Method for catalytically synthesizing p-hydroxybenzonitrile by using copper polymer catalyst

Abstract

The invention relates to a method for catalytically synthesizing p-hydroxybenzonitrile by using a copper polymer catalyst. Under the action of the copper polymer catalyst, p-chlorobenzonitrile and hydroxide are coupled to prepare p-hydroxybenzonitrile. The copper polymer catalyst prepared by the method is high in stability and can be recycled for multiple times. The synthesis method disclosed by the invention is mild in reaction condition and simple in step, and can better meet the requirements of industrial production from the aspects of society, environment, economy and the like.

Description

Technical Field

[0001] The invention relates to a novel method for synthesizing p-hydroxybenzonitrile, and relates to a method for synthesizing p-hydroxybenzonitrile by catalyzing a copper polymer catalyst, and in particular to a method for synthesizing p-hydroxybenzonitrile by one step by catalyzing p-chlorobenzonitrile and a copper polymer catalyst. Background Art

[0002] p-Hydroxybenzonitrile is an intermediate of organophosphorus insecticides chloranil and benzonitrile phosphorus, and is also an intermediate of herbicide bromoxynil, and is also an intermediate of liquid crystal materials, spices, etc. There are many synthetic routes, and the early method is the T.Sandmeyer method, but the synthetic method has many steps, harsh reaction conditions, uses cyanide as raw material, and an equivalent amount of CuCN as catalyst, which is easy to cause serious pollution to the environment, and the production cost is high. These problems seriously restrict industrial application, so people try to use other approaches to realize the synthesis of p-hydroxybenzonitrile, thereby avoiding the use of this type of highly toxic cyanide reagent. At present, the p-hydroxybenzoate amination method is mainly used in China, which utilizes p-hydroxybenzoic acid and urea under the action of a dehydrating agent, heats and melts, and dehydrates under reduced pressure. Commonly used dehydrating agents include phosphorus pentoxide, phosphorus oxychloride, thionyl chloride, etc., and the use of a dehydrating agent is a restriction to its industrial production. The synthesis of p-hydroxybenzonitrile by the p-hydroxybenzaldehyde aldoxime method is a good method. The method first dissolves p-hydroxybenzaldehyde and hydroxylamine hydrochloride in formic acid, heats up and stirs to reflux, and then neutralizes with sodium hydroxide solution, filters, and washes with water to obtain the product. However, a large amount of formic acid and sodium hydroxide are used in the reaction, and the reaction is carried out in two steps, and there is a problem of three wastes, so there are considerable restrictions from the economic and operational perspectives. Therefore, the synthesis of p-hydroxybenzonitrile avoids the use of toxic substances, simplifies the reaction steps, reduces the process flow, and reduces the equipment requirements, which is an urgent need for industrial production. For example, the application of the pyridine amide scaffold such as Daniel W.Widlicka (Org.Process Res.Dev.2024,28,2732-2742) has been extended to the copper-catalyzed hydroxylation reaction of halogenated aromatics to obtain a higher yield of hydroxylated products, but the preparation process of the catalyst is relatively complicated, and the corresponding side chains need to be prepared in advance, and the preparation conditions are complicated and cannot be put into industrial production in large quantities. For example, Xia et al. (J.Am.Chem.Soc.2016,138,13493-13496 13496) provided a powerful catalytic system for the hydroxylation of halogenated (hetero) aromatic groups by combining Cu with N,N′-bis(4-hydroxy-2,6-dimethylphenyl)acetamide (BHMPO), which enabled the hydroxylation reaction to proceed smoothly. However, this method is complicated to operate. Although the reaction conditions are mild, the cost of raw materials is high, which is not conducive to industrial production.

[0003] Chinese patent document CN102311364A reports a method: ortho (p) halogenated benzonitrile as raw material, and anhydrous alcohol solution of alkali metal alkoxide with a solution concentration of 5-50%, under the conditions of reaction molar ratio of 1:2-5, reaction temperature of 100-250°C, reaction pressure of 0.5-6MPa, reaction for 1-24 hours, cooling, cooling, desolventizing by vacuum distillation, and acidification with hydrochloric acid to obtain ortho (p) hydroxybenzonitrile solid. However, this method requires a higher temperature and a longer reaction time.

[0004] Chinese patent document CