Patent GB-388734-A (GB)
Title: Process for the production of valuable products from aliphatic or alicyclic hydrocarbons, and hydrocarbon mixtures, containing at least one tertiary carbon atom
IPC: C07C45/47
Filed: 1931-05-30
Abstract: Products comprising ketones and in some cases aldehydes also are obtained by treating aliphatic or alicyclic hydrocarbons containing at least one tertiary carbon atom, or natural or artificial mixtures containing such hydrocarbons, with carbon monoxide or substances containing carbon monoxide, or with phosgene, at temperatures appreciably below normal, and at normal or increased pressures, in the presence of anhydrous metallic bromides or iodides, preferably aluminium bromide, and with or without the addition of cuprous halides or halogen hydrides such as hydrobromic acid.  When it is desired to obtain aldehydes, the temperature is reduced as soon as the reaction begins, and the resulting oily product is decomposed with acidulated water.  By operating at higher temperatures the formation of ketones is reduced, and viscous high-boiling condensation products are obtained.  In carrying out the process, the reaction mixtures may be subjected to intensive stirring, grinding, stamping, or kneading.  Solvents, and distributing agents of large superficial area such as silical gel or active carbon may be present. The reagents or the hydrocarbons treated may be forced through the reaction mass by means of pumps or distributing nozzles.  By suitably choosing the reaction conditions, only one or more of the constituents of the hydrocarbon mixture can be allowed to take part in the reaction, which can thus be used for separating or improving mixtures of tertiary hydrocarbons, if necessary in stages.  By reducing the ketones formed by employing carbon monoxide, tertiary hydrocarbons are again formed, which can be transformed by the same process into other ketones, and then again into tertiary hydrocarbons.  The initial materials may comprise petroleum, natural gas, hydrogenated brown coal tars, hydrogenation products of carbon monoxide and other substances, and cracking distillates previously freed from unsaturated and aromatic constituents.  The products, including both condensation products and improved hydrocarbons, are intended for use in the perfumery, acid, and soap industries, as solvents, lubricants, transformer oils, and similar applications. According to examples (1) isopentane is treated in an autoclave of V4A alloy at 9 to -20 DEG  C. with carbon monoxide under pressures of 150-300 atmospheres in the presence of aluminium bromide and cuprous bromide.  The oily mass obtained is poured on to ice, and the precipitated condensation product is driven off with steam and distilled.  The main product is a ketone containing six carbon atoms. Natural pentane can be similarly treated, so that only the isopentane reacts, the normal pentane being separated unchanged. (2) A ketone and higher boiling product are obtained by the action of carbon monoxide in presence of aluminium bromide and cuprous bromide on methylcyclohexane, (3) an ethereal oil is obtained by treating a heptane fraction in the same manner, and (4) isopentane is treated in the presence of aluminium bromide with phosgene, an ethereal oil being obtained.  The Specification as open to inspection under Sect. 91 comprises also the use of carbon dioxide or of substances such as ferrous carbonyl instead of carbon monoxide or phosgene.  Other examples are also given, in which the starting materials employed are (1) isopentane, (2) a Californian mineral oil fraction boiling at 160-170 DEG  C., (3) methylcyclohexane, (4) an American mineral oil fraction boiling at 230-280 DEG  C., (5) commercial pentane, (6) n-butane or mixtures containing n-heptane, and (7) cyclohexane, the temperatures employed in the last three cases ranging from 50 DEG  to 80 DEG  C.  This subject-matter does not appear in the Specification as accepted.