CN101885836B - Polymer of selenium-contained heterocyclic compound and application thereof in preparation of luminescent material - Google Patents

Abstract

The present invention relates to a polymer of a selenium-containing heterocyclic compound and its application in the preparation of luminescent materials. The polymer includes one or more than one heterocyclic component containing elemental selenium; it may also include another component unit polyfluorene , polyparaphenylene, polyphenylene vinylene, poly SPIRO-paraphenylene, ladder-polyphenylene (ladder-PPP) in one or more. The polymer has high quantum efficiency, good color purity and long-term stability, and is suitable for high-resolution, full-color flat display devices and photovoltaic devices.

Description

Polymers of selenium-containing heterocyclic compounds and their applications in the preparation of luminescent materials

technical field

The present invention relates to polymers, more particularly polymers of selenium-containing heterocyclic compounds. The invention also relates to the application of the polymer in the preparation of luminescent materials. This application is a divisional application of 200810210612.8.

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 photoactive conjugated materials, including polyacetylene, polypyrrole, polythiophene, polyaniline, polyfluorene, etc. When an electron transitions from a bonding orbital to an antibonding orbital (π-π ^* transition), polymers with an aromatic ring or heterocyclic structure usually absorb light at a wavelength of 300-500 nanometers, and when electrons transition from an antibonding orbital to a bonding orbital When orbiting, energy is released, and photons of corresponding wavelengths in the visible region are usually emitted, which is the luminescent polymer material.

Luminescent polymer materials have set off a revolution in electronic display technology due to their outstanding advantages. In the past decade, a large number of light-emitting polymers have been developed. To make a commercially available light-emitting device, the material's luminous color coordinates, luminous quantum efficiency, operating voltage (power consumption), and long-term stability of the device must all be optimized. Researchers have been working hard to find ways to improve and enhance the performance of polymer light-emitting diodes, and materials are one of the most important factors. So many research groups have been working on developing light-conducting polymers with high quantum efficiency, good color purity and long-term stability.

Contents of the invention

The object of the present invention is to provide a polymer containing selenium heterocyclic compound, which has high quantum efficiency, good color purity and long-term stability, and is suitable for high-resolution and full-color flat display.

The invention also relates to the application of the selenium-containing heterocyclic compound polymer in the preparation of light-emitting materials; the application of the selenium-containing heterocyclic compound polymer in the preparation of photovoltaic materials. Application of the polymer containing selenium heterocyclic compound in the preparation of light-emitting diodes and light-emitting layers in flat-panel displays. Application of polymers containing selenium heterocyclic compounds in the preparation of active layers of solar photovoltaic cells.

The polymer monomer of the selenium-containing heterocyclic compound of the present invention includes a heterocyclic compound containing elemental selenium.

The heterocyclic compound containing element selenium has one or more structural units as follows:

其中R₁，R₂为H，C₁-C₂₀的烷基，烷氧基；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl, alkoxy;

其中R₁，R₂为H，C₁-C₂₀的烷基，烷氧基；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl, alkoxy;

其中R₁，R₂为H，C₁-C₂₀的烷基；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl;

其中R₁，R₂为H，C₁-C₂₀的烷基，X为S，Se，N-Me；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl, X is S, Se, N-Me;

X为S，Se，N-Me；

X is S, Se, N-Me;

X为S，Se，N-Me；

X is S, Se, N-Me;

X is S, Se, N-Me;

其中R₁，R₂为H，C₁-C₂₀的烷基；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl;

其中R₁，R₂为H，C₁-C₂₀的烷基；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl;

其中R₁，R₂为H，C₁-C₂₀的烷基，X为S，Se，N-Me；

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl, X is S, Se, N-Me;

X is S, Se;

X为S，Se，N-Me；

X is S, Se, N-Me;

X为S，Se；

X is S, Se;

The heterocyclic compound containing elemental selenium accounts for 0.1-100 mole % in the polymer.

The polymer of selenium-containing heterocyclic compound also includes another component polyfluorene, polyparaphenylene, polyphenylene vinylene, poly SPIRO-paraphenylene, ladder-polyphenylene (ladder-PPP) conjugated polymer or one Above, wherein the heterocyclic compound containing element selenium accounts for 0.1-99% mole in the polymer, and the molecular structure of another component is as follows:

其中R₁，R₂为H，C₁-C₂₀的烷基；Polyfluorene:

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl;

其中R₁，R₂为H，C₁-C₂₀的烷基，烷氧基；Polyphenylene:

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl, alkoxy;

其中R₁，R₂为H，C₁-C₂₀的烷氧基；Polyphenylene vinylene:

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkoxy;

其中R₁，R₂为H，C₁-C₂₀的烷基；Poly SPIRO-paraphenylene:

Wherein R ₁ and R ₂ are H, C ₁ -C ₂₀ alkyl;

其中R₁，R₂，R₃，R₄，R₅，R₆为H，C₁-C₂₀的烷基。Ladder-PPP:

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are H, C ₁ -C ₂₀ alkyl.

The polymer containing selenium heterocyclic compounds emits light in the range of 400-1100 nanometers; it is soluble in common organic solvents.

The invention uses selenium-containing heterocyclic compounds, benzoselenodiazole, selenophene and their derivatives as monomers to synthesize a series of brand new copolymers. At the same time, a series of homopolymers of alkyl-substituted benzoselenodiazoles and selenophenes were also synthesized. Using this kind of polymer as the light-emitting layer, polymer light-emitting diodes were made, and their photoelectric properties were studied. Selenium atom and sulfur atom both belong to the sixth main group. Compared with sulfur, selenium has weaker non-metallicity and stronger metallicity. The atomic radius of selenium (116pm) is 13pm larger than that of sulfur (103pm), the radius of divalent anions (198pm) is 14pm larger than that of sulfur (184pm), and the electron affinity and first ionization energy are also significantly reduced. The increase of ionic radius leads to the increase of steric hindrance, which weakens the interaction force between chains, which may weaken the generation of excimer complexes, which is beneficial to the improvement of luminous efficiency. On the other hand, the red-shifted wavelength of copolymer luminescence (compared with sulfur compounds) can be explored in the application of near-infrared light-emitting devices.

Materials that may serve as the host of the copolymer in the present invention will not be limited to polyfluorene. All host materials reported in the literature can be used for copolymerization with selenium-containing heterocyclic compounds. For example, polyparaphenylene, polyparaphenylene vinylene, polySPIRO-PPP, ladder-PPP and the like. In particular, we pointed out that the copolymers obtained by using the conjugated polycarbazole prepared by the SUZUKI method as the main body have good characteristics (Huang et al, Macromolecules, in press). Compared with fluorene, polycarbazole is a good hole-transporting material because nitrogen atom is substituted for carbon atom at the 9-position, and the homopolymer of carbazole itself emits blue light. When carbazole is copolymerized with benzoselenodiazole, selenophene and their derivatives, the energy level structure can be changed, and the luminescent wavelength can be further red-shifted, which is also a luminescent material with potential application value.

One of the methods to prepare polymers of selenium-containing heterocyclic compounds is to synthesize a series of derivatives containing selenodiazole and selenophene structures using benzoselenodiazole and selenophene as the basic structural monomers, and polymerize on this basis , and copolymerized with alkyl-substituted fluorene and carbazole to synthesize a conjugated light-emitting polymer with selenadiazole and selenophene structures in the main chain. Its emission wavelength is adjustable throughout the visible region. It is expected to be used in the light-emitting layer of polymer light-emitting diodes (PLEDs), and will be widely used in flat-panel displays of electronic instruments, personal digital assistants (PDAs) and laptop computers in the future.

Compared with the prior art, the present invention has the following advantages:

The polymer synthesized by the invention has the highest electroluminescent external quantum efficiency of 1%, has potential application value, and has a red-shifted luminescent wavelength, and is expected to develop new red, green and blue luminescent materials for full-color display.

Detailed ways

The preparation of monomers, copolymers and homopolymers of conjugated luminescent polymer materials containing selenodiazole and selenophene derivatives on the main chain is further illustrated by the following examples.

