Patent GB-1277764-A (GB)
Title: Process for adding anionic groups onto olefinically unsaturated compounds
IPC: C07D307/24
Filed: 1969-10-28
Abstract: 1277764 Anionic oxidation BADISCHE ANILIN- & SODA-FABRIK AG 28 Oct 1969 [29 Oct 1968] 52694/69 Heading C2C [Also in Divisions C5 and C7] Anionic groups are added to olefinically unsaturated compounds in which the double bond is not activated, by the anodic oxidation of a compound MZ or RMgX in the presence of the olefinically unsaturated compound and a polar solvent. The anionic groups are (a) R1-CH-R<SP>2</SP>, in which R<SP>1</SP> and R<SP>2</SP> are independently an acyl group (2-10 C), carboxylic ester groups (2-10 C) derived from aliphatic, cycloaliphatic or araliphatic alcohol (up to 9 C) or phenol, a nitrile group, a phenyl group or a sulphone group substituted by an aliphatic, cycloaliphatic, araliphatic or aromatic radical; where R<SP>3</SP> and R<SP>4</SP> denote a hydrogen atom or an aliphatic, cycloaliphatic, araliphatic or aromatic radical with up to 10 carbon atoms; (c) R<SP>5</SP>-C#C, where R<SP>5</SP> denotes a hydrogen atom or alkyl radical (1-4 C) or a phenyl group; (d) CN or N 3  and an aliphatic, cycloaliphatic, araliphatic or aromatic radical. M represents a metal of Group 1A of the Periodic System and X a chlorine or bromine atom. Olefinic compounds are aliphatic (3-20 C) and cycloaliphatic (5- 12 C) olefines, vinyl ethers or araliphatic olefines such as styrene or vinyl naphthalene. The anodic oxidation preferably is at anode voltages of 0À1 to 1À2 volts, and 0À01 to 0À1 amp/cm.<SP>2</SP> and a diaphragm may be present, and suitable polar solvents are alkanols, aliphatic nitriles, sulphoxides and disubstituted amides. Examples describe the reaction of dimethyl malonate with styrene to give 2,2-dimethoxy-5- phenyltetrahydrofuran-3-carboxylic methyl ester, with cyclohexene to give dimethyl cyclohexylmalonate and dimethyl-2-cyclohexenyl malonate, with vinyl ethyl ether to give the methyl ethyl acetal of α-malonic ester acetaldehyde; of ethylacetoacetate with styrene to give 2,7-diacetyl-4,5-diphenyloctane-1,8-dicarboxylic acid methyl ester and 4-carbomethoxy-5- methyl - 2 - phenyl-2, 3 - dihydrofuran, with α- methyl styrene to give 4-carbomethoxy-5- methoxy-5-methyl-2-phenyltetrahydrofuran; of acetylacetone with vinyl ethyl ether to give 4- acetyl - 2 - ethoxy - 5 - methyl - 2,3 - dihydrofuran, with butadiene to give trans, transtetradeca-5,9-diene-2,1,3-dione, with styrene to give 5,6-diphenyldecane-2,9-dione and 4-acetyl- 5-methyl-2-phenyl-2,3-dihydrofuran; methylcyanoacetate with styrene to give 1-phenyl-1- methoxy-3-cyano-3-carbomethoxypropane, with vinyl ethyl ether to give 1-ethoxy-l-methoxy-3- cyano - 3-carbomethoxy-propane; nitropropane with styrene to give 2,7-dinitro-2,7-dimethyl- 4,5-diphenyloctane or 2,3-dinitro-2,3-dimethylbutane, with vinyl ether to give 1-methoxy-1- ethoxy-3-nitro-3-methylbutane; nitroethane with styrene to give 1-phenyl-1-methoxy-3- nitrobutane; lithium azide with styrene to give 1-phenyl-1-methoxy-2-amino-ethane; sodium azide with styrene or cyclohexane to give 1,4- diamino-2,3-diphenyl butane and 2,2<SP>1</SP>-diaminodicyclohexane respectively; and n-butyl magnesium bromide with styrene to give 5, 7 and 6,7-diphenyl dodecane.