3-tert-butyl-1,5-dimethyl-2,2-bis(trimethylsilyl)-2,3-dihydro-1H-1,3-benzazaphosphole | 1613265-35-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 3-tert-butyl-1,5-dimethyl-2,2-bis(trimethylsilyl)-2,3-dihydro-1H-1,3-benzazaphosphole
• 英文别名: (3-Tert-butyl-1,5-dimethyl-2-trimethylsilyl-1,3-benzazaphosphol-2-yl)-trimethylsilane；(3-tert-butyl-1,5-dimethyl-2-trimethylsilyl-1,3-benzazaphosphol-2-yl)-trimethylsilane
• CAS: 1613265-35-2
• 化学式: C₁₉H₃₆NPSi₂
• 分子量: 365.646
• InChiKey: CFIYORQIVZTMLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 1,5-dimethyl-1H-1,3-benzazaphosphole 、 叔丁基锂 以 四氢呋喃 、 正戊烷 为溶剂， 以58%的产率得到3-tert-butyl-1,5-dimethyl-2,2-bis(trimethylsilyl)-2,3-dihydro-1H-1,3-benzazaphosphole
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2014.04.014

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.