3-(1',2'-dimethylpropylidene)-1-oxa-spiro[4,5]decane-2,4-dione | 359845-33-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3-(1',2'-dimethylpropylidene)-1-oxa-spiro[4,5]decane-2,4-dione
• 英文别名: 3-(1,2-Dimethylpropylidene)-1-oxaspiro[4.5]decane-2,4-dione；3-(3-methylbutan-2-ylidene)-1-oxaspiro[4.5]decane-2,4-dione
• CAS: 359845-33-3
• 化学式: C₁₄H₂₀O₃
• 分子量: 236.311
• InChiKey: VKGWDIACYQLYQP-UHFFFAOYSA-N

物化性质

• 沸点：
  414.3±34.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.79
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-(1',2'-dimethylpropylidene)-1-oxa-spiro[4,5]decane-2,4-dione 在 氧气 、 对甲苯磺酸 、 copper(II) sulfate 、 iron(II) bromide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 4,5,5-trimethyl-2-oxofuran-3-carboxylic acid
  参考文献：
  名称：

  Hydroperoxide and Endoperoxide Lactones from Photooxygenation of 3-Alkylidenedihydrofuran-2,4-diones

  摘要：

  3-Alkylidenedihydrofuran-2,4-diones 1 can be photooxygenated with O-2/TBHP to hydroperoxides 3 which slowly decompose to diols 5. Stable endoperoxides 4 are best prepared by photooxygenation of 1 with 2 equiv of O-2 in the presence of CuSO4 and p-TosOH following a nonradical mechanism. They are rapidly reduced by anhydrous FeBr2 to give butenolide 9 indicating a potential antimalarial activity.

  DOI：

  10.1021/jo030270a
• 作为产物：
  描述：

  4-(3-Methylbut-2-enoxy)-1-oxaspiro[4.5]dec-3-en-2-one 以 甲苯 为溶剂， 反应 24.0h， 以65%的产率得到3-(1',2'-dimethylpropylidene)-1-oxa-spiro[4,5]decane-2,4-dione
  参考文献：
  名称：

  Tetrones的Claisen异常重排和中间螺环丙烷的立体选择性开环

  摘要：

  烯丙基四酸酯的热[2,3]-σ重排通过3-（螺环丙基）二氢呋喃-2,4-二酮进行；在某些情况下，可以将其分离，并用醇或水将其环丙烷环立体选择性地打开，得到3-（β-顺式烷氧基）tetronic酸。用LDA处理5，5-二取代的苄基四乙酸也通过阴离子[1，3]重排产生了3-取代的四氢苯甲酸。

  DOI：

  10.1016/s0040-4039(01)00773-0

文献信息

• Oxidations of 3-alkenyltetronic acids with dimethyldioxirane (DMD) and air: regioselectivity and formation of a spirotricyclic hemiketal endoperoxide lactone
  作者：Rainer Schobert、Sven Siegfried、Jochen Weingärtner、Mark Nieuwenhuyzen

  DOI：10.1039/b104227k

  日期：——

  The endocyclic CC bond of 3-allyltetronic acid 1 can be selectively oxidised with dimethyldioxirane to give 3-allyl-3-hydroxydihydrofuran-2,4-dione 2 while 3-exo-alkylidenedihydrofuran-2,4-diones 9 are rapidly autooxidised to furnish the spirotricyclic hemiketal endoperoxide lactones 10.

  3-烯丙基四氢呋喃酸1的内循环CC键可被二甲基二氧杂环己烷选择性氧化，生成3-烯丙基-3-羟基二氢呋喃-2,4-二酮2，而3-外烯丙基二氢呋喃-2,4-二酮9则迅速自动氧化，生成螺三环半缩醛内过氧化物内酯10。
• Abnormal Claisen rearrangements of tetronates and stereoselective ring opening of intermediate spirocyclopropanes
  作者：Rainer Schobert、Sven Siegfried、Gary Gordon、Daniel Mulholland、Mark Nieuwenhuyzen

  DOI：10.1016/s0040-4039(01)00773-0

  日期：2001.7

  Thermal [2,3]-sigmatropic rearrangements of allyltetronates proceed via 3-(spirocyclopropyl)dihydrofuran-2,4-diones; in some cases these could be isolated and their cyclopropane rings stereoselectively opened with alcohols or water to give 3-(β-syn-alkoxy)tetronic acids. Treatment of a 5,5-disubstituted benzyltetronate with LDA also produced a 3-substituted tetronic acid by an anionic [1,3]-rearrangement

  烯丙基四酸酯的热[2,3]-σ重排通过3-（螺环丙基）二氢呋喃-2,4-二酮进行；在某些情况下，可以将其分离，并用醇或水将其环丙烷环立体选择性地打开，得到3-（β-顺式烷氧基）tetronic酸。用LDA处理5，5-二取代的苄基四乙酸也通过阴离子[1，3]重排产生了3-取代的四氢苯甲酸。
• Hydroperoxide and Endoperoxide Lactones from Photooxygenation of 3-Alkylidenedihydrofuran-2,4-diones
  作者：Rainer Schobert、Ralf Stehle、Wolfgang Milius

  DOI：10.1021/jo030270a

  日期：2003.12.1

  3-Alkylidenedihydrofuran-2,4-diones 1 can be photooxygenated with O-2/TBHP to hydroperoxides 3 which slowly decompose to diols 5. Stable endoperoxides 4 are best prepared by photooxygenation of 1 with 2 equiv of O-2 in the presence of CuSO4 and p-TosOH following a nonradical mechanism. They are rapidly reduced by anhydrous FeBr2 to give butenolide 9 indicating a potential antimalarial activity.