Embodiment 1: the preparation of 2,7-dibromofluorene

2,7-Dibromofluorene was prepared according to the method disclosed in World Patent WO 99 05184 in 1997 and the method disclosed in "Chem. Mater" (Chem. Mater) 11 (1997) 11083. Weigh fluorene (16.6 g, 0.1 mol) and iron powder (88 mg, 1.57 mmol) into a three-necked flask, add 100 ml of chloroform, cool in an ice-water bath, add bromine (35.2 g, 0.22 mol) and 35 milliliters of chloroform, the temperature in the bottle should not exceed 5°C during the dropwise addition. After the reaction was completed, it was filtered and recrystallized with chloroform to obtain white crystals (26.9 g, 83%). ¹³ C NMR and GC-MASS tests showed that it was the target product 2,7-dibromofluorene.

Example 2: Preparation of 2,7-dibromo-9,9-disubstituted fluorene

The preparation of 2,7-dibromo-9,9-di-n-octylfluorene is taken as an example to illustrate. 2,7-Dibromo-9,9-di-n-octylfluorene was prepared according to the method disclosed in World Patent WO 99 05184 in 1997 and the method disclosed in "Chem. Mater" (Chem. Mater) 11 (1997) 11083. Get 2,7-dibromofluorene (9.72 grams, 0.03 moles) obtained in Example 1, and pour benzyltriethylammonium chloride (0.07 grams, 0.3 mmoles) into a three-necked flask, and add 90 milliliters of dimethyl sulfoxide , 45 ml of 50% aqueous sodium hydroxide solution by weight, stirred vigorously at room temperature to form a suspension, added dropwise 1-bromo-n-octane (12.5 g, 65 mmol), continued to stir for 3 hours, then extracted with ether, combined ether phase, washed with saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and purified by column chromatography using n-hexane as eluent to obtain white crystals. ¹³ C NMR and GC-MASS tests showed that it was the target product 2,7-dibromo-9,9-di-n-octylfluorene.

The substituents in 2,7-dibromo-9,9-disubstituted fluorene include: n-hexyl, n-octyl, 2-ethylhexyl, decyl, etc., but not limited thereto.

Embodiment 3: 3, the preparation of 6-dibromocarbazole

Add carbazole (12.54 grams, 75 mmoles), 375 milliliters of refined carbon disulfide and 24 milliliters of anhydrous pyridine in a 1000 milliliter three-necked flask, stir with a mechanical stirrer while cooling with ice water, when cooled to 0 ° C, start to drop Liquid bromine (28.30 g, 177 mmol) dissolved in 75 ml of carbon disulfide was added dropwise for about 1 hour. After dropping, remove the cooling device, gradually raise to 15°C, keep stirring at 15°C for 2.5 hours, and the reaction ends. The reaction solution was poured into 400 ml of dilute hydrochloric acid, a pale yellow precipitate formed, filtered, washed with dilute sodium hydroxide solution 3 times, then washed with distilled water until neutral, and dried. Recrystallized with absolute ethanol and dried to obtain white needle-like crystals with a yield of 83%. ¹ HNMR and GC-MASS tests showed that it was the target product 3,6-dibromocarbazole.

Embodiment 4: Preparation of 3,6-dibromo-N-substituted carbazole

The preparation of 3,6-dibromo-N-2-ethylhexylcarbazole is taken as an example to illustrate. Under nitrogen protection, 60% sodium hydride (1.104 g, 27.6 mmol) and 25 ml of tetrahydrofuran were added to a 250 ml flask, and 3,6-dibromocarbazole (5 g, 15.4 mmol) solution, now there are small bubbles to generate, and the solution also turns light green from off-white. After stirring at room temperature for a period of time, the reaction temperature is raised to the solution reflux, and 4.5 milliliters of 1-bromo-2-ethylhexane are added (4.86 g, 25.2 mmol), reacted under reflux for 24 hours, and ended the reaction. Evaporate the solvent, add dichloromethane and water for extraction, wash the organic layer 4 times with water, add anhydrous magnesium sulfate to dry, remove the solvent to obtain a light yellow viscous liquid, and use a mixed solvent of ethyl acetate and n-hexane (1: 10) Further purification by eluent column chromatography to obtain white crystals with a yield of 75%. ¹ HNMR and GC-MASS tests showed that it was the target product 3,6-dibromo-N-2-ethylhexylcarbazole. The substituents in 3,6-dibromo-N-substituted carbazole include: n-hexyl, n-octyl, 2-ethylhexyl, etc., but not limited thereto.

Example 5: Preparation of 9,9-disubstituted-2,7-diboronate fluorene

The preparation of 9,9-di-n-octyl-2,7-diboronate fluorene is taken as an example to illustrate. 9,9-Di-n-octyl-2,7-diboronate fluorene was prepared as described in Macromolecules 30 (1997) 7686. The dried 2,7-dibromo-9,9-dioctylfluorene (5.6 g, 10.22 mmol) obtained in Example 2 was dissolved in 130 ml of tetrahydrofuran (THF) after refining and drying, and dried under the protection of argon. At -78°C, 20 ml of n-butyllithium (1.6 mol/L, n-hexane as solvent, 32 mmol) was added dropwise, and the reaction mixture was stirred at -78°C for at least 1.5 hours, followed by the rapid addition of 2-iso Propoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxyborate (25 mL, 123.24 mmol), stirring was continued at -78°C for 2 hours. The reaction mixture was then allowed to gradually warm to room temperature and the reaction was stirred for at least 36 hours. Then the reaction mixture was poured into water, extracted with ether, the ether phases were combined, washed with brine and dried over anhydrous magnesium sulfate, the solvent was evaporated, the residue was recrystallized from tetrahydrofuran and methanol, and further purified by column chromatography (silica gel, n-hexane: Ethyl acetate=9:1 as the eluent) to obtain a white solid. ¹³ C NMR, GC-MASS and elemental analysis showed that the obtained product was the target product 9,9-di-n-octyl-2,7-diboronate fluorene.

The substituents in 9,9-disubstituted-2,7-diboronate fluorene include: n-hexyl, n-octyl, 2-ethylhexyl, decyl, but not limited thereto.

Embodiment 6: Preparation of N-substituted-3,6-diboronate carbazole

The preparation of 3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxoborate)-N-(2'-ethylhexyl)carbazole is illustrated as an example. Add 3,6-dibromo-N-2-ethylhexylcarbazole (4.5 g, 10.30 mmol) and 80 ml of tetrahydrofuran into a three-necked flask, stir evenly, cool the reaction solution to -78°C, and add dropwise 24 mL of 2M n-BuLi (48 mmol). After the dropwise addition, continue to stir at -78°C for 2 hours, then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethylenedioxy borate in one go (25 ml, 123.24 mmol), continued to stir at -78°C for 2 hours, then raised the reaction temperature to room temperature, reacted for 36 hours, and ended the reaction. Extracted with ether, washed 4 times with saturated brine, dried the organic layer with anhydrous magnesium sulfate, removed the solvent, and purified by column chromatography using ethyl acetate and n-hexane mixed solvent (1:9) as the eluent to obtain a white Crystals, 45% yield. ¹ HNMR and GC-MASS tests showed that the target product was 3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxoborate)-N-(2′-ethyl Hexyl) carbazole.

The substituents in N-substituted-3,6-diboronate carbazole include: n-hexyl, n-octyl, 2-ethylhexyl, etc., but not limited thereto.

The following is the preparation of benzoselenodiazole and selenophene and its derivative monomers:

Example 7: Preparation of 4,7-dibromo-2,1,3-benzoselenadiazole

Method A

4,7-Dibromo-2,1,3-benzoselenadiazole was prepared according to the method disclosed in J. Chem. Soc. (1963) 4767. Weigh 2,1,3-benzoselenodiazole (1.83 g, 0.01 mole), silver sulfate (3.12 g, 0.01 mole), dissolve in 20 ml of concentrated sulfuric acid, stir, add bromine (3.2 g, 0.02 mole) dropwise ), the addition was completed, reacted at room temperature for 75 minutes, filtered off the silver bromide precipitate, poured the filtrate into ice water, and then recrystallized with 450 milliliters of ethyl acetate to obtain golden yellow needle crystals. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 4,7-dibromo-2,1,3-benzoselenadiazole.

