CN115417805A - Seven-membered ring benzocarbazole organic phosphorescent material intermediate and synthesis method thereof - Google Patents
Seven-membered ring benzocarbazole organic phosphorescent material intermediate and synthesis method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of organic luminescent materials, and discloses a synthetic method of a seven-membered ring benzocarbazole organic phosphorescent material intermediate, which comprises the following steps: step 1, 2-bromo-6-nitroaniline is coupled with o-chlorobenzeneboronic acid SUZUKI to produce an intermediate 2' -chloro-3-nitrobiphenyl-2-amine, step 2 amino is subjected to diazotization iodination reaction, step 3, the intermediate 2' -chloro-2-iodo-3-nitrobiphenyl and 1-naphthoic acid are subjected to selective coupling to produce an intermediate 1- (2 ' -chloro-3-nitro-biphenyl-2-yl) -naphthalene, step 4, nitro ring closure is carried out in a triethyl phosphite system to produce a chlorophenyl benzocarbazole intermediate, and step 5, potassium hydroxide is used for catalyzing ring closure in a quinoline system to produce a target product 7CBC. The technical method takes 2-bromo-6-nitroaniline as a starting material to react with o-chlorophenylboronic acid, and effectively solves the problems of poor selectivity, more byproducts and low purification yield in the synthesis process of the prior patents A-2 and B-1.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a synthetic method of a seven-membered ring benzocarbazole organic phosphorescent material intermediate.
Background
Organic electroluminescent (OLED) devices have made great progress over thirty years and have been widely used in the fields of full-screen mobile phones, foldable notebook computers, curved displays, wearable devices, high-end vehicles, and the like. The OLED display device can provide three colors of red, green and blue with high saturation, does not need an additional backlight source, and has the advantages of colorful color, high response speed, wide luminous visual angle, light weight, thinness, softness and the like.
Among them, the organic light emitting material is the core of the OLED display technology, and the common functionalized organic materials are: a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron transport material, an electron blocking material, a light emitting host material, a light emitting guest (dye), and the like. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, thereby generating excitons and emitting light. Organic light emitting materials can be classified into fluorescent materials and phosphorescent materials according to the light emitting principle, and the research of people in recent years is mainly focused on the field of phosphorescent light emitting materials due to the low light emitting efficiency of fluorescent materials.
With the market of OLED products, people have higher and higher performance requirements on the products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, service life, cost and the like. The development and synthesis of various phosphorescent materials with high luminous efficiency and low driving voltage and the reduction of synthesis cost are problems to be solved in the field. With the market of OLED products, people have higher and higher performance requirements on the products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, service life, cost and the like. The development and synthesis of various phosphorescent materials with high luminous efficiency and low driving voltage and the reduction of synthesis cost are problems to be solved in the field. According to a large amount of literature search, no patent is provided for a benzocarbazole intermediate material with a seven-membered ring structure to clearly explain and protect the synthesis process of the product. Korean patent No. 20210054737, shanghai yuri chemical patent No. CN110872276, and seihua laboratory patent No. CN114195794 describe processes for synthesizing the intermediate compound in protecting organic light-emitting terminal materials and devices, but all have disadvantages such as low yield, many impurities, difficulty in purification, synthesis cost, difficulty in mass production, and the like. The specific route and the existing problems are as follows:
(1) Lines of patent KR20210054737
The method has the problems that 1, the total yield of the process is extremely low and is only 2.3 percent, and particularly, the yield of a single step of synthesizing the intermediate A-3 is only 8.4 percent; 2. the requirement on equipment is high due to the need of using concentrated sulfuric acid; 3. the price of the raw materials is high, and the product cost is extremely high due to low yield, so that the industrial mass production is difficult.
