1-(2-Formylbenzylidene)-1,3-dihydroisobenzofuran | 176660-77-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-(2-Formylbenzylidene)-1,3-dihydroisobenzofuran
• 英文别名: (Z)‑2‑(isobenzofuran‑1(3H)‑ylidenemethyl)benzaldehyde；(z)-2-(Isobenzofuran-1(3h)-ylidenemethyl)benzaldehyde；2-[(Z)-3H-2-benzofuran-1-ylidenemethyl]benzaldehyde
• CAS: 176660-77-8
• 化学式: C₁₆H₁₂O₂
• 分子量: 236.27
• InChiKey: SFCDGHBHGDRGGF-SXGWCWSVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(2-Formylbenzylidene)-1,3-dihydroisobenzofuran 在 ammonium chloride 、 氯化铵 作用下， 生成 3'-Oxospiro<3H-1,4-dihydro-2-benzopyran-3,1'(3'H)-isobenzofuran>
  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：

  2,2'-(ethyne-1,2-diyl)dibenzaldehyde 在 sodium tetrahydroborate 、 caesium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.33h， 生成 1-(2-Formylbenzylidene)-1,3-dihydroisobenzofuran
  参考文献：
  名称：

  Regio- and stereoselective intramolecular hydroalkoxylation of aromatic alkynols: an access to dihydroisobenzofurans under transition-metal-free conditions

  摘要：

  一种高效的无过渡金属合成二氢异苯并呋喃衍生物的方法已被开发，该方法通过介导铯碳酸盐对芳香族炔醇进行分子内氢烷氧化反应。反应以区位选择性进行，专一生成5-exo-dig产物，并且仅观察到新生成双键的Z-异构体。该新方法具有反应条件温和、操作便捷和选择性满意的特点。

  DOI：

  10.1007/s11696-020-01159-5

文献信息

• Intramolecular Addition to an Unactivated Carbon-Carbon Triple Bond via an Apparent 6-Endo Digonal Pathway
  作者：M Weingarten

  DOI：10.1016/00404-0399(50)0891f-

  日期：1995.7.3