1-hydro-5-carbaphosphatrane | 340254-88-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-hydro-5-carbaphosphatrane
• CAS: 340254-88-8
• 化学式: C₃₁H₃₇O₃P
• 分子量: 488.607
• InChiKey: VMNHINLJWIDMFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.54
• 重原子数：
  35.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-hydro-5-carbaphosphatrane 在 次氯酸叔丁酯 作用下， 以 氘代氯仿 为溶剂， 生成 1-chloro-5-carbaphosphatrane
  参考文献：
  名称：

  基于五价正膦与三价环状亚膦酸酯之间的互变异构，1-氢-5-氨基甲叉膦酸酯的反应性。

  摘要：

  检查了1-氢-5-氨基甲叉膦（1a）的反应行为。用氧化剂例如3-氯过氧苯甲酸（mCPBA）和tBuOCl处理1a，通过环状亚膦酸酯3（1a的互变异构体）分别得到环状膦酸酯2和1-氯-5-氨基甲膦酸酯（4）。化合物4易于水解得到2。化合物1a也通过3被元素硫磺硫化，得到环状硫代膦酸酯5，其也通过在碱存在下的反应获得。用碱处理1a的过程也进行到3，得到相应的酚盐阴离子10和磷酰胺阴离子9的平衡混合物，将其用MeI淬灭，得到11和1-甲基-5-咔a膦的混合物（1 b） 。这种反应性对于中性膦烷来说是典型的。

  DOI：

  10.1002/chem.200500864
• 作为产物：
  描述：

  在 碘代三甲硅烷 、 水 作用下， 以 氘代氯仿 为溶剂， 生成 1-hydro-5-carbaphosphatrane
  参考文献：
  名称：

  Synthesis and Structure of 5-Carbaphosphatrane

  摘要：

  1-Hydro-5-carbaphosphatrane 4, the first 5-carbon analog of a phosphatrane, was synthesized. X-ray crystallographic analysis showed that it has a typical TBP structure and that it is a 10-P-5 phosphorane in a perfectly "anti-apicophilic" arrangement.

  DOI：

  10.1080/10426500108546641

文献信息

• Synthesis, Structure, and Bonding Properties of 5-Carbaphosphatranes:  A New Class of Main Group Atrane
  作者：Junji Kobayashi、Kei Goto、Takayuki Kawashima、Michael W. Schmidt、Shigeru Nagase

  DOI：10.1021/ja011458j

  日期：2002.4.1

  phosphorane in the perfectly "anti-apicophilic" arrangement. Apical P-C and P-H bond lengths were 1.921(2) and 1.38(2) A, respectively. The (1)J(PH) value of 1 and the (1)J(PC)(P-CH(3)) value of 2 were 852 and 215 Hz, respectively, which are extraordinarily large for the apical coupling constants of phosphoranes, but close to those of the reported phosphatranes with a 5-nitrogen atom. IR and Raman spectra

  1-Hydro-5-carbaphosphatrane (1) 和 1-methyl-5-carbaphosphatrane (2) 是 phosphatranes 的第一个 5-碳类似物，是通过环次膦酸盐 3 的去甲基化反应合成的。 X 射线分析显示 1 具有一个典型的三角双锥结构，在顶端位置有氢和碳原子，在赤道位置有三个氧原子，表明 1 是完美“反亲亲亲油性”排列的正膦。顶端 PC 和 PH 键长分别为 1.921(2) 和 1.38(2) A。(1)J(PH)值为1，(1)J(PC)(P-CH(3))值为2，分别为852Hz和215Hz，这对于正膦的顶端耦合常数来说是非常大的，但接近于报道的具有 5 个氮原子的磷酯。还报告了 IR 和拉曼光谱。
• Chemistry of Carbaphosphatranes
  作者：Takayuki Kawashima

  DOI：10.1080/10426500701734398

  日期：2008.1.14

  A 5-carbaphosphatrane and a 6-carbaphosphatrane were synthesized by utilizing triarylmethyl-type tetradentate ligands. Their structures were determined by X-ray crystallographic analysis to reveal that they have nealy ideal trigonal bipyramidal structures with a perfectly anti-apicophilic arrangement. (1)J(PH) and (1)J(PC) values of carbaphosphatranes were shown to be extraordinarily large as an apical coupling constant. The reactivities of carbaphosphatranes based on the tautomerization with their corresponding phosphonites were demonstrated in some reactions.
• 5-Carbaphosphatranes:  The First Main Group Atrane Bearing a 1−5 Covalent Bond
  作者：Junji Kobayashi、Kei Goto、Takayuki Kawashima

  DOI：10.1021/ja0056264

  日期：2001.4.1
• Perfectly “Anti-Apicophilic” Phosphoranes: Conversion of a 1-Hydro-5-carbaphosphatrane into 1-Alkyl- and 1-Aryl-5-carbaphosphatranes
  作者：Junji Kobayashi、Takayuki Kawashima

  DOI：10.1080/10426500902748080

  日期：2009.4.7

  1-Alkyl- and 1-aryl-5-carbaphosphatranes were prepared by the reaction of 1-hydro-5-carbaphosphatrane with nucleophiles and subsequent intramolecular oxidative cyclization. X-ray crystallographic investigation of the t-butyl derivative revealed that it has a perfectly anti-apicophilic arrangement. The apical 1JPC coupling constants of the 5-carbaphosphatranes were extraordinarily large.
• Reactions of 1-Hydro-5-carbaphosphatrane: Tautomerization between Five-Coordinate and Three-Coordinate Species
  作者：Junji Kobayashi、Kei Goto、Takayuki Kawashima

  DOI：10.1080/10426500212207

  日期：2002.6.1

  Oxidation, sulfurization, and selenation of a 1-hydro-5-carbaphosphatrane afforded the corresponding cyclic phosphonate, cyclic phosphonothioate, and cyclic phosphonoselenoate, respectively. These results indicate the existence of the tautomerization between the five-coordinate 5-carbaphosphatrane and the three-coordinate cyclic phosphonite.