Patent GB-565745-A (GB)
Title: Manufacture of organo-metal compounds and amines
IPC: C07D295/084
Filed: 1942-07-27
Abstract: Organo-metal compounds are prepared by causing a halogen-amine in which a halogen atom and an amino-group are connected together by at least 3 carbon atoms to react with a metal known to be capable of forming organo-metal compounds, e.g. magnesium, zinc, potassium, lithium or sodium.  Amines are made by reaction of the organo-metal compound with an aldehyde, ketone, ester, or nitrile. Examples of amines are chloropropyl- and bromopropyldiethylamine, bromopropyldibutylamine, iodopropylpiperidine, chloro - butyl - dimethylamine, chlorobutyl - diphenylamine, chloro - butyl - methyl - cyclohexylamine, chlorobutylethyl-cyclohexylamine, halogen - octyl - dialkylamines, m- or p - halogen - cyclohexyl - dialkylamines, dialkylamino - alkyl - cyclohexyl halides, N-methyl - g  - halogen - piperidines, chlorethyl-diethylaminoethyl ether, chloropropyl-dibutylamine, and chloropropyl-diamylamine.  Compounds which may react with the organo-metal compounds include benzaldehyde, cumic aldehyde, veratric aldehyde, anisaldehyde, piperonal, naphthaldehyde, benzonitrile, benzoic acid ester, formaldehyde, acetaldehyde, trichlor- or tribromo - acetaldehyde, isobutyraldehyde, oenanthol, citral, pyridyl-aldehydes, furfurol, benzophenone, acetophenone, desoxybenzoin, diphenylketene, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, and camphor.  Examples are given of the preparation of diethylaminopropyl - magnesium chloride from 1 - chloropropyl - 3 - diethylamine and heating with benzophenone gives the hydrochloride of diphenyl - 3 - diethylaminopropyl - carbinol.  Phenyl - benzyl - 3 - diethylaminopropyl - carbinol is obtained similarly.  Other compounds obtained are phenyl - 3 - diethylaminopropyl - carbinol, phenyl - p - dimethylaminocyclohexyl - carbinol, furyl-3-diethylamino-propyl-carbinol, pyridyl - (31) - 3 - diethylaminopropyl - carbinol, naphthyl-(11)-3-diethylamino-propyl-carbinol, methyl-phenyl-3-diethylaminopropyl-carbinol, p - methoxyphenyl - 3 - diethylaminopropyl - carbinol, 31,41-methylenedioxyphenyl - 3 - diethylaminopropyl-carbinol, 31,41-dimethoxyphenyl-3 - diethylaminopropyl - carbinol, diphenyl - 3 - piperidinopropyl-carbinol, phenyl-3-piperidinopropyl-carbinol, p-methoxyphenyl-3-piperidinopropyl-carbinol, 31, 41-methylenedioxy-phenyl-3-piperidinopropyl-carbinol, phenyl-3-dimethylaminopropyl - carbinol, 31,41 - methylenedioxyphenyl - 3 - dimethylaminopropyl - carbinol, phenyl - 3 - di - n - butylaminopropyl - carbinol, 11-(3-di-n-butylaminopropyl)-cyclohexanol-(11), 41-isopropyl-phenyl-3-di-n-butylamino-propyl-carbinol, 21-(3-di-n-butylaminopropyl)-borneol, phenyl - 5 - diethylaminopentyl - carbinol, 4-diethylamino - butanol - (1), 10 - diethylamino - decanol-(7), w-diethylamino-n-butyrophenone, m - benzyloxy - phenyl - 3 - diethylaminopropyl-carbinol, a  - (3 - diethylaminopropyl) - geraniol, styryl-3-diethylaminopropyl-carbinol, p-benzyloxyphenyl - 3 - diethylamino-propyl-carbinol, p-dimethylaminophenyl - 3 - diethylamino - propyl-carbinol, diphenyl-3-dibutyl-aminopropyl-carbinol, and hexyl-3-dibutylaminopropyl-carbinol.