endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo[2.2.2]oct-5-ene-8,9-dicarboximide 3-sulfide | 122093-00-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo[2.2.2]oct-5-ene-8,9-dicarboximide 3-sulfide
• 英文别名: endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo<2.2.2>oct-5-ene-8,9-dicarboximide 3-sulfide
• CAS: 122093-00-9
• 化学式: C₁₇H₁₈NO₄PS
• 分子量: 363.374
• InChiKey: AYFSWFYYCTUDDY-FHABWPKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo[2.2.2]oct-5-ene-8,9-dicarboximide 3-sulfide 在 水 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 O-Ethyl-O,O-dihydrogen phosphorothioate
  参考文献：
  名称：

  Quin, Louis D.; Osman, F. H.; Sadanani, N. D., Phosphorus, Sulfur and Silicon and the Related Elements, 1989, vol. 41, p. 297 - 310

  摘要：

  DOI：
• 作为产物：
  描述：

  endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo<2.2.2>oct-5-ene-8,9-dicarboxamide 3-oxide 在 tetraphosphorus decasulfide 作用下， 以 二氯甲烷 为溶剂， 反应 144.0h， 以40%的产率得到endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo[2.2.2]oct-5-ene-8,9-dicarboximide 3-sulfide
  参考文献：
  名称：

  O-烷基偏硫代磷酸酯的生成和捕获

  摘要：

  合成这些 d'O-烷基 O-乙基硫代磷酸酯 a partir d'un 衍生 d'etheno oxaphosphorinne et de pentasulfure dephosphore

  DOI：

  10.1021/ja00199a061

文献信息

• Reaction of epoxides with metaphosphoric acid derivatives
  作者：Ryszard Bodalski、Louis D. Quin

  DOI：10.1021/jo00008a017

  日期：1991.4

  Ethyl metaphosphate (EtOPO2), eliminated in the thermolysis of the bridged cyclic phosphonate endo-3-ethoxy-6-methyl-N-phenyl-2,3-oxaphosphabicyclo[2.2.2]oct-5-ene-8,9-dicarboximide 3-oxide, has been found to cause ring opening of epoxides, resulting in formation of 2-ethoxy-4-substituted 1,3,2-dioxaphospholane 2-oxides as major products. N,N-Diethyl metaphosphoramidate (Et2NPO2) reacted similarly. With ethyl metathiophosphate (EtOP(S)O), the 1,3,2-oxathiaphospholane 2-oxide ring was formed. Products of these reactions were characterized by P-31 NMR spectroscopy and by GC-MS. These reactions are presumed to be initiated by electrophilic attack of the metaphosphate on the epoxide oxygen to form a cyclic oxonium ion.
• Quin, Louis D.; Sadanani, Narayan D.; Bourdieu, Catherine, Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 313 - 316
  作者：Quin, Louis D.、Sadanani, Narayan D.、Bourdieu, Catherine、Wu, Xiao-Ping、Quin, Gyongyi S.、Bodalski, Ryszard

  DOI：——

  日期：——
• Mechanistic studies on metaphosphate generation from fragmentation of 2,3-oxaphosphabicyclo[2.2.2]octene derivatives
  作者：Stefan Jankowski、Louis D. Quin

  DOI：10.1021/ja00018a045

  日期：1991.8

  The rates of fragmentation of 3-R-6-methyl-N-phenyl-2,3-oxaphosphabicyclo[2.2.2]oct-5-ene-8,9-dicarboximide 3-oxide, where R = Et2N or EtO, and of the 3-sulfide, where R = EtO, were determined in various solvents and at various temperatures. All reactions were first-order, as they were also when alcohols were present as trapping agents for the released metaphosphoric acid derivatives. From the small solvent effects on rates and activation parameters, it was concluded that the thermal fragmentations occurred by a retrocycloaddition process. This was supported by the similarity in rates for the three substrates, which differ considerably in polarity at phosphorus. The metaphosphates showed selectivity in their reactivity to alcohol mixtures; rates were faster with more nucleophilic alcohols (ethanol vs 2,2,2-trifluoroethanol) and less crowded alcohols (ethanol vs tert-butyl alcohol). A secondary reaction of the released metaphosphate with two of the substrates was detected by kinetics measurements; first-order rate constants were larger when alcohol was not present to remove metaphosphate. Quantum yields in photochemical fragmentations of the substrates were unchanged when alcohols were present; metaphosphates generated in this fashion showed selectivity effects toward alcohols as seen in the thermal fragmentation. No evidence was found for radical intermediates in either process.