Aryl-substituted halogenated s-triazine compounds and methods for their preparation

Abstract

The application belongs to the technical field of organic synthesis, and relates to an aryl-substituted halogenated s-triazine compound and a preparation method thereof. The aryl-substituted halogenated s-triazine compound is shown as formula (I). The preparation method of the compound is as follows: a benzonitrile derivative, ethylene glycol methyl ether, dicyandiamide and potassium hydroxide are mixed and heated, and compound 1 is obtained through reaction; compound 1 and acetonitrile are mixed, and a sulfuric acid solution, sodium nitrate and a cuprous chloride solution are added dropwise in sequence, and then reaction is carried out after dropwise addition is completed; and a target product is obtained. The synthesis method has the advantages of less impurity generation, high conversion rate and high product quality.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology and relates to an aryl-substituted halotriazine compound and its preparation method. Background Technology

[0002] Triazine compounds, especially mesityriazine compounds, possess diverse biological activities and are widely used in pharmaceuticals, OLEDs, and other fields. Triazine organic semiconductor materials containing three strongly electron-withdrawing nitrogen atoms have excellent optoelectronic properties, such as high thermal stability and glass transition temperature, making them widely applicable in optoelectronic devices. Aryl-substituted halotriazine compounds are important intermediates in the preparation of many triazine compounds, but current synthetic methods have many limitations.

[0003] Patent CN113980008 discloses a naphthyl-substituted chlorotriazine compound. The synthesis method has a conversion rate of 30%, but the debromination impurities are approximately 60%. The impurities generated after coupling are difficult to remove even by crystallization and column chromatography, making it impossible to obtain a high-quality target product. Patent CN114702508 discloses a naphthyl-substituted chlorotriazine compound synthesized via a Suzuki reaction. Due to the high reactivity of the chlorine at positions 1, 3, and 5 of cyanuric chloride, multi-substituted impurities are inevitably generated. Furthermore, the reaction has a low conversion rate, with a large proportion of disubstituted and trisubstituted impurities. Additionally, the substrate undergoes deboric acid coupling to generate coupling impurities, which are difficult to remove, resulting in low product yields and making it impossible to purify a product suitable for industrial production.

[0004] In summary, the development of a synthetic method with low impurity generation and high conversion rate is of great significance for the industrial production of aryl-substituted halotriazine compounds. Summary of the Invention

[0005] The present invention aims to provide an aryl-substituted halotriazine compound and its preparation method. The method of the present invention avoids the formation of coupling impurities and multi-substituted impurities, and achieves high conversion rate and high purity.

[0006] For the purposes described above, the present invention relates to an aryl-substituted halotriazine compound, the structure of which is shown in formula (I):

[0007]

[0008] X is a halogen atom, and R is selected from...

[0009] On the other hand, the present invention relates to a method for preparing an aryl-substituted halotriazine compound, comprising:

[0010] Benzonitrile derivative, ethylene glycol methyl ether, dicyandiamide and potassium hydroxide were mixed and heated, and reacted for 2 to 4 hours. Part of the solvent was distilled off, cooled to 25°C to 30°C, pH was adjusted to 7 to 8, stirred, filtered, and dried to obtain compound 1.

[0011] Under argon protection, compound 1 and acetonitrile were mixed and the temperature was controlled at -5℃ to 0℃. Sulfuric acid solution, sodium nitrate and cuprous chloride solution were added in sequence, and the reaction was carried out. The pH was adjusted to neutral to obtain the target product.

[0012] The structural formula of compound 1 is as follows:

[0013]

[0014] The R is selected from

[0015] Furthermore, the present invention provides a method for preparing an aryl-substituted halotriazine compound, wherein the benzonitrile derivative is 4-(naphthyl-2-yl)benzonitrile, 4-(anthrayl-2-yl)benzonitrile, or 4-(pyrene-2-yl)benzonitrile.

[0016] Furthermore, the present invention provides a method for preparing an aryl-substituted halotriazine compound, wherein the benzonitrile derivative, ethylene glycol methyl ether, dicyandiamide and potassium hydroxide are mixed and heated at a temperature of 40°C to 50°C.

