Patent GB-787748-A (GB)
Title: Improvements relating to oxygenated organic compounds
IPC: B01J19/24
Filed: 1954-04-14
Abstract: Oxygenated organic compounds are prepared by reacting an organic compound (as hereinafter defined) in the liquid state with a reactive oxygen-containing gas continuously produced by the influence of a continuous silent electric <PICT:0787748/IV (b)/1> discharge on a feed gas containing free oxygen, the discharge being produced by electrodes forming parts of an ozone generator, the feed gas and the organic compound being continuously introduced into the generator in countercurrent flow, the organic compound always being present in sufficient quantity to react with the reactive gas as rapidly as the latter is formed, and continuously withdrawing the oxygenated compound produced.  The organic compounds which may be oxygenated are unsaturated aliphatic mono- and poly-carboxylic acids such as acrylic, crotonic, hexadecenoic, oleic, elaidic, linoleic and ricininoleic acids; esters of such acids, e.g. maleic esters; unsaturated aliphatic aldehydes and ketones such as acrolein, crotonaldehyde and citral; olefines, e.g. pentene, hexene, octene, decene and undecene; unsaturated materials present in tall oil; terpenes; cyclic unsaturated aliphatic hydrocarbons such as cyclohexene; aryl-substituted aliphatic hydrocarbons such as diphenyl methane; saturated aliphatic mono-carboxylic acids from propionic acid up to stearic acid; saturated aliphatic dicarboxylic acids, e.g. glutaric, pimelic and azelaic acids; esters of these mono- and di-basic acids; homologous ketones ranging from acetone to octadecanone; saturated aliphatic hydrocarbons from hexane upwards; hydro aromatics, e.g. cyclohexane; and saturated alkanols ranging from methanol to stearyl alcohol.  These reagents are used in the liquid state but may be normally gaseous, liquid or solid.  The free-oxygen containing gas may be oxygen as such or admixed with inert gases.  The reaction may be effected at pressures from 30 atmospheres down to 1/100 atmosphere and at a temperature of - 76 DEG C. to + 110 DEG  C.; an inert solvent may be present.  The products obtained include acids, per-acids, peroxides, aldehydes, ketones and esters from the saturated organic reagents and ozonides from the unsaturated reagents.  The preferred apparatus comprises two concentric glass tubes 1, 2 forming a generator space which may be packed.  The inner tube 2 contains a high-voltage brass electrode 3 immersed in an electrolyte solution and the outer tube 1 is provided with a water-jacket 4 serving as an earth electrode and used also for cooling or heating.  The oxygen-containing gas is fed in at 6 and the organic reagent at 5; the product is continuously withdrawn into a receiver 7 and spent gas is vented at 8.  According to examples using this apparatus, oleic acid, diethyl maleate, tall oil, methyl oleate, linoleic acid, ricinoleic acid and elaidic acid are converted into their ozonides; octanols-1 and 2, octanone-2, diphenylmethane and hexadecane are converted into acids and peroxides; ethyl-hexoic acid and diethyl malonate are converted into the corresponding peracid and per-ester; and liquid polybutadiene dissolved in a paraffin oil or in dibutyl glutarate is ozonized and the product, after oxidative cleavage, yields acids in which formic acid predominates.  The ozonide products may be used as polymerization catalysts, bleaching agents for vegetable oils, acetate rayon and wool, curing agents for natural and synthetic rubbers including silicone rubber, oxidation agents and as bacterial and fungicidal materials.ALSO:Ozonides of the following olefinically unsaturated compounds may be used as bleaching agents for wool and acetate rayon: unsaturated aliphatic mono- and poly-carboxyclic acids, esters thereof, aldehydes and ketones, olefines including terpenes and the unsaturated material in tall-oil. Their preparation is described (see Group IV (b)].ALSO:Ozonides of the following olefinically unsaturated compounds may be used as bleaching agents for vegetable oils: unsaturated aliphatic mono- and polycarboxylic acids, esters thereof, aldehydes and ketones, olefines including terpenes and the unsaturated materials in tall-oil.  Their preparation is described (see Group IV (b)).