(2) Routes of patents CN110872276 and CN114195794
There are problems:
1. the Buckwald reaction in the first step has low selectivity and more byproducts in the actual amplification reaction;
2. the fourth step of reaction adopts AlCl3 to catalyze the cyclization reaction, so that the cycle is long and the yield is low;
3. the total yield of the process is low (only 17.5%), the use amount of the noble metal Pd catalyst in the whole process is large, and the synthesis cost is high
Therefore, a synthetic method of the seven-membered ring benzocarbazole organic phosphorescent material intermediate is provided.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a synthetic method of a heptatomic ring benzocarbazole organic phosphorescent material intermediate, which comprises the following reaction steps:
(1) Step 1: 2-bromo-6-nitroaniline and o-chlorobenzoic acid are coupled to produce an intermediate M-1 in an alkaline system under the catalysis of PdCl2 (PPh 3) 2, wherein the molar ratio of the 2-bromo-6-nitroaniline, the o-chlorobenzoic acid, the PdCl2 (PPh 3) 2 and potassium carbonate is 1:1.1 to 1.5: 1-3 ‰:2 to 3, wherein 1:1.2:2 per mill: 2;
(2) Step 2: carrying out diazotization iodination by utilizing sodium nitrite, potassium iodide and an intermediate M-1 in an acidic system, wherein the molar ratio of the intermediate M-1 to the sodium nitrite to the potassium iodide is 1:1.1 to 1.4:1.1 to 1.4, wherein 1:1.2:1.3;
(3) And step 3: coupling an intermediate M-2 and 1-naphthalene boric acid in an alkaline system under the catalysis of tetrakis (triphenyl) phosphonium palladium to produce an intermediate M-3, wherein the molar ratio of the intermediate M-2 to 1-naphthalene boric acid to the tetrakis (triphenyl) phosphonium palladium to potassium carbonate is 1:1.0 to 1.2:5 per mill-1%: 2 to 3, wherein 1:1.2:6 per mill: 2;
(4) And 4, step 4: the intermediate M-3 is used for producing an intermediate M-4 in a triethyl phosphite system in a ring closing manner, wherein the intermediate triethyl phosphite participates in the reaction and also serves as a solvent;
(5) And 5: catalyzing intermediate M-4 to close the ring in quinoline by using potassium hydroxide to produce target product 7CBC, wherein the molar ratio of the intermediate M-4 to the potassium hydroxide is 1:10 to 15, wherein 1:10.
preferably, M-1 in the step 1 is specifically 2' -chloro-3-nitrobiphenyl-2-amine, and the preparation of M-1 is that under the protection of nitrogen, 2-bromo-6-nitroaniline, o-chlorophenylboronic acid, potassium carbonate, toluene, ethanol, water and PdCl2 (PPh 3) 2 are added into a three-neck flask provided with a thermometer, a stirrer and a condenser in sequence; heating to reflux reaction for 8-10 hr; cooling the system, standing, separating liquid, washing an organic phase to be neutral, concentrating under reduced pressure, drying by toluene recrystallization, filtering, and drying in vacuum at 60 ℃ to obtain the product.
Preferably, the M-2 in the step 3 is specifically 2' -chloro-2-iodo-3-nitrobiphenyl, and the M-2) is prepared by adding water and concentrated hydrochloric acid into a three-neck flask provided with a thermometer, a stirrer and a condenser to prepare a solution, cooling to below 40 ℃, adding M-1 and glacial acetic acid into the system, and then heating; controlling the temperature to be 65-70 ℃, dropwise adding a sodium nitrite aqueous solution (NaNO 2 is dissolved in water) into the system, and controlling the temperature to react for 1h after the dropwise adding is finished; then dropwise adding a KI and water solution into the system, and controlling the temperature to be 65-70 ℃ for reaction after dropwise adding; after the reaction is finished, cooling, adding toluene and sodium bisulfite solution, standing, separating liquid, washing an organic phase with sodium bicarbonate solution, and then washing with water to be neutral; refluxing and water separating the organic phase, passing through a silica gel column, concentrating under reduced pressure to dry, recrystallizing with methanol, and drying in vacuum to obtain the product.
Preferably, M-3 in said step 3 is in particular 1- (2' -chloro-3-nitro-biphenyl-2-yl) -naphthalene, wherein the preparation of M-3: under the protection of nitrogen, adding M-2, 1-naphthalene boric acid, potassium carbonate, toluene, ethanol, water and tetrakis (triphenylphosphine) palladium into a three-neck flask provided with a thermometer, a stirrer and a condenser, and then heating to reflux reaction for about 20 hours; and (3) cooling after the reaction is finished, adding toluene into the system, separating, washing an organic phase with water to be neutral, refluxing, separating water, passing through a silica gel column, concentrating under reduced pressure to be dry, and recrystallizing with ethyl acetate to obtain a yellow solid.
