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CN103554130A - 2-(4-substituted benzoyl)-4,6-dibromo thiophene bithiophene and preparation method and application thereof - Google Patents

2-(4-substituted benzoyl)-4,6-dibromo thiophene bithiophene and preparation method and application thereof Download PDF

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CN103554130A
CN103554130A CN201310508714.9A CN201310508714A CN103554130A CN 103554130 A CN103554130 A CN 103554130A CN 201310508714 A CN201310508714 A CN 201310508714A CN 103554130 A CN103554130 A CN 103554130A
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substituted benzoyl
thiophene
thienothiophene
benzoyl
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陈军武
孙江曼
曹镛
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South China University of Technology SCUT
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/18—Definition of the polymer structure conjugated
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene

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Abstract

本发明涉及一种2-(4-取代苯甲酰基)-4,6-二溴噻吩并噻吩及其制备方法与应用。2-(4-取代苯甲酰基)-4,6-二溴噻吩并噻吩的取代基包括对氟苯甲酰基，对三氟甲基苯甲酰基，对烷基苯甲酰基；所述的制备方法包括2-(4-氟苯甲酰基)-4,6-二溴噻吩并噻吩或2-(4-三氟甲基苯甲酰基)-4,6-二溴噻吩并噻吩或2-(4-烷基苯甲酰基)-4,6-二溴噻吩并噻吩的制备，制备方法具有工艺简便和快捷制备的特征。本发明可用于构造新型含有2-(4-取代苯甲酰基)噻吩并噻吩的分子材料和基于2-(4-取代苯甲酰基)噻吩并噻吩的聚合物，以应用于具有广阔前景的有机光电子器件。The invention relates to 2-(4-substituted benzoyl)-4,6-dibromothienothiophene and its preparation method and application. The substituents of 2-(4-substituted benzoyl)-4,6-dibromothienothiophene include p-fluorobenzoyl, p-trifluoromethylbenzoyl, p-alkylbenzoyl; the preparation Methods include 2-(4-fluorobenzoyl)-4,6-dibromothienothiophene or 2-(4-trifluoromethylbenzoyl)-4,6-dibromothienothiophene or 2-( The preparation of 4-alkylbenzoyl)-4,6-dibromothienothiophene has the characteristics of simple and fast preparation process. The present invention can be used to construct novel molecular materials containing 2-(4-substituted benzoyl)thienothiophenes and polymers based on 2-(4-substituted benzoyl)thienothiophenes to be applied in promising organic optoelectronic devices.

Description

A kind of 2-(4-substituted benzoyl)-4,6-dibromo thiophene thiophthene and preparation method thereof and application
Technical field
The present invention relates to a kind of compound that is applied to photoelectron material and devices field, more specifically relate to a kind of 2-(4-substituted benzoyl)-4,6-dibromo thiophene thiophthene and preparation method thereof is in application.
Background technology
Since Japanese scientist's Hideki Shirakawa in 1977 is found polyacetylene conduction, this being called as the conductive polymers of " the 4th generation polymer " material with its outstanding photoelectric properties, attracted numerous scientists to study.Conducting polymer is compared with the inorganic materials with identical or close purposes, has density low, and easily processing, synthesizes the advantages such as range of choice is wide.Due to the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may being applied on many electronics or opto-electronic device, for example comprise polymer LED, photovoltaic cell, field effect transistor etc.Potential application prospect and wide application field impel scientist competitively to study the conjugation material that this class has photoelectric activity, comprise the small molecules of multiple conjugated structure, and polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes, polycarbazole etc.
Researchist is making great efforts to seek to improve polymer LED always, photovoltaic cell, and the method for field effect transistor performance, material is one of most important factor.So being devoted to exploitation always, many research groups there is high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good, and the polymkeric substance that visible-range absorption bands is wide, carrier mobility is high.Realize these targets, need to develop more novel conjugated molecular material and polymer materials, wherein design synthesizing new conjugate unit and just seem very important.
