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

Abstract

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-dibromothienothiophene and its preparation method and application

technical field

The invention relates to a compound used in the field of optoelectronic materials and devices, and more particularly to 2-(4-substituted benzoyl)-4,6-dibromothienothiophene and its preparation method and application.

Background technique

Since Japanese scientist Hideki Shirakawa discovered that polyacetylene conducts electricity in 1977, this conductive polymer, known as the "fourth generation polymer" material, has attracted many scientists for its outstanding photoelectric properties. Compared with inorganic materials with the same or similar uses, conductive polymers have the advantages of low density, easy processing, and wide range of synthesis options. Due to the conjugation characteristics of this type of material structure, it can transport charges and be excited to emit light, so it can or has the potential to be applied in many electronic or optoelectronic devices, such as polymer light-emitting diodes, photovoltaic cells, field effect transistors, etc. . Potential application prospects and a wide range of application fields have prompted scientists to study this kind of conjugated materials with photoelectric activity, including small molecules with various conjugated structures, as well as polyacetylene, polypyrrole, polythiophene, polyaniline, polyfluorene, poly Carbazole etc.

Researchers have been working hard to find ways to improve and enhance the performance of polymer light-emitting diodes, photovoltaic cells, and field effect transistors, and materials are one of the most important factors. Therefore, many research groups have been working on the development of light-emitting polymers with high quantum efficiency, good color purity and long-term stability, as well as polymers with wide absorption band in the visible light range and high carrier mobility. To achieve these goals, it is necessary to develop more new conjugated molecular materials and polymer materials, among which the design and synthesis of new conjugated units is very important.

In recent years, some dibromothienothiophene molecules have been widely used in organic photovoltaic cells. "Nat.Photonics" (Nat.Photonics) 6 (2012) 591 lists the performance of thienothiophene molecules in organic solar cells outstanding performance.

Contents of the invention

The object of the present invention is to provide 2-(4-substituted benzoyl)-4,6-dibromothienothiophene for the deficiencies in the prior art, which can be used to construct novel 2-(4-substituted benzoyl)- Molecular materials of 4,6-dibromothienothiophene and novel polymer materials containing 2-(4-substituted benzoyl)-4,6-dibromothienothiophene.

The object of the present invention is also to provide the preparation method of said 2-(4-substituted benzoyl)-4,6-dibromothienothienothiophene.

2-(4-substituted benzoyl)-4,6-dibromothienothiophene of the present invention has the following structure:

Wherein, R ₁ is fluorine or trifluoromethyl, hydrogen or C ₁ -C ₂₃ alkyl.

The preparation method of structure 2-(4-substituted benzoyl)-4,6-dibromothienothiophene comprises the following five steps:

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;

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.

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.

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 .

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.

The present invention can also be used to construct novel molecular materials containing 2-(4-substituted benzoyl)-4,6-dibromothienothiophene and based on 2-(4-substituted benzoyl)-4,6-dibromothienothiophene Bromothienothiophene is a polymer of main chain structural units.

Compared with prior art, the present invention has following advantage and effect:

The invention provides a novel thienothiophene unit, which is original and greatly enriches the use of thienothiophene units to construct corresponding molecular materials and polymer materials, thereby providing more material choices for the application of these materials in optoelectronic devices . The present invention also provides a specific preparation method of 2-(4-substituted benzoyl)-4,6-dibromothienothiophene unit, which has the characteristics of simple and fast preparation, which is an important method for the preparation of novel thienothiophene-containing units. Molecular materials and polymer materials provide good technical support.

Detailed ways

Example 1:

The preparation of 2-(4-fluorobenzoyl)thiophene, the reaction formula is as follows:

In a 250 ml two-necked flask, add 100 mmoles of thiophene, add 100 mls of dichloromethane as a solvent, add 100 mmoles of 4-fluorobenzoyl chloride, cool under an ice-water bath, add 120 mmoles of aluminum trichloride in batches, and react For 3 hours, pour the mixture into 200 grams of ice, add 25 milliliters of concentrated hydrochloric acid, stir, separate the layers and extract the aqueous layer three times with dichloromethane, dry the organic phase with anhydrous magnesium sulfate, remove the solvent after separation, and separate and purify with silica gel chromatography to obtain Off-white solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-fluorobenzoyl)thiophene.