Preferably, M-4 in step 4 is specifically 11- (2-chlorophenyl) -7H-benzocarbazole, wherein the preparation of M-4: dissolving M-3 solid in 1.4L of triethyl phosphate, adding triethyl phosphite into a three-neck flask provided with a thermometer, a stirrer and a condenser under the protection of nitrogen, heating to reflux, dropwise adding the prepared M-3 triethyl phosphite solution, and carrying out reflux reaction after dropwise adding is finished; after the reaction is finished, decompressing and concentrating triethyl phosphite in the system, adding toluene after the concentration is finished, dissolving, passing through a silica gel column, decompressing and concentrating to dryness, and recrystallizing toluene to obtain the product.
Preferably, in the target product 7CBC in step 5, the preparation of seven-membered ring benzocarbazole (target product 7 CBC):
under the protection of nitrogen, adding potassium hydroxide and quinoline into a three-neck flask provided with a stirring paddle and a condensing tube, heating to 200-220 ℃, then dropwise adding an A-4 quinoline solution (M-4 is dissolved in quinoline) into the system, and controlling the temperature to 200-220 ℃ to react for 2-4 h after the dropwise adding is finished; after the reaction is finished, cooling, adding glacial acetic acid into the system, stirring for 10min, adding ethyl acetate and water, filtering out insoluble substances, separating the filtrate, using a hot water phase with the temperature of 60-70 ℃ for an organic phase, and concentrating under reduced pressure; the concentrate is boiled and washed by toluene and water, cooled, separated, washed by water, concentrated and dried, and recrystallized by toluene to obtain yellow solid.
Preferably, the catalyst in step 1 may be one of PdCl2 (PPh 3) 2, tetrakis (triphenyl) phosphonium palladium, pd-132, pdCl2 (dppf), etc., wherein PdCl2 (PPh 3) 2 is preferred; the base can be potassium carbonate, sodium carbonate, etc., wherein potassium carbonate is preferred; the solvent is toluene, ethanol and water system, and can also be toluene and water system.
Preferably, the acid used in step 2 may be one of concentrated sulfuric acid and concentrated hydrochloric acid, and the solvent is glacial acetic acid and a water system.
Preferably, the base used in step 5 may be one of potassium hydroxide, sodium hydroxide, strontium carbonate, etc., especially potassium hydroxide, and the solvent used is one or more of quinoline, o-dichlorobenzene, xylene, DMF and DMAC, especially quinoline.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
(1) The technical method takes 2-bromo-6-nitroaniline as the starting material to react with the o-chlorophenylboronic acid, and effectively solves the problems of poor selectivity, more byproducts and low purification yield in the synthesis process of the prior patents A-2 and B-1.
(2) The seven-membered cyclic ring in the technical route adopts an alkaline system, and the conversion rate and the yield are high, which are the most advanced methods in the prior patent.
(3) The dosage of the noble metal Pd catalyst in the technical route is less, and the synthesis cost of the product is effectively reduced.
(4) The technical method has the advantages of cheap and easily-obtained raw materials, reasonable design route, adoption of classical reaction, short reaction time, higher single-step yield and high total product yield (more than 30 percent), and is easy for industrial mass production.
(5) The technical route is novel and unique in design, is green and environment-friendly, realizes the ever-highest product yield by adopting the most common reaction types and product purification modes, and greatly reduces the production cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other implementation drawings may be derived by those of ordinary skill in the art without inventive effort from the drawings provided.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 is a process scheme of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In an embodiment, as shown in fig. 1, a method for synthesizing a seven-membered ring benzocarbazole organic phosphorescent material intermediate is characterized by comprising the following steps:
(1) Step 1: 2-bromo-6-nitroaniline and o-chlorobenzoic acid are coupled to produce an intermediate M-1 in an alkaline system under the catalysis of PdCl2 (PPh 3) 2, wherein the molar ratio of the 2-bromo-6-nitroaniline, the o-chlorobenzoic acid, the PdCl2 (PPh 3) 2 and potassium carbonate is 1:1.1 to 1.5: 1-3 ‰:2 to 3, wherein 1:1.2:2 per mill: 2;
(2) Step 2: carrying out diazotization iodination by utilizing sodium nitrite, potassium iodide and an intermediate M-1 in an acidic system, wherein the molar ratio of the intermediate M-1 to the sodium nitrite to the potassium iodide is 1:1.1 to 1.4:1.1 to 1.4, wherein 1:1.2:1.3;
(3) And step 3: coupling an intermediate M-2 and 1-naphthalene boric acid in an alkaline system under the catalysis of tetrakis (triphenyl) phosphonium palladium to produce an intermediate M-3, wherein the molar ratio of the intermediate M-2 to 1-naphthalene boric acid to the tetrakis (triphenyl) phosphonium palladium to potassium carbonate is 1:1.0 to 1.2:5 per mill-1%: 2 to 3, wherein 1:1.2:6 per mill: 2;
(4) And 4, step 4: the intermediate M-3 is used for producing an intermediate M-4 in a triethyl phosphite system in a ring closing manner, wherein the intermediate triethyl phosphite participates in the reaction and also serves as a solvent;
(5) And 5: catalyzing intermediate M-4 to close the ring in quinoline by using potassium hydroxide to produce target product 7CBC, wherein the molar ratio of the intermediate M-4 to the potassium hydroxide is 1:10 to 15, wherein 1:10.
