2-叠氮基-2-(4-甲氧基苯基)乙酸乙酯 | 77629-84-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2-叠氮基-2-(4-甲氧基苯基)乙酸乙酯
• 英文名称: ethyl 2-azido-2-(4-methoxyphenyl)acetate
• CAS: 77629-84-6
• 化学式: C₁₁H₁₃N₃O₃
• 分子量: 235.243
• InChiKey: VBNSEPWSCZVBSN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  49.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-叠氮基-2-(4-甲氧基苯基)乙酸乙酯 在 palladium on activated charcoal 吡啶 、 lithium hydroxide 、 氢气 、 对甲苯磺酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、689.47 kPa 条件下， 反应 52.0h， 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：

  ethyl 2-diazo-2-(4-methoxyphenyl)acetate 在 叠氮基三甲基硅烷 、 三(五氟苯基)硼烷 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以78%的产率得到2-叠氮基-2-(4-甲氧基苯基)乙酸乙酯
  参考文献：
  名称：

  硼催化的α-芳基α-重氮酸酯叠氮化物插入

  摘要：

  首次开发了在B（C 6 F 5）3（5 mol％）存在下具有挑战性的无金属的α-芳基α-重氮酸酯叠氮化物插入物。该反应具有易于操作，底物范围宽和条件温和的特点，并以中等至高收率提供了相应的产物。更重要的是，由于未观察到环丙烷化或环丙烷化，因此对烯烃和炔烃官能团的耐受性良好。此外，在简单转化后，相应的叠氮化物产物可以转化为伯胺或1,2,3-三唑衍生物。

  DOI：

  10.1021/acs.joc.8b03278

文献信息

• Phosphine-Catalyzed Doubly Stereoconvergent γ-Additions of Racemic Heterocycles to Racemic Allenoates: The Catalytic Enantioselective Synthesis of Protected α,α-Disubstituted α-Amino Acid Derivatives
  作者：Marcin Kalek、Gregory C. Fu

  DOI：10.1021/jacs.5b05528

  日期：2015.7.29

  specifically, that a chiral phosphepine can catalyze the stereoconvergent γ-addition of a racemic nucleophile to a racemic electrophile; through the choice of an appropriate heterocycle as the nucleophilic partner, this new method enables the synthesis of protected α,α-disubstituted α-amino acid derivatives in good yield, diastereoselectivity, and enantioselectivity.

  最近开发了将亲核试剂不对称 γ-加成到容易获得的烯丙酸酯和炔酸酯的方法，以生成有用的 α,β-不饱和羰基化合物，这些化合物在 γ 或 δ 位置（但不是两者）带有立体中心具有高立体选择性。如果可以有效控制新键两端的立体化学，则该方法的实用性将大大增强。在本报告中，我们描述了这一目标的实现，具体而言，手性膦可以催化外消旋亲核试剂与外消旋亲电试剂的立体会聚γ-加成；通过选择合适的杂环作为亲核伙伴，这种新方法能够以良好的收率合成受保护的 α,α-二取代 α-氨基酸衍生物，
• Synthesis of <font>α</font>-Azido Ketones and Esters Using Recyclable Hypervalent Iodine Reagent
  作者：Vikas N. Telvekar、Hemlata V. Patile

  DOI：10.1080/00397910903531888

  日期：2010.12.21

  A simple and mild method for the preparation of α-azido ketones and esters using hypervalent iodine reagent, 4,4′-bis-(dichloroiodo)-biphenyl, and sodium azide in 1,4-dioxane is discussed. Advantages of this system are easy workup, recyclable reagent, and moderate to good yields.

