(Z)-chloromethylene-(2,4,6-tri-tert-butylphenyl)phosphane | 92957-42-1

• 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: (Z)-chloromethylene-(2,4,6-tri-tert-butylphenyl)phosphane
• 英文别名: E-2-chloro-1-(2,4,6-tri-t-butylphenyl)-1-phospha-ethylene；(E)-2-chloro-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene；(Z)-2-chloro-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene；Chloromethylidene-(2,4,6-tritert-butylphenyl)phosphane
• CAS: 92957-42-1；92957-44-3；100281-30-9
• 化学式: C₁₉H₃₀ClP
• 分子量: 324.874
• InChiKey: OKXZZPHJYOAWDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 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：

  (Z)-chloromethylene-(2,4,6-tri-tert-butylphenyl)phosphane 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 以53%的产率得到2-(2,4,6-tri-tert-butylphenyl)phosphaacetylene
  参考文献：
  名称：

  通过苯基从磷到碳的迁移形成磷炔

  摘要：

  E-2-Chloro-1-(2,4,6-tri-t-butylphenyl)-1-phospha-乙烯与作为碱的叔丁基锂反应得到 2-(2,4,6-tri -t-丁基苯基)-1-磷酸-乙炔，表明生成了异腈的磷类似物，随后苯基从磷迁移到碳。

  DOI：

  10.1246/cl.1988.1733
• 作为产物：
  描述：

  2,2-dichloro-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethene 在 正丁基锂 、 水 作用下， 以 四氢呋喃 为溶剂， 生成 (Z)-chloromethylene-(2,4,6-tri-tert-butylphenyl)phosphane
  参考文献：
  名称：

  A New Preparative Route to Phosphaethynes from Dichlorophosphaethenes by Lithiation, Photoisomerization, and Re-lithiation Involving Migration

  摘要：

  以 2,2-二氯-1-(2,4,6-三丁基苯基)-1-膦乙烯为原料，通过反氯原子的石碳酸化反应，然后进行水解、光异构化和涉及迁移的重复石碳酸化反应制备了 2-(2,4,6-三丁基苯基)-1-膦乙烯。该方法被成功应用于制备 2-(2,4,6-三戊基苯基)-1-膦乙烯。

  DOI：

  10.1246/cl.1992.1053

文献信息

• A New Preparative Route to Phosphaethynes from Dichlorophosphaethenes by Lithiation, Photoisomerization, and Re-lithiation Involving Migration
  作者：Masaaki Yoshifuji、Hajime Kawanami、Yoshinori Kawai、Kozo Toyota、Masafumi Yasunami、Takashi Niitsu、Naoki Inamoto

  DOI：10.1246/cl.1992.1053

  日期：1992.6

  2-(2,4,6-Tri-t-butylphenyl)-1-phosphaethyne was prepared from 2,2-dichloro-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene by lithiation of anti-chloro atom followed by hydrolysis, photoisomerization, and repeated lithiation involving migration. The present method was successfully applied to the preparation of 2-(2,4,6-tri-t-pentylphenyl)-1-phosphaethyne.

  以 2,2-二氯-1-(2,4,6-三丁基苯基)-1-膦乙烯为原料，通过反氯原子的石碳酸化反应，然后进行水解、光异构化和涉及迁移的重复石碳酸化反应制备了 2-(2,4,6-三丁基苯基)-1-膦乙烯。该方法被成功应用于制备 2-(2,4,6-三戊基苯基)-1-膦乙烯。
• Preparation of Some Multifunctionalized Methylenephosphines by Reactions of Chloro[(2,4,6-tri-<b><i>t</i></b>-butylphenyl)phosphinidene]methyllithiums with Carbonyl Compounds
  作者：Masaaki Yoshifuji、Shigekazu Ito、Kozo Toyota、Masafumi Yasunami

  DOI：10.1246/bcsj.68.1206

  日期：1995.4

  methylenephosphines. Although the stereochemistry of the products was retained during the initial step of the reaction, in some cases E/Z isomerization reactions occurred to the resulting methylenephosphines. Imidazolidinediones bearing the P=C bond were obtained for the first time by a reaction of the E-lithium reagent with phenyl isocyanate; the structure of the Z-isomer was determined by X-ray analysis

  (Z)-或(E)-氯(亚膦)甲基锂试剂，分别由二氯亚甲基-或(E)-氯亚甲基-膦与丁基锂制备，与羰基化合物反应得到相应的官能化亚甲基膦。尽管在反应的初始步骤中保留了产物的立体化学，但在某些情况下，生成的亚甲基膦会发生 E/Z 异构化反应。E-锂试剂与异氰酸苯酯反应，首次得到带有P=C键的咪唑烷二酮类化合物；Z-异构体的结构通过X-射线分析确定。
• Formation of a Phospha-alkyne via Migration of the Phenyl Group from Phosphorus to Carbon
  作者：Masaaki Yoshifuji、Takashi Niitsu、Naoki Inamoto

  DOI：10.1246/cl.1988.1733

  日期：1988.10.5

  -ethylene was allowed to react with t-butyllithium as a base to give 2-(2,4,6-tri-t-butylphenyl)-1-phospha-acetylene, suggesting the generation of a phosphorus analogue of isonitrile followed by migration of the phenyl group from phosphorus to carbon.