wherein, the synthesis of 2' -chloro-3-nitrobiphenyl-2-amine (M-1):
under the protection of nitrogen, 217g of 2-bromo-6-nitroaniline, 187.5g of o-chlorobenzeneboronic acid, 276g of potassium carbonate, 1000ml of toluene, 500ml of ethanol, 500ml of water and 1.4g of PdCl2 (PPh 3) 2 are added into a three-neck flask provided with a thermometer, a stirrer and a condenser in sequence; heating to reflux reaction for 8-10 hr; and cooling the system, standing, separating liquid, washing an organic phase to be neutral, concentrating under reduced pressure, drying by toluene recrystallization, filtering, and drying in vacuum at 60 ℃ to obtain 218.8g of a product, wherein the yield is 88% and the purity of the product is more than 98%.
Synthesis of 2' -chloro-2-iodo-3-nitrobiphenyl (M-2):
adding 440mL of water and 880mL of concentrated hydrochloric acid 880 into a three-neck flask provided with a thermometer, a stirrer and a condenser to prepare a solution, cooling to below 40 ℃, adding 218.8g of M-1 and 880mL of glacial acetic acid into the system, and then heating; controlling the temperature to be 65-70 ℃, dropwise adding an aqueous solution of sodium nitrite (71.8gNaNO2 is dissolved in 280ml of water) into the system, and controlling the temperature to react for 1h after the dropwise adding is finished; then, adding a solution of 189.9g KI and 190mL water dropwise into the system, and controlling the temperature to be 65-70 ℃ for reaction after finishing adding dropwise; after the reaction is finished, cooling, adding 2.5L of toluene and sodium bisulfite solution, standing, separating, washing an organic phase with sodium bicarbonate solution, and then washing with water to be neutral; refluxing and water separating the organic phase, passing through a silica gel column, concentrating the organic phase under reduced pressure to dryness, recrystallizing the organic phase with methanol, and drying the organic phase in vacuum to obtain 246.5g of a product, wherein the yield is 78 percent, and the purity of the product is more than 98.5 percent.
Synthesis of 1- (2' -chloro-3-nitro-biphenyl-2-yl) -naphthalene (M-3):
under the protection of nitrogen, 246.5g of M-2, 123.4g of 1-naphthalene boric acid, 188.5g of potassium carbonate, 500ml of toluene, 250ml of ethanol, 250ml of water and 4.5g of tetrakis (triphenylphosphine) palladium are added into a three-neck flask provided with a thermometer, a stirrer and a condenser, and then the temperature is increased to reflux reaction for about 20 hours; and (3) after the reaction is finished, cooling, adding 2.5L of toluene into the system, separating, washing an organic phase with water to be neutral, refluxing, separating water, passing through a silica gel column, concentrating under reduced pressure to dry, and recrystallizing with ethyl acetate to obtain 176g of yellow solid, wherein the yield is 71.5%, and the product purity is more than or equal to 98.5%.
Synthesis of 11- (2-chlorophenyl) -7H-benzocarbazole (M-4):
first 176g of M-3 solid was dissolved in 1.4L of triethyl phosphate. Adding 530ml of triethyl phosphite into a three-neck flask provided with a thermometer, a stirrer and a condenser under the protection of nitrogen, heating to reflux, dropwise adding the prepared triethyl phosphite solution of M-3, and carrying out reflux reaction after the dropwise adding is finished; after the reaction is finished, decompressing and concentrating triethyl phosphite in the system, adding 1.6L of methylbenzene after the concentration is finished, dissolving, passing through a silica gel column, decompressing and concentrating to dryness, and recrystallizing the methylbenzene to obtain 136g of a product, wherein the yield is 84.5 percent, and the purity of the product is more than or equal to 94 percent.
