4,5,7-三甲基香豆素 | 14002-91-6

• 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: 4,5,7-三甲基香豆素
• 英文名称: 4,5,7-trimethylcoumarin
• 英文别名: 4,5,7-trimethyl-2H-chromen-2-one；4,5,7-trimethyl-chromen-2-one；4,5,7-Trimethyl-cumarin；4,5,7-trimethylchromen-2-one
• CAS: 14002-91-6
• 化学式: C₁₂H₁₂O₂
• mdl: MFCD01861448
• 分子量: 188.226
• InChiKey: PUBIEFXQKSKEBE-UHFFFAOYSA-N

物化性质

• 熔点：
  177-178 °C(Solv: hexane (110-54-3); ethyl acetate (141-78-6))
• 沸点：
  333.0±31.0 °C(Predicted)
• 密度：
  1.122±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xn

反应信息

• 作为反应物：
  描述：

  4,5,7-三甲基香豆素 在 氯磺酸 、 ammonium hydroxide 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 9.5h， 生成 ethyl N-(4,5,7-trimethyl-8-coumarinylsulphonyl)carbamate
  参考文献：
  名称：

  Husain; Gupta; Srivastava, Journal of the Indian Chemical Society, 1982, vol. 59, # 10, p. 1193 - 1195

  摘要：

  DOI：
• 作为产物：
  描述：

  3,5-二甲基苯酚 在 palladium diacetate 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 4,5,7-三甲基香豆素
  参考文献：
  名称：

  Pt^IV-Catalyzed Cyclization of Arene−Alkyne Substrates via Intramolecular Electrophilic Hydroarylation

  摘要：

  [GRAPHICS]We herein report that PtCl4 has proven to be a hydroarylation catalyst with an efficiency and substrate scope superior to previously known methods. This catalyst demonstrated consistent performance with arene-yne substrates of diverse structural features, including propargyl ethers, propargylamines, and alkynoate esters, providing good to excellent yields of the 6-endo products (chromenes, dihydroquinolines, and coumarins). In contrast, Pt(II), Pd(II), and Ga(III) salts were shown to be sensitive to the substitution on the alkyne moiety.

  DOI：

  10.1021/ol034177k

文献信息

• Synthesis of Coumarins Catalyzed by Heterobimetallic Co/Rh Nanoparticles
  作者：Young Chung、Kang Park、Il Jung

  DOI：10.1055/s-2004-834826

  日期：——

  Described here is the use of cobalt/rhodium (Co2Rh2) heterobimetallic nanoparticles in the catalytic synthesis of coumarins via cyclocarbonylation of alkynes with 2-iodophenol under 1 atm of carbon monoxide and reaction of phenol with propiolic ­esters.

  这里描述了钴/铑（Co2Rh2）杂合双金属纳米颗粒在催化合成香豆素中的应用，通过在1个大气压的一氧化碳下将炔烃与2-碘苯酚进行环状羰基化，以及苯酚与丙炔酸酯的反应。
• Improved Synthesis of Coumarins by Iron(III)-Catalyzed Cascade Reaction of Propiolic Acids and Phenols
  作者：Tsugio Kitamura、Md. Kutubi、Takuya Hashimoto

  DOI：10.1055/s-0030-1258473

  日期：2011.4

  presence of FeCl3/AgOTf catalyst proceeded efficiently in a mixed solvent of trifluoroacetic acid and 1,2-dichloroethane, and provided coumarins in good to high yields. This iron-catalyzed reaction offers a much-improved synthesis of coumarins. iron - hydroarylation - coumarins - propiolic acids - propynoic acids - phenols

  在FeCl 3 / AgOTf催化剂存在下，丙酸与苯酚的反应在三氟乙酸和1,2-二氯乙烷的混合溶剂中有效地进行，并提供了高至高收率的香豆素。这种铁催化的反应大大改善了香豆素的合成。 铁-氢芳基化-香豆素-丙酸-丙酸-酚
• A solvent-free synthesis of coumarins using 1,3-disulfonic acid imidazolium hydrogen sulfate as a reusable and effective ionic liquid catalyst
  作者：Farhad Shirini、Asieh Yahyazadeh、Kamal Mohammadi

