1-(1-Methoxy-2-propoxy)-3-methyl-3-phospholene 1-oxide

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦酸及其衍生物
• 英文名称: 1-(1-Methoxy-2-propoxy)-3-methyl-3-phospholene 1-oxide
• 英文别名: 1-(1-Methoxypropan-2-yloxy)-3-methyl-2,5-dihydro-1lambda5-phosphole 1-oxide；1-(1-methoxypropan-2-yloxy)-3-methyl-2,5-dihydro-1λ5-phosphole 1-oxide
• 化学式: C₉H₁₇O₃P
• 分子量: 204.206
• InChiKey: XOMGMLDFSAOLPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(1-Methoxy-2-propoxy)-3-methyl-3-phospholene 1-oxide 以100%的产率得到
  参考文献：
  名称：

  Bodalski Ryszard, Jankowski Stefan, Glowka Marek L., Filipiak Tomasz, Qui+, J. Org. Chem., 59 (1994) N 18, S 5173-5178

  摘要：

  DOI：
• 作为产物：
  描述：

  丙二醇甲醚 、 1-chloro-3-methyl-3-phospholene-1-oxide 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以44.1%的产率得到1-(1-Methoxy-2-propoxy)-3-methyl-3-phospholene 1-oxide
  参考文献：
  名称：

  Anchimeric Participation of a Methoxy Group in a Reaction of a Metathiophosphate

  摘要：

  Thermolysis of derivatives of the 2,3-oxaphosphabicyclo[2.2.2]octene ring system with phosphorus in the phosphonothionoate state accomplishes the extrusion of O-alkyl metathiophosphates, ROP(S)O, as highly reactive intermediates. With alcohol present, the intermediate is trapped as an O,O-dialkyl phosphorothionoate, (RO)(R'O)P(S)OH. With R = (RS)-sec-butyl in the metathiophosphate released, the phosphorothionoate is formed as a 1:1 mixture of diastereoisomers, but when R = (RS)-1-methoxy-2-propyl in the metathiophosphate, a 4:1 isomer mixture is formed in CHCl3, and 2:1 in toluene. This can be explained by anchimeric participation of the methoxy group, giving diastereoisomeric 1,3,2-dioxaphospholane intermediates in amounts that are unequal due to small stability differences that arise from steric effects. The structure of the bicyclic precursor was established by X-ray diffraction analysis and led to the prediction that the major isomer would have the R*(c),S*(p) configuration. This was proved by an independent synthesis of the same 1:1 isomer mixture from thionation of (RO)PH(O)(OR'), separation by chromatography, and X-ray diffraction analysis of the dicyclohexylamine salt of one of the isomers. This isomer had the R*(c),R*(p) configuration and was identical to the minor isomer (with the more upfield P-31 NMR signal) obtained from the metathiophosphate.

  DOI：

  10.1021/jo00097a018

文献信息

• Bodalski Ryszard, Jankowski Stefan, Glowka Marek L., Filipiak Tomasz, Qui+, J. Org. Chem., 59 (1994) N 18, S 5173-5178
  作者：Bodalski Ryszard, Jankowski Stefan, Glowka Marek L., Filipiak Tomasz, Qui+

  DOI：——

  日期：——
• Anchimeric Participation of a Methoxy Group in a Reaction of a Metathiophosphate
  作者：Ryszard Bodalski、Stefan Jankowski、Marek L. Glowka、Tomasz Filipiak、Louis D. Quin

  DOI：10.1021/jo00097a018

  日期：1994.9

  Thermolysis of derivatives of the 2,3-oxaphosphabicyclo[2.2.2]octene ring system with phosphorus in the phosphonothionoate state accomplishes the extrusion of O-alkyl metathiophosphates, ROP(S)O, as highly reactive intermediates. With alcohol present, the intermediate is trapped as an O,O-dialkyl phosphorothionoate, (RO)(R'O)P(S)OH. With R = (RS)-sec-butyl in the metathiophosphate released, the phosphorothionoate is formed as a 1:1 mixture of diastereoisomers, but when R = (RS)-1-methoxy-2-propyl in the metathiophosphate, a 4:1 isomer mixture is formed in CHCl3, and 2:1 in toluene. This can be explained by anchimeric participation of the methoxy group, giving diastereoisomeric 1,3,2-dioxaphospholane intermediates in amounts that are unequal due to small stability differences that arise from steric effects. The structure of the bicyclic precursor was established by X-ray diffraction analysis and led to the prediction that the major isomer would have the R*(c),S*(p) configuration. This was proved by an independent synthesis of the same 1:1 isomer mixture from thionation of (RO)PH(O)(OR'), separation by chromatography, and X-ray diffraction analysis of the dicyclohexylamine salt of one of the isomers. This isomer had the R*(c),R*(p) configuration and was identical to the minor isomer (with the more upfield P-31 NMR signal) obtained from the metathiophosphate.