Synthesis method of dark blue organic light emitting diode material benzo [k] fluoranthene structure
By using a Diels-Alder reaction and oxidation of halogenated aromatic hydrocarbons with polycyclic aromatic hydrocarbons under a catalytic system, the high risk and high cost of benzo[k]fluoranthene synthesis have been solved, achieving a low-cost, industrially suitable synthesis of benzo[k]fluoranthene with high yield and environmental friendliness.
Patent Information
- Application Number
- CN202511630637.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-10
- Publication Date
- 2026-02-24
AI Technical Summary
Existing methods for synthesizing benzo[k]fluoranthene are characterized by high risk, high cost, severe pollution, and unsuitability for industrial production.
Using haloaromatic hydrocarbons as starting materials, a Diels-Alder reaction was carried out with polycyclic aromatic hydrocarbons under the action of a catalytic system. The reaction was further oxidized by the synergistic effect of light and metal catalyst, and then an oxidant was added to obtain benzo[k]fluoranthene.
The synthesis of benzo[k]fluoranthene was achieved, which is simple to operate, low in cost, and suitable for industrial production. It avoids expensive raw materials and high-temperature reactions, conforms to the concept of green chemistry, and has a high yield and simplified post-processing.
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Figure CN121554347A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of chemical synthesis technology, and in particular to a method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure. Background Technology
[0002] Benzo[k]fluoranthene, molecular formula C 20 H 12 The CAS number is 207-08-9, and the structure is as follows: In recent years, organic light-emitting diodes (OLEDs) have become the mainstream light source for display applications, and they can now be seen in a large number of consumer electronic devices used daily. This success is attributed to the rich light-emitting properties of organic materials. OLEDs, proposed by Tang and Van Slyke, are a novel type of electroluminescent device, consisting of a multilayer organic thin film structure sandwiched between a transparent conductive oxide and a metal cathode. Notably, OLED technology is one of the rare examples of unconventional semiconductor technologies achieving successful commercialization, apart from silicon-based semiconductor technologies. High-performance organic light-emitting materials are the material basis for designing OLEDs. Among them, anthracene fluorescent dyes are widely used in the development of small-molecule organic light-emitting materials due to their superior photophysical properties. Benzo[k]fluoranthene, an anthracene derivative, can be used as an important electro-excitation light source material in the preparation of OLED materials; therefore, its synthesis method has certain research value.
[0003] Currently, the main methods for preparing benzo[k]fluoranthene reported in domestic and international literature are as follows: The literature The intramolecular Heck reaction reports a synthetic method using 1,1,1-trifluoromethanesulfonic acid [1,2-binaphthyl]-3-ester as a starting material. The metal catalyst used in this reaction is dichlorobis(triphenylphosphine)palladium, which is relatively expensive. The starting material is not readily available for commercial purchase. The reaction needs to be carried out at high temperature and the post-processing is relatively difficult, which is not conducive to large-scale production.
[0004] Currently, the synthetic methods reported in the literature have many problems, such as high risk, serious pollution, high cost, and complex processes. Therefore, developing a simple method for the preparation of benzo[k]fluoranthene is of great significance. . Summary of the Invention
[0005] The purpose of this invention is to provide a method for synthesizing the deep blue organic light-emitting diode material benzo[k]fluoranthene, which has the advantages of simple operation, readily available raw materials, low cost, mild reaction conditions, and suitability for industrial-scale production.
[0006] The above-mentioned technical objective of the present invention is achieved through the following technical solution: A method for synthesizing a deep blue organic light-emitting diode (OLED) material, benzo[k]fluoranthene, is characterized by using a haloaromatic hydrocarbon as a starting material and reacting it with a polycyclic aromatic hydrocarbon under light irradiation in the presence of a catalytic system; the reaction product is then separated and purified to obtain benzo[k]fluoranthene; the catalytic system includes, but is not limited to, the wavelength of the light source, an inorganic base, a metal catalyst, an oxidant, and an organic solvent. Specifically, the following steps are included: S1: Reflux the mixture of haloaromatic hydrocarbons, inorganic base and organic solvent for half an hour; S2: Add polycyclic aromatic hydrocarbons dissolved in organic solvents dropwise, add a metal catalyst, and react under light for 3 hours; S3: Add an oxidizing agent and continue the reaction under light for 1-3 hours; S4: Monitor the reaction progress, concentrate the reaction solution and recrystallize it with cyclohexane to obtain the crude product of benzo[k]fluoranthene; S5: The crude benzo[k]fluoranthene product was separated and purified to obtain benzo[k]fluoranthene.
