HI, AII3, SnI4, TiI4, CrI3 and CoI2 or similar) is particularly useful for the production of difunctional monomers. And the intermediates in the synthesis of atipic acid, the following representative reaction shows butadiene in the presence of methanol under catalytic conditions that yield the intermediate 3-methoxybutene-1 (an isomer related to methylcrotyl ether), which is subsequently combined with carbon monoxide to produce methylphentinoate. Total carbonyls are shown (chemical formula).

Claims (4)

1. The carbonylation process of allylic butenyl ether or a mixture of butadiene and alcohol and the production of unsaturated beta-gamma carboxylic acid esters consisting of the steps of (a) the reaction of allylic butenyl ether or a mixture of butadiene and alcohol with carbon monoxide in the presence of a rhodium-containing catalyst and an iodine-containing promoter, and (b) the recovery of the unsaturated beta-gamma carboxylic acid esters. 2. The process of claim 1 in which allyl butenyl ether is selected from a group consisting of methylcrotyl ether 3-methoxybutene-1 and a mixture of these compounds and the unsaturated beta-gamma carboxylic acid ester is methyl 3-pentenoate. 3. The process of claim 1, in which such carbonylation involves the reaction of butadiene and methanol and beta-gamma carboxylic acid, results in the ester methyl-3-pentenoate. 4. The process of claim 2 or 3 in which a promoter containing such iodide is selected from a group consisting of HI, AII3, SnI4, TiI4, CrI3, and CoI2, and a catalyst containing such rhodium is dicarboxylate acetylacetone rhodium (I).