2-(2-aminophenyl) malonic acid dimethyl ester | 86162-61-0

• 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: 2-(2-aminophenyl) malonic acid dimethyl ester
• 英文别名: Dimethyl 2-(2-aminophenyl)propanedioate；dimethyl 2-(2-aminophenyl)propanedioate
• CAS: 86162-61-0
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: PAYWIXUOHPAGBF-UHFFFAOYSA-N

物化性质

• 沸点：
  332.6±27.0 °C(Predicted)
• 密度：
  1.228±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  78.62
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-(2-aminophenyl) malonic acid dimethyl ester 在 吡啶 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 1,3-双(二苯基膦)丙烷 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 dimethyl-1-(4-methylphenylsulfonyl)-3-vinyl-2,3-dihydroquinoline-4,4(1H)-dicarboxylate
  参考文献：
  名称：

  Regio- and enantioselective synthesis of functionalized tetrahydroquinolines by palladium-catalyzed cyclization of 2-amidophenylmalonates with allylic bisacetates

  摘要：

  A palladium-catalyzed cyclization of 2-amidophenylmalonates with allylic bisacetates is described. Tetrahydroquinolines having a vinyl group at the 3- or 2-position were produced, in which the regioselectivity of the resulting products was altered depending on the substituent on the amino group. The product was transformed to the azabicyclo[3.3.1]nonene via the ring-closing metathesis. Enantioselective reactions also successfully proceeded in the presence of (S)-BINAP to give the optically active tetrahydroquinoline with high enantioselectivity. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.09.075
• 作为产物：
  描述：

  丙二酸二甲酯 在 10% Pd/C 、 potassium tert-butylate 、 氢气 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 20.0~90.0 ℃ 、354.66 kPa 条件下， 反应 4.17h， 生成 2-(2-aminophenyl) malonic acid dimethyl ester
  参考文献：
  名称：

  Regio- and enantioselective synthesis of functionalized tetrahydroquinolines by palladium-catalyzed cyclization of 2-amidophenylmalonates with allylic bisacetates

  摘要：

  A palladium-catalyzed cyclization of 2-amidophenylmalonates with allylic bisacetates is described. Tetrahydroquinolines having a vinyl group at the 3- or 2-position were produced, in which the regioselectivity of the resulting products was altered depending on the substituent on the amino group. The product was transformed to the azabicyclo[3.3.1]nonene via the ring-closing metathesis. Enantioselective reactions also successfully proceeded in the presence of (S)-BINAP to give the optically active tetrahydroquinoline with high enantioselectivity. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.09.075

文献信息

• Asymmetric Triple Relay Catalysis: Enantioselective Synthesis of Spirocyclic Indolines through a One-Pot Process Featuring an Asymmetric 6π Electrocyclization
  作者：Xiao-Ping Yin、Xing-Ping Zeng、Yun-Lin Liu、Fu-Min Liao、Jin-Sheng Yu、Feng Zhou、Jian Zhou

  DOI：10.1002/anie.201407677

  日期：2014.12.8

  A rare example of a one‐pot process that involves asymmetric triple relay catalysis is reported. The key step is an asymmetric [1,5] electrocyclic reaction of functionalized ketimines. The substrates for this process were obtained in situ in a two‐step process that involved the hydrogenation of nitroarenes with a Pd/C catalyst to yield aryl amines and their subsequent coupling with isatin derivatives

  报道了涉及不对称三重中继催化的一锅法罕见案例。关键步骤是官能化酮亚胺的不对称[1,5]电环反应。此过程的底物是通过两步过程原位获得的，该过程涉及用Pd / C催化剂将硝基芳烃氢化以生成芳基胺，然后在布朗斯台德酸催化的酮亚胺形成反应中将它们与Isatin衍生物偶联。通过双官能手性布朗斯台德碱/氢键供体催化剂催化电环化。一锅法以高收率和出色的对映选择性提供了所需的产物。
• Photocatalytic <i>para</i>-Selective C–H Functionalization of Anilines with Diazomalonates
  作者：Ujjwal Karmakar、Ho Seong Hwang、Yunjeong Lee、Eun Jin Cho

  DOI：10.1021/acs.orglett.2c02228

  日期：2022.8.26

  para-selective radical–radical cross coupling proceeded via C-centered radical intermediates generated from both anilines and diazomalonates. The photochemistry of anilines could be extended to other N-heterocycles, such as indole and carbazole. The reaction pathway for the selective C–C coupling was validated by electrochemical and photophysical experiments as well as computational studies.

  在 Ir(III) 光催化剂的帮助下，使用重氮丙二酸盐开发了可见光诱导的苯胺在 N-H 插入上的对位选择性 C-H 官能化。对位选择性自由基-自由基交叉偶联是通过苯胺和重氮丙二酸酯产生的以 C 为中心的自由基中间体进行的。苯胺的光化学可以扩展到其他 N-杂环，例如吲哚和咔唑。通过电化学和光物理实验以及计算研究验证了选择性 C-C 偶联的反应途径。
• 一种5-氰基吲哚的制备方法
  申请人：苏州永健生物医药有限公司

  公开号：CN116082213A

  公开（公告）日：2023-05-09

  本发明公开了5‑氰基吲哚的制备方法，S1)将邻氯苯胺和丙二酸二甲酯溶解，进行催化反应，制得2‑(2‑氨基苯基)丙二酸二甲酯；S2)将2‑(2‑氨基苯基)丙二酸二甲酯溶解，加入碱进行水解反应，然后加入酸进行高温脱羧反应，制得邻氨基苯乙酸；S3)将邻氨基苯乙酸溶解，进行氨基对位溴化，制得2‑(2‑氨基‑5‑溴苯基)乙酸；S4)将2‑(2‑氨基‑5‑溴苯基)乙酸溶解，加入缩合剂进行分子内缩合，制得5‑溴氧化吲哚；S5)将5‑溴氧化吲哚进行还原反应，制得5‑溴吲哚啉；S6)将5‑溴吲哚啉进行氧化反应，制得5‑溴吲哚；S7)采用氰基对5‑溴吲哚的溴进行取代反应，制得5‑氰基吲哚。本发明工艺简单、环保无污染、成本低廉、操作安全、易于规模化生产，且反应条件温和，转化率高，产品品质好。
• Diphosphine-Catalyzed Mixed Double-Michael Reaction: A Unified Synthesis of Indolines, Dihydropyrrolopyridines, Benzimidazolines, Tetrahydroquinolines, Tetrahydroisoquinolines, Dihydrobenzo-1,4-oxazines, and Dihydrobenzo-3,1-oxazines
  作者：Vardhineedi Sriramurthy、Ohyun Kwon

  DOI：10.1021/ol100078w

  日期：2010.3.5

  Seven different types of benzannulated N-heterocycles-indolines, dihydropyrrolopyridines, benzimidazolines, dihydrobenzo-3,1-oxazines, benzomorpholines, tetrahydroquinolines, and tetrahydroisoquinolines-can be obtained from simple dinucleophiles and electron-deficient acetylenes in one synthetic step. This powerful methodology was made possible through the use of diphenylphosphinopropane (DPPP) as the catalyst, with acetic acid and sodium acetate used as additives in some cases. The benzannulated N-heterocycles were isolated in excellent yields under mild metal-free conditions; they were purified without the need for aqueous workups.