In recent years, some dibromo thiophene thiophthene molecule application aspect organic photovoltaic battery are rather extensive, and " Nature Photonics " be 6(2012 (Nat.Photonics)) 591 enumerated the outstanding behaviours of the performance of thienothiophene molecule aspect organic solar batteries.
Summary of the invention
The object of the invention is to the deficiency existing for prior art; 2-(4-substituted benzoyl)-4 is provided; 6-dibromo thiophene thiophthene; can be used for constructing novel 2-(4-substituted benzoyl)-4; the molecular material of 6-dibromo thiophene thiophthene and novel containing 2-(4-substituted benzoyl)-4,6-dibromo thiophene thiophthene polymer materials.
The present invention also aims to the 2-(4-substituted benzoyl)-4 that provides described, the preparation method of 6-dibromo thiophene thiophthene thiophthene.
2-of the present invention (4-substituted benzoyl)-4,6-dibromo thiophene thiophthene has structure as follows:
Figure BDA0000401583670000021
Wherein, R 1for fluorine or trifluoromethyl or hydrogen or C 1～C 23alkyl.
Structure 2-(4-substituted benzoyl)-4, the preparation method of 6-dibromo thiophene thiophthene, comprises following five steps:
The first step is prepared 2-(4-substituted benzoyl) thiophene: in the dichloromethane solution flask of thiophene is housed, add 4-fluorobenzoyl chloride or 4-trifluoromethyl benzoyl chloride or 4-alkylbenzene formyl chloride, start to stir, under ice bath, add aluminum chloride, normal-temperature reaction three hours, reactant is poured in the beaker that mixture of ice and water is housed, add appropriate concentrated hydrochloric acid, stir, use dichloromethane extraction product, use anhydrous magnesium sulfate drying organic phase, after separated, except desolventizing, with silica gel chromatographic column separation, obtain target product;
Second step prepares 4; 5-dichloromethyl-2-(4-substituted benzoyl) thiophene: add 2-(4-substituted benzoyl) thiophene in reaction flask; add chloromethyl methyl ether; start to stir, under ice bath, drip titanium tetrachloride, be heated to 50 degrees Celsius of reactions 6 hours; cooling; reactant is poured on ice and stirred, with dichloromethane extraction, after separation, remove desolventizing and obtain target product.
The 3rd step prepares 4; 6-dihydro-2-(4-substituted benzene formyl) thienothiophene: add methyl alcohol and be heated to boiling in reaction flask; add 4; 5-dichloromethyl-2-(4-substituted benzoyl) thiophene; the methanol solution that slowly adds sodium sulphite; react 2 hours cooling, remove methanol solvate, with silica gel chromatographic column separation, obtain target product.
The 4th step is prepared 2-(4-substituted benzoyl) thienothiophene: in reaction flask, add 4; 6-dihydro-2-(4-substituted benzene formyl) thienothiophene, adds chloroform to stir, and adds benzoyl peroxide formic acid under-40 degrees Celsius; room temperature reaction spends the night; remove organic solvent, the reactant obtaining is dissolved with acetic anhydride, be heated to 138 degree; react two hours; cooling, remove acid anhydrides, with silica gel chromatographic column separating-purifying, obtain target product.
The 5th step is prepared 2-(4-substituted benzoyl)-4; 6-dibromo thiophene thiophthene: add 2-(4-substituted benzoyl) thienothiophene in reaction flask; and add dimethyl formamide to dissolve; add N-bromo-succinimide reaction 30 minutes; with dichloromethane extraction, dimethyl formamide is removed in washing, uses anhydrous magnesium sulfate drying organic phase; after separated, except desolventizing, with silica gel chromatographic column separating-purifying, obtain target product.
The present invention also can be used for constructing novel containing 2-(4-substituted benzoyl)-4, the molecular material of 6-dibromo thiophene thiophthene and based on containing 2-(4-substituted benzoyl)-4, and 6-dibromo thiophene thiophthene is the polymkeric substance of backbone structure unit.