  DOI：10.1007/s11164-014-1733-3

  日期：2015.9

  1,3-Disulfonic acid imidazolium hydrogen sulfate has been used as an effective and reusable ionic liquid catalyst for the synthesis of coumarins from phenol derivatives with β-ketoesters via the Von Pechmann condensation under solvent-free conditions. This method consistently has the advantages of excellent yields, easy and quick isolation of the products, short reaction times, and green aspects by avoiding toxic catalysts and solvents. Further, the catalyst can be recovered and reused for four times without loss of activity.

  1,3-二磺酸咪唑鎓氢硫酸盐被用作一种有效且可重复使用的离子液体催化剂，用于在无溶剂条件下通过Von Pechmann缩合反应合成来自酚衍生物的香豆素与β-酮酯。该方法始终具有优秀的产率、产品易于迅速分离、反应时间短以及通过避免有毒催化剂和溶剂体现的绿色特性。此外，催化剂可以回收并重复使用四次而不损失活性。
• Sulfonated Core-Shell Magnetic Nanoparticle (Fe₃O₄@SiO₂@PrSO₃H) as a Highly Active and Durable Protonic Acid Catalyst; Synthesis of Coumarin Derivatives through Pechmann Reaction
  作者：Farhad Kabiri Esfahani、Daryoush Zareyee、Reza Yousefi

  DOI：10.1002/cctc.201402547

  日期：2014.12

  Sulfonic acid supported silica coated magnetic nanoparticles (Fe3O4@SiO2@PrSO3H), was prepared by using low cost precursors and a facile immobilization technique. The final catalyst, which was characterized by XRD, FT‐IR, vibrating sample magnetometer (VSM), TEM, and TGA techniques, was found to be an efficient and environmentally benign solid acid for the Pechmann condensation of substituted phenols

  磺酸负载的二氧化硅涂覆的磁性纳米粒子（Fe 3 O 4 @SiO 2 @PrSO 3H）是通过使用低成本前体和简便的固定技术制备的。最终的催化剂以XRD，FT-IR，振动样品磁力计（VSM），TEM和TGA技术为特征，被发现是一种高效，环境友好的固体酸，可用于取代酚与乙酰乙酸乙酯的Pechmann缩合反应，从而产生香豆素衍生物的形成。反应后，可通过外部磁体轻松地分离催化剂，并重复使用22次，而不会显着降低催化效率。通过避免有毒的常规催化剂和溶剂，提出的催化体系为有效合成香豆素，简化操作和绿色反应提供了可重复使用的策略。
• Synthesis and heterogeneous catalytic activity of covalently immobilized hexamine cation as a magnetically-recoverable nanocatalyst
  作者：Sahar Kangari、Issa Yavari、Bakhshali Maasoumi

  DOI：10.1007/s13738-015-0652-6

  日期：2015.10

  Functionalized magnetic core–shell nanoparticles Fe3O4-SiO2-HMTA are prepared by co-precipitation method and characterized by SEM, TEM, FT-IR, XRD, and VSM. The particles are spherical with an average size of approximately 48 nm. The catalytic activity of these nanoparticles was tested in solvent-free synthesis of coumarin derivatives. The catalyst was readily recycled by the use of an external magnetic field and can be reused four times without significant loss of activity or mass.

  功能化的磁性核壳纳米粒子Fe3O4-SiO2-HMTA通过共沉淀法制备，并通过SEM、TEM、FT-IR、XRD和VSM进行表征。粒子呈球形，平均大小约为48纳米。这些纳米粒子的催化活性在无溶剂合成香豆素衍生物中进行了测试。催化剂通过外部磁场易于回收，且可重复使用四次，活动性或质量几乎没有显著损失。