2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2λ⁵-dioxaphosphole | 22922-28-7

• 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: 2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2λ⁵-dioxaphosphole
• 英文别名: Heptachlor-benzo-1,3,2-dioxaphosph(V)ol；2,2,2,4,5,6,7-heptachlorobenzo[d]-λ⁵-1,3,2-dioxaphosphol；2,2,2,4,5,6,7-heptachloro-2λ⁵-benzo[1,3,2]dioxaphosphole；2,2,4,5,6,7-hexachloro-benzo[1,3,2]dioxaphospholium; chloride；2,2,2,4,5,6,7-heptachloro-1,3,2λ5-benzodioxaphosphole
• CAS: 22922-28-7
• 化学式: C₆Cl₇O₂P
• 分子量: 383.21
• InChiKey: MSQQYJWSRWGITL-UHFFFAOYSA-N

物化性质

• 熔点：
  120-130 °C (sublm)(Press: 0.06 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  6.92
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2λ⁵-dioxaphosphole 以 二氯甲烷 为溶剂， 反应 0.66h， 生成
  参考文献：
  名称：

  Lewis 超酸性儿茶酚合膦离子：磷-配体协同 C-H 键活化

  摘要：

  一系列儿茶酚鏻离子，包括第一个稳定的双（儿茶酚）取代衍生物，被分离出来并得到充分表征。这些阳离子在 Gutmann-Beckett 和离子亲和性尺度上属于最有效的文献中已知的路易斯酸。与卤化或多电荷磷阳离子相比，路易斯超酸性是由结构约束赋予的，如能量分解分析所揭示的。模块化通路提供了一个可调节的支架，同时保持了极高的亲和力，手性路易斯超强酸的合成证明了这一点。亲电磷和碱性氧取代基的组合通过磷-配体协同作用利用了新的反应模式。这样，就完成了磷介导的 C-H 键活化。

  DOI：

  10.1021/jacs.1c07905
• 作为产物：
  描述：

  邻四氯苯醌 在 三氯化磷 作用下， 以 二氯甲烷 为溶剂， 以97%的产率得到2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2λ⁵-dioxaphosphole
  参考文献：
  名称：

  Lewis 超酸性儿茶酚合膦离子：磷-配体协同 C-H 键活化

  摘要：

  一系列儿茶酚鏻离子，包括第一个稳定的双（儿茶酚）取代衍生物，被分离出来并得到充分表征。这些阳离子在 Gutmann-Beckett 和离子亲和性尺度上属于最有效的文献中已知的路易斯酸。与卤化或多电荷磷阳离子相比，路易斯超酸性是由结构约束赋予的，如能量分解分析所揭示的。模块化通路提供了一个可调节的支架，同时保持了极高的亲和力，手性路易斯超强酸的合成证明了这一点。亲电磷和碱性氧取代基的组合通过磷-配体协同作用利用了新的反应模式。这样，就完成了磷介导的 C-H 键活化。

  DOI：

  10.1021/jacs.1c07905

文献信息

• Reaction of Phenylenedioxytrihalogenophosphoranes with Arylacetylenes. Synthesis and Spatial Structure of the Derivatives of 2-Oxo-4-Aryl-5,6-Benzo-1,2-Oxaphosphorin-2-Enes
  作者：Vladimir F. Mironov、Aidar T. Gubaidullin、Ravil R. Petrov、Igor A. Litvinov、Alfiya A. Shtyrlina、Tatyana A. Zyablikova、Nail M. Azancheev、Alexander I. Konovalov、Rashid Z. Musin

  DOI：10.1080/10426509908546260

  日期：1999.1.1

  New method of synthesis of six-membered heterocycles – 2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes has been developed. It includes the interaction of arylenedioxy trihalogenophosphoranes with arylacetylenes. The formation of phosphoryl group and P-C bond, ipso-substitution of the aromatic oxygen and halogenation of the benzene ring take place in this unusual reaction. The influence of the

  已开发出合成六元杂环的新方法 - 2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes。它包括亚芳基二氧基三卤代正膦与芳基乙炔的相互作用。在这个不寻常的反应中发生了磷酰基和 PC 键的形成、芳香氧的同位取代和苯环的卤化。讨论了正膦结构对合成结果的影响。如果正膦苯环的两个对位都被卤素占据，就会产生卤素分子。2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes 的结构是通过 X 射线分析确定的。
• Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes
  作者：E. N. Varaksina、V. F. Mironov、A. A. Shtyrlina、A. B. Dobrynin、K. Yu. Cherkin、A. T. Gubaidullin、I. A. Litvinov、A. I. Konovalov

  DOI：10.1134/s1070428008070087

  日期：2008.7

  By P-31, C-13, C-13-H-1}, and H-1 NMR spectroscopy the chlorination of 4- and 5-methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloro- and 6-methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxaphosphols. Their hydrolysis led to the formation of difficultly available 4-methyl-5-chloro- and 3-methyl-4-chloro-1,2-dihydroxybenzenes. The structure of the latter compound was established by XRD analysis. The 5-methyl-2-chlorobenzo-1,3,2-dioxaphosphol treated with excess chlorine was converted in succession into 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate and 5-methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate. The hydrolysis resulted in 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-2-en-1-yl dihydrophosphate. The configuration of three chiral carbon atoms in the latter was established by XRD study. In the course of the chlorination the aromaticity of the ortho-phenylene fragment was distorted and 3,3-sigmatropic shift of the dichlorophosphoryl group occurred. The reaction with chlorine of 5-tert-butyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol and 2,2,2-trichloro-benzo-1,3,2-dioxaphosphol was not selective: The reaction product obtained in excess chlorine transformed on hydrolysis into tetrachloropyrocatechol. Its solvates with water and dioxane were studies by XRD analysis.
• Gloede,J.; Gross,H., Journal fur praktische Chemie (Leipzig 1954), 1970, vol. 312, p. 326 - 334
  作者：Gloede,J.、Gross,H.

  DOI：——

  日期：——
• Studies of the oxidation of elemental phosphorus by substituted ortho-benzoquinones
  作者：Theodore A. Annan、Zhigang Tian、Dennis G. Tuck

  DOI：10.1039/dt9910000019

  日期：——

  The phosphorus compounds P(O2C6R)2Br (R = Cl4, Br4 or Bu2H2) have been prepared by the reaction of P4, Br2 and the substituted o-benzoquinone RC6O2-o. There is no reaction between Bu2H2C6O2-o, P4 and Ph2Se2, but in the presence of catalytic quantities of Br2 the product is P(O2C6H2Bu2)2(SePh). ESR spectra identify the presence of the corresponding o-semiquinone species in these reactions. The C-13 and P-31 NMR spectra of these phosphoranes are reported, and compared with those of P(O2C6R)X3 (X3 = Ph3, Ph2Cl, Br3 or Cl3) prepared by the reaction of PX3 and RC6O2-o.
• ——
  作者：V. F. Mironov

  DOI：10.1023/a:1023349414864

  日期：——

  As shown by NMR and IR spectroscopy and high-resolution mass spectrometry, the major products of the reaction of 2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2lambda(5)-dioxaphosphole with phenylacetylene are a six-membered heterocyclic compound, 2-oxo-4-phenyl-2,5,6,7,8-pentachlorobenzo[e]-1,2,5(2H)-oxaphosphorine, and the E and Z isomers of 2-(2,3,4,4,5-pentachlorocyclohexadienon-6-yl)-2-phenylvinylphosphonic dichloride. The molecular and supramolecular structure of the heterocycle and phosphorus-containing products of its hydrolysis were studied by single crystal X-ray diffraction.