4-氨基-6-氯-2H-色烯-2-酮 | 885269-61-4

• 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
• 中文名称: 4-氨基-6-氯-2H-色烯-2-酮
• 英文名称: 4-amino-6-chloro-2H-chromen-2-one
• 英文别名: 4-amino-6-chlorochromen-2-one
• CAS: 885269-61-4
• 化学式: C₉H₆ClNO₂
• mdl: MFCD08234552
• 分子量: 195.605
• InChiKey: JBJOPQHVOOSYPS-UHFFFAOYSA-N

物化性质

• 沸点：
  379.3±42.0 °C(Predicted)
• 密度：
  1.453±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 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：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-氨基-6-氯-2H-色烯-2-酮 、 ethyl 2-oxo-4-(p-methoxyphenyl)but-3-enoate 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 neat (no solvent) 为溶剂， 反应 0.5h， 以83%的产率得到ethyl 9-cholro-4-(4-methoxyphenyl)-5-oxo-5H-chromeno[4,3-b]pyridine-2-carboxylate
  参考文献：
  名称：

  Efficient Cu(OTf) 2 -catalyzed and microwave-assisted rapid synthesis of 3,4-fused chromenopyridinones under neat conditions

  摘要：

  An efficient, solvent-free, environmentally benign, Cu(OTf)(2)-catalyzed and microwave-assisted fast synthesis of a fascinating class of a number of angularly fused chromenopyridinones having a carboxylate group at C-2 position on the pyridine ring via a one-pot [3+3] annulation reaction of several aminocoumarins/cyclic beta-enaminones with different kinds of gamma-aryI/styryI/heteroaryl-substituted-beta,gamma-unsaturated alpha-ketoesters as Michael acceptors under open atmosphere. This eco-friendly method delivers good to excellent yields of pyridine-fused-heterocycles within (15-40 min) without using any traditional oxidants and allows several important functionalities. Furthermore, by this method, stereos elective synthesis of trans-7,8-diaryl-8.9-dihydrochromeno[4,3-b]cyclopenta[e]pyridine-6,10-diones were obtained in an excellent diastereoselective manner (dr <= 99:1). (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2017.08.006
• 作为产物：
  描述：

  2-羟基-5-氯苯乙酮 在 ammonium acetate 、 sodium hydride 作用下， 以 甲苯 为溶剂， 生成 4-氨基-6-氯-2H-色烯-2-酮
  参考文献：
  名称：

  不同溶剂中碘催化 4-氨基香豆素和 Aurone 多样性定向合成 3,4-杂环稠合香豆素

  摘要：

  开发了一种前所未有的方案，用于通过碘催化级联反应从 4-氨基香豆素和橙酮合成 3,4-杂环稠合香豆素。当分别使用CH 3 CN、AcOH和DMSO作为溶剂时，二氢吡啶稠合香豆素、吡啶稠合香豆素和吡咯稠合香豆素衍生物均具有良好的产率和高选择性。该方案具有起始原料易得、原子经济性高、环境友好、操作简单等优点。

  DOI：

  10.1021/acs.joc.4c00496

文献信息

• Synthesis of Polyheteroaromatic Compounds via Rhodium-Catalyzed Multiple C–H Bond Activation and Oxidative Annulation
  作者：Shiyong Peng、Suna Liu、Sai Zhang、Shengyu Cao、Jiangtao Sun

  DOI：10.1021/acs.orglett.5b02510

  日期：2015.10.16

  Transition-metal-catalyzed multiple C–H activation and sequential oxidative annulation allows rapidly assembling of those compounds from readily available starting materials. A rhodium-catalyzed cascade oxidative annulation of β-enamino esters or 4-aminocoumarins with internal alkynes is described to access those compounds, featuring multiple C–H/N–H bond cleavages and sequential C–C/C–N bond formations in one pot

  由于其电和光化学特性，多杂芳族化合物是潜在的光电共轭材料。过渡金属催化的多个C–H活化和顺序的氧化环化使这些化合物可以从容易获得的起始原料中快速组装。用铑催化的β-烯胺酯或4-氨基香豆素与内部炔烃的级联氧化环氧化法可得到这些化合物，具有多个C–H / N–H键裂解和一个连续的C–C / C–N键形成锅。
• Palladium-Catalyzed Oxidative Annulation<i>via</i>CH/NH Functionalization: Access to Substituted Pyrroles
  作者：Shiyong Peng、Lei Wang、Jiayao Huang、Shaofa Sun、Haibing Guo、Jian Wang

  DOI：10.1002/adsc.201300512

  日期：2013.9.16

  Pyrroles, ubiquitous bioactive heterocycles in nature, are readily prepared via a palladium‐catalyzed oxidative annulation of cyclic trans‐enamines to various internal alkynes in the absence of a directing group.

