2-溴-2-(4-甲氧基苯基)乙酸乙酯 | 77629-83-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 2-溴-2-(4-甲氧基苯基)乙酸乙酯
• 英文名称: ethyl 2-bromo-2-(4-methoxyphenyl) acetate
• 英文别名: Ethyl 2-bromo-2-(4-methoxyphenyl)acetate
• CAS: 77629-83-5
• 化学式: C₁₁H₁₃BrO₃
• 分子量: 273.126
• InChiKey: FHWIEWRPKMWFTE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-溴-2-(4-甲氧基苯基)乙酸乙酯 在 palladium on activated charcoal 吡啶 、 lithium hydroxide 、 sodium azide 、 15-冠醚-5 、 氢气 、 对甲苯磺酸 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， 20.0 ℃ 、689.47 kPa 条件下， 反应 60.0h， 生成 2-acetamido-2-(4-methoxyphenyl) acetic acid
  参考文献：
  名称：

  Diastereochemical Diversity of Imidazoline Scaffolds via Substrate Controlled TMSCl Mediated Cycloaddition of Azlactones

  摘要：

  We report herein a trimethylsilyl chloride mediated substrate controlled 1,3-dipolar cycloaddition for the diastereoselective synthesis of either syn- or anti-imidazolines. This method provides scaffolds with four points of diversity and control over two stereocenters.

  DOI：

  10.1021/ol052118w
• 作为产物：
  描述：

  乙酯4-甲氧基苯并基甲酸盐 在 sodium tetrahydroborate 、 三溴化磷 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 1.25h， 生成 2-溴-2-(4-甲氧基苯基)乙酸乙酯
  参考文献：
  名称：

  2-芳基取代肉桂酸酯的可靠和多功能合成

  摘要：

  2-芳基取代的膦酰基乙酸酯可以通过四步序列从各自的芳烃容易地合成。即使在涉及敏感部分时，成功的 Horner-Wadsworth-Emmons 烯化也可立体选择性地提供 2-芳基肉桂酸酯。

  DOI：

  10.1055/s-2006-942404

文献信息

• Synthesis of 2,3-dihydrobenzo[b][1,4]dioxine-5-carboxamide and 3-oxo-3,4-dihydrobenzo[b][1,4]oxazine-8-carboxamide derivatives as PARP1 inhibitors
  作者：Xuwei Shao、Steven Pak、Uday Kiran Velagapudi、Shruthi Gobbooru、Sai Shilpa Kommaraju、Woon-Kai Low、Gopal Subramaniam、Sanjai Kumar Pathak、Tanaji T. Talele

  DOI：10.1016/j.bioorg.2020.104075

  日期：2020.9

  using recombinant PARP1 enzyme assay that resulted in the acquisition of three PARP1 inhibitors: 3 (IC50 = 12 μM), 4 (IC50 = 5.8 μM), and 10 (IC50 = 0.88 μM). Compound 4 (2,3-dihydro-1,4-benzodioxine-5-carboxamide) was selected as a lead and it was subjected to further chemical modifications, involving analogue synthesis and scaffold hopping. These efforts led to the identification of (Z)-2-(4-hydroxy

  聚（ADP-核糖）聚合酶 1 (PARP1) 是一种广泛探索的抗癌药物靶点，在单链 DNA 断裂修复过程中发挥着重要作用。使用 PARP1-苯并咪唑-4-甲酰胺晶体结构和药效团模型对 Maybridge 小分子文库进行高通量虚拟筛选 (HTVS)，鉴定出 11 种化合物。使用重组 PARP1 酶测定法评估这些化合物，从而获得三种 PARP1 抑制剂：3 (IC 50 = 12 μM)、4 (IC 50 = 5.8 μM) 和10 (IC 50 = 0.88 μM)。化合物4(2,3-dihydro-1,4-benzodioxine-5-carboxamide) 被选为先导化合物，并对其进行了进一步的化学修饰，包括类似物合成和支架跳跃。这些努力导致了 ( Z )-2-(4-hydroxybenzylidene)-3-oxo-3,4-dihydro-2 H - benzo[ b ][1,4]o
• Synthesis of α,α-Disubstituted α-Amino Esters: Nucleophilic Addition to Iminium Salts Generated from Amino Ketene Silyl Acetals
  作者：Shingo Hata、Hiroshi Koyama、Makoto Shimizu

  DOI：10.1021/jo201692x

  日期：2011.12.2

  Alkoxycarbonyl iminium species are prepared easily by the oxidation of tetrasubstituted amino ketene silyl acetals, and subsequent nucleophilic addition of Grignard reagents to the iminium salts gives α,α-disubstituted α-amino ester derivatives in moderate to good yields, in which aryl and ethynyl substituents are readily introduced.

