Patent GB-682424-A (GB)
Title: A process for the production of organic hydroperoxides and the organic hydroperoxides so produced
IPC: C07C409/04
Filed: 1950-06-29
Abstract: Hydroperoxides are produced by reacting an alcohol with hydrogen peroxide in the liquid phase and in the presence of an acidic catalyst in an amount not exceeding 0.4 mole. per mole. of the alcohol.  The invention is particularly useful for the production of tertiary-alkyl hydroperoxides such as tertiary butyl, and tertiary amyl hydroperoxide, 2,3-dimethylbutan - 3 - hydroperoxide; 4 - methyl - pentan - 4-hydroperoxide and 2,2,3-trimethyl-butan-3 hydroperoxide. The acidic catalyst may be either a strong acid or a substance which generates strong acid in situ and the reaction is preferably conducted at a temperature which does not exceed 90  DEG  C., e.g. at 40 DEG  to 70 DEG  C.  Suitable acidic catalysts include the heteropoly acids which are defined as those inorganic acids which contain a plurality of acidic radicals and which include an acidic radical of at least one metal element and an acidic radical of at least one other, preferably non-metallic, element; the acids being inorganic complexes of high molecular weight comprising a nuclear element which is usually phosphorus, silicon, boron, or arsenic, surrounded by a co-ordinated group of one or more oxides of other metallic or non-metallic elements such as one or more of the oxides of tungsten, molybdenum, vanadium, chromium, sulphur, selenium and tellurium.  The complex may be associated with varying amounts of water and water of hydration and may have a molecular weight up to 3000 or more.  Partial salts of the heteropoly acids, e.g. with ammonium or alkali metals, may also be used.  The structure of the heteropoly acids is generally represented as containing the central tetrahedral group XO4 as an essential feature, where X is, for example, phosphorus, arsenic, boron, thorium, silicon, tin, germanium, zirconium or titanium, associated with the radicals of one or more dissimilar acids.  Examples of such acids are silicomolybdic, phosphotungstic, borotungstic, metatungstic, phosphomolybdic, arsenimolybdic, manganimolybdic, titanimolybdic, germanitungstic, arsenitungstic and silicotungstic acids as well as the iso and hydrated forms of the acids.  Other acidic catalysts are the halide-type Fridel-Craft's catalysts, including the boron halides, especially boron trifluoride and trichloride; the halides of amphoteric polyvalent metals, e.g. the chlorides of aluminium, iron, antimony, tin, or titanium, especially aluminium trichloride, ferric chloride, antimony trichloride, stannic chloride and titanium tetrachloride; strong acids such as p-toluene sulphonic acid, benzene sulphonic acid, 1,3,5-trimethyl benzene monosulphonic acid, o-xylene-sulphonic acid, fluorobenzene-4-sulphonic acid, o-dichlorobenzene-4-sulphonic acid, nitrobenzene-3-sulphonic acid and amylsulphonic acid; hydrohalogen acids, e.g. hydrofluoric acid, or a strong mineral oxy-acid, e.g. sulphuric acid, or ortho-, meta-, or pyrophosphoric acid, selenic acid or tungstic acid.  Specified alcohols are tertiary-amyl alcohols, dimethyl propyl carbinol, methyl-diethyl carbinol, triethyl carbinol, diethyl propyl carbinol, and homologues and substitution products thereof, e.g. their chloro and bromo substitution products, tertiary-hexanols, tertiary-heptanols, 1-methylcyclohexanol and other aliphatic and cycloaliphatic, preferably saturated, tertiary alcohols, as well as primary and secondary alcohols such as ethanol, isopropanol, isobutanol, methylisobutyl carbinol and cyclohexanol.  It is preferred to use hydrogen peroxide in an amount up to 250 per cent of the theoretical requirement, preferably an excess of about 40 to 90 per cent over the theoretical requirement is used.  The process may be carried out in a batchwise, intermittent, or continuous manner and inert water-immiscible organic solvents, preferably having boiling-points below that of the hydroperoxide may be included in the mixture.  These solvents may be paraffinic or aromatic hydrocarbons or halogen substituted lower paraffins such as ethylene dichloride, methylene chloride and chloroform.  In examples: (1) tertiary-butyl alcohol and a 50 per cent by weight aqueous solution of hydrogen peroxide are mixed and silicotungstic acid added, tertiary butyl hydroperoxide being separated from the water immiscible organic phase; (2) tertiary butyl hydroperoxide is obtained by adding boron trifluoride-diethyl ether complex dissolved in tertiary-butyl alcohol to aqueous hydrogen peroxide; (3) tertiary-butyl alcohol is added to a solution of paratoluene sulphonic acid in aqueous hydrogen peroxide; (4) 0.70 per cent sulphuric acid is added to a mixture of tertiary-butyl alcohol and aqueous hydrogen peroxide, the latter being in excess; (5) tertiary-amyl hydroperoxide is obtained by mixing a small excess of tertiary-amyl alcohol, aqueous hydrogen peroxide and 70 per cent sulphuric acid; (6) benzene is added to the mixture used in (5), the product being obtained from the benzene layer.