CN114436971A - Di (4- (benzoxazol-2-yl) phenyl) methylamine derivative and preparation method thereof - Google Patents
Di (4- (benzoxazol-2-yl) phenyl) methylamine derivative and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a di (4- (benzoxazol-2-yl) phenyl) methylamine derivative and a preparation method thereof, wherein the general formula of the derivative is as follows:
wherein R is hydrogen, alkyl, halogen, cyano, nitro or aryl; x is oxygen, sulfur or nitrogen atom. The raw materials are cheap and easy to obtain, and the method has no much danger, adopts a conventional reaction kettle, has simple and convenient synthetic operation process, has less corresponding energy consumption compared with other schemes, has simpler post-treatment, can obtain high-purity products after simple post-treatment, and has high yieldCompared with other methods, the method has the advantages of lower cost, no waste solvent, less waste water and high atom utilization rate, and is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative and a preparation method thereof.
Background
The di (4- (benzoxazol-2-yl) phenyl) methylamine derivative has various applications due to the special structure. The introduction of different active groups at the 1.4.5.6.7 th position of benzo heterocycle in the structure of the organic electroluminescent device can have different applications and more excellent performances in different fields, and scientists continuously research and develop organic electroluminescent to luminescent materials in recent years, so that introduction of various substituents at the 1.4.5.6.7 th position requires higher and higher purity and yield, and with continuous breakthrough and marketization of OLED organic luminescent materials, intermediate materials of the organic electroluminescent device have higher requirements, so continuous innovation and continuous optimization and improvement of processes are required.
The existing bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative has the disadvantages of large pollution of raw materials, high price, long reaction steps, complex reaction, low yield and complex post-treatment.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the embodiment of the invention provides a di (4- (benzoxazol-2-yl) phenyl) methylamine derivative, which has a general formula as follows:
wherein R is hydrogen, alkyl, halogen, cyano, nitro or aryl; x is oxygen, sulfur or nitrogen atom.
A bis (4- (benzooxazol-2-yl) phenyl) methylamine derivative according to claim 1, wherein the alkyl group is C1-C40 and the aryl group is benzene, toluene, biphenyl, naphthalene, anthracene, phenanthrene or substituted naphthyl.
In the scheme, the alkyl is C1-C5, and the aryl is a benzene ring or toluene.
In the above scheme, the compound is selected from the following specific structural formulas:
an embodiment of the present invention further provides a method for preparing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to any one of the above schemes, wherein the method includes:
substituted aniline and p-bromobenzoic acid are taken as raw materials to react to obtain a 2- (4-bromophenyl) benzoxazole derivative;
substituted aniline and p-aminobenzoic acid are used as raw materials to react to obtain a 2- (4-aminophenyl) benzo-azole derivative;
and (2- (4-bromophenyl) benzole derivative and 2- (4-aminophenyl) benzole derivative are subjected to catalytic coupling to obtain the bis (4- (benzole-2-yl) phenyl) methylamine derivative.
In the scheme, the substituted aniline and p-bromobenzoic acid are used as raw materials to react to obtain the 2- (4-bromophenyl) benzoxazole derivative: the 2- (4-bromophenyl) benzo-azole derivative is obtained by twice dehydration condensation of substituted aniline and p-bromobenzoic acid in the presence of a dehydration condensation agent and a solvent.
In the scheme, in the presence of a dehydration condensation agent and a solvent, substituted aniline and p-bromobenzoic acid are subjected to twice dehydration condensation to obtain the 2- (4-bromophenyl) benzooxazole derivative, which specifically comprises the following steps: adding a dehydration condensing agent and a solvent into a reaction vessel, heating to 80-100 ℃, starting stirring, then adding p-bromobenzoic acid and substituted aniline, stirring for 1-5 hours at 150-180 ℃, cooling to 80-100 ℃, introducing into water for quenching, stirring for 1-5 hours, then performing suction filtration to obtain a solid, dissolving by ethyl acetate, passing through a silica gel column, and concentrating to obtain the 2- (4-bromophenyl) benzoxazole derivative.