  烷氧基羰基亚胺盐类很容易通过氧化四取代的氨基乙烯酮甲硅烷基乙缩醛来制备，随后将格氏试剂亲核加到亚胺盐中，可以中等至良好的收率得到α，α-二取代的α-氨基酯衍生物，其中芳基和乙炔基取代基容易介绍。
• 1-Aryl-3-azabicyclo[3.1.0]hexanes, a new series of nonnarcotic analgesic agents
  作者：Joseph W. Epstein、Herbert J. Brabander、William J. Fanshawe、Corris M. Hofmann、Thomas C. McKenzie、Sidney R. Safir、Arnold C. Osterberg、D. B. Cosulich、F. M. Lovell

  DOI：10.1021/jm00137a002

  日期：1981.5

  of 19, followed by base hydrolysis of the amide 25. The greatest analgesic potency in mouse writhing and rat paw-pain assays was observed for para-substituted compounds. Bicifadine, 1-(4-methylphenyl)-3-azabicyclo[3.1.0]hexane (2b), was the most potent member of the series and is presently undergoing clinical trials in man. Analgesic activity of 2b is limited to the (+) enantiomer 2v, which has the

  通过氢化还原1-芳基环丙烷二芳基酰亚胺，合成了一系列1-芳基-3-氮杂双环[3.1.0]己烷。羟苯基类似物20、22和24是通过EtSNa-DMF醚裂解相应的甲氧基苯基类似物2m，2n和23制备的，仲胺20和22通过N-甲酰基中间体19和21。对甲氧基类似物26是通过19的O-乙基化，然后是酰胺25的碱水解而获得的。对对位取代的化合物，在小鼠扭体和大鼠爪痛试验中观察到了最大的镇痛效果。比西法定是1-（4-甲基苯基）-3-氮杂双环[3.1.0]己烷（2b），是该系列中最有效的成员，目前正在人体中进行临床试验。2b的镇痛活性仅限于（+）对映体2v，其具有1R，通过单晶X射线分析确定5S绝对构型。2b的N-甲基类似物（27d）显示出明显的止痛效果，而N-烯丙基（27a），N-（环丙基甲基）（27b）和N-（正己基）（27c）类似物没有活性。比西法定（2b）显示出与类似的氮杂双环烷烃和3-苯基吡咯烷镇痛药不同的非麻醉性特征。
• Synthesis of Oxygen-Containing Heterocyclic Compounds by Iron-Catalyzed Alkylative Cyclization of Unsaturated Carboxylic Acids and Alcohols
  作者：Masayuki Iwasaki、Yasuki Kazao、Takumi Ishida、Yasushi Nishihara

  DOI：10.1021/acs.orglett.0c02671

  日期：2020.9.18

  Iron-catalyzed alkylative cyclization of alkenes bearing oxygen nucleophiles with secondary and tertiary alkyl bromides through carbon–carbon and carbon–oxygen bond formations has been developed. A broad substrate scope is an attractive feature of this synthetic method, providing a variety of potentially bioactive five- and six-membered oxygen-containing heterocycles. The reaction pathway is proposed

  通过碳-碳和碳-氧键的形成，已开发出铁催化的带有氧亲核体的烯烃与仲和叔烷基溴的烷基化环化反应。广泛的底物范围是该合成方法的一个吸引人的特征，它提供了多种潜在的具有生物活性的五元和六元含氧杂环。提出的反应途径包括将原位形成的烷基自由基加成到烯烃上，然后形成碳氧键形成分子内环化。
• π-Extension of a 4-ethoxy-1,3-thiazole via aryl alkyne cross coupling: synthesis and exploration of the electronic structure
  作者：Stefanie H. Habenicht、Stefan Schramm、Mingming Zhu、Robert R. A. Freund、Teresa Langenstück、Rainer Strathausen、Dieter Weiß、Christoph Biskup、Rainer Beckert

  DOI：10.1039/c5pp00219b

  日期：2015.11

  A series of four donor aryl alkynyl substituted thiazole derivatives 3a–d and three similar aryl donor–acceptor systems 6a–c have been synthesized. All compounds bear different electron-donating groups in the 5-position of the thiazole core. The influence of both electron donor strength and the additional phenylethynyl unit on photophysical properties, i.e. UV/Vis absorption, fluorescence emission and fluorescence lifetime, has been evaluated. Additionally, theoretical calculations have been performed at the CAM-B3LYP/6-31+G(d,p) level and good agreement with the experimental data has been achieved. The new derivatives synthesized via palladium catalyzed cross coupling are characterised by moderately strong emission between 474 and 538 nm (ΦF = 0.35–0.39) and Stokes’ shifts ranging from 0.54 to 0.79 eV (4392–6351 cm−1). The smaller chromophores of type 6 exhibit modest to high fluorescence emission (ΦF = 0.45–0.76) between 470 and 529 nm and their Stokes’ shifts range from 0.59 to 0.65 eV (4765–5251 cm−1).

  已经合成了四种供体芳基乙炔基取代的噻唑衍生物3a-d和三种类似的供体-受体体系6a-c。所有化合物均在噻唑核心的5-位上带有不同的电子供体基团。评估了电子供体强度和附加的苯乙炔单元对光物理性质（即UV/Vis吸收、荧光发射和荧光寿命）的影响。此外，在CAM-B3LYP/6-31+G(d,p)水平进行了理论计算，得到了与实验数据良好的吻合。通过钯催化的交叉耦合合成的新衍生物具有中等强度的发射（474至538 nm，ΦF = 0.35-0.39）和斯托克斯位移从0.54至0.79 eV（4392-6351 cm−1）。类型6的较小色团显示出适度的至高荧光发射（ΦF = 0.45-0.76），在470至529 nm之间，其斯托克斯位移范围从0.59至0.65 eV（4765-5251 cm−1）。