Method B

4,7-Dibromo-2,1,3-benzoselenadiazole was prepared according to the method disclosed in "Journal of Organic Chemistry" (J. Org. Chem.) 57, (1992) 6749-6755. Bromination of 2,1,3-benzothiadiazole gave 4,7-dibromo-2,1,3-benzothiadiazole with a yield of 95%. Weigh 4,7-dibromo-2,1,3-benzothiadiazole (5.88 g, 0.02 mol), add 190 ml of ethanol to form a suspension, add sodium borohydride (14 g, 0.37 mol), the mixture was stirred and reacted at room temperature for 20 hours, and the solvent was evaporated to obtain 3,6-dibromo-1,2-phenylenediamine (4.5 g) as a pale yellow solid with a yield of 85%. Take 3,6-dibromo-1,2-phenylenediamine (2.7 g, 10 mmol), 55 ml of ethanol, reflux, add dropwise an aqueous solution of selenium dioxide (1.17 g, 10.5 mmol) (22 ml of hot water) , the reaction mixture was refluxed for 2 hours, and filtered to obtain 3 g of yellow precipitate with a yield of 88%. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 4,7-dibromo-2,1,3-benzoselenadiazole.

Embodiment 8: the preparation of 2,5-dibromoselenophene

2,5-Dibromoselenophene was prepared according to the method disclosed in "Chemica Scripta" 7 (1975) 111-119. Selenophene (5 g, 38.2 mmol) was weighed, 10 ml of acetic acid was added, nitrogen was blown and the temperature was cooled to around 0°C, and a mixed solution of bromine (13.2 g, 82.6 mmol) and 8 ml of acetic acid was added dropwise. React for 24 hours, heat up and reflux for 3 hours, pour the reaction solution into saturated ice-cold sodium bisulfite solution, extract with ether, neutralize with frozen 2N aqueous sodium hydroxide solution, wash with water, dry with anhydrous calcium chloride, and distill under reduced pressure to obtain The target product 2,5-dibromoselenophene was obtained.

Example 9: Preparation of 4,7-dibromo-5-methyl-2,1,3-benzoselenadiazole

Weigh 3,4-diaminotoluene (4.88 g, 0.04 mol), dissolve it in 18 ml of ethanol, heat to reflux, add selenium dioxide (4.66 g, 0.042 mol) aqueous solution (10 ml of hot water), dropwise , refluxing for half an hour, and recrystallized from n-hexane to obtain needle-like white crystals of 5-methyl-2,1,3-benzoselenadiazole. This product was brominated according to Example 6, Method A. Weigh 5-methyl-2,1,3-benzoselenodiazole (1.97 g, 0.01 mole), silver sulfate (3.12 g, 0.01 mole), dissolve in 20 ml of concentrated sulfuric acid, stir, add bromine ( 3.2 g, 0.02 mol), after the addition was completed, reacted at room temperature for 75 minutes, filtered off the silver bromide precipitate, poured the filtrate into ice water, and then recrystallized with 450 ml of ethyl acetate to obtain golden yellow needle crystals. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 4,7-dibromo-5-methyl-2,1,3-benzoselenadiazole.

Example 10: Preparation of 4,7-dibromo-5,6-dimethyl-2,1,3-benzoselenadiazole

Weigh 4,5-dimethyl-1,2-phenylenediamine (5.45 grams, 0.04 moles), dissolve in 18 milliliters of ethanol, heat to reflux, add dropwise an aqueous solution of selenium dioxide (4.66 grams, 0.042 moles) (hot 10 milliliters of water), the dropwise addition was completed, and refluxed for half an hour. Recrystallize from n-hexane to obtain needle-like white slightly yellow crystals of 5,6-dimethyl-2,1,3-benzoselenadiazole. This product was brominated according to Example 6, Method A. Weigh 5,6-dimethyl-2,1,3-benzoselenodiazole (2.11 g, 0.01 mole), silver sulfate (3.12 g, 0.01 mole), dissolve in 20 ml of concentrated sulfuric acid, stir, drop Add bromine (3.2 g, 0.02 mol), after the addition is complete, react at room temperature for 75 minutes, filter off the precipitated silver bromide, pour the filtrate into ice water, and then recrystallize with 450 ml of ethyl acetate to obtain golden yellow needle crystals. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 4,7-dibromo-5,6-dimethyl-2,1,3-benzoselenadiazole.

Example 11: Preparation of 4,7-dibromo-5-alkyl-2,1,3-benzoselenadiazole

The preparation of 4,7-dibromo-5-n-octyl-2,1,3-benzoselenadiazole is taken as an example to illustrate. Weigh 4-chloro-1,2-phenylenediamine (5.70 g, 0.04 mol), dissolve it in 20 ml of ethanol, heat to reflux, add dropwise an aqueous solution of selenium dioxide (4.66 g, 0.042 mol) (10 ml of hot water) , the dropwise addition was completed, and refluxed for one hour. Recrystallized with a mixed solvent (n-hexane:ethyl acetate=9:1) to obtain off-white flaky crystals of 5-chloro-2,1,3-benzoselenoadiazole.

Take 1-bromo-n-octane (2.90 g, 15 mmol) and magnesium powder (0.41 g, 17 mmol) in a three-necked flask, add 10 ml of tetrahydrofuran after anhydrous treatment, and reflux until the magnesium powder is left to react. . In another three-necked flask, weigh the dried 5-chloro-2,1,3-benzoselenodiazole (2.17 g, 0.01 mol), add 50 ml of anhydrous tetrahydrofuran, dropwise add Grignard reagent n-octyl Magnesium bromide, reacted for 24 hours, then poured the reactant into water, extracted with ether, combined the ether phase, dried over anhydrous magnesium sulfate, evaporated the solvent, and recrystallized to obtain 5-n-octyl-2,1,3-benzene And selenium diazole.

Weigh 5-n-octyl-2,1,3-benzoselenadiazole (2.95 g, 0.01 mol), silver sulfate (3.12 g, 0.01 mol), dissolve in 20 ml of concentrated sulfuric acid, stir, add bromine dropwise (3.2 g, 0.02 mol), after addition, react at room temperature for 90 minutes, filter off the silver bromide precipitate, pour the filtrate into ice water, then recrystallize with 500 ml of ethyl acetate to obtain needle crystals. ¹ HNMR, GC-MASS, and elemental analysis showed that it was the target product 4,7-dibromo-5-n-octyl 2,1,3-benzoselenadiazole. The substituents in 4,7-dibromo-5-alkyl-2,1,3-benzoselenadiazole include: n-hexyl, n-octyl, 2-ethylhexyl, decyl, but not limited thereto.

Example 12: Preparation of 4,7-dibromo-5,6-dialkyl-2,1,3-benzoselenadiazole

The preparation of 4,7-dibromo-5,6-di-n-octyl-2,1,3-benzoselenadiazole is taken as an example for illustration. Weigh 4,5-dichloro-1,2-phenylenediamine (7.08 g, 0.04 mole), dissolve it in 20 ml of ethanol, heat to reflux, add dropwise an aqueous solution of selenium dioxide (4.66 g, 0.042 mole) (hot water 10 ml), the dropwise addition was completed, and refluxed for 1.5 hours. Recrystallized with a mixed solvent (n-hexane:ethyl acetate=9:1) to obtain off-white flaky crystals of 5,6-dichloro-2,1,3-benzoselenadiazole. Take 1-bromo-n-octane (4.83 g, 25 mmol) and magnesium powder (0.65 g, 27 mmol) in a three-necked flask, add 10 ml of anhydrous-treated tetrahydrofuran, and reflux until the magnesium powder is almost gone. In another three-necked flask, weigh the dried 5,6-dichloro-2,1,3-benzoselenadiazole (2.52 g, 0.01 mol), add 50 ml of anhydrous tetrahydrofuran, dropwise add Grignard Reagent n-octyl magnesium bromide, reacted for 24 hours, then poured the reactant into water, extracted with ether, combined the ether phase, dried with anhydrous magnesium sulfate, evaporated the solvent, and recrystallized to obtain 5,6-di-n-octyl-2 , 1,3-Benzoselenadiazole.

Weigh 5,6-di-n-octyl-2,1,3-benzoselenadiazole (4.07 g, 0.01 mole), silver sulfate (3.12 g, 0.01 mole), dissolve in 20 ml of concentrated sulfuric acid, stir, Bromine (3.2 g, 0.02 mol) was added dropwise. After the addition was complete, the reaction was carried out at room temperature for 120 minutes. The precipitated silver bromide was filtered off. The filtrate was poured into ice water, and then recrystallized with 500 ml of ethyl acetate to obtain needle crystals. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 4,7-dibromo-5,6-di-n-octyl 2,1,3-benzoselenadiazole.

The substituents in 4,7-dibromo-5,6-dialkyl-2,1,3-benzoselenoadiazole include: n-hexyl, n-octyl, 2-ethylhexyl, but not limited thereto.

