Methyl 3-(4-methylphenyl)-2,3-dioxopropanoate | 229633-45-8

• 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: Methyl 3-(4-methylphenyl)-2,3-dioxopropanoate
• CAS: 229633-45-8
• 化学式: C₁₁H₁₀O₄
• 分子量: 206.198
• InChiKey: DGYLPUCZOQINEI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-氧代-3-(4-甲苯基)丙酸甲酯 在 2,2,6,6-四甲基哌啶氧化物 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙腈 为溶剂， 反应 12.08h， 生成 3-(4-tolyl)-2-hydroxy-3-oxopropionic acid methyl ester 、 Methyl 3-(4-methylphenyl)-2,3-dioxopropanoate
  参考文献：
  名称：

  DDQ-mediated oxidation of sp3 C–H bond for the direct synthesis of vicinal tricarbonyl compounds

  摘要：

  A facile and direct synthetic method was developed for the construction of vicinal tricarbonyl compounds (VTCs) in moderate to excellent yields (46-92%), by treating the readily available 1,3-dicarbonyl compounds with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The reaction pathway involves the DDQ-mediated oxidative activation of sp(3) C-H bond and subsequent coupling to TEMPO to form the key intermediate TEMPO-substrate adduct, which can be further converted to VTC products promoted by DDQ (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.04.021

文献信息

• Rhodium-catalyzed aerobic conversion of 2-diazo-1,3-dicarbonyls to vicinal tricarbonyl compounds and their in-situ stability toward oxidative degradation
  作者：Yi-Ting Tsai、Jia-Liang Zhu

  DOI：10.1016/j.molstruc.2022.134521

  日期：2023.2

  Wolff rearrangement via weak interaction with the substrate carbonyl group (ROC=O or RC=O). The reactions of α-diazo-β-ketoesters and 2-diazo-1,3-diketones give the desirable α,β-diketoesters and vic-triketones in 27-78% isolated yields, along with carboxylic acids and/or 2-oxoacids generated by in-situ oxidative C-C single bond cleavage of the former products. Moreover, the bond cleavage process is completely

  几种类型的 2-重氮-1,3-二羰基化合物 ( 3 )，包括α-重氮-β-酮酯、2-重氮-1,3-二酮和重氮丙二酸酯，被转化为相应的邻位三羰基化合物 (VTC) ( 4 ) 暴露于 Rh 2 (OAc) 4催化剂和氧气。提议通过铑类胡萝卜中间体的有氧氧化发生转化，通过与底物羰基（ROC=O 或 RC=O）的弱相互作用抑制Wolff 重排促进。α-重氮-β-酮酯和 2-重氮-1,3-二酮反应生成理想的α,β-二酮酯和vic-三酮以 27-78% 的分离产率，以及前者产物的原位氧化 CC 单键裂解产生的羧酸和/或 2-含氧酸。此外，当使用重氮丙二酸盐进行反应时，键断裂过程被完全抑制，从而导致良好至极好的草酮酸盐形成（高达 92% 的产率）。
• US6288061B1
  申请人：——

  公开号：US6288061B1

  公开（公告）日：2001-09-11
• DDQ-mediated oxidation of sp3 C–H bond for the direct synthesis of vicinal tricarbonyl compounds
  作者：Zheng-Lin Wang、Xing-Lan An、Li-Shi Ge、Jing-Hai Jin、Xiaoyan Luo、Wei-Ping Deng

  DOI：10.1016/j.tet.2014.04.021

  日期：2014.6

  A facile and direct synthetic method was developed for the construction of vicinal tricarbonyl compounds (VTCs) in moderate to excellent yields (46-92%), by treating the readily available 1,3-dicarbonyl compounds with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The reaction pathway involves the DDQ-mediated oxidative activation of sp(3) C-H bond and subsequent coupling to TEMPO to form the key intermediate TEMPO-substrate adduct, which can be further converted to VTC products promoted by DDQ (C) 2014 Elsevier Ltd. All rights reserved.