Patent GB-754359-A (GB)
Title: Improvements in or relating to the production of oxirane compounds and the resulting compounds
Filed: 1954-06-04
Abstract: A process for producing an oxirane compound comprises oxidizing an ethylenic compound with hydrogen peroxide in the presence of an inorganic peracid catalyst and at a temperature not exceeding 100 DEG C., and thereafter removing or neutralizing substantially all of said catalyst and any strong acid not being a catalyst which may also be present without allowing the temperature of the mixture to exceed 100 DEG  C.  Preferred methods for removing the catalyst and/or the aforesaid acid are contact with anion-exchange resins and, for water insoluble oxirane products, water washing. Specified resins are phenolic-formaldehyde-polyamine type resins and those prepared by condensing aliphatic polyamines with polyhalo hydrocarbons, and it is stated to be preferable to remove any suspended catalyst or other material by settling and decantation or filtration before contacting the reaction mixture with the resin.  Water-washing may be combined with neutralization, or solvent extraction may be used.  It is stated that ethylenic compounds of all kinds may be converted to oxirane compounds and a wide range of starting materials are specified including ethylenic hydrocarbons, ethylenic halides, alcohols, ethers, acids, esters, ketones, aldehydes, and sulphur analogues thereof.  The preferred starting materials are however polycyclic ethylenic compounds which form stable epoxides, such as 1,4-methano-2,5-cyclohexadiene, hexa- and octa-hydronaphthalenes, 2,3-dichloro - 1,4 - methano - 2,5 - cyclohexadiene, halo - hexahydro - 1,4,5,8 - dimethanonaphthalenes such as 2,3-dichloro-1,4,4a,5,8,8a-hexahydro - 1,4,5,8 - exo - endo - dimethano naphthalene and halo - 4,7 - methanotetrahydro indenes such as 5,6-dichloro-4,7-methano-3a, 4,7,7a-tetrahydroindene.  Any of the inorganic peracids known to be effective in promoting hydroxylation of ethylenic compounds by hydrogen peroxide can be used as catalysts. The catalyst may be formed in situ in the reaction mixture and in a modification of the process of the invention a metal oxide is so used, and any metal oxide present at the end of the reaction is removed from the reaction mixture without exposing the reaction product to temperatures above 100 DEG  C.  The preferred catalysts are tungstic acid or tungsten trioxide, which form pertungstic acid. Simple, poly- and hetero-poly peracids, and sulphuric acid in the presence of hydrogen peroxide, are referred to as catalysts.  The hydrogen peroxide may be anhydrous or aqueous and it may be generated in situ.  The reaction is preferably carried out in the liquid phase, non-acidic organic solvents being preferred.  Ethylenic alcohols being epoxidized may serve as reactant and solvent.  Preferred temperatures for the reaction are from about - 10 DEG  C. to about 75 DEG  C.  In examples: (1) 1,2,3,4,10,10-hexachloro-1,4,4a-5,8,8a - hexahydro - 1,4,5,8 - endo - exodimethanonaphthalene is epoxidized with hydrogen peroxide and tungsten trioxide in an aqueous-alcoholic solvent at 70 DEG  C.  The reaction mixture is poured into water containing potassium carbonate to precipitate the product, 1,2,3,4,10,10 - hexachloro - 6,7 - epoxy-1,4,4a,5,6,7,8,8a - octahydro - 1,4,5,8 - endoexo - dimethanonaphthalene.  Pervanadic acid catalyst may be used; (2) by the same method 1,2,3,4,10,10 - hexachloro - 6,7 - epoxy-1,4,4a,5,6,7,8,8a - octahydro - 1,4,5,8 - endo-endo-dimethanonaphthalene is obtained from 1,2,3,4,10,10 - hexachloro - 1,4,4a,5,8,8a - hexahydro - 1,4,5,8 - endo - endo - dimethanonaphthalene and 1,2 - epoxy - 4,5,6,7,8,8-hexachloro - 4,7 - methano - 3a,4,7,7a - tetrahydroindane is obtained from 4,5,6,7,8,8-hexachloro - 4,7 - methano - 3a,4,7,7a - tetrahydroindene; (3) allyl alcohol is epoxidized with hydrogen peroxide and tungstic acid at 50 DEG  C. and the reaction mixture is percolated through an anion exchange resin.  The thus treated mixture gives glycidol on distillation, glycerol allyl ether and glycerol being formed as by products.  Similarly, an excess of di-allyl ether with hydrogen peroxide gives allyl glycidyl ether; (4) allyl chloride with hydrogen peroxide and pertungstic acid at 50 DEG  C. gives epichlorhydrin after removal of the catalyst as in Example (3). Similarly cyclohexene gives epoxycyclohexane. Specification 692,547 is referred to.