2,3-diethyl-1,4-diphenyl-1,4-butanedione | 34880-83-6

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 二苄基丁烷木脂素
• 英文名称: 2,3-diethyl-1,4-diphenyl-1,4-butanedione
• 英文别名: 2,3-Diethyl-1,4-diphenylbutane-1,4-dione
• CAS: 34880-83-6
• 化学式: C₂₀H₂₂O₂
• 分子量: 294.393
• InChiKey: VPTYWKURXRCQFU-UHFFFAOYSA-N

物化性质

• 沸点：
  443.1±28.0 °C(Predicted)
• 密度：
  1.050±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-diethyl-1,4-diphenyl-1,4-butanedione 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 40.0h， 以72%的产率得到3,4-Diethyl-2,5-diphenylfuran
  参考文献：
  名称：

  Intermediates in the Paal-Knorr Synthesis of Furans

  摘要：

  New experimental evidence for the mechanism of the Paal-Knorr reaction involving the acid-catalyzed cyclization of a 1,4-diketone to form a furan is reported. In aqueous or alcoholic solutions containing hydrochloric acid and in chloroform containing boron trifluoride-etherate d,l- and meso-3,4-diethyl-2,5-hexanediones (2r and 2m) cyclize at unequal rates; the stereochemical configuration of the unchanged done is preserved during the reaction. This disagrees with the commonly accepted mechanism involving the ring closure of the rapidly formed monoenol (11b) followed by loss of water. A pathway involving the rapid protonation of one of the carbonyls followed by the electrophilic attack on the protonated carbonyl by the enol being formed at the other carbonyl group (10c) is proposed to account for the difference in reaction rates between the diastereomers of 3,4-disubstituted 2,5-hexanediones (1-3). The following results also seem to support the intermediacy of 10c. The presence of two isopropyl groups in 3,4-diisopropyl-2,5-hexanedione (3) considerably reduces the rate of cyclization, The catalytic constants k(H)(+) for the cyclization of 2r and 2m are larger than the constants for enolization of methyl ketones. The diastereomers of 2,3-dimethyl-and 2,3-diethyl-1,4-diphenyl-1,4-butanediones (4 and 5), which could enolize only toward the center of the molecule, also react at different rates. The d,l and meso dideuterio analogs (d(2)-4r and d(2)-4m) exhibit a primary isotope effect during cyclization. The order of cyclization of 1,4-diphenyl-1,4-butanedione (6) and its analogs (7-9) reveals that the presence of electron-donating groups facilitate the reaction.

  DOI：

  10.1021/jo00107a006
• 作为产物：
  描述：

  1-苯基-2-丙烯基-1-酮 在 2,2-dichloroethanol,oxovanadium(2+) 作用下， 以 二氯甲烷 为溶剂， 反应 44.0h， 生成 2,3-diethyl-1,4-diphenyl-1,4-butanedione
  参考文献：
  名称：

  烯醇化物的选择性分子间氧化交叉偶联

  摘要：

  烯醇化物的选择性分子间氧化交叉偶联是碳负离子等价物之间的键形成反应，尽管其在直接合成不对称 1,4-二酮方面具有潜在用途，但它仍然是一个未解决的问题。主要困难来自不可避免的同质耦合。我们的策略取决于一种烯醇化物的选择性单电子氧化以提供亲电羰基α-自由基物种，然后用另一种烯醇化物捕获。本研究证明了硼和甲硅烷基烯醇化物之间选择性氧钒 (V) 诱导的交叉偶联。

  DOI：

  10.1021/jacs.5b05058

文献信息

• The reaction of carbanions with 2-substituted-2-nitropropanes
  作者：Glen A. Russell、Boguslaw Mudryk、Francisco Ros、Mikolaj Jawdosiuk

  DOI：10.1016/0040-4020(82)80123-3

  日期：1982.1

  The reaction of mono-enolate anions with O2NCMe2X where X = Cl, NO2, p-MePhSO2 yield coupling (RCOCH(R′)(CMe2NO2) and enolate dimerization products (RCOCH(R′)CH(R′)COR) by free radical chain mechanisms involving bimolecular substitution or electron transfer reactions between the enolate anion and the intermediate nitro alkane radical anion (XCMe2NO2−).

