2-(2,2-dimethyl-[1,3]dioxolan-4-ylmethylene)-malonic acid dimethyl ester | 70107-43-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(2,2-dimethyl-[1,3]dioxolan-4-ylmethylene)-malonic acid dimethyl ester
• 英文别名: dimethyl 2-[[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methylidene]propanedioate
• CAS: 70107-43-6
• 化学式: C₁₁H₁₆O₆
• 分子量: 244.244
• InChiKey: IUMZIORBHMYPIM-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-(2,2-dimethyl-[1,3]dioxolan-4-ylmethylene)-malonic acid dimethyl ester 在 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 75.0h， 生成 methyl 4-hydroxymethyl-6,6-dimethyl-2-oxo-3-oxa[3.1.0]heptane-1-carboxylate
  参考文献：
  名称：

  Hemisynthesis of methyl pyrethroates from γ-alkoxy-alkylidene malonates and isopropylidenediphenylsulfurane and isopropylidenetriphenylphosphorane

  摘要：

  Hemi synthesis of methyl pyrethroates from gamma-alkoxy-alkylidene malonates and isopropylidenediphenylsulfurane and isopropylidenetriphenylphosphorane is disclosed. It takes advantage of the high degree of stereocontrol observed in the cyclopropanation of gamma-alkoxy-alkylidene malonates by the above mentioned ylides. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.06.035
• 作为产物：
  描述：

  丙二酸二甲酯 、 双丙酮-D-甘露糖醇 在 lead(IV) acetate 、 乙酸酐 作用下， 以 四氢呋喃 为溶剂， 反应 24.17h， 以85%的产率得到2-(2,2-dimethyl-[1,3]dioxolan-4-ylmethylene)-malonic acid dimethyl ester
  参考文献：
  名称：

  Hemisynthesis of methyl pyrethroates from γ-alkoxy-alkylidene malonates and isopropylidenediphenylsulfurane and isopropylidenetriphenylphosphorane

  摘要：

  Hemi synthesis of methyl pyrethroates from gamma-alkoxy-alkylidene malonates and isopropylidenediphenylsulfurane and isopropylidenetriphenylphosphorane is disclosed. It takes advantage of the high degree of stereocontrol observed in the cyclopropanation of gamma-alkoxy-alkylidene malonates by the above mentioned ylides. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.06.035

文献信息

• Diastereoselective addition of silyl- and stannyl metals to γ-alkoxy-alkylidene malonates
  作者：Alain Krief、Willy Dumont、Diane Baillieul

  DOI：10.1016/j.tetlet.2005.09.063

  日期：2005.11

  Stereochemical control of the addition of silyl- and stannyl metals to chiral γ-alkoxy-alkylidene malonates proved to be dependant on the nature of the counter ion and of the solvent but in an unpredictable way.

  立体化学控制向手性γ-烷氧基-亚烷基丙二酸酯中添加甲硅烷基和苯乙烯基金属的方法取决于抗衡离子和溶剂的性质，但以不可预测的方式。
• Photolysis of Chiral 1-Pyrazolines to Cyclopropanes:  Mechanism and Stereospecificity
  作者：Elena Muray、Ona Illa、José A. Castillo、Ángel Álvarez-Larena、José L. Bourdelande、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo0342471

  日期：2003.6.1

  The photodenitrogenation of chiral trisubstituted 1-pyrazolines has been studied by laser flash photolysis. These experiments have permitted the detection of two transients that have been assigned, for each pyrazoline, to the trimethylene-type diradical resultant from the extrusion of nitrogen (lifetime tau = 0.1-0.8mus) and to the pyrazoline triplet (r < 9 ns), respectively. The efficiency of the photosensitization process has been evaluated by determination of the corresponding quenching rate constant in each instance. Theoretical calculations support a mechanistic pathway involving a trimethylene radical as intermediate that rapidly evolves to the corresponding cyclopropane derivative. The cyclopropane ring-closure is predicted to be faster than rotation around the C-C bond, thus accounting for the observed stereospecificity.