  讨论了一种使用高价碘试剂、4,4'-双-(二氯碘)-联苯和叠氮化钠在 1,4-二恶烷中制备 α-叠氮酮和酯的简单温和的方法。该系统的优点是易于处理、可回收试剂和中等至良好的产量。
• The effects of .alpha.-substituents on the kinetic and thermodynamic stability of 4-methoxybenzyl carbocations: carbocation lifetimes that are independent of their thermodynamic stability
  作者：Tina L. Amyes、Ishmael W. Stevens、John P. Richard

  DOI：10.1021/jo00074a036

  日期：1993.10

  The following new rate constants for reaction of alpha-substituted 4-methoxybenzyl carbocations, 4-MeOC6H4CR1(R2)+, With a solvent of 50:50 (v/v) trifluoroethanol/water at 25-degrees-C and ionic strength 0.50 (NaClO4) are reported: 4-MeOC6H4CH(OMe)+, k(S) = 2.2 X 10(7) s-1; 4-MeOC6H4CH(N3)+, k(S) = 3.3 X 10(5) s-1; 4-MeOC6H4C(CH3)2+, k(S) = 1.3 x 10(7) s-1; 4-MeOC6H4CH(CO2Et)+, k(S) = 1.4 X 10(7) s-1; 4-MeOC6H4CCH3(CF3)+, k(S) = 2.5 x 10(7) s-1. The values of k(S) for reaction of 4-MeOC6H4CR1(R2)+ with 50:50 (v/v) trifluoroethanol/water are nearly independent of very large changes in the thermodynamic stability of these carbocations caused by the addition of a wide range of electron-withdrawing or electron-donating groups at the alpha-position. In the most extreme case, the change from an alpha-methoxy to two alpha-(trifluoromethyl) substituents leads to a 23 kcal/mol thermodynamic destabilization of 4-MeOCrH4CR1(R2)+ relative to the neutral azide ion adducts but a 5-fold decrease in its reactivity toward solvent. The data show that the effects of alpha-substituents on the kinetic stability of 4-MeOC6H4CR1(R2)+ are complex and do not parallel the thermodynamic stability of these carbocations. The results are explained by consideration of the polar and resonance effects of the alpha-substituents on both the thermodynamic driving force and the intrinsic barrier for capture of the carbocations by solvent. These reactions are a new example of the consequences of the ''principle of nonperfect synchronization''.41
• Iminyl Radicals from α-Azido <i>o</i>-Iodoanilides via 1,5-H Transfer Reactions of Aryl Radicals: New Transformation of α-Azido Acids to Decarboxylated Nitriles
  作者：Giorgio Bencivenni、Tommaso Lanza、Rino Leardini、Matteo Minozzi、Daniele Nanni、Piero Spagnolo、Giuseppe Zanardi

  DOI：10.1021/jo800453z

  日期：2008.6.1

  The radical reaction of tributyltin hydride with o-iodo-N-methylanilides derived from alpha-azido acids provides an excellent access to alpha-(aminocarbonyl)iminyl radicals through 1,5-hydrogen transfer reaction of initially formed aryl radicals followed by beta-elimination of dinitrogen from ensuing alpha-azido-alpha-(aminocarbonyl)alkyl radicals. The outcoming iminyls display a peculiar tendency to form corresponding nitriles by beta-elimination of aminocarbonyl radicals.
• Generation of Iminyl Copper Species from α-Azido Carbonyl Compounds and Their Catalytic C−C Bond Cleavage under an Oxygen Atmosphere
  作者：Shunsuke Chiba、Line Zhang、Gim Yean Ang、Benjamin Wei-Qiang Hui

  DOI：10.1021/ol100522z

  日期：2010.5.7

  A copper-catalyzed reaction of a-azidocarbonyl compounds under an oxygen atmosphere is reported where nitriles are formed via C C bond cleavage of a transient Iminyl copper intermediate. The transformation is carried out by a sequence of denitrogenative formation of iminyl copper species from alpha-azidocarbonyl compounds and their C C bond cleavage, where molecular oxygen (1 atm) is a prerequisite to achieve the catalytic process and one of the oxygen atoms of O-2 was found to be incorporated Into the beta-carbon fragment as a carboxylic acid.