Synthesis of seven-membered ring benzocarbazole (target product 7 CBC):
under the protection of nitrogen, 232g of potassium hydroxide and 680g of quinoline are added into a three-neck flask provided with a stirring paddle and a condenser tube, the mixture is heated to 200-220 ℃, then quinoline solution A-4 (136 g of M-4 is dissolved in 1360g of quinoline) is dripped into the system, and the temperature is controlled to be 200-220 ℃ to react for 2-4 h after the dripping is finished; after the reaction is finished, cooling, adding 250g of glacial acetic acid into the system, stirring for 10min, adding 1.2L of ethyl acetate and 500ml of water, filtering out insoluble substances, separating the filtrate, using a 60-70 ℃ hot water phase as an organic phase, and concentrating under reduced pressure; the concentrate is boiled and washed by 1.2L of toluene and 500ml of water, cooled, separated, washed by water, concentrated and dried, and recrystallized by toluene to obtain 72g of yellow solid, the yield is 59.5%, and the product purity is more than or equal to 99%.
The total yield of the product of the process is 33.18 percent.
The working principle of the invention is as follows: the invention aims to overcome the defects of the prior art and provides a novel synthesis method of a seven-membered ring benzocarbazole organic phosphorescent material intermediate. By adopting the method, the raw materials are cheap and easy to obtain, the route is reasonable, the product yield is high, the process is green and environment-friendly, and the method is more suitable for industrial mass production.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A synthetic method of a seven-membered ring benzocarbazole organic phosphorescent material intermediate is characterized by comprising the following reaction steps:
(1) Step 1: 2-bromo-6-nitroaniline and o-chlorobenzoic acid are coupled to produce an intermediate M-1 in an alkaline system under the catalysis of PdCl2 (PPh 3) 2, wherein the molar ratio of the 2-bromo-6-nitroaniline, the o-chlorobenzoic acid, the PdCl2 (PPh 3) 2 and potassium carbonate is 1:1.1 to 1.5: 1-3 ‰:2 to 3, wherein 1:1.2:2 per mill: 2;
(2) Step 2: carrying out diazotization iodination by utilizing sodium nitrite, potassium iodide and an intermediate M-1 in an acidic system, wherein the molar ratio of the intermediate M-1 to the sodium nitrite to the potassium iodide is 1:1.1 to 1.4:1.1 to 1.4, wherein 1:1.2:1.3;
(3) And step 3: coupling an intermediate M-2 and 1-naphthalene boric acid in an alkaline system under the catalysis of tetra (triphenyl) phosphorus palladium to produce an intermediate M-3, wherein the molar ratio of the intermediate M-2 to the 1-naphthalene boric acid to the tetra (triphenyl) phosphorus palladium to potassium carbonate is 1:1.0 to 1.2:5 per mill-1%: 2 to 3, wherein 1:1.2:6 per mill: 2;
(4) And 4, step 4: the intermediate M-3 is used for producing an intermediate M-4 in a triethyl phosphite system in a ring closing manner, wherein the intermediate triethyl phosphite participates in the reaction and also serves as a solvent;
(5) And 5: catalyzing intermediate M-4 to close the ring in quinoline by using potassium hydroxide to produce target product 7CBC, wherein the molar ratio of the intermediate M-4 to the potassium hydroxide is 1:10 to 15, wherein 1:10.
2. the method for synthesizing the seven-membered benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: the M-1 in the step 1 is specifically 2' -chloro-3-nitrobiphenyl-2-amine, and the preparation of the M-1 is that under the protection of nitrogen, 2-bromo-6-nitroaniline, o-chlorobenzeneboronic acid, potassium carbonate, toluene, ethanol, water and PdCl2 (PPh 3) 2 are added into a three-neck flask provided with a thermometer, a stirrer and a condenser in sequence; heating to reflux reaction for 8-10 hr; cooling the system, standing, separating liquid, washing an organic phase to be neutral, concentrating under reduced pressure, drying by toluene recrystallization, filtering, and drying in vacuum at 60 ℃ to obtain the product.
3. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: m-2 in the step 3 is specifically 2' -chloro-2-iodo-3-nitrobiphenyl, and the preparation of M-2 is to add water and concentrated hydrochloric acid into a three-neck flask provided with a thermometer, a stirrer and a condenser pipe to prepare a solution, cool the solution to below 40 ℃, add M-1 and glacial acetic acid into the system, and then heat the solution; controlling the temperature to be 65-70 ℃, dropwise adding a sodium nitrite aqueous solution (NaNO 2 is dissolved in water) into the system, and controlling the temperature to react for 1h after the dropwise adding is finished; then dropwise adding a KI and water solution into the system, and controlling the temperature to be 65-70 ℃ for reaction after dropwise adding; after the reaction is finished, cooling, adding toluene and sodium bisulfite solution, standing, separating, washing an organic phase with sodium bicarbonate solution, and then washing with water to be neutral; refluxing and water separating the organic phase, passing through a silica gel column, concentrating under reduced pressure to dry, recrystallizing with methanol, and drying in vacuum to obtain the product.
4. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: m-3 in the step 3 is specifically 1- (2' -chloro-3-nitro-biphenyl-2-yl) -naphthalene, wherein the preparation of M-3: under the protection of nitrogen, adding M-2, 1-naphthalene boric acid, potassium carbonate, toluene, ethanol, water and tetrakis (triphenylphosphine) palladium into a three-neck flask provided with a thermometer, a stirrer and a condenser, and then heating to reflux reaction for about 20 hours; and (3) cooling after the reaction is finished, adding toluene into the system, separating, washing an organic phase with water to be neutral, refluxing, separating water, passing through a silica gel column, concentrating under reduced pressure to dry, and recrystallizing with ethyl acetate to obtain a yellow solid.
5. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: m-4 in the step 4 is specifically 11- (2-chlorphenyl) -7H-benzocarbazole, wherein the preparation of M-4: dissolving M-3 solid in 1.4L of triethyl phosphate, adding triethyl phosphite into a three-neck flask provided with a thermometer, a stirrer and a condenser under the protection of nitrogen, heating to reflux, dropwise adding the prepared M-3 triethyl phosphite solution, and carrying out reflux reaction after dropwise adding is finished; after the reaction is finished, decompressing and concentrating triethyl phosphite in the system, adding methylbenzene after concentration, dissolving, passing through a silica gel column, decompressing and concentrating to dry, and recrystallizing the methylbenzene to obtain the product.
6. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: in the target product 7CBC in step 5, preparation of seven-membered ring benzocarbazole (target product 7 CBC):
under the protection of nitrogen, adding potassium hydroxide and quinoline into a three-neck flask provided with a stirring paddle and a condensing tube, heating to 200-220 ℃, then dropwise adding an A-4 quinoline solution (M-4 is dissolved in quinoline) into the system, and controlling the temperature to 200-220 ℃ to react for 2-4 h after the dropwise adding is finished; after the reaction is finished, cooling, adding glacial acetic acid into the system, stirring for 10min, adding ethyl acetate and water, filtering out insoluble substances, separating the filtrate, using a hot water phase with the temperature of 60-70 ℃ for an organic phase, and concentrating under reduced pressure; the concentrate is boiled and washed by toluene and water, cooled, separated, washed by water, concentrated and dried, and recrystallized by toluene to obtain yellow solid.
7. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: the catalyst in the step 1 can be one of PdCl2 (PPh 3) 2, tetrakis (triphenyl) phosphonium palladium, pd-132, pdCl2 (dppf) and the like, wherein PdCl2 (PPh 3) 2 is preferred; the base can be potassium carbonate, sodium carbonate, etc., wherein potassium carbonate is preferred; the solvent is a toluene, ethanol and water system, and can also be a toluene and water system.
8. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: the acid used in the step 2 can be one of concentrated sulfuric acid and concentrated hydrochloric acid, and the solvent is glacial acetic acid and a water system.
9. The method for synthesizing the seven-membered ring benzocarbazole organic phosphorescent material intermediate according to claim 1, characterized in that: the alkali used in the step 5 can be one of potassium hydroxide, sodium hydroxide, strontium carbonate and the like, particularly potassium hydroxide, and the solvent used is one or a combination of quinoline, o-dichlorobenzene, xylene, DMF and DMAC, particularly quinoline.
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2022
- 2022-09-26 CN CN202211175492.9A patent/CN115417805A/en active Pending
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