Direct formation of a novel cyclic formal, 1,3,5,7,10,13-hexaoxacyclopentadecane, by the reaction of 1,3,5-trioxane with ethylene oxide

We synthesized a novel cyclic formal, 1,3,5,7,10,13-hexaoxacyclopentadecane (HOCP), which is a direct reaction product of 1 mol of trioxane and 3 mol of ethylene oxide. The novel cyclic compound was separated and collected us ing a micro-distillation apparatus and gas chromatographic method. The chem ical structure was determined using H-1-NMR, C-13-NMR, mass spectrum and el emental analyses. Formation of HOCP was critical. When the mole ratio of et hylene oxide to trioxane was below 0.026, only 1,3,5,7-tetraoxacyclononane (TOCN), which was the reaction product of 1 mol of trioxane and 1 mol of et hylene oxide was formed. When the mole ratio of ethylene oxide to trioxane was around 0.033, 1,3,5,7,10-pentaoxacyclododecane (POCD), which was the re action product of 1 mol of trioxane and 2 mol of ethylene oxide was formed additionally to TOCN. When the mole ratio of ethylene oxide to trioxane was around 0.039, HOCP was formed additionally to TOCN and POCD. In the commer cial base acetal copolymer which was produced by the copolymerization of tr ioxane and ethylene oxide, it is known that there is a consecutive three-un it sequences of ethylene oxide, and this consecutive sequences might be pos tulated to come from the ring-opening polymerization of the novel cyclic fo rmal of HOCP. Direct reaction between trioxane and: ethylene oxide is thoug ht to supply us a posssibility of a new type and new route of crown ether.