Patent GB-399258-A (GB)
Title: Improvements in the manufacture and production of alcohols
IPC: C07C29/00
Filed: 1932-05-19
Abstract: Aralkyl alcohols are manufactured by acting with an alkylene oxide or an alkylene halogenhydrin capable of forming such oxide on an about equimolecular proportion of a metal compound of an aromatic hydrocarbon in the absence of Friedel-Crafts condensing agents. Suitable metal compounds of aromatic hydrocarbons are those from alkali metals such as sodium, potassium, lithium, caesium and rubidium, from alkaline-earth metals such as barium, strontium and calcium, from magnesium, aluminium, cadmium, zinc and mercury, e.g. phenyl mercury, phenyl, tolyl, xylyl or naphthyl sodium, phenyl potassium or diphenyl sodium.  Suitable alkylene oxides are ethylene oxide, 1 : 2- and 1 : 3-propylene oxides, 2 : 3- and 1 : 2-butylene oxides, trimethylethylene oxide, phenylethylene oxide, 1-phenyl-1 : 2-propylene oxide, tolyl- and naphthyl-ethylene oxides. Alternatively there may be used the corresponding halogenhydrins, e.g. glycol chlor-, brom- or iod-hydrin, epichlorhydrin or 1 : 2-butylene chlorhydrin.  The process is carried out by leading the alkylene oxide, if desired together with an inert gaseous diluent, e.g. nitrogen, argon, hydrogen or methane, ethane, propane or butane, at atmospheric, reduced or increased pressure (up to about 100 atmospheres) into a suspension of the metal compound of an aromatic hydrocarbon in an inert solvent which remains liquid at the working temperature, e.g. hydrocarbons such as pentane, hexane, butylene, amylene, hexahydrobenzene, tetrahydronaphthalene, petroleum ether, ligroin, benzene or alkylated benzenes, e.g. toluene or xylene, or ethers such as diethyl, methyl ethyl, di-n-butyl or di-isobutyl ether, anisol or phenetol.  Alternatively an alkylene halogenhydrin as such or dissolved in an inert solvent is allowed to flow into such a suspension, or the suspension of the metal compound of an aromatic hydrocarbon is allowed to flow into a solution of alkylene oxide or halogenhydrin, the last method being especially recommended in the case of the halogenhydrins.  The reaction is performed at about--80 DEG  to 50 DEG  C., preferably below 0 DEG  C., and preferably while stirring well.  When working at very low temperatures it is advantageous to add accelerators, e.g. solid substances of large superficial area such as active carbon, silica gel, asbestos or bleaching earths.  In examples: (1) gaseous ethylene oxide, preferably diluted with nitrogen or a solution of ethylene oxide in toluene, is introduced into a suspension of phenyl sodium in toluene at -50 DEG  C., yielding phenylethyl alcohol; (2) a suspension of phenyl potassium in petroleum ether is allowed to flow into a solution of ethylene chlorhydrin in petroleum ether at -10 DEG  to 0 DEG  C., producing phenylethyl alcohol; (3) a gaseous mixture of ethylene oxide and nitrogen is led into a suspension of p-tolyl sodium in benzene at 2-4 DEG  C., to produce p-tolylethyl alcohol, the phenylurethane of which is described.  Metal compounds of aromatic hydrocarbons are manufactured by reacting halogen aryls with metals in indifferent solvents, e.g. benzene or petroleum ether. Alkylene oxides are manufactured by treating the corresponding alkylenes with chlorine in the presence of water and treating the resulting chlorhydrins with aqueous caustic soda or potash.  Thus ethylethylene oxide (1 : 2-butylene oxide) is prepared from 1 : 2-butylene, and phenyl propylene oxide, tolyl-and naphthylethylene oxides from n-propylene benzene, methylstyrene and naphthylethylene respectively (which alkylenes are obtainable by catalytic dehydrogenation of the corresponding alkylated benzene or naphthalene).