Direct Formation of a Novel Cyclic Formal, 1,3,5,7,10,13-Hexaoxacyclopen-
tadecane, by the Reaction of 1,3,5-Trioxane with Ethylene Oxide

Naoaki YAMASAKI†, Junzo MASAMOTO*, Nobuaki OHNISHI†† and Hajime NAGAHARA†††

Department of Polymer Science and Engineering, Kyoto Institute of Technology; Matsugasaki, Sakyo-ku, Kyoto-shi 606-8585 Japan
† Functional Additives Technology Department One, Asahi Chemical Industry Co., Ltd.; 6-2700, Asahi-machi, Nobeoka-shi 882-0847 Japan
†† Department of Chemistry and Material Technology, Kyoto Institute of Technology;Matsugasaki, Sakyo-ku, Kyoto-shi 606-8585 Japan
††† Division of Research and Development, Asahi Chemical Industry Co. Ltd.; 1-1-2 Yuraku-cho, Chiyoda-ku, Tokyo 100-8440 Japan

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 1 mol 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 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 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.


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