In the scheme, the 2- (4-bromophenyl) benzo-oxazole derivative obtained by twice dehydration condensation of substituted aniline and p-bromobenzoic acid in the presence of polyphosphoric acid is as follows: the 2- (4-aminophenyl) benzo-azole derivative is obtained by twice dehydration condensation of substituted aniline and p-aminobenzoic acid in the presence of a dehydration condensation agent and a solvent.
In the above scheme, in the presence of a dehydration condensation agent and a solvent, the substituted aniline and p-aminobenzoic acid are subjected to twice dehydration condensation to obtain the 2- (4-aminophenyl) benzoxazole derivative, specifically: adding polyphosphoric acid and phosphoric acid into a reaction container, heating to 80-100 ℃, starting stirring, adding p-bromobenzoic acid and substituted aniline, stirring at 150-180 ℃ for 1-5 hours, cooling to 80-100 ℃, introducing into water for quenching, stirring for 1-5 hours, carrying out suction filtration to obtain a solid, dissolving with ethyl acetate, passing through a silica gel column, and concentrating to obtain the 2- (4-bromophenyl) benzo-triazole derivative.
In the above scheme, the catalytic coupling of the 2- (4-bromophenyl) benzooxazole derivative and the 2- (4-aminophenyl) benzooxazole derivative to obtain a bis (4- (benzooxazol-2-yl) phenyl) methylamine derivative specifically includes: adding an organic solvent into a reaction container, adding a 2- (4-bromophenyl) benzole derivative and a 2- (4-aminophenyl) benzole derivative, replacing with argon or other inert gases, adding a catalyst and alkali, heating to 80-120 ℃, stirring for 1-5 hours, cooling to below 40 ℃, performing suction filtration to obtain a crude product, dissolving the crude product with ethyl acetate, passing through a silica gel column, and concentrating to obtain the bis (4- (benzole-2-yl) phenyl) methylamine derivative.
Compared with the prior art, the raw materials are cheap and easy to obtain, and the method has no much danger, adopts a conventional reaction kettle, has simple and convenient synthetic operation process, has less corresponding energy consumption compared with other schemes, has simpler post-treatment, can obtain high-purity products after simple post-treatment, has high yield, lower cost compared with other methods, does not produce waste solvents, produces less waste water, has high atom utilization rate, and is more environment-friendly.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a schematic diagram of a synthetic route for a process for preparing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic spectrum of W1 as a yellow solid obtained by the method for preparing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to example 1 of the present invention;
FIG. 3 is a nuclear magnetic spectrum of W2 as a yellow solid prepared by the method for preparing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, article, or apparatus that comprises the element.
The embodiment of the invention provides a di (4- (benzoxazol-2-yl) phenyl) methylamine derivative, which has a general formula as follows:
wherein R is hydrogen, alkyl, halogen, cyano, nitro or aryl; x is oxygen, sulfur or nitrogen atom.
Optionally, the alkyl group is C1-C40, and the aryl group is benzene, toluene, biphenyl, naphthalene, anthracene, phenanthrene, or substituted naphthyl.
Optionally, the alkyl is C1-C5, and the aryl is a benzene ring or toluene.
Selected from the following specific structural formulas:
the embodiment of the present invention further provides a preparation method of a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative, as shown in fig. 1, the method includes:
step 101: substituted aniline and p-bromobenzoic acid are taken as raw materials to react to obtain a 2- (4-bromophenyl) benzoxazole derivative;
specifically, in the presence of a dehydration condensation agent and a solvent, substituted aniline and p-bromobenzoic acid are subjected to twice dehydration condensation to obtain a 2- (4-bromophenyl) benzooxazole derivative;
adding a dehydration condensing agent and a solvent into a reaction vessel, heating to 80-100 ℃, starting stirring, then adding p-bromobenzoic acid and substituted aniline, stirring for 1-5 hours at 150-180 ℃, cooling to 80-100 ℃, introducing into water for quenching, stirring for 1-5 hours, then performing suction filtration to obtain a solid, dissolving by ethyl acetate, passing through a silica gel column, and concentrating to obtain the 2- (4-bromophenyl) benzoxazole derivative.
