WO2003059853A1

WO2003059853A1 - Substituted rubenes, a kind of novel functional fluoresent material

Info

Publication number: WO2003059853A1
Application number: PCT/CN2003/000044
Authority: WO
Inventors: Zhizhi Hu; Masaru Kimura; Zhiqiang Zhang; Peng Lei
Original assignee: Zhizhi Hu; Masaru Kimura; Zhiqiang Zhang; Peng Lei
Priority date: 2002-01-17
Filing date: 2003-01-17
Publication date: 2003-07-24
Also published as: AU2003203329A1; CN1418857A

Abstract

This invention relates to substituted rebrenes, which are a kind of novel functional fluoresent materials and can be synthesized by reaction of 6,7-disubstituted-1,4-naphthoquinone and 1,3-diphenyl-(4,5-disubstituted)benzofuran. It is found that the novel functional fluoresent materials can be obtained by introducing certain groups onto the rubrene matrix, for example, a conjugated aromatic or a heteroaromatic ring will form an extended conjugated system and cause the adsorption red-shiftted, which allows to produce a type of new red fluoresent materials. The novel fluoresent materials may be widely used in communication, automation, war industry, chemistry, pharmaceuticals and agriculturals industries etc.

Description

A new type of functional fluorescent material replaces rubrene TECHNICAL FIELD

The present invention relates to a novel functional fluorescent material which replaces rubrene, and belongs to the field of functional pigment technology. Background technique

Functional pigments are pigments such as dyes and pigments that are used outside the fields of fibers, synthetic resins, and coatings. It can generate some special responses under various energy stimuli such as light, heat, electricity, etc. These properties can be used as information recording and display materials for electronic products; photosensitive materials for copiers and laser printers; laser energy conversion materials; solar energy conversion and Storage materials are widely used in communication, automatic control, military, chemical, pharmaceutical, pesticide and other fields.

Organic electroluminescent materials and chemiluminescent materials are very important two kinds of functional pigments.

Organic electroluminescence is a new technology that directly converts electrical energy into light energy by means of chemically functional materials. His research started in the 1960s, and Pope first realized electroluminescence on anthracene single crystals (Pope M et al. J. Chem. Phys., 1963, 38 (8): 2042-2043), but because Obvious luminescence can be observed at a driving voltage of 100V, and the ion efficiency is also low. Due to various constraints, the problems of poor film formation quality and low charge injection efficiency cannot be solved well. The development of electroluminescence has been stagnant. Until 1987, Tang and Vanslyke used 8-hydroxyquinoline aluminum complex (Alq ₃ ) as the light-emitting layer, using ITO electrode and Mg: Ag electrode as the anode and cathode, respectively, to produce high-brightness and high-efficiency green light. Organic electroluminescence thin film devices (Tang CW, Vanslyke SA, Appl. Phys. Lett., 1987, 51 (12): 913-915, whose driving voltage has dropped below 10V, thus achieving a landmark in the history of organic electroluminescence research. Progress. Due to their work, people have paid more attention to the research of organic electroluminescence. In 1990, Burroughes and Braun et al. Used polymer thin film electroluminescent devices made of polyparastyrene (PPV) and its derivatives. Further advances the research work in the field of organic electroluminescence (Burroughes JH et al. Nature, 1990,347 (6293): 539-541; Braun D et al. Thin sold Film s, 1992, 216 (1): 96 ~ 98).