Example 2:

The preparation of 2-(4-trifluoromethylbenzoyl)thiophene, the reaction formula is as follows:

In a 250ml two-necked flask, add 100mmol of thiophene, add 100ml of dichloromethane as a solvent, add 100mmol of 4-trifluoromethylbenzoyl chloride, cool in an ice-water bath, and add 120mmol of trichloride in batches. Aluminum, reacted for 3 hours, poured the mixture into 200 g of ice, added 25 ml of concentrated hydrochloric acid, stirred, separated and extracted the aqueous layer three times with dichloromethane, dried the organic phase with anhydrous magnesium sulfate, removed the solvent after separation, and used a silica gel chromatographic column Separation and purification afforded an off-white solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-trifluoromethylbenzoyl)thiophene.

Example 3:

The preparation of 2-(4-alkylbenzoyl)thiophene, the reaction formula is as follows:

Now take the preparation of 2-(4-nonylbenzoyl)thiophene as an example. In a 250ml two-necked flask, add 100mmol of thiophene, add 100ml of dichloromethane as a solvent, and add 100mmol of 4-nonyl Benzoyl chloride, cooled in an ice-water bath, added 120 mmol of aluminum chloride in batches, reacted for 3 hours, poured the mixture into 200 g of ice, added 25 ml of concentrated hydrochloric acid, stirred, separated and extracted the water layer three times with dichloromethane , dried the organic phase with anhydrous magnesium sulfate, removed the solvent after separation, separated and purified with silica gel chromatography to obtain off-white solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-nonylbenzoyl)thiophene.

Wherein R alkyl also includes: methyl, ethyl, hexyl, n-dodecyl, etc., but not limited thereto.

Example 4:

The preparation of 4,5-dichloromethyl-2-(4-fluorobenzoyl)thiophene, the reaction formula is as follows:

Add 90 mmoles of 2-(4-fluorobenzoyl)thiophene to a 250 ml two-necked bottle, add 450 mmoles of chloromethyl methyl ether, stir until dissolved, and add 108 mmoles of titanium tetrachloride to the drop solution In the funnel, add it dropwise into the flask under an ice-water bath, react at room temperature for 1 hour, heat to 50 degrees Celsius and reflux for 5 hours, cool to room temperature, pour the mixture into ice water and stir for one hour, add dichloromethane for extraction, separate the liquids, and evaporate the solvent to dryness , the product was used directly in the next step without purification.

Example 5:

The preparation of 4,5-dichloromethyl-2-(4-trifluoromethylbenzoyl)thiophene, the reaction formula is as follows:

Add 90 mmol 2-(4-trifluoromethylbenzoyl)thiophene to a 250 ml two-necked bottle, add 450 mmol chloromethyl methyl ether, stir until dissolved, add 108 mmol titanium tetrachloride Put it into the dropping funnel, drop it into the flask under the ice-water bath, react at room temperature for 1 hour, heat to 50 degrees Celsius and reflux for 5 hours, cool to room temperature, pour the mixture into ice water and stir for one hour, add dichloromethane for extraction, and separate the liquids. The solvent was evaporated to dryness to obtain the target product 4,5-dichloromethyl-2-(4-trifluoromethylbenzoyl)thiophene, which was directly used in the next step without purification.

Embodiment 6:

The preparation of 4,5-dichloromethyl-2-(4-alkylbenzoyl)thiophene, the reaction formula is as follows:

Taking the preparation of 4,5-dichloromethyl-2-(4-nonylbenzoyl)thiophene as an example, add 90 mmoles of 2-(4-nonylbenzoyl)thiophene to a 250 ml two-necked bottle , add 450 millimoles of chloromethyl methyl ether, stir until dissolved, add 108 millimoles of titanium tetrachloride into the dropping funnel, add it dropwise into the flask under an ice-water bath, react at room temperature for 1 hour, heat to 50 ° C and reflux for 5 hours, cooled to room temperature, poured the mixture into ice water and stirred for one hour, added dichloromethane for extraction, separated the layers, and evaporated the solvent to dryness. The target product 4,5-dichloromethyl-2-(4-nonylbenzoyl ) Thiophene was used directly in the next step without purification.

Wherein R alkyl also includes: methyl, ethyl, hexyl, n-dodecyl, etc., but not limited thereto.

Embodiment 7:

The preparation method of 4,6-dihydro-2-(4-fluorobenzoyl)thienothiophene, the reaction formula is as follows:

Add 4,5-dichloromethyl-2-(4-fluorobenzoyl)thiophene to a flask containing 1 liter of boiling methanol, dissolve sodium sulfide in 200 ml of methanol to form a solution, and dissolve sodium sulfide The methanol solution was injected into the reaction flask, reacted for 3 hours, cooled, and evaporated to dry methanol. Separation and purification with silica gel column to obtain a yellow solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 4,6-dihydro-2-(4-fluorobenzoyl)thienothiophene.

