ethyl (E)-3-(4-bromo-2-formylphenoxy)acrylate | 954374-78-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl (E)-3-(4-bromo-2-formylphenoxy)acrylate
• 英文别名: ethyl (E)-3-(4-bromo-2-formylphenoxy)prop-2-enoate
• CAS: 954374-78-8
• 化学式: C₁₂H₁₁BrO₄
• 分子量: 299.121
• InChiKey: TYLSIXBCDOXWLE-AATRIKPKSA-N

物化性质

• 熔点：
  64-66 °C
• 沸点：
  377.8±42.0 °C(Predicted)
• 密度：
  1.463±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  6
• 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：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (E)-3-(4-bromo-2-formylphenoxy)acrylate 在 四氢吡咯 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 生成 diethyl 4-(5-bromo-2-hydroxyphenyl)-1-(4-methylphenyl)-4H-pyridine-3,5-dicarboxylate
  参考文献：
  名称：

  Domino Reaction of 3-(2-Formylphenoxy)propenoates and Amines:  A Novel Synthesis of 1,4-Dihydropyridines from Salicaldehydes, Ethyl Propiolate, and Amines

  摘要：

  [GRAPHICS]A novel synthesis of Hantzsch-type N-substituted 1,4-dihydropyridines from salicaldehydes, ethyl propiolate, and amines has been developed. Salicaldehydes were treated with ethyl propiolate in the presence of N-methylmorpholine to give ethyl 3-(2-formylphenoxy)propenoates. Three equivalents of ethyl 3-(2-formylphenoxy)propenoates reacted with 1 equiv of amines under trifluoroacetic acid (TFA) catalyst to furnish the corresponding N-substituted 1,4-dihydropyridines in good to excellent yields, recovering the starting material salicaldehydes. A possible mechanism for the domino process was proposed. Furthermore, the products can be easily derived via further transformations and three of them exhibited strong fluorescence (Phi(f) = 0.36-0.63).

  DOI：

  10.1021/jo7013593
• 作为产物：
  描述：

  5-溴水杨醛 、 丙炔酸乙酯 在 N-甲基吗啉 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以85%的产率得到ethyl (E)-3-(4-bromo-2-formylphenoxy)acrylate
  参考文献：
  名称：

  非对映选择性合成3,3-二取代的3-硝基-4-苯并二氢吡喃酮衍生物作为潜在的抗肿瘤药

  摘要：

  我们报告了一种高效和高度非对映选择性的协议，可通过不饱和酯单元的α-硝基芳基酮的分子内迈克尔型环化来快速构建3-硝基取代的4-苯并二氢吡喃酮。发现催化量的KO t Bu对于该转化的高非对映选择性控制至关重要。通过该方案，可以高收率和优异的合成率合成具有高非对映选择性的一系列3,3-二取代的3-硝基-4-苯并二氢呋喃酮，并显示出中等至良好的体外抗肿瘤活性，代表了有望用于进一步药物开发的抗肿瘤药物。

  DOI：

  10.1039/c8ob02761g

文献信息

• Intramolecular [3 + 2] nitrone cycloaddition reaction: highly regio and diastereoselective synthesis of bicyclo[3.2.1]octane scaffolds
  作者：Manickam Bakthadoss、Mohammad Mushaf

  DOI：10.1039/d0ob01960g

  日期：——

  and diastereoselective strategy has been developed for the synthesis of complex bicyclo[3.2.1]octane scaffolds from the reaction of readily accessible vinylogous carbonates with N-substituted hydroxylamine hydrochlorides via intramolecular 1,3-dipolar nitrone cycloaddition reaction. Wide varieties of bicyclic isoxazolidines were synthesized in high yields under catalyst free conditions through a highly

  已经开发了一种区域和非对映选择性策略，用于通过分子内 1,3-偶极硝酮环加成反应，通过容易获得的乙烯基碳酸酯与N-取代的盐酸羟胺反应合成复杂的双环 [3.2.1] 辛烷支架。通过高效且操作简单的方案，在无催化剂条件下以高产率合成了多种双环异恶唑烷。
• Construction of Fused Heterocyclic Architectures by Formal [4+1]/[3+2] Cycloaddition Cascade of Sulfur Ylides and Nitroolefins
  作者：Liang-Qiu Lu、Fang Li、Jing An、Ji-Ji Zhang、Xiao-Lei An、Qiu-Lin Hua、Wen-Jing Xiao

  DOI：10.1002/anie.200904766

  日期：2009.12.7

  Under control: A formal [4+1]/[3+2] cycloaddition cascade of sulfur ylides and alkene‐tethered nitroolefins has been developed, and provides an efficient synthesis of fused polycyclic heterocyclic compounds in good to excellent overall yields with excellent diastereocontrol (see scheme). A catalytic asymmetric variant of this reaction has also been disclosed.