Compared with prior art, tool of the present invention has the following advantages and effect:
The invention provides novel thienothiophene unit, there is originality, greatly enriched with thienothiophene unit and constructed corresponding molecular material and polymer materials, thereby aspect optoelectronic device applications, providing more material to select for these materials.The present invention also provides concrete 2-(4-substituted benzoyl)-4; the preparation method of 6-dibromo thiophene thiophthene unit; the feature with easy and quick preparation, this provides good technical support for preparing novel molecular material and polymer materials containing thienothiophene unit.
Embodiment
Embodiment 1:
2-(4-fluoro benzoyl) preparation of thiophene, reaction formula is as follows:
Figure BDA0000401583670000041
In 250 milliliters of two mouthfuls of flasks, add 100 mmole thiophene, add 100 milliliters of methylene dichloride to make solvent, add 100 mmole 4-fluorobenzoyl chlorides, cooling under ice-water bath, add 120 mmole aluminum chlorides in batches, react 3 hours, mixture is poured into and in 200 grams of ice, added 25 milliliters of concentrated hydrochloric acids, stir separatory dichloromethane extraction water layer three times, anhydrous magnesium sulfate drying organic phase, after separated, except desolventizing, with silica gel chromatographic column separating-purifying, obtain pale solid.Warp 1hNMR, 13cNMR, and the bright target product 2-(4-of ultimate analysis test chart fluoro benzoyl) thiophene.
Embodiment 2:
2-(4-trifluoromethyl benzoyl) preparation of thiophene, reaction formula is as follows:
Figure BDA0000401583670000042
In 250 milliliters of two mouthfuls of flasks, add 100 mmole thiophene, add 100 milliliters of methylene dichloride to make solvent, add 100 mmole 4-trifluoromethyl benzoyl chlorides, cooling under ice-water bath, add 120 mmole aluminum chlorides in batches, react 3 hours, mixture is poured into and in 200 grams of ice, added 25 milliliters of concentrated hydrochloric acids, stir separatory dichloromethane extraction water layer three times, anhydrous magnesium sulfate drying organic phase, after separated, except desolventizing, with silica gel chromatographic column separating-purifying, obtain pale solid.Warp 1hNMR, 13cNMR, and the bright target product 2-(4-of ultimate analysis test chart trifluoromethyl benzoyl) thiophene.
Embodiment 3:
2-(4-alkylbenzene formyl radical) preparation of thiophene, reaction formula is as follows:
Figure BDA0000401583670000051
Now take preparation 2-(4-nonyl benzene formyl radical) thiophene is explained as example; in 250 milliliters of two mouthfuls of flasks; add 100 mmole thiophene; add 100 milliliters of methylene dichloride to make solvent; add 100 mmole 4-nonyl benzene formyl chlorides; cooling under ice-water bath; add 120 mmole aluminum chlorides in batches; react 3 hours, mixture is poured in 200 grams of ice and added 25 milliliters of concentrated hydrochloric acids, stir; separatory dichloromethane extraction water layer three times; anhydrous magnesium sulfate drying organic phase, separated rear except desolventizing, with silica gel chromatographic column separating-purifying, obtain pale solid.Warp 1hNMR, 13cNMR, and the bright target product 2-(4-of ultimate analysis test chart nonyl benzene formyl radical) thiophene.
Wherein R alkyl also comprises: methyl, and ethyl, hexyl, dodecyl etc., but be not limited only to this.
Embodiment 4:
4,5-dichloromethyl-2-(4-fluoro benzoyl) preparation of thiophene, reaction formula is as follows:
Figure BDA0000401583670000052
In the two-mouth bottle of 250 milliliters, add 90 mmole 2-(4-fluoro benzoyls) thiophene, add 450 mmole chloromethyl methyl ethers, be stirred to dissolving; the titanium tetrachloride of saying 108 mmoles joins in dropping funnel; under ice-water bath, be added dropwise in flask, normal-temperature reaction 1 hour, is heated to 50 degrees Celsius and refluxes 5 hours; be cooled to room temperature; mixture is poured in frozen water and stirred one hour, add dichloromethane extraction, separatory; solvent evaporated, product is directly used in next step without purification.
