Dimethyl 2-(3-Fluorobenzylidene)Malonate | 59832-46-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: Dimethyl 2-(3-Fluorobenzylidene)Malonate
• 英文别名: dimethyl 2-[(3-fluorophenyl)methylidene]propanedioate
• CAS: 59832-46-1
• 化学式: C₁₂H₁₁FO₄
• 分子量: 238.215
• InChiKey: MWQHCGHNOACJDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Dimethyl 2-(3-Fluorobenzylidene)Malonate 在 sodium hydride 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 1.0h， 生成 dimethyl 2-(2-(3-fluorophenyl)-4,4-diphenylbut-3-en-1-yl)malonate
  参考文献：
  名称：

  三氟甲磺酸钪 (III) 催化供体-受体环丙烷与 1,1-二苯基乙醇的选择性反应：多取代烯烃的一种方法

  摘要：

  通过三氟甲磺酸钪 (III) 催化供体-受体环丙烷与 1,1-二苯基乙醇的开环反应，开发了一种出人意料的多取代烯烃合成方法。该反应在实验上易于处理，具有各种官能团的耐受性和温和的反应条件。在实验证据的基础上，还提出了一个合理的机制。

  DOI：

  10.1002/ejoc.201700221
• 作为产物：
  描述：

  丙二酸二甲酯 、 3-氟苯甲醛 在 哌啶 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 12.0h， 生成 Dimethyl 2-(3-Fluorobenzylidene)Malonate
  参考文献：
  名称：

  供体-受体环丙烷的电力驱动 1,3-氧代羟基化：温和而直接地获得 β-羟基酮

  摘要：

  一种采用芳环电化学氧化原理的简便方案已被用于减轻供体-受体环丙烷的应变，并进一步捕获分子氧以提供 1,3-双功能化产物。因此，该方法为β-羟基酮的可扩展合成提供了一条新途径。

  DOI：

  10.1002/ejoc.202101022

文献信息

• The Friedel–Crafts Reaction of Indoles with Michael Acceptors Catalyzed by Magnesium and Calcium Salts
  作者：Irina Beletskaya、Mikhail Feofanov、Maxim Anokhin、Alexei Averin

  DOI：10.1055/s-0036-1589068

  日期：2017.11

  the addition to various unsaturated carbonyl compounds, while calcium triflimide [Ca(NTf2)2] efficiently catalyzed the addition to nitroolefins. Friedel–Crafts alkylation of indole and its derivatives with a variety of electron-deficient alkenes catalyzed by Mg and Ca salts has been studied. The dependence of the results on the nature of the starting olefins, substituents on indole, and Michael acceptors

  摘要 已经研究了Mg和Ca盐催化的吲哚及其衍生物与多种电子缺陷的烯烃的Friedel-Crafts烷基化反应。讨论了结果对起始烯烃的性质，吲哚和迈克尔受体上的取代基以及路易斯酸的组成的依赖性。将吲哚添加到β，γ-不饱和α-酮酸酯和香豆素衍生物，一些硝基烯烃和芳基丙二酸酯中可实现高收率的加成产物。发现涉及芳基丙二酸酯的反应是最通用和最平滑的，最高收率达到92％。在所测试的Mg和Ca盐中，除了各种不饱和羰基化合物外，碘化镁（MgI 2）被证明是最合适的催化剂，而三氟甲磺酸钙[Ca（NTf2）2 ]有效地催化了向硝基烯烃的加成。 已经研究了Mg和Ca盐催化的吲哚及其衍生物与多种电子缺陷的烯烃的Friedel-Crafts烷基化反应。讨论了结果对起始烯烃的性质，吲哚和迈克尔受体上的取代基以及路易斯酸的组成的依赖性。将吲哚添加到β，γ-不饱和α-酮酸酯和香豆素衍生物，一些硝基烯烃和芳基丙二酸酯中可实
• Electricity Driven 1,3‐Oxohydroxylation of Donor‐Acceptor Cyclopropanes: a Mild and Straightforward Access to β‐Hydroxy Ketones
  作者：Debarshi Saha、Irshad Maajid Taily、Prabal Banerjee

  DOI：10.1002/ejoc.202101022

  日期：2021.9.24

  principle of electrochemical oxidation of aryl rings has been utilized to relieve the strain of donor-acceptor cyclopropane and further trap the molecular oxygen to deliver the 1,3-bifunctionalized product. Hence, the methodology bestows a novel route towards the scalable synthesis of β-hydroxy ketones.

