3-diazo-2,3-dihydro-2-benzofuranone | 34073-50-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 3-diazo-2,3-dihydro-2-benzofuranone
• 英文别名: 3-diazo-3H-benzofuran-2-one；3-diazobenzofuran-2-one；3-diazo-3H-benzofuran-2-one；3-Diazo-2-oxo-2,3-dihydrobenzofuran；3-Diazo-2,3-dihydrobenzofuranon；3-Diazonio-1-benzofuran-2-olate
• CAS: 34073-50-2
• 化学式: C₈H₄N₂O₂
• 分子量: 160.132
• InChiKey: DAOHCEFLHDAZRO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  64.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-diazo-2,3-dihydro-2-benzofuranone 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以75%的产率得到chloro-3 dihydro-2,3 benzofurannone-2
  参考文献：
  名称：

  Demerseman, Pierre; Risse, Simone; Royer, Rene, Journal of Heterocyclic Chemistry, 1981, vol. 18, p. 695 - 696

  摘要：

  DOI：
• 作为产物：
  描述：

  (2-hydroxyphenyl)oxoacetic acid 在 乙酸酐 、 对甲苯磺酰肼 作用下， 生成 3-diazo-2,3-dihydro-2-benzofuranone
  参考文献：
  名称：

  Kinetics and mechanism of hydrolysis of 3-diazobenzofuran-2-one and its hydrolysis product (3-hydroxybenzofuran-2-one)

  摘要：

  在浓盐酸和盐酸水溶液中测量的3-重氮基苯并呋喃-2-酮的酸催化水解速率，发现与Cox-Yates Xo过量酸度函数相关良好，给出kH+ = 1.66×10^-4 M^-1 s^-1，m = 0.86，kH+/kD+ = 2.04。这种同位素效应的正向方向（kH/kD>1）表明，水解是通过在其重氮基碳原子上速率决定的质子化反应发生的。以前发现，目前底物的下一个更高同系物，4-重氮基异色茉莉酮，也通过这种反应机制发生水解，但速率常数比目前底物大15倍；这种反应活性的差异可以用这些底物结构所贡献的各种共振形式来理解。目前水解反应的产物是3-羟基苯并呋喃-2-酮，它本身很快发生随后的酸催化水解，形成2-羟基苦杏酸。这种后续水解的酸度依赖性比重氮化合物前体浅得多，反应速率与[H+]和Xo相关良好。这部分是由于3-羟基苯并呋喃-2-酮的羟基上的非生产性质子化的干扰，阻碍了水解并产生了酸催化的饱和。羟基化合物的水解速率也在稀HClO4和NaOH溶液以及CH3CO2H、H2PO4-、(CH2OH)3CNH3+和NH4+缓冲液中测量，由此构建的速率曲线显示存在未催化和羟离子催化的反应。这种羟离子催化在[NaOH] [Formula: see text] 0.05 M处饱和，意味着发生了另一种非生产性底物电离。关键词：重氮化合物水解，内酯水解，Cox-Yates过量酸度，酸催化，醇质子化。

  DOI：

  10.1139/v01-191

文献信息

• Kinetics and mechanism of hydrolysis of 3-diazobenzofuran-2-one and its hydrolysis product (3-hydroxybenzofuran-2-one)
  作者：Y Chiang、A J Kresge、Q Meng

  DOI：10.1139/v01-191

  日期：2002.1.1

  Rates of acid-catalyzed hydrolysis of 3-diazobenzofuran-2-one, measured in concentrated aqueous perchloric acid and hydrochloric acid solutions, were found to correlate well with the Cox–Yates X_o excess acidity function, giving k_H+ = 1.66 × 10^–4 M^–1 s^–1, m^‡ = 0.86 and k_H+ /k_D+ = 2.04. The normal direction (k_H/k_D > 1) of this isotope effect indicates that hydrolysis occurs by rate-determining protonation of the substrate on its diazo-carbon atom. It was found previously that the next higher homolog of the present substrate, 4-diazoisochroman-3-one, also undergoes hydrolysis by this reaction mechanism but with a rate constant 15 times greater than that for the present substrate; this difference in reactivity can be understood in terms of the various resonance forms that contribute to the structures of these substrates. The product of the present hydrolysis reaction is 3-hydroxybenzofuran-2-one, which itself quickly undergoes subsequent acid-catalyzed hydrolysis to 2-hydroxymandelic acid. The acidity dependence of this subsequent hydrolysis is much shallower than that of the diazo compound precursor, and rates of reaction correlate as well with [H⁺] as with X_o. This is due in part to incursion of a nonproductive protonation on the hydroxy group of 3-hydroxy benzo furan-2-one that impedes hydrolysis and produces saturation of acid catalysis. Rates of hydrolysis of the hydroxy compound were also measured in dilute HClO₄ and NaOH solutions as well as in CH₃CO₂H, H₂PO₄^–, (CH₂OH)₃CNH₃⁺, and NH₄⁺ buffers, and the rate profile constructed from these data showed the presence of uncatalyzed and hydroxide ion-catalyzed reactions. This hydroxide-ion catalysis became saturated at [NaOH] [Formula: see text] 0.05 M, implying occurrence of yet another nonproductive substrate ionization. Key words: diazo compound hydrolysis, lactone hydrolysis, Cox–Yates excess acidity, acid catalysis, alcohol protonation.

