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    • 4. 发明专利
    • Hydroxylation of olefinic compounds
    • GB654764A
    • 1951-06-27
    • GB335048
    • 1948-02-05
    • DISTILLERS CO YEAST LTDDONALD PETER YOUNG
    • C07C31/18
    • Compounds having at least two hydroxyl groups attached to two adjacent carbon atoms are manufactured by the hydroxylation of compounds with one olefinic link with aqueous hydrogen peroxide in the presence of a catalyst, initially in the form of tungsten oxide and/or molybdenum oxide, at a temperature between 50 DEG and 100 DEG C. The reaction may be carried out with or without the presence of an inert organic water-miscible diluent, e.g. acetone, tertiary butanol, dioxane or acetic acid. Olefinic compounds which may be used as starting materials are hydrocarbons such as n-oct-1-ene cyclohexene, but-1-ene, 2 : 4 : 4-trimethyl-pent-1-ene, 2 : 4 : 4-trimethyl-pent-2-ene and 4-ethyl-pent-2-ene; alcohols such as allyl alcohol, crotyl alcohol, but-3-en-2-ol, pent-3-en-2-ol and 4-methyl-pent-4-en-2-ol and olefinic acids such as acrylic acid, crotonic acid and maleic acid. Olefinic aldehydes such as acrolein and crotonaldehyde may also be hydroxylated in this way but they may be oxidized simultaneously to the corresponding acids. When acetic acid is used as a diluent it is desirable to react it first with the hydrogen peroxide, dissolve the tungstic and/or molybdic oxide therein and then react the mixture with the olefinic compound. In the examples: (a) glycerol is prepared from allyl alcohol; (b) butane-1,2,3-triol is prepared from crotyl alcohol; (c) 1.2-dihydroxybutyric acid is prepared from crotonic acid; (d) octane-1.2-diol is prepared from n-oct-1-ene; (e) trans-cyclohexane-1.2-diol is prepared from 3-ethyl-pent-2-ene by the action of aqueous hydrogen peroxide in the presence of a catalyst as described above. Specification 508,526 is referred to.
    • 6. 发明专利
    • Production of amino-hydrazines
    • GB581153A
    • 1946-10-02
    • GB1230944
    • 1944-06-28
    • JAMES GORDON NAPIER DREWITTDONALD PETER YOUNG
    • C07D237/32
    • Aminohydrazines of the formula NH2RN2H3 are obtained by reacting with hydrazine a substituted ester of the formula ANRX, where AN is a dicarboxyacylimido group, e.g. diacetimido, succinimido or phthalimido, X a negative radical of a strong acid, e.g. a halogen, hydrogen sulphate or para-toluene sulphonate and R an aliphatic radicle. The latter may be branched chain or cycloalkyl and may be substituted, e.g. with a hydroxy group. The chain may also be interrupted by oxygen, sulphur or other atoms or by an aryl radicle. An intermediate hydrazinohydrazide compound may be first formed, but this is readily hydrolysed with aqueous mineral acid to the aminohydrazine and, for example phthalhydrazide. In the example, potassium phthalimide and hexamethylene dichloride are heated under reflux in an atmosphere of nitrogen. The product is distilled and the residue extracted by light petroleum, from which 6-chlorohexyl phthalimide is crystallized. The bromo compound can be prepared similarly. The 6-chlorohexylphthalimide is warmed with alcoholic hydrazine hydrate solution, and the solution then acidified with hydrochloric acid and refluxed. The phthalyl hydrazide is filtered off and the filtrate further acidified with hydrochloric acid, evaporated in vacuo and hydrazine dihydrochloride removed as it forms. The residue is dried by azeotroping with benzene and recrystallized from alcoholic hydrogen chloride giving 6-aminohexylhydrazine dihydrochloride. The product may also be recovered by distillation or extraction. Residual hydrazine may be removed by treatment with benzaldehyde which reacts preferentially with the organic hydrazine product to give a benzalazine. Other examples of substituted esters which may be used are 2-chloro-ethyl-, 3-chloropropyl-, 4-chlorobutyl-, 5 - chloro - p - methylamyl-, 4 - chlorocyclohexyl, o - chloro - p - xylenyl-, 2 - chloroethoxyethyl - phthalimides and the corresponding bromo derivatives. They may be made by reacting an aliphatic dihalide with phthalimide in the presence of anhydrous alkali, e.g. potassium carbonate. An anhydrous solvent such as alcohol may be used. In the Provisional Specification, the production of compounds of the formula NH2RN(NH2)RNH2 by reacting the phthalimide derivative with a small amount of hydrazine is described.