Bi-thienopyridine type derivative and preparation method thereof

A technology of phenopyridines and derivatives is applied in the field of organic synthesis, which can solve the problem of high yield and achieve the effects of high yield, high atom economy and simple operation process

Inactive Publication Date: 2015-11-04
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The compound has a novel structure, has not been reported in the literature, and has good performa

Method used

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  • Bi-thienopyridine type derivative and preparation method thereof
  • Bi-thienopyridine type derivative and preparation method thereof
  • Bi-thienopyridine type derivative and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0029] Add 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile (1mmol) and cyclohexanone (3mL) into a 25ml single-necked flask, stir until uniformly dispersed, add AlCl 3 (2mmol), and then rapidly heated to reflux, and reacted with magnetic stirring for 3.0h. After the reaction, directly filter and wash with water to obtain a solid mixture. The crude product was recrystallized from DMF to obtain a white solid (1) with a yield of 74% (the recrystallization mother liquor was recovered). The reaction formula of 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile and cyclohexanone is:

[0030]

[0031] The spectral data of product (1) is: 1 H NMR (DMSO-d 6 ,400MHz)δ:7.25(s,4H,NH 2 ),3.27(s,4H,CH 2 ),2.57(s,4H,CH 2 ), 1.83(s,8H,CH2). 13 C NMR (DMSO-d 6 ,100MHz) δ: 153.8, 149.7, 145.2, 143.9, 118.9, 111.4, 109.2, 31.0, 23.3, 21.76.

Embodiment 2

[0033] Add 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile (1mmol) and cyclopentanone (5mL), 2ml toluene into a 10ml microwave tube, stir until uniformly dispersed, add ZnCl 2 (0.5 mmol), reacted at 120° C. for 30 min with a microwave reaction synthesizer. After the reaction, filter and wash with water. The crude product was recrystallized from ethanol to obtain a light brown solid (2) with a yield of 70% (recovered from the recrystallized mother liquor). The reaction formula of 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile and cyclopentanone is:

[0034]

[0035] The spectral data of product (2) is: 1 H NMR (DMSO-d 6 ,400MHz)δ:7.36(s,4H,NH 2 ),3.20(t,J=7.77Hz,4H,CH 2 ), 2.87(t, J=7.33Hz, 4H, CH 2 ),2.21-2.17(m,4H,CH 2 ). 13 C NMR (DMSO-d 6,100MHz) δ: 162.0, 148.1, 145.0, 144.4, 119.6, 116.4, 32.9, 27.6, 22.0.

Embodiment 3

[0037] In a 25 mL mortar, add 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile (1 mmol) and cycloheptanone (6 mL), 3 mL of methanol, stir until uniformly dispersed, Add p-toluenesulfonic acid (3 mmol) and triturate at room temperature for 30 min. After the reaction, 5 mL of ethanol was added, filtered and washed with water. The crude product was recrystallized from a mixed solvent of methanol and dichloromethane to obtain an off-white solid (3) with a yield of 67% (recovered from the recrystallization mother liquor). The reaction formula of 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile and cycloheptanone is:

[0038]

[0039] The spectral data of product (3) is 1 H NMR (DMSO-d 6 ,400MHz)δ:7.20(s,4H,NH 2 ), 3.35 (d, J=9.25, 4H, CH 2 ), 2.88 (d, J=9.15, 4H, CH 2 ),1.82(s,4H,CH 2 ),1.69(s,4H,CH 2 ), 1.59 (d, J=6.94, 4H, CH 2 ). 13 C NMR (DMSO-d 6 ,100MHz) δ: 160.8, 148.8, 143.1, 120.4, 116.9, 43.2, 36.5, 30.8, 29.8, 26.3, 23.6.

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Abstract

The invention discloses a bi-thienopyridine type derivative and a preparation method thereof. The bi-thienopyridine derivative disclosed by the invention adopts a rigid near plane structure, a skeleton structure is the combination of thiophthene and pyridine, a conjugation system is larger, and the double-thienopyridine derivative belongs to the technical field of synthesis. The general formula of a preparation reaction is shown as follows. The coordination compound uses 3, 4-diamino thieno [2, 3-b] thiophene -2, 5- denitrile as a raw material, under the induction of a catalyst, the raw material and ketone or aldehyde generate a Friedlander reaction, and a series of bi-thienopyridine derivatives are synthesized in a one-pot method. The operation process is simple, the atom economy is high, the reaction conditions are mild, and the yield is high. The material of the derivative can be used as a luminescent material, and can be used as the material of a luminous layer in a light emitting device. The synthetic method is one of the manners of magnetic stirring, hydrothermal reactions, microwaves, solid phase synthesis and the like. Through the adoption of the preparation method disclosed by the invention, different substrates can be used for synthesizing various bi-thienopyridine type derivatives which are not reported in literatures.

Description

(1) Technical field [0001] The invention discloses a novel bisthienopyridine derivative and a preparation method thereof, belonging to the technical field of organic synthesis. (2) Background technology [0002] As one of the most widely used ligands in coordination chemistry, pyridine compounds have been widely used in many fields, such as molecular catalysis, pharmaceutical and chemical industries (such as anti-tumor drugs, nucleic acid probes), optoelectronics (solar cells, Organic electroluminescence materials), etc. (Chem.Soc.Rev., 2014.43(15):5302-5325.). In recent years, the research work on pyridine ligands mainly focuses on the following types: quinoline (ql), 8-hydroxyquinoline (8-oql), naphthyridine (naph), bipyridine (dp), terpyridine (tp ), o-phenanthroline (phen) and other skeleton structures (Chem.Soc.Rev., 2009.38(6):1690-1700.Scheme 1). Taking o-phenanthroline as an example, as a bidentate ligand with a planar rigid structure, it contains two nitrogen atom...

Claims

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Application Information

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IPC IPC(8): C07D495/22C09K11/06
CPCC07D495/22C09K11/06C09K2211/1029C09K2211/1092
Inventor 李加荣杨俊娟邱发东史大昕张奇
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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