The dehydration condensing agent is polyphosphoric acid.
The solvent is phosphoric acid.
The substituted aniline is o-aminophenol, o-aminothiophenol, o-phenylenediamine, 2-amino-5-chlorophenol, 2-amino-4-fluorophenylthiol, 2-amino-6-methylphenol, etc.
Step 102: substituted aniline and p-aminobenzoic acid are used as raw materials to react to obtain a 2- (4-aminophenyl) benzo-azole derivative;
specifically, in the presence of a dehydration condensation agent and a solvent, substituted aniline and p-aminobenzoic acid are subjected to twice dehydration condensation to obtain a 2- (4-aminophenyl) benzoxazole derivative;
adding a dehydration condensing agent and a solvent into a reaction vessel, heating to 80-100 ℃, starting stirring, then adding p-aminobenzoic acid and substituted aniline, stirring for 1-5 hours at 150-180 ℃, cooling to 80-100 ℃, introducing into water for quenching, stirring for 1-5 hours, then carrying out suction filtration to obtain a solid, dissolving by ethyl acetate, passing through a silica gel column, and concentrating to obtain the 2- (4-aminophenyl) benzoheteroazole derivative.
The dehydration condensing agent is polyphosphoric acid.
The solvent is phosphoric acid.
The substituted aniline is o-aminophenol, o-aminothiophenol, o-phenylenediamine, 2-amino-5-chlorophenol, 2-amino-4-fluorophenylthiol, 2-amino-6-methylphenol, etc.
Step 103: and (2- (4-bromophenyl) benzole derivative and 2- (4-aminophenyl) benzole derivative are subjected to catalytic coupling to obtain the bis (4- (benzole-2-yl) phenyl) methylamine derivative.
Specifically, adding an organic solvent into a reaction container, adding a 2- (4-bromophenyl) benzole derivative and a 2- (4-aminophenyl) benzole derivative, replacing with argon or other inert gases, adding a catalyst and alkali, heating to 80-120 ℃, stirring for 1-5 hours, cooling to below 40 ℃, performing suction filtration to obtain a crude product, dissolving the crude product with ethyl acetate, passing through a silica gel column, and concentrating to obtain the bis (4- (benzole-2-yl) phenyl) methylamine derivative.
The organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dioxane, toluene, xylene and the like.
The catalyst is one of palladium acetate, 1' -bis (diphenylphosphino) ferrocene palladium dichloride or tris (dibenzylideneacetone) dipalladium.
The alkali is sodium tert-butoxide, potassium acetate, sodium hydroxide, potassium hydroxide, cesium carbonate and the like.
The application also provides an application of the bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative, and the bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative is applied to synthetic drugs, organic electroluminescent materials, high molecular materials or organic flexible materials.
The effect of quenching the reaction with water in the present invention: the first point can destroy polyphosphoric acid to make it lose the effect of dehydrating agent so that the reaction stops, the second point can dilute the concentration of phosphoric acid with water to make the acid become dilute and handle, the third normal temperature water can reduce the temperature of the reaction solution to reach the effect of cooling, and the fourth water treatment can make the product generated in the reaction system convert from the dissolved state into insoluble solid to precipitate out to reach the effect of separation and purification.
The product is obtained after the product is filtered by a filter funnel, a solid crude product needs to be further purified, the product is better dissolved in ethyl acetate, and the product becomes a liquid state after being dissolved, and the ethyl acetate belongs to a chemical substance with little toxicity.
The lower side of the silica gel column is the silica gel column, which is a method for chemically purifying a product, and most of media needing a filling medium in the silica gel column are silica gel, because the silica gel is cheap and has a stable structure and cannot pollute or react with the product, the principle of the method is equivalent to the purification of purified water, and the water containing impurities is purified by blocking the impurities with small crushed stones.
