3-acetoacetylcoumarin | 13252-79-4

• 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: 3-acetoacetylcoumarin
• 英文别名: 3-(1,3-dioxobutan-1-yl)-2H-chromen-2-one；3-Acetoacetyl-2-chromenone；(1-(2-oxo-2H-chromen-3-yl)butane-1,3-dione)；Coumarin, 3-acetoacetyl-；1-(2-oxochromen-3-yl)butane-1,3-dione
• CAS: 13252-79-4
• 化学式: C₁₃H₁₀O₄
• 分子量: 230.22
• InChiKey: AZAIGYUDADTJHD-UHFFFAOYSA-N

物化性质

• 熔点：
  150-152 °C(Solv: methanol (67-56-1))
• 沸点：
  442.1±45.0 °C(Predicted)
• 密度：
  1.304±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-acetoacetylcoumarin 在 一水合肼 作用下， 以 异丙醇 为溶剂， 反应 7.0h， 以82%的产率得到2-methyl-4a,10b-dihydro-4H,5H-pyrano[3,2-c]chromene-4,5-dione
  参考文献：
  名称：

  Interaction of 3-acetoacetyl-2H-chromen-2-one with azanucleophilic reagents

  摘要：

  The reactions of 3-acetoacetylchromen-2-one with mono-and binucleophilic reagents, under the action of microwave irradiation have been studied. It was shown that depending on the nucleophilicity of the reactant new heterocyclic systems were formed involving the oxo group of the substituent in position 3 of the heterofragment, its opening, or recyclization.

  DOI：

  10.1007/s10593-011-0700-9
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 水 作用下， 生成 3-acetoacetylcoumarin
  参考文献：
  名称：

  Trenknerowna, Roczniki Chemii, 1936, vol. 16, p. 12,16

  摘要：

  DOI：
• 作为试剂：
  描述：

  哌啶 、 4-[(1-oxo-3,4-dihydro-2H-naphthalen-2-ylidene)methyl]benzoic acid 在 3-acetoacetylcoumarin 作用下， 以 乙醇 为溶剂， 反应 36.0h， 以50%的产率得到4-[(1-oxo -1,2,3,4-tetrahydronaphthalen-2-yl)(piperidin-1-yl)methyl]benzoic acid
  参考文献：
  名称：

  Synthesis of Hybrid Compounds on the Basis of 4-[(1-Oxo-3,4-dihydro-2H-naphthalen-2-ylidene)methyl]benzoic acid

  摘要：

  The reactions of 4-[(1-oxo-3,4-dihydro-2H-naphmalen-2-ylidene)methyl]benzoic acid with 3-(1,3-dioxobutane-1-yl)-2H-chromen-2-one in the presence of nitrogenous bases (piperidine, triethylamine or pyridine) were used to synthesize for the first time hybrid systems containing the pharmacophoric fragments of the reagents. The reaction scheme involves formation of a condensed dihydropyran structure and its subsequent aromatization into a benzodihydrochromenilium salt under the action of HCl. The process may be accompanied by the competing addition of an azanucleophile by the double bond of the chalcone.

  DOI：

  10.1134/s1070428019080244

文献信息

• A highly sensitive and selective off–on fluorescent chemosensor for hydrazine based on coumarin β-diketone
  作者：Wei-Na Wu、Hao Wu、Yuan Wang、Xian-Jie Mao、Xiao-Lei Zhao、Zhou-Qing Xu、Yun-Chang Fan、Zhi-Hong Xu

  DOI：10.1016/j.saa.2017.06.062

  日期：2018.1

  A coumarin-based sensor C1, namely 3-acetoacetylcoumarin was designed, synthesized and applied for hydrazine detection. Hydrazinolysis of the chemosensor gives a fluorescent coumarin-pyrazole product C1 − N2H4 [3-(3-methyl-1H-pyrazol-5-yl)coumarin], and thus resulting in a prominent fluorescence off-on response toward hydrazine under physiological conditions. The probe is highly selective toward hydrazine

  设计，合成了基于香豆素的传感器C1，即3-乙酰乙酰香豆素，并将其用于肼的检测。化学传感器的水合肼分解产生荧光香豆素-吡唑产物C1  -N 2 H 4 [3-（3-甲基-1H-吡唑-5-基）香豆素]，因此导致在以下条件下对肼的显着荧光关闭响应生理条件。该探针对肼对阳离子，阴离子和其他生物学/环境上丰富的分析物具有高度选择性。探针的检出限为3.2 ppb。感应机制由1支持1 H NMR，IR，MS和DFT计算。还证明了荧光探针在监测神经胶质瘤细胞系U251中细胞内肼的应用。
• Synthesis of xanthene and coumarin derivatives in water by using β-Cyclodextrin
  作者：Siddharth R. Kamat、Ananda H. Mane、Audumbar D. Patil、Trushant R. Lohar、Rajashri S. Salunkhe

  DOI：10.1007/s11164-020-04308-3

  日期：2021.3

  Simple and green procedure was developed for the synthesis of various xanthene and coumarin derivatives using beta-cyclodextrin (β-CD) as reusable catalyst at 70 °C in water. Condensation of salicylaldehyde (1 mmol) and dimedone (2 mmol) or 1,3 cyclohexadione (2 mmol) gave corresponding xanthene derivatives, while condensation of salicylaldehyde (1 mmol) with Meldrum’s acid (1 mmol) or 4-Hydroxy-6