  一种采用芳环电化学氧化原理的简便方案已被用于减轻供体-受体环丙烷的应变，并进一步捕获分子氧以提供 1,3-双功能化产物。因此，该方法为β-羟基酮的可扩展合成提供了一条新途径。
• A N,N′-dioxide/Mg(OTf)₂ complex catalyzed enantioselective α-addition of isocyanides to alkylidene malonates
  作者：Weiwei Luo、Xiao Yuan、Lili Lin、Pengfei Zhou、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/c6sc00689b

  日期：——

  A simple and efficient catalytic asymmetric [small alpha]-addition of isocyanides to alkylidene malonates was realized using a chiral N,N[prime or minute]-dioxide/MgII catalyst. A variety of 2-alkyl-5-aminoxazoles were obtained in up to 99% yield and 96% ee, and could be converted to imides and dipeptides.

  使用手性N，N [伯或分钟]二氧化物/ Mg II催化剂，可以实现简单有效的异氰酸酯向亚烷基丙二酸酯的催化不对称α-小加成反应。以高达99％的收率和96％的ee获得了各种2-烷基-5-氨基恶唑，并且可以将其转化为酰亚胺和二肽。
• Cs₂CO₃ catalyzed direct aza-Michael addition of azoles to α,β-unsaturated malonates
  作者：Zi-Yu Jiang、Zhe-Yao Huang、Hong Yang、Lin Zhou、Qing-Han Li、Zhi-Gang Zhao

  DOI：10.1039/d2ra02314h

  日期：——

  A highly efficient method for the synthesis of azole derivatives via a direct aza-Michael addition of azoles to α,β-unsaturated malonates using Cs2CO3 as a catalyst, has been successfully developed. A series of azole derivatives have been obtained in up to 94% yield and the reaction could be amplified to gram scale in excellent yield in the presence of 10 mol% of Cs2CO3.

  已成功开发出一种以 Cs 2 CO 3为催化剂，通过唑类直接 aza-Michael 加成到 α,β-不饱和丙二酸酯上合成唑类衍生物的高效方法。一系列唑类衍生物的收率高达 94%，并且在 10 mol% Cs 2 CO 3存在下，反应可以以优异的收率放大至克级。
• Selection, synthesis, and anti-inflammatory evaluation of the arylidene malonate derivatives as TLR4 signaling inhibitors
  作者：Shuting Zhang、Kui Cheng、Xiaohui Wang、Hang Yin

  DOI：10.1016/j.bmc.2012.08.022

  日期：2012.10

  Inhibition of TLR4 signaling is an important therapeutic strategy for intervention in the etiology of several pro-inflammatory diseases. There has been intensive research in recent years aiming to explore this strategy, and identify small molecule inhibitors of the TLR4 pathway. However, the recent failure of a number of advanced drug candidates targeting TLR4 signaling (e.g., TAK242 and Eritoran) prompted us to continue the search for novel chemical scaffolds to inhibit this critical inflammatory response pathway. Here we report the identification of a group of new TLR4 signaling inhibitors through a cell-based screening. A series of arylidene malonate analogs were synthesized and assayed in murine macrophages for their inhibitory activity against LPS-induced nitric oxide (NO) production. The lead compound 1 (NCI126224) was found to suppress LPS-induced production of nuclear factor-kappaB (NF-kappa B), tumor necrosis factor (TNF-alpha), interleukin-1 beta (IL-1 beta), and nitric oxide (NO) in the nanomolar-low micromolar range. Taken together, this study demonstrates that 1 is a promising potential therapeutic candidate for various inflammatory diseases. (C) 2012 Elsevier Ltd. All rights reserved.