6-氯-3-氰基-4-甲基香豆素 | 56394-24-2

• 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
• 中文名称: 6-氯-3-氰基-4-甲基香豆素
• 英文名称: 6-chloro-3-cyano-4-methylcoumarin
• 英文别名: 6-chloro-4-methyl-2-oxochromene-3-carbonitrile
• CAS: 56394-24-2
• 化学式: C₁₁H₆ClNO₂
• 分子量: 219.627
• InChiKey: JYTVXFGXASPMRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-氯-3-氰基-4-甲基香豆素 在 哌啶 作用下， 以 乙醇 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Madkour, Hassan M. F., Heterocycles, 1993, vol. 36, # 5, p. 947 - 959

  摘要：

  DOI：
• 作为产物：
  描述：

  乙酸-4-氯苯酯 在 aluminum (III) chloride 、 sodium ethanolate 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 6-氯-3-氰基-4-甲基香豆素
  参考文献：
  名称：

  Synthesis and biological evaluation of 4-styrylcoumarin derivatives as inhibitors of TNF-α and IL-6 with anti-tubercular activity

  摘要：

  A series of 4-styrylcoumarin have been synthesized by Knoevenagel condensation between substituted 4-methylcoumarin-3-carbonitrile and different heterocyclic or aromatic aldehydes. 4-Methylcoumarin-3-carbonitrile has been synthesized by the base catalyzed reaction between substituted 2-hydroxyacetophenone and ethyl cyanoacetate. The structures of the newly synthesized compounds were confirmed by H-1 NMR, IR and mass spectral analysis. All the compounds were evaluated for their anti-inflammatory activity (against TNF-alpha and IL-6) and anti-tubercular activity. Compounds 6a, 6h and 6j exhibited promising activity against IL-6 with 72-87% inhibition and compound 6v showed potent activity against TNF-alpha with 73% inhibition at 10 mu M concentration. Whereas compounds 6n, 6o, 6r and 6u showed very good anti-tubercular activity against Mycobacterium tuberculosis H37Rv strain at < 6.25 mu M. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2011.02.016

文献信息

• Palladium‐Catalyzed Regioselective and Diastereoselective <i>C</i> ‐Glycosylation by Allyl‐Allyl Coupling
  作者：Junhao Li、Nan Zheng、Xuelun Duan、Rui Li、Wangze Song

  DOI：10.1002/adsc.202001136

  日期：2021.2.2

  A Pd‐catalyzed C‐glycosylation reaction was developed by allyl‐allyl coupling process using Achmatowicz rearrangement products as donors and methylcoumarins as acceptors under mild conditions. This method featured regio‐ and diastereoselectivities, stereodivergent synthesis of C‐glycosides. The glycosyl donors with controlled stereodiversity and glycosyl acceptors with fluorescent performace further

  在温和条件下，使用Achmatowicz重排产物作为供体，甲基香豆素作为受体，通过烯丙基-烯丙基偶联过程开发了Pd催化的C-糖基化反应。该方法具有区域选择性和非对映选择性，C-糖苷的立体发散合成。具有控制的立体多样性的糖基供体和具有荧光性能的糖基受体进一步强调了该方法。
• Iridium-catalyzed direct asymmetric vinylogous allylic alkylation
  作者：Chang-Yun Shi、Jun-Zhao Xiao、Liang Yin

  DOI：10.1039/c8cc07249c

  日期：——

  alkylation of α,β-unsaturated lactones (including coumarins) was achieved with excellent regio- and enantioselectivity. Transformations of the product were carried out by means of the versatile terminal olefin and lactone moieties. The synthetic application of the present methodology was showcased by the asymmetric synthesis of an advanced synthetic Merck intermediate toward a new drug candidate.

  α，β-不饱和内酯（包括香豆素）的催化不对称乙烯基烯丙基烷基化反应具有出色的区域和对映选择性。借助通用的末端烯烃和内酯部分进行产物的转化。通过先进的合成默克中间体向新药物候选者的不对称合成，展示了本方法学的合成应用。
• Catalytic Enantioselective Vinylogous Allylic Alkylation of Coumarins
  作者：Satavisha Kayal、Santanu Mukherjee

  DOI：10.1021/acs.orglett.7b02421

  日期：2017.9.15

  An unprecedented, organocatalytic enantioselective vinylogous γ-allylic alkylation of 4-methylcoumarins has been developed. Using allylic carbonates as the allyl source, this reaction is catalyzed by Lewis basic dimeric Cinchona alkaloid (QD)2PHAL and proceeds exclusively in a γ- and branched-selective manner to produce densely functionalized coumarin derivatives generally in good yields with good

  已经开发了空前的4-甲基香豆素的有机催化对映选择性乙烯基γ-烯丙基烷基化反应。使用路易斯酸碱性二聚体金鸡纳生物碱（QD）2 PHAL催化该反应使用烯丙基碳酸酯作为烯丙基源，并且该反应仅以γ和支化选择性方式进行，从而通常以高收率和良好至高对映选择性生产出高密度官能化香豆素衍生物。 （最多97：3 er）。
• Vinylogous Nucleophiles Bearing the Endocyclic Double Bond in the Allylic Alkylation with Morita-Baylis-Hillman Carbonates
  作者：Dorota Kowalczyk、Łukasz Albrecht

  DOI：10.1002/adsc.201701185

  日期：2018.2.1

  nucleophilicity in the allylic alkylation with Morita‐Baylis‐Hillman carbonates can be accomplished through the endocyclic double bond in 3‐cyano‐4‐methylcoumarins. The developed reaction provides a straightforward access to functionalized coumarin derivatives of biological and synthetic relevance. Target, highly functionalized products have been chemoselectively and efficiently obtained in very high yield

  这项研究表明，通过Morita-Baylis-Hillman碳酸酯进行的烯丙基烷基化中的亲核性的乙烯基转移可以通过3-氰基-4-甲基香豆素中的内环双键来完成。发达的反应提供了直接获得具有生物学和合成相关性的功能化香豆素衍生物的途径。以非常高的收率（高达98％）和优异的对映选择性（高达99.5：0.5 er），以化学选择性和有效的方式获得了目标高度功能化的产品。
• Chiral Hypervalent Bromine(III) (Bromonium Salt): Hydrogen- and Halogen-Bonding Bifunctional Asymmetric Catalysis by Diaryl-λ³-bromanes
  作者：Yasushi Yoshida、Takashi Mino、Masami Sakamoto

  DOI：10.1021/acscatal.1c04070

  日期：2021.11.5

  Bromonium salts, which are hypervalent bromine reagents, have been explored as being strong electrophiles owing to their extremely high nucleofugalities. Only one example of their catalytic application has been reported by our group; however, their chiral versions have not yet been researched. Halogen-bonding (XB) has been widely applied in chemistry; however, its successful application to highly enantioselective

  溴鎓盐是高价溴试剂，由于其极高的离核性，已被研究为强亲电试剂。我们小组只报道了一个催化应用的例子；然而，他们的手性版本尚未被研究。卤素键合（XB）在化学中得到了广泛的应用；然而，其在高对映选择性路易斯酸催化中的成功应用尚未实现。在此，我们报告了手性环状二芳基溴鎓盐的设计和开发。这些催化剂实现了高度对映选择性的路易斯酸 XB 催化，提供了高达 96% ee 的产物。