Patent GB-596779-A (GB)
Title: Improvements in or relating to peroxycarbonate esters of organic hydroxy compounds
IPC: C07D307/12
Filed: 1943-11-12
Abstract: Organic peroxy carbonates are used as driers for linseed, tung, soya bean, and similar oils.ALSO:Organic peroxycarbonates are prepared by reacting a haloformate with an aqueous solution or suspension of a basic metal peroxide or with an inorganic peroxide in the presence of water and an alkaline agent.  Methyl, ethyl, propyl, butyl, isobutyl, hexyl, lauryl, stearyl, allyl, methallyl, crotyl, dimethallyl, methyl vinyl carbinyl, linallyl, oleyl, cinnamyl, propargyl and butadienyl chloroformates, the chloroformates of methyl ethyl, dipropyl, b -phenyl ethynyl, b -methyl ethynyl, b -allyl ethynyl and b -cyclohexyl ethynyl carbinols or of hydroxy acids and their esters such as methyl, ethyl, propyl, allyl, crotyl, methallyl, oleyl, glycol or glycerol lactates, glycolates, hydroxy butyrates, salicylates, ricinoleates, or the corresponding bromoformates are specified, also chloroformates of aromatic or other cyclic or heterocyclic hydroxy compounds such as phenol, naphthol, resorcinol, cresol, phthalyl alcohol, benzyl alcohol, cyclohexyl alcohol and dioxane diols.  Basic metal peroxides specified are those of sodium, potassium, lithium, borium and lead.  Hydrogen peroxide in presence of water and sodium or calcium hydroxide or carbonate may be used. Temperatures are generally below 10 DEG  C. Polymeric peroxycarbonates may be prepared by reacting sodium peroxide with a di- or poly-haloformate such as ethylene, diethylene, triethylene, 1,2-propylene, trimethylene or butylene glycol dichloroformate, glycerol or a -methyl glycerol di- or tri-chloroformate, resorcinol dichloroformate or dibromoformate. The peroxycarbonates decompose on heating or even at room temperatures, sometimes with explosion. These may be stored as a 10-15 per cent solution in, for example, ethylene glycol bis-(allyl or ethyl carbonate).  They may be used for bleaching flour, as driers for linseed, tung, soya bean and like oils, as sterilizing agents, and as catalysts for the polymerization of methyl methacrylate, vinyl acetate, styrene, butadiene, b -chlorbutadiene, allyl esters such as diallyl or dimethallyl phthalate, maleate, oxalate or succinate, or ethylene glycol bis-(allyl carbonate), or other compounds containing olefinic or acetylenic linkages.  In examples: (1) sodium peroxide is added to ethylene glycol bis-(chloroformate) in water at 0 DEG  C. and the solid polymeric peroxide separated.  A 5 per cent solution in ethylene glycol bis-(allyl carbonate) polymerizes on heating to 70 DEG  C. for several hrs.; (2) aqueous sodium peroxide is added to ethyl chloroformate at -10 DEG  C. and the oil layer washed and dried. It is miscible with and catalyses polymerization of ethylene or diethylene glycol bis-(allyl carbonate) and diethylene glycol bis-(methallyl carbonate); (3) diethylene glycol dichloroformate is used in the process of (1); (4) and (5) methyl or allyl chloroformate is used in the process of (2); (6) aqueous hydrogen peroxide and caustic soda are added to butyl chloroformate at below 5 DEG  C.; (7) a -carbethoxyethyl chloroformate (chloroformate of ethyl lactate) is reacted similarly; (8) isopropyl chloroformate is added to aqueous hydrogen peroxide and caustic soda at below 5 DEG  C.; (9) and (10) tetrahydrofurfuryl and lauryl chloroformates are reacted similarly; (11) and (12) cyclohexyl and benzyl peroxycarbonates are made by similar processes.  The Specification as open to inspection under Sect. 91 is not limited to reaction in aqueous media.ALSO:Organic peroxycarbonates are used for bleaching flour