Patent GB-626048-A (GB)
Title: A process of oxidizing primary or secondary alcoholic hydroxyl groups and aldehyde groups
IPC: C07C63/06
Filed: 1945-09-28
Abstract: Alkanols and alkanals, which are defined as primary and secondary aliphatic alcohols and aliphatic aldehydes, their derivatives and substitution products, including those derived from cycloparaffins or having aryl substituents, but excluding compounds having both alcohol and aldehyde groups, are oxidized to compounds containing carboxyl, aldehyde or keto groups by reaction with an amount of bromine stoichiometrically small in proportion to the amount of compound to be oxidized, and an amount of a bromate stoichiometrically corresponding to the desired amount of oxidation product.  Pure bromides can be prepared using pure bromates as oxidizing agents. The bromine may be initially added as such, as hypobromite or as bromide ion.  Solvents may be present, for example another portion of the reaction product when a more concentrated solution is obtained. Reduced pressure may be used, particularly when reacting at the boiling temperature. Copper or molybdate ions, for example as copper bromate or MoO3, act as catalysts.  Among examples: (1) ethyl alcohol is mixed with potassium bromate and bromine, and kept at 50 DEG  C. for 6 hours, any unreacted bromine reduced, and ethyl acetate recovered by distillation, the residue yielding pure potassium bromide.  The speed of reaction increases with the excess of alcohol used and the concentration of free bromine.  In the example, the alcohol is originally present in an excess of six times the amount oxidized to acetic acid and the bromine concentration is about 0.5 moles/l.; (4) n-butyl alcohol is oxidized with aqueous calcium bromate and hydrogen bromide to give butyl butyrate and calcium bromide.  The Specification as open to inspection under Sect. 91 comprises the oxidation of alcoholic hydroxy and aldehyde groups generally. An additional example describes the oxidation of benzaldehyde to benzoic acid.  This subject-matter does not appear in the Specification as accepted.ALSO:Alkanols and alkanals, which are defined as primary and secondary aliphatic alcohols and aliphatic aldehydes, their derivatives and substitution products, including those derived from cycloparaffins or having aryl substituents, but excluding compounds having both alcohol and aldehyde groups, are oxidized to compounds containing carboxyl, aldehyde or keto groups by reaction with an amount of bromine stoichiometrically small in proportion to the amount of compound to be oxidized, and an amount of an oxidizing agent capable of oxidizing bromide ion, stoichiometrically corresponding to the desired amount of oxidation product.  Suitable oxidizing agents include bromate and chlorate ions, chlorine, hypochlorites, manganese dioxide, chromic acid, and bichromates.  The bromine may be initially added as such, as hypobromite or as bromide ion.  Solvents may be present; for example another portion of the reaction product when a more concentrated solution is obtained.  Reduced pressure may be used, particularly when reacting at the boiling temperature. Copper or molybdate ions, for example as copper bromate or MoO3, act as catalysts.  With starting materials containing both primary and secondary hydroxyl groups, the latter is generally oxidized far quicker.  In examples: (1) ethyl alcohol is mixed with potassium bromate and bromine, and kept at 50 DEG  C. for 6 hours, any unreacted bromine reduced, and ethyl acetate recovered by distillation, the residue yielding pure potassium bromide.  The speed of reaction increases with the excess of alcohol used and the concentration of free bromine.  In the example, the alcohol is originally present in an excess of six times the amount oxidized to acetic acid, and the bromine concentration is about 0.5 moles/l.; (2) aqueous solutions of calcium bromate and hydrogen bromide are refluxed with ethyl alcohol to yield ethyl acetate; (3) variation of the conditions by gradual addition of reactants and using an ordinary Liebig condenser yields acetaldehyde also; (4) n-butyl alcohol is oxidized with aqueous calcium bromate and hydrogen bromide to give butyl butyrate; (5) n-hexyl alcohol, similarly gives hexyl caproate; (6) lauryl alcohol is similarly converted to lauryl laurate; (7) aqueous ethylene chlorhydrin yields chloracetic acid and its ester; (8) 2-benzoxy-ethanol is oxidized with potassium bromate and hydrobromic acid solution to the corresponding ester; (9) ethyl alcohol is treated with ethyl acetate, calcium bromate, and hydrobromic acid to obtain ethyl acetate; (10) potassium chlorate and hydrobromic acid oxidize ethyl alcohol to ethyl acetate; (11) chlorine is passed into ethyl alcohol and cupric bromide solution to give the same product; (12) manganese dioxide and potassium bromide are mixed with ethyl alcohol and sulphuric added to yield ethyl acetate; (13) manganese dioxide and hydrobromic acid solution act similarly; (14) n-butyl alcohol with cupric bromide, and sodium hypochlorite solutions yields butyl butyrate; (15) sodium bichromate, sulphuric acid and hydrogen bromide react similarly; (16) butyl acetate is obtained by oxidizing acetaldehyde in n-butyl alcohol with potassium bromate and bromine; (17) isopropyl alcohol is oxidized with calcium bromate and hydrobromic acid solutions to acetone; (18) 2-dodecanol is similarly oxidized to the corresponding ketone; (19) cyclohexanol similarly yields cyclohexanone; (20) 1,3-butylene glycol is oxidized to 80 per cent at the secondary hydroxyl group but only to 20 per cent at the primary; (21) oxidation of ethyl alcohol with hydrobromic acid, and calcium or cupric bromate alone or a mixture of both bromates shows the promoting effect of cupric ion.  The Specification as open to inspection under Sect. 91 comprises the oxidation of alcoholic hydroxy and aldehyde groups generally. An additional example describes the oxidation of benzaldehyde to benzoic acid.  This subject-matter does not appear in the Specification as accepted.