[0017] Furthermore, the present invention provides a method for preparing an aryl-substituted halotriazine compound, wherein the amount of solvent distilled off accounts for 65 wt% to 75 wt% of the total solvent amount.

[0018] Furthermore, the present invention provides a method for preparing an aryl-substituted halotriazine compound, wherein the concentration of the cuprous chloride solution is 0.45 g / mL to 0.50 g / mL.

[0019] Furthermore, the present invention provides a method for preparing an aryl-substituted halotriazine compound, wherein the drying conditions for compound 1 are as follows: drying at 125°C to 135°C for 10 to 14 hours.

[0020] On the other hand, the aryl-substituted halotriazine compounds prepared by this invention have high purity, are free of coupling impurities and multi-substituted impurities, and have high product quality. Therefore, this invention protects the application of an aryl-substituted halotriazine compound in the field of organic light-emitting diodes (OLEDs).

[0021] Compared with the prior art, the present invention has the following beneficial effects or advantages.

[0022] This invention uses dicyandiamide and benzonitrile derivatives as raw materials. Through a ring-closure reaction, a diamino-substituted intermediate compound is generated. A subsequent diazotization substitution reaction directly yields the target product at the corresponding substitution position, avoiding the formation of multi-substituted products and improving the conversion rate of the diamino-substituted intermediate compound. This invention directly prepares aryl-substituted halotriazine compounds in two steps. This method generates fewer impurities, has a high conversion rate, and produces high-quality products, which is of great significance for the industrial production of aryl-substituted halotriazine compounds. Detailed Implementation

[0023] To more clearly illustrate the advantages of this invention, the following specific examples are used for detailed description, but the invention is by no means limited thereto. Unless otherwise specified, the experimental methods used in the examples are conventional methods. Unless otherwise specified, the materials and reagents used in the examples are commercially available.

[0024] Example 1

[0025] This embodiment provides a method for preparing 2,4-dichloro-6-(4-naphthylbenzene)-1,3,5-triazine.

[0026] In a 3L three-necked flask, 115g of 4-(naphth-2-yl)benzonitrile and 575mL of ethylene glycol methyl ether were added sequentially. Then, 50.4g of dicyandiamide and 2.8g of potassium hydroxide were slowly added. The mixture was stirred and heated to 45°C and refluxed for 3 hours. After stirring, 70% of the total solvent was distilled off. The reaction solution was cooled to below 30°C, and 10% dilute sulfuric acid was added under stirring until the pH of the reaction system was 7-8. The mixture was stirred for 10 minutes, filtered, and the filter cake was dried at 130°C for 12 hours under normal pressure to obtain 160.54g of white solid 6-(4-(naphth-2-yl)phenyl)-1,3,5-triazine-2,4-diamine (yield 92%).

[0027] The characterization results of 6-(4-(naphthyl-2-yl)phenyl)-1,3,5-triazine-2,4-diamine are as follows: C 22 H 18 N2: m / z: 310.15 (100%), 311.15 (23.8%), 312.15 (2.7%).

[0028] 1H NMR (600MHz, DMSO-d6): δ7.53 (1H, dd, J=8.0, 7.6, 1.8, 0.4Hz), 7.63-8.16 (9H, 7.7 0 (dddd, J=8.1, 7.6, 2.8, 0.5Hz), 7.83 (dd, J=8.3, 1.5, 0.5Hz), 7.83 (dt, J=8.1, 2.0 , 1.8, 0.5Hz), 7.90 (dd, J=8.3, 2.8, 0.5Hz), 7.97 (dd, J=8.7, 2.3, 0.5Hz), 8.04 (d, J =8.0, 2.8, 0.5Hz), 8.10 (dd, J=8.7, 1.9, 0.5Hz)), 8.52 (1H, dd, J=2.0, 1.5, 0.5Hz).

[0029] Under argon protection, 69.8 g of the prepared 6-(4-(naphthyl-2-yl)phenyl)-1,3,5-triazine-2,4-diamine and 700 mL of acetonitrile were added to a 3 L three-necked flask. The temperature was controlled at -3 °C, and 318.66 g of 34.28% sulfuric acid solution was added dropwise. After the addition was complete, the reaction was maintained at -3 °C for 2 h. Then, 33.78 g of NaNO3 was added, followed by the addition of a CuCl hydrochloric acid solution (66.17 g CuCl + 139.6 mL 35% hydrochloric acid). The reaction was maintained at -3 °C for 2 h. The reaction was quenched with NaOH, and the pH was adjusted to neutral. The organic and aqueous phases were separated. The organic phase was recrystallized from toluene to obtain the target product as a white solid, 2,4-dichloro-6-(4-naphthylphenyl)-1,3,5-triazine, 63.39 g (90% yield, 99.92% purity).

