N-4-tolyl-p-trichloroiminophosphorane | 58052-35-0

• 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: N-4-tolyl-p-trichloroiminophosphorane
• 英文别名: p-tolyltrichloroiminophosphorane；N-p-Tolyl-phosphonimidsaeure-trichlorid；Trichloro-(4-methylphenyl)imino-lambda5-phosphane；trichloro-(4-methylphenyl)imino-λ5-phosphane
• CAS: 58052-35-0
• 化学式: C₇H₇Cl₃NP
• 分子量: 242.472
• InChiKey: XHBQHPCAGKAMCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,3-二对甲苯基碳二酰亚胺 、 N-4-tolyl-p-trichloroiminophosphorane 以 甲苯 为溶剂， 生成 2,2,2-trichloro-N,1,3-tris(4-methylphenyl)-1,3,2lambda5-diazaphosphetidin-4-imine
  参考文献：
  名称：

  Catalytic Double-Bond Metathesis without the Transition Metal

  摘要：

  Iminophosphoranes of the type X3P=NR (X=Cl, pyrrolyl; R=alkyl, aryl) catalytically metathesize C=N bonds of carbodiimides via an addition/elimination mechanism that, despite the lack of d orbital participation in P-N bonding, conserves the key features of metal-catalyzed olefin metathesis. Diazaphosphetidine intermediates, produced by the formal [2+2] addition of carbodiimides to the P=N bond, have been isolated and characterized. All phosphorus-containing species in the complex catalytic reaction mixtures have been identified and their origins explained. The kinetics of addition of diisopropylcarbodiimide to Cl3P=NPl and subsequent elimination were studied, and rate constants were determined: k(add)=1.7x10(-3) (+/-0.1x10(-3)) M s(-1) and k(elim)=4.0x10(-4) (+/-0.3x10(-4)) s(-1). The rate of these reactions corresponds well with the observed catalytic TOF of 1.44 TO/P/h.

  DOI：

  10.1021/ja020494v
• 作为产物：
  描述：

  乙烷,三氯氟- 在 五氯化磷 作用下， 以 1,1,2,2-四氯乙烷 为溶剂， 反应 14.0h， 以56.2%的产率得到N-4-tolyl-p-trichloroiminophosphorane
  参考文献：
  名称：

  Catalytic Double-Bond Metathesis without the Transition Metal

  摘要：

  Iminophosphoranes of the type X3P=NR (X=Cl, pyrrolyl; R=alkyl, aryl) catalytically metathesize C=N bonds of carbodiimides via an addition/elimination mechanism that, despite the lack of d orbital participation in P-N bonding, conserves the key features of metal-catalyzed olefin metathesis. Diazaphosphetidine intermediates, produced by the formal [2+2] addition of carbodiimides to the P=N bond, have been isolated and characterized. All phosphorus-containing species in the complex catalytic reaction mixtures have been identified and their origins explained. The kinetics of addition of diisopropylcarbodiimide to Cl3P=NPl and subsequent elimination were studied, and rate constants were determined: k(add)=1.7x10(-3) (+/-0.1x10(-3)) M s(-1) and k(elim)=4.0x10(-4) (+/-0.3x10(-4)) s(-1). The rate of these reactions corresponds well with the observed catalytic TOF of 1.44 TO/P/h.

  DOI：

  10.1021/ja020494v

文献信息

• Two new high-nuclearity copper(II) chloride oligomers with herringbone stacking patterns synthesized by in situ templation
  作者：Zhiyong Fu、Tristram Chivers

  DOI：10.1139/v05-237

  日期：2006.2.1

  produced two new copper(II) chloride oligomers. The nature of the organic substituent R was a factor in determining the chain lengths. For n-propyltrichloroiminophosphorane, the hexanuclear cluster [n-PrNH3]2[Cu6Cl14] (1) was obtained, while p-tolyltrichloroiminophosphorane generated the tetranuclear copper chloride salt [4-CH3C6H4NH3][2-Cl-4-CH3C6H3NH3][Cu4Cl10] (2). In both structures a two-dimensional

  使用三氯亚氨基膦 Cl3P=NR 来控制模板阳离子 [RNH3]+ 和氯化物配体的同时释放，通过原位 P??N 和 P??Cl 键裂解产生了两种新的氯化铜 (II) 低聚物。有机取代基 R 的性质是决定链长的一个因素。对于正丙基三氯亚氨基正膦，得到六核簇 [n-PrNH3]2[Cu6Cl14] (1)，而对甲苯基三氯亚氨基正膦生成四核氯化铜盐 [4-CH3C6H4NH3][2-Cl-4-CH3C6H3NH3][Cu4Cl10] (2). 在这两种结构中，显示人字形排列的二维框架是由 Cu 2 Cl 二次键合相互作用产生的。在相同的反应条件下，将 [n-PrNH3]+ 阳离子直接添加到 CuCl2·2H2O 溶液中，生成 [n-PrNH3]2[CuCl4]。关键词: 卤化铜, 模板,
• Catalytic Double-Bond Metathesis without the Transition Metal
  作者：Stephen A. Bell、Tara Y. Meyer、Steven J. Geib

  DOI：10.1021/ja020494v

  日期：2002.9.1

  Iminophosphoranes of the type X3P=NR (X=Cl, pyrrolyl; R=alkyl, aryl) catalytically metathesize C=N bonds of carbodiimides via an addition/elimination mechanism that, despite the lack of d orbital participation in P-N bonding, conserves the key features of metal-catalyzed olefin metathesis. Diazaphosphetidine intermediates, produced by the formal [2+2] addition of carbodiimides to the P=N bond, have been isolated and characterized. All phosphorus-containing species in the complex catalytic reaction mixtures have been identified and their origins explained. The kinetics of addition of diisopropylcarbodiimide to Cl3P=NPl and subsequent elimination were studied, and rate constants were determined: k(add)=1.7x10(-3) (+/-0.1x10(-3)) M s(-1) and k(elim)=4.0x10(-4) (+/-0.3x10(-4)) s(-1). The rate of these reactions corresponds well with the observed catalytic TOF of 1.44 TO/P/h.