Compared with the electroluminescence of inorganic materials, organic electroluminescent materials have many incomparable advantages, which are mainly manifested in the following three aspects: First, organic materials can obtain full-color light emission in the visible spectral range, especially inorganic The material is difficult to obtain blue light. Second, it can be directly driven by a DC low voltage of dozens of volts or even a few volts. Can be directly matched with integrated circuits. Third, the manufacturing process of the organic electroluminescent device is simple, and an ultra-flat display device can be manufactured at a low cost, so it is easy to be industrialized. It can be seen that since organic electroluminescence technology may be the main technology for making the next generation of ultra-thin flat panel displays, it has aroused great interest in the research of organic electroluminescence materials and devices. Due to the discovery of some excellent electroluminescent materials and the continuous optimization of device structures, some breakthroughs have been made in organic electroluminescence. (See US Pat. No. 5,683,823, 5,645,948, 5,623,080, etc.). Domestic Tian He et al. Reported the preparation and application of electroluminescent materials containing functional groups such as 1,8-naphthylimide and carbazole (CN1272523A, CN1048491C); Qiu Yong et al. Reported containing 8-hydroxyquinoline or 2 - at (2-hydroxyphenyl) benzoxazole and the like functional group preparation and application of an organic electroluminescent material (CN1258710A) _o but in general, good overall performance electroluminescent materials is still very small, especially red Fewer materials, which is an obstacle to full-color organic electroluminescence display and eventual industrialization. Therefore, it is very important to develop electroluminescent materials with excellent performance.

The chemiluminescence phenomenon was discovered as early as 1928, and chemiluminescence devices used as lighting were pushed to practical use in the 1960s. Since chemiluminescence is luminescence at room temperature, chemiluminescence devices can be made into any shape, small in size, light in weight, low in cost, do not need external energy, and can be used underwater or in various other places, so they are widely used. The current chemiluminescent materials are mainly composed of hydrogen peroxide, oxalate derivatives and fluorescent compounds. At present, the problem of developing new chemiluminescent materials with excellent performance is also faced.

Rubrene (Rubrene, 5,6,11,12-tetraphenyltetraphenyl) is a functional pigment with high fluorescence efficiency. It can be used as an electroluminescent material, chemiluminescence sensitizer, and fluorescent material. Wait. At present, Sanyo Corporation of Japan uses rubrene as a guest luminophore, and disperses rubrene in a 10-hydroxybenzoquinoline beryllium layer or a hole transporting layer. The results of both kinds of doping can produce more than 1000cd / m. The blue light with ² brightness has increased the luminous intensity by 100 times, and prolonged the service life of the components, reaching a practical level (Miyata Kiyomizu, "Forefront of Industrialization of Organic EL Elements," NTS (Japan), 1998).

If the rubrene compound can be combined with the polymer material and dispersed uniformly in the polymer film, it is expected that a new functional pigment material exceeding the above-mentioned properties can be prepared. In addition, in this field, the research and development of red electroluminescent materials is at the commanding heights of competition in various countries in the world. This requires a functional rubrene compound with a substituent that can chemically react with a polymer film to form a highly efficient optoelectronic device. Summary of the Invention

The invention aims to provide a new type of organic solid functional material with high fluorescence quantum yield and good low temperature characteristics, instead of rubrene. Utilizing the excellent properties of this material, it can be used to prepare bendable, good low temperature characteristics, It can display a large area, has a wide range of luminous colors, is compatible with various existing technologies, and is a low-cost flat-panel display device. This new material will be widely used in communication, automatic control, military, chemical, pharmaceutical, pesticide and other fields, and develop a new type of red fluorescent material in the field of functional materials for our country.

The invention is implemented as follows:

The preparation of a substituted rubrene is characterized in that the general formula of the substituted rubrene is:

Wherein R, ~ R ₂ may be alkyl, alkenyl, alkynyl, halogen atom, halofluorenyl, phenyl, substituted phenyl, aryl, substituted aryl, acyl, aldehyde, carboxyl, amido, hydroxyl , Alkoxy, sulfanyl, nitro, amino, substituted amino, heterocyclyl, substituted heterocyclyl, sulfonate and other groups.

The substituted rubrene can be synthesized from 6,7-disubstituted-1,4-naphthoquinone and 1,3-diphenyl- (4,5-disubstituted) benzofuran as raw materials.