Example 13: Preparation of 4,9-dibromo-6,7-dialkylselenadiazoquinoxaline

Weigh 5,6-dinitro-2,1,3-benzoselenoadiazole (546 mg, 2.0 mmol), iron powder (1.33 g, 24.0 mmol) was dissolved in 40 ml of acetic acid, at 30 ° C The reaction mixture was stirred for 4 hours, then the reaction mixture was poured into 50 ml of cold 5% sodium hydroxide solution, a precipitate was precipitated, the solution was extracted with ether, the organic layer was washed with brine, dried over sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was Purify by silica gel column chromatography (dichloromethane as the eluent), and then recrystallize in chloroform to obtain the diamine compound.

Get above gained 5,6-diamino-2,1,3-benzoselenodiazole 0.1-0.2 mmol, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen ), or 1.6-2.0 times of 1,2-diketone (butanedione, the product alkyl is methyl; 7,8-tetradecyl dione, the product alkyl is hexyl), mix well, at room temperature After stirring for 10 minutes, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography and recrystallization.

Take the above product 6,7-dialkylselenodiazoquinoxaline (0.01 mole), silver sulfate (0.01 mole), be dissolved in 20 milliliters of concentrated sulfuric acid, stir, add dropwise bromine (0.02 mole), and finish, After reacting at room temperature for 100 minutes, the silver bromide precipitate was filtered off, the filtrate was poured into ice water, and then recrystallized with 450 ml of ethyl acetate to obtain needle crystals. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 4,9-dibromo-6,7-dialkylselenadiazoquinoxaline.

Example 14: Preparation of 5′, 5″-dibromo-6,7-dialkyl-4,9-(2′, 2″)-dithienylselenodiazoquinoxaline

Weigh 4,7-dibromo-5,6-dinitro-2,1,3-benzoselenodiazole (4.27 g, 9.9 mmol), tributyl-2-thienyl tin (8.51 g, 22.8 mmol), was dissolved in 30 milliliters of tetrahydrofuran, then added PdCl ₂ (PPh ₃ ) ₂ (143 mg, 2mol%), the mixture was refluxed for 3 hours, cooled, and a solid was precipitated, filtered, washed with acetonitrile and collected, and then in Recrystallized from tetrahydrofuran.

Get the above gained dinitro compound (874 mg, 2.0 mmol), iron powder (1.33 g, 24.0 mmol) was dissolved in 40 ml of acetic acid, stirred at 30 ° C for 4 hours, then the reaction mixture was poured into 50 ml of cold In 5% sodium hydroxide solution, there was a precipitate, the solution was extracted with ether, the organic phase was washed with brine, dried over sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent dichloromethane) , and then recrystallized in chloroform to obtain diamine compounds.

Weigh 0.1-0.2 mmol of the diamine compound obtained above, 1.4 times of 2,3-dihydroxy-1,4-dioxane (product alkyl is hydrogen), or 1.6-2.0 times of 1,2-diketone (Butanedione, the product alkyl is methyl; 7,8-tetradecyl dione, the product alkyl is hexyl), mix well, stir at room temperature for 10 minutes, evaporate the solvent under reduced pressure, and the residue is Purified by column chromatography and recrystallization.

Weigh the above product 6,7-dialkyl-4,9-(2′,2″)-dithienylselenodiazoquinoxaline (0.01 mole), silver sulfate (0.01 mole), dissolve in 20 ml concentrated In sulfuric acid, stir, add bromine (0.02 mol) dropwise, after the addition is complete, react at room temperature for 100 minutes, filter off the precipitated silver bromide, pour the filtrate into ice water, and then recrystallize with 450 ml of ethyl acetate to obtain needle crystals. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 5′,5″-dibromo-6,7-dialkyl-4,9-(2′,2″)-dithienylselenadiazole quinoxaline.

Example 15: Preparation of 5′,5″-dibromo-6,7-dialkyl-4,9-(2′,2″)-bis-N-methylpyrrolylselenodiazoquinoxaline

The method is the same as in Example 14. Weigh 4,7-dibromo-5,6-dinitro-2,1,3-benzoselenoadiazole (3.02 g, 7.0 mmol), tributyl-2-N-methylpyrrolyl tin (5.75 grams, 15.5 mmol), PdCl ₂ (PPh ₃ ) ₂ (98 mg, 2mol%), was dissolved in 20 milliliters of tetrahydrofuran, the mixture was refluxed for 3 hours, cooled, and a solid was separated out, filtered, washed with acetonitrile and collected, It was then recrystallized from tetrahydrofuran.

Get the above gained dinitro compound (861.5 mg, 2.0 mmol), iron powder (1.33 g, 24.0 mmol) was dissolved in 40 ml of acetic acid, stirred at 30 ° C for 4 hours, then the reaction mixture was poured into 50 ml of cold In 5% sodium hydroxide solution, there was a precipitate, the solution was extracted with ether, the organic phase was washed with brine, dried over sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent dichloromethane) , and then recrystallized in chloroform to obtain diamine compounds. Take by weighing above gained diamine compound 0.1-0.2 mmol, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen), 1.6-2.0 times of 1,2-diketone ( Butanedione, the product alkyl is methyl; 7,8-tetradecyl dione, the product alkyl is hexyl), mix well, stir at room temperature for 10 minutes, evaporate the solvent under reduced pressure, and the residue is collected by column Purified by chromatography and recrystallization.

Weigh the above product 6,7-dialkyl-4,9-(2′,2″)-bis-N-methylpyrrolylselenodiazoquinoxaline (0.01 mole), silver sulfate (0.01 mole), Dissolve in 20 ml of concentrated sulfuric acid, stir, add bromine (0.02 mol) dropwise, and react at room temperature for 100 minutes, filter off the silver bromide precipitate, pour the filtrate into ice water, then recrystallize with 450 ml of ethyl acetate, Needle crystals were obtained. ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 5′,5″-dibromo-6,7-dialkyl-4,9-(2′,2″)-bis -N-Methylpyrrolylselenodiazoquinoxaline.

Example 16: Preparation of 5′,5″-dibromo-6,7-dialkyl-4,9-(2′,2″)-diselenylselenodiazoquinoxaline

The method is the same as in Example 14. Weigh 4,7-dibromo-5,6-dinitro-2,1,3-benzoselenodiazole (3.02 g, 7.0 mmol), tributyl-2-selenophenyltin (6.50 g , 15.5 mmol), PdCl ₂ (PPh ₃ ) ₂ (98 mg, 2mol%), dissolved in 20 ml of tetrahydrofuran, the mixture was refluxed for 3 hours, cooled, a solid precipitated, filtered, washed with acetonitrile and collected, then in tetrahydrofuran Medium recrystallization.

Get the above gained dinitro compound (1.06 g, 2.0 mmol), iron powder (1.33 g, 24.0 mmol) was dissolved in 40 ml of acetic acid, stirred at 30 ° C for 4 hours, then the reaction mixture was poured into 50 ml of cold In 5% sodium hydroxide solution, there was a precipitate, the solution was extracted with ether, the organic phase was washed with brine, dried over sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent dichloromethane) , and then recrystallized in chloroform to obtain diamine compounds. Take by weighing above gained diamine compound 0.1-0.2 mmol, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen), 1.6-2.0 times of 1,2-diketone ( Butanedione, the product alkyl is methyl; 7,8-tetradecyl dione, the product alkyl is hexyl), mix well, stir at room temperature for 10 minutes, evaporate the solvent under reduced pressure, and the residue is collected by column Purified by chromatography and recrystallization.

Weigh the above product 6,7-dialkyl-4,9-(2′,2″)-diselenylselenodiazoquinoxaline (0.01 mole), silver sulfate (0.01 mole), dissolve in 20 ml In concentrated sulfuric acid, stir, add bromine (0.02 mol) dropwise, and react at room temperature for 100 minutes, filter off the silver bromide precipitate, pour the filtrate into ice water, and then recrystallize with 450 ml of ethyl acetate to obtain needle crystals .The ¹ H NMR, GC-MASS, and elemental analysis showed that it was the target product 5′,5″-dibromo-6,7-dialkyl-4,9-(2′,2″)-diselenylselenium Diazolequinoxaline.

