5-chlorocoumarin | 38169-98-1

• 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: 5-chlorocoumarin
• 英文别名: 5-Chloro-2h-chromen-2-one；5-chlorochromen-2-one
• CAS: 38169-98-1
• 化学式: C₉H₅ClO₂
• 分子量: 180.59
• InChiKey: VYFHMNIBSWVKIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-chlorocoumarin 在 chromium(VI) oxide 、 溴 、 安息香精油 作用下， 以 氯仿 、 水 、 溶剂黄146 、 丙酮 为溶剂， 反应 34.0h， 生成 5-chloro-2,2-dimethylchroman-4-one
  参考文献：
  名称：

  某些氯-2,2-二甲基色烯的合成与反应

  摘要：

  已经从相应的氯香豆素制备了5-，6-，7-和8-氯-2,2-二甲基苯并二恶英，并描述了它们向3,4-二卤代苯并二氢吡喃衍生物的转化。通过将产生的卤代醇转化成苯并二氢吡喃酮和环氧化物，显示4-卤素原子更易于水解。据报道在3-卤代铬烷酮的脱卤过程中双铬的形成。

  DOI：

  10.1016/s0040-4020(01)98965-3
• 作为产物：
  描述：

  (2E)-3-(2,6-二氯苯基)丙烯酸 反应 0.02h， 生成 5-chlorocoumarin
  参考文献：
  名称：

  Photocyclization of Ortho-Substituted Cinnamic Acids

  摘要：

  Mono and di (i.e. 2, 6) o-chloro- and o-methoxycinnamic acids undergo photocyclization to give the corresponding coumarins. The reaction occurs in aqueous and organic media, with a prototypical reaction giving evidence of being favored at pH > 6. Cyclization of the dimethoxy acid is relatively inefficient (Phi for the PSS = 0.0015), and a photostationary state of the cis/trans acids is formed early into the reaction, The photocyclization of the dichloro analog is more efficient (Phi exceeds 0.04) and therefore time dependent since product formation competes with trans/cis isomerization. Methyl o-chlorocinnamate also photocyclizes (Phi for the PSS = 0.0022 in acetonitrile) but the o-methoxy ester is virtually photoinert, It is proposed that the acid photocyclizes through intramolecular nucleophilic attack by the carboxylate group followed by heterolysis of the nucleofuge. Methyl o-chlorocinnamate appears to photocyclize through a [4 + 2] cycloaddition of the carbonyl group followed by homolysis of the Cl and Me moieties, possibly through the intermediacy of a ketene as proposed by earlier workers.

  DOI：

  10.1021/jo00112a018

文献信息

• Gold(I)-Catalyzed Intramolecular Hydroarylation of Phenol-Derived Propiolates and Certain Related Ethers as a Route to Selectively Functionalized Coumarins and 2<i>H</i>-Chromenes
  作者：Aymeric Cervi、Yen Vo、Christina L. L. Chai、Martin G. Banwell、Ping Lan、Anthony C. Willis

  DOI：10.1021/acs.joc.0c02011

  日期：2021.1.1

  Methods are reported for the efficient assembly of a series of phenol-derived propiolates, including the parent system 56, and their Au(I)-catalyzed cyclization (intramolecular hydroarylation) to give the corresponding coumarins (e.g., 1). Simple syntheses of natural products such as ayapin (144) and scoparone (145) have been realized by such means, and the first of these subject to single-crystal

  报道了有效组装一系列由苯酚衍生的丙酸酯的方法，包括母体系统56，以及它们的Au（I）催化的环化（分子内氢芳基化），得到相应的香豆素（例如1）。通过这样的方法已经实现了天然产物例如ayapin（144）和scoparone（145）的简单合成，并且首先对它们进行单晶X射线分析。描述了一种用于将诸如156的炔丙基醚转化为天然存在的少年激素生物合成抑制剂的异构体2 H-苯并二茂烯I（159）的方法。
• Metal‐free, Visible‐Light‐Mediated Direct Csp ² −H Radical Mono‐ and Bis‐trifluoromethylation of Coumarins and Bioactivity Evaluation
  作者：Xiang Yu、Peng Dai、Yu‐Chuan Zhu、Peng Teng、Wei‐Hua Zhang、Chao Deng

