3,5-diphenyldithieno[3,2-b:2',3'-d]thiophene | 500772-25-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩并噻吩类
• 英文名称: 3,5-diphenyldithieno[3,2-b:2',3'-d]thiophene
• 英文别名: DDT；5,9-Diphenyl-3,7,11-trithiatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene
• CAS: 500772-25-8
• 化学式: C₂₀H₁₂S₃
• 分子量: 348.513
• InChiKey: DIWKYECCXUZVHT-UHFFFAOYSA-N

物化性质

• 熔点：
  130-132 °C
• 沸点：
  567.6±50.0 °C(Predicted)
• 密度：
  1.357±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  84.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,5-diphenyldithieno[3,2-b:2',3'-d]thiophene 在 四(三苯基膦)钯 、 tetrakis(triphenylarsine)palladium(0) N-溴代丁二酰亚胺(NBS) 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 溶剂黄146 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 133.0h， 生成 2-(5-methylthien-2-yl)-3,5-diphenyl-6-[5-dimethyl(chloromethyl)silylthien-2-yl]dithieno[3,2-b:2',3'-d]thiophene-4,4-dioxide
  参考文献：
  名称：

  Rigid-Core Fluorescent Oligothiophene-S,S-dioxide Isothiocyanates. Synthesis, Optical Characterization, and Conjugation to Monoclonal Antibodies

  摘要：

  In this paper we report the synthesis of a new class of fluorescent thiophene-based isothiocyanates containing a 3,5-disubstituted dithieno[3,2-b:2',3'-d]thiophene-4,4-dioxide moiety as the rigid core, using the palladium-catalyzed cross-coupling reaction of aryl stannanes with aryl bromides (Stille coupling). By changing the molecular structure through the progressive addition of thienylene or phenylene units, light emission from blue to orange was obtained. Photoluminescence quantum yields ranged from 0.65 to 0.90 for blue and green light emitters to 0.10-0.35 for yellow and orange ones. Optically and chemically stable fluorescent bioconjugates were prepared by spontaneous reaction of the isothiocyanates with monoclonal antibodies anti-CD3 and anti-CD8 in slightly basic solutions.

  DOI：

  10.1021/jo026298o
• 作为产物：
  描述：

  2,5-二溴-3-苯基噻吩 在 正丁基锂 、 溴 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 13.0h， 生成 3,5-diphenyldithieno[3,2-b:2',3'-d]thiophene
  参考文献：
  名称：

  Rigid-Core Fluorescent Oligothiophene-S,S-dioxide Isothiocyanates. Synthesis, Optical Characterization, and Conjugation to Monoclonal Antibodies

  摘要：

  In this paper we report the synthesis of a new class of fluorescent thiophene-based isothiocyanates containing a 3,5-disubstituted dithieno[3,2-b:2',3'-d]thiophene-4,4-dioxide moiety as the rigid core, using the palladium-catalyzed cross-coupling reaction of aryl stannanes with aryl bromides (Stille coupling). By changing the molecular structure through the progressive addition of thienylene or phenylene units, light emission from blue to orange was obtained. Photoluminescence quantum yields ranged from 0.65 to 0.90 for blue and green light emitters to 0.10-0.35 for yellow and orange ones. Optically and chemically stable fluorescent bioconjugates were prepared by spontaneous reaction of the isothiocyanates with monoclonal antibodies anti-CD3 and anti-CD8 in slightly basic solutions.

  DOI：

  10.1021/jo026298o

文献信息

• NOVEL ORGANIC COMPOUND AND ELECTROCHROMIC ELEMENT HAVING THE SAME
  申请人：CANON KABUSHIKI KAISHA

  公开号：US20130190513A1

  公开（公告）日：2013-07-25

  An organic compound represented by the following general formula [1] is provided. In the general formula [1], A 1 to A 4 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group. However, at least one of A 1 to A 4 represents the alkyl group, the alkoxy group, or the aryl group.

  以下是用以下一般式[1]表示的有机化合物。在一般式[1]中，A1到A4分别独立地选自包括氢原子、具有1至20个碳原子的烷基基团、具有1至20个碳原子的烷氧基团和芳基的群。但是，至少有一个A1到A4代表烷基基团、烷氧基团或芳基。
• A new reaction of P4S10 and Lawesson's reagent; a new method for the synthesis of dithieno[3,2-b;2′,3′-d]thiophenes
  作者：Erdal Ertas、Turan Ozturk

  DOI：10.1016/j.tetlet.2004.03.023

  日期：2004.4

  A new reaction of P4S10 and Lawesson's reagent for the synthesis of fused thiophenes has been uncovered. It has given easy access to the synthesis of derivatives of the technologically important heterocycle dithieno[3,2-b;2′,3′-d]thiophene, DTT. Electrochemical polymerization of one of the derivatives has been demonstrated.

