1-(1-Adamantoxy)-3-methyl-3-phospholene 1-oxide | 153577-33-4

• 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-Adamantoxy)-3-methyl-3-phospholene 1-oxide
• 英文别名: 1-(1-Adamantyloxy)-3-methyl-2,5-dihydro-1lambda5-phosphole 1-oxide；1-(1-adamantyloxy)-3-methyl-2,5-dihydro-1λ5-phosphole 1-oxide
• CAS: 153577-33-4
• 化学式: C₁₅H₂₃O₂P
• 分子量: 266.32
• InChiKey: ZNDMFBPLZAJHOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(1-Adamantoxy)-3-methyl-3-phospholene 1-oxide 在 溴 、 三乙胺 作用下， 以 氯仿 、 苯 为溶剂， 反应 120.0h， 生成 7-syn-(1-Adamantoxy)-2-methyl-N-phenyl-7-phosphabicyclo<2.2.1>hept-2-ene-endo-5,6-dicarboximide 7-oxide
  参考文献：
  名称：

  Synthesis, fragmentation, and photorearrangement of neopentyl and adamantyl phosphonates in the 2,3-oxaphosphabicyclo[2.2.2]octene system

  摘要：

  Precursors for the generation of neopentyl and 1-adamantyl metaphosphates were prepared by the insertion of oxygen into a ring carbon-phosphorus bond of some 7-phosphanorbornene derivatives. The stereochemistry of the resulting products, which possess the 2,3-oxaphosphabicyclo[2.2.2]octene ring system, was established by NMR spectroscopy, and by X-ray analysis in one case. The O-insertion (by MCPBA) generally proceeds with retention of phosphorus configuration, but in one precursor with a syn-neopentoxy group a minor product from an inversion process was isolated. The 7-phosphanorbornene isomer with the uncommon anti neopentoxy structure was synthesized by rearrangement of the syn isomer; O-insertion gave exclusively the product of retention, identical to the minor product from the syn isomer. Conditions were developed for the photochemical fragmentation of the precursors at room temperature to release the metaphosphates; these highly reactive species were trapped as phosphates when alcohols were included in the medium. Thermal fragmentation also was effective for generating the neopentyl ester. Irradiation was also performed at -75 degrees C in an attempt to stabilize the metaphosphates so as to allow their spectral characterization, but a rearrangement occurred to give a novel tricyclic compound. In this rearrangement, the ring oxygen shifted stereospecifically to the adjacent sp(2) carbon, and a cyclopropane ring was formed.

  DOI：

  10.1021/jo00080a020
• 作为产物：
  描述：

  1-金刚烷醇 、 1-chloro-3-methyl-3-phospholene-1-oxide 在 三乙胺 作用下， 以 苯 为溶剂， 反应 24.0h， 以89.8%的产率得到1-(1-Adamantoxy)-3-methyl-3-phospholene 1-oxide
  参考文献：
  名称：

  Synthesis, fragmentation, and photorearrangement of neopentyl and adamantyl phosphonates in the 2,3-oxaphosphabicyclo[2.2.2]octene system

  摘要：

  Precursors for the generation of neopentyl and 1-adamantyl metaphosphates were prepared by the insertion of oxygen into a ring carbon-phosphorus bond of some 7-phosphanorbornene derivatives. The stereochemistry of the resulting products, which possess the 2,3-oxaphosphabicyclo[2.2.2]octene ring system, was established by NMR spectroscopy, and by X-ray analysis in one case. The O-insertion (by MCPBA) generally proceeds with retention of phosphorus configuration, but in one precursor with a syn-neopentoxy group a minor product from an inversion process was isolated. The 7-phosphanorbornene isomer with the uncommon anti neopentoxy structure was synthesized by rearrangement of the syn isomer; O-insertion gave exclusively the product of retention, identical to the minor product from the syn isomer. Conditions were developed for the photochemical fragmentation of the precursors at room temperature to release the metaphosphates; these highly reactive species were trapped as phosphates when alcohols were included in the medium. Thermal fragmentation also was effective for generating the neopentyl ester. Irradiation was also performed at -75 degrees C in an attempt to stabilize the metaphosphates so as to allow their spectral characterization, but a rearrangement occurred to give a novel tricyclic compound. In this rearrangement, the ring oxygen shifted stereospecifically to the adjacent sp(2) carbon, and a cyclopropane ring was formed.

  DOI：

  10.1021/jo00080a020

文献信息

• Sunko D. E., Vanik H., Mihali Z., Shiner V. J. (Jr.), Wiglis F. P., J. Org. Chem, 59 (1994) N 23, S 7051-7055
  作者：Sunko D. E., Vanik H., Mihali Z., Shiner V. J. (Jr.), Wiglis F. P.

  DOI：——

  日期：——
• Synthesis, fragmentation, and photorearrangement of neopentyl and adamantyl phosphonates in the 2,3-oxaphosphabicyclo[2.2.2]octene system
  作者：Louis D. Quin、Xiao-Ping Wu、Narayan D. Sadanani、Ivan Lukes、Alexey S. Ionkin、Roberta O. Day

  DOI：10.1021/jo00080a020

  日期：1994.1

  Precursors for the generation of neopentyl and 1-adamantyl metaphosphates were prepared by the insertion of oxygen into a ring carbon-phosphorus bond of some 7-phosphanorbornene derivatives. The stereochemistry of the resulting products, which possess the 2,3-oxaphosphabicyclo[2.2.2]octene ring system, was established by NMR spectroscopy, and by X-ray analysis in one case. The O-insertion (by MCPBA) generally proceeds with retention of phosphorus configuration, but in one precursor with a syn-neopentoxy group a minor product from an inversion process was isolated. The 7-phosphanorbornene isomer with the uncommon anti neopentoxy structure was synthesized by rearrangement of the syn isomer; O-insertion gave exclusively the product of retention, identical to the minor product from the syn isomer. Conditions were developed for the photochemical fragmentation of the precursors at room temperature to release the metaphosphates; these highly reactive species were trapped as phosphates when alcohols were included in the medium. Thermal fragmentation also was effective for generating the neopentyl ester. Irradiation was also performed at -75 degrees C in an attempt to stabilize the metaphosphates so as to allow their spectral characterization, but a rearrangement occurred to give a novel tricyclic compound. In this rearrangement, the ring oxygen shifted stereospecifically to the adjacent sp(2) carbon, and a cyclopropane ring was formed.