p-tolyl diphenyl orthoformate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: p-tolyl diphenyl orthoformate
• 化学式: C₂₀H₁₈O₃
• 分子量: 306.361
• InChiKey: LVPQAQNBZLCVSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  23.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  碳酸二苯酯 在 一水合肼 、 sodium sulfate 、 三氟乙酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 84.0h， 生成 p-tolyl diphenyl orthoformate
  参考文献：
  名称：

  Diarylo×ycarbenes from o×adiazolines

  摘要：

  Symmetric and unsymmetric 2,2-diaryloxy-5,5-dimethyl-Delta (3)-1,3,4-oxadiazolines were synthesized by oxidative cyclization of aryloxycarbonyl hydrazones of acetone with lead tetraacetate and subsequent treatment of the product mixture with a phenol in acidic solution. Thermolysis of the oxadiazolines in benzene solution at 110 degreesC afforded carbonyl ylide intermediates that cyclize, in part, to the corresponding 2,2-diaryloxyoxirane intermediates. The oxiranes, which were not observed, are required to account for the 1,1-diaryloxy-2-methylpropenes (ketene acetals) that were isolated. Most of the carbonyl ylides fragment to acetone and diaryloxycarbenes. The latter form dimers (tetraaryloxyethenes) or they can be trapped with phenols to form orthoformates. Diphenoxycarbene was also trapped with dimethyl acetylenedicarboxylate (DMAD). The method appears to be the first for generating the parent diphenoxycarbene under relatively mild conditions in solution, and the only one to date for generating unsymmetrically substituted diaryloxycarbenes. Minor competing fragmentations of the oxadiazolines to 2-diazopropane and the appropriate diaryl carbonates, were also observed.

  DOI：

  10.1139/cjc-79-3-319

文献信息

• Diarylo×ycarbenes from o×adiazolines
  作者：Xiaosong Lu、Darren L. Reid、John Warkentin

  DOI：10.1139/cjc-79-3-319

  日期：——

  Symmetric and unsymmetric 2,2-diaryloxy-5,5-dimethyl-Delta (3)-1,3,4-oxadiazolines were synthesized by oxidative cyclization of aryloxycarbonyl hydrazones of acetone with lead tetraacetate and subsequent treatment of the product mixture with a phenol in acidic solution. Thermolysis of the oxadiazolines in benzene solution at 110 degreesC afforded carbonyl ylide intermediates that cyclize, in part, to the corresponding 2,2-diaryloxyoxirane intermediates. The oxiranes, which were not observed, are required to account for the 1,1-diaryloxy-2-methylpropenes (ketene acetals) that were isolated. Most of the carbonyl ylides fragment to acetone and diaryloxycarbenes. The latter form dimers (tetraaryloxyethenes) or they can be trapped with phenols to form orthoformates. Diphenoxycarbene was also trapped with dimethyl acetylenedicarboxylate (DMAD). The method appears to be the first for generating the parent diphenoxycarbene under relatively mild conditions in solution, and the only one to date for generating unsymmetrically substituted diaryloxycarbenes. Minor competing fragmentations of the oxadiazolines to 2-diazopropane and the appropriate diaryl carbonates, were also observed.