The preparation method of this substituted rubrene mainly includes the following steps:

In a light-shielded round bottom flask wrapped with aluminum platinum paper, add a certain amount of 6,7-disubstituted-1,4-naphthoquinone and 1,3-diphenyl- (4,5-disubstituted) benzo Furan is reacted under reflux in a non-polar solvent under the protection of nitrogen for several hours, during which other reaction reagents and catalysts are added dropwise according to the specific reaction. High pressure liquid chromatography (HPLC) and thin layer chromatography (TLC) were used to track the entire reaction process and determine the end point of the reaction. After the reaction is completed, the reaction solution is subjected to washing, extraction and the like, and the obtained extract is concentrated by evaporation on a rotary evaporator, and the mixture is obtained after removing the solvent. The mixture was separated by column chromatography to obtain the target intermediate (1), and (I) was treated with phenyllithium or phenylmagnesium bromide to obtain the target product monosubstituted rubrene after post-treatment. After IR, ¾- Identify product structure by NMR, MS and elemental analysis.

Compared with the existing rubrene, the substituted rubrene of the present invention has the following advantages:

Due to the introduction of other groups on the rubrene precursor, a new type of functional pigment material will be synthesized. For example, the introduction of a conjugated aromatic ring or an aromatic heterocyclic ring can make the conjugated system larger and produce a red shift, thereby obtaining a new red fluorescent material.

Below are 2-methyl-5,6,11,12-tetraphenyltetrabenzene and 2- (4,5-diphenyl-2-imidazolyl) -5,6,11,12-tetra The present invention is described in detail by the synthesis of two substituted rubrenes, phenyltetrabenzene. detailed description

Example 1: Synthesis of 2-methyl-5,6,11,12-tetraphenyltetrabenzene (2-methyl substituted rubrene)

(1) Synthesis of 2-methyl-6,11-diphenyl-5,12-tetrabenzoquinone

In a light-shielded 50 mL two-neck round bottom flask wrapped with aluminum platinum paper, add 6-methyl-1,4-naphthoquinone (1.22 g, 7.02 mmol) and 1,3-diphenylbenzofuran ( 1.90 g, 7.04 mmol), methylene chloride solution (50 mL), and under reflux of nitrogen for 48 hours, the solution was added dropwise with BBr ₃ solution (2.74 mL), and then the reaction was continued for 13 hours. The whole reaction process was followed by HPLC and TLC to determine the end point of the reaction. After the reaction was completed, the reaction solution was neutralized with a saturated sodium bicarbonate aqueous solution, and then washed with water, and then the water washing solution was extracted with a methylene chloride solution. The obtained extract was concentrated by evaporation using a rotary evaporator, and the mixture was obtained after removing the solvent. The mixture was separated by column chromatography to obtain 2-methyl-6,11-diphenyl-5,12-tetrabenzoquinone as a yellow crystal product.

(2.29 g, 78%).

The product structural formula is as follows:

Μρ: 249-250

IR (KBr, cm- '): 1673 (C = 0)

'H-NMR (500MHz, CDCl ₃ ): 2.42 (S, 3H); 7.30-7.32 (dd, J = 7.5, 2.0Hz, 2H) _; 7.46 (d, J = 8.0Hz, 1H); 7.48-7.50 ( m, 2H); 7.54-7.60 (m, Sa); 7.88 (s, 1H); 7.98 (d, J = 8.0Hz, 1H)

MS (ED m / z: 425 (M ⁺ + l, 23); 424 (M ⁺ , 87); 423 (M + -1, 100)

(2) Synthesis of 2-methyl-5,6,11,12-tetraphenyltetrabenzene (2-methyl substituted rubrene)

The 2-methyl-6,11-diphenyl-5,12-tetrabenzoquinone and phenyllithium were refluxed in an ether solution under the protection of N ₂ for 60 hours and hydrolyzed under acidic conditions. After the product was treated, Reflux with Fe / AcOH under the protection of N ₂ for 36 hours. The crude product was washed, extracted, and dried to obtain 2-methyl-5,6,11,12-tetraphenyltetraphenyl (2-methyl substituted red fluorescent). Ene).

