2-(Phenyl-trifluoromethanesulfonyloxy-methylene)-malonic acid diethyl ester | 184776-80-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 2-(Phenyl-trifluoromethanesulfonyloxy-methylene)-malonic acid diethyl ester
• 英文别名: Diethyl 2-[phenyl(trifluoromethylsulfonyloxy)methylidene]propanedioate
• CAS: 184776-80-5
• 化学式: C₁₅H₁₅F₃O₇S
• 分子量: 396.341
• InChiKey: TTZBIDJTXRLMKP-UHFFFAOYSA-N

物化性质

• 沸点：
  405.3±45.0 °C(Predicted)
• 密度：
  1.398±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  哌啶 、 2-(Phenyl-trifluoromethanesulfonyloxy-methylene)-malonic acid diethyl ester 以 乙腈 为溶剂， 反应 3.0h， 以25%的产率得到diethyl 2-(phenyl(piperidin-1-yl)methylene)malonate
  参考文献：
  名称：

  Triflate/Mesylate Ratios and Competing C−O and S−O Bond Cleavages in Nucleophilic Vinylic Substitution

  摘要：

  In an attempt to develop the k(OTf)/K-OMs ratio as a mechanistic tool for the ''addition-elimination'' route in nucleophilic vinylic substitution, several pairs of vinyl mesylates and triflates were prepared. Whereas reactions of ArC(LG)=C(CO(2)Et)(2) (LG = OTf, OMs) with piperidine and morpholine in MeCN or THF gave the normal substitution product with k(OTf)/k(OMs) ratios of 4.3-10.6, the reaction of the mesylates, Ar = p-O2NC6H4, and of PhC(OMs)=C(Me)CN with MeS(-) gave a ketone via an S-O bond cleavage. A related mesityl-substituted tosylate also reacted with p-MeC(6)H(4)X(-) (X = O, S) via an S-O bond cleavage. Hence, k(OTf)/k(OMs) ratios cannot be used as a general mechanistic tool. Several reactivity ratios in vinylic substitution are briefly discussed.

  DOI：

  10.1021/jo961108t
• 作为产物：
  描述：

  三氟甲磺酸酐 、 diethyl benzoylmalonate 在 三乙胺 作用下， 以 四氯化碳 为溶剂， 以44%的产率得到2-(Phenyl-trifluoromethanesulfonyloxy-methylene)-malonic acid diethyl ester
  参考文献：
  名称：

  Triflate/Mesylate Ratios and Competing C−O and S−O Bond Cleavages in Nucleophilic Vinylic Substitution

  摘要：

  In an attempt to develop the k(OTf)/K-OMs ratio as a mechanistic tool for the ''addition-elimination'' route in nucleophilic vinylic substitution, several pairs of vinyl mesylates and triflates were prepared. Whereas reactions of ArC(LG)=C(CO(2)Et)(2) (LG = OTf, OMs) with piperidine and morpholine in MeCN or THF gave the normal substitution product with k(OTf)/k(OMs) ratios of 4.3-10.6, the reaction of the mesylates, Ar = p-O2NC6H4, and of PhC(OMs)=C(Me)CN with MeS(-) gave a ketone via an S-O bond cleavage. A related mesityl-substituted tosylate also reacted with p-MeC(6)H(4)X(-) (X = O, S) via an S-O bond cleavage. Hence, k(OTf)/k(OMs) ratios cannot be used as a general mechanistic tool. Several reactivity ratios in vinylic substitution are briefly discussed.

  DOI：

  10.1021/jo961108t