4-methyl-7-methoxy-2-oxo-2H-1-benzopyran-3-carboxylic acid | 91570-50-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: 4-methyl-7-methoxy-2-oxo-2H-1-benzopyran-3-carboxylic acid
• 英文别名: 7-methoxy-4-methyl-2-oxo-2H-chromene-3-carboxylic acid；7-Methoxy-4-methyl-8-carboxy-cumarin；7-Methoxy-4-methyl-2-oxo-2H-chromen-3-carbonsaeure；7-methoxy-4-methyl-2-oxochromene-3-carboxylic acid
• CAS: 91570-50-2
• 化学式: C₁₂H₁₀O₅
• 分子量: 234.208
• InChiKey: POKMINGWSPXHFR-UHFFFAOYSA-N

物化性质

• 熔点：
  184-185 °C
• 沸点：
  424.2±45.0 °C(Predicted)
• 密度：
  1.383±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-methyl-7-methoxy-2-oxo-2H-1-benzopyran-3-carboxylic acid 在 磺酰氯 、 过氧化苯甲酰 作用下， 生成 4-chloromethyl-7-methoxy-2-oxo-2H-chromene-3-carbonyl chloride
  参考文献：
  名称：

  Baker et al., Journal of the Chemical Society, 1950, p. 170,172

  摘要：

  DOI：
• 作为产物：
  描述：

  2,2-dimethyl-5-<(2,4-dimethoxyphenyl)-α-methylmethylene>-1,3-dioxane-4,6-dione 在 硫酸 作用下， 反应 1.5h， 以73%的产率得到4-methyl-7-methoxy-2-oxo-2H-1-benzopyran-3-carboxylic acid
  参考文献：
  名称：

  An Efficient Preparation of Coumarins

  摘要：

  o-methoxyaryl-aldehydes (or -ketones) react in solid-phase with Meldrum's acid under mild conditions, to give benzylidene derivatives which are cyclized in high yield, with cold sulfuric acid to substituted 3-carboxycoumarins. Thermal decarboxylation, speed up by copper powder, provided an easy access to numerous coumarins.

  DOI：

  10.1080/00397919308013801

文献信息

• A green chemical synthesis of coumarin-3-carboxylic and cinnamic acids using crop-derived products and waste waters as solvents
  作者：Serena Fiorito、Vito Alessandro Taddeo、Salvatore Genovese、Francesco Epifano

  DOI：10.1016/j.tetlet.2016.09.023

  日期：2016.10

  solvents is described. Coumarin-3-carboxylic and cinnamic acids have been synthesized in excellent yields by ultrasound irradiation from differently substituted 2-hydroxybenzaldehydes, 2-hydroxyacetophenones, and benzaldehydes, and Meldrum’s acid as starting substrates. The findings described herein enforce the concept of the usefulness of products and byproducts derived from agriculture and food industry

  近年来，诸如可食用的水果和蔬菜中的果汁以及来自农业和工业加工的废水之类的作物衍生产品已被有效利用，以有效促进多种“经典”和创新的合成有机反应。这种绿色化学方法可以避免使用有毒，污染和有害的材料，同时可以提高农作物产品和工业副产品的商业价值。香豆素-3-羧酸和肉桂酸代表具有有趣和有希望的药理活性的天然和半合成化合物。在这封信中，一种新的，经过改进的方法，用于进行Knoevenagel缩合反应，使用可食用水果和蔬菜（柠檬，葡萄柚，胡萝卜，石榴，猕猴桃，醋，番茄）的汁液生产标题化合物，描述了利口酒（柠檬酒）和废水（酪乳和橄榄加工的残渣）作为溶剂。香豆素-3-羧酸和肉桂酸是通过超声辐照由不同取代的2-羟基苯甲醛，2-羟基苯乙酮和苯甲醛以及Meldrum酸作为起始底物以优异的产率合成的。本文描述的发现加强了源自农业和食品工业的产品和副产品对完成绿色化学过程的有用性的概念。以Meldrum酸为起始底物
• A convenient synthesis of coumarin-3-carboxylic acids via Knoevenagel condensation of Meldrum's acid with ortho-hydroxyaryl aldehydes or ketones
  作者：Aimin Song、Xiaobing Wang、Kit S Lam

