α-Diazo-2-ethynylacetophenone | 142458-70-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: α-Diazo-2-ethynylacetophenone
• 英文别名: 2-ethynyl-α-diazoacetophenone；2-Diazonio-1-(2-ethynylphenyl)ethen-1-olate；2-diazo-1-(2-ethynylphenyl)ethanone
• CAS: 142458-70-6
• 化学式: C₁₀H₆N₂O
• 分子量: 170.17
• InChiKey: HKSKZOWLSTVADP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  19.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-Diazo-2-ethynylacetophenone 以 solid matrix 为溶剂， 生成 Cyclopropinden-6(6aH)-one
  参考文献：
  名称：

  Komnick, Peter; Sander, Wolfram, Liebigs Annalen, 1996, # 1, p. 7 - 9

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 2-(3-hydroxy-3-methylbut-1-yn-1-yl)benzoate 在 sodium hydride 作用下， 以 甲苯 为溶剂， 生成 α-Diazo-2-ethynylacetophenone
  参考文献：
  名称：

  Rhodium carbenoid mediated cyclizations of o-alkynyl-substituted .alpha.-diazoacetophenones

  摘要：

  o-Alkynyl-substituted alpha-diazoacetophenones undergo facile cyclization to indenone derivatives upon treatment with catalytic quantities of Rh(II) carboxylates. A variety of structural influences were encountered by varying the nature of the substituent group attached to the alkyne carbon atom. The cyclization reaction involves addition of a rhodium stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid. The vinyl carbenoid was found to undergo both CH and CC migration as well as delta-CH insertion into the alkyl backbone. Different catalysts were shown to result in significant variation in the product ratios for these reactions. Treatment of o-(5-(allyloxy)-1-pentynyl)-alpha-diazoacetophenone with rhodium(II) mandelate afforded 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran in high yield. The formation of this compound involves initial formation of a vinyl carbenoid which reacts with the neighboring oxygen atom to give an oxonium ylide which subsequently undergoes a 2,3-sigmatropic rearrangement. When 2-ethynyl-alpha-diazoacetophenone is used, only products derived from 6-endo closure are observed. Substituted o-alkynyl alpha-diazoacetophenones give products derived from 5-exo cyclization. The mode of ring closure is controlled by both steric and electronic factors.

  DOI：

  10.1021/jo00044a032

文献信息

• Novel Ag(I)-catalysis of an intramolecular 1,3-dipolar cycloaddition
  作者：Andrew S. Kende、Michel Journet

  DOI：10.1016/0040-4039(95)00470-w

  日期：1995.5

  Acetylenic α-diazoketones, bearing gem-dimethyl substituents in the α′ position, were found to undergo an intramolecular 1,3-dipolar cycloaddition reaction in the presence of silver(I) as catalyst. In that instance, bicyclic pyrazole derivatives were isolated in 47 to 55% yield, even in the conditions of the Arndt-Eistert reaction. The requirement for gem-dimethyl substitution in acyclic substrates is rationalized

  发现在银（I）作为催化剂的存在下，在α'位置带有宝石-二甲基取代基的乙炔α-二氮杂环酮发生分子内的1,3-偶极环加成反应。在这种情况下，即使在Arndt-Eistert反应条件下，也以47％至55％的收率分离出双环吡唑衍生物。根据过渡态对构象能的空间效应，合理化了无环底物中对宝石二甲基取代的要求。
• Rhodium carbenoid mediated cyclizations of o-alkynyl-substituted .alpha.-diazoacetophenones
  作者：Albert Padwa、Keith E. Krumpe、Jamal M. Kassir

  DOI：10.1021/jo00044a032

  日期：1992.8

  o-Alkynyl-substituted alpha-diazoacetophenones undergo facile cyclization to indenone derivatives upon treatment with catalytic quantities of Rh(II) carboxylates. A variety of structural influences were encountered by varying the nature of the substituent group attached to the alkyne carbon atom. The cyclization reaction involves addition of a rhodium stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid. The vinyl carbenoid was found to undergo both CH and CC migration as well as delta-CH insertion into the alkyl backbone. Different catalysts were shown to result in significant variation in the product ratios for these reactions. Treatment of o-(5-(allyloxy)-1-pentynyl)-alpha-diazoacetophenone with rhodium(II) mandelate afforded 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran in high yield. The formation of this compound involves initial formation of a vinyl carbenoid which reacts with the neighboring oxygen atom to give an oxonium ylide which subsequently undergoes a 2,3-sigmatropic rearrangement. When 2-ethynyl-alpha-diazoacetophenone is used, only products derived from 6-endo closure are observed. Substituted o-alkynyl alpha-diazoacetophenones give products derived from 5-exo cyclization. The mode of ring closure is controlled by both steric and electronic factors.
• Komnick, Peter; Sander, Wolfram, Liebigs Annalen, 1996, # 1, p. 7 - 9
  作者：Komnick, Peter、Sander, Wolfram

  DOI：——

  日期：——