  单烯酸根阴离子与X = Cl，NO 2，p -MePhSO 2的O 2 NCMe 2 X反应产生偶联（RCOCH（R'）（CMe 2 NO 2）和烯醇二聚产物（RCOCH（R'）CH （R'）COR）通过涉及烯醇阴离子和中间体硝基烷烃自由基阴离子之间的双分子取代或电子转移反应的自由基链机构（XCMe 2 NO 2 - ）。
• Electron transfer processes. 31. Coupling of enolates of phenones with 2-chloro-2-nitropropane
  作者：Glen A. Russell、Boguslaw Mudryk、Mikolaj Jawdosiuk、Zbigniew Wrobel

  DOI：10.1021/jo00349a012

  日期：1982.5
• Alkylation and oxidative dimerization of enolate anions by radical chain processes
  作者：Glen A. Russell、Boguslaw Mudryk、Mikolaj Jawdosiuk

  DOI：10.1021/ja00405a066

  日期：1981.7
• Selective Intermolecular Oxidative Cross-Coupling of Enolates
  作者：Toru Amaya、Yusuke Maegawa、Takaya Masuda、Yuma Osafune、Toshikazu Hirao

  DOI：10.1021/jacs.5b05058

  日期：2015.8.19

  Selective intermolecular oxidative cross-coupling of enolates, which is a bond-forming reaction between carbanion equivalents, remains as an unsolved issue despite its potential utility for the direct synthesis of unsymmetrical 1,4-diones. The main difficulty derives from the unavoidable homo-coupling. Our strategy depends on the selective one-electron oxidation of one enolate to afford an electrophilic

  烯醇化物的选择性分子间氧化交叉偶联是碳负离子等价物之间的键形成反应，尽管其在直接合成不对称 1,4-二酮方面具有潜在用途，但它仍然是一个未解决的问题。主要困难来自不可避免的同质耦合。我们的策略取决于一种烯醇化物的选择性单电子氧化以提供亲电羰基α-自由基物种，然后用另一种烯醇化物捕获。本研究证明了硼和甲硅烷基烯醇化物之间选择性氧钒 (V) 诱导的交叉偶联。
• Intermediates in the Paal-Knorr Synthesis of Furans
  作者：Venkataraman Amarnath、Kalyani Amarnath

  DOI：10.1021/jo00107a006

  日期：1995.1

  New experimental evidence for the mechanism of the Paal-Knorr reaction involving the acid-catalyzed cyclization of a 1,4-diketone to form a furan is reported. In aqueous or alcoholic solutions containing hydrochloric acid and in chloroform containing boron trifluoride-etherate d,l- and meso-3,4-diethyl-2,5-hexanediones (2r and 2m) cyclize at unequal rates; the stereochemical configuration of the unchanged done is preserved during the reaction. This disagrees with the commonly accepted mechanism involving the ring closure of the rapidly formed monoenol (11b) followed by loss of water. A pathway involving the rapid protonation of one of the carbonyls followed by the electrophilic attack on the protonated carbonyl by the enol being formed at the other carbonyl group (10c) is proposed to account for the difference in reaction rates between the diastereomers of 3,4-disubstituted 2,5-hexanediones (1-3). The following results also seem to support the intermediacy of 10c. The presence of two isopropyl groups in 3,4-diisopropyl-2,5-hexanedione (3) considerably reduces the rate of cyclization, The catalytic constants k(H)(+) for the cyclization of 2r and 2m are larger than the constants for enolization of methyl ketones. The diastereomers of 2,3-dimethyl-and 2,3-diethyl-1,4-diphenyl-1,4-butanediones (4 and 5), which could enolize only toward the center of the molecule, also react at different rates. The d,l and meso dideuterio analogs (d(2)-4r and d(2)-4m) exhibit a primary isotope effect during cyclization. The order of cyclization of 1,4-diphenyl-1,4-butanedione (6) and its analogs (7-9) reveals that the presence of electron-donating groups facilitate the reaction.