methyl 4-diazo-3-methyl-5-oxohex-2-enoate | 1263416-75-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-diazo-3-methyl-5-oxohex-2-enoate
• 英文别名: methyl (E)-4-diazo-3-methyl-5-oxohex-2-enoate
• CAS: 1263416-75-6
• 化学式: C₈H₁₀N₂O₃
• 分子量: 182.179
• InChiKey: XXIVGXFTZJYIBP-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  13
• 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：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4-diazo-3-methyl-5-oxohex-2-enoate 以 苯 为溶剂， 以85%的产率得到5-acetyl-4-methyl-1(2)H-pyrazole-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: experimental and computational study

  摘要：

  反式结构的非氟乙烯基重氮化合物，无论 3-R1 取代基（R1 = H、Me、TBSO）的性质如何，即使在环境条件下也很容易环化生成吡唑，而顺式立体异构体只有在温度升高时才会发生类似的闭环，或者分解生成乙烯基氧羰基反应产物。顺式或反式构型的 3-CF3 取代类似物根本不会产生吡唑，而是在加热时只产生乙烯基羰基衍生产物。对理论能垒的 DFT 计算充分解释了立体异构体乙烯基二氮羰基化合物的不同实验反应性，并提出了通过相应吡唑实现相互转化的新模型。

  DOI：

  10.1039/c3ob42102c
• 作为产物：
  描述：

  甲氧羰基亚甲基三苯基正膦 、 乙酰丙酮 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60%的产率得到methyl 4-diazo-3-methyl-5-oxohex-2-enoate
  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

• Diazo Strategy for the Synthesis of Pyridazines: Pivotal Impact of the Configuration of the Diazo Precursor on the Process
  作者：Valerij A. Nikolaev、David Cantillo、C. Oliver Kappe、Jury J. Medvedev、G. K. Surya. Prakash、Murat B. Supurgibekov

  DOI：10.1002/chem.201503448

  日期：2016.1.4

  vinyldiazocarbonyl compounds having cis stereochemistry of the functional groups on the vinyl bond readily produce pyridazines by a diaza‐Wittig process, whereas their counterparts with trans configuration remain intact under similar reaction conditions. Upon UV irradiation trans‐phosphazenes furnish pyridazines through a tandem trans‐to‐cis isomerization followed by intramolecular cyclization. At elevated temperatures

  具有乙烯基键上官能团的顺式立体化学的乙烯基重氮羰基化合物的磷酸根可通过diaza -Wittig工艺轻松生成哒嗪，而在相似的反应条件下，具有反式构型的对应物则保持完整。当UV照射反通过串联-phosphazenes配料哒嗪的反式-到-顺式异构化，接着分子内环化。在高温下反-（三苯基）磷腈分解生成最初的乙烯基重氮化合物，该化合物高产率生产吡唑。在M06-2X / 6-31G（d）理论水平上通过DFT计算对diaza-Wittig过程机理的第一个理论研究表明，对于顺式-磷腈，快速串联[2 + 2]环加成/环消除过程低能垒比反式异构体更可取。