Patent GB-682022-A (GB)
Title: A process for the production of organic hydroperoxides and the organic hydroperoxides so produced
IPC: C07C409/04
Filed: 1950-06-30
Abstract: Organic hydroperoxides are obtained by reacting hydrogen peroxide in aqueous solution with a water-soluble alkylating agent for the hydrogen peroxide in the presence of an acidic substance, other than an alkylating agent for the hydrogen peroxide, as a catalyst, the reaction being carried out also in the presence of an inert water-immiscible organic solvent for the organic hydroperoxide in an amount sufficient to form a separate organic solvent phase in contact with the aqueous reaction liquid and separating the organic solvent phase which contains substantially pure organic hydroperoxide dissolved therein from the aqueous phase.  The term alkylating agent is defined as including compounds capable of introducing a cycloalkyl group as well as those capable of introducing an acyclic alkyl group. The process is particularly valuable for the production of tertiary alkyl hydroperoxides, e.g. tertiary-butyl and tertiaryamyl hydroperoxide; 2,3-dimethyl - butan-3-hydroperoxide; 4 - methyl - pentan - 4 - hydroperoxide; and 2,2,3-trimethyl-butan-3-hydroperoxide, as well as the tertiary alkyl hydroperoxides formed by the substitution of the hydroperoxy radical for a hydrogen atom on one or more of the tertiary carbon atoms of saturated aliphatic hydrocarbons such as 2-ethylbutane, 2- (or 3-) ethyl pentane; 2,4-dimethylpentane and their homologues; and to primary and secondary hydroperoxides such as ethyl-, iopropyl-, butyl-, and amyl hydroperoxides, and cycloaliphatic hydroperoxides such as cyclohexyl hydroperoxide and the various homologues thereof. The alkylating agent is preferably the alcohol corresponding to the required hydroperoxide, e.g. tertiary butyl alcohol, tertiary amyl alcohol, tertiary hexanols, tertiary heptanols, 1-methylcyclohexanol, and like aliphatic and cycloaliphatic, preferably saturated, alcohols, as well as primary and secondary alcohols, such as ethanol, isopropanol, isobutanol, methyl isobutyl carbinol and cyclohexanol. Other alkylating agents may be used, e.g. the alkyl hydrogen sulphate or other monoalkyl esters of inorganic acids which may be prepared according to known methods by reacting the corresponding alcohol or olefine with the inorganic acid, e.g. concentrated sulphuric acid, and the preparation may take place in situ.  As acidic catalyst a strong acid such as sulphuric acid, ortho- or pyro-phosphoric acid, hydrochloric acid, selenic acid or tungstic acid may be used, a strong non-volatile mineral acid being preferred.  Also useful as catalysts are the heteropoly acids such as silicotungstic acid, phosphomolybdic acid and phosphotungstic acids and strong organic acids such as oxalic acid and mono-, di-, or tri-chloracetic acid as well as strong organic acids containing an inorganic acidic radical, such as the sulpho radical, as in the aryl and alkyl sulphonic acids, e.g. p-toluenesulphonic acid, benzene sulphonic acid; 1,3,5 - trimethylbenzenemonosulphonic acid, the xylenesulphonic acids, fluorobenzene-4-sulphonic acid, o-dichlorobenzene-4-sulphonic acid, nitrobenzene-3-sulphonic acid and amylsulphonic acid. Other acidic catalysts specified are the halide type Friedel-Crafts catalysts including boron trichloride, boron trifluoride, and halides of amphoteric polyvalent metals such as chlorides of aluminium, iron, antimony, tin and titanium.  Several water-immiscible organic solvents are specified including especially halogen-containing hydrocarbons, especially paraffins, having up to eight carbon atoms in the molecule and particularly the chlormethanes, chloroform and methylene chloride being preferred.  Other solvents specified include aromatic hydrocarbons such as benzene, toluene and xylene and aliphatic hydrocarbons, e.g. heptanes, octanes, nonanes and decanes, also nitrosubstituted hydrocarbons such as nitromethane, 1 - nitro - propane, 2 - nitropropane, nitrobutanes and the nitropentanes. The solvent used should preferably boil at a temperature below that of the alkyl hydroperoxide.  The hydrogen peroxide is conveniently used in the form of a 50 per cent aqueous solution and it may be used in an amount up to 250 per cent of the theoretical requirement.  The reaction temperature may be as high as 90 DEG  C. but is preferably 40 DEG  to 70 DEG  C. although the minimum temperature may be as low as - 10 DEG  C. or below.  The process may be effected at atmospheric or higher or lower pressure and may be carried out in a batchwise, intermittent or continuous manner to which it is particularly suited. In examples: (1) chloroform is added to a mixture of tertiary butyl alcohol and an aqueous solution of hydrogen peroxide, the mixture agitated, and aqueous 70 per cent sulphuric acid then added.  The mixture is maintained at 60 DEG  C. and then cooled when two phases separate out, tertiary butyl hydroperoxide being obtained by evaporation of the chloroform phase; (2) as in (1) except that methylene chloride is used as solvent and the reaction is effected at 40 DEG  C.; (3) benzene is added to a mixture of tertiary amyl alcohol, hydrogen peroxide and sulphuric acid and the mixture maintained at 50 DEG  C. Tertiary amyl hydroperoxide is obtained from the benzene layer. Specification 682,424 is referred to.