2,5-二氨基-3,4-噻吩二羧酸二乙酯 | 80691-81-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 中文名称: 2,5-二氨基-3,4-噻吩二羧酸二乙酯
• 英文名称: diethyl 2,5-diaminothiophene-3,4-dicarboxylate
• 英文别名: 2,5-diaminothiophene-3,4-dicarboxylic acid diethyl ester；diethyl 2,5-diamino-3,4-thiophene dicarboxylate
• CAS: 80691-81-2
• 化学式: C₁₀H₁₄N₂O₄S
• 分子量: 258.298
• InChiKey: UCZCHDINMZWYIQ-UHFFFAOYSA-N

物化性质

• 熔点：
  155-156 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  403.3±40.0 °C(Predicted)
• 密度：
  1.343
• 溶解度：
  29.9 [ug/mL]

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：
  0.4
• 拓扑面积：
  133
• 氢给体数：
  2
• 氢受体数：
  7

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  2,5-二氨基-3,4-噻吩二羧酸二乙酯 在 sodium ethanolate 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 六氯乙烷 、 乙腈 为溶剂， 反应 16.0h， 生成
  参考文献：
  名称：

  Application of Bis(iminophosphorane) in Heterocyclic Synthesis:  New Entries to Symmetrically or Unsymmetrically Substituted Thieno[2,3-d:5,4-d‘]dipyrimidine-4,5(3H,6H)-diones

  摘要：

  The bis(carbodiimides) 4, obtained from bis-aza-Wittig reactions of bis(iminophosphorane) 3 with 2 equiv of aromatic isocyanates, were reacted with secondary amine to give symmetrically substituted 2,7-diaminothieno[2,3-d:5,4-d']dipyrimidine-4,5(3H,6H)-dione 6 in the presence of a catalytic amount of EtO-Na+ Reactions of 4 with phenols or ROH in the presence of a catalytic amount of potassium carbonate or RO-Na+ gave symmetrically substituted 2,7-diaryl(alkyl)oxythieno[2,3-d:5,4-d']dipyrimidine-4,5(3H,6H)-diones 6 in satisfactory yields. However, iminophosphoranes 9 were obtained via reaction of bis(iminophosphorane) 3 with 1 equiv of aromatic isocyanate and subsequent reaction with an amine in the presence of a catalytic amount of EtO-Na+. Further reaction of iminophosphoranes 9 with aromatic isocyanates and various nucleophile generated unsymmetrically substituted thieno[2,3-d:5,4-d']dipyrimidine-4,5(3H,6H)-diones 12 in good yields.

  DOI：

  10.1021/jo048691v
• 作为产物：
  描述：

  氰乙酸乙酯 在 sulfur 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 以9%的产率得到2,5-二氨基-3,4-噻吩二羧酸二乙酯
  参考文献：
  名称：

  Photophysical, crystallographic, and electrochemical characterization of novel conjugated thiopheno azomethines

  摘要：

  本文介绍了使用稳定的 2,5-二氨基噻吩前体的新型共轭噻吩偶氮甲烷。对这些化合物进行的光谱和光物理研究证实，它们主要通过内部转换而不是系统间交叉来耗散激发态能量。晶体学数据显示，这些化合物形成了热力学上有利的 E 异构体，而且高度共轭的偶氮甲烷既是线性的又是平面的。偶氮亚甲基化合物的电化学氧化过程会产生一种持久的自由基阳离子，这种阳离子会发生交叉偶合。由此产生的氧化产物可逆地形成自由基阳离子，并显示出与共轭程度增加相一致的光谱特性。

  DOI：

  10.1039/b615325a

文献信息

• Towards materials with reversible oxidation and tuneable colours using heterocyclic conjugated azomethines
  作者：Stéphane Dufresne、Andréanne Bolduc、W. G. Skene

  DOI：10.1039/c0jm00557f

  日期：——

  The spectroelectrochemical behaviour of heterocyclic azomethines prepared by condensing complementary aldehydes and amines was observed as intense colour changes of the oxidized products relative to the neutral form. The tuneable colours and reversible oxidation were contingent on the heterocycles.

