Benzoylformic anhydride

• 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: Benzoylformic anhydride
• 英文别名: 2-oxo-2-phenylacetic anhydride；benzoic anhydride；(2-Oxo-2-phenylacetyl) 2-oxo-2-phenylacetate
• 化学式: C₁₆H₁₀O₅
• 分子量: 282.252
• InChiKey: ZROHOPZAPOYUOJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  77.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Benzoylformic anhydride 在 dipotassium peroxodisulfate 、 硫酸 、 silver nitrate 作用下， 以 水 、 1,2-二氯乙烷 为溶剂， 反应 15.0h， 以64%的产率得到联苯甲酰
  参考文献：
  名称：

  酸和酐的银催化脱羧偶联：1,2-二酮和芳基取代的乙烷的入口

  摘要：

  开发了银催化的羧酸和酸酐的氧化脱羧偶联反应，生成1,2-二酮和取代的乙烷。该反应可通过相应的α-酮酸，烷基酸和酸酐的脱羧作用来生成酰基或烷基，它们依次偶联以有效地构建新的C-C键。该反应代表采用自由基终止策略的羧酸脱羧替代方案。

  DOI：

  10.1002/adsc.201701567
• 作为产物：
  描述：

  1,2,3,4-四苯基-1,3-环戊二烯 在 18-冠醚-6 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以28%的产率得到cis-1,2,4,5-Tetraphenyl-2-pentene-1,5-dione
  参考文献：
  名称：

  Superoxide-Mediated Base-Catalyzed Autoxidation of Tetraphenylcyclopentadiene

  摘要：

  The superoxide (KO2/18-crown-6)-mediated oxidation of tetraphenylcyclopentadiene (1) in aprotic media generated a variety of products following aqueous workup, including 2-hydroxy-2,4,5-triphenylfuranone (3), 2,3,4,5-tetraphenylfuran (4), cis-dibenzoylstilbene (5), cis- and trans-1,2,4,5-tetraphenyl-2-pentene-1,5-dione (6 and 7), and the novel benzoylformic anhydride(8). Treatment of the acid fraction with diazomethane yielded methyl benzoate (9) as the major component. The mechanism of product formation involves a series of well-precedented, base-catalyzed autoxidative processes including deprotonation of 1 by O-2(.-), oxygenation, dehydration or cyclization of the resulting peroxy anion, and oxidative cleavage. Lactol 3, furan 4, and benzoic acid (the putative precursor to 9) are known oxidative cleavage products of tetracyclone (2), which was detected in trace amounts in the reaction mixture. Isomeric 2-ene-1,5-diones 6 and 7 each isomerize to give an equilibrium mixture of the two in a 8:5 ratio. Molecular-modeling studies confirm the greater stability of the cis-6 isomer over that of trans-7.

  DOI：

  10.1021/jo00119a032

文献信息

• Gold-Catalyzed Addition of Propargyl Acetates to Olefins via <i>O</i>-Acyl Migration/Cyclopropanation Sequence: Insight into the Diastereoselective Formation of the Alkene
  作者：Marion Barbazanges、Yves Gimbert、Louis Fensterbank

  DOI：10.1021/acs.joc.2c02623

  日期：2023.3.3

  well-known addition of propargyl acetates to olefins via an O-acyl migration/cyclopropanation sequence. Herein, we show that the stereochemical outcome of the olefin is strongly dependent on the gold catalyst and reaction parameters (concentration, temperature, and alkene partner equivalents); the E- and Z-isomers can be selectively formed by the judicious choice of reaction conditions.

  这篇文章公开了一项众所周知的通过O-酰基迁移/环丙烷化顺序将乙酸炔丙酯加成到烯烃上的研究。在此，我们表明烯烃的立体化学结果在很大程度上取决于金催化剂和反应参数（浓度、温度和烯烃伙伴当量）；E-和Z-异构体可以通过明智地选择反应条件而选择性地形成。
• US5091171A
  申请人：——

  公开号：US5091171A

  公开（公告）日：1992-02-25
• Silver-Catalyzed Decarboxylative Couplings of Acids and Anhydrides: An Entry to 1,2-Diketones and Aryl-Substituted Ethanes
  作者：Hua-Xu Zou、Yang Li、Yuan Yang、Jin-Heng Li、Jiannan Xiang

  DOI：10.1002/adsc.201701567

  日期：2018.4.3

  Silver‐catalyzed oxidative decarboxylative couplings of carboxylic acids and anhydrides to produce 1,2‐diketones and substituted ethanes were developed. This reaction allows the generation of acyl or alkyl radicals by decarboxylation of the corresponding α‐keto acids, alkyl acids and anhydrides, which are sequentially coupled to efficiently construct a new C−C bond. This reaction represents a carboxylic

  开发了银催化的羧酸和酸酐的氧化脱羧偶联反应，生成1,2-二酮和取代的乙烷。该反应可通过相应的α-酮酸，烷基酸和酸酐的脱羧作用来生成酰基或烷基，它们依次偶联以有效地构建新的C-C键。该反应代表采用自由基终止策略的羧酸脱羧替代方案。
• Superoxide-Mediated Base-Catalyzed Autoxidation of Tetraphenylcyclopentadiene
  作者：Aryeh A. Frimer、Gila Strul、Hugo E. Gottlieb

  DOI：10.1021/jo00119a032

  日期：1995.7

  The superoxide (KO2/18-crown-6)-mediated oxidation of tetraphenylcyclopentadiene (1) in aprotic media generated a variety of products following aqueous workup, including 2-hydroxy-2,4,5-triphenylfuranone (3), 2,3,4,5-tetraphenylfuran (4), cis-dibenzoylstilbene (5), cis- and trans-1,2,4,5-tetraphenyl-2-pentene-1,5-dione (6 and 7), and the novel benzoylformic anhydride(8). Treatment of the acid fraction with diazomethane yielded methyl benzoate (9) as the major component. The mechanism of product formation involves a series of well-precedented, base-catalyzed autoxidative processes including deprotonation of 1 by O-2(.-), oxygenation, dehydration or cyclization of the resulting peroxy anion, and oxidative cleavage. Lactol 3, furan 4, and benzoic acid (the putative precursor to 9) are known oxidative cleavage products of tetracyclone (2), which was detected in trace amounts in the reaction mixture. Isomeric 2-ene-1,5-diones 6 and 7 each isomerize to give an equilibrium mixture of the two in a 8:5 ratio. Molecular-modeling studies confirm the greater stability of the cis-6 isomer over that of trans-7.