Patent GB-417496-A (GB)
Title: Process for the oxidation of isoaldehydes
IPC: C07C51/235
Filed: 1934-01-19
Abstract: Carboxylic acids are manufactured by the oxidation of aldehydes containing the grouping <FORM:0417496/IV/1> by bringing them, if desired in a substantially anhydrous state, into intimate contact with elementary oxygen or gases containing it, and controlling the temperature so that it does not substantially exceed 45 DEG  C., the reaction being preferably carried out in the presence of a carboxylic acid, which may be the product of the oxidation, or another acid, e.g. formic, acetic, propionic, n- or isobutyric, n- or isovaleric or methylethylacetic acid.  The process may be conducted in the presence of oxidation catalysts, e.g. elements of the eighth group of the Periodic Table or the rare earths, or the salts or oxides of these elements, e.g. platinum black, ferrous or ferric salts, e.g. ferrous or ferric isobutyrate or acetate, or ferrous sulphate, or metallic iron, or cerium, nickel or cobalt salts, particularly those of carboxylic acids, cerium nitrate or vanadium pentoxide.  In examples: (1) isobutyraldehyde, isobutyric acid and a little iron isobutyrate are charged into a vertical tower with a cooling coil, and are circulated by a pump and injected into the tower at the bottom, the suction from the injector drawing in oxygen in small bubbles, the temperature being kept at 30 DEG  C.; (2) air or oxygen is blown in fine bubbles or with rapid agitation through an isoaldehyde at 30 DEG C. containing a catalyst such as platinum black or a peroxide-destroying metal salt, e.g. a ferric or cerium salt; (3) an isoaldehyde, with or without a catalyst, is fed into the top of a packed tower and an oxygen-containing gas is passed countercurrently or concurrently through the tower; (4) the oxidation is effected by a continuous system as follows: (a) as in (2), fresh isoaldehyde being added during the operation; (b) as in (3), the mixture being recirculated and fresh isoaldehyde added to it before it enters the tower or in the tower itself; (c) in the injector system of (1), the unabsorbed oxygen being recirculated; (d) in a chamber filled with an oxygen-containing gas into which the acid-aldehyde mixture is sprayed, or in a rotary pump in which the aldehyde-acid mixture is churned up with oxygen; (5) a mixture of 2 : 4 : 4-trimethylvaleraldehyde-1 and tertiary butyl isopropyl ketone (obtained by rearrangement with dilute sulphuric acid of the mixture of unsaturated alcohols obtained by hydrolysis of chlorinated diisobutylene) is dissolved in acetic acid, iron isobutyrate is added and the mixture is stirred at 35 DEG  C. while oxygen is blown in; the product is fractionated and a mixture of the acid and an ester thereof is obtained and is boiled with caustic soda solution producing sodium isooctylate; (6) 2 : 5 - dimethylhexandial - 1 : 6 (obtained by rearrangement of 2 : 5-dimethylhexane-1 : 2-5 : 6-dioxide) is dissolved in glacial acetic acid, platinum black is added and the mixture is treated at 30--35 DEG  C. in an autoclave with air under 5 atmospheres pressure, producing a -a <1>-dimethyladipic acid; (7) a solution of b -phenylisobutyraldehyde in isobutyric acid, with the addition of iron isobutyrate, is stirred at 30 DEG  C. while oxygen is bubbled into it, yielding a -methylhydrocinnamic acid; (8) hydratropic aldehyde is similarly oxidized to hydratropic acid.  The products may be purified as follows: (a) most of the impurities may be removed by adding a small amount of water and distilling off the azeotropic mixture of water with the impurities; (b) the last traces of impurities are removed by the action of an amount equivalent to or slightly in excess of the amount of impurities present of an oxidizing agent stronger than oxygen, e.g. hydrogen peroxide, ozone, permanganates, hausmannite or nitric acid, and separating the product from the reduction product of the oxidizing agent.  Examples describe the application of these methods to the purification of crude isobutyric acid.