  吡咯是自然界中普遍存在的生物活性杂环，可以通过在环向烯胺的钯催化氧化下将其环氧化成各种内部炔烃而容易地制得。
• Synthesis and Photophysical Properties of 1,4-Dihydro-2H,5H-chromeno[4,3-d][1,3]oxazin-5-ones, and Derivatives Containing Tethered 1,2,3-Triazoles, from 4-Aminocoumarins
  作者：Marina C. Dilelio、Nathan P. Brites、Larissa A. Vieira、Bernardo A. Iglesias、Teodoro S. Kaufman、Claudio C. Silveira

  DOI：10.1055/s-0037-1612428

  日期：2019.8

  A facile protocol for the unprecedented one-pot H2SO4-mediated hydroxymethylation/cyclative N,O-acetalization of 4-aminocoumarins to 1,4-dihydro-2H,5H-chromeno[4,3-d][1,3]oxazin-5-ones, in moderate to good yields, was developed and optimized. The scope and limitations of the transformation, which takes place in water or water/THF mixtures, were also studied. The nitrogen atom of the resulting tricycles was used to tether alkyl, aryl and 1,2,3-triazolylmethyl moieties, employing a two-step click chemistry approach for the latter. The photophysical properties of the heterocycles, as well as of their 1,2,3-triazole derivatives, were also examined. The N-aryl derivatives exhibited high quantum yields of fluorescence (up to Φf = 0.69) and very large Stokes shifts (up to 201 nm).

  一种简便的方法用于将4-氨基香豆素经H2SO4介导的羟甲基化/环化N,O-缩醛化反应转化为1,4-二氢-2H,5H-色诺[4,3-d][1,3]噁唑啉-5-酮，产率中等至良好，已经开发并优化。还研究了该转化的范围和限制，该反应发生在水或水/THF混合物中。所得三环化合物的氮原子用于连接烷基、芳基和1,2,3-三唑基甲基基团，对后者采用两步点击化学方法。还研究了杂环化合物以及它们的1,2,3-三唑衍生物的光物理性质。N-芳基衍生物表现出高量子产率的荧光（高达Φf = 0.69）和非常大的斯托克斯位移（高达201 nm）。
• One-pot multi-component synthesis of novel chromeno[4,3-b]pyrrol-3-yl derivatives as alpha-glucosidase inhibitors
  作者：Malihe Karami、Alireza Hasaninejad、Hossein Mahdavi、Aida Iraji、Somayeh Mojtabavi、Mohammad Ali Faramarzi、Mohammad Mahdavi

  DOI：10.1007/s11030-021-10337-w

  日期：2022.10

  green and efficient one-pot multi-component protocol was developed for the synthesis of some novel dihydrochromeno[4,3-b]pyrrol-3-yl derivatives through the reaction of arylglyoxals, malono derivatives, and different 4-amino coumarins in ethanol at reflux condition. In this method, all products were obtained in good to excellent yield. Next, all synthesized derivatives were evaluated for their α-glucosidase

  通过芳基乙二醛、丙二酸衍生物和不同的 4-氨基香豆素在乙醇中的反应，开发了一种绿色高效的一锅多组分方案，用于合成一些新型二氢色素[4,3-b]吡咯-3-基衍生物在回流条件下。在该方法中，所有产品均以良好至优异的收率获得。接下来，评估所有合成衍生物的α-葡萄糖苷酶抑制活性。与标准抑制剂阿卡波糖（IC 50  = 750.90 ± 0.14 μM）相比，大多数化合物显示出有效的抑制活性，IC 50值在 48.65 ± 0.01–733.83 ± 0.10 μM 范围内。化合物5e作为最有效衍生物的动力学研究(IC 50 = 48.65 ± 0.01 μM) 显示出K i值为 42.6 μM 的竞争机制。此外，对接研究表明，dihydrochromeno[4,3-b]pyrrol-3-yl 与 α-葡萄糖苷酶活性位点中的重要残基有效相互作用。
• Transition-metal free C(sp²)–C(sp²) bond formation: arylation of 4-aminocoumarins using arynes as an aryl source
  作者：Abhilash Sharma、Pranjal Gogoi

  DOI：10.1039/c9ob01919g

  日期：——

  A mild, efficient and transition-metal free synthetic strategy has been developed for the α-arylation of 4-aminocoumarins using arynes as an aryl source. This synthetic strategy proceeds via C(sp²)–C(sp²) bond formation between 4-aminocoumarins and aryne precursors in a single step in the absence of a metal-catalyst.

  已开发出一种温和、高效且无过渡金属的合成策略，用于利用芳炔作为芳基源对4-氨基香豆素进行α-芳基化。这种合成策略通过在无金属催化剂的情况下，在一个步骤中在4-氨基香豆素和芳炔前体之间形成C(sp²)–C(sp²)键。