Example 17: Preparation of 4,8-dibromo-2,1,3-(5,6,7)-benzodiselenazole

Weigh 5,6-diamino-2,1,3-benzoselenadiazole (8.52 g, 40 mmol), dissolve it in 20 ml of ethanol, reflux, drop heated selenium dioxide (4.66 g, 42 mmol mol) aqueous solution, the addition was completed, refluxed for 1 hour, and purified by n-hexane recrystallization. The product was brominated according to method A of Example 6 to obtain 4,8-dibromo-2,1,3-(5,6,7)-benzodiselenazole.

Example 18: Preparation of 4,8-dibromo-6-thio-2,1,3-benzodiselenadiazole

Method A

Weigh 4,7-dibromo-5,6-dinitrobenzothiadiazole (3.84 g, 10 mmol), dissolve it in acetic acid, and reduce it with iron powder (6.72 g, 120 mmol) to give 4 , 7-dibromo-5,6-diaminobenzothiadiazole. Take the diamine compound (3.24 g, 10 mmol), dissolve it in 5 ml of ethanol, reflux, add hot selenium dioxide (1.22 g, 11 mmol) aqueous solution, dropwise complete, reflux for 1 hour, ethyl acetate Purify by recrystallization to obtain 4,8-dibromo-6-thio-2,1,3-benzobiselenodiazol.

Method B

Weigh 4,7-dibromo-5,6-dinitrobenzoselenoadiazole (4.31 g, 10 mmol), dissolve it in acetic acid, and reduce it with iron powder (6.72 g, 120 mmol) to give 4 , 7-dibromo-5,6-diaminobenzoselenadiazole. Get this diamine compound (1.11 g, 3.0 mmol), thionyl anilide (834 mg, 6.0 mmol), trimethylchlorosilane (592 mg, 5.4 mmol), be dissolved in 15 milliliters of pyridine, 80 ℃ The reaction was stirred for 24 hours, and then 50 ml of carbon tetrachloride was added to produce a solid precipitate, which was filtered and collected, and purified to obtain 4,8-dibromo-6-thio-2,1,3-benzodiseleniadiazole .

Example 19: 5', 5"-dibromo-4,8-(2', 2")-dithienyl-2,1,3-(5,6,7)-benzobiselenoadiazole preparation

Weigh 5,6-diamino-4,7-(2′,2″)-dithienyl-2,1,3-benzoselenadiazole (3.77 g, 10 mmol), dissolve in 5 ml of ethanol In, reflux, add hot selenium dioxide (1.22 grams, 11 mmol) aqueous solution, dropwise, reflux 1 hour, normal hexane recrystallization is purified.By the bromination of this product of embodiment 6 method A, obtain 5 ', 5 "-Dibromo-4,8-(2',2")-dithienyl-2,1,3-(5,6,7)-benzobiselenodiazole.

Example 20: 5′,5″-dibromo-4,8-(2′,2″)-bis-N-methylpyrrolyl-2,1,3-(5,6,7)-benzo Preparation of Biselenodiazol

The method is the same as in Example 19. Weigh 5,6-diamino-4,7-(2′,2″)-bis-N-methylpyrrolyl-2,1,3-benzoselenadiazole (3.71 g, 10 mmol), Be dissolved in 5 milliliters of ethanol, reflux, add hot selenium dioxide (1.22 grams, 11 mmol) aqueous solution, dropwise, reflux 1 hour, normal hexane recrystallization purifies.By the product of embodiment 6 method A bromination, 5′, 5″-dibromo-4,8-(2′,2″)-bis-N-methylpyrrolyl-2,1,3-(5,6,7)-benzodiselenide azole.

实施例21：5′，5″-二溴-4，8-(2′，2″)-二硒吩基-2，1，3-(5，6，7)-苯并双硒二唑的制备

Example 21: 5′,5″-Dibromo-4,8-(2′,2″)-diselenyl-2,1,3-(5,6,7)-benzodiselenyl preparation of

The method is the same as in Example 19. Weigh 5,6-diamino-4,7-(2′,2″)-diselenyl-2,1,3-benzoselenodiazole (4.71 g, 10 mmol), dissolve in 5 ml In ethanol, reflux, add hot selenium dioxide (1.22 grams, 11 mmol) aqueous solution, dropwise, reflux 1 hour, n-hexane recrystallization purification.By the product of embodiment 6 method A bromination, obtain 5 ', 5"-Dibromo-4,8-(2',2")-diselenyl-2,1,3-(5,6,7)-benzodiselenyl.

Example 22: Preparation of 5′, 5″-dibromo-4,8-(2′, 2″)-dithienyl-6-thio-2,1,3-benzodiselenyl

Weigh 5,6-diamino-4,7-(2′,2″)-dithienyl-2,1,3-benzothiadiazole (990 mg, 3.0 mmol), dissolve in 3 ml ethanol In, reflux, add the hot selenium dioxide (0.35 gram, 3.1 mmol) aqueous solution, dropwise complete, reflux 1 hour, normal hexane recrystallization is purified.By the bromination of this product of embodiment 6 method A, obtain 5 ', 5 "-Dibromo-4,8-(2',2")-dithienyl-6-thio-2,1,3-benzobiselenoadiazole.

Example 23: 5′,5″-Dibromo-4,8-(2′,2″)-bis-N-methylpyrrolyl-6-thio-2,1,3-benzodiselenide Preparation of azole

The method is the same as in Example 22. Weigh 5,6-diamino-4,7-(2′,2″)-bis-N-methylpyrrolyl-2,1,3-benzothiadiazole (3.24 g, 10 mmol), Be dissolved in 5 milliliters of ethanol, reflux, add hot selenium dioxide (1.22 grams, 11 mmol) aqueous solution, dropwise, reflux 1 hour, normal hexane recrystallization purifies.By the product of embodiment 6 method A bromination, 5′,5″-dibromo-4,8-(2′,2″)-bis-N-methylpyrrolyl-6-thioxo-2,1,3-benzodiselenodiazol was obtained.

Example 24: Preparation of 5′, 5″-dibromo-4,8-(2′, 2″)-diselenyl-6-thio-2,1,3-benzodiselenyl

The method is the same as in Example 22. Weigh 5,6-diamino-4,7-(2′,2″)-diselenyl-2,1,3-benzothiadiazole (4.24 g, 10 mmol), dissolve in 5 ml In ethanol, reflux, add hot selenium dioxide (1.22 grams, 11 mmol) aqueous solution, dropwise, reflux 1 hour, n-hexane recrystallization purification.By the product of embodiment 6 method A bromination, obtain 5 ', 5"-Dibromo-4,8-(2',2")-diselenyl-6-thio-2,1,3-benzodiselenyl.

Example 25: Preparation of 5′, 5″-dibromo-4,7-(2′, 2″)-diselenyl-2,1,3-benzothiadiazole

Weigh 4,7-dibromo-2,1,3-benzothiadiazole (4.41 g, 15.0 mmol), tributyl-2-selenyltin (15.1 g, 36.1 mmol), dissolve in To 100 ml of tetrahydrofuran, PdCl ₂ (PPh ₃ ) ₂ (213 mg, 2 mol%) was added. The reaction mixture was refluxed for 10 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, dichloromethane/n-hexane, 1:1), then recrystallized in ethanol-toluene mixed solvent, brominated , separation and purification to obtain the target product 5′,5″-dibromo-4,7-(2′,2″)-diselenyl-2,1,3-benzothiadiazole.

Example 26: Preparation of 5′, 5″-dibromo-4,7-(2′, 2″)-dithienyl-2,1,3-benzoselenadiazole

The method is the same as in Example 25. Weigh 4,7-dibromo-2,1,3-benzoselenadiazole (5.1 g, 15.0 mmol), tributyl-2-thienyl tin (13.47 g, 36.1 mmol), dissolve in 100 To mL tetrahydrofuran, PdCl ₂ (PPh ₃ ) ₂ (213 mg, 2 mol%) was added. The reaction mixture was refluxed for 10 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, dichloromethane/n-hexane, 1:1), then recrystallized in ethanol-toluene mixed solvent, brominated , separation and purification to obtain the target product 5′,5″-dibromo-4,7-(2′,2″)-dithienyl-2,1,3-benzoselenadiazole.