Embodiment 5:
4,5-dichloromethyl-2-(4-trifluoromethyl benzoyl) preparation of thiophene, reaction formula is as follows:
Figure BDA0000401583670000061
In the two-mouth bottle of 250 milliliters, add 90 mmole 2-(4-trifluoromethyl benzoyls) thiophene, add 450 mmole chloromethyl methyl ethers, be stirred to dissolving, the titanium tetrachloride of saying 108 mmoles joins in dropping funnel, under ice-water bath, be added dropwise in flask, normal-temperature reaction 1 hour, being heated to 50 degrees Celsius refluxes 5 hours, be cooled to room temperature, mixture is poured in frozen water and stirred one hour, add dichloromethane extraction, separatory, solvent evaporated, obtain target product 4, 5-dichloromethyl-2-(4-trifluoromethyl benzoyl) thiophene is directly used in next step without purification.
Embodiment 6:
4,5-dichloromethyl-2-(4-alkylbenzene formyl radical) preparation of thiophene, reaction formula is as follows:
With 4, 5-dichloromethyl-2-(4-nonyl benzene formyl radical) thiophene is prepared as example, in the two-mouth bottle of 250 milliliters, add 90 mmole 2-(4-nonyl benzene formyl radicals) thiophene, add 450 mmole chloromethyl methyl ethers, be stirred to dissolving, the titanium tetrachloride of saying 108 mmoles joins in dropping funnel, under ice-water bath, be added dropwise in flask, normal-temperature reaction 1 hour, being heated to 50 ℃ refluxes 5 hours, be cooled to room temperature, mixture is poured in frozen water and stirred one hour, add dichloromethane extraction, separatory, solvent evaporated, target product 4, 5-dichloromethyl-2-(4-nonyl benzene formyl radical) thiophene is directly used in next step without purification.
Wherein R alkyl also comprises: methyl, and ethyl, hexyl, dodecyl etc., but be not limited only to this.
Embodiment 7:
4,6-dihydro-2-(4-fluorobenzoyl) preparation method of thienothiophene, reaction formula is as follows:
Figure BDA0000401583670000071
In the flask of methyl alcohol that 1 liter of boiling is housed, add 4,5-dichloromethyl-2-(4-fluoro benzoyl) thiophene, sodium sulphite is dissolved in to wiring solution-forming in the methyl alcohol of 200 milliliters, the methanol solution of sodium sulphite is injected to reaction flask, react 3 hours, cooling, evaporate to dryness methyl alcohol.With silica gel chromatographic column separating-purifying, obtain yellow solid.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 4,6-dihydro-2-(4-fluorobenzoyl) thienothiophene.
Embodiment 8:
4,6-dihydro-2-(4-trifluoromethyl benzoyl) preparation method of thienothiophene, reaction formula is as follows:
Figure BDA0000401583670000072
In the flask of methyl alcohol that 1 liter of boiling is housed, add 4,5-dichloromethyl-2-(4-trifluoromethyl benzoyl) thiophene, sodium sulphite is dissolved in to wiring solution-forming in the methyl alcohol of 200 milliliters; the methanol solution of sodium sulphite is injected to reaction flask; react 3 hours, cooling, evaporate to dryness methyl alcohol.With silica gel chromatographic column separating-purifying, obtain yellow solid.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 4,6-dihydro-2-(4-trifluoromethyl benzoyl) thienothiophene.
Embodiment 9:
4,6-dihydro-2-(4-alkylbenzene formyl) preparation method of thienothiophene, reaction formula is as follows:
Figure BDA0000401583670000081
Now to prepare 4; 6-dihydro-2-(4-nonyl benzene formyl) thienothiophene is that example is explained; in the flask of methyl alcohol that 1 liter of boiling is housed, add 4; 5-dichloromethyl-2-(4-nonyl benzene formyl radical) thiophene; sodium sulphite is dissolved in to wiring solution-forming in the methyl alcohol of 200 milliliters, the methanol solution of sodium sulphite is injected to reaction flask, react 3 hours; cooling, evaporate to dryness methyl alcohol.With silica gel chromatographic column separating-purifying, obtain yellow solid.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 4,6-dihydro-2-(4-nonyl benzene formyl) thienothiophene.