[0007] Preferably, the halogenated aromatic hydrocarbon is selected from one or more of 1,2-di(bromomethyl)benzene, 1,2-di(chloromethyl)benzene, 1,2-di(fluoromethyl)benzene, 1,2-di(iodomethyl)benzene, 1-bromo-2-chlorobenzene, 1-bromo-2-fluorobenzene, 1-bromo-2-iodobenzene, 1-chloro-2-fluorobenzene, 1-chloro-2-iodobenzene, and 1-fluoro-2-iodobenzene.
[0008] Preferably, the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate, and tert-butyllithium.
[0009] Preferably, the organic solvent is selected from one of acetonitrile, toluene, dimethyl sulfoxide, N,N-dimethylformamide, tert-butanol, hexafluoroisopropanol, isopropanol, methanol, trifluoroethanol, ethanol, methyl tert-ethyl ether, tetrahydrofuran, dioxane, dichloromethane, dichloroethane, and ethyl acetate.
[0010] Preferably, the polycyclic aromatic hydrocarbon is selected from one of naphthalene, phenanthrene, anthracene, fluorene, carbazole, 9,9'-biphenanthrene, 3,3'-pyridine, benzothiophene, fluoranthene, indene, dihydroacenaphthene, benzofluoranthene, basil, perylene, and xanthene.
[0011] Preferably, the metal catalyst is selected from one or more of ferric chloride, ferrous chloride, zinc chloride, manganese chloride, silver chloride, copper bromide, cuprous bromide, manganese bromide, silver bromide, silver acetate, ferrous acetate, copper chloride, cuprous chloride, copper sulfate, and copper trifluoromethanesulfonate.
[0012] Preferably, the oxidant is selected from one or more of air, oxygen, 2,3-dichloro-5,6-dicyanobenzoquinone, tert-butylhydrogen peroxide, ozone, and dimethyl sulfoxide.
[0013] Preferably, the illumination conditions are selected from one of the following: 380-400nm violet light, 400-480nm blue light, 480-490nm cyan light, 490-500nm blue-green light, and 500nm-560nm green light.
[0014] Preferably, the molar ratio of the polycyclic aromatic hydrocarbon, halogenated aromatic hydrocarbon, oxidant and inorganic base is 1:(1.1-2.5):(0.1-0.5):(0.5-5.0).
[0015] Preferably, the amount of the metal catalyst is 5%-20% of the amount of polycyclic aromatic hydrocarbons.
[0016] The beneficial effects of this invention are as follows: a simple and low-cost method for preparing benzo[k]fluoranthene, a deep blue organic light-emitting diode (OLED) material. Starting with haloaromatic hydrocarbons, the mixture is activated with an inorganic base under heating in the presence of a catalytic system. Under light irradiation, a DA reaction occurs under the synergistic catalytic action of the polycyclic aromatic hydrocarbons and the metal catalyst. Following oxidation with an oxidant, benzo[k]fluoranthene is obtained. The polycyclic aromatic hydrocarbons exhibit autocatalytic activity under light irradiation, synergistically acting as a metal halide catalyst to activate the carbon-halogen bonds on the haloaromatic hydrocarbons, leading to a Diels-Alder cycloaddition reaction with the polycyclic aromatic hydrocarbons. Aromalation then yields the target product, benzo[k]fluoranthene. All raw materials involved in this synthetic route are inexpensive and readily available, avoiding expensive and hazardous chemical raw materials. The reaction is carried out under light irradiation, with mild conditions, which are superior to traditional high-temperature reaction conditions, conforming to the principles of green chemistry and sustainable development. The reaction yield is high, requiring only simple post-processing for subsequent reactions, largely avoiding complex purification operations, making it suitable for industrial-scale production. Furthermore, this invention also provides ideas for the preparation of other anthracene compounds. Attached Figure Description
[0017] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the product obtained in step 6 of Example 1; Figure 2 The image shows the carbon NMR spectrum of the product obtained in step 6 of Example 1. Detailed Implementation
[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.
