3,3'-dimethyl-2λ⁵-2,2'(3H,3'H)spirobi[1,3,2-benzoxazaphosphole] | 38057-89-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 3,3'-dimethyl-2λ⁵-2,2'(3H,3'H)spirobi[1,3,2-benzoxazaphosphole]
• 英文别名: 3,3'-dimethyl-2',3'-dihydro-3H-2λ⁵-[2,2']spirobi(benzo[1,3,2]oxazaphosphole)；3,3'-dimethyl-2,2'-spirobi[1,3,2λ5-benzoxazaphosphole]
• CAS: 38057-89-5
• 化学式: C₁₄H₁₅N₂O₂P
• 分子量: 274.259
• InChiKey: NHRQHCXZTLPXRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  24.94
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  3,3'-dimethyl-2λ⁵-2,2'(3H,3'H)spirobi[1,3,2-benzoxazaphosphole] 在 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以85%的产率得到
  参考文献：
  名称：

  Deprotonation of a hydrophosphorane and synthesis of the Ni(II) metallophosphorane [NiCl{P(OC6H4N(CH3))2}(P(CH3)3)2]

  摘要：

  The hydrophosphorane [HP(OC6H4N(CH3))(2)] has been deprotonated using lithium tetramethylpiperidide to produce Li[P(OC6H4N(CH3))(2)] (1). Compound 1 reacts further with NiCl2(PMe3)(2) to form the Ni(II) phosphoranide complex [NiCl{P(OC6H4N(CH3))(2)}(P(CH3)(3))(2)] (2). The crystal structures of both 1 and 2 were determined. The structure of 1 is dimeric with bridging lithium cations and also features one THF solvent molecule coordinated to each lithium cation; the geometry about the lithium atom is tetrahedral. The structure of 2 displays tetrahedral distortion from an idealized square-planar geometry. Both 1 and 2 characterized by H-1 and P-31 NMR, with C-13 NMR for 2 also. DFT calculations (B3LYP/6311++G(2df,2p)) were also done on 2; both the NMR and DFT studies indicate p-donation from the metal to the pentacoordinate phosphorus. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2013.12.042
• 作为产物：
  描述：

  三(二甲胺基)膦 、 2-甲氨基苯酚 生成 3,3'-dimethyl-2λ⁵-2,2'(3H,3'H)spirobi[1,3,2-benzoxazaphosphole]
  参考文献：
  名称：

  Mécanisme德形成和de变换DES spirophosphoranes：V. SYNTHESE等tautomérieP III ⇌P V DES spirophosphoranes联络PH衍生物DESαaminoalcoolssubstituésAU Carbone的等A L'AZOTE

  摘要：

  合成约40个含PH键的新螺磷杂环戊烷提供了三配位和五配位形式之间互变异构平衡新情况的例子，如：（a）记录20至150°之间的31 P NMR光谱，（b）使用a P III形式的化学测试。这些结果让我们来讨论影响平衡P因素III ⇌P V。

  DOI：

  10.1016/s0022-328x(00)91489-x

文献信息

• Phosphoramidite complexes of Pd(II), Pt(II) and Rh(I): An effective hydrosilylation catalyst of 1-hexyne and 1-octene
  作者：Hannah K. Carroll、Fraser G.L. Parlane、Noah Reich、Benson J. Jelier、Craig D. Montgomery

  DOI：10.1016/j.ica.2017.04.065

  日期：2017.8

  The hydrophosphorane HP(OC6H4NMe)(2) was used to prepare the diastereotopic complexes [MCI2P(OC6H4NMe)OC6H4NHMe}] (M = Pd, Pt) by reaction with [MCl2(PhCN)(2)], and [RhCI(PPh3)P(OC6H4NMe) OC6H4NHMe}] by reaction with [RhCl(PPh3)(3)]. To form these complexes, the phosphorane undergoes ring-opening, whereby it is coordinated as the tautomeric neutral phosphoramidite-amino chelating ligand. The crystal structure of [RhCI(PPh3)P(OC6H4NMe)OC6H4NHMe}] was determined and the geometry about the Rh(I) atom is square-planar with cis-disposed phosphorus-donor ligands. The Rh-P distance is shortened (2.1056(6) angstrom) due to Rh(d) -> P pi-backbonding. In addition, [RhCI(PPh3)P (OC6H4NMe)OC6H4NHMe}] was shown to be an effective regio- and stereoselective catalyst for the hydrosilylation of 1-octene and 1-hexyne. (C) 2017 Elsevier B.V. All rights reserved.
• Laurenco,C.; Burgada,R., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1972, vol. 275, p. 237 - 239
  作者：Laurenco,C.、Burgada,R.

  DOI：——

  日期：——