4-[2,2']-(bithiophen-5-yl)pyrimidine | 63463-01-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 双噻吩和低聚噻吩
• 英文名称: 4-[2,2']-(bithiophen-5-yl)pyrimidine
• 英文别名: 4-[5-(2-Thienyl)-2-thienyl]pyrimidine；4-(5-thiophen-2-ylthiophen-2-yl)pyrimidine
• CAS: 63463-01-4
• 化学式: C₁₂H₈N₂S₂
• 分子量: 244.341
• InChiKey: SCMHIYCRXHXJAJ-UHFFFAOYSA-N

物化性质

• 熔点：
  113-115 °C
• 沸点：
  397.8±32.0 °C(Predicted)
• 密度：
  1.317±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  82.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-[2,2']-(bithiophen-5-yl)pyrimidine 在 N-溴代丁二酰亚胺(NBS) 、 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.5h， 生成 diphenyl[4-(5'-pyrimidin-4-yl-[2,2']bitiophenyl-5-yl)-phenyl]amine
  参考文献：
  名称：

  含嘧啶染料作为染料敏化太阳能电池的光敏剂的合成，光谱和电化学性质

  摘要：

  通过微波辅助的Suzuki交叉偶联和氢反应的亲核芳族取代相结合，以高收率获得了六种以嘧啶为锚定基团的新型供体-π-受体有机染料。对其吸收，光致发光和电化学性质进行了详细的研究。吸附在TiO 2上的染料的红外光谱表明，在染料的嘧啶环与TiO 2表面的路易斯酸位点（暴露的Ti n +阳离子）之间形成了配位键。这项工作表明染料敏化剂的嘧啶环与TiO 2的路易斯酸位点形成配位键表面是有希望的候选物作为吸电子锚定基团。来自量子计算的数据表明，对于染料敏化太阳能电池，所有染料都是潜在的良好光敏剂。

  DOI：

  10.1016/j.dyepig.2013.09.006
• 作为产物：
  描述：

  5-bromo-4-(5-bromothiophen-2-yl)-3,4-dihydropyrimidinium trifluoroacetate 在 四(三苯基膦)钯 、 potassium carbonate 、 二乙胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 24.25h， 生成 4-[2,2']-(bithiophen-5-yl)pyrimidine
  参考文献：
  名称：

  Suzuki-Miyaura交叉偶联与氢的亲核芳族取代（小号ñH）反应作为带有噻吩片段的嘧啶的通用途径

  摘要：

  研究表明，Suzuki-Miyaura交叉偶联和亲核氢取代反应是合成4-（噻吩-2-基）-，5-（噻吩-2-基）-，和来自市售的5-溴嘧啶的4，5-二（噻吩-2-基）取代的嘧啶。这小号ñH （AE）-和 小号ñH气相色谱/质谱法研究了5-溴嘧啶与噻吩和2-溴噻吩的（AO）反应。中间σ的结构ħ -adducts，以及噻吩（噻吩基）嘧啶和bithiophene-（噻吩基）嘧啶二分体已首先通过X射线晶体学分析确定。

  DOI：

  10.1016/j.tet.2012.04.095

文献信息

• Synthesis, photophysics, and electrochemistry of thiophene–pyridine and thiophene–pyrimidine dyad comonomers
  作者：Andréanne Bolduc、Stéphane Dufresne、Garry S. Hanan、W. G. Skene

