|Budget Amount *help
¥4,200,000 (Direct Cost : ¥4,200,000)
Fiscal Year 1999 : ¥4,200,000 (Direct Cost : ¥4,200,000)
|Keywords||Spiro[3.3]phosphorane / Spirobi[1, 2-oxasiletanide] / Spirobi[1, 2-oxaselenetane] / Siprobi[1, 2-oxatelluretane] / Homo-Brook rearrangement / Oxirane formation reaction / X-ray crystallographic analysis / Highly coordinate main group compound / スピロ[3.3]ホスホラン / スピロビ[1,2-オキサシレタニド] / スピロビ[1,2-オキサセレネタン] / スピロビ[1,2-オキサテルレタン] / homo-Brook転位 / オキシラン生成反応 / X線結晶構造解析 / 高配位典型元素化合物 / homoーBrook転位 / スピロビ[1,2ーオキサシレタニド] / スピロビ[1,2ーオキサセレネタン] / スピロビ[1,2ーオキサテルレタン] / スピロ[3.3]骨格 / オキシラン生成 / 5配位1,2-オキサホスフェタン / 5配位1,2-オキサシレタニド / スピロ[3.3]シリカート / Wittig型反応|
1. 2, 2, 6, 6-Tetra(p-chlorophenyl)-3, 5-dimethyl-1, 5-dioxa-4λィイD15ィエD1- phosphaspiro [3.3] heptane was synthesized as a stable compound. In a trivalent bis (β-hydroxyalkyl) phosphine, which is a synthetic intermediate for the alternative synthesis of the [3.3] phosphorane, interaction between oxygen and phosphorus atoms was observed. It was suggested by theoretical calculation of simplified models that this is interaction between the lone pair of the oxygen and σ* of the P-C bond. 2. Spirobi[1, 2-oxasiletanidel], which is a Si analog of the spiro [3.3] phosphorane, was also synthesized, but it gradually decomposed at room temperature to give the corresponding homo-Brook rearrangement product (alcohol) after treatment with water. Even in pentac60rdinate 1, 2-oxasiletanides bearing the Martin ligand, which usually undergo the Peterson reaction, can afford the homo-Brook rearrangement products depending on the substituent at the 3-position and the reaction conditions. 3. A 1, 5-dioxa-λィイD14ィエD1-selenaspiro [3.3] heptane was synthesized according to the research proposal. dl-and meso-isomers of Se(CH(SPh)C(CFィイD23ィエD2)ィイD22ィエD2OH)ィイD22ィエD2, which were prepared from bis (phenylthiomethyl) selenide, were allowed to react with BrィイD22ィエD2 in the presence of triethylamine to afford trans-trans- and cis-trans-isomers of the desired compound. Their thermolysis gave two molar equivalents of the corresponding oxirane and elemental selenium. The compound having phenyl groups instead of phenylthio groups of the 3, 5-positions was also synthesized but only as a trans-trans-isomer. 4. The synthesis of tellurium analog was achieved by sequential treatment of PhSCHPhC(CFィイD23ィエD2)ィイD22ィエD20H with lithium p, p'-di-t-butylbiphenylide and TeClィイD24ィエD2. X-ray crystallographic analyses of some of these spiro [3.3] compounds were carried out. The present research project has been achieved successfully.