[0030] The characterization results of 2,4-dichloro-6-(4-naphthylbenzene)-1,3,5-triazine are as follows: C 22 H 14 Cl2: m / z: 348.05 (100.0%), 350.04 (63.9%), 349.05 (23.8%), 351.05 (15.2%), 352.04 (10.2%), 350.05 (2.7%), 353.04 (2.4%), 352.05 (1.7%).

[0031] 1H NMR (600MHz, DMSO-d6): δ7.63-7.91(3H, 7.71(dddd, J=7.9, 7.6, 2.0, 0.5Hz), 7.71(dddd , J=7.9, 7.6, 2.7, 0.5Hz), 7.84 (ddd, J=8.3, 1.5, 0.5Hz)), 7.93-8.21 (7H, 8.00 (ddd, J=8 .7, 2.3, 0.5Hz), 8.06 (dtq, J=7.9, 2.8, 0.5Hz), 8.08 (ddq, J=8.3, 2.8, 0.5Hz), 8.10 (dtt , J=7.9, 2.0, 0.5Hz), 8.15 (ddd, J=8.7, 1.9, 0.5Hz), 8.54 (1H, ddq, J=2.0, 1.5, 0.5Hz)).

[0032] Example 2

[0033] This embodiment provides a method for preparing 2,4-dichloro-6-(4-anthraylbenzene)-1,3,5-triazine.

[0034] In a 3L three-necked flask, 115g of 4-(anthracene-2-yl)benzonitrile and 575mL of ethylene glycol methyl ether were added sequentially. Then, 50.4g of dicyandiamide and 2.8g of potassium hydroxide were slowly added. The mixture was stirred and heated to 40°C, and refluxed for 2 hours. Distillation was then performed to remove 65% of the total solvent. The reaction solution was cooled to below 30°C, and 10% (w / w) dilute sulfuric acid was added under stirring until the pH of the reaction system reached 7–8. The mixture was stirred for 10 minutes, filtered, and the filter cake was dried at 125°C for 10 hours under normal pressure to obtain 185.54g of the target product, a white solid 6-(4-(anthracene-2-yl)phenyl)-1,3,5-triazine-2,4-diamine, with a yield of 93%.

[0035] The characterization results of 6-(4-(anthracene-2-yl)phenyl)-1,3,5-triazine-2,4-diamine are as follows: C 26 H 20 N2: m / z: 360.16 (100.0%), 361.17 (28.1%), 362.17 (2.7%), 362.17 (1.1%).

[0036] 1H NMR (600MHz, DMSO-d6): δ7.52-7.68 (2H, 7.60 (dd, J=8.27.7, 1.9, 0.5Hz), 7.60 (dd, J=8.0, 7.7, 1.6, 0 .4Hz)), 7.89-8.42 (8H, 7.95 (dd, J=8.3, 1.8, 0.5Hz), 8.04 (dd, J=8.7, 2.2, 0.5Hz), 8.16 (dd, J=8.0, 2 .6, 1.90.Hz), 8.28 (t, J=8.2, 2.0, 1.6, 0.4Hz), 8.31 (t, J=8.7, 2.0, 0.5Hz), 8.36 (t, J=8.3, 2.0, 0.4H z)), 8.50 (1H, th, J=2.0, 0.5Hz), 8.64-8.79 (2H, 8.70 (t, J=2.6, 1.9, 0.4Hz), 8.73 (tt, J=1.8, 0.4Hz).