Example 27: Preparation of 5′, 5″-dibromo-4,7-(2′, 2″)-bis-N-methylpyrrolyl-2,1,3-benzoselenadiazole

The method is the same as in Example 25. Weigh 4,7-dibromo-2,1,3-benzoselenadiazole (5.1 g, 15.0 mmol), tributyl-2-N-methylpyrrolyl tin (13.35 g, 36.1 mmol) , was dissolved in 100 ml THF, and PdCl ₂ (PPh ₃ ) ₂ (213 mg, 2 mol%) was added. The reaction mixture was refluxed for 10 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, dichloromethane/n-hexane, 1:1), then recrystallized in ethanol-toluene mixed solvent, brominated , separation and purification to obtain the target product 5′,5″-dibromo-4,7-(2′,2″)-bis-N-methylpyrrolyl-2,1,3-benzoselenadiazole.

Example 28: Preparation of 5′, 5″-dibromo-4,7-(2′, 2″)-diselenyl-2,1,3-benzoselenodiazole

The method is the same as in Example 25. Weigh 4,7-dibromo-2,1,3-benzoselenadiazole (5.1 g, 15.0 mmol), tributyl-2-selenyl tin (15.15 g, 36.1 mmol), dissolve in To 100 ml of tetrahydrofuran, PdCl ₂ (PPh ₃ ) ₂ (213 mg, 2 mol%) was added. The reaction mixture was refluxed for 10 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, dichloromethane/n-hexane, 1:1), then recrystallized in ethanol-toluene mixed solvent, brominated , separation and purification to obtain the target product 5′,5″-dibromo-4,7-(2′,2″)-diselenyl-2,1,3-benzoselenodiazole.

Example 29: Preparation of 5′,5″-dibromo-2,3-dialkyl-5,8-(2′,2″)-diselenylquinoxaline

Weigh 4,7-dibromo-2,1,3-benzothiadiazole (4.41 g, 15.0 mmol), tributyl-2-selenyl tin (15.15 g, 36.1 mmol), dissolve in To 100 ml of tetrahydrofuran, PdCl ₂ (PPh ₃ ) ₂ (213 mg, 2 mol%) was added. The reaction mixture was refluxed for 10 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, dichloromethane/n-hexane, 1:1), and then recrystallized in ethanol-toluene mixed solvent to obtain 4 , 7-(2',2")-diselenyl-2,1,3-benzothiadiazole.

Weigh 4,7-(2′, 2″)-diselenyl-2,1,3-benzothiadiazole (394 mg, 1.00 mmol), zinc powder (1.33 g, 20.3 mmol), Dissolve in 15 milliliters of acetic acid, reflux 25 minutes.The reaction mixture is filtered, and the residue is washed with ether, and 100 milliliters of ether are added in the filtrate, and are washed with 5% sodium hydroxide and brine respectively, and the organic layer is dried over magnesium sulfate. The solvent was evaporated and purified by silica gel column chromatography (dichloromethane as eluent) to obtain 1,2-diamino-3,6-(2′,2″)diselenylbenzene.

Take 1,2-diamino-3,6-(2′,2″)-diselenylbenzene (136 mg, 0.37 mmol), 1.0-1.5 times of 1,2-diketone (butanedione, The product alkyl is methyl; 7,8-tetradecyl dione, the product alkyl is hexyl), was dissolved in 5 milliliters of acetic acid, stirred and reacted at room temperature for 20 minutes, evaporated the solvent under reduced pressure, and the residue was collected by column Chromatography and recrystallization purification. Bromination, separation and purification to obtain the target product 5', 5"-dibromo-2,3-dialkyl-5,8-(2', 2")-diselenylquinoxa phylloline.

Example 30: Preparation of 5′,5″-dibromo-2,3,7,8-tetramethyl-5,10-(2′,2″)-diselenylpyrazinoquinoxaline

Weigh 5,6-dinitro-4,7-(2′,2″)-diselenylbenzothiadiazole (247 mg, 0.51 mmol), zinc powder (693 mg, 10.6 mmol) , dissolved in 5 ml of acetic acid, stirred and reacted at 60°C for 1 hour, cooled to room temperature, diethyl ketone (0.35 g, 4.1 mmol) was added to the reaction flask, the mixture was stirred for another 1 hour, and the solvent was evaporated under reduced pressure, The residue was purified by silica gel column chromatography (eluent dichloromethane), then recrystallized with tetrahydrofuran, brominated, separated and purified to obtain the target product 5',5"-dibromo-2,3,7,8-tetramethyl Base-5,10-(2′,2″)-diselenylpyrazinoquinoxaline.

Example 31: Preparation of 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-diselenylthienopyrazine

Weigh 2,5-dibromo-3,4-dinitrothiophene (5.01 g, 15.1 mmol), tributyl-2-selenyltin (15.15 g, 36.1 mmol), dissolve in 100 ml THF , PdCl ₂ (PPh ₃ ) ₂ (108 mg, 1 mol%) was added. The mixture was refluxed for 20 hours, cooled, concentrated under reduced pressure, n-hexane was added to the residue, a precipitate was formed and filtered, the precipitate was washed with n-hexane, and recrystallized in a methanol-toluene mixed solvent to obtain a dinitro compound.

Get this dinitro compound (3.91 g, 9.05 mmol), form a suspension in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acid, add dropwise anhydrous tin dichloride (51.20 g, 270 mmol) ethanol solution (60 milliliter), the mixture was stirred and reacted at 30°C for 18 hours, poured into 200 milliliters of cold 25% sodium hydroxide solution, added 100 milliliters of toluene, shaken the reaction mixture vigorously, then filtered through diatomaceous earth, separated the phases, and the aqueous layer Extract with toluene, wash the organic layer with brine, dry over sodium sulfate, evaporate the solvent under reduced pressure, and recrystallize from ethanol to obtain the diamino compound.

Get this diamino compound 0.1-0.2 millimoles, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen), or 1.2-2.0 times of 1,2-diketone (butylene Diketone, the product alkyl is methyl; 7,8-tetradecyl diketone, the product alkyl is hexyl), mix well, stir in 5-10 ml of methanol solution at 60°C for 2 hours, evaporate under reduced pressure The solvent was removed, and the crude product was purified by column chromatography and recrystallization. Bromination, separation and purification, the target product 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-diselenylthienopyrazine was obtained.

Example 32: Preparation of 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-dithienylselenophenopyrazine

The method is the same as in Example 31. Weigh 2,5-dibromo-3,4-dinitroselenophene (5.72 g, 15.1 mmol), tributyl-2-thienyl tin (13.47 g, 36.1 mmol), dissolve in 100 ml THF , PdCl ₂ (PPh ₃ ) ₂ (108 mg, 1 mol%) was added. The mixture was refluxed for 16 hours, cooled, concentrated under reduced pressure, n-hexane was added to the residue, a precipitate was formed and filtered, the precipitate was washed with n-hexane, and recrystallized in a methanol-toluene mixed solvent to obtain a dinitro compound. Get this dinitro compound (3.49 g, 9.05 mmol), form a suspension in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acid, add dropwise anhydrous tin dichloride (51.20 g, 270 mmol) ethanol solution (60 milliliter), the mixture was stirred and reacted at 30°C for 18 hours, poured into 200 milliliters of cold 25% sodium hydroxide solution, added 100 milliliters of toluene, shaken the reaction mixture vigorously, then filtered through diatomaceous earth, separated the phases, and the aqueous layer Extract with toluene, wash the organic layer with brine, dry over sodium sulfate, evaporate the solvent under reduced pressure, and recrystallize from ethanol to obtain the diamino compound.

Get this diamino compound 0.1-0.2 millimoles, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen), or 1.2-2.0 times of 1,2-diketone (butylene Diketone, the product alkyl is methyl; 7,8-tetradecyl diketone, the product alkyl is hexyl), mix well, stir in 5-10 ml of methanol solution at 60°C for 2 hours, evaporate under reduced pressure The solvent was removed, and the crude product was purified by column chromatography and recrystallization. Bromination, separation and purification, the target product 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-dithienylselenophenopyrazine was obtained.

Example 33: Preparation of 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-diselenylselenophenopyrazine

The method is the same as in Example 31. Weigh 2,5-dibromo-3,4-dinitroselenophene (5.72 g, 15.1 mmol), tributyl-2-selenophenyltin (15.15 g, 36.1 mmol), dissolve in 100 ml In tetrahydrofuran, PdCl ₂ (PPh ₃ ) ₂ (108 mg, 1 mol%) was added. The mixture was refluxed for 20 hours, cooled, concentrated under reduced pressure, n-hexane was added to the residue, a precipitate was formed and filtered, the precipitate was washed with n-hexane, and recrystallized in a methanol-toluene mixed solvent to obtain a dinitro compound. Get this dinitro compound (4.34 g, 9.05 mmol), form a suspension in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acid, add dropwise anhydrous tin dichloride (51.20 g, 270 mmol) ethanol solution (60 milliliter), the mixture was stirred and reacted at 30°C for 18 hours, poured into 200 milliliters of cold 25% sodium hydroxide solution, added 100 milliliters of toluene, shaken the reaction mixture vigorously, then filtered through diatomaceous earth, separated the phases, and the aqueous layer Extract with toluene, wash the organic layer with brine, dry over sodium sulfate, evaporate the solvent under reduced pressure, and recrystallize from ethanol to obtain the diamino compound.

