6-tert-butyl-6-methyl-5,7-dioxa-1,2-diazaspiro[2.5]oct-1-ene-4,8-dione | 834898-18-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-tert-butyl-6-methyl-5,7-dioxa-1,2-diazaspiro[2.5]oct-1-ene-4,8-dione
• 英文别名: 6-methyl-6-tert-butyl-4,8-dioxa-5,7-dioxo-1,2-diazaspiro[2.5]oct-1-ene
• CAS: 834898-18-9
• 化学式: C₉H₁₂N₂O₄
• 分子量: 212.205
• InChiKey: ULLCQUKVOJPBST-UHFFFAOYSA-N

物化性质

• 熔点：
  71-73 °C(Solv: ligroine (8032-32-4); ethyl ether (60-29-7))
• 沸点：
  409.7±55.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  77.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-tert-butyl-6-methyl-5,7-dioxa-1,2-diazaspiro[2.5]oct-1-ene-4,8-dione 在 二苯甲酮 作用下， 以 异丙醇 为溶剂， 以97%的产率得到2-methyl-2-tert-butyl-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  重氮羰基化合物的化学：XXVII。1,3-二恶烷-4,6-二酮衍生物二嗪类的热解和光解

  摘要：

  Photolysis of diazirines, 1,3-dioxane-4,6-dione derivatives, occurs in the presence of methanol or dimethyl sulfide as carbene traps without a formation of carbene intermediates. It was established for the first time that the thermolysis and photolysis of diazirines from the 1,3-dioxane-4,6-dione series led mainly to Wolff rearrangement with a subsequent formation of 5-oxo-1,3-dioxolane-4-carboxylic acids or their derivatives. The data obtained show that the alpha-oxodiazirines are the key intermediates in the photolysis and Wolff rearrangement of alpha-diazocarbonyl compounds.

  DOI：

  10.1134/s1070428006080197
• 作为产物：
  描述：

  2-methyl-2-tert-butyl-1,3-dioxane-4,6-dione 在 potassium fluoride 、 对甲苯磺酰叠氮 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 38.5h， 生成 6-tert-butyl-6-methyl-5,7-dioxa-1,2-diazaspiro[2.5]oct-1-ene-4,8-dione
  参考文献：
  名称：

  Chemistry of diazocarbonyl compounds: XXV. Comparative photochemistry of diazo compounds and sulfur ylides of the 1,3-dioxane-4,6-dione series

  摘要：

  Photochemical decomposition of 2,2-dialkyl-5-diazo-1,3-dioxane-4,6-diones in the presence of pyridine, methanol.. or dimethyl sulfide as carbene traps involves mainly the Wolff rearrangement which is likely to follow a concerted pattern, while the yield of the "carbene" products does not exceed 27-28%. No carbene intermediates are formed in the photolysis of the corresponding dioxo sulfonium ylides under analogous conditions, and the main photochemical process is 1,2-methyl shift (Stevens rearrangement), followed by photochemical transformations of the primary products according to the Norrish type 11 pattern.

  DOI：

  10.1134/s1070428006060029

文献信息

• Search for dioxocarbenes in photochemical reactions of 5-diazo-4,6-dioxo-1,3-dioxanes, associated diazirines, and S-ylides
  作者：V.V. Shevchenko、N.N. Khimich、M.S. Platz、V.A. Nikolaev

  DOI：10.1016/j.tetlet.2004.11.102

  日期：2005.1

  On direct photolysis of 2,2-dialkyl-5-diazo-4,6-dioxo-1,3-dioxanes in the presence of pyridine, methanol or dimethyl sulfide as carbene traps, the yield of ‘carbene’ products does not exceed 27–28%. At the same time photochemical transformations of the related 3,3-diacyldiazirines and dioxosulfonium ylides of this series, evidently, occur without generation of carbene intermediates.

  在存在吡啶，甲醇或二甲基硫醚作为卡宾捕集剂的情况下，对2,2-二烷基-5-重氮-4,6-二氧代-1,3-二恶烷进行直接光解时，“卡宾”产物的收率不超过27 –28％。同时，与此相关的3，3-二酰基二叠氮基和该系列二氧代ulf鎓的光化学转化显然发生了，而没有产生卡宾中间体。