2-benzyloxy-2-methoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline | 270921-28-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-benzyloxy-2-methoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline
• 英文别名: 2-Methoxy-5,5-dimethyl-2-phenylmethoxy-1,3,4-oxadiazole
• CAS: 270921-28-3
• 化学式: C₁₂H₁₆N₂O₃
• 分子量: 236.271
• InChiKey: AKDNMOXQZBBLQT-UHFFFAOYSA-N

物化性质

• 沸点：
  302.6±42.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-benzyloxy-2-methoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline 在 亚苄基丙二酸二甲酯 作用下， 以 苯 为溶剂， 反应 24.0h， 生成 苯乙酸甲酯
  参考文献：
  名称：

  Cyclopropanation of benzylidenemalononitrile with dialko×ycarbenes and free radical rearrangement of the cyclopropanes

  摘要：

  Thermolysis of 2-cinnamyloxy-2-methoxy-5,5-dimethyl-Delta (3)-1,3,4-oxadiazoline (1a) and the analogous 2-benzyloxy-2-methoxy compound (1b) at 110 degreesC, in benzene containing benzylidenemalononitrile, afforded products of apparent regiospecific addition of methoxycarbonyl and cinnamyl (or benzyl) radicals to the double bond. When the thermolysis of 1a was run with added TEMPO, methoxycarbonyl and cinnamyl radicals were captured. Thermolysis of the 2,2-dibenzyloxy analogue (1c) in the presence of benzylidenemalononitrile gave an adduct that is formally the product of addition of benzyloxycarbonyl and benzyl radicals to the double bond. In this case, a radical addition mechanism could be ruled out, because the rate constant for decarboxylation of benzyloxycarbonyl radicals is very large. A mechanism that fits all of the results is predominant cyclopropanation of benzylidenemalononitrile by the dialkoxycarbenes derived from the oxadiazolines, in competition with fragmentation of the carbenes to radical pairs. The cyclopropanes so formed then undergo homolytic ring-opening to the appropriate diradicals. Subsequent beta -scission of the diradicals to afford radical pairs, and coupling of those pairs, gives the final products. Thus, both carbene and radical chemistry are involved in the overall processes.

  DOI：

  10.1139/cjc-79-3-312
• 作为产物：
  描述：

  methyl-2,3-diaza-4-methyl-4-acetoxypent-2-enoate 、 苯甲醇 在 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 生成 2-benzyloxy-2-methoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline
  参考文献：
  名称：

  Radicals from fragmentation of benzyloxymethoxycarbenes in solution

  摘要：

  2-苄氧基-2-甲氧基-5,5-二甲基-Δ3-1,3,4-噁二唑啉，包括母体和对位取代物，可以在苯中在100°C下发生热解反应，生成混合产物。已确定了噁二唑啉的两种主要裂解途径。主要途径涉及1,3-二极环反应生成N2和相应的羰基亚烯。后者解离为丙酮和相应的苄氧基（甲氧基）卡宾，后者经裂解生成ArCH2和MeOCO自由基对，再结合形成甲基芳基乙酸酯。未观察到卡宾二聚体，表明裂解过程比卡宾二聚化更快。噁二唑啉的第二种裂解途径是另一种环反应生成相应的苄基甲基碳酸酯和2-二氮代丙烷。来自二氮代丙烷的产物包括丙酮噁唑啉和在某些情况下的微量丙烯。关键词：苄氧基（甲氧基）卡宾，卡宾，自由基对，重排。

  DOI：

  10.1139/v00-021