2-bromo-3-phenyl-1-(2,4,6-tri-tert-butylphenyl)-3-trimethylsiloxy-1-phospha-1-propene | 862852-62-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-bromo-3-phenyl-1-(2,4,6-tri-tert-butylphenyl)-3-trimethylsiloxy-1-phospha-1-propene
• 英文别名: (1-Bromo-2-phenyl-2-trimethylsilyloxyethylidene)-(2,4,6-tritert-butylphenyl)phosphane
• CAS: 862852-62-8
• 化学式: C₂₉H₄₄BrOPSi
• 分子量: 547.631
• InChiKey: QRNGYQMYYOUYEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.27
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-3-phenyl-1-(2,4,6-tri-tert-butylphenyl)-3-trimethylsiloxy-1-phospha-1-propene 在 叔丁基锂 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 0.17h， 以91%的产率得到1,2-diphenyl-3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]cyclobutene
  参考文献：
  名称：

  Improved Preparative Method for 1,2-Diaryl-3,4-diphosphinidenecyclobutenes and Its Application to the Studies of 1,2-Bis(arylthienyl)-3,4-diphosphinidenecyclobutenes

  摘要：

  合成了空间保护的1,2-二芳基-3,4-二膦烯环丁烯，起始材料为3-芳基-2-溴-1-(2,4,6-三叔丁基苯基)-3-(三甲基硅氧基)-1-膦丙烯，采用了叔丁基锂和1,2-二溴乙烷。研究了产物的性质，例如1,2-二(2,2′-双噻吩-5-基)-3,4-二膦烯环丁烯。该方法是一种优秀的合成这些化合物的方法。

  DOI：

  10.1246/bcsj.80.1580
• 作为产物：
  描述：

  [(dibromomethylene)(2,4,6-tri-tertbutylphenyl)phosphine] 在 正丁基锂 作用下， 生成 2-bromo-3-phenyl-1-(2,4,6-tri-tert-butylphenyl)-3-trimethylsiloxy-1-phospha-1-propene
  参考文献：
  名称：

  Facile [3+2] dimerization and formal dehydrogenative coupling mode of a cyanophenylphosphaallene

  摘要：

  Due to a facile head-to-tail [3+ 2] dimerization, even a sterically demanding group such as the Mes* (2,4,6-tri-tert-butylphenyl) group around the P = C = C moiety did not allow us to isolate 3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene from the elimination reaction of 2-bromo-3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaprop-1-ene with DBU (1,8-diazabicyclo[ 5.4.0] undec-7-ene), and the corresponding 1,4-diphosphafulvene containing cyano groups was obtained and characterized. Theoretical studies on the [3+ 2] dimerization of phosphaallene characterize possible intermediates affording 1,4-diphosphafulvenes and also suggest the cyano group effect to facilitate the saturation of the P = C double bonds. On the other hand, 1,2-bis(4-cyanophenyl)-3,4-bis[(2,4,6-tritertbutylphenyl) phosphinidene]cyclobutene was obtained from 2-bromo-3-(4-cyanophenyl)-3-trimethylsiloxy-1-(2,4,6-tri-tert-butylphenyl)1- phosphaprop-1-ene together with the 3-(4-cyanophenyl)-1-phosphaallene. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.07.063

文献信息

• π-Extended DPCB for Activation-Free Homogeneous Gold Catalysis
  作者：Shigekazu Ito、Masaki Nanko、Koichi Mikami

  DOI：10.1002/cctc.201402158

  日期：2014.8

  complexes that bear the 3,4‐bis(2,4,6‐tri‐tert‐butylphenyl)‐3,4‐diphosphinidenecyclobutene (DPCB) ligand could be improved by suitable extension of the π‐conjugation. If the 1‐naphthyl substituent was employed in the 1,2‐positions in the kinetically stabilized DPCB skeleton, high catalytic activity of the DPCB‐bis(chlorogold) complex was induced in the intermolecular alkoxycyclization of 1,6‐enyne without

  带有3,4-二（2,4,6-三叔丁基）的bis [chlorogold（I）]配合物的催化特性通过适当扩展π共轭可改善（丁基苯基）-3,4-二亚膦酰基环丁烯（DPCB）的配体。如果在动态稳定的DPCB骨架的1,2-位使用1-萘基取代基，则在1,6-烯炔的分子间烷氧基环化反应中会诱导DPCB-双（氯金）配合物的高催化活性，而不会被a活化。 Ag助催化剂。1,2-二芳基取代的DPCB衍生物的DFT计算表明，LUMO含量的适当降低和配体结构的空间特征对于高催化活性都很重要。
• An Efficient Synthetic Method of 1-(2,4,6-Tri-<i>t</i>-butylphenyl)-3-phenyl-1-phosphaallenes [Mes^*P=C=CR–Ph; R = H, SiMe₃] from Dibromophosphaethene [Mes^*P=CBr₂] (Mes^*= 2,4,6-<i>t</i>-Bu₃C₆H₂)
  作者：Shigekazu Ito、Satoshi Sekiguchi、Matthias Freytag、Masaaki Yoshifuji

  DOI：10.1246/bcsj.78.1142

  日期：2005.6

  2-Bromo-3-phenyl-1-(2,4,6-tri-t-butylphenyl)-3-trimethylsiloxy-1-phospha-1-propene reacted with t-butyllithium and chlorotrimethylsilane to afford 3-phenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaallene and/or 3-phenyl-3-trimethylsilyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaallene through the elimination of lithium trimethylsiloxide or hexamethyldisiloxane. The molecular structure of the latter phosphaallene

  2-Bromo-3-phenyl-1-(2,4,6-tri-t-butylphenyl)-3-trimethylsiloxy-1-phospha-1-propene 与叔丁基锂和氯三甲基硅烷反应得到 3-phenyl-1- (2,4,6-三叔丁基苯基)-1-磷丙烯和/或3-苯基-3-三甲基甲硅烷基-1-(2,4,6-三叔丁基苯基)-1-磷丙烯通过消除三甲基硅氧化锂或六甲基二硅氧烷。后者磷丙二烯的分子结构由 X 射线晶体学证实。