diethyl (1,2,2-triphenylethenyl)phosphate | 95954-11-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: diethyl (1,2,2-triphenylethenyl)phosphate
• 英文别名: α--benzylphosphonsaeure-diaethylester；α-(Diphenylmethylen)-benzylphosphonsaeure-diaethylester；Diethyl (1,2,2-triphenylvinyl)phosphonate；(2-diethoxyphosphoryl-1,2-diphenylethenyl)benzene
• CAS: 95954-11-3
• 化学式: C₂₄H₂₅O₃P
• 分子量: 392.434
• InChiKey: ZBHHAPIFXKBQHC-UHFFFAOYSA-N

物化性质

• 沸点：
  492.2±45.0 °C(Predicted)
• 密度：
  1.136±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  三苯溴乙烯 、 亚磷酸二乙酯 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 0.33h， 以9%的产率得到diethyl (1,2,2-triphenylethenyl)phosphate
  参考文献：
  名称：

  Competition of Mechanisms in the Photochemical Cleavage of the C−X Bond of Aryl-Substituted Vinyl Halides

  摘要：

  The photolysis of aryl halides causes homolysis of the carbon-halogen bond and formation of aryl radicals. In contrast, photolysis of vinyl halides can induce both heterolysis of the C-X bond, thereby generating vinyl cations, and homolysis, giving vinyl radicals. Examples of this competition among pathways is reported here for three vinylic precursors, namely, 1,2,2-triphenylbromoethene (1), 1-phenyl-2,2-bis(o-methoxyphenyl)-1-bromoethene (11), and beta-bromostyrene (19). Incursion of the photoinduced S(RN)1 process, through the intermediacy of the vinyl radical, is verified in the presence of reducing nucleophiles, such as the enolate ions of ketones, and in part with (EtO)(2)PO-. Conversely, incursion of the heterolytic path, and intermediacy of the vinyl cation, occurs in the presence of weak electron-donor anions, such as NO2-, N-3(-), and Cl-. The vinyl cation produced from 19, which is less stable than those derived from 1 and 11, gives phenylacetylene via an E1-type elimination. An estimate is provided for the intramolecular rate of interception of the vinyl cation derived from 11 by the ortho-methoxy groups of the beta-o-anisyl substituents. Finally, evidence against a photoinduced electron transfer from RO- ions to vinyl halide 1 is presented.

  DOI：

  10.1021/jo981164p

文献信息

• Efficient Palladium-Catalyzed Double Arylation of Phosphonoalkynes and Diarylalkynes in Water: Use of a Dinuclear Palladium(I) Catalyst
  作者：K. V. Sajna、Venu Srinivas、K. C. Kumara Swamy

  DOI：10.1002/adsc.201000579

  日期：2010.11.22

  A novel use of the dinuclear palladium(I) catalyst [(OCH2CMe2CH2O)P-S-Pd(PPh3)]2 in aqueous medium for the double arylation of phosphonoalkynes as well as diarylalkynes is reported. This double arylation requires both the iodoarene and arylboronic acid along with the catalyst. The structures of some key products have been proven by X-ray crystallography.

  报道了在水介质中双核钯（I）催化剂[（OCH 2 CMe 2 CH 2 O）PS-Pd（PPh 3）] 2在膦酰基炔烃和二芳基炔烃的双芳基化中的新用途。该双重芳基化需要碘芳烃和芳基硼酸以及催化剂。X射线晶体学已经证明了一些关键产品的结构。
• Competition of Mechanisms in the Photochemical Cleavage of the C−X Bond of Aryl-Substituted Vinyl Halides
  作者：Carlo Galli、Patrizia Gentili、Alessandra Guarnieri、Shinjiro Kobayashi、Zvi Rappoport

  DOI：10.1021/jo981164p

  日期：1998.12.1

  The photolysis of aryl halides causes homolysis of the carbon-halogen bond and formation of aryl radicals. In contrast, photolysis of vinyl halides can induce both heterolysis of the C-X bond, thereby generating vinyl cations, and homolysis, giving vinyl radicals. Examples of this competition among pathways is reported here for three vinylic precursors, namely, 1,2,2-triphenylbromoethene (1), 1-phenyl-2,2-bis(o-methoxyphenyl)-1-bromoethene (11), and beta-bromostyrene (19). Incursion of the photoinduced S(RN)1 process, through the intermediacy of the vinyl radical, is verified in the presence of reducing nucleophiles, such as the enolate ions of ketones, and in part with (EtO)(2)PO-. Conversely, incursion of the heterolytic path, and intermediacy of the vinyl cation, occurs in the presence of weak electron-donor anions, such as NO2-, N-3(-), and Cl-. The vinyl cation produced from 19, which is less stable than those derived from 1 and 11, gives phenylacetylene via an E1-type elimination. An estimate is provided for the intramolecular rate of interception of the vinyl cation derived from 11 by the ortho-methoxy groups of the beta-o-anisyl substituents. Finally, evidence against a photoinduced electron transfer from RO- ions to vinyl halide 1 is presented.