  开发了一种简单而绿色的方法，用于在70℃的水中使用β-环糊精（β -CD）作为可重复使用的催化剂来合成各种various吨和香豆素衍生物。水杨醛（1 mmol）与二甲酮（2 mmol）或1,3环己二酮（2 mmol）缩合得到相应的x吨衍生物，而水杨醛（1 mmol）与Meldrum酸（1 mmol）或4-羟基-6-甲基缩合-2 H-吡喃-2-酮（1 mmol）以令人印象深刻的产率得到了香豆素衍生物。通过在70°C下通过1 H NMR分析β -CD-水杨醛的夹杂物来确定β -CD作为催化剂的参与度。 图形摘要
• 10-(4-Hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-3-methyl-1H,10H-pyrano[4,3-b] chromen-1-ones from a pseudo-multicomponent reaction and evaluation of their antioxidant activity
  作者：Liza Saher、Malika Makhloufi-Chebli、Leila Dermeche、Samia Dermeche、Baya Boutemeur-Khedis、Cherifa Rabia、Maamar Hamdi、Artur M.S. Silva

  DOI：10.1016/j.tet.2018.01.009

  日期：2018.2

  A series of novel 10-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-3-methyl-1H,10H-pyrano[4,3-b]chromen-1-ones were synthesized by a pseudo-three-component reaction of 4-hydroxy-6-methyl-2-oxo-2H-pyran-2-one (TAL) with 2-hydroxyarylaldehydes using different acids as catalysts and solvents. The approach relies on a regioselective cascade reaction involving two molar equiv of the TAL iteratively acting as

  一系列新颖的10-（4-羟基-6-甲基-2-氧代-2 H-吡喃-3-基）-3-甲基-1 H，10 H-吡喃[4,3- b ] chromen -1通过使用不同的酸作为催化剂和溶剂，通过4-羟基-6-甲基-2-氧-2- H -2吡喃-2-酮（TAL）与2-羟基芳基醛的拟三组分反应合成α-酮。该方法依赖于区域选择性级联反应，该反应涉及两个摩尔当量的TAL在Knoevenagel缩合反应和Michael加成反应中反复充当活性亚甲基。使用DPPH清除测定法测定合成的化合物的抗氧化活性，其结果取决于色酮取代基的性质和数量。邻位化合物-二羟基（邻苯二酚）部分在较低浓度下显示出优异的活性，而带有烷氧基作为取代基的衍生物则表现出前氧化活性。
• One-pot multicomponent synthesis of novel 1-thiazolyl-5-coumarin-3-yl-pyrazole derivatives and evaluation of their cytotoxic activity
  作者：Ravibabu Velpula、Rajitha Deshineni、Rajitha Gali、Rajitha Bavantula

  DOI：10.1007/s11164-015-2114-2

  日期：2016.3

  A series of novel 1-thiazolyl-5-coumarin-3-yl-pyrazole derivatives (4a–l) were synthesized via one-pot multicomponent reaction of 5-substituted salicylaldehydes (1a–c), 4-hydroxy-6-methyl-2H-pyran-2-one (2) and 2-hydrazinyl-4-arylthiazoles (3a–d) in acetonitrile using a catalytic amount of piperidine under reflux conditions. This multicomponent approach has advantages such as reduced reaction time and a high product yield percentage when compared with corresponding multistep approaches. All the synthesized compounds were evaluated for their cytotoxic activity against Hep G2 (hepatocellular liver carcinoma) and MCF-7 (breast cancer) cell lines and compared with the standard drug Doxorubicin. Among all the compounds, compounds 4d against Hep G2, 4k against MCF-7 and 4e against both Hep G2 & MCF-7 showed excellent cytotoxic activity.

  一系列新型1-噻唑基-5-香豆素-3-基吡唑衍生物（4a–l）通过在 reflux 条件下，使用少量的 Piperidine 催化剂，在乙腈中进行 5-取代水杨 aldehydes（1a–c）、4-羟基-6-甲基-2H-吡喃-2-酮（2）和 2-肼基-4-芳基噻唑（3a–d）的单锅多组分反应合成而成。这种多组分的方法相比于相应的多步骤方法具有缩短反应时间和提高产率的优点。所有合成的化合物都评估了其对 Hep G2（肝细胞肝癌）和 MCF-7（乳腺癌）细胞系的细胞毒性活性，并与标准药物多柔比星进行了比较。在所有化合物中，化合物 4d 对 Hep G2、4k 对 MCF-7 和 4e 对 Hep G2 及 MCF-7 的细胞毒性活性表现出色。
• 3-(1,3-dioxobutan-1-yl)-2H-chromen-2-one in reactions with electrophilic and nucleophilic reagents
  作者：A. A. Shkel’、O. A. Mazhukina、O. V. Fedotova、N. V. Pchelintseva

  DOI：10.1134/s1070363214070172

  日期：2014.7

  Reactions of 3-(1,3-dioxobut-1-yl)-2H-chromen-2-one with electrophilic (boron trifluoride diethyl etherate and phosphorus pentachloride) and nucleophilic (phosphorus pentasulfide and hydrogen sulfide) compounds have been studied. The reactions proceed mainly with the enol form of the substrate which is more stable both in polar and nonpolar solvents. The substrate ability to undergo aromatization into

  研究了3-（1,3-二氧代丁-1-基）-2 H-铬-2--2-酮与亲电（三氟化硼二乙基醚化物和五氯化磷）和亲核（五硫化二磷和硫化氢）化合物的反应。该反应主要以底物的烯醇形式进行，该底物在极性和非极性溶剂中都更稳定。已经证明了底物在亲电子试剂的作用下和在氧代基团上的硫代作用下能够芳构化成4-氧代吡喃铬鎓盐的能力。已经描述了建议的杂环化方案。已经发现在酸性介质中与硫化氢相互作用时半缩酮的原位竞争形成的可能性。