(1Z,3E)-2-diazonio-1,5-dimethoxy-5-oxo-3-(trifluoromethyl)penta-1,3-dien-1-olate | 1431534-76-7

• 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: (1Z,3E)-2-diazonio-1,5-dimethoxy-5-oxo-3-(trifluoromethyl)penta-1,3-dien-1-olate
• CAS: 1431534-76-7
• 化学式: C₈H₇F₃N₂O₄
• 分子量: 252.15
• InChiKey: FFQJFNYEXFFBSG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1Z,3E)-2-diazonio-1,5-dimethoxy-5-oxo-3-(trifluoromethyl)penta-1,3-dien-1-olate 在 2,5-二甲基呋喃 、 辛酸铑 作用下， 以 neat liquid 为溶剂， 以64%的产率得到methyl 5-methoxy-3-(trifluoromethyl)-2-furoate
  参考文献：
  名称：

  内部三氟甲基对铑（II）催化的乙烯基重氮羰基化合物反应的影响

  摘要：

  在4-（烷氧基羰基）乙烯基重氮羰基化合物的结构中引入三氟甲基基团大大降低了在Rh（II）催化的反应过程中形成的类胡萝卜素中间体经历分子间过程的趋势。相反，它们倾向于经历分子内的[1,5]-和[1,3]-电环化反应以生成反应性环丙烯和呋喃，并且它们能够进一步转化。

  DOI：

  10.1021/jo302726m
• 作为产物：
  描述：

  dimethyl 3-(trifluoromethyl)pent-2-enedioate 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以18%的产率得到(1Z,3E)-2-diazonio-1,5-dimethoxy-5-oxo-3-(trifluoromethyl)penta-1,3-dien-1-olate
  参考文献：
  名称：

  Two-Stage Synthesis of 3-(Perfluoroalkyl)-Substituted Vinyldiazocarbonyl Compounds and Their Nonfluorinated Counterparts: A Comparative Study

  摘要：

  Two approaches for the synthesis of fluorinated (F) and nonfluorinated (H) 4-(alkoxycarbonyl)-substituted cis- and trans-vinyldiazocarbonyl compounds with substituents of variable stereoelectronic nature (H, Me, Ph, CF3, OTBS) at the C-3 atom of the vinyl double bond from the relevant 1,3-dicarbonyl compounds were compared: a pathway using the Wittig reaction followed by a diazo transfer reaction was most efficient for the synthesis of the H-vinyldiazocarbonyl compounds (total yields of up to 60%), while the yields of their F-analogues under similar conditions did not exceed 16-37%. An approach via diazo transfer followed by the Wittig reaction, in contrast, is more effective for the preparation of F-vinyldiazocarbonyl compounds (total yields 37-69%). The configuration of the resulting F-and H-vinyldiazocarbonyl compounds is evidently controlled by the steric bulk of the substituent at the C-3 atom of the vinyl double bond and, in addition, depends on the specific synthetic pathway.

  DOI：

  10.1055/s-0032-1318309

文献信息

• Influence of an Internal Trifluoromethyl Group on the Rhodium(II)-Catalyzed Reactions of Vinyldiazocarbonyl Compounds
  作者：Valerij A. Nikolaev、Murat B. Supurgibekov、Huw M. L. Davies、Joachim Sieler、Valerija M. Zakharova

  DOI：10.1021/jo302726m

  日期：2013.5.3

  Incorporation of a trifluoromethyl group into the structure of 4-(alkoxycarbonyl)vinyldiazocarbonyl compounds greatly decreases the tendency of the carbenoid intermediates formed during Rh(II)-catalyzed reactions to undergo intermolecular processes. Instead, they are prone to experience intramolecular [1,5]- and [1,3]-electrocyclizations to produce reactive cyclopropenes and furans, and these are capable

  在4-（烷氧基羰基）乙烯基重氮羰基化合物的结构中引入三氟甲基基团大大降低了在Rh（II）催化的反应过程中形成的类胡萝卜素中间体经历分子间过程的趋势。相反，它们倾向于经历分子内的[1,5]-和[1,3]-电环化反应以生成反应性环丙烯和呋喃，并且它们能够进一步转化。
• Two-Stage Synthesis of 3-(Perfluoroalkyl)-Substituted Vinyldiazocarbonyl Compounds and Their Nonfluorinated Counterparts: A Comparative Study
  作者：G. Prakash、Valerij Nikolaev、Murat Supurgibekov

  DOI：10.1055/s-0032-1318309

  日期：——

  Two approaches for the synthesis of fluorinated (F) and nonfluorinated (H) 4-(alkoxycarbonyl)-substituted cis- and trans-vinyldiazocarbonyl compounds with substituents of variable stereoelectronic nature (H, Me, Ph, CF3, OTBS) at the C-3 atom of the vinyl double bond from the relevant 1,3-dicarbonyl compounds were compared: a pathway using the Wittig reaction followed by a diazo transfer reaction was most efficient for the synthesis of the H-vinyldiazocarbonyl compounds (total yields of up to 60%), while the yields of their F-analogues under similar conditions did not exceed 16-37%. An approach via diazo transfer followed by the Wittig reaction, in contrast, is more effective for the preparation of F-vinyldiazocarbonyl compounds (total yields 37-69%). The configuration of the resulting F-and H-vinyldiazocarbonyl compounds is evidently controlled by the steric bulk of the substituent at the C-3 atom of the vinyl double bond and, in addition, depends on the specific synthetic pathway.