2,2-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene | 111888-04-1

• 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: 2,2-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene
• 英文别名: 2,2-diphenyl-1-(2,4,6-tri-t-butylphenyl)phosphaethylene；(diphenylmethylene)(2,4,6-tri-t-butylphenyl)phosphine；(2,4,6-tri-tert-butylphenyl)diphenyl phosphaalkene；(Diphenylmethylen)(2,4,6-tri-tert-butylphenyl)phosphan；2,2-diphenyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethene；Benzhydrylidene-(2,4,6-tritert-butylphenyl)phosphane
• CAS: 111888-04-1
• 化学式: C₃₁H₃₉P
• 分子量: 442.624
• InChiKey: ACFVOZKYVCKMHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 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：

  2,2-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene 在 sulfur 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 反应 24.0h， 以96%的产率得到3,3-diphenyl-2-(2,4,6-tri-t-butylphenyl)-1,2-thiaphosphirane 2-sulfide
  参考文献：
  名称：

  Valence Isomerism between Sterically Protected MethylenephosphineP-Sulfide and 1,2-Thiaphosphirane

  摘要：

  (二苯基亚甲基)(2,4,6-三丁基苯基)膦与元素硫反应，通过亚甲基膦 P 硫化物得到 3,3-二苯基-2-(2,4,6-三丁基苯基)-1,2-硫代磷环烷 2-硫化物。硫代环氧乙烷 2-硫化物与三(二甲基氨基)膦发生脱硫反应，生成 3,3-二苯基-2-(2,4,6-三丁基苯基)-1,2-硫代环氧乙烷。通过加热或光照，亚甲基硫化膦和硫代环氧乙烷之间发生了价态异构。X 射线晶体学分析了亚甲基膦、亚甲基膦 P-硫化物和硫代环氧乙烷的结构。

  DOI：

  10.1246/bcsj.69.141
• 作为产物：
  描述：

  P-trimethylsilyl-2,4-6-tri-tert-butylphenylphosphine 在 正丁基锂 、 aluminum tri-bromide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 3.5h， 生成 2,2-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene
  参考文献：
  名称：

  Phospha-Bora-​​Wittig 反应

  摘要：

  我们报告了从醛、酮、酯或酰胺直接制备磷烯烃的 phospha-bora-Wittig 反应。瞬态磷硼烯 Mes*P=B-NR 2与羰基化合物反应形成 1,2,3-磷硼氧杂环丁烷，这是经典 Wittig 反应中氧杂磷杂环丁烷中间体的类似物。1,2,3-磷酸硼氧杂环丁烷经历热或路易斯酸促进的环转化，产生磷烯烃。实验和密度泛函理论研究揭示了经典反应和 phospha-bora-Wittig 反应之间深远的相似之处。

  DOI：

  10.1021/jacs.1c06228

文献信息

• Stereoselective Catalytic Synthesis of Alkynylated Phosphaethenes Leading to Activation-Free Gold Catalysis
  作者：Shigekazu Ito、Tomokazu Shinozaki、Koichi Mikami

  DOI：10.1002/ejoc.201701259

  日期：2017.12.15

  screening of their catalytic activity revealed that both employing appropriate π-conjugative substituents and the stereochemistry were decisive for efficiency of the gold-catalyzed reactions under the activation-free conditions.

  类烯烃磷酸乙烯 (-P=C<) 的 π 接受特性对开发路易斯酸性过渡金属催化剂具有吸引力。通过 Sonogashira 方法完成了空间受阻的 gem-二溴磷腈的立体选择性单炔化反应，并获得了相应的 2-炔基-2-溴磷腈。随后通过 Kumada-Tamao-Corriu (KTC) 反应的钯形式对 2-bromo-2-alkynyl-1-phosphaethenes 进行芳基化，通过构型反转得到相应的 2-aryl-1-phosphaethen-3-ynes。2-炔基-2-芳基-1-磷酸乙烯转化为相应的氯金（I）配合物，
• A general method for preparing diphosphiranes
  作者：Guita Etemad-Moghadam、Jacques Bellan、Christine Tachon、Max Koenig

  DOI：10.1016/s0040-4020(01)81490-3

  日期：1987.1

  Diphosphiranes 3a-3f are obtained by action of diazo derivatives and carbenes on the trans-diphosphene 1. The structures are elucidated by spectroscopic methods. In all cases the cycloaddition reaction is stereoselective.

  通过重氮衍生物和碳烯在反式二膦1上的作用获得二膦3a-3f。通过光谱法阐明其结构。在所有情况下，环加成反应都是立体选择性的。
• Preparation and X-Ray Structure Analysis of 3,3-Diphenyl-2-(2,4,6-tri-<i>t</i>-butylphenyl)-1,2-thiaphosphirane
  作者：Kozo Toyota、Kazuho Shimura、Hiroaki Takahashi、Masaaki Yoshifuji

  DOI：10.1246/cl.1994.1927

  日期：1994.10

  elemental sulfur afforded the corresponding 1,2-thiaphosphirane 2-sulfide 6 via methylene(thioxo)phosphorane 5. Desulfurization reaction of 6 gave the corresponding thiaphosphirane 7 and the structure was analyzed by X-ray crystallography. Valence isomerism between 5 and 7 by heat or light was studied.

  低配位的 2,2-二苯基-1-(2,4,6-三叔丁基苯基) 膦与元素硫反应通过亚甲基(硫代)正膦 5 得到相应的 1,2-硫代膦 2-硫化物 6。 6的反应得到相应的噻吩7，并通过X射线晶体学分析其结构。通过热或光研究了 5 和 7 之间的价异构。
• Preparation and Palladium Complex Formation of Several (2-Phosphaethenyl)benzenes
  作者：Hajime Kawanami、Kozo Toyota、Masaaki Yoshifuji

  DOI：10.1246/cl.1996.533

  日期：1996.7

  Phenylphosphaethenes carrying two to four phosphoruscarbon double bonds on a benzene ring were prepared and their palladium complex formations were studied. The palladium complexes reacted with alkyllithium reagents to give the corresponding o-alkylation products.

  研究人员制备了苯环上带有 2 至 4 个磷碳双键的苯基磷杂环丁烷，并研究了它们的钯络合物形成。钯络合物与烷基锂试剂反应生成相应的邻烷基化产物。
• 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.