3-methyl-3-phenyl-3H-benzofuran-2-one | 4355-42-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: 3-methyl-3-phenyl-3H-benzofuran-2-one
• 英文别名: 3-methyl-3-phenylbenzofuran-2(3H)-one；3-methyl-3-phenylbenzofuran-2-one；3-methyl-3-phenyl-3H-benzofuran-2-one；3-Methyl-3-phenyl-3H-benzofuran-2-on；2-Keto-3-methyl-3-phenyl-2,3-dihydrobenzofuran；8-Methyl-3-phenyl-2-benzofuranon；3-Methyl-3-phenyl-1-benzofuran-2-one
• CAS: 4355-42-4
• 化学式: C₁₅H₁₂O₂
• 分子量: 224.259
• InChiKey: JXULSJAOPCOAQY-UHFFFAOYSA-N

物化性质

• 沸点：
  181 °C(Press: 10 Torr)
• 密度：
  1.188±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 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-methyl-3-phenyl-3H-benzofuran-2-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 2-Phenyl-2-(o-hydroxyphenyl)-1-propanol
  参考文献：
  名称：

  Photochemical transformations of small ring heterocyclic compounds. 91. Photochemistry of the chroman and 3-chromanone ring systems. An example of tautomeric control of excited-state chemistry

  摘要：

  DOI：

  10.1021/jo00396a028
• 作为产物：
  描述：

  2,2-二苯基丙酸 在 碘苯二乙酸 、 silver(I) acetate 、 cesium acetate 、 sodium acetate 、 palladium diacetate 作用下， 以 氯苯 、 叔丁醇 为溶剂， 反应 12.0h， 以47%的产率得到3-methyl-3-phenyl-3H-benzofuran-2-one
  参考文献：
  名称：

  Direct Lactonization of 2-Arylacetic Acids through Pd(II)-Catalyzed C–H Activation/C–O Formation

  摘要：

  Palladium-catalyzed direct lactonization of 2-arylacetic acids through a reaction sequence that includes C-H activation/C-O formation is reported. This method provides a concise and efficient pathway to synthesize fully functionalized benzofuranone derivatives, which are highly relevant to bioactive natural and synthetic products.

  DOI：

  10.1021/ol303569b

文献信息

• Imidazole Derivatives as Accelerators for Ruthenium-Catalyzed Hydroesterification and Hydrocarbamoylation of Alkenes: Extensive Ligand Screening and Mechanistic Study
  作者：Hideyuki Konishi、Takashi Muto、Tsuyoshi Ueda、Yayoi Yamada、Miyuki Yamaguchi、Kei Manabe

  DOI：10.1002/cctc.201402986

  日期：2015.3

  Imidazole derivatives are effective ligands for promoting the [Ru3(CO)12]‐catalyzed hydroesterification of alkenes using formates. Extensive ligand screening was performed to identify 2‐hydroxymethylated imidazole as the optimal ligand. Neither carbon monoxide gas nor a directing group was required, and the reaction also showed a wide substrate generality. The Ru–imidazole catalyst system also promoted

  咪唑衍生物是使用甲酸酯促进[Ru 3（CO）12 ]催化的烯烃加氢酯化反应的有效配体。进行了广泛的配体筛选，以确定2-羟甲基化的咪唑为最佳配体。既不需要一氧化碳气体也不需要引导基团，并且该反应还显示出广泛的底物通用性。Ru-咪唑催化剂体系还促进了分子内的氨基甲酰化作用，以提供内酰胺。通过X射线晶体学分析明确地分析了Ru-咪唑配合物，它具有源自[[Ru 3（CO）12 ]和两个配体的三核结构。该配合物也已成功用于加氢酯化。通过使用D详细检查了该机制－和13 C标记的甲酸酯，表明加氢酯化反应是通过脱羰基－再羰基化途径进行的。
• Dimethyldioxirane Epoxidation of 3-Phenyl-Substituted Benzofurans: A Reversible Valence Isomerization between Benzofuran Epoxides and Quinone Methides
  作者：Waldemar Adam、Karl Peters、Markus Sauter