  在控制之下：已开发出由硫代烷基化物和链烯键合的硝基烯烃形成的正式的[4 + 1] / [3 + 2]环加成级联反应，可有效合成稠合的多环杂环化合物，并具有良好的非对映异构控制性（优异的总收率）（参见方案）。还已经公开了该反应的催化不对称变体。
• Organocatalytic Asymmetric Sulfa-Michael/Michael Addition Reactions: A Strategy for the Synthesis of Highly Substituted Chromans with a Quaternary Stereocenter
  作者：Xu-Fan Wang、Qiu-Lin Hua、Ying Cheng、Xiao-Lei An、Qing-Qing Yang、Jia-Rong Chen、Wen-Jing Xiao

  DOI：10.1002/anie.201004534

  日期：2010.11.2

  Simply complex: Diverse and structurally complex chroman derivatives with a quaternary stereocenter have been obtained through the titled reaction of thiols with nitroolefin enoates using the bifunctional catalyst 1. The reaction features simple experimental procedures, high yield, enantiomeric excess, and excellent diastereoselectivity.

  简单复杂：使用双功能催化剂1，通过巯基与硝基烯烃烯酸酯的标题反应，获得了具有四级立体中心的多样且结构复杂的苯并二氢吡喃衍生物。该反应具有简单的实验步骤，高收率，对映体过量和优异的非对映选择性。
• Asymmetric synthesis and biological evaluation of 3-nitro-2H-chromenes as potential antibacterial agents
  作者：Muyao Li、Xiaofei Zhao、Wen Yang、Fangrui Zhong、Lujiang Yuan、Qiao Ren

  DOI：10.1016/j.tetlet.2018.07.046

  日期：2018.9

  dual-nucleophile is disclosed. This straightforward strategy assembles the optically active (R)-2-alkyl 3-nitro-2H-chromenes with good to excellent enantioselectivities (up to 93% ee) and a broad substrate scope. Preliminary in vitro antibacterial evaluation revealed most of the chiral 3-nitro-2H-chromene derivatives exhibit antibacterial activities against four Gram-positive bacteria. Compound 3p with two bromine

  公开了各种水杨醛衍生物与硝基甲烷作为双亲核试剂的一锅法有机催化多米诺骨牌亨利/迈克尔/脱水序列。这种简单的策略组装了具有良好至优异的对映选择性（高达93％ee）和较宽的底物范围的旋光性（R）-2-烷基3-硝基-2 H-色烯。初步的体外抗菌评估显示，大多数手性3-硝基-2 H-色烯衍生物对四种革兰氏阳性细菌均表现出抗菌活性。在核心支架上具有两个溴取代基的化合物3p被证明是针对金黄色葡萄球菌，枯草芽孢杆菌的最佳抗菌剂。和蜡样芽胞杆菌，4微克/毫升的最小杀菌浓度（MBC）值，和针对表皮葡萄球菌具有8微克/毫升的MBC值。
• Diastereoselective synthesis of 3,3-disubstituted 3-nitro-4-chromanone derivatives as potential antitumor agents
  作者：Huiqing Chen、Jia Xie、Dong Xing、Jinping Wang、Jie Tang、Zhengfang Yi、Fei Xia、Wen-Wei Qiu、Fan Yang

  DOI：10.1039/c8ob02761g

  日期：——

  protocol, a series of 3,3-disubstituted 3-nitro-4-chromanones were synthesized in good to excellent yields with high diastereoselectivities and showed moderate to good in vitro antitumor activities, representing promising antitumor hits for further drug discovery.

  我们报告了一种高效和高度非对映选择性的协议，可通过不饱和酯单元的α-硝基芳基酮的分子内迈克尔型环化来快速构建3-硝基取代的4-苯并二氢吡喃酮。发现催化量的KO t Bu对于该转化的高非对映选择性控制至关重要。通过该方案，可以高收率和优异的合成率合成具有高非对映选择性的一系列3,3-二取代的3-硝基-4-苯并二氢呋喃酮，并显示出中等至良好的体外抗肿瘤活性，代表了有望用于进一步药物开发的抗肿瘤药物。