  DOI：10.1139/v09-166

  日期：2010.3

  A series of new π-conjugated donor (D) and acceptor (A) dyad comonomers were prepared using Suzuki coupling protocols. The D–A comonomers consisting of thiophene/bithiophene as donors and pyridine/pyrimidine as acceptors were prepared to investigate their photophysical and electrochemical properties. The dyads were spectroscopically confirmed to be highly conjugated. This was further supported by the X-ray crystal structure of the bithophene–pyridine dyad that showed all the heterocycles to be coplanar. It was further found that the fluorescence yields (Φ_fl) of the dyads were highly dependent on the number of thiophenes. The bithiophene derivatives exhibited Φ_fl values ≥ 0.3 while the thiophene derivatives did not fluoresce. The suppressed fluorescence observed for the thiophene derivatives was due to their higher triplet energy resulting in efficient intersystem crossing (ISC) to the triplet state with Φ_ISC ≥ 0.8. This was confirmed both by time-resolved and steady-state measurements. The singlet excited state of both thiophene and bithiophene dyads was deactivated solely by either fluorescence and (or) ISC. Owing to their donor and acceptor character, the dyads could be oxidized and reduced both electrochemically and photochemically to afford the radical cation and anion, respectively.

  利用铃木偶联协议制备了一系列新的π-共轭供体（D）和受体（A）二元共聚物。以噻吩/联噻吩为给体，吡啶/嘧啶为受体制备了 D-A 共聚单体，以研究它们的光物理和电化学性质。这些二元体经光谱证实具有高度共轭性。双噻吩-吡啶二元化合物的 X 射线晶体结构进一步证实了这一点，该结构显示所有杂环都是共面的。研究还发现，二元化合物的荧光产率（Φfl）与噻吩的数量密切相关。噻吩衍生物的 Φfl 值≥ 0.3，而噻吩衍生物则不产生荧光。噻吩衍生物的荧光被抑制的原因是它们的三重态能量较高，从而导致高效的系统间交叉（ISC）到三重态（ΦISC ≥ 0.8）。时间分辨和稳态测量都证实了这一点。噻吩和双噻吩二元体的单线激发态仅通过荧光和（或）ISC 失活。由于其供体和受体特性，二元化合物可以通过电化学和光化学方式氧化和还原，分别产生自由基阳离子和阴离子。
• Synthesis, and structure–activity relationship for C(4) and/or C(5) thienyl substituted pyrimidines, as a new family of antimycobacterial compounds
  作者：Egor V. Verbitskiy、Ekaterina M. Cheprakova、Pavel A. Slepukhin、Marionella A. Kravchenko、Sergey N. Skornyakov、Gennady L. Rusinov、Oleg N. Chupakhin、Valery N. Charushin

  DOI：10.1016/j.ejmech.2015.05.007

  日期：2015.6

  Combination of the Suzuki cross-coupling and nucleophilic aromatic substitution of hydrogen (SNH) reactions proved to be a convenient method for the synthesis of C(4) and/or C(5) mono(thienyl) and di(thienyl) substituted pyrimidines from commercially available 5-bromopyrimidine. All new pyrimidines were found to be active in micromolar concentrations in vitro against H37Rv, avium, terrae, rifampicin

  铃木交叉偶联和亲核氢取代的结合（小号ñH）反应被证明是从市售的5-溴嘧啶合成C（4）和/或C（5）单（噻吩基）和二（噻吩基）取代的嘧啶的简便方法。所有新的嘧啶被发现是在微摩尔浓度的活性在体外针对ħ 37 RV，鸟，terrae，利福平的和异烟肼耐药的菌株结核分枝杆菌。对于这些化合物，已经获得了小鼠急性体内毒性的数据，这些化合物似乎是有希望的抗结核药。
• Synthesis of 6-thienyl-substituted 2-amino-3-cyanopyridines
  作者：E. V. Verbitskiy、E. M. Cheprakova、M. G. Pervova、G. G. Danagulyan、G. L. Rusinov、O. N. Chupakhin、V. N. Charushin

  DOI：10.1007/s11172-015-0920-8

  日期：2015.3

  An efficient method for the synthesis of 6-thienyl-substituted 2-amino-3-cyanopyridines by the ring transformation in the corresponding pyrimidines was developed. Further modification of the pyridines obtained under conditions of a room temperature aerobic Suzuki reaction in the presence of trans-bis(dicyclohexylamine)palladium(II) acetate as a catalyst was studied