Embodiment 8:

The preparation method of 4,6-dihydro-2-(4-trifluoromethylbenzoyl)thienothiophene, the reaction formula is as follows:

Add 4,5-dichloromethyl-2-(4-trifluoromethylbenzoyl)thiophene to a flask containing 1 liter of boiling methanol, dissolve sodium sulfide in 200 ml of methanol to form a solution, The methanol solution of sodium sulfide was injected into the reaction flask, reacted for 3 hours, cooled, and evaporated to dryness of methanol. Separation and purification with silica gel column to obtain a yellow solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 4,6-dihydro-2-(4-trifluoromethylbenzoyl)thienothiophene.

Embodiment 9:

The preparation method of 4,6-dihydro-2-(4-alkylbenzoyl)thienothiophene, the reaction formula is as follows:

Taking the preparation of 4,6-dihydro-2-(4-nonylbenzoyl)thienothiophene as an example, add 4,5-dichloromethyl- For 2-(4-nonylbenzoyl)thiophene, dissolve sodium sulfide in 200 ml of methanol to make a solution, inject the methanol solution of sodium sulfide into the reaction flask, react for 3 hours, cool, and evaporate the methanol to dryness. Separation and purification with silica gel column to obtain a yellow solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 4,6-dihydro-2-(4-nonylbenzoyl)thienothiophene.

Wherein R alkyl also includes: methyl, ethyl, hexyl, n-dodecyl, etc., but not limited thereto.

Example 10:

The preparation method of 2-(4-fluorobenzoyl)thienothiophene, the reaction is as follows:

Add 10 mmoles of 4,6-dihydro-2-(4-fluorobenzoyl) thienothiophene to a 150 ml flask, add 50 ml of chloroform as a solvent, and dissolve the peroxybenzoic acid solution in 20 ml of chloroform Add dropwise to the reaction system at -40 degrees Celsius, keep warm for 2 hours, overnight at normal temperature, remove the organic solvent, add the obtained product into a 50 ml two-necked bottle, use 15 ml of acetic anhydride as a solvent, reflux for 2 hours, remove the anhydride, and use Separation and purification by silica gel column to obtain yellow powder. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-fluorobenzoyl)thienothiophene.

Example 11:

The preparation of 2-(4-trifluoromethylbenzoyl)thienothiophene, the reaction formula is as follows:

Add 10 mmoles of 4,6-dihydro-2-(4-trifluoromethylbenzoyl) thienothiophene to a 150 ml flask, add 50 ml of chloroform as a solvent, and dissolve peroxygen in 20 ml of chloroform Benzoic acid solution was added dropwise to the reaction system at -40 degrees Celsius, kept at room temperature for 2 hours, overnight at room temperature, and the organic solvent was removed. Acid anhydride, separated and purified by silica gel column to obtain yellow powder. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-trifluoromethylbenzoyl)thienothiophene.

Example 12:

The preparation of 2-(4-alkylbenzoyl)thienothiophene, the reaction formula is as follows:

Now take the preparation of 2-(4-nonylbenzoyl)thienothiophene as an example to illustrate, add 10 mmoles of 4,6-dihydro-2-(4-nonylbenzoyl)thiophene to a 150 ml flask And thiophene, add 50 milliliters of chloroform as a solvent, drop the peroxybenzoic acid solution dissolved in 20 milliliters of chloroform into the reaction system at -40 degrees Celsius, keep it warm for 2 hours, overnight at room temperature, evaporate the organic solvent to dryness, and add the obtained product In a 50 ml two-necked bottle, use 15 ml of acetic anhydride as a solvent, reflux for 2 hours, remove the anhydride, separate and purify with a silica gel column to obtain a white powder. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-nonylbenzoyl)thienothiophene.

Wherein R alkyl also includes: methyl, ethyl, hexyl, n-dodecyl, etc., but not limited thereto.

Example 13:

The preparation of 2-(4-fluorobenzoyl)-4,6-dibromothienothiophene, the reaction formula is as follows:

Add 8 mmoles of 2-(4-fluorobenzoyl)thienothiophene to a 50 ml flask, add 10 ml of DMF as a solvent, add 16 mmoles of NBS to react for 30 minutes, pour the mixture into water, extract with dichloromethane, Wash the organic layer with water, dry the organic layer with anhydrous magnesium sulfate, remove the organic solvent, separate and purify with silica gel chromatography to obtain a yellow needle-like solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-bromobenzoyl)-4,6-dibromothienothiophene.

