3-(4-溴苯基)-3H-2-苯并呋喃-1-酮 | 25933-36-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 中文名称: 3-(4-溴苯基)-3H-2-苯并呋喃-1-酮
• 英文名称: 3-(4'-bromophenyl)phthalide
• 英文别名: 3-(4-bromophenyl)isobenzofuran-1(3H)-one；1(3H)-Isobenzofuranone, 3-(4-bromophenyl)-；3-(4-bromophenyl)-3H-2-benzofuran-1-one
• CAS: 25933-36-2
• 化学式: C₁₄H₉BrO₂
• 分子量: 289.128
• InChiKey: NOBDTJIRKOOPJW-UHFFFAOYSA-N

物化性质

• 熔点：
  139-140 °C(Solv: benzene (71-43-2); methylcyclohexane (108-87-2))
• 沸点：
  411.2±45.0 °C(Predicted)
• 密度：
  1.550±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  3-(4-溴苯基)-3H-2-苯并呋喃-1-酮 在 锂硼氢 、 硫酸 、 氢溴酸 、 碘 作用下， 生成 2(4-Brombenzyl)benzylbromid
  参考文献：
  名称：

  Fouche; Blondel; Horclois, Bulletin de la Societe Chimique de France, 1972, vol. 8, p. 3113 - 3130

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4’-二溴二苯甲酮 在 sodium tetrahydroborate 、 copper(l) cyanide 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 37.5h， 生成 3-(4-溴苯基)-3H-2-苯并呋喃-1-酮
  参考文献：
  名称：

  Reductive Heterocyclization of 2-Cyanobenzophenones by the Action of NaBH4. New Efficient Synthesis of 3-Arylphthalides

  摘要：

  The reduction of 2-cyclopropylcarbonyl-, 2-(thiophen-2-yl)carbonyl-, and 2-arylcarbonylbenzonitriles with sodium tetrahydridoborate afforded 3-cyclopropyl-, 3-(2-thiophen-2-yl)-, and 3-arylphthalides, respectively, in high yields. Under analogous conditions, 3-cyanobenzophenones were converted to the corresponding 3-cyanobenzhydrols.

  DOI：

  10.1134/s1070428018040085

文献信息

• Rhenium-Catalyzed Phthalide Synthesis from Benzamides and Aldehydes via C–H Bond Activation
  作者：Bing Jia、Yunhui Yang、Xiqing Jin、Guoliang Mao、Congyang Wang

  DOI：10.1021/acs.orglett.9b02142

  日期：2019.8.16

  The [4 + 1] annulation of benzamides and aldehydes for phthalide synthesis was achieved via rhenium-catalyzed C–H activation, which demonstrates an unprecedented reaction pattern distinct from those of other transition-metal catalyses. The reaction also features readily available starting materials, a wide scope for both electro-rich and electro-deficient substrates, and the elimination of homoannulation

  苯甲酰胺和醛用于邻苯二甲酸酯合成的[4 +1]环化是通过rh催化的C–H活化而实现的，这证明了其与其他过渡金属催化剂截然不同的反应模式。该反应还具有容易获得的起始原料，对于富电和缺电的底物都有广泛的应用范围，并且消除了均环化副产物。
• Synthesis of Chiral 3-Substituted Phthalides via Rhodium(I)-catalyzed Crossed Alkyne Cyclotrimerisation
  作者：Bernhard Witulski、Axel Zimmermann

  DOI：10.1055/s-2002-34883

  日期：——

  3-Substituted phthalides were synthesized for the first time by crossed alkyne cyclotrimerisations with Wilkinson’s catalyst. Esterification of propiolic acids with chiral propargylic alcohols by either the DCC/DMAP or the Mitsunobu method allows the synthesis of either enantiomeric form of diyne esters, that are used in crossed alkyne cyclotrimerisations with acetylene to provide 3-substituted phthalides in both enantiomeric forms.

  首次通过与威尔金森催化剂的交叉炔烃环三聚反应合成了3-取代的邻苯二甲酸内酯。用DCC/DMAP或三苯基膦的方法对丙炔酸与手性炔丙醇进行酯化，可以合成任一对映体形式的二烯酯，这些二烯酯被用于与乙炔的交叉炔烃环三聚反应，从而得到两种对映体形式的3-取代邻苯二甲酸内酯。
• Synthesis of biarylketones and phthalides from organoboronic acids and aldehydes catalyzed by cobalt complexes
  作者：Jaganathan Karthikeyan、Kanniyappan Parthasarathy、Chien-Hong Cheng

  DOI：10.1039/c1cc13771a

  日期：——

  A cobalt-catalyzed addition of aryl- and alkenylboronic acids to aldehydes and phthalaldehyde to give the corresponding biarylketones and 3-aryl phthalides in good to excellent yields in one pot is described.

  描述了一种钴催化的芳基和烯基硼酸与醛和邻苯二甲醛的加成反应，可以在一个反应锅中以良好到优异的产率生成相应的双芳基酮和3-芳基邻苯二甲酰亚胺。
• Catalytic asymmetric synthesis of 3-aryl phthalides enabled by arylation–lactonization of 2-formylbenzoates
  作者：Andressa M. M. Carlos、Rafael Stieler、Diogo S. Lüdtke

  DOI：10.1039/c8ob02872a

  日期：——

  The catalytic asymmetric synthesis of 3-aryl phthalides is reported through a sequential asymmetric arylation–lactonization reaction. The reaction is enabled by a boron–zinc exchange to generate reactive arylating agents, which react with 2-formylbenzoates in the presence of a chiral amino naphthol ligand. The enantiodetermining step is the arylation of the aldehyde, which then undergoes a lactonization

  据报道，通过顺序的不对称芳基化-内酯化反应可以催化3-芳基邻苯二甲酸酯的不对称合成。硼锌交换使该反应产生反应性芳基化剂，在手性氨基萘酚配体存在下与2-甲酰基苯甲酸酯反应。对映体确定步骤是醛的芳基化，然后进行内酯化反应，以良好的收率和对映选择性产生相应的邻苯二甲酸酯。
• Visible-Light-Mediated Intramolecular Lactonization of Benzylic C(sp3)–H Bonds Promoted by DDQ and tert-Butyl Nitrite
  作者：Chunmei Li、Meichao Li、Zhenlu Shen、Miaomiao Hu、Jiangyu Yang、Mengyu Niu、Meng Xu

  DOI：10.1055/a-2185-4286

  日期：——

  A functionalization of benzylic C(sp3)–H bonds was established through a mild metal-free intramolecular lactonization protocol in the presence of DDQ/tert-butyl nitrite as photocatalysts, allowing practical and low-cost access to a series of phthalide products in moderate to excellent yields. Compared with many existing methodologies, this visible-light-driven process exhibits an excellent substrate scope and fascinating features, including the formation of water as the sole byproduct, an abundant and green energy source, commercially available catalysts, and room-temperature reaction. Finally, detailed mechanistic investigations clearly revealed the role of the photocatalysts and molecular oxygen.

  摘要 在以 DDQ/亚硝酸叔丁酯为光催化剂的条件下，通过温和的无金属分子内内酯化协议建立了苄基 C(sp3)-H键的官能化，从而以中等至极好的产率获得了一系列邻苯二甲酸酯产品，而且成本低廉，非常实用。与许多现有方法相比，这种可见光驱动的工艺具有极佳的底物范围和引人入胜的特点，包括以水的形成为唯一副产物、丰富的绿色能源、市场上可买到的催化剂以及室温反应。最后，详细的机理研究清楚地揭示了光催化剂和分子氧的作用。