Get this diamino compound 0.1-0.2 millimoles, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen), or 1.2-2.0 times of 1,2-diketone (butylene Diketone, the product alkyl is methyl; 7,8-tetradecyl diketone, the product alkyl is hexyl), mix well, stir in 5-10 ml of methanol solution at 60°C for 2 hours, evaporate under reduced pressure The solvent was removed, and the crude product was purified by column chromatography and recrystallization. Bromination, separation and purification, the target product 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-diselenylselenophenopyrazine was obtained.

Example 34: Preparation of 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-bis-N-methylpyrrolylselenophenopyrazine

The method is the same as in Example 31. Weigh 2,5-dibromo-3,4-dinitroselenophene (5.72 g, 15.1 mmol), tributyl-2-N-methylpyrrolyl tin (13.35 g, 36.1 mmol), dissolve In 100 ml of tetrahydrofuran, PdCl ₂ (PPh ₃ ) ₂ (108 mg, 1 mol%) was added. The mixture was refluxed for 18 hours, cooled, and concentrated under reduced pressure. Added n-hexane to the residue to form a precipitate and filtered it. The precipitate was washed with n-hexane and recrystallized in a methanol-toluene mixed solvent to obtain a dinitro compound. Get this dinitro compound (3.43 g, 9.05 mmol), form a suspension in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acid, add dropwise anhydrous tin dichloride (51.20 g, 270 mmol) ethanol solution (60 milliliter), the mixture was stirred and reacted at 30°C for 18 hours, poured into 200 milliliters of cold 25% sodium hydroxide solution, added 100 milliliters of toluene, shaken the reaction mixture vigorously, then filtered through diatomaceous earth, separated the phases, and the aqueous layer Extract with toluene, wash the organic layer with brine, dry over sodium sulfate, evaporate the solvent under reduced pressure, and recrystallize from ethanol to obtain the diamino compound.

Get this diamino compound 0.1-0.2 millimoles, 1.4 times of 2,3-dihydroxyl-1,4-dioxane (product alkyl is hydrogen), or 1.2-2.0 times of 1,2-diketone (butylene Diketone, the product alkyl is methyl; 7,8-tetradecyl diketone, the product alkyl is hexyl), mix well, stir in 5-10 ml of methanol solution at 60°C for 2 hours, evaporate under reduced pressure The solvent was removed, and the crude product was purified by column chromatography and recrystallization. Bromination, separation and purification, the target product 5′,5″-dibromo-2,3-dialkyl-5,7-(2′,2″)-bis-N-methylpyrrolylselenophenopyridine Zinc.

Example 35: Preparation of 4,6-Dibromoselenophenoselenadiazole

Weigh 2,5-dibromo-3,4-diaminoselenophene (3.19 g, 10 mmol), dissolve in 5 ml of ethanol solution, reflux, drop heated selenium dioxide (1.22 g, 11 mmol) The aqueous solution, after dropping, was refluxed for half an hour, and recrystallized from n-hexane-ethyl acetate to obtain the target product 4,6-dibromoselenophenoselenadiazole.

Example 36: Preparation of 4,6-Dibromoselenophenothiadiazole

The method is the same as in Example 35. Weigh 2,5-dibromo-3,4-diaminoselenophene (3.19 g, 10 mmol), dissolve in 7 ml of pyridine, reflux, add dropwise thionanilide (2.78 g, 20 mmol), After dropping, reflux for half an hour, and recrystallize from n-hexane-ethyl acetate to obtain the target product 4,6-dibromoselenophenothiadiazole.

Example 37: Preparation of 4,6-dibromothienoselenadiazole

The method is the same as in Example 35. Weigh 2,5-dibromo-3,4-diaminothiophene (2.72 g, 10 mmol), dissolve in 6 ml of ethanol solution, reflux, drop heated selenium dioxide (1.22 g, 11 mmol) aqueous solution , After dropping, reflux for half an hour, and recrystallize from n-hexane-ethyl acetate to obtain the target product 4,6-dibromothienoselenadiazole.

Example 38: Preparation of 2,5-dibromo-3-alkylselenophene

Weigh 3-bromoselenophene (2.10 g, 10 mmol), magnesium powder (0.26 g, 11 mmol), add 5 milliliters of tetrahydrofuran, nitrogen protection, when the magnesium reaction is nearly complete, add bromoalkane (10 mmol) dropwise. mol), purified by column chromatography and recrystallization. Bromination, separation and purification, in 2,5-dibromo-3-alkylselenophene.

Alkyl groups include: n-hexyl, n-octyl, 2-ethylhexyl, cyclohexyl, p-n-octylphenyl, etc.

Example 39: Preparation of 2,5-dibromo-3,4-dialkylselenophene

The method is the same as in Example 38. Weigh 3-alkylselenophene, brominate the 4-position to obtain 3-bromo-4-alkylselenophene, and then substitute Grignard reagent at the 3-position to obtain 3,4-dialkylselenophene. Bromination at 2,5-position, separation and purification to obtain the target product 2,5-dibromo-3,4-dialkylselenophene.

Alkyl groups include: 3-methyl-4-cyclohexyl, 3,4-dioctyl, etc.

实施例40：5，5′-二溴-2，2′-连硒吩的制备

Example 40: Preparation of 5,5'-dibromo-2,2'-selenophene

Weigh 2-bromoselenophene (2.10 g, 10 mmol), magnesium (0.26 g, 11 mmol), add 5 ml of tetrahydrofuran to make Grignard reagent, add dropwise 2-bromoselenophene (2.10 mmol) to the reaction mixture g, 10 mmol) in tetrahydrofuran, column chromatography. Bromination, separation and purification, the target product 5,5'-dibromo-2,2'-selenophene was obtained.

Example 41: Preparation of 5,5'-dibromo-1'-thio-2,2'-selenophene

The method is the same as in Example 40. Weigh 2-bromothiophene (1.63 g, 10 mmol), magnesium (0.26 g, 11 mmol), add 5 ml of tetrahydrofuran to make Grignard reagent, add 2-bromoselenophene (2.10 g , 10 mmol) THF solution, column chromatography. Bromination, separation and purification, the target product 5,5'-dibromo-1'-thio-2,2'-selenophene was obtained.

Example 42: Preparation of 5′,5″-dibromo-2,5-(2′,2″)-dithienylselenophene

The method is the same as in Example 40. Weigh 2-bromothiophene (3.59 g, 22 mmol), magnesium (0.58 g, 24 mmol), add 10 ml of tetrahydrofuran to make Grignard reagent, add 2,5-dibromoselenophene dropwise to the reaction mixture (2.10 g, 10 mmol) in tetrahydrofuran, column chromatography. Bromination, separation and purification, the target product 5′,5″-dibromo-2,5-(2′,2″)-dithienylselenophene was obtained.

Example 43: Preparation of 5′,5″-dibromo-2,5-(2′,2″)-diselenylthiophene

The method is the same as in Example 40. Weigh 2-bromoselenophene (4.62 g, 22 mmol), magnesium (0.58 g, 24 mmol), add 10 ml of tetrahydrofuran to make Grignard reagent, add 2,5-dibromothiophene dropwise to the reaction mixture (1.63 g, 10 mmol) in tetrahydrofuran, column chromatography. Bromination, separation and purification, the target product 5′,5″-dibromo-2,5-(2′,2″)-diselenylthiophene was obtained.