  已经发现了P 4 S 10和Lawesson试剂合成稠合噻吩的新反应。它给了容易进入技术上重要的杂环二噻吩并的衍生物的合成[3,2- b ; 2 ' ，3 ' - d ]噻吩，DTT。已经证明了一种衍生物的电化学聚合。
• Selective syntheses of vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs); building blocks for π-conjugated systems
  作者：Ipek Osken、Onur Sahin、Ali S. Gundogan、Hakan Bildirir、Asli Capan、Erdal Ertas、Mehmet S. Eroglu、John D. Wallis、Kevser Topal、Turan Ozturk

  DOI：10.1016/j.tet.2011.11.059

  日期：2012.1

  Selective syntheses of 3,4-vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs), having Ph, 4-CH3OC6H4, 4-BrC6H4, 4-NO2C6H4 and 4-(CH3)2NC6H4 groups, were achieved through the reaction of 1,8-diketone with phosphorus decasulfide (P4S10). The reaction could be shifted between VDTT and DTT by adding base (sodium bicarbonate) or acid (para-toluenesulfonic acid), respectively,

  的3,4- vinylenedithiathiophenes（VDTTs）和二噻吩并[2,3-选择性合成b ; 2'，3'- d ]噻吩（税收协定），具有的pH值，4-CH 3 OC 6 H ^ 4，4- BRC 6 ħ通过4，4 -NO 2 C 6 H 4和4-（CH 3）2 NC 6 H 4基团是通过1，8-二酮与十硫化磷（P 4 S 10）反应而获得的。通过添加碱（碳酸氢钠）或酸（对-甲苯磺酸）分别加入到反应混合物中。虽然VDTT的产量中等，但DTT的合成却取得了重要的成就，与以前的报道相比，DTT的产率更高。VDTT的聚合物是乙二氧基噻吩EDOT的类似物，是使用FeCl 3制备的。不幸的是，所有对其电聚合的尝试都失败了。自旋密度计算表明，在噻吩环的“α”碳原子上，没有任何VDTT具有明显的正自旋密度。考虑到它们的溶解度和官能团（可以进一步衍生），它们是制备新有机材料的有用组成部分。
• ELECTROCHROMIC ELEMENT
  申请人：Canon Kabushiki Kaisha

  公开号：EP2719702B1

  公开（公告）日：2016-05-11
• Fluorene–Dithienothiophene-<i>S,S</i>-dioxide Copolymers. Fine-Tuning for OLED Applications
  作者：Ipek Osken、Ali Senol Gundogan、Emine Tekin、Mehmet S Eroglu、Turan Ozturk

  DOI：10.1021/ma4016592

  日期：2013.12.10

  Three groups of fluorene-dithieno[3,2-b;2',3'-d]-thiophene-S,S-dioxides (DTT-S,S-dioxide) copolymers, each having four different ratios of DTT-S,S-dioxide (5, 15, 25, and 50%) were successfully synthesized through Suzuki coupling method. While the first group copolymers PI had direct connection of fluorene to the peripheral thiophenes of DTT-S,S-dioxide, second group copolymers P2 had a thiophene extension between fluorene and DTT-S,S-dioxide, and in the third group, copolymers P3, fluorene had a connection with DTT-S,S-dioxide through the phenyl moiety of DTT. Absorbance and emission measurements of first two groups P1 and P2 displayed a regular bathochromic shift with increasing content of DTT-S,S-dioxide, which was more clearly observed in their solid state fluorescence measurements. Introduction of thiophene to the peripherals of the DTT-S,S-dioxide in copolymers P2 caused even further bathochromic shift in absorbances and emissions. As the absorbance and emission of PI went up to 447 and 558 nm in solution, respectively, P2 had them at 472 and 592 nm, respectively. In solid state, emissions of 131 and P2 even went further up to 585 and 646 nm, respectively. The bathochromic trend of 131 and P2 became opposite with absorbance and solid state emission of P3, which had a hypsochromic shift with increasing content of DTT-S,S-dioxide. Solid state emission of P3, particularly the copolymers having 5, 15 and 50% DTT-S,S-dioxide, covered a wide region between 400 and 675 nm. A spread of colors from light blue (border of white) to red through green and yellow was obtained with the OLED applications of the copolymers. Their optical and electronic band gaps varied between 2.17 and 2.99 eV and between 2.68 and 3.57 eV, respectively. While the highest quantum yield was obtained with P2 (5%) as 0.66, the lowest was observed with P2 (50%) as 0.03. Almost all of the polymers displayed good thermal stabilities. No weight loss was observed with the copolymers P2 (5-15%) and P3 up to 400 degrees C.