Example 14:

The preparation of 2-(4-trifluoromethylbenzoyl)-4,6-dibromothienothiophene, the reaction formula is as follows:

Add 8 mmol 2-(4-trifluoromethylbenzoyl) thienothiophene to a 50 ml flask, add 10 ml DMF as a solvent, add 16 mmol NBS to react for 30 minutes, pour the mixture into water, and use two Extract with methyl chloride, wash the organic layer with water, dry the organic layer with anhydrous magnesium sulfate, remove the organic solvent, separate and purify with silica gel chromatography to obtain a light green solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-trifluoromethylbenzoyl)-4,6-dibromothienothiophene.

Example 15:

The preparation of 2-(4-alkylbenzoyl)-4,6-dibromothienothiophene, the reaction formula is as follows:

Now take the preparation of 2-(4-alkylbenzoyl)-4,6-dibromothienothiophene as an example to illustrate, add 8 mmoles of 2-(4-nonylbenzoyl)thiophene to a 50 ml flask And thiophene, add 10 milliliters of DMF as a solvent, add 16 mmoles of NBS to react for 30 minutes, pour the mixture into water, extract with dichloromethane, wash the organic layer with water, dry the organic layer with anhydrous magnesium sulfate, separate and remove the organic solvent, and use Separation and purification on a silica gel column yielded a red solid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-nonylbenzoyl)-4,6-dibromothienothiophene.

Wherein R alkyl also includes: methyl, ethyl, hexyl, n-dodecyl, etc., but not limited thereto.

Example 16:

The preparation of 2-(4-fluorobenzoyl)-4,6-bis(3-octylthiophene)thienothiophene, the reaction formula is as follows:

Add 1 mmol each of 2-(4-fluorobenzoyl)-4,6-dibromothienothiophene and 3-octyltrimethyltinthiophene to the reaction flask under an argon atmosphere, dissolve in 6 mL of toluene 10 mg of tetrakis(triphenylphosphine) palladium, stirred and reacted for 8 hours under heating and reflux, after cooling, pour the mixture into water, extract with dichloromethane, wash the organic layer with water, dry the organic layer with anhydrous magnesium sulfate, Separation and removal of the organic solvent, separation and purification with a silica gel column to obtain a red oily liquid. ¹ HNMR, ¹³ CNMR, and elemental analysis showed that the target product was 2-(4-fluorobenzoyl)-4,6-bis(3-octylthiophene)thienothiophene.

Example 17:

The preparation of 2-(4-substituted benzoyl)-4,6-dibromothienothiophene and BDT conjugated polymer, the reaction method is as follows:

Add 2-(4-fluorobenzoyl)-4,6-dibromothienothiophene and 2,6-bistrimethyltin-4,8-bis(2,3 -dihexylthiophene) each 0.5 mmoles of benzodithiophene, dissolved in 6 milliliters of toluene, then added 1 milliliter of DMF, 10 milligrams of tetrakis (triphenylphosphine) palladium, stirred under reflux for 20 hours, cooled Finally, the polymer was precipitated with methanol, and the dried product was dissolved in toluene, followed by silica gel column chromatography, using toluene as the eluent, concentrating the eluent, and settling in methanol, and finally the product was dried under vacuum to obtain a dark blue color polymer.

The number average molecular weight of the obtained polymer was 17,000, and the weight average molecular weight was 24,700. The polymer tetrahydrofuran solution has UV absorption peaks at 649 nm and 709 nm.

Claims (3)

1. a 2-(4-substituted benzoyl)-4,6-dibromo thiophene thiophthene, is characterized in that this compound has following chemical structural formula:

Wherein, R ₁for fluorine or trifluoromethyl or hydrogen or C ₁～C ₂₃alkyl.

2. the 2-(4-substituted benzoyl)-4 with chemical structural formula described in claim 1, the preparation method of 6-dibromo thiophene thiophthene, is characterized in that comprising the 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.

3. 2-(4-substituted benzoyl)-4 described in claim 1, the application of the molecular material that 6-dibromo thiophene thiophthene contains 2-(4-substituted benzoyl) thienothiophene in preparation or the polymkeric substance based on 2-(4-substituted benzoyl) thienothiophene.