  在浓盐酸和盐酸水溶液中测量的3-重氮基苯并呋喃-2-酮的酸催化水解速率，发现与Cox-Yates Xo过量酸度函数相关良好，给出kH+ = 1.66×10^-4 M^-1 s^-1，m = 0.86，kH+/kD+ = 2.04。这种同位素效应的正向方向（kH/kD>1）表明，水解是通过在其重氮基碳原子上速率决定的质子化反应发生的。以前发现，目前底物的下一个更高同系物，4-重氮基异色茉莉酮，也通过这种反应机制发生水解，但速率常数比目前底物大15倍；这种反应活性的差异可以用这些底物结构所贡献的各种共振形式来理解。目前水解反应的产物是3-羟基苯并呋喃-2-酮，它本身很快发生随后的酸催化水解，形成2-羟基苦杏酸。这种后续水解的酸度依赖性比重氮化合物前体浅得多，反应速率与[H+]和Xo相关良好。这部分是由于3-羟基苯并呋喃-2-酮的羟基上的非生产性质子化的干扰，阻碍了水解并产生了酸催化的饱和。羟基化合物的水解速率也在稀HClO4和NaOH溶液以及CH3CO2H、H2PO4-、(CH2OH)3CNH3+和NH4+缓冲液中测量，由此构建的速率曲线显示存在未催化和羟离子催化的反应。这种羟离子催化在[NaOH] [Formula: see text] 0.05 M处饱和，意味着发生了另一种非生产性底物电离。关键词：重氮化合物水解，内酯水解，Cox-Yates过量酸度，酸催化，醇质子化。
• DEMERSEMAN, P.;RISSE, S.;ROYER, R., J. HETEROCYCL. CHEM., 1981, 18, N 4, 695-696
  作者：DEMERSEMAN, P.、RISSE, S.、ROYER, R.

  DOI：——

  日期：——
• Photoreactions of 3-Diazo-3<i>H</i>-benzofuran-2-one; Dimerization and Hydrolysis of Its Primary Photoproduct, A Quinonoid Cumulenone:  A Study by Time-Resolved Optical and Infrared Spectroscopy
  作者：Yvonne Chiang、Martin Gaplovsky、A. Jerry Kresge、King Hung Leung、Christian Ley、Marek Mac、Gabriele Persy、David L. Phillips、Vladimir V. Popik、Christoph Rödig、Jakob Wirz、Yu Zhu

  DOI：10.1021/ja0365476

  日期：2003.10.1

  nanosecond flash photolysis with optical (lambda(max) approximately 460 nm) as well as Raman (1526 cm(-1)) and IR detection (2050 cm(-)(1)). Remarkably, the reactivity of 3 is that expected from its valence isomer, the cyclic carbene 3H-benzofuran-2-one-3-ylidene, 2. In aqueous solution, acid-catalyzed addition of water forms the lactone 3-hydroxy-3H-benzofuran-2-one (5). The reaction is initiated by protonation

  溶液中 3-diazo-3H-benzofuran-2-one (1) 的光诱导脱氮伴随着简单的 (CO)-O 键裂解，产生 6-(oxoehenylidene)-2,4-cyclohexadien-1-one (3 )，其上升时间为 28 ps。未形成预期的 Wolff 重排产物 7-oxabicyclo[4.2.0]octa-1,3,5-trien-8-ylidenemethanone (4)。醌类cumulenone 3 的有效光诱导形成为确定溶液中的cumulenone 的反应性开辟了道路。3 的反应动力学由纳秒闪光光解与光学 (λ(max) 约 460 nm) 以及拉曼 (1526 cm(-1)) 和红外检测 (2050 cm(-)(1)) 监测。值得注意的是，3 的反应性是其价异构体，环状卡宾 3H-苯并呋喃-2-one-3-ylidene，2 预期的反应性。在水溶液中，水的酸催化加成形成内酯
• Demerseman, Pierre; Risse, Simone; Royer, Rene, Journal of Heterocyclic Chemistry, 1981, vol. 18, p. 695 - 696
  作者：Demerseman, Pierre、Risse, Simone、Royer, Rene

  DOI：——

  日期：——