The product structural formula is as follows:

Mp:> 300 ° C

IR (KBr'cm ¹ ): 3050 (CH of aromatic ring); 2905, 2850 (CH of methyl); 762, 741, 685, 667 (CH of aromatic ring);

Erbium-NMR (300MHz, CDCl ₃ ): 2.37 (S, 3H); 6.82-7.08 (m, 27H)

Example 2: 2- (4,5-diphenyl-2-imidazolyl) -5,6,11,12-tetraphenyltetraphenyl (2- (4,5-diphenyl-2-imidazole) (Synthesis) of substituted rubrene)

(1) Synthesis of 2-dibromomethyl-6,11-diphenyl-5,12-tetrabenzoquinone

In a 50 mL two-necked round-bottomed flask, add the 2-methyl-6,11-diphenyl-5,12-tetrabenzoquinone (619 mg, 1.63 mmol) and N-bromine obtained in Example 1 above. Succinimide (NBS) (1.08 g, 4.89 mmol) and benzoyl peroxide (BPO) (32 mg), dry carbon tetrachloride solution (45 mL), reflux under nitrogen The reaction was conducted for 32 hours. The whole reaction process was followed by HPLC4 and TLC. When the content of the dibromo product began to decrease, the reaction was stopped. The insoluble matter was filtered off, evaporated and concentrated on a rotary evaporator, and the solvent CC1 _{4 was} removed. The product mixture was separated by column chromatography to obtain 2-dibromomethyl-6,11-diphenyl-5,12-tetrabenzoquinone (617.5 mg, 65.1%) as a yellow powdery solid.

The product structural formula is as follows:

Mp: 144-146 ⁰ C

UV (CH ₃ OH) max (log s): 257 (2.93); 249 (3.07); 395 (0.50) IR (KBr, cm '): 1678 (C = 0)

Ή-NMR (200MHz, CDC1 ₃ ): 6.62 (s, IH); 7.29-7.34 (m, 4H); 7.51-7.65 (m, 10H); 7.86-7.91 (dd, J = 8.3, 1.8Hz, IH) ; 8.12 (d, J = 8.3Hz, IH); 8.24 (d, J = 1.8Hz, IH) MS (ΕΓ) m / z: 586 (M ++ 4, 3); 585 (M ⁺ +3, 17); 584 (M ++ 2, 55); 583 (M ++ 1, 57); 584 ( M ⁺ , 100)

(2) Synthesis of 2-formyl-6,11-diphenyl-5,12-tetrabenzoquinone

In a 100 mL two-neck round bottom flask, add 2-dibromomethyl-6,11-diphenyl-5,12-tetrabenzoquinone (429.6 mg, 0.74 mmol) and anhydrous sodium acetate (7.59 g , 92.5 mmol), glacial acetic acid solution (50 mL), under the protection of nitrogen, oil bath temperature of 140 ° C, after refluxing for 24 hours, use HPLC to detect and analyze the changes of raw materials and products in the reaction system. When the product content no longer increases, the entire reaction is stopped. The reaction solution was neutralized with a saturated aqueous solution of sodium bicarbonate, and then washed with water, and then the water washing solution was extracted with ethyl acetate. The obtained extract was concentrated by evaporation on a rotary evaporator, and the solvent was removed to obtain a mixture. The mixture was separated by column chromatography to obtain 2-formyl-6,11-diphenyl-5,12-tetrabenzoquinone (251 mg, 77%) as a yellow powdery solid product.

