Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer

A bis-thienylpyrrole, 4-c technology is applied in the field of chemical preparation of high molecular polymer materials, which can solve the problems of poor stability of raw material organometallic reagents, inability to be prepared, poisoning human and animal health, etc., and achieves improved atom economy and efficiency. Environmental friendliness, avoidance of organometallic waste, and beneficial effects on industrial production

Inactive Publication Date: 2013-04-03
SICHUAN UNIV
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Problems solved by technology

However, this type of traditional coupling reaction has obvious disadvantages: (1) From the starting raw material aromatic (hetero) ring to the coupling product, there are at least three organic synthesis steps, involving the synthesis of intermediate C-X compounds and the synthesis of C-M compounds. Synthesis and coupling reactions, many steps, long routes, complex organic synthesis operations, harsh conditions, and low overall yield; (2) One of the reaction intermediates is an organometallic reagent, which is difficult to prepare, except for raw materials (boric acid reagents, organic tin Reagents, etc.) are expensive, the steps are cumbersome, the conditions are harsh (such as anhydrous and oxygen-free environment, etc.), the operation difficulty is increased, the total yield is reduced, and the cost is increased; at the same time, the raw material organometallic reagents have poor stability, and some cannot withstand acceptance. Some of the following coupling reactions cannot even be prepared and exist stably, which greatly limits the breadth of raw materials and products, and limits the possibility of molecular modification and property adjustment of materials; (3) traditional coupling reactions It will produce an equivalent amount of metal organic reagent waste, such as tin reagent waste, poisoning human and animal health and causing environmental pollution

Method used

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  • Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer
  • Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer
  • Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Step (1): Raw material A is 2,5-bis(2-octyldodecyl)-3,6-bis(2-thienyl)pyrrolo[3,4- c ]pyrrole-1,4-dione (1.72 g, 2.0 mmol), starting material B is 4,7-dibromo-2,1,3-benzothiadiazole (588 mg, 2.0 mmol), catalyst is palladium acetate (22 mg, 0.1 mmol), the ligand is triphenylphosphine (105 mg, 0.4 mmol), the additive is pivalic acid (204 mg, 2.0 mmol), the base is potassium carbonate (829 mg, 6.0 mmol), the solvent is N, N -Dimethylacetamide (10 mL), add the above reagents into the reactor, stir evenly under anhydrous and oxygen-free conditions, heat to 120 °C, and react for 24 hours;

[0039]Step (2): After the reaction is completed, cool the reaction bottle to room temperature, add a small amount of chloroform and stir evenly, pour into the mixed system of methanol and water, stir, and filter. The collected solids were placed in a Soxhlet extractor, extracted with methanol, acetone, and n-hexane in sequence, and the remaining solids were extracted with chloroform, the...

Embodiment 2

[0041] Step (1): Raw material A is 2,5-bis(2-octyldodecyl)-3,6-bis(2-(4-fluorothiophene)yl)pyrrolo[3,4- c ]pyrrole-1,4-dione (1.79 g, 2.0 mmol), starting material B is 4,7-dibromo-5,6-dimethyl-2,1,3-benzothiadiazole (515 mg, 1.6 mmol), the catalyst is trans-di( mu -acetic acid) bis[o-(bis(o-tolylphosphino)benzyl]dipalladium(II) (18.8 mg, 0.02 mmol), ligand tris(o-methoxyphenyl)phosphine (28.2 mg, 0.08 mmol), the additive is adamantane acid (541 mg, 3.0 mmol), the base is cesium carbonate (2.28 g, 7.0 mmol), and the solvent is tetrahydrofuran (4 mL). Stir evenly under the conditions and then heat to 90°C for 48 hours of reaction;

[0042] Step (2): Refer to the operation step (2) of Example 1 to obtain 1.39 g of the target copolymer, with a yield of 82%, M n = 14600 Da, M w / M n = 4.67. Proton NMR spectrum (deuterated chloroform as solvent, Bruker AMX-400 NMR instrument) 1 H NMR (400 MHz, CDCl 3 ): 1 H NMR (400 MHz, CDCl 3 ): δ = 0.85 (br, 12H), 1.20-1.60 (m...

Embodiment 3

[0044] Step (1): Raw material A is 2,5-bis(2-(2-ethoxy)ethoxy)methyl)-3,6-bis(2-(3,4-dimethylthienyl) ) pyrrolo[3,4- c ]pyrrole-1,4-dione (1.12 g, 2.0 mmol), starting material B is 2,7-dibromo- N -(2-Octyldodecyl)carbazole (1.51 g, 2.5 mmol), the catalyst is palladium chloride (7.1 mg, 0.04 mmol), and the ligand is tricyclohexylphosphine tetrafluoroborate (14.7 mg, 0.04 mmol), without additives, the base is potassium phosphate (849 mg, 4.0 mmol), the solvent is N, N -Dimethylacetamide / xylene=1:1 (v / v, 20 mL), add the above reagents into the reactor, stir evenly under anhydrous and oxygen-free conditions, heat to 135 °C, and react for 3 hours;

[0045] Step (2): Refer to the operation step (2) of Example 1 to obtain 1.73 g of the target copolymer, with a yield of 86%. M n = 32000 Da, M w / M n = 3.85. Proton NMR spectrum (deuterated chloroform as solvent, Bruker AMX-400 NMR instrument) 1 H NMR (400 MHz, CDCl 3 ): δ = 0.79 (br, 6H), 1.16-1.61 (m, 38H), 1.96-2.35...

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Abstract

The invention relates to preparation method of a bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer, which belongs to the technical field of chemical preparation of high-molecular polymer materials. According to the preparation method, under an appropriate condition, bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone as a raw material A and a dibromo-(hybrid) aromatic compound as a raw material B are directly react to obtain a target copolymer. Compared with the traditional method, the preparation method provided by the invention has obvious advantages, prevents the preparation link of an organic metal reagent, decreases the preparation steps, increases the overall yield, reduces the cost, prevents a great amount of toxic and harmful organic metal reagent wastes from being generated and is more conductive to the industrialized production.

Description

technical field [0001] The present invention relates to a class of bisthienylpyrrolo[3,4- c ] The preparation method of pyrrole-1, 4-dione and (hetero) arene copolymer belongs to the chemical preparation technology of high molecular polymer materials. Background technique [0002] Pyrrolo[3,4- c ]Pyrrole-1,4-diketone polymers have a special planar molecular structure, which can form good intermolecular packing, and have unique optoelectronic properties, such as low energy gap, high electron / hole mobility, and large molar absorptivity , especially in the near-infrared spectral region, has strong absorption, strong fluorescence emission, high quantum yield, and good light and thermal stability, so it has received extensive attention and attention in the fields of biochemistry, medicine, analytical chemistry, and material science. application. In recent years, the use of this type of polymer to develop various photovoltaic functional materials has become a very active field ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G61/12
Inventor 吴迪郭强游劲松董嘉兴
Owner SICHUAN UNIV
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