[0019] Implementation Example 1 S1: Add 471.82 mg (2.0 mmol) of 1,2-di(bromomethyl)benzene, 120 mg (3 mmol) of sodium hydroxide, and 10 mL of dichloromethane to a dry reaction flask, and reflux for 30 minutes; S2: Cool the reaction to room temperature and add 304 mg (2.0 mmol) of naphthoethylene and 19.8 mg (0.2 mmol) of cuprous chloride dissolved in 5 ml of dichloromethane. S3: Place the reaction system under 450 nm blue light for 3 hours; S4: Add a small amount of tert-butyl hydrogen peroxide to the reaction system; S5: Place the reaction system under 450 nm blue light and continue the reaction for 3 hours; S6: The reaction solution was concentrated, recrystallized from cyclohexane (30 ml), filtered, washed, and dried to obtain 428.4 mg of crude benzo[k]fluoranthene, with a yield of 85%.
[0020] Take 20 mg of the purified product obtained in step 6, dissolve it in 0.50 mL of CDCl3, and perform a 1H NMR spectrum. Figure 1 The 1H NMR spectrum of the product obtained in step 6: 1H NMR (400 MHz, CDCl3) δ 8.54 (s, 2H), 8.15 (dd, J = 6.9, 0.6 Hz, 2H), 8.10 – 7.95 (m, 2H), 7.88 (dd, J = 8.3, 0.6 Hz, 2H), 7.75 (d, J = 7.0 Hz,1H), 7.69 (d, J = 7.0 Hz, 1H), 7.50 – 7.545 (m, 2H).
[0021] Perform nuclear magnetic resonance carbon spectroscopy. Figure 2 The carbon NMR spectrum of the product obtained in step 6: 13C NMR (101 MHz, CDCl3) δ 138.8, 137.9, 136.3, 134.5, 131.5, 129.7,129.2, 127.2, 125.0, 119.2,118.2.
[0022] Implementation Example 2 S1: Add 2.83 g (10.0 mmol) of 1,2-di(chloromethyl)benzene, 1.33 g (12.0 mmol) of potassium tert-butoxide, and 50 mL of dimethyl sulfoxide to a dry reaction flask, and reflux for 30 minutes; S2: Cool the reaction to room temperature and add 2.28 g (15.0 mmol) of naphthoethylene dissolved in 10 ml of dimethyl sulfoxide and 251 mg (0.5 mmol) of ferric trifluoromethanesulfonate. S3: Place the reaction system under 380 nm ultraviolet light for 1.5 hours; S4: Add 2.27 g (10.0 mmol) of DDQ to the reaction system. S5: Place the reaction system under 380 nm ultraviolet light and continue the reaction for 1 hour; S6: The reaction solution was concentrated, recrystallized from cyclohexane (120 ml), filtered, washed, and dried to obtain 1.77 g of crude benzo[k]fluoranthene, with a yield of 71%.
[0023] Implementation Example 3 S1: Add 329.2 mg (1.0 mmol) of 1,2-di(iodomethyl)benzene, 138 mg (1.0 mmol) of potassium carbonate, and 5 mL of toluene to a dry reaction flask, and reflux for 30 minutes; S2: Cool the reaction to room temperature and add 304 mg (2.0 mmol) of naphthoethylene dissolved in 5 ml of toluene and 36.1 mg (0.1 mmol) of copper trifluoromethanesulfonate. S3: Place the reaction system under 530 nm green light for 4 hours; S4: Add 227 mg (1.0 mmol) of DDQ to the reaction system; S5: Place the reaction system under 530 nm green light and continue the reaction for 3 hours; S6: The reaction solution was concentrated, recrystallized from cyclohexane (20 ml), filtered, washed, and dried to obtain 103 mg of crude benzo[k]fluoranthene, with a yield of 40.3%.
[0024] Based on the summary of the above implementation cases, we found that using haloaromatic hydrocarbons as starting materials, under the action of a catalytic system, activation is achieved with inorganic bases under heating. Under light irradiation, a Diels-Alder reaction occurs under the synergistic catalytic action of polycyclic aromatic hydrocarbons and metal catalysts. Subsequent oxidation with an oxidant yields benzo[k]fluoranthene. The polycyclic aromatic hydrocarbons exhibit autocatalytic activity under light irradiation, synergistically acting as a catalyst to activate the carbon-halogen bonds on the haloaromatic hydrocarbons, leading to a cycloaddition Diels-Alder reaction with the polycyclic aromatic hydrocarbons. Aromalation then yields the target product, benzo[k]fluoranthene. This synthetic method involves few reaction steps, mild conditions, and simple operation. The reaction product only requires simple post-treatment before use in subsequent work, largely avoiding complex purification processes, making it suitable for industrial-scale production. The reaction yields are good to excellent, with an overall yield ranging from 40% to 87%.
