(E)-6,6-dimethyl-4,8-dioxa-1-ethylidenespiro[2,5]octane | 130221-64-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-6,6-dimethyl-4,8-dioxa-1-ethylidenespiro[2,5]octane
• 英文别名: (2E)-2-ethylidene-6,6-dimethyl-4,8-dioxaspiro[2.5]octane
• CAS: 130221-64-6
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: KNFIZACRTJDLRR-XBXARRHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (E)-6,6-dimethyl-4,8-dioxa-1-ethylidenespiro[2,5]octane 在 盐酸 作用下， 以 四氢呋喃 、 氘代苯 为溶剂， 反应 6.5h， 生成
  参考文献：
  名称：

  Synthesis of Dimethyleneketene Acetals and Their [2+2] Cycloaddition to Olefins and [60]Fullerene as Cyclopropanecarboxylate Synthons

  摘要：

  本报告描述了二亚甲基烯丙酸酯 3 的合成及其合成应用。将亚甲基环丙酮酯 1 在 150°C 下进行热重排，可得到二亚甲基烯丙酸酯 3，后者作为烷基环丙烷羧酸酯的烯醇盐的反应性替代物，而烷基环丙烷羧酸酯迄今为止难以制备。烯丙酸酯 3 不仅在水解后生成相应的烷基环丙烷羧酸酯 4，还能顺利与电子缺乏的烯烃（包括 C60）发生平滑的 [2+2] 环加成反应。环加成产物在水相处理后容易发生环裂解，生成迈克尔加成产物 6，产率高。由于 3 和 C60 的反应生成的环加成产物 8 在热解时不稳定，会生成 C60，但在酸性条件下尝试水解醇酯基时，会量化水解裂解生成酯 10。3 与双烷基偶氮二羧酸酯的环加成也顺利进行，生成了优秀产率的环丙基氨基酸衍生物。

  DOI：

  10.1055/s-1996-4392
• 作为产物：
  描述：

  6,6-二甲基-4,8-二氧杂螺[2.5]辛-1-烯 在 正丁基锂 、 potassium tert-butylate 作用下， 以 乙醚 、 二甲基亚砜 为溶剂， 反应 1.83h， 生成 (E)-6,6-dimethyl-4,8-dioxa-1-ethylidenespiro[2,5]octane
  参考文献：
  名称：

  Thermal Hetero [3 + 2] Cycloaddition of Dipolar Trimethylenemethane to O-Alkyloximes. Straightforward Synthetic Routes to Substituted Pyrrolidines and Prolines

  摘要：

  Thermal hetero [3 + 2] cycloaddition reaction of a dipolar trimethylenemethane 2 with an O-alkyloxime produces a substituted pyrrolidine. Thus, heating of a mixture of an alkylidenecyclopropane 1 an anti-O-alkyloxime 3 proceeds smoothly in good yield to give a substituted pyrrolidine 4 bearing a ketene acetal group in its 3-position, which upon hydrolysis under mild conditions gives a 3-alkoxycarbonylpyrrolidne 5 in quantitative yield. On the other hand, the cycloaddition to a syn-oxime is extremely slow. The cycloaddition reaction can be achieved by starting with nearly equimolar quantities of the two starting materials, and the reaction is quite insensitive to the choice of solvent and to the presence of oxygen and water. In the reaction of a substituted methylenecyclopropane 1 (R not equal H), the reaction may take place with high regio-and stereoselectivity, which is in consonance with the concerted nature of the cycloaddition reaction. The present synthesis represents one of the rare examples of the imine-based route to pyrrolidines, which have been much less explored than the 1,3-dipolar cycloaddition route using olefin and azomethine ylide.

