2-[(4-Nitro-phenyl)-trifluoromethanesulfonyloxy-methylene]-malonic acid diethyl ester | 184776-78-1

• 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-[(4-Nitro-phenyl)-trifluoromethanesulfonyloxy-methylene]-malonic acid diethyl ester
• 英文别名: Diethyl 2-[(4-nitrophenyl)-(trifluoromethylsulfonyloxy)methylidene]propanedioate
• CAS: 184776-78-1
• 化学式: C₁₅H₁₄F₃NO₉S
• 分子量: 441.339
• InChiKey: JJUNNNWDEQASIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  29
• 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：
  150
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  4-甲基苯硫酚钠 、 2-[(4-Nitro-phenyl)-trifluoromethanesulfonyloxy-methylene]-malonic acid diethyl ester 以 乙醇 为溶剂， 反应 2.0h， 以77%的产率得到diethyl 2-(p-tolylthio)-2-(p-nitrophenyl)ethylene-1,1-dicarboxylate
  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 (p-nitrobenzoyl)malonate 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以24%的产率得到2-[(4-Nitro-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

文献信息

• Triflate/Mesylate Ratios and Competing C−O and S−O Bond Cleavages in Nucleophilic Vinylic Substitution
  作者：Ettie Z. Schottland、Zvi Rappoport

  DOI：10.1021/jo961108t

  日期：1996.1.1

  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.