Patent GB-254819-A (GB)
Title: Improvements in the synthesis of organic compounds
IPC: C07C51/12
Filed: 1925-03-09
Abstract: 254,819. Johnson, J. Y., (Badische Anilin & Soda Fabrik). March 9, 1925. Alcohols, aldehydes, carboxylic acids, esters, and other oxygenated organic compounds; amines.-Organic compounds containing oxygen are obtained by the reaction at high temperatures and pressures of carbon monoxide or gases containing it upon a vapourized aliphatic alcohol or ester or mixtures thereof in the presence of hydrating catalysts or hydrating and hydrogenating catalysts. In place of an alcohol vapour, a mixture of aldehyde vapour and hydrogen may be used. Or in place of employing separated alcohols, a mixture of carbon monoxide and hydrogen may be passed at high temperatures and pressures over a methanol-forming catalyst and the resulting gas mixture containing methanol vapours then treated with carbon monoxide as described above. Suitable hydrating catalysts are oxides of titanium, zirconium, thorium, vanadium, niobium, manganese, cerium, lanthanum, tantalum, chromium, molybdenum, tungsten, uranium, didymium, beryllium, aluminium, etc.; alkali or alkaline-earth compounds may be added, mixtures of zinc or cadmium oxide with alkali, &c. are also suitable. As hydrogenating constituents, copper, silver, gold, tin, lead, antimony, bismuth, zinc, cadmium, or thallium, or their oxides &c., may be used. Iron, nickel, or cobalt, or their oxides may be employed, provided they are present in a chemically combined condition or in the form of alloys. According to examples :-Methanol vapour and carbon monoxide are passed over a mixture of iron and manganese oxides, the resulting product containing butyric and valeric acid, &c., methanol vapour mixed with carbon monoxide, hydrogen, and nitrogen is passed over a cobalt oxide-molybdic acid catalyst, giving in addition to oxygen compounds nitrogen compounds such as methylamines; barium uranate or iron vanadate gives similar results; methanol vapour and carbon monoxide are passed over a potassium chromatepotassium molybdate. catalyst, the products including higher alcohols, aldehydes, and esters; ethyl alcohol vapour and carbon monoxide passed over a chromium oxide-manganese oxide catalyst give products boiling at 100-250‹ C. including aldehydes, acids, esters, and alcohols; a mixture of methanol vapour, carbon monoxide, hydrogen, and nitrogen, passed over a potassium bichromate-zinc oxide catalyst gives a product containing isobutyl, n-propyl, amyl, and higher alcohols, and free or combined acids; methyl formate vapour, carbon monoxide, hydrogen, and methane, passed over a catalyst prepared from potassium permanganate, zinc chromate, and copper chromate, give similar products; carbon monoxide and hydrogen are passed over a catalyst consisting of cadmium and copper oxides and vanadic acid, and the resulting methanol-containing mixture is passed over a contact mass prepared from caustic potash, thallium oxide, and potassium permanganate, giving isobutyl alcohol, etc.; a mixture of purified water-gas and ethyl alcohol is passed over a mixture of potassium carbonate, zinc chromate and copper oxide, giving liquid water-insoluble products. Specification 238,319 is referred to.