Example 44: Preparation of 4,9-dibromo-2,1,3-naphthoselenadiazole

2,3-Diaminonaphthalene was recrystallized in hot water to obtain white crystals. The recrystallized product of 2,3-diaminonaphthalene (0.513 g, 3.20 mmol) was weighed and placed in a 50 ml three-neck flask, 15 ml of glacial acetic acid was added, and magnetically stirred to dissolve it. Separately take bromine (1.07 g, 6.7 mmol) and dissolve it in 3 ml of glacial acetic acid, drop it into the glacial acetic acid solution of diaminonaphthalene, and stir vigorously at the same time, and continue stirring for 15 minutes after the addition is complete, at this time brown precipitate appear, filter and wash successively with 15 ml of glacial acetic acid, 80 ml of 2% sodium carbonate solution and 50 ml of distilled water, the color of the filtrate turns pink, put it in a vacuum drying oven at 40°C and dry for 24 hours to obtain the crude product dibromo 0.91 grams of diaminonaphthalene.

Take 0.9 g (2.83 mmol) of the crude product of dibromodiaminonaphthalene and dissolve it in 100 ml of ethanol, filter to obtain a dark red clear solution, and transfer the solution to a 500 ml beaker with a mechanical stirrer. Selenium dioxide (0.33 g, 3.0 mmol) was dissolved in 10 milliliters of distilled water, and the selenium dioxide solution was poured into a beaker while stirring vigorously, and a large amount of purple precipitates appeared immediately, continued to stir for 30 minutes, and then filtered, and dissolved in ethyl acetate Recrystallization gave 0.61 g of purple floc. After detection, it was the target product 4,9-dibromo-2,1,3-naphthoselenadiazole.

Example 45: Preparation of 4,7-dibromo-2,1,3-benzothiadiazole

4,7-Dibromo-2,1,3-benzothiadiazole was prepared according to the method disclosed in J. Heterocycl. Chem. 7 (1970) 629. Weigh benzothiadiazole (13.6 g, 0.1 mol), dissolve it in 20 ml of 45% hydrobromic acid, heat and stir until reflux, and add bromine (48 g, 0.3 mol) dropwise. After the dropwise addition was completed, an additional 10 ml of hydrobromic acid was added and reflux was continued for 2.5 hours. The reaction mixture was filtered while it was hot, cooled, filtered again, washed with water, dried, and recrystallized from chloroform to obtain 4,7-dibromo-2,1,3-benzothiadiazole.

Example 46: Preparation of 4,9-dibromo-2,1,3-naphthothiadiazole

The method was the same as in Example 44. 2,3-Diaminonaphthalene was recrystallized in hot water to obtain white crystals. The recrystallized product of 2,3-diaminonaphthalene (0.513 g, 3.20 mmol) was weighed and placed in a 50 ml three-neck flask, 15 ml of glacial acetic acid was added, and magnetically stirred to dissolve it. Another bromine (1.07 g, 6.7 mmol) was dissolved in 3 ml of glacial acetic acid, and the bromine was dropped into the glacial acetic acid solution of diaminonaphthalene while vigorously stirring. After the addition was completed, the stirring was continued for 15 minutes, and a brown precipitate appeared at this time. appear, filter and wash successively with 15 ml of glacial acetic acid, 80 ml of 2% sodium carbonate solution and 50 ml of distilled water. Substituted diaminonaphthalene 0.91 grams. Take 0.9 g (2.83 mmol) of the crude product of dibromodiaminonaphthalene, thionanilide (0.79 g, 5.66 mmol), trimethylchlorosilane (587 mg, 5.4 mmol), be dissolved in 15 ml of pyridine , stirred and reacted at 80°C for 24 hours, then added 50 ml of carbon tetrachloride, resulting in solid precipitation, which was collected by filtration and purified to obtain 4,9-dibromo-2,1,3-naphthothiadiazole.

The following are polymerization examples:

Example 47: Preparation of fluorene-containing copolymer

Take 5 millimoles of 9,9-disubstituted-2,7-fluorene diboronic acid ester and 5 millimoles of dibrominated compound, dissolve them in 30 milliliters of toluene, add 5 milliliters of phase transfer catalyst ALIQUAT 336, triphenyl Phosphopalladium 70-80 mg, 2M sodium carbonate aqueous solution 10 ml. The mixture was heated to reflux, and the reaction was stirred for 48 hours, then 1 ml of bromobenzene was added for capping, and the reaction was continued for 3 hours. The reaction mixture was cooled, slowly poured into 1 liter of methanol solution with stirring, and filtered to collect the precipitated fibrous polymer. It was washed with 300 ml of methanol, dried, then dissolved in 150 ml of toluene, and purified by silica gel column chromatography using toluene as eluent. Concentrate the eluent, slowly pour it into 1 liter of methanol solution with stirring, filter out the precipitate, pour it into 500 ml of acetone, stir for 5 hours, filter, and dry under vacuum to obtain a copolymer. The composition ratio of some polymers, the ultraviolet absorption peak of the film, the photoluminescence spectrum peak, the electroluminescence spectrum peak, the photoluminescence efficiency, and the electroluminescence efficiency are listed in Table 4.

Example 48: Preparation of carbazole-containing copolymer

The method is the same as in Example 47. N-substituted-3,6-carbazole diboronate was used instead of 9,9-disubstituted-2,7-fluorene diboronate.

Example 49: Preparation of Selenium-Containing Heterocyclic Conjugated Homopolymers (Preparation of Homopolymers of Benzoselenodiazole and Selenophene Derivatives)

The reaction flask was rinsed several times with dry argon flow, and 5 mmoles of dibromoalkyl-substituted benzoselenodiazole (or dibromoalkyl-substituted selenophene) were weighed, and 0.08 mmoles of catalyst Ni(COD) ₂ -pyridine complex , adding 8 ml of refined and dry mixed solvent of N,N-dimethylformamide and toluene, raising the temperature to 90°C and stirring for 48 hours, adding 10 ml of toluene in batches each time. The reaction mixture was poured into 200 ml of chloroform solution, filtered, and the solvent was evaporated under reduced pressure. Using toluene as the eluent, the solvent was removed, washed with acetone, collected, and dried in vacuo.

The following examples illustrate the fabrication and characteristics of devices made of the luminescent material proposed in the present invention. But the present invention will not be limited to the listed examples

Example 50: Preparation of polymer electroluminescent device

After the ITO glass is ultrasonically cleaned and treated with oxygen-Plasma, the sheet resistance of the ITO glass is 10Ω/□. The polymer of the hole injection layer is PEDT or PVK, and the polymer synthesized above is used for the light emitting layer. Both the hole injection layer and the polymer light-emitting layer are fabricated by spin coating. Cathode electrode adopts Ca/Al, Ba/Al metal respectively. A positive bias was applied between the ITO and the metal electrode to obtain a luminous intensity of 100Cd/m ² to test the characteristics of the device.

The aforementioned ITO refers to indium tin oxide conductive glass; PEDT refers to polyethylenedioxythiophene; PVK refers to polyvinylcarbazole.

Schedule:

Table 1 Table 1

Table 2 Table 2

table 3

Bromide monomers of benzoselenadiazole and selenophene derivatives

Table 4

Claims (6)

1. polymkeric substance that contains selenium heterocyclic compound, the light emitting region that it is characterized in that described polymkeric substance is dissolved in organic solvent in the 400-1100 nanometer, comprises the heterocycle component that contains elemental selenium; The described heterocycle component that contains elemental selenium has following one or more structural units:

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl, alkoxyl group;

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl;

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl;

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl, X is S, Se, N-Me;

X is S, Se;

X is S, Se, N-Me;

2. polymkeric substance according to claim 1, be characterised in that also comprise another component unit gather fluorenes, poly-to benzene, p-phenylene vinylene, poly-SPIRO-to benzene, trapezoidal poly-in the benzene (ladder-PPP) one or more, the heterocycle component that wherein contains elemental selenium accounts for the 0.1-99% mole in multipolymer, the unitary molecular structure of described another component is as follows:

Poly-fluorenes:

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl;

Poly-to benzene:

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl, alkoxyl group;

The p-phenylene vinylene:

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkoxyl group;

Poly-SPIRO-is to benzene:

R wherein ₁, R ₂Be H, C ₁-C ₂₀Alkyl;

Trapezoidal poly-to benzene (ladder-PPP):

R wherein ₁, R ₂, R ₃, R ₄, R ₅, R ₆Be H, C ₁-C ₂₀Alkyl.

3. the application of the described polymkeric substance of one of claim 1-2 in the preparation luminescent material.

4. the application of the described polymkeric substance of one of claim 1-2 in the preparation photovoltaic material.

5. the application in the luminescent layer of the described polymkeric substance of one of claim 1-2 in preparation photodiode, flat-panel monitor.

6. the application of the described polymkeric substance of one of claim 1-2 in the active coating of preparation solar cell.