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Synthesis of Spiro [3.3] Compounds Containing Highly Coordinate Main Group Elements and Development of Novel Reactions

高度配位主族元素Spiro[3.3]化合物的合成及新反应的进展

基本信息

批准号：
10440212
负责人：
KAWASHIMA Takayuki
金额：
$ 2.69万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

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.

1. 2, 2, 6日6-Tetra (p-chlorophenyl) 3, 5-dimethyl-1, 5-dioxa-4λィイD15ィエD1 - phosphaspiro[3.3]庚烷合成作为一种稳定的化合物。三价双（β-羟基烷基）磷化氢是替代合成[3.3]磷烷的合成中间体，氧和磷原子之间的相互作用被观察到。简化模型的理论计算表明，这是氧的孤对与P-C键的σ*之间的相互作用。2. Spirobi[1,2 -oxasiletanidel]是一种类似于spiro[3.3]磷烷的Si类似物，也被合成，但它在室温下经水处理后逐渐分解得到相应的homo-Brook重排产物（醇）。即使在含Martin配体的五羧基1,2 -氧基硅烷中，通常发生彼得森反应，但根据3位取代基和反应条件的不同，也能产生同源-布鲁克重排产物。3. 根据研究方案合成了1,5 -二氧杂A -λ γ γ γ γ - 1-硒代阿斯皮索[3.3]庚烷。由双（苯硫甲基）硒化物制备的Se(CH(SPh)C(CF φ φ D23 φ φ D2OH) φ φ D22 φ D2OH) φ φ D22 φ D2和中位异构体在三乙胺的存在下与Br φ φ D22 φ D2反应，得到所需化合物的反式、反式和顺式异构体。它们的热分解得到两个摩尔当量的氧环烷和元素硒。以苯基取代3,5位苯基硫代的化合物也被合成，但只是作为反式反式异构体。4. 采用锂p、p′-二丁基联苯醚和TeCl φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ。对其中一些螺旋[3.3]化合物进行了x射线晶体学分析。目前的研究项目已圆满完成。