Wherein R alkyl also comprises: methyl, and ethyl, hexyl, dodecyl etc., but be not limited only to this.
Embodiment 10:
2-(4-fluoro benzoyl) preparation method of thienothiophene, reacts as follows:
Figure BDA0000401583670000091
In 150 ml flasks, add 10 mmoles 4,6-dihydro-2-(4-fluorobenzoyl) thienothiophene, adds 50 milliliters of chloroforms to make solvent, by being dissolved in 20 milliliters of benzoyl hydroperoxide solution in chloroform, under-40 degrees Celsius, is added dropwise to reaction system, be incubated 2 hours, normal temperature spends the night, and removes organic solvent, the product obtaining is joined in the two-mouth bottle of 50 milliliters, with 15 milliliters of acetic anhydride, make solvent, reflux 2 hours, remove acid anhydrides, with silica gel chromatographic column separating-purifying, obtain yellow powder.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-fluoro benzoyl) thienothiophene.
Embodiment 11:
2-(4-trifluoromethyl benzoyl) preparation of thienothiophene, reaction formula is as follows:
Figure BDA0000401583670000092
In 150 ml flasks, add 10 mmoles 4,6-dihydro-2-(4-trifluoromethyl benzoyl) thienothiophene, adds 50 milliliters of chloroforms to make solvent, by being dissolved in 20 milliliters of benzoyl hydroperoxide solution in chloroform, under-40 degrees Celsius, is added dropwise to reaction system, be incubated 2 hours, normal temperature spends the night, and removes organic solvent, the product obtaining is joined in the two-mouth bottle of 50 milliliters, with 15 milliliters of acetic anhydride, make solvent, reflux 2 hours, remove acid anhydrides, with silica gel chromatographic column separating-purifying, obtain yellow powder.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-trifluoromethyl benzoyl) thienothiophene.
Embodiment 12:
2-(4-alkylbenzene formyl radical) preparation of thienothiophene, reaction formula is as follows:
Figure BDA0000401583670000101
Now take preparation 2-(4-nonyl benzene formyl radical) thienothiophene is explained as example, in 150 ml flasks, add 10 mmoles 4, 6-dihydro-2-(4-nonyl benzene formyl) thienothiophene, add 50 milliliters of chloroforms to make solvent, by being dissolved in 20 milliliters of benzoyl hydroperoxide solution in chloroform, under-40 degrees Celsius, be added dropwise to reaction system, be incubated 2 hours, normal temperature spends the night, evaporate to dryness organic solvent, the product obtaining is joined in the two-mouth bottle of 50 milliliters, with 15 milliliters of acetic anhydride, make solvent, reflux 2 hours, remove acid anhydrides, with silica gel chromatographic column separating-purifying, obtain white powder.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-nonyl benzene formyl radical) thienothiophene.
Wherein R alkyl also comprises: methyl, and ethyl, hexyl, dodecyl etc., but be not limited only to this.
Embodiment 13:
2-(4-fluoro benzoyl)-4, the preparation of 6-dibromo thiophene thiophthene, reaction formula is as follows:
Figure BDA0000401583670000102
At 50 ml flasks, add 8 mmole 2-(4-fluoro benzoyls) thienothiophene; add 10 milliliters of DMF to make solvent; add 16 mmole NBS reaction 30 minutes; mixture is poured into water; with dichloromethane extraction, wash organic layer with water, use anhydrous magnesium sulfate drying organic layer; remove organic solvent, with silica gel chromatographic column separating-purifying, obtain yellow needle-like solid.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-benzoyl bromide)-4,6-dibromo thiophene thiophthene.
