2-(p-cyanophenoxy)-5,5-dimethyl-2-phenoxy-Δ³-1,3,4-oxadiazoline | 351197-67-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(p-cyanophenoxy)-5,5-dimethyl-2-phenoxy-Δ³-1,3,4-oxadiazoline
• 英文别名: 2-p-cyanophenoxy-5,5-dimethyl-2-phenoxy-Δ³-1,3,4-oxadiazoline；4-[(5,5-Dimethyl-2-phenoxy-1,3,4-oxadiazol-2-yl)oxy]benzonitrile
• CAS: 351197-67-6
• 化学式: C₁₇H₁₅N₃O₃
• 分子量: 309.324
• InChiKey: LLGLDITUBRMENF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  76.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  对甲酚 、 2-(p-cyanophenoxy)-5,5-dimethyl-2-phenoxy-Δ³-1,3,4-oxadiazoline 以 苯 为溶剂， 反应 24.0h， 以84%的产率得到p-tolyl p-cyanophenyl phenyl 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
• 作为产物：
  描述：

  双(4-氰基苯基)碳酸酯 在 一水合肼 、 sodium sulfate 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 52.0h， 生成 2-(p-cyanophenoxy)-5,5-dimethyl-2-phenoxy-Δ³-1,3,4-oxadiazoline
  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

• Mechanism of ipso aromatic substitution by reaction of aryloxy(methoxy)carbenes and diaryloxycarbenes with DMAD
  作者：Xiaosong Lu、John Warkentin

  DOI：10.1139/v01-029

  日期：2001.4.1

  Some aryloxy(methoxy)carbenes and diaryloxycarbenes attack dimethyl acetylenedicarboxylate (DMAD) with aryl group transfer to an alkyne carbon of DMAD. In this study diaryloxycarbenes with different aryl groups that could be transferred competitively, were generated in the presence of DMAD to probe for the mechanism of that ipso aromatic substitution. It was found that a para electron-withdrawing substituent, relative to an electron-donating substituent, facilitated migration of an aryl group. Mechanisms in accord with these findings involve initial nucleophilic attack by the carbene at an alkyne carbon of DMAD. That step is followed by either nucleophilic, ipso attack on the aromatic ring or by electron transfer, from the side chain of the aromatic ring into the ring itself.Key words: aromatic substitution, diaryloxycarbene, DMAD, ipso, nucleophilic.

  一些芳氧基（甲氧基）卡宾和二芳氧基卡宾会攻击二甲基乙炔二羧酸酯（DMAD），将芳基转移到DMAD的炔烃碳上。在这项研究中，生成了具有不同芳基的二芳氧基卡宾，这些芳基可以竞争性地转移，在DMAD存在的情况下探究那种偶极芳基取代的机制。发现对于电子给予取代基而言，相对于电子吸引取代基，对芳基的迁移起到促进作用。与这些发现一致的机制涉及卡宾在DMAD的炔烃碳上的最初亲核攻击。该步骤之后要么是对芳环的亲核偶极攻击，要么是从芳环的侧链向环本身的电子转移。关键词：芳基取代，二芳氧基卡宾，DMAD，偶极，亲核。