Methyl 2-<2-<2-(1-hydroxy-1-propyl)phenyl>ethynyl>benzoate | 166757-17-1

• 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: Methyl 2-<2-<2-(1-hydroxy-1-propyl)phenyl>ethynyl>benzoate
• 英文别名: Methyl 2-[2-[2-(1-hydroxypropyl)phenyl]ethynyl]benzoate
• CAS: 166757-17-1
• 化学式: C₁₉H₁₈O₃
• 分子量: 294.35
• InChiKey: YRDVWXNOKFCTGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 2-<2-<2-(1-hydroxy-1-propyl)phenyl>ethynyl>benzoate 在 硫酸 、 sodium hydride 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 11.0h， 生成 Methyl 2-[2-(2-propanoylphenyl)acetyl]benzoate
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047
• 作为产物：
  描述：

  2-[(三甲基硅基)乙炔基]苯甲醛 在 copper(l) iodide 、 bis(triphenylphosphine)palladium(II)-chloride 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 48.0h， 生成 Methyl 2-<2-<2-(1-hydroxy-1-propyl)phenyl>ethynyl>benzoate
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047