Embodiment 14:
2-(4-trifluoromethyl benzoyl)-4, the preparation of 6-dibromo thiophene thiophthene, reaction formula is as follows:
Figure BDA0000401583670000111
In 50 ml flasks, add 8 mmole 2-(4-trifluoromethyl benzoyls) thienothiophene; add 10 milliliters of DMF to make solvent; add 16 mmole NBS reaction 30 minutes; mixture is poured into water; with dichloromethane extraction, wash organic layer with water, use anhydrous magnesium sulfate drying organic layer; remove organic solvent, with silica gel chromatographic column separating-purifying, obtain light green solid.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-trifluoromethyl benzoyl)-4,6-dibromo thiophene thiophthene.
Embodiment 15:
2-(4-alkylbenzene formyl radical)-4, the preparation of 6-dibromo thiophene thiophthene, reaction formula is as follows:
Figure BDA0000401583670000121
Now with preparation 2-(4-alkylbenzene formyl radical)-4; 6-dibromo thiophene thiophthene is that example is explained; in 50 ml flasks, add 8 mmole 2-(4-nonyl benzene formyl radicals) thienothiophene, add 10 milliliters of DMF to make solvent, add 16 mmole NBS reaction 30 minutes; mixture is poured into water; with dichloromethane extraction, wash organic layer with water, anhydrous magnesium sulfate drying organic layer; organic solvent is removed in separation, with silica gel chromatographic column separating-purifying, obtains red solid.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-nonyl benzene formyl radical)-4,6-dibromo thiophene thiophthene.
Wherein R alkyl also comprises: methyl, and ethyl, hexyl, dodecyl etc., but be not limited only to this.
Embodiment 16:
2-(4-fluoro benzoyl)-4, the preparation of 6-bis-(3-octyl group thiophene) thienothiophene, reaction formula is as follows:
Figure BDA0000401583670000122
In argon gas atmosphere downhill reaction bottle, add 2-(4-fluoro benzoyl)-4; each 1 mmole of 6-dibromo thiophene thiophthene and 3-octyl group tin trimethyl thiophene, is dissolved in 6 milliliters of toluene, and 10 milligram four (triphenyl phosphorus) closes palladium; under reflux, stirring reaction is 8 hours; after cooling, mixture is poured into water, with dichloromethane extraction; wash organic layer with water; anhydrous magnesium sulfate drying organic layer, organic solvent is removed in separation, with silica gel chromatographic column separating-purifying, obtains red oily liquids.Warp 1hNMR, 13cNMR, and the bright target product of ultimate analysis test chart is 2-(4-fluoro benzoyl)-4,6-bis-(3-octyl group thiophene) thienothiophene.
Embodiment 17:
2-(4-substituted benzoyl)-4, the preparation of 6-dibromo thiophene thiophthene and BDT conjugated polymers, reactive mode is as follows:
In argon gas atmosphere downhill reaction bottle, add 2-(4-fluoro benzoyl)-4, 6-dibromo thiophene thiophthene and 2, two tin trimethyl-4 of 6-, 8-bis-(2, 3-bishexane base thiophene) each 0.5 mmole of benzene 1,4-Dithiapentalene, be dissolved in 6 milliliters of toluene, add again 1 milliliter of DMF, 10 milligram four (triphenyl phosphorus) closes palladium, under reflux, stirring reaction is 20 hours, after cooling, with methyl alcohol sedimentation, go out polymkeric substance, dried product is dissolved in toluene, adopt silica gel column chromatography, with toluene, make eluent, concentrate eluant, sedimentation in methyl alcohol, final product is the dry mazarine polymkeric substance that obtains under vacuum.
The number-average molecular weight of resulting polymers is 17000, and weight-average molecular weight is 24700.In 649 nanometers and 709 nanometers, there is UV absorption peak in the tetrahydrofuran solution of polymkeric substance.

