| 173464-52-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 173464-52-3
• 化学式: C₁₁H₁₈NPSi
• 分子量: 223.33
• InChiKey: YSZAJOGFIPQQAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  在 正丁基锂 作用下， 以 乙二醇二甲醚 、 正己烷 为溶剂， 生成
  参考文献：
  名称：

  Paasch, Karin; Nieger, Martin; Niecke, Edgar, Angewandte Chemie, 1995, vol. 107, # 21, p. 2600 - 2602

  摘要：

  DOI：
• 作为产物：
  描述：

  苯基膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 17.75h， 生成
  参考文献：
  名称：

  Paasch, Karin; Nieger, Martin; Niecke, Edgar, Angewandte Chemie, 1995, vol. 107, # 21, p. 2600 - 2602

  摘要：

  DOI：

文献信息

• Phosphaalkenes as Building Blocks in Ene Reactions:  Synthesis and Reactivity of 3-Amino-1,2-dihydro-1,2-diphosphetes
  作者：Thomas W. Mackewitz、Christoph Peters、Uwe Bergsträsser、Stefan Leininger、Manfred Regitz

  DOI：10.1021/jo9707186

  日期：1997.10.1

  Phospha-ene reactions of the type II between methylidenephosphanes as enophiles and C-aminophosphaalkenes possessing allylic hydrogen atoms proceed by P-P bond formation to furnish the corresponding functionalized diphosphanes. Thus, the reaction of the methylidenephosphane 1 with the C-amino-substituted ethylidenephosphane 3a runs smoothly at room temperature to afford the unsymmetrical 1,2-diphosphane 4 as a 60:40 mixture of two diastereomers in 64% yield. Rotation about the P-N bond in 4 is hindered at room temperature, but free enthalpies of activation of Delta G(double dagger)(PN) = 16.3 kcal.mol(-1) (major diastereomer) and 15.2 kcal . mol(-1) (minor diastereomer) were determined by variable temperature H-1 NMR spectroscopy; In contrast, reactions of the ethylidenephosphanes 3a-c with the chlorophosphane 2 as enophile follow an unusual course involving a regiospecific ene reaction of the type II and a subsequent intramolecular ring closure reaction to furnish the 3-amino-1,2-dihydro-1,2-diphosphetes 7a-e in good yields (53-79%). The reactivity of this new class of heterocyclic compounds has been studied exemplarily for product 7a. The trans form of 7a obtained by synthesis can be converted to the corresponding cis form photochemically. Complexation of both phosphorus centers in 7a is possible by reaction with 2 equiv of diiron nonacarbonyl and gives rise to complex 8, the constitution of which has been confirmed by X-ray crystallography. Unexpectedly, hydrolysis of ?a does not proceed by attack at the endocyclic enamine unit but rather by way of P-P bond cleavage to afford the functionalized phosphaalkene 9. On the other hand, oxidation of 7a by bis(trimethylsilyl) peroxide takes place with retention of the P2C2 skeleton: a selective increase in coordination at P-1 results in the formation of the 1-oxo-1,2-dihydrodiphosphete 10, the structure of which was confirmed by X-ray crystallography. The reactions of 7a with the electron-poor acetylenes 11a-d also follow an unusual course. Nucleophilic attack of P-1 at the C=C triple bond and proton shift lead stereospecifically to the 1-methylene-1,2-dihydro-1,2-diphosphetes 12a-d as thermolabile addition products. The constitution and configuration of 12c were unambiguously confirmed by X-ray crystallography.