Example 1:
the method comprises the following steps: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g of o-aminophenol (molecular weight of 109.13, 0.92mol), stirring for half an hour, and then adding 184.2g of p-bromobenzoic acid (molecular weight of 201.02, 0.92 mol); heating to 150 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration through a suction filtration funnel to obtain a solid crude product, adding 200ml of water, performing drip filtration, dissolving the solid crude product with 2000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 2- (4-bromophenyl) benzoxazole, wherein the HPLC (high performance liquid chromatography) yield is 99.5%, and the yield is 89% at 223.6g (molecular weight 274.12, 0.92 mol).
Step two: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g of o-aminophenol (molecular weight of 109.13, 0.92mol), stirring for half an hour, and then adding 125.7g of p-aminobenzoic acid (molecular weight of 137.14, 0.92 mol); heating to 150 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filtration funnel to obtain a crude solid product, adding 200ml of water, performing drip filtration, dissolving the crude solid product by using 3000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 2- (4-aminophenyl) benzoxazole, wherein the HPLC (high performance liquid chromatography) is 99.2 percent, and the yield is 86 percent, and is 165.7g (molecular weight is 210.24, 0.92 mol).
Step three: under nitrogen protection, S1,100.0g (molecular weight 274.12, 0.36mol), S2,76.7g (molecular weight 210.24, 0.36mol), tris (dibenzylideneacetone) dipalladium 1.1g (molecular weight 915.72, 0.003mol), sodium t-butoxide 105.2g (molecular weight 96.1, 1.09mol), and 1000mL of toluene were charged into a reaction flask equipped with a mechanical stirrer, reflux condenser, thermometer, and oil bath heater. Heating to 100 ℃, reacting for 5-10 hours, finishing the reaction, cooling to room temperature, passing through a chromatographic column, and distilling the obtained liquid under reduced pressure to obtain yellow solid W1, 114.8g (with the molecular weight of 403.44, 0.36 mol); the yield thereof was found to be 78%.
Example 2:
the method comprises the following steps: 480ml of polyphosphoric acid and 120ml of phosphoric acid are added into a 1000ml reactor, the temperature is raised to 80 ℃, stirring is started, then 100.0g of o-aminothiophenol (molecular weight 125.19, 0.80mol) is added, stirring is carried out for half an hour, and then 168.6g of p-bromobenzoic acid (molecular weight 201.02, 0.84mol) is added; heating to 160 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filter to obtain a crude solid product, adding 200ml of water, performing drip washing, dissolving the crude solid product by using 2000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 2- (4-bromophenyl) benzothiazole, wherein the HPLC (high performance liquid chromatography) is 99.6 percent, and the yield is 87 percent from 201.7g (the molecular weight is 290.18, 0.80 mol).
Step two: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g of o-aminobenzenethiol (molecular weight 125.19, 0.80mol), stirring for half an hour, and then adding 115.0g of p-aminobenzoic acid (molecular weight 137.14, 0.84 mol); heating to 150 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filtration funnel to obtain a crude solid product, adding 200ml of water, performing drip filtration, dissolving the crude solid product by using 3000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 2- (4-aminophenyl) benzothiazole, wherein the HPLC (high performance liquid chromatography) is 99.1 percent, and the yield is 85 percent, 180.8g (the molecular weight is 226.30, 0.80 mol).
Step three: under nitrogen protection, 3,100.0g (molecular weight 290.18, 0.34mol), S4,78.0g (molecular weight 226.30, 0.34mol), 1.1g (molecular weight 915.72, 0.003mol) of tris (dibenzylideneacetone) dipalladium, 142.7g (molecular weight 138, 1.03mol) of potassium carbonate and 1000mL of N, N-dimethylformamide were put into a reaction flask equipped with a mechanical stirring, reflux condenser, thermometer and oil bath heating device. Heating to 110 ℃, reacting for 5-10 hours, then finishing the reaction, cooling to room temperature, introducing into 3000ml of water, precipitating a large amount of solid, performing suction filtration on the solid by using a suction filtration funnel to obtain a solid crude product, dissolving the solid crude product by using 3000ml of ethyl acetate, then passing through a chromatographic column, and performing reduced pressure distillation on the obtained liquid to obtain a yellow-green solid W2, 105.1g (molecular weight 435.56, 0.34 mol); the yield thereof was found to be 70%.