  通过冷凝互补醛和胺制备的杂环亚胺的光谱电化学行为表现出相对于中性形式的氧化产物的显著颜色变化。可调颜色和可逆氧化取决于杂环的结构。
• Synthesis and in vitro biological evaluation of novel diaminothiophene scaffolds as antitumor and anti-influenza virus agents. Part 2
  作者：Khurshed Bozorov、Jiang yu Zhao、Li Fei Nie、Hai-Rong Ma、Khayrulla Bobakulov、Rui Hu、Nigora Rustamova、Guozheng Huang、Thomas Efferth、Haji A. Aisa

  DOI：10.1039/c7ra04808d

  日期：——

  building block analysis methods, herein we report the synthesis and biological evaluation of a novel series of diethyl 2,5-diaminothiophene-3,4-dicarboxylate derivatives. All of the prepared Schiff bases (with mono-, di- and poly-substituents at the aromatic portion), mono- and bis-amides of diethyl 2,5-diaminothiophene-3,4-dicarboxylate, were evaluated against various human cancer and non-cancerous (only

  在高通量筛选，基于片段的药物发现，结构-活性关系和构件分析方法的基础上，本文报道了一系列新的2,5-二氨基噻吩-3,4-二羧酸二乙酯系列化合物的合成和生物学评价。衍生品。对所有制备的席夫碱（在芳族部分带有单，双和多取代基），2,5-二氨基噻吩-3,4-二羧酸二乙酯的单酰胺和双酰胺进行了抗多种人类癌症的评估，非癌性（仅针对活性化合物）细胞系，以及甲型流感（FM / 1/47 / H1N1亚型，hanfang / 359/95 / H3N2）和乙型流感病毒（jifang / 13/97）。获得的结果表明，某些选定的化合物显示出有希望的抗肿瘤和抗病毒活性，并且可以用作进一步药物发现和开发的先导化合物。
• Photophysical, Crystallographic, and Electrochemical Characterization of Symmetric and Unsymmetric Self-Assembled Conjugated Thiopheno Azomethines
  作者：Sergio Andrés Pérez Guarìn、Marie Bourgeaux、Stéphane Dufresne、W. G. Skene

  DOI：10.1021/jo070100o

  日期：2007.3.1

  crystallographic studies. These also demonstrated that the azomethine bonds and the thiophene units are highly planar and linear. The fluorescence and phosphorescence of the thiopheno azomethines measured are similar to those of thiophene analogues currently used in functional devices, but with the advantage of low triplet formation and band-gaps as low as 1.9 eV. The time-resolved and steady-state temperature-dependent

  提出了新颖的由噻吩单元组成的共轭偶氮甲亚胺。通过稳定的二氨基噻吩（2）与其互补的噻吩醛的简单缩合来合成高度共轭的化合物。这些有趣的含氮噻吩单元表现出可变的反应性，导致受控的醛添加。由于不同的氨基反应性，通过明智地选择溶剂和仔细控制试剂的化学计量关系，可以一锅法合成不对称和对称的共轭偶氮甲硫氨酸，其中噻吩单元的数目不同。所得的共价共轭连接具有还原性和水解抗性。热力学E对于所有合成的甲亚胺而言，异构体是唯一形成的，这已通过晶体学研究得到证实。这些也证明了偶氮甲碱键和噻吩单元是高度平面和线性的。测得的噻吩甲亚胺的荧光和磷光与当前在功能装置中使用的噻吩类似物的荧光和磷光相似，但具有三重态形成低和带隙低至1.9 eV的优势。时间分辨和稳态温度相关的光物理现象表明，噻吩甲亚胺不会通过系统间交叉而广泛地占据其三重态流形。而是，它们的激发态能量主要通过内部转换的非辐射方式消散。发现了噻吩单元的准可逆电化学自由基阳离子形成。
• Thienylpyrazoloquinolines: potent agonists and inverse agonists to benzodiazepine receptors
  作者：Susumu Takada、Hirohisa Shindo、Takashi Sasatani、Nobuo Chomei、Akira Matsushita、Masami Eigyo、Kazuo Kawasaki、Shunji Murata、Yukio Takahara、Haruyuki Shintaku

