Reactions of Organometallic Compounds with Ethylenically Unsaturated Compounds

摘要

1,170,825. Reactions of organometallic compounds with unsaturated organic compounds. HERCULES Inc. 25 Sept., 1967, No. 43599/67. Heading C2C. [Also in Division C5] Organic compounds are obtained by reacting an ethylenically unsaturated compound of formula in which R 1 , R 2 , R 3 and R 4 are hydrogen or hydrocarbon radicals having 1-30 carbon atoms, thienyl or furyl radicals which may be substituted by 1-3 of the following non- hydrocarbon groups: -OH, halogen, -OR6, -OCOR6, -NO, -CHO, -COOR6, -NR5 2 , -CONR5 2 , -CN, -SO 2 R6, -COOH, -COO Metal or -COR6, in which R5 represents a C 2 -C 12 hydrocarbon group free of ethylenic or acetylenic unsaturation and R6 represents R5, CH 3 or a non-hydrocarbon group as specified above except for -OH, with an organometallic compound of the platinum or palladium sub-groups of Group VIII in which the organic group of the organo metallic compound is a saturated carboalkoxy group containing 1-4 carbon atoms in the alkoxy group or a saturated C 1 -C 20 hydrocarbon group, at least one of which carbons is attached to the metal and is not attached to a carbon atom carrying hydrogen and optionally carrying 1-5 substituents from the following: C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -CHO, -COOH, -COOalkyl (C 1 -C 4 ), -CO-, -Cl, -NO 2 , -NHCOCH 3 , N(C 2 H 5 ) 2 or a thienyl, furyl, benzothienyl or benzofuryl group. The organometallic compound of the Group VIII metal may be produced in situ for an organometallic compound of a metal of Group II B , III A or IV A of the Periodic System, preferably of mercury and a salt of the Group VIII metal. The preferred organometallic compound used is one of formula QM1X in which X is a C 1 -C 4 carboalkoxy group, a C 1 -C 20 hydrocarbon group as defined above optionally carrying from 1 to 5 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -CHO, -COOH, -COO (C 1 -C 4 alkyl), -CO-, -Cl, -NO 2 , -NHCO CH 3 or -N(C 2 H 5 ) 2 groups or a thienyl, furyl, benzothienyl or benzofuryl group. It is desirable that a cupric salt should be added to the reaction mixture to act as a redox component in the regeneration of the Group VIII metal. The nature of the products depends on the groups present in the starting materials and more than one group in the olefinic starting material may react. Numerous examples of the process are given and among the products are unsaturated aldehydes, alcohols, ketones, esters, ethers, nitriles, halides and also carboxylic esters which may carry ketone, aldehyde, hydroxy, amine, cyanide, amide or nitro groups and saturated halohydrocarbons, aldehydes, ketenes, carboxylic acids, ketones, nitro compounds and esters.