GB656112A - Manufacture of tertiary alcohols - Google Patents

Abstract

Tertiary alcohols are produced by a process comprising reacting at elevated temperatures a hydroperoxide compound in which the hydroperoxide group is linked to a tertiary carbon atom with an amine compound of general formula <FORM:0656112/IV (b)/1> wherein R and R1 are alkyl, cycloalkyl, substituted alkyl, aryl or aralkyl or the methylene groups adjacent to the nitrogen atom of cyclic nitrogen compounds such as piperidine and piperazine and R1 may in addition be hydrogen and R2 stands for hydrogen or an alkyl, cycloalkyl, substituted alkyl, aryl, aralkyl or acyl group. Suitable amines include mono-, di- and tri-methyl, ethyl, propyl, isopropyl and butylamines, aniline, mono- and di-methyl and ethylaniline, mono- and di-ethyltoluidine, mono-, di- and triethanolamine, dimethyl formamide, diethyl formamide, piperidine, piperazine, hexamine and ethylene diamine. Suitable hydroperoxides include the hydroperoxides of isopropyl benzene, methylcyclopentane, a - and b -isopropyl naphthalene and tertiary butyl and the mono- and di-hydroperoxides of diisopropylbenzene. The amine compound, the hydroperoxide compound or the hydrocarbon from which the hydroperoxide has been derived may serve as solvent. The reaction rate increases when the proportion of amine compound to hydroperoxide compound is increased. The reaction is exothermic and it is advantageous to provide means for controlling the reaction temperature. The carbinols and unchanged amine compound may be recovered by fractionation or the latter by extraction with aqueous acid. Ketones and unsaturated compounds are also produced when prolonged heating has been necessary. Phenyl dimethyl carbinol is produced by heating isopropyl benzene hydroperoxide with, in examples (1), (2) and (3), triethylamine, isopropyl benzene being present as solvent in the latter; (4) dimethylaniline; (5) diethylamine; (6) n-butylamine; (7) hexamine; (8) triethanolamine; (9) diethanolamine; (10) dimethylformamide; (11) piperidine; (12) piperazine with isopropylbenzene as solvent. In examples: (13) diisopropyl benzene monohydroperoxide is heated with trimethylamine; (15) methyl cyclopentane is heated with trimethylamine; (16) tertiary butyl peroxide is heated with triethanolamine, dimethyl (isopropyl phenyl) alcohol, bis-(2-hydroxypropyl-2-) benzene and tertiary butyl alcohol being obtained respectively. In example (3) acetophenone is also obtained.