  DOI：

  10.1021/jo972302y

文献信息

• Regioselective and endo-stereoselective [3 + 2] cycloaddition of dipolar trimethylenemethane to electron-deficient olefin
  作者：Satoshi Ejiri、Shigeru Yamago、Eiichi Nakamura

  DOI：10.1021/ja00048a058

  日期：1992.10
• YAMAGO, SHIGERU;NAKAMURA, EIICHI, J. ORG. CHEM., 55,(1990) N1, C. 5553-5555
  作者：YAMAGO, SHIGERU、NAKAMURA, EIICHI

  DOI：——

  日期：——
• Thermal Hetero [3 + 2] Cycloaddition of Dipolar Trimethylenemethane to <i>O</i>-Alkyloximes. Straightforward Synthetic Routes to Substituted Pyrrolidines and Prolines
  作者：Shigeru Yamago、Masaharu Nakamura、Xiao Qun Wang、Masao Yanagawa、Shuzo Tokumitsu、Eiichi Nakamura

  DOI：10.1021/jo972302y

  日期：1998.3.1

  Thermal hetero [3 + 2] cycloaddition reaction of a dipolar trimethylenemethane 2 with an O-alkyloxime produces a substituted pyrrolidine. Thus, heating of a mixture of an alkylidenecyclopropane 1 an anti-O-alkyloxime 3 proceeds smoothly in good yield to give a substituted pyrrolidine 4 bearing a ketene acetal group in its 3-position, which upon hydrolysis under mild conditions gives a 3-alkoxycarbonylpyrrolidne 5 in quantitative yield. On the other hand, the cycloaddition to a syn-oxime is extremely slow. The cycloaddition reaction can be achieved by starting with nearly equimolar quantities of the two starting materials, and the reaction is quite insensitive to the choice of solvent and to the presence of oxygen and water. In the reaction of a substituted methylenecyclopropane 1 (R not equal H), the reaction may take place with high regio-and stereoselectivity, which is in consonance with the concerted nature of the cycloaddition reaction. The present synthesis represents one of the rare examples of the imine-based route to pyrrolidines, which have been much less explored than the 1,3-dipolar cycloaddition route using olefin and azomethine ylide.
• Synthesis of Dimethyleneketene Acetals and Their [2+2] Cycloaddition to Olefins and [60]Fullerene as Cyclopropanecarboxylate Synthons
  作者：Shigeru Yamago、Atsuo Takeichi、Eiichi Nakamura

  DOI：10.1055/s-1996-4392

  日期：1996.11

  The synthesis and synthetic utilization of the dimethyleneketene acetal 3 are described in this report. Thermal rearrangement of the methylenecyclopropanone acetal 1 at 150°C gives the dimethyleneketene acetal 3, which serves as a reactive surrogate of the enolate of alkyl cyclopropanecarboxylate, which has thus far been difficult to prepare. The ketene acetal 3 not only gives the corresponding alkyl cyclopropanecarboxylate 4 upon hydrolysis but also undergoes smooth [2+2] cycloaddition to electron-deficient olefins including C60. The cycloadduct undergoes facile ring cleavage upon aqueous workup to give the Michael addition product 6 in high yield. While the cycloadduct 8 due to the reaction between 3 and C60 is thermally unstable to generate C60 upon thermolysis, it undergoes quantitative hydrolytic cleavage to give the ester 10 upon attempted hydrolysis of the acetal moiety under acidic conditions. The cycloaddition of 3 with dialkyl azodicarboxylate also proceeds smoothly to afford cyclopropyl amino acid derivative in excellent yield.

  本报告描述了二亚甲基烯丙酸酯 3 的合成及其合成应用。将亚甲基环丙酮酯 1 在 150°C 下进行热重排，可得到二亚甲基烯丙酸酯 3，后者作为烷基环丙烷羧酸酯的烯醇盐的反应性替代物，而烷基环丙烷羧酸酯迄今为止难以制备。烯丙酸酯 3 不仅在水解后生成相应的烷基环丙烷羧酸酯 4，还能顺利与电子缺乏的烯烃（包括 C60）发生平滑的 [2+2] 环加成反应。环加成产物在水相处理后容易发生环裂解，生成迈克尔加成产物 6，产率高。由于 3 和 C60 的反应生成的环加成产物 8 在热解时不稳定，会生成 C60，但在酸性条件下尝试水解醇酯基时，会量化水解裂解生成酯 10。3 与双烷基偶氮二羧酸酯的环加成也顺利进行，生成了优秀产率的环丙基氨基酸衍生物。