  DOI：10.1021/jm00117a012

  日期：1988.9

  of magnitude higher affinity for the receptors than diazepam. Planarity was one of the structural requirements for binding to benzodiazepine receptors. The activities of agonists and inverse agonists were assessed on the basis of inhibition or facilitation of the pentylenetetrazole-induced convulsions, respectively. Thien-3-yl compounds exhibited inverse agonist activity whereas thien-2-yl analogues

  一系列2-（thien-3-yl）-和2-（thien-2-yl）-2,5-dihydro-3H-pyrazolo [4,3-c] quinolin-3的合成及构效关系-报告一个。与地西epa相比，许多化合物对受体的亲和力高1个数量级。平面度是与苯并二氮杂receptor受体结合的结构要求之一。激动剂和反向激动剂的活性分别基于戊烯四唑诱导的惊厥的抑制或促进进行评估。噻吩-3-基化合物表现出反向激动剂活性，而具有5'-烷基的噻吩-2-基类似物表现出激动剂活性。喹啉部分上的取代不增强体内活性。
• Tunable spectroscopic and electrochemical properties of conjugated push–push, push–pull and pull–pull thiopheno azomethines
  作者：Stéphane Dufresne、Marie Bourgeaux、W. G. Skene

  DOI：10.1039/b616379c

  日期：——

  Novel azomethines consisting uniquely of thiophene units were examined. The highly conjugated compounds were prepared by condensing air stable aminothiophenes with 2-thiophene aldehydes, which were substituted with various electronic groups. The resulting azomethines are highly conjugated and are both reductively and hydrolytically resistant. Various electron donating and accepting groups placed in the 2-position of 5-thiophene carboxaldehyde lead to electronically delocalized push–push, pull–pull, and push–pullazomethines. These electronic groups affect both the HOMO and the LUMO levels, which influence the absorption and emission spectra. Colors spanning the entire visible spectrum ranging from yellow to blue are possible with these nitrogen containing conjugated compounds. Excited state deactivation of the singlet excited state occurs predominately by internal conversion while only a small amount of energy is dissipated by intersystem crossing to the triplet state and by fluorescence. The ensuing fluorescence and phosphorescence of the thiopheno azomethines are similar to those of their thiophene analogues currently used in functional devices, but with the advantage of a low triplet state and tunable HOMO–LUMO energy levels extending from 3.0 to 1.9 eV. Quasi-reversible electrochemical radical cation formation is possible while the oxidation potential is dependent on the nature of the electronic group appended to the thiophene. The crystallographic data of the electronic push–push system show the azomethine bonds are planar and linear and they adopt the E isomer.

  我们研究了仅由噻吩单元组成的新型偶氮甲烷。这些高度共轭的化合物是通过将空气稳定的氨基噻吩与 2-噻吩醛缩合而制备的，后者被各种电子基团取代。所制备的偶氮甲烷具有高度共轭性，并具有抗还原性和抗水解性。在 5-噻吩醛的 2 位上放置了各种电子供体和受体，从而产生了电子分散的推推、拉拉和推拉偶氮甲烷。这些电子基团会影响 HOMO 和 LUMO 水平，从而影响吸收和发射光谱。这些含氮共轭化合物的颜色横跨从黄色到蓝色的整个可见光谱。单重激发态的激发态失活主要是通过内部转换实现的，只有少量能量是通过系统间转换到三重态和荧光而耗散的。噻吩偶氮甲烷随之产生的荧光和磷光与目前用于功能器件的噻吩类似物相似，但其优点是三重态较低，HOMOâLUMO 能级可调，从 3.0 到 1.9 eV。这种化合物可以形成准可逆的电化学自由基阳离子，而氧化电位则取决于噻吩所附电子基团的性质。电子推挽系统的晶体学数据显示，偶氮甲基键是平面和线性的，它们采用 E 异构体。