Patent GB-461879-A (GB)
Title: Manufacture of oxidising or reducing agents or combined oxidising and reducing agents more particularly intended for promoting metabolic changes in living organisms
IPC: C07C33/025
Filed: 1935-05-22
Abstract: Products of therapeutic value are obtained from certain organic substances, as specified below, by heating them with at least twice the weight of fuming sulphuric acid or an equivalently strong phosphoric acid, preferably to about 250--350 DEG  C., and passing a current of gas through the mixture or the reaction vessel to carry over the reaction products as a distillate. According to the second Provisional Specification, the gas passed through the mixture or the reaction vessel may be ethylene.  The organic substances specified are ethyl alcohol, ethyl ether, glycollic acid, glyoxalic acid, glyoxal, acetaldehyde, acetic acid, glycerol, glyceric acid, methylglyoxal, lactic acid, formic acid, oxalic acid, malonic acid, maleic acid, malic acid, other organic substances obtainable by oxidizing monosaccharides such as fructose or glucose, and also the monosaccharides themselves.  The substances are preferably mixed with sulphuric acid before they are treated with fuming sulphuric acid. The products may be used as such or they may be after-treated in any of the following ways: (1) the distillate may be extracted with ether and the extract evaporated and then treated with hydrogen peroxide; (2) the liquid residue from the ether extraction may be concentrated and treated with a solution of barium or calcium chloride, and the precipitate filtered and extracted with warm water; the solution so obtained is crystallized (A), and the filtrate from the crystals is treated with sodium sulphate to remove barium or calcium; the filtrate from this operation is evaporated or diluted ready for use; the crystals from step A may also be dissolved ready for use; (3) the first filtrate obtained in step 2 may be evaporated and treated with hydrogen peroxide; (4) the original products may be converted into peroxides by treatment in aqueous solution with ultra-violet light in the presence of a catalyst, which is selected to resonate the wavelength of the light employed; thus, a sulphate or other salt of mercury, lead, bismuth, antimony or arsenic is used with light of a wavelength of 2500 m m , 3573 m m , 3067 m m , 2597 m m  and 2780 m m , respectively.  The reactions involved in the initial treatment are illustrated by reference to the treatment of diethyl ether with fuming sulphuric acid; this is stated to produce di-, tetra- and hexa-sulpho substitution products of diethyl ether, which on distillation or high dilution with water, lose their sulpho groups and produce a variety of unsaturated compounds of which HOCH : CHOCH : CHOH, OC : CHOCH : CO, HOC : COC : COH and OC : CO are typical. Acetaldehyde similarly forms a disulphonate from which unsaturated products such as HOCH : CO are stated to be produced.  The first Provisional Specification refers to processes wherein (5) propargyl aldehyde, acrolein, acetaldehyde or formic acid, alone or mixed and dissolved or not in ether, are treated with hydrogen peroxide or passed with air or oxygen over a platinum catalyst at a temperature below red heat, in order to produce peroxides of the starting materials and of their dehydration products, and (6) acetaldehyde, acrolein or proparglic aldehyde, or a derivative thereof, or a ketose such as fructose, is treated as such or in ether solution with a dehydrating and oxidizing agent such as concentrated sulphuric, phosphoric or hydrochloric acid to produce unsaturated compounds and their oxidation products.  The second Provisional Specification states that process (5) above may be applied to proparglic acid, acetylene, acetylenedicarboxylic acid, diacetylenedicarboxylic acid, oxalic acid, vinyl alcohol, vinyl ether, and formaldehyde, and also to the initial products obtained by the process described in the Complete Specification.  It states further that peroxides may be produced from any of these starting materials by process (4) above.ALSO:Organic peroxides are obtained from certain organic substances, as specified below, by heating them with at least twice the weight of fuming sulphuric acid or an equivalently strong phosphoric acid, preferably to about 250--350 DEG  C., passing a current of gas through the mixture or the reaction vessel to carry over the reaction products as a distillate, and irradiating the distillate. The organic substances specified are ethyl alcohol, ethyl ether, glycollic acid, glyoxalic acid, glyoxal, acetaldehyde, acetic acid, glycerol, glyceric acid, methylglyoxal, lactic acid, formic acid, oxalic acid, malonic acid, maleic acid, malic acid, other organic substances obtainable by oxidizing monosaccharides such as fructose or glucose, and also the monosaccharides themselves. The irradiation is effected by treating the distillate in aqueous solution with ultraviolet light in the presence of a catalyst, which is selected to resonate the wave-length of the light employed; thus, a sulphate or other salt of mercury, lead, bismuth, antimony or arsenic is used with light of a wave length of 2500m m . 3573m m , 3067m m , 2597m m , and 2780m m  respectively.  The second Provisional Specification states that propargyl aldehyde, acrolein, acetaldehyde, formic acid, propargylic acid, acetylene, acetylenedicarboxylic acid, diacetylene dicarboxylic acid, oxalic acid, vinyl alcohol, vinyl ether, and formaldehyde, may be similarly converted into peroxides.