1,5-dimethyl-2-trimethylsilyl-1H-1,3-benzazaphosphole | 1395459-86-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,5-dimethyl-2-trimethylsilyl-1H-1,3-benzazaphosphole
• 英文别名: (1,5-Dimethyl-1,3-benzazaphosphol-2-yl)-trimethylsilane；(1,5-dimethyl-1,3-benzazaphosphol-2-yl)-trimethylsilane
• CAS: 1395459-86-5
• 化学式: C₁₂H₁₈NPSi
• 分子量: 235.341
• InChiKey: YZWYLQZDBFFWMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2-amino-5-methyl-phenylphosphonic acid diethylester 在 lithium aluminium tetrahydride 、 potassium tert-butylate 、 水 、 叔丁基锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 水 、 甲苯 、 正戊烷 为溶剂， 反应 96.0h， 生成 1,5-dimethyl-2-trimethylsilyl-1H-1,3-benzazaphosphole
  参考文献：
  名称：

  σ2-P Ligands: convenient syntheses of N-methyl-1,3-benzazaphospholes

  摘要：

  A convenient three-step route to 1,5-dimethyl-1,3-benzazaphosphole via Cu- or Pd-catalyzed phosphonylation of 2-iodo-4-methylaniline, reduction to 2-phosphino-4-methylaniline, and disproportionative cyclization with excess formaldehyde is reported. N-Methylbenzazaphospholes can be functionalized in the 2-position via alpha-CH-lithiation with tBuLi and are pi-acidic sigma P-2-ligands. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.07.037

文献信息

• Solvent-controlled lithiation of PC–N-heterocycles: Synthesis of mono- and bis(trimethylsilyl)-tert-butyl-dihydrobenzazaphospholes – A new type of highly bulky and basic phosphine ligands
  作者：Mohammed Ghalib、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1016/j.jorganchem.2014.04.014

  日期：2014.8

  The influence of solvents on the lithiation of N-methyl-1,3-benzazaphospholes is reported; these are accessible via catalytic phosphonylation of 2-bromoanilines, subsequent reduction to 2-phosphinoanilines and acid-catalysed disproportionative ring closure with excess paraformaldehyde. Reactions with tBuLi in polar solvents (THF, Et2O), particularly in the presence of tBuOK, lead to 2-lithiobenzazaphospholes (CH-lithiation) whereas hydrocarbons favour "normal" (hexane) or "inverse" (toluene) addition at the P=C bond. Reactive Li-species were trapped by ClSiMe3, present during the lithiation in hydrocarbons, and give rise to 2- and 3-trimethylsilyl-dihydro-1,3-benzazaphospholes, respectively. In hexane, via preferred lithiation of the primary adduct, the 2,2'-bis(trimethylsilyl)-dihydro-1,3-benzazaphosphole is the main product. 5-Methyl-1,3-benzazaphosphole, with NH function, reacts in toluene in the "normal" mode to 3-tert-butyl-1,2-bis(trimethylsilyl)-5-methyl-dihydrobenzazaphosphole. The sterically demanding tert-butyl and trimethylsilyl groups are arranged in anti-position as shown by crystal structure analyses, the second 2-SiMe3 group in gauche position. The P-tert-butyl-2,2'-bis(trimethylsilyl)-dihydrobenzazaphospholes represent a new type of sterically congested dialkylaryl phosphine ligands with increased basicity by the +I-effect of the silyl groups and +M-effect of the basic nitrogen in o-position. (C) 2014 Elsevier B.V. All rights reserved.
• σ2-P Ligands: convenient syntheses of N-methyl-1,3-benzazaphospholes
  作者：Mohammed Ghalib、Basit Niaz、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1016/j.tetlet.2012.07.037

  日期：2012.9

  A convenient three-step route to 1,5-dimethyl-1,3-benzazaphosphole via Cu- or Pd-catalyzed phosphonylation of 2-iodo-4-methylaniline, reduction to 2-phosphino-4-methylaniline, and disproportionative cyclization with excess formaldehyde is reported. N-Methylbenzazaphospholes can be functionalized in the 2-position via alpha-CH-lithiation with tBuLi and are pi-acidic sigma P-2-ligands. (C) 2012 Elsevier Ltd. All rights reserved.