2-amino-5-[(thiophen-2-ylmethylene)amino]thiophene-3,4-dicarboxylic acid diethyl ester | 833459-88-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 2-amino-5-[(thiophen-2-ylmethylene)amino]thiophene-3,4-dicarboxylic acid diethyl ester
• 英文别名: diethyl 2-amino-5-[(E)-(thiophen-2-ylmethylidene)amino]thiophene-3,4-dicarboxylate；diethyl (E)-2-[(thiophen-2-ylmethylene)amino]-5-aminothiophene-3,4-dicarboxylate；diethyl 2-((thiophen-2-yl)methyleneamino)-5-aminothiophene-3,4-dicarboxylate；(e)-Diethyl 2-amino-5-(2-thienylmethyleneamino)thiophene-3,4-dicarboxylate；diethyl 2-amino-5-[(E)-thiophen-2-ylmethylideneamino]thiophene-3,4-dicarboxylate
• CAS: 833459-88-4
• 化学式: C₁₅H₁₆N₂O₄S₂
• 分子量: 352.435
• InChiKey: DGNAHGQXCGFUSS-CAOOACKPSA-N

物化性质

• 熔点：
  145-147 °C
• 沸点：
  565.6±50.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  148
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-amino-5-[(thiophen-2-ylmethylene)amino]thiophene-3,4-dicarboxylic acid diethyl ester 、 2,2-联噻吩-5-乙醛 在 三氟乙酸 作用下， 以 异丙醇 为溶剂， 反应 12.0h， 以40%的产率得到diethyl (2E,5E)-2-[(5-(thiophen-2-yl)thiophen-2-ylmethylene)amino]-5-[(thiophen-2-ylmethylene)amino]thiophene-3,4-dicarboxylate
  参考文献：
  名称：

  对称和非对称自组装共轭噻吩甲亚胺的光物理，晶体学和电化学表征

  摘要：

  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。

  DOI：

  10.1021/jo070100o
• 作为产物：
  描述：

  氰乙酸乙酯 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 正丁醇 为溶剂， 反应 72.67h， 生成 2-amino-5-[(thiophen-2-ylmethylene)amino]thiophene-3,4-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  2,5-二氨基噻吩-3,4-二羧酸二乙酯衍生物的发现作为有效的抗癌药和抗菌剂以及抗糖尿病活性的筛选：合成和体外生物学评估。第1部分

  摘要：

  2，5-二氨基噻吩-3，4-二羧酸二乙酯（DDTD）衍生物系列：DDTD的甲亚胺（2a - 1）已经合成并筛选出其抗癌，抗微生物和抗糖尿病活性。新型合成化合物的特征在于1 H，1313 C NMR，MS和FT-IR分析。评估了所有化合物对三种类型的癌细胞系（例如T47D和MCF-7（人类乳腺癌），Hela（人类宫颈癌）和Ishikawa（人类子宫内膜癌））的抗增殖活性。结果表明，大多数化合物对乳腺癌细胞显示出显着的抗增殖活性。大多数偶氮甲碱DDTD对乳腺癌细胞T47D和MCF-7有强烈影响，其中化合物2b（2.3μM），2c（12.1μM），2e（13.2μM），2i（14.9μM），2j（16.0μM），2k（7.1μM），2公升（8.6μM）比阿霉素（DOX，15.5μM）表现出对癌细胞T47D的有效抗癌活性。化合物2j已同时显示出对所有三种类型癌细胞的有效活性，与阳性对照DOX相比，IC

  DOI：

  10.1016/j.ejmech.2014.07.065

文献信息

• 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。
• Conjugated Thiophenes Having Conducting Properties and Synthesis of Same
  申请人：Skene G. William

  公开号：US20070287842A1

  公开（公告）日：2007-12-13

  The present invention relates to conjugated oligomers and polymers comprising aromatic thiophene cores. The conjugated materials are obtained by simple and efficient condensation of an aryl diamine and an aryl dialdehyde or a bifunctional aryl moiety comprising both an aldehyde and an amine. Condensation of the complementary moieties at temperatures ranging from ambient to refluxing temperatures in various solvents resulted in conjugated oligomers and polymers that can subsequently be cast into thin films. Oligomerization and polymerization can be done under mild conditions with removal of the resulting water bi-product responsible for shifting the equilibrium in favour of the conjugated products. The resulting conjugated compounds can be made conducting with dopants affording electrically conducting materials of either p-type or n-type conductors depending on the dopant selected.