The product structural formula is as follows:

Mp: 261-263 ° C

IR (KBr'cm- ¹ ): 1700 (C = 0 in aldehyde group); 1678 (C = 0 in quinone structure)

H-NMR (200MHZ, CDC1 ₃ ): 7.28-7.34 (m, 4H); 7.51-7.62 (m, 10H); 8.16 (d, J = 8.6Hz, 1H); 8.23 (d, J = 8.6Hz, 1H); 8.58 (s, 1H); 10.10 (s, 1H)

MS (ΕΓ) m / z: 439 (M ++ 1, 30); 438 (M ⁺ , 100); 437 (M + -1, 98)

(3) Synthesis of 2- (4,5-diphenyl-2-imidazolyl) -6,11-diphenyl-5,12-tetrabenzoquinone

Under the protection of nitrogen, 2-formyl-6,11-diphenyl-5,12-tetrabenzoquinone (100 mg, 0.23 mmol), benzene (53 mg, 0.25 mmol), and anhydrous acetic acid were added to the reaction flask. Sodium (225 mg, 2.74 mmol) and glacial acetic acid (15 ml) were refluxed at 135 ° C for 24 hours. The end point of the reaction was detected by TLC. The reaction solution was neutralized with a saturated sodium bicarbonate aqueous solution, washed with water, and then extracted with ethyl acetate. The solvent was distilled off to obtain 2- (4,5-diphenyl-2-imidazolyl) as orange crystals. ) -6,11-diphenyl-5,12-tetrabenzoquinone (140mg, 98%).

The product structural formula is as follows −

Mp _: 275-277 ° C

UV (CH3OH) A max (log ε): 404 (4.00); 366 (4.02); 269 (4.87) IR (KBr, cm- ') _: 3510 (NH); 1676 (C = 0); 1600 (C = N)

Ή-NMR (300MHz, DMSO): 7.25-7.40 (m, 12H); 7.43-7.60 (m, 10H); 7.62-7.67 (m, 2H); 8.00 (d, J = 8.4Hz, 1H); 8.47 ( d, J = 8.4Hz, 1H); 8.68 (s, 1H); 13.14 (s, 1H)

MS (ED m / z: 630 (M ++ 2, 10); 629 (M ++ l, 45); 628 (M ⁺ , 100); 627 (M + -1, 34)

(4) Synthesis of 2- (4,5-diphenyl-2-imidazolyl) -5,6,11,12-tetraphenyl-5,12-dihydroxytetrabenzene

Under the protection of nitrogen, add 2- (4,5-diphenyl-2-imidazolyl) -6,11-diphenyl-5,12-tetrabenzoquinone to a 100 mL two-necked round bottom flask. (163 mg, 0.26 mmol) and anhydrous ether (50 ml). After irradiating with an ultrasonic bath for 15 minutes, phenyllithium (0.5 ml, 2M) was added, and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the reaction solution was neutralized by hydrolysis, washed with water, and the mixture was separated by column chromatography to obtain a white powdery solid product 2- (4,5-diphenyl-2-imidazolyl) -5, 6,11,12-tetraphenyl-5,12-dihydroxytetrabenzene (121 mg, 60%).

The product structural formula is as follows:

Mp: 244-247 ° C

IR (KBr'cm. ¹ ): 3570 (OH); 3300 (NH); 1597 (C = N); 1000 (CO) 'H-NMR (300MHz, CDC1 ₃ ): 5.60 (br s, 1H); 5.74 (br s, 1H); 6.00 (d, J = 7.5Hz, 1H); 6.14 (d, J = 7.5Hz, 1H); 6.54 (d, J = 7.5Hz, 1H); 6.63 (d, J = 7.5 Hz, 1H); 6.75-7.22 (m, 20H); 7.27-7.62 (m, 13H); 10.03 (br s, 1H)

MS (ED m / z: 766 (M + -18, 2); 750 (2); 94 (100)

(5) 2- (4,5-diphenyl-2-imidazolyl) -5,6,11,12-tetraphenyltetraphenyl (2- (4,5-diphenyl-2-imidazolyl) ) Synthesis of substituted rubrene)

