| 摘要 |
Tertiary alkyl hydro-peroxides and di-(tertiary alkyl) peroxides are produced by reaction of a hydrocarbon containing at least one tertiary carbon atom of aliphatic character or a halo-substituted derivative thereof with oxygen or oxygen-containing gas in the presence of a hydrogen halide at an elevated temperature below that producing spontaneous combustion. The initial hydrocarbons have the formula <FORM:0577841/IV/1> , where each R is a like or different alkyl, aryl, aralkyl or alicyclic radical, two of which together may form an alicyclic ring. Mixtures of such hydrocarbons may be used to produce asymmetrical peroxides. Hydrocarbons specified are isobutane, 2-methyl and 2-ethyl butane, 2-methyl and 3-methyl pentane, 2,3- and 2,4-dimethyl butane, and their homologues, isopropyl benzene, and 1-phenyl-1- or 2-methyl propane. Temperatures are generally about 150-200, but may range from 100-250 DEG C. or more, especially when inert diluents are present, e.g. steam, nitrogen, carbon monoxide and methane. Hydrogen bromide is the preferred catalyst, but other hydrogen halides, for example the chloride, may be used. Proportions of reactants and conditions are generally the same as described in Specification 574,958. The products, besides alcohols, are hydro-peroxides, and peroxides of the formula <FORM:0577841/IV/2> , where each R in particular represents a saturated alkyl radical, e.g. tertiary butyl. Such peroxides are used to catalyse formation of plastics such as diallyl phthalate and/or acrylate resins, and to improve the octane value of diesel fuels. In an example, isobutane, oxygen and hydrogen bromide in a ratio of 2 : 2 : 1 is passed through a coil of glass tubing at 158 DEG C. for a time of about 3 mins. and di-(tertiary butyl) peroxide isolated from the products which also include tert.-butyl alcohol.
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