[0025] The innovation of this invention lies in: 1. The synthetic route is short, the reaction raw materials are cheap and readily available, the yield is excellent, the overall yield is high, and the synthesis cost of benzo[k]fluoranthene is greatly reduced; 2. It avoids the use of heavy metal compounds and compounds containing toxic groups, conforms to the concepts of green chemistry and sustainable development, is suitable for the synthesis and development of high-purity small molecule organic light-emitting materials, and has the potential for industrial production.
[0026] 3. The reaction is carried out under light and mild conditions. The operation is simple and the reaction products only need simple post-processing before they can be used for subsequent work, which greatly simplifies the operation.
[0027] All the raw materials listed in this invention, as well as the upper and lower limits and ranges of the raw materials and the upper and lower limits and ranges of the process parameters (such as temperature, time, etc.), can realize this invention. Examples are not listed one by one here.
[0028] The above description is merely a preferred embodiment of the present invention, and should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications are also considered to be within the scope of protection of the present invention.
Claims
1. A method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure, characterized in that, Using haloaromatic hydrocarbons as starting materials, a DA reaction is carried out with polycyclic aromatic hydrocarbons under light irradiation in the presence of a catalytic system; the reaction products are then separated and purified to obtain benzo[k]fluoranthene; the catalytic system includes, but is not limited to, light source wavelength, inorganic base, metal catalyst, oxidant and organic solvent; Specifically, the following steps are included: S1: Reflux the mixture of haloaromatic hydrocarbons, inorganic base and organic solvent for half an hour; S2: Add polycyclic aromatic hydrocarbons dissolved in organic solvents dropwise, add a metal catalyst, and react under light for 3 hours; S3: Add an oxidizing agent and continue the reaction under light for 1-3 hours; S4: Monitor the reaction progress, concentrate the reaction solution and recrystallize it with cyclohexane to obtain the crude product of benzo[k]fluoranthene; S5: The crude benzo[k]fluoranthene product was separated and purified to obtain benzo[k]fluoranthene.
2. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The halogenated aromatic hydrocarbon is selected from one or more of 1,2-di(bromomethyl)benzene, 1,2-di(chloromethyl)benzene, 1,2-di(fluoromethyl)benzene, 1,2-di(iodomethyl)benzene, 1-bromo-2-chlorobenzene, 1-bromo-2-fluorobenzene, 1-bromo-2-iodobenzene, 1-chloro-2-fluorobenzene, 1-chloro-2-iodobenzene, and 1-fluoro-2-iodobenzene.
3. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate, and tert-butyllithium.
4. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The organic solvent is selected from one of acetonitrile, toluene, dimethyl sulfoxide, N,N-dimethylformamide, tert-butanol, hexafluoroisopropanol, isopropanol, methanol, trifluoroethanol, ethanol, methyl tert-ethyl ether, tetrahydrofuran, dioxane, dichloromethane, dichloroethane, and ethyl acetate.
5. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The polycyclic aromatic hydrocarbon is selected from one of naphthalene, phenanthrene, anthracene, fluorene, carbazole, 9,9'-biphenanthrene, 3,3'-pyridine, benzothiophene, fluoranthene, indene, dihydroacenaphthene, benzofluoranthene, flavonoid, perylene, and xanthene.
6. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The metal catalyst is selected from one or more of the following: ferric chloride, ferrous chloride, zinc chloride, manganese chloride, silver chloride, copper bromide, cuprous bromide, manganese bromide, silver bromide, silver acetate, ferrous acetate, copper chloride, cuprous chloride, copper sulfate, and copper trifluoromethanesulfonate.
7. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The oxidant is selected from one or more of air, oxygen, 2,3-dichloro-5,6-dicyanobenzoquinone, tert-butylhydrogen peroxide, ozone, and dimethyl sulfoxide.
8. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The illumination conditions are selected from one of the following: 380-400nm violet light, 400-480nm blue light, 480-490nm cyan light, 490-500nm blue-green light, and 500nm-560nm green light.
9. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The molar ratio of the polycyclic aromatic hydrocarbons, halogenated aromatic hydrocarbons, oxidant and inorganic base is 1:(1.1-2.5):(0.1-0.5):(0.5-5.0).
10. The method for synthesizing a deep blue organic light-emitting diode material benzo[k]fluoranthene structure according to claim 1, characterized in that, The amount of the metal catalyst used is 5%-20% of the amount of polycyclic aromatic hydrocarbons.