Claims (3)

1.一种2-(4-取代苯甲酰基)-4,6-二溴噻吩并噻吩，其特征在于该化合物具有如下化学结构式：1. a 2-(4-substituted benzoyl)-4,6-dibromothienothiophene, characterized in that the compound has the following chemical structural formula:
Figure FDA0000401583660000011
Figure FDA0000401583660000011
 其中，R1为氟或三氟甲基或氢或C1～C23的烷基。Wherein, R 1 is fluorine or trifluoromethyl, hydrogen or C 1 -C 23 alkyl. 2.具有权利要求1所述化学结构式的2-(4-取代苯甲酰基)-4,6-二溴噻吩并噻吩的制备方法，其特征在于包括如下步骤：2. have the preparation method of the 2-(4-substituted benzoyl)-4,6-dibromothienothiophene of chemical structural formula described in claim 1, it is characterized in that comprising the steps: 第一步制备2-(4-取代苯甲酰基)噻吩：在装有噻吩的二氯甲烷溶液烧瓶中加入4-氟苯甲酰氯或4-三氟甲基苯甲酰氯或4-烷基苯甲酰氯，开始搅拌，在冰浴下加入三氯化铝，常温反应三个小时，将反应物倒入装有冰水混合物的烧杯中，加入适量浓盐酸，搅拌，用二氯甲烷萃取产品，用无水硫酸镁干燥有机相，分离后除去溶剂，用硅胶色谱柱分离得到目标产物；The first step is to prepare 2-(4-substituted benzoyl)thiophene: add 4-fluorobenzoyl chloride or 4-trifluoromethylbenzoyl chloride or 4-alkylbenzene in a dichloromethane solution flask containing thiophene Formyl chloride, start stirring, add aluminum trichloride under ice bath, react at room temperature for three hours, pour the reactant into a beaker with ice-water mixture, add an appropriate amount of concentrated hydrochloric acid, stir, and extract the product with dichloromethane, Dry the organic phase with anhydrous magnesium sulfate, remove the solvent after separation, and separate with a silica gel chromatographic column to obtain the target product; 第二步制备4,5-二氯甲基-2-(4-取代苯甲酰基)噻吩：在反应瓶中加入2-(4-取代苯甲酰基)噻吩，加入氯甲基甲醚，开始搅拌，在冰浴下滴加四氯化钛，加热至50摄氏度反应6小时，冷却，将反应物倒入冰上并且搅拌，用二氯甲烷萃取，分离后除去溶剂得到目标产物；The second step is to prepare 4,5-dichloromethyl-2-(4-substituted benzoyl)thiophene: add 2-(4-substituted benzoyl)thiophene to the reaction flask, add chloromethyl methyl ether, and start Stir, add titanium tetrachloride dropwise under an ice bath, heat to 50 degrees Celsius to react for 6 hours, cool, pour the reactant on ice and stir, extract with dichloromethane, separate and remove the solvent to obtain the target product; 第三步制备4,6-二氢-2-(4-取代苯甲酰)噻吩并噻吩：在反应瓶中加入甲醇并加热至沸腾，加入4,5-二氯甲基-2-(4-取代苯甲酰基)噻吩，缓慢加入硫化钠的甲醇溶液，反应2小时冷却，除去甲醇溶剂，用硅胶色谱柱分离得到目标产物；The third step is to prepare 4,6-dihydro-2-(4-substituted benzoyl)thienothiophene: add methanol to the reaction flask and heat to boiling, add 4,5-dichloromethyl-2-(4 -substituted benzoyl)thiophene, slowly added methanol solution of sodium sulfide, reacted for 2 hours and cooled, removed the methanol solvent, and separated with a silica gel chromatographic column to obtain the target product; 第四步制备2-(4-取代苯甲酰基)噻吩并噻吩：在反应瓶中加入4,6-二氢-2-(4-取代苯甲酰)噻吩并噻吩，加入氯仿搅拌，在-40摄氏度下加入过氧化苯甲酸，室温反应过夜，除去有机溶剂，将得到的反应物用醋酸酐溶解，加热至138度，反应两小时，冷却，除去酸酐，用硅胶色谱柱分离提纯得到目标产物；The fourth step is to prepare 2-(4-substituted benzoyl)thienothiophene: add 4,6-dihydro-2-(4-substituted benzoyl)thienothiophene to the reaction flask, add chloroform and stir, and in- Add benzoic acid peroxide at 40 degrees Celsius, react overnight at room temperature, remove the organic solvent, dissolve the obtained reactant with acetic anhydride, heat to 138 degrees, react for two hours, cool, remove the anhydride, separate and purify with silica gel chromatography to obtain the target product ; 第五步制备2-(4-取代苯甲酰基)-4,6-二溴噻吩并噻吩：在反应瓶中加入2-(4-取代苯甲酰基)噻吩并噻吩，并加入二甲基甲酰胺溶解，加入N-溴代丁二酰亚胺反应30分钟，用二氯甲烷萃取，水洗除去二甲基甲酰胺，用无水硫酸镁干燥有机相，分离后除去溶剂，用硅胶色谱柱分离提纯得到目标产物。