[0037] Under argon protection, 69.8 g of 6-(4-(anthrayl-2-yl)phenyl)-1,3,5-triazine-2,4-diamine and 700 mL of acetonitrile were added to a 3 L three-necked flask. The temperature was maintained at -5 °C, and 318.66 g of 34.28% sulfuric acid solution was added dropwise. After the addition was complete, the reaction was maintained at -5 °C for 2 h. Then, 33.78 g of NaNO3 was added, followed by dropwise addition of a CuCl hydrochloric acid solution (62.82 g CuCl + 139.6 mL 35% hydrochloric acid). The reaction was maintained at -5 °C for 2 h. The reaction was quenched with NaOH, and the pH was adjusted to neutral. The organic and aqueous phases were separated. The organic phase was recrystallized from toluene to obtain the target product, a white solid 2,4-dichloro-6-(4-anthraylphenyl)-1,3,5-triazine, 73.6 g, with a yield of 91.5%.

[0038] The characterization results of 2,4-dichloro-6-(4-anthraylbenzene)-1,3,5-triazine are as follows: C 26 H 16 Cl2: m / z: 398.06 (100.0%), 400.06 (63.9%), 399.07 (28.1%), 401.06 (18.0%), 402.06 (10.2%), 403.06 (2.9%), 400.07 (2.7%), 402.07 (1.7%), 400.07 (1.1%).

[0039] 1H NMR (600MHz, DMSO-d6): δ7.54-7.82 (2H, 7.61 (dd, J=7.9, 7.7, 1.7, 0.4Hz), 7.75 (t, J=8.2, 7.7, 2.5, 0.4Hz) ), 7.91-8.17 (4H, 7.97 (ddd, J=8.3, 1.9, 0.5Hz), 8.09 (dd, J=7.9, 2.7, 2.5, 0.5Hz), 8.11 (t, J=8.7, 2.2, 0.5H z)), 8.19-8.44 (4H, 8.25 (dd, J=8.7, 1.5, 0.5Hz), 8.29 (dd, J=8.2, 2.0, 1.7, 0.5Hz), 8.37 (t, J=8.3, 2.0, 0.4 Hz)), 8.51 (1H, th, J=2.0, 0.4Hz), 8.71-8.85 (2H, 8.76 (t, J=2.7, 1.6, 0.4Hz), 8.79 (dd, J=1.9, 1.6, 0.4Hz).

[0040] Example 3

[0041] This embodiment provides a method for preparing 2,4-dichloro-6-(4-pyrene)-1,3,5-triazine.

[0042] In a 3L three-necked flask, 115g of 4-(pyrene-2-yl)benzonitrile and 575mL of ethylene glycol methyl ether were added sequentially, followed by the slow addition of 50.4g of dicyandiamide and 2.8g of potassium hydroxide. The mixture was stirred and heated to 50°C, refluxed for 3 hours, and then distilled to remove 75% of the total solvent. The reaction solution was cooled to below 30°C, and 10% (w / w) dilute sulfuric acid was added under stirring until the pH of the reaction system reached 7–8. The mixture was stirred for 10 minutes, filtered, and the filter cake was dried at 135°C for 14 hours under normal pressure to obtain 194.58g of 6-(4-(pyrene-2-yl)phenyl)-1,3,5-triazine-2,4-diamine, with a yield of 92%.

[0043] The characterization results of 6-(4-(pyrene-2-yl)phenyl)-1,3,5-triazine-2,4-diamine are as follows: C 28 H 22 N2: m / z: 386.18 (100.0%), 387.18 (30.3%), 388.19 (2.7%), 388.19 (1.7%).

[0044] 1HNMR (600MHz, DMSO-d6): δ7.66 (1H, d, J=8.0, 7.6, 0.4Hz), 8.11 (2H, d, J=8.7, 2.1, 0.4Hz), 8.29-8.53 (6H, 8.36 (t, J=7.8, 2.0, 1.9, 0 .5Hz), 8.44 (t, J=6.8, 1.9, 0.5Hz), 8.46 (d, J=8.7, 1.6, 0.4Hz)), 8.62 (2H, dd, J=6.8, 1.9, 0.4Hz), 8.80 (2H, dd, J=1.9, 1.7, 0.5Hz)).

