Direct Formation of a Novel Cyclic Formal, 1, 3, 5, 7, 10, 13-Hexaoxacyclopentadecane, by the Reaction of 1, 3, 5-Trio x ane with Ethylene Oxide

Abstract

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 using a micro-distillation apparatus and gas chromatographic method. The chemical structure was determined using ¹H-NMR, ¹³C-NMR, mass spectrum and elemental analyses. Formation of HOCP was critical. When the mole ratio of ethylene 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 1mol of ethylene 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 reaction product of 1 mol of trioxane and 2mol 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 commercial base acetal copolymer which was produced by the copolymerization of trioxane and ethylene oxide, it is known that there is a consecutive three-unit sequences of ethylene oxide, and this consecutive sequences might be postulated to come from the ring-opening polymerization of the novel cyclic formal of HOCP. Direct reaction between trioxane and ethylene oxide is thought to supply us a posssibility of a new type and new route of crown ether.