  本发明涉及含有芳香硫吡咯核的共轭寡聚物和聚合物。这些共轭材料是通过芳香族二胺和芳香族二醛或具有同时含有醛和胺的双官能团芳香族基团的简单而有效的缩合反应获得的。在各种溶剂中，在从常温到沸点温度的温度范围内缩合互补的官能团，得到了可以随后铸造成薄膜的共轭寡聚物和聚合物。在温和的条件下进行寡聚和聚合，去除产生的水副产物，有利于使平衡向共轭产物方向移动。所得的共轭化合物可以通过掺杂制成导电材料，根据所选择的掺杂剂，可以得到p型或n型导体的电导材料。
• CONJUGATED THIOPHENES HAVING CONDUCTING PROPERTIES AND SYNTHESIS OF SAME
  申请人：Skene William G.

  公开号：US20120004386A1

  公开（公告）日：2012-01-05

  The present invention relates to conjugated oligomers and polymers comprising aromatic thiophene cores. The conjugated materials are obtained by simple and efficient condensation of an aryl diamine and an aryl dialdehyde or a bifunctional aryl moiety comprising both an aldehyde and an amine. Condensation of the complementary moieties at temperatures ranging from ambient to refluxing temperatures in various solvents resulted in conjugated oligomers and polymers that can subsequently be cast into thin films. Oligomerization and polymerization can be done under mild conditions with removal of the resulting water bi-product responsible for shifting the equilibrium in favour of the conjugated products. The resulting conjugated compounds can be made conducting with dopants affording electrically conducting materials of either p-type or n-type conductors depending on the dopant selected.

  本发明涉及含有芳香硫杂苯核的共轭寡聚物和聚合物。这些共轭材料是通过芳香族二胺和芳香族二醛或含有醛和胺的双官能团芳香族基团的简单高效缩合反应得到的。在各种溶剂中，将互补的官能团在环境温度到沸腾温度范围内缩合，得到共轭寡聚物和聚合物，随后可以将其铸造成薄膜。在温和的条件下进行寡聚和聚合反应，通过去除生成的水分子，使平衡向共轭产物倾斜。所得的共轭化合物可以通过掺杂剂使其导电，从而获得p型或n型导体的电导材料。
• Unsymmetric Pyrrole, Thiophene, and Furan-Conjugated Comonomers Prepared Using Azomethine Connections: Potential New Monomers for Alternating Homocoupled Products
  作者：Stéphane Dufresne、W. G. Skene

  DOI：10.1021/jo8002503

  日期：2008.5.1

  Unsymmetric comonomers consisting of thiophene, pyrrole, and furan heterocycles were prepared using azomethine bonds. Photophysical investigation of the novel pi-donor-donor-donor segmented compounds revealed that their singlet excited state is only partially deactivated by internal conversion unlike their all-thiophene azomethine analogues. Temperature-dependent steady-state and time-resolved emission studies demonstrated that the unsymmetric compounds deactivated efficiently their singlet excited state by intersystem crossing to populate the triplet manifold. This lower energy state is rapidly deactivated by nonradiative self-quenching. The comonomers and their anodically prepared conjugated homocoupled products are both electrochemically active, resulting in new compounds that can be mutually oxidized and reduced. Meanwhile, the oxidation potentials of the coupled products are shifted by up to 400 mV to more cathodic potentials relative to their corresponding comonomers, confirming their increased degree of conjugation.
• US8034895B2
  申请人：——

  公开号：US8034895B2

  公开（公告）日：2011-10-11