  E-2-Chloro-1-(2,4,6-tri-t-butylphenyl)-1-phospha-乙烯与作为碱的叔丁基锂反应得到 2-(2,4,6-tri -t-丁基苯基)-1-磷酸-乙炔，表明生成了异腈的磷类似物，随后苯基从磷迁移到碳。
• Reaction of lithium (2,4,6-tri-tert-butylphenyl)silylphosphide with haloform
  作者：Shigeru Sasaki、Masaaki Yoshifuji、Naoki Inamoto

  DOI：10.3998/ark.5550190.0013.203

  日期：——

  The reaction of lithium (tert-butyldimethylsilyl)(2,4,6-tri-tert-butylphenyl)phosphide with chloroform afforded (Z)-2-(tert-butyldimethylsilyl)-2-chloro-1-(2,4,6-tri-tert-butylphenyl)-1phosphaethene. The NMR study revealed a secondary phosphine resulting from a formal insertion of a dichlorocarbene to the P-Si bond as a reaction intermediate. The reaction is specific to the reactants and substrates

  (叔丁基二甲基甲硅烷基)(2,4,6-三-叔丁基苯基)磷化锂与氯仿反应得到(Z)-2-(叔丁基二甲基甲硅烷基)-2-氯-1-(2,4,6) -三-叔丁基苯基)-1磷酸乙烯。核磁共振研究揭示了二氯卡宾作为反应中间体正式插入 P-Si 键所产生的二级膦。该反应特定于反应物和底物。使用溴仿得到溴甲硅烷基膦和 2bromo-1-phosphaethene。受阻较小的三甲基甲硅烷基磷化物得到双（2,4,6-三叔丁基苯基）二膦。
• Phosphinidene Transfer Reactions of the Terminal Phosphinidene Complex Cp2Zr(:PC6H2-2,4,6-t-Bu3)(PMe3)
  作者：Tricia L. Breen、Douglas W. Stephan

  DOI：10.1021/ja00153a013

  日期：1995.12

  The terminal zirconium phosphinidene complex Cp(2)Zr(PR*)(PMe(3)) (R* = C6H2-2,4,6-t-Bu(3)) 2 has been synthesized in high yield, and its reactivity has been investigated. The compound Cp(2)ZrMe(PHR*) 1 is unstable with respect to the loss of methane; in the presence of PMe(3) this reaction yielded 2. Reactions of 2 with benzophenone, benzaldehyde, or isophthalaldehyde produced phosphaalkenes PhCH=PR* 3, Ph(2)C=PR* 4, and 1,3-C6H2(CH=PR*)(2) 5, respectively. PhN=C=PR* 6 resulted from the reaction of 2 with phenyl isothiocyanate while the use of cyclohexanone afforded the enolate Cp(2)Zr(PHR*)(OC6H9) 7. Phosphinidene group transfer also took place in reactions of 2 with the appropriate organic dihalide or epoxide. In this way phosphaalkenes CH2=PR* 8 and CHCl=PR* 9, phosphirane (CH(2)CH(2)PR*) 10, phospholane 1,2-C6H4(CH(2)PR*)(2) 11 and substituted phosphiranes (CH2CH)(CHCH2-PR*) 12, CH2C(CCH(2)PR*) 13, (PhCHCH(Ph)PR*) 15, and trans-(PhCHCH(2)PR*) 16 were synthesized. The use of propylene oxide yielded the enolate Cp(2)Zr(PHR*)(OCH2CH=CH2) 17. Similar reactions of 2 with heavier group 14 dihalides and sulfides furnished Cp(2)Zr(PR*(SiMe(2)Cl))Cl 18, PR*(SiMe(2)Cl)(2) 19, (Me(2)GeCl)(2) PR* 20, (Me(2)GePR*)(2) 21, (t-Bu(2)SnPR*)(2) 22, and (Me(2)SnPR*)(2) 23. Intramolecular phosphinidene transfer occurred in reactions of 2 with benzonitrile and dicyclohexylcarbodiimide, giving Cp(2)Zr(PMe(3))(NC(Ph)(PR*)) 25 and Cp(2)Zr(N(Cy))(2)C=PR* 26, respectively. Crystallographic data are reported for compounds 22, 25b, and 26.