  开发了一种通过相应嘧啶的环变换高效合成6-噻吩基取代的2-氨基-3-氰基吡啶的方法。在室温空气中使用反式双（环己胺）钯（II）乙酸酯作为催化剂的条件下，对其获得的吡啶进行了进一步的修饰研究。
• Synthesis and characterization of new complexes derived from 4-thienyl substituted pyrimidines
  作者：Ekaterina M. Cheprakova、Egor V. Verbitskiy、Mikhail A. Kiskin、Grigory G. Aleksandrov、Pavel A. Slepukhin、Aleksei A. Sidorov、Denis V. Starichenko、Yuri N. Shvachko、Igor L. Eremenko、Gennady L. Rusinov、Valery N. Charushin

  DOI：10.1016/j.poly.2015.07.016

  日期：2015.11

  in details. In particular, mononuclear Co(II) complexes 1 and 4 proved to exhibit paramagnetism with large positive zero-field splitting parameters. Dinuclear Co(II) complexes 2a,b show weak antiferromagnetic interactions. Dinuclear Cu(II) complexes 5a,b demonstrate strong antiferromagnetic superexchange interactions via four carboxylate bridges. The systems 2a,b and 5a,b are isolated as exchange coupled

  摘要研究了4-噻吩基取代的嘧啶配体（L1-3）与3d金属的各种盐（Co，Zn，Ni，Cu）和铂类化合物（Pt，Pd）的一系列反应。特别是单核Co（OTf）2（L1-3）2（H2O）2（MeCN）2（1），双核Co2（Piv）2（L1-3）4（2a，b），Cu2（Piv）2已获得（L1-3）2（5a，b），多金属多核Li2Co2（Piv）6（L1-3）2（4）和螯合[（L1）Pd（OAc）] 2（6）配合物。所有配合物的结构均已通过X射线衍射确定。还详细研究了配位化合物1、2、4和5的磁性。特别是，单核Co（II）配合物1和4被证明具有大正零场分裂参数的顺磁性。双核Co（II）配合物2a，b显示弱的反铁磁相互作用。双核Cu（II）配合物5a，b显示了通过四个羧酸盐桥的强反铁磁超交换相互作用。系统2a，b和5a，b被隔离为交换耦合二聚体。
• Microwave-assisted palladium-catalyzed C–C coupling versus nucleophilic aromatic substitution of hydrogen (SNH) in 5-bromopyrimidine by action of bithiophene and its analogues
  作者：Egor V. Verbitskiy、Ekaterina M. Cheprakova、Ekaterina F. Zhilina、Mikhail I. Kodess、Marina A. Ezhikova、Marina G. Pervova、Pavel A. Slepukhin、Julia O. Subbotina、Aleksandr V. Schepochkin、Gennady L. Rusinov、Oleg N. Chupakhin、Valery N. Charushin

  DOI：10.1016/j.tet.2013.04.062

  日期：2013.6

  5-Bromopyrimidine reacts with 2,2'-bithiophene, [2,2':5',2 '']terthiophene and 2-phenylthiophene in the presence of a palladium catalyst to give 5-(het)aryl substituted pyrimidines due to the palladium-catalyzed aryl-aryl C-C coupling. However 5-bromo-4-(het)aryl-pyrimidines have been prepared from the same starting materials through the S-N(H)-reaction catalyzed by a Lewis acid. Conditions for both types of reactions were optimized. All components of the reaction mixtures, including by-products, have been elucidated by gas-liquid chromatography/mass-spectrometry. Evidence for the structure of 4- and 5-bithiophenyl-substituted pyrimidines has first been obtained by means of X-ray crystallography analysis. Molecular orbital calculations (TDDFT), as well as the redox and optical measurements for all new compounds have also been performed. (C) 2013 Elsevier Ltd. All rights reserved.