2,2,2-trichloro-4-methylbenzo[d]-1,3,2-dioxaphosphole | 880138-02-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2,2,2-trichloro-4-methylbenzo[d]-1,3,2-dioxaphosphole
• 英文别名: 4-methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol；2,2,2-trichloro-4-methyl-1,3,2λ5-benzodioxaphosphole
• CAS: 880138-02-3
• 化学式: C₇H₆Cl₃O₂P
• 分子量: 259.456
• InChiKey: MEGCYXHKKKLEIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,2-trichloro-4-methylbenzo[d]-1,3,2-dioxaphosphole 在 氯 作用下， 以 二氯甲烷 为溶剂， 反应 144.0h， 生成 2,2,2,5-tetrachloro-4-methylbenzo[d]-1,3,2-dioxaphosphole
  参考文献：
  名称：

  Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes

  摘要：

  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.

  DOI：

  10.1134/s1070428008070087
• 作为产物：
  描述：

  2-chloro-4-methylbenzo[d]-1,3,2-dioxaphosphole 在 氯 作用下， 以 二氯甲烷 为溶剂， 以97%的产率得到2,2,2-trichloro-4-methylbenzo[d]-1,3,2-dioxaphosphole
  参考文献：
  名称：

  Regioselective chlorination of 4- and 5-methyl-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphospholes

  摘要：

  The reactions of 4- and 5-methyl-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphospholes with molecular chlorine in an 1:1 ratio occur selectively to give 4-methyl-2,2,2,5-tetrachloro- and 5-methyl-2,2,2,6-tetrachlorobenzo[d]-1,3,2-dioxaphospholes, which undergo hydrolysis to 4-chloro-3-methyl- and 4-chloro-5-methyl-1,2-dihydroxybenzenes, respectively.

  DOI：

  10.1070/mc2005v015n03abeh002069

文献信息

• Regioselective chlorination of 4- and 5-methyl-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphospholes
  作者：Elena N. Varaksina、Vladimir F. Mironov、Alfia A. Shtyrlina、Alexey B. Dobrynin、Igor A. Litvinov、Alexander I. Konovalov

  DOI：10.1070/mc2005v015n03abeh002069

  日期：2005.1

  The reactions of 4- and 5-methyl-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphospholes with molecular chlorine in an 1:1 ratio occur selectively to give 4-methyl-2,2,2,5-tetrachloro- and 5-methyl-2,2,2,6-tetrachlorobenzo[d]-1,3,2-dioxaphospholes, which undergo hydrolysis to 4-chloro-3-methyl- and 4-chloro-5-methyl-1,2-dihydroxybenzenes, respectively.
• 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.