[0045] Under argon protection, 69.8 g of the prepared 6-(4-(naphthyl-2-yl)phenyl)-1,3,5-triazine-2,4-diamine and 700 mL of acetonitrile were added to a 3 L three-necked flask. The temperature was maintained at 0 °C, and 318.66 g of a 34.28% sulfuric acid solution was added dropwise. After the addition was complete, the reaction was maintained at -3 °C for 2 h. Then, 33.78 g of NaNO3 was added, followed by the addition of a CuCl hydrochloric acid solution (69.8 g CuCl + 139.6 mL 35% hydrochloric acid). The reaction was maintained at -3 °C for 3 h. The reaction was quenched with NaOH, and the pH was adjusted to neutral. The organic and aqueous phases were separated. The organic phase was recrystallized from toluene to give 78.63 g of a white solid 2,4-dichloro-6-(4-pyrenephenyl)-1,3,5-triazine, with a yield of 92.5% and a purity of 99.91%.

[0046] The characterization results of 2,4-dichloro-6-(4-pyrenephenyl)-1,3,5-triazine are as follows: C 28 H 18 Cl2: m / z: 424.08 (100.0%), 426.08 (63.9%), 425.08 (30.3%), 427.08 (19.4%), 428.07 ( 10.2%), 429.08 (3.1%), 426.09 (2.7%), 428.08 (1.7%), 426.09 (1.7%), 428.08 (1.1%).

[0047] 1H NMR (600MHz, DMSO-d6): δ7.54-7.82 (2H, 7.61 (t, J=7.9, 7.7, 1.7, 0.4Hz), 7.75 (t, J=8.2, 7.7, 2.5, 0.4Hz)) , 7.91-8.17 (4H, 7.97 (t, J=8.3, 1.9, 0.5Hz), 8.09 (dd, J=7.9, 2.7, 2.5, 0.5Hz), 8.11 (dd, J=8.7, 2.2, 0.5Hz) ), 8.19-8.44 (4H, 8.25 (dd, J=8.7, 1.5, 0.5Hz), 8.29 (dd, J=8.2, 2.0, 1.7, 0.5Hz), 8.37 (t, J=8.3, 2.0, 0.4H z)), 8.51 (1H, th, J=2.0, 0.4Hz), 8.71-8.85 (2H, 8.76 (dd, J=2.7, 1.6, 0.4Hz), 8.79 (t, J=1.9, 1.6, 0.4Hz)).

[0048] As described above, the present invention can be well implemented. The above embodiments are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, all changes and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the present invention.

Claims

1. A method for preparing an aryl-substituted halotriazine compound, characterized in that, include: Benzonitrile derivative, ethylene glycol methyl ether, dicyandiamide and potassium hydroxide were mixed and heated, and reacted for 2 to 4 hours. Part of the solvent was distilled off, cooled to 25°C to 30°C, pH was adjusted to 7 to 8, stirred, filtered, and dried to obtain compound 1. Under argon protection, compound 1 and acetonitrile were mixed and the temperature was controlled at -5℃ to 0℃. Sulfuric acid solution, sodium nitrate and cuprous chloride solution were added in sequence, and the reaction was carried out. The pH was adjusted to neutral to obtain the target product. The structural formula of compound 1 is as follows: ； The structure of the target product is shown in formula (Ⅰ): ； X is a halogen atom; The compound 1 has the same R as in formula (I), and R is selected from... , , One of them.

2. The method for preparing aryl-substituted halotriazine compounds according to claim 1, characterized in that, The benzonitrile derivatives are 4-(naphthyl-2-yl)benzonitrile, 4-(anthrayl-2-yl)benzonitrile, and 4-(pyrene-2-yl)benzonitrile.

3. The method for preparing the aryl-substituted halotriazine compound according to claim 1, characterized in that, The mixture of benzonitrile derivative, ethylene glycol methyl ether, dicyandiamide, and potassium hydroxide is heated to a temperature of 40°C to 50°C.

4. The method for preparing aryl-substituted halotriazine compounds according to claim 1, characterized in that, The amount of solvent distilled off accounts for 65wt% to 75wt% of the total solvent volume.

5. The method for preparing aryl-substituted halotriazine compounds according to claim 1, characterized in that, The concentration of the cuprous chloride solution is 0.45 g / mL to 0.50 g / mL.

6. The method for preparing aryl-substituted halotriazine compounds according to claim 1, characterized in that, The drying conditions for compound 1 are as follows: drying at 125°C to 135°C for 10 to 14 hours.

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