Example 3:
the method comprises the following steps: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g (molecular weight 143.57, 0.70mol) of 2-amino-4-chlorophenol, stirring for half an hour, and then adding 154.0g (molecular weight 201.02, 0.77mol) of p-bromobenzoic acid; heating to 155 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filtration funnel to obtain a crude solid product, adding 200ml of water, performing drip filtration, dissolving the crude solid product by using 2000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 5-chloro-2- (4-bromophenyl) benzoxazole, wherein the HPLC (high performance liquid chromatography) is 99.2%, and the yield is 84% for 180.5g (molecular weight 308.56, 0.92 mol).
Step two: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g (molecular weight of 143.57, 0.70mol) of 2-amino-4-chlorophenol, stirring for half an hour, and then adding 105.1g (molecular weight of 137.14, 0.77mol) of p-aminobenzoic acid; heating to 145 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filter to obtain a crude solid product, adding 200ml of water, performing drip filtration, dissolving the crude solid product by using 3000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 5-chloro-2- (4-aminophenyl) benzoxazole, wherein the HPLC (high performance liquid chromatography) is 99.0%, and the yield is 74% of 126.1g (molecular weight 244.68, 0.70 mol).
Step three: under the protection of nitrogen, 5,100.0g (molecular weight of 308.56, 0.32mol), S6,79.3g (molecular weight of 244.68, 0.32mol), 1.0g (molecular weight of 731.7, 0.003mol) of 1,1' -bis-diphenylphosphino ferrocene palladium dichloride, 93.4g (molecular weight of 96.1, 1.09mol) of sodium tert-butoxide and 1000mL of dioxane are added into a reaction bottle with a mechanical stirring, reflux condenser, thermometer and oil bath heating device. Heating to 100 ℃, reacting for 5-10 hours, finishing the reaction, cooling to room temperature, passing through a chromatographic column, and distilling the obtained liquid under reduced pressure to obtain yellow solid W4, 116.3g (molecular weight 472.33, 0.32 mol); the yield thereof was found to be 76%.
Example 4:
the method comprises the following steps: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g (molecular weight 139.22, 0.72mol) of 2-amino-3-methylthiophenol, stirring for half an hour, and then adding 144.4g (molecular weight 201.02, 0.72mol) of p-bromobenzoic acid; heating to 150 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filtration funnel to obtain a crude solid product, adding 200ml of water, performing drip filtration, dissolving the crude solid product by using 2000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product, namely 4-methyl-2- (4-bromophenyl) benzothiazole, wherein the HPLC (high performance liquid chromatography) ═ 99.2%, and the yield of 177.0g (molecular weight 304.21, 0.72mol) is 81%.
Step two: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g (molecular weight 139.22, 0.72mol) of 2-amino-3-methylphenylthiol, stirring for half an hour, and then adding 125.7g (molecular weight 137.14, 0.72mol) of p-aminobenzoic acid; heating to 160 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filtration funnel to obtain a crude solid product, adding 200ml of water, performing drip filtration, dissolving the crude solid product by using 3000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product, namely 4-methyl-2- (4-aminophenyl) benzothiazole, wherein the HPLC (high performance liquid chromatography) ═ 99.1%, and the yield of 147.4g (molecular weight 256.48, 0.72mol) is 80%.