  DOI：10.1002/cctc.201801332

  日期：2018.11.22

  A clean, transition metal‐ and oxidant‐free photochemical protocol was described for the direct trifluoromethylation of coumarins with Togni reagent. The reaction proceeded smoothly under mild condition to afford regioselective 3‐trifluoromethyl coumarins, moreover novel bis‐trifluoromethylated coumarins were formed. Preliminary bioactivity evaluation on some products showed potential antifungal activities

  描述了使用Togni试剂对香豆素进行直接三氟甲基化的清洁，无过渡金属和氧化剂的光化学方案。反应在温和的条件下平稳进行，得到区域选择性的3-三氟甲基香豆素，而且形成了新型的双三氟甲基化香豆素。对某些产品的初步生物活性评估显示出潜在的抗真菌活性。
• A Quick and Advantageous Synthesis of 2<i>H</i>-1-Benzopyran-2-ones Unsubstituted on the Pyranic Nucleus
  作者：George Bratulescu

  DOI：10.1055/s-2008-1067238

  日期：2008.9

  The synthesis of 2H-1-benzopyran-2-ones (coumarins) unsubstituted on the pyranic nucleus was realized by condensation of malic acid and phenols under mild conditions. A short reaction time, improved yields, good purity of the products, and an easy clean experimental protocol are the advantages of this procedure.

  2H-1-苯并吡喃-2-酮（香豆素）在吡喃核上未被取代是通过苹果酸和酚类在温和条件下缩合实现的。反应时间短、产率提高、产品纯度高和易于清洁的实验方案是该程序的优点。
• Visible light-enabled regioselective chlorination of coumarins using CuCl₂<i>via</i> LMCT excitation
  作者：Weiming Li、Jinshan Liu、Min Zhou、Lin Ma、Min Zhang

  DOI：10.1039/d2ob01134d

  日期：——

  efficient, regioselective chlorination of coumarins using Earth-abundant and cost-effective CuCl2 under visible light irradiation is reported. A key feature of this protocol is the photocatalytic dissociation of the copper(II) complex in acetonitrile through ligand-to-metal charge transfer (LMCT) to give the chlorine atom which then selectively chlorinates the coumarin. This method can chlorinate a broad

  报道了在可见光照射下使用地球丰富且具有成本效益的 CuCl 2对香豆素进行有效的区域选择性氯化。该协议的一个关键特征是通过配体到金属电荷转移 (LMCT) 将乙腈中的铜 ( II ) 配合物光催化解离，从而产生氯原子，然后选择性地氯化香豆素。该方法可以用吸电子或给电子取代基对范围广泛的香豆素进行氯化，以区域选择性地提供 3-氯香豆素，并以良好至优异的产率进一步扩展到其他缺电子杂环和烯烃，例如黄酮、8-甲氧基补骨脂素和萘醌。
• Photocatalytic Regio‐ and Site‐Selective Alkylamination of Coumarins: Access to 3‐Amino‐ and 4‐Amino Dihydrocoumarins
  作者：Yu‐Shi Jiang、Feng Liang、Ai‐Min Chen、Shan‐Shan Li、Xue‐Ling Luo、Peng‐Ju Xia

  DOI：10.1002/adsc.202201391

  日期：——

  Functionalized dihydrocoumarins, including 3-amino- and 4-amino dihydrocoumarins serving as α- and β-amino acid derivatives, have been synthesized using one-step site- and regioselective alkylamination from coumarins. This conversion offers 35 examples in 24% to 81% yields.

  功能化的二氢香豆素，包括用作 α- 和 β- 氨基酸衍生物的 3-氨基-和 4-氨基二氢香豆素，已经使用香豆素的一步位点和区域选择性烷基胺化合成。这种转化提供了 35 个例子，收率为 24% 到 81%。