2-benzyl-5-methoxy-2,5-dimethyl-1,3,4-oxadiazole | 154196-70-0

• 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-benzyl-5-methoxy-2,5-dimethyl-1,3,4-oxadiazole
• CAS: 154196-70-0
• 化学式: C₁₂H₁₆N₂O₂
• 分子量: 220.271
• InChiKey: MOUJKNONRBDZGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.18
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-benzyl-5-methoxy-2,5-dimethyl-1,3,4-oxadiazole 以 甲苯 为溶剂， 反应 7.0h， 生成 3-Benzyl-3-methyl-3H-pyrazole-5-carboxylic acid methyl ester
  参考文献：
  名称：

  Studies of thermal rearrangements of methyl 3-alkyl-3-methyl-3H-pyrazole-5-carboxylates. Concerted, stepwise, and unclassified mechanisms

  摘要：

  Studies of the thermal rearrangements of five 3H-pyrazoles are described, in which the migrating groups were methoxymethyl, tert-butyl, 1-adamantyl, p-methoxybenzyl, and benzyl. On the basis of reaction products, rearrangement of the (methoxymethyl)pyrazole in benzene, dichloromethane, and methanol at room temperature occurs by a stepwise mechanism, involving discrete ion-pair intermediates. Observed first-order rate constants, for the rearrangement of four of the 3H-pyrazoles in benzene-d(6) and acetone-d(6) at higher temperatures, were determined The tert-butyl compound also rearranges by a stepwise mechanism in benzene d(6), acetone-d(6), and methanol-d(4) based on the fact that isobutene and tert-butyl methyl ether (in methanol) are coproducts of rearrangement. The mechanism of rearrangement of the adamantyl and methoxybenzyl systems, in both benzene d(6) and acetone-d(6) solvents, is ambiguous, the distinction between stepwise, with tight ion-pair intermediates, and concerted, with some charge separation, being unclear. However, both afforded a methyl ether in low yield during rearrangement in methanol solvent, which suggests a stepwise, ion-pair mechanism for rearrangement in that medium. No methanolysis product could be detected from the rearrangement of the benzyl compound in methanol, which suggests concerted rearrangement. Additional evidence that it rearranges by a concerted mechanism is the fact that it affords only one pyrazole product, whereas the others afford two or more.

  DOI：

  10.1021/jo00081a028
• 作为产物：
  描述：

  甲醇 、 N-[(E)-1-phenylpropan-2-ylideneamino]acetamide 在 lead(IV) acetate 作用下， 生成 2-benzyl-5-methoxy-2,5-dimethyl-1,3,4-oxadiazole
  参考文献：
  名称：

  Studies of thermal rearrangements of methyl 3-alkyl-3-methyl-3H-pyrazole-5-carboxylates. Concerted, stepwise, and unclassified mechanisms

  摘要：

  Studies of the thermal rearrangements of five 3H-pyrazoles are described, in which the migrating groups were methoxymethyl, tert-butyl, 1-adamantyl, p-methoxybenzyl, and benzyl. On the basis of reaction products, rearrangement of the (methoxymethyl)pyrazole in benzene, dichloromethane, and methanol at room temperature occurs by a stepwise mechanism, involving discrete ion-pair intermediates. Observed first-order rate constants, for the rearrangement of four of the 3H-pyrazoles in benzene-d(6) and acetone-d(6) at higher temperatures, were determined The tert-butyl compound also rearranges by a stepwise mechanism in benzene d(6), acetone-d(6), and methanol-d(4) based on the fact that isobutene and tert-butyl methyl ether (in methanol) are coproducts of rearrangement. The mechanism of rearrangement of the adamantyl and methoxybenzyl systems, in both benzene d(6) and acetone-d(6) solvents, is ambiguous, the distinction between stepwise, with tight ion-pair intermediates, and concerted, with some charge separation, being unclear. However, both afforded a methyl ether in low yield during rearrangement in methanol solvent, which suggests a stepwise, ion-pair mechanism for rearrangement in that medium. No methanolysis product could be detected from the rearrangement of the benzyl compound in methanol, which suggests concerted rearrangement. Additional evidence that it rearranges by a concerted mechanism is the fact that it affords only one pyrazole product, whereas the others afford two or more.

  DOI：

  10.1021/jo00081a028

文献信息

• Photolysis of 5,5-dibenzyl-Δ³-1,3,4-oxadiazolines
  作者：John Warkentin、John Mck.R. Woollard

  DOI：10.1139/v97-033

  日期：1997.3.1

  Photolysis of dibenzyl-Δ3-1,3,4-oxadiazolines (3) in the presence of dimethyl acetylenedicarboxylate (DMAD) gives only modest yields of the expected symmetrical 3,3-dibenzylcyclopropenes (4), but these are accompanied by more than six by-products, including unsymmetrical cyclopropenes, methylenecyclopropanes, and various pyrazoles. The origin of this array of products can be explained by a series of

  在乙炔二甲酸二甲酯 (DMAD) 存在下二苄基-Δ3-1,3,4-恶二唑啉 (3) 的光解仅产生预期的对称 3,3-二苄基环丙烯 (4) 的适度产率，但这些伴随着超过六个副产物，包括不对称环丙烯、亚甲基环丙烷和各种吡唑。这一系列产品的起源可以通过一系列步骤来解释，从 3 的光解开始形成重氮烷，该重氮烷经过 1,3-偶极环加成到 DMAD，生成 3H-吡唑作为初始产物。后者通过热 1,5-sigmatropic 或离子对重排进一步光解为对称的环丙烯，与苄基迁移竞争，得到 4H-吡唑。4H-吡唑依次经过光解生成不对称的环丙烯，重排为亚甲基环丙烷。4H-吡唑也在空气存在下进行自氧化，得到苯甲酰基-4H-吡唑。此外，在与重排的竞争中，v...