Under the protection of nitrogen, add iron powder (199mg, 3.5mmol), 2- (4,5-diphenyl-2-imidazolyl) -5,6,11, 12-tetraphenyl to a 50ml light-shielded reaction flask. -5,12-dihydroxytetrabenzene (121 mg, 0.16 mmol) and glacial acetic acid (20 ml). After refluxing for 12 hours. After the reaction, the insoluble matter was filtered out in a dark room. The reaction solution was neutralized with a saturated sodium bicarbonate aqueous solution, washed with water, and then extracted with ethyl acetate. The solvent was distilled off to obtain 2- (4,5-di Phenyl-2-imidazolyl) -5,6,11,12-tetraphenyltetraphenyl (substituted rubrene) (llmg, 95

%). '

The product structural formula is as follows:

Mp: 182-185 ° C

UV (C ₂ H ₅ OH) A max (log ε): 538 (4.12); 502 (4.12); 468 (3.91); 306 (5.23)

IR (KBr'cm- ¹ ): 3350 (NH); 3050 (imidazole ring CH); 1603 (C = N)

Ή-NMR (300MHz, CDC1 ₃ ): 6.87 (d, J = 6.4Hz, 2H); 6.93 (d, J = 6.4Hz, 1H); 7. 05-7.75 (m, 34H); 9.34 (br s, 1H)

MS (ΕΓ) m / z: 753 (M ⁺ +3, 19); 752 (M ++ 2, 38); 751 (M ++ l, 63); 750 (M ⁺ , 100)

Claims

Rights request

1. A new type of functional fluorescent material, substituted rubrene, which is characterized in that the name of this fluorescent material is substituted rubrene, which has the following structure:

Where R, ~ R ₂ may be alkyl, alkenyl, alkynyl, halogen atom, haloalkyl, phenyl, substituted phenyl, aryl, substituted aryl, acyl, aldehyde, carboxyl, amido, hydroxyl, fluorene Oxy, sulfanyl, nitro, amino, substituted amino, heterocyclyl, substituted heterocyclyl, sulfonic acid and other groups.

2. A novel functional fluorescent material, substituted rubrene, according to claim 1, characterized in that the substituted rubrene can be substituted by 1,4-naphthoquinone and 1,3-diphenyl. -Synthesis of substituted benzofuran as raw material.

3. The substituted -1,4-naphthoquinone according to claim 2, wherein its structural formula is:

Wherein R may be alkyl, alkenyl, alkynyl, halogen atom, halofluorenyl, phenyl, substituted phenyl, aryl, substituted aryl, acyl, aldehyde, carboxyl, amido, hydroxyl, fluorenyl Groups such as alkyl, sulfanyl, nitro, amino, substituted amino, heterocyclyl, substituted heterocyclyl, and sulfonic acid.

4. The 1,3-diphenyl-substituted benzofuran according to claim 2, which has a general structural formula:

Wherein R ₂ may be fluorenyl, alkenyl, alkynyl, halogen atom, haloalkyl, phenyl, substituted phenyl, aryl, substituted aryl, acyl, aldehyde, carboxyl, amido, hydroxyl, methyloxy, Alkylthio, nitro, amino, substituted amino, heterocyclyl, substituted heterocyclyl, sulfonate and other groups.

5. A novel functional fluorescent material-substituted rubrene according to claim 1, characterized in that the functional group R in the general formula of rubrene is substituted with the following groups:

Fluorenyl, alkenyl, alkynyl, halogen atom, halogenated fluorenyl, phenyl, substituted phenyl, aryl, substituted aryl, acyl, aldehyde, carboxyl, amido, hydroxyl, methoxy, sulfanyl , Nitro, amino, substituted amino, heterocyclyl, substituted heterocyclyl, sulfonic acid and other groups.

6. A new type of functional fluorescent material-substituted rubrene according to claim 1, wherein the functional group R _{2 in the} general formula of the substituted rubrene structure may be the following group:

Fluorenyl, alkenyl, alkynyl, halogen atom, halogenated fluorenyl, phenyl, substituted phenyl, aryl, substituted aryl, acyl, aldehyde, carboxyl, amido, hydroxyl, methoxy, alkylthio , Nitro, amino, substituted amino, heterocyclyl, substituted heterocyclyl, sulfonic acid and other groups.