The fifth step is to prepare 2-(4-substituted benzoyl)-4,6-dibromothienothiophene: add 2-(4-substituted benzoyl)thienothiophene to the reaction flask, and add dimethyl formaldehyde Dissolve the amide, add N-bromosuccinimide to react for 30 minutes, extract with dichloromethane, wash with water to remove dimethylformamide, dry the organic phase with anhydrous magnesium sulfate, remove the solvent after separation, and separate with silica gel column Purify to obtain the target product. 3.权利要求1所述2-(4-取代苯甲酰基)-4,6-二溴噻吩并噻吩在制备含有2-(4-取代苯甲酰基)噻吩并噻吩的分子材料或基于2-(4-取代苯甲酰基)噻吩并噻吩的聚合物的应用。3. 2-(4-substituted benzoyl)-4,6-dibromothienothiophene described in claim 1 is preparing molecular materials containing 2-(4-substituted benzoyl) thienothiophene or based on 2- Use of polymers of (4-substituted benzoyl)thienothiophenes.
CN201310508714.9A 2013-10-24 2013-10-24 2-(4-substituted benzoyl)-4,6-dibromo thiophene bithiophene and preparation method and application thereof Pending CN103554130A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104788650A (en) * 2015-04-20 2015-07-22 中国科学院化学研究所 Conjugated polymer with thieno-[3,4-b] thiophene unit containing fluothane chain, preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482421A (en) * 2009-07-24 2012-05-30 朔荣有机光电科技公司 Conjugated polymers with carbonyl-substituted thieno[3,4-B]thiophene units for active layer materials in polymer solar cells
CN102796246A (en) * 2011-05-23 2012-11-28 三星电子株式会社 Electron donating polymer and solar cell including the same
KR20130090702A (en) * 2012-02-06 2013-08-14 삼성전자주식회사 Electron donating polymer and organic solar cell including the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482421A (en) * 2009-07-24 2012-05-30 朔荣有机光电科技公司 Conjugated polymers with carbonyl-substituted thieno[3,4-B]thiophene units for active layer materials in polymer solar cells
CN102796246A (en) * 2011-05-23 2012-11-28 三星电子株式会社 Electron donating polymer and solar cell including the same
KR20130090702A (en) * 2012-02-06 2013-08-14 삼성전자주식회사 Electron donating polymer and organic solar cell including the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杜学峰等: "含噻吩单元的间苯共聚物及其电致发光性能", 《应用化学》, vol. 24, no. 12, 31 December 2007 (2007-12-31), pages 1359 - 1363 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104788650A (en) * 2015-04-20 2015-07-22 中国科学院化学研究所 Conjugated polymer with thieno-[3,4-b] thiophene unit containing fluothane chain, preparation method and application
CN104788650B (en) * 2015-04-20 2017-03-08 中国科学院化学研究所 Conjugated polymer with thieno[3,4-b]thiophene unit containing fluorine-containing alkyl chain, preparation method and application thereof

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