  DOI：10.1055/s-1994-25416

  日期：——

  Low-temperature oxidation of the phenyl-substituted benzofurans 1 by dimethyldioxirane afforded the rather labile benzofuran epoxides 2, which are in equilibrium with their equally labile quinone methides 3 through valence isomerization. This reversible valence isomerization was established on the basis of the chemical transformations displayed by the benzofuran epoxides 2 and quinone methides 3. These include tetraethylammonium bromide catalyzed rearrangement of epoxide 2a to benzofuran-2-one 4a, dimerization of quinone methide 3c to dibenzofurodioxane 4c, nucleophilic trapping by methanol in the form of the adducts 5, the 1,3-dipolar cycloaddition with tetracyanoethylene (TCNE) to afford 6, and the inverse Diels-Alder reaction to the [4+2] cycloadducts 7 with ethyl vinyl ether. Also styrene gave with epoxide 2a the benzodihydropyran 8a through cycloaddition to its quinone methide valence isomer 3a, while with acetic anhydride the diacetylated adduct 9a was obtained. The driving force for these latter transformations derives from strain relief and aromatization. The labile benzofuran epoxides function as effective alkylating agents, which add nucleophiles at subambient temperatures without acid and base activation.

  苯基取代的苯并呋喃 1 被二甲基二环氧乙烷低温氧化后，产生了相当易变的苯并呋喃环氧化物 2，通过价式异构化，这些环氧化物与同样易变的醌类甲酯 3 达到了平衡。根据苯并呋喃环氧化物 2 和醌类甲化物 3 的化学变化，可以确定这种可逆的化合价异构化作用。其中包括环氧化物 2a 在四乙基溴化铵催化下重排为苯并呋喃-2-酮 4a，醌类甲化物 3c 二聚为二苯并呋喃二恶烷 4c，甲醇亲核捕获形成加合物 5、与四氰基乙烯（TCNE）发生 1,3-二极环加成反应生成 6，与乙烯基乙醚发生反向 Diels-Alder 反应生成 [4+2] 环加成物 7。此外，苯乙烯与环氧化物 2a 发生环加成反应，生成苯并二氢吡喃 8a，而与醋酸酐发生环加成反应，则生成二乙酰化加合物 9a。后一种转化的驱动力来自应变释放和芳香化。 易变的苯并呋喃环氧化物可作为有效的烷基化剂，在亚环境温度下添加亲核物而无需酸碱活化。
• Palladium-catalyzed bisarylation of 3-alkylbenzofurans to 3-arylalkyl-2-arylbenzofurans on water: tandem C(sp³)–H and C(sp²)–H activation reactions of 3-alkylbenzofurans
  作者：Beom Shin Cho、Young Keun Chung

  DOI：10.1039/c5cc04052c

  日期：——

  A protocol involving facile sequential C(sp³)–H and C(sp²)–H activation reactions of 3-alkylbenzofurans catalyzed by Pd(OAc)₂ in the presence of pivalic acid, silver salt, and tricyclohexylphosphine ‘on water’ was developed.

  在水相中，使用Pd(OAc)₂、对三甲基乙酸、银盐和三环己基膦催化，发展了一种简便的序列C(sp³)–H和C(sp²)–H活化反应的协议，用于3-烷基苯并呋喃的反应。
• Remarkable Improvement Achieved by Imidazole Derivatives in Ruthenium-Catalyzed Hydroesterification of Alkenes Using Formates
  作者：Hideyuki Konishi、Tsuyoshi Ueda、Takashi Muto、Kei Manabe

  DOI：10.1021/ol301850y

  日期：2012.9.21

  Imidazole derivatives are revealed to be effective ligands in the Ru-catalyzed hydroesterification of alkenes using formates, affording one-carbon-elongated esters in high yields. Further, intramolecular hydroesterification was successfully performed to give lactones for the first time. Imidazole derivatives can contribute to promote the reaction as well as to suppress the undesired decarbonylation of formate. Toxic CO gas, a directing group, and large excess alkenes are not required.
• Direct Lactonization of 2-Arylacetic Acids through Pd(II)-Catalyzed C–H Activation/C–O Formation
  作者：Mingyu Yang、Xingyu Jiang、Wen-Juan Shi、Qi-Lei Zhu、Zhang-Jie Shi

  DOI：10.1021/ol303569b

  日期：2013.2.1

  Palladium-catalyzed direct lactonization of 2-arylacetic acids through a reaction sequence that includes C-H activation/C-O formation is reported. This method provides a concise and efficient pathway to synthesize fully functionalized benzofuranone derivatives, which are highly relevant to bioactive natural and synthetic products.