  DOI：10.1016/s0040-4039(03)00108-4

  日期：2003.2

  Coumarin-3-carboxylic acids were obtained in high yields with excellent purity from ortho-hydroxybenzaldehydes and Meldrum's acid after a 2 h reflux in ethanol. The less reactive ketones were first reacted with alcoholic ammonia to form ketimines, which were then condensed with Meldrum's acid to generate 4-alkylcoumarin-3-carboxylic acids in moderate yields.

  在乙醇中回流2小时后，从邻羟基苯甲醛和Meldrum酸以高收率获得了香豆素-3-羧酸。反应性较低的酮首先与乙醇氨反应形成酮亚胺，然后与Meldrum's酸缩合以生成中等收率的4-烷基香豆素-3-羧酸。
• Migratory Decarboxylative Coupling of Coumarins: Synthetic and Mechanistic Aspects
  作者：Ranjan Jana、James J. Partridge、Jon A. Tunge

  DOI：10.1002/anie.201100765

  日期：2011.5.23

  On the move: Decarboxylative coupling of allyl 4‐methyl‐3‐carboxycoumarins provides the products of γ‐allylation of the methyl group rather than the typical regiospecific α‐allylation. Mechanistic studies show that intramolecular proton transfer from the 4‐methyl group to the 3‐carboxylate allows allylation of the remote methyl group. The resulting 4‐butenyl‐3‐carboxyl coumarin undergoes Pd0‐catalyzed

  进展：烯丙基 4-甲基-3-羧基香豆素的脱羧偶联提供了甲基 γ-烯丙基化的产物，而不是典型的区域特异性 α-烯丙基化。机理研究表明，分子内质子从 4-甲基转移到 3-羧酸酯可以实现远程甲基的烯丙基化。所得的 4-丁烯基-3-羧基香豆素经过 Pd 0催化脱羧，得到观察到的产物（参见方案）。
• Synthesis and pharmacological evaluation of carboxycoumarins as a new antitumor treatment targeting lactate transport in cancer cells
  作者：Nihed Draoui、Olivier Schicke、Antony Fernandes、Xavier Drozak、Fady Nahra、Amélie Dumont、Jonathan Douxfils、Emmanuel Hermans、Jean-Michel Dogné、Romu Corbau、Arnaud Marchand、Patrick Chaltin、Pierre Sonveaux、Olivier Feron、Olivier Riant

  DOI：10.1016/j.bmc.2013.09.010

  日期：2013.11

  Under hypoxia, cancer cells consume glucose and release lactate at a high rate. Lactate was recently documented to be recaptured by oxygenated cancer cells to fuel the TCA cycle and thereby to support tumor growth. Monocarboxylate transporters (MCT) are the main lactate carriers and therefore represent potential therapeutic targets to limit cancer progression. In this study, we have developed and implemented a stepwise in vitro screening procedure on human cancer cells to identify new potent MCT inhibitors. Various 7-substituted carboxycoumarins and quinolinone derivatives were synthesized and pharmacologically evaluated. Most active compounds were obtained using a palladium-catalyzed Buchwald-Hartwig type coupling reaction, which proved to be a quick and efficient method to obtain aminocarboxycoumarin derivatives. Inhibition of lactate flux revealed that the most active compound 19 (IC50 11 nM) was three log orders more active than the CHC reference compound. Comparison with warfarin, a conventional anticoagulant coumarin, further showed that compound 19 did not influence the prothrombin time which, together with a good in vitro ADME profile, supports the potential of this new family of compounds to act as anticancer drugs through inhibition of lactate flux. (C) 2013 Elsevier Ltd. All rights reserved.
• Baker; Collis, Journal of the Chemical Society, 1949, p. Spl. 12, 14
  作者：Baker、Collis

  DOI：——

  日期：——