(1-bromo-2-phenylethylidene)-(2,4,6-tritert-butylphenyl)phosphane | 716379-90-7

• 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: (1-bromo-2-phenylethylidene)-(2,4,6-tritert-butylphenyl)phosphane
• CAS: 716379-90-7
• 化学式: C₂₆H₃₆BrP
• 分子量: 459.45
• InChiKey: YOIFEXRFQWJOFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1-bromo-2-phenylethylidene)-(2,4,6-tritert-butylphenyl)phosphane 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以78%的产率得到1-(2,4,6-tri-t-butylphenyl)-3-phenyl-1-phosphaallene
  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
• 作为产物：
  描述：

  溴甲苯 、 [(dibromomethylene)(2,4,6-tri-tertbutylphenyl)phosphine] 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.25h， 以64%的产率得到(1-bromo-2-phenylethylidene)-(2,4,6-tritert-butylphenyl)phosphane
  参考文献：
  名称：

  Formation and Electrochemical Properties of a 1,4-Diphosphafulvene Including Formal Dimerization of Phosphaallene

  摘要：

  Reactions of sterically protected 2-bromo-3-phenyl-1-phosphapropenes with bases such as tert-butyllithium and potassium tert-butoxide successfully afforded a bulky 1,4-diphosphafulvene (Mes* = 2,4,6-tBu(3)C(6)H(2)) through a novel and formal dimerization pathway of 1-phosphaallene, together with small amounts of 3-phenyl-1-phosphaallene and 3,4-diphosphanylidenecyclobutene. The structure of the 1,4-diphosphafulvene was confirmed by X-ray crystallography indicating somewhat flattened phosphorus atoms due to the bulky Mes* groups. The electrochemical properties of the 1,4-diphosphafulvene were investigated to show promising suitability as an electron donor, and indeed, it afforded a charge-transfer complex with TCNQ. Preparation and structural elucidation of an alkoxy-functionalized 1-phosphaallene was also performed, and the effect of the alkoxy group on the 1-phosphaallene moiety was characterized.

  DOI：

  10.1021/jo0497407

文献信息

• Ligand effect of bulky 2,2-dialkyl-1-phosphaethenes on Au-catalyzed cycloisomerization of 1,6-enynes and lactonization of pent-4-ynoic acids
  作者：Shigekazu Ito、Shuhei Kusano、Noboru Morita、Koichi Mikami、Masaaki Yoshifuji

  DOI：10.1016/j.jorganchem.2009.09.040

  日期：2010.1

  2,2-Dimethyl- and 2-benzyl-2-methyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethenes were employed as ligand of mononuclear chlorogold(I) complexes, which catalyzed cycloisomerization of 1,6-enyne affording vinylcyclopentene exclusively in the absence of silver co-catalyst. The reaction mechanisms are discussed based on DFT calculations. In addition to the cycloisomerization, the phosphaalkene-chlorogold(I) complexes catalyzed cyclization of pent-4-ynoic acids providing gamma-methylene-gamma-lactones under basic conditions. (C) 2009 Elsevier B.V. All rights reserved.
• Formation and Electrochemical Properties of a 1,4-Diphosphafulvene Including Formal Dimerization of Phosphaallene
  作者：Shigekazu Ito、Satoshi Sekiguchi、Masaaki Yoshifuji

  DOI：10.1021/jo0497407

  日期：2004.6.1

  Reactions of sterically protected 2-bromo-3-phenyl-1-phosphapropenes with bases such as tert-butyllithium and potassium tert-butoxide successfully afforded a bulky 1,4-diphosphafulvene (Mes* = 2,4,6-tBu(3)C(6)H(2)) through a novel and formal dimerization pathway of 1-phosphaallene, together with small amounts of 3-phenyl-1-phosphaallene and 3,4-diphosphanylidenecyclobutene. The structure of the 1,4-diphosphafulvene was confirmed by X-ray crystallography indicating somewhat flattened phosphorus atoms due to the bulky Mes* groups. The electrochemical properties of the 1,4-diphosphafulvene were investigated to show promising suitability as an electron donor, and indeed, it afforded a charge-transfer complex with TCNQ. Preparation and structural elucidation of an alkoxy-functionalized 1-phosphaallene was also performed, and the effect of the alkoxy group on the 1-phosphaallene moiety was characterized.
• Facile [3+2] dimerization and formal dehydrogenative coupling mode of a cyanophenylphosphaallene
  作者：Shigekazu Ito、Sou Hashino、Noboru Morita、Masaaki Yoshifuji、Daisuke Hirose、Masae Takahashi、Yoshiyuki Kawazoe

  DOI：10.1016/j.tet.2007.07.063

  日期：2007.10

  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.