2-di-tert-butylphosphanyl-1,3-benzazaphosphole | 1044276-85-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: 2-di-tert-butylphosphanyl-1,3-benzazaphosphole
• 英文别名: Ditert-butyl-[1-(2,2-dimethylpropyl)-1,3-benzazaphosphol-2-yl]phosphane
• CAS: 1044276-85-8
• 化学式: C₂₀H₃₃NP₂
• 分子量: 349.436
• InChiKey: RDBHBSKGADNGFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 2-di-tert-butylphosphanyl-1,3-benzazaphosphole 以 四氢呋喃 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Π-Rich σ²P-Ligands: Unusual Coordination Behavior of 1H-1,3-Benzazaphospholes Toward Late Transition Metals

  摘要：

  Coordination chemical studies of 1H-1,3-benzazaphospholes, pi-excess aromatic sigma P-2-ligands, demonstrate similar ligand properties to those of phosphabenzenes toward M-VI(CO)(n) but marked differences toward nonzerovalent transition metals. Benzazaphosphole d(8)-metal halide complexes are more strongly destabilized and undergo consecutive reactions, whereas benzazaphosphole coinage metal halide and HgCl2 complexes generally display mu P-2- and/or bent eta P-1-coordination with pi-P donor bond contribution, contrasting with the preference of phosphinine CuX complexes for eta P-1-coordination within the ring plane.

  DOI：

  10.1080/10426507.2014.984029
• 作为产物：
  描述：

  二叔丁基氯化膦 、 生成 2-di-tert-butylphosphanyl-1,3-benzazaphosphole
  参考文献：
  名称：

  Ambident Reactivity of P˭CH‒N‒Heterocycles: Lithiation and Substitution Sites

  摘要：

  Benzofused 1H-1,3-azaphospholes are lithiated at the N-atom by tBuLi but phosphinylation takes place at either the N- or the P-atom. Smaller chlorophosphines react at nitrogen, bulkier react at phosphorus. Substituents at C2 promote the latter mode. N- Substituted 2H-1,3-benzazaphospholes undergo CH-metalation or addition at the P=C bond, depending on the conditions, and allow access to 2-functionally substituted benzazaphospholes or their 2,3-dihydro derivatives, new sigma P-2,X or sigma P-3,X hybrid ligands (X=O,P).

  DOI：

  10.1080/10426507.2010.514486

文献信息

• Phosphanyl-substituted π-excess σ2P heterocycles: Coordination behaviour of 2-di-tert-butylphosphanyl-1-neopentyl-1,3-benzazaphosphole towards CuCl, HgCl2 and [Rh(COD)2]BF4
  作者：Mohammed Ghalib、Peter G. Jones、Gottfried J. Palm、Joachim W. Heinicke

  DOI：10.1039/c3ra43706j

  日期：——

  Reaction of the heterocyclic –PC(PtBu2)–N– hybrid ligand 1 with CuCl or HgCl2 in THF provided the metal complexes 2 and 3. The crystal structure analysis showed dimeric η1-phosphanyl and μ-chloro-coordinated species with the dicoordinated P-atom remote from the metal. In solution broadened phosphorus resonances are observed indicating low kinetic stability and ligand exchange reactions. The reaction of 1 with [Rh(COD)2]BF4 was much slower, required heating and led finally to the four-membered dihydrobenzazaphosphole Rh(COD) P⁁P′-chelate complex 4. The initial Rh(COD)+ complex proved very labile and added moisture traces at the PC bond, whereas the free ligand is stable to aqueous acids and bases.

  杂环âPC(PtBu2)âNâ杂配体 1 与 CuCl 或 HgCl2 在 THF 中反应生成了金属配合物 2 和 3。晶体结构分析显示了二聚δ-1-膦酰基和δ-氯配位物种，其中二配位的 P 原子远离金属。在溶液中观察到磷共振频率变宽，表明其动力学稳定性较低，且存在配体交换反应。1 与[Rh(COD)2]BF4 的反应要慢得多，需要加热，最后生成四元二氢苯并唑膦 Rh(COD) PâPâ²-chelate 复合物 4。事实证明，最初的 Rh(COD)+ 复合物非常易变，并在 PC 键处增加了水分痕迹，而游离配体对水性酸碱稳定。
• Novel Benzo-and Pyrido-Anellated 1, 3-Azaphospholes
  作者：J. Heinicke、B. R. Aluri、M. S.S. Adam、P. G. Jones

  DOI：10.1080/10426500701807905

  日期：2008.1.14

  We present the synthesis of OH-functional and balky N-substituted benzazophospholes, novel pyrido-azaphospholes, addition versus CH-metalation by tBuLi and reactions with electrophiles yielding a novel asymmetric P,N-heterocyclic ethylene-1,2-bis(phosphine) and phosphino-functional benzazaphospholes for hemilabile sigma(3),sigma(2)-P,P' coordination.