Step three: under the protection of nitrogen, S7,100.0g (molecular weight 304.21, 0.33mol), S8,84.3g (molecular weight 256.48, 0.33mol), tris (dibenzylideneacetone) dipalladium 1.1g (molecular weight 915.72, 0.003mol), potassium tert-butoxide 110.6g (molecular weight 112.2, 1.09mol), xylene 1000m L were put into a reaction flask equipped with a mechanical stirring, reflux condenser, thermometer and oil bath heating device. Heating to 120 ℃, reacting for 5-10 hours, finishing the reaction, cooling to room temperature, passing through a chromatographic column, and distilling the obtained liquid under reduced pressure to obtain yellow solid W17, 117.3g (molecular weight 463.62, 0.33 mol); the yield thereof was found to be 77%.
Example 5:
the method comprises the following steps: 480ml of polyphosphoric acid and 120ml of phosphoric acid are added into a 1000ml reactor, the temperature is raised to 80 ℃, stirring is started, then 100.0g (molecular weight is 185.23, 0.54mol) of 2-amino-5-phenylphenol is added, stirring is carried out for half an hour, and then 168.6g (molecular weight is 201.02, 0.54mol) of p-bromobenzoic acid is added; heating to 160 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, carrying out suction filtration by a suction filtration funnel to obtain a solid crude product, adding 200ml of water, leaching, dissolving the solid crude product by 2000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 6-phenyl-2- (4-bromophenyl) benzoxazole, wherein the HPLC (high performance liquid chromatography) is 99.4%, and the yield is 79.4 g (molecular weight is 350.22, 0.54 mol).
Step two: adding 480ml of polyphosphoric acid and 120ml of phosphoric acid into a 1000ml reactor, heating to 80 ℃, starting stirring, then adding 100.0g (molecular weight is 185.23, 0.54mol) of 2-amino-5-phenylphenol, stirring for half an hour, and then adding 74.0g (molecular weight is 137.14, 0.54mol) of p-aminobenzoic acid; heating to 150 ℃, reacting for 1-5 hours, cooling to 80 ℃, adding into 1200ml of water, quenching for 1-2 hours, performing suction filtration by using a suction filtration funnel to obtain a crude solid product, adding 200ml of water for leaching, dissolving the crude solid product by using 3000ml of ethyl acetate, passing through a silica gel column, and concentrating to obtain a refined product 6-phenyl-2- (4-aminophenyl) benzoxazole, wherein the HPLC (high performance liquid chromatography) is 99.0%, and the yield is 75% for 115.9g (molecular weight 286.33, 0.54 mol).
Step three: under nitrogen protection, S9,100.0g (molecular weight 350.22, 0.29mol), S10,78.0g (molecular weight 286.33, 0.29mol), 1.1g (molecular weight 915.72, 0.003mol) of tris (dibenzylideneacetone) dipalladium, 118.2g (molecular weight 138, 0.86mol) of potassium carbonate and 1000mL of N, N-dimethylformamide were charged into a reaction flask equipped with a mechanical stirrer, reflux condenser, thermometer and oil bath heater. Heating to 110 ℃, reacting for 5-10 hours, then finishing the reaction, cooling to room temperature, introducing into 3000ml of water, precipitating a large amount of solid, performing suction filtration on the solid by using a suction filtration funnel to obtain a solid crude product, dissolving the solid crude product by using 3000ml of ethyl acetate, then passing through a chromatographic column, and performing reduced pressure distillation on the obtained liquid to obtain a yellow-green solid W28, 107.9g (with the molecular weight of 555.64, 0.29 mol); the yield thereof was found to be 68%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (10)
1. A bis (4- (benzooxazol-2-yl) phenyl) methylamine derivative having the formula:
wherein R is hydrogen, alkyl, halogen, cyano, nitro or aryl; x is oxygen, sulfur or nitrogen atom.
2. A bis (4- (benzooxazol-2-yl) phenyl) methylamine derivative according to claim 1, wherein the alkyl group is C1-C40 and the aryl group is benzene, toluene, biphenyl, naphthalene, anthracene, phenanthrene or substituted naphthyl.
3. Bis (4- (benzooxazol-2-yl) phenyl) methylamine derivative according to claim 1, wherein the alkyl group is C1-C5 and the aryl group is a phenyl ring or toluene.
4. A bis (4- (benzooxazol-2-yl) phenyl) methylamine derivative according to any one of claims 1 to 3, selected from the following specific structural formulae:
5. a process for the preparation of a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to any one of claims 1 to 4, which comprises:
substituted aniline and p-bromobenzoic acid are taken as raw materials to react to obtain a 2- (4-bromophenyl) benzoxazole derivative;
substituted aniline and p-aminobenzoic acid are used as raw materials to react to obtain a 2- (4-aminophenyl) benzo-azole derivative;
and (2- (4-bromophenyl) benzole derivative and 2- (4-aminophenyl) benzole derivative are subjected to catalytic coupling to obtain the bis (4- (benzole-2-yl) phenyl) methylamine derivative.
6. The method for preparing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to claim 5, wherein the substituted aniline and p-bromobenzoic acid are reacted to obtain the 2- (4-bromophenyl) benzoxazole derivative as follows: the 2- (4-bromophenyl) benzo-azole derivative is obtained by twice dehydration condensation of substituted aniline and p-bromobenzoic acid in the presence of a dehydration condensation agent and a solvent.
7. The method for producing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to claim 6, wherein the substituted aniline and p-bromobenzoic acid are subjected to two dehydration condensation reactions in the presence of a dehydration condensation agent and a solvent to obtain a 2- (4-bromophenyl) benzoxazole derivative, specifically: adding a dehydration condensing agent and a solvent into a reaction vessel, heating to 80-100 ℃, starting stirring, then adding p-bromobenzoic acid and substituted aniline, stirring for 1-5 hours at 150-180 ℃, cooling to 80-100 ℃, introducing into water for quenching, stirring for 1-5 hours, then carrying out suction filtration to obtain a solid, dissolving by ethyl acetate, then passing through a silica gel column, and concentrating to obtain the 2- (4-bromophenyl) benzoxazole derivative.
8. The process for producing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to any one of claims 5 to 7, wherein the 2- (4-bromophenyl) benzoxazole derivative obtained by twice dehydrocondensation of a substituted aniline and p-bromobenzoic acid in the presence of polyphosphoric acid is: the 2- (4-aminophenyl) benzo-azole derivative is obtained by twice dehydration condensation of substituted aniline and p-aminobenzoic acid in the presence of a dehydration condensation agent and a solvent.
9. The process for producing a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative according to claim 8, wherein the substituted aniline and p-aminobenzoic acid are subjected to two dehydration condensation reactions in the presence of a dehydration condensation agent and a solvent to obtain a 2- (4-aminophenyl) benzoxazole derivative, specifically: adding polyphosphoric acid and phosphoric acid into a reaction container, heating to 80-100 ℃, starting stirring, adding p-bromobenzoic acid and substituted aniline, stirring at 150-180 ℃ for 1-5 hours, cooling to 80-100 ℃, introducing into water for quenching, stirring for 1-5 hours, carrying out suction filtration to obtain a solid, dissolving with ethyl acetate, passing through a silica gel column, and concentrating to obtain the 2- (4-bromophenyl) benzo-triazole derivative.
10. The process for the preparation of bis (4- (benzoxazol-2-yl) phenyl) methylamine derivatives according to claim 9, characterized in that said catalytic coupling of said 2- (4-bromophenyl) benzoxazole derivative with a 2- (4-aminophenyl) benzoxazole derivative yields a bis (4- (benzoxazol-2-yl) phenyl) methylamine derivative, in particular: adding an organic solvent into a reaction container, adding a 2- (4-bromophenyl) benzole derivative and a 2- (4-aminophenyl) benzole derivative, replacing with argon or other inert gases, adding a catalyst and alkali, heating to 80-120 ℃, stirring for 1-5 hours, cooling to below 40 ℃, performing suction filtration to obtain a crude product, dissolving the crude product with ethyl acetate, passing through a silica gel column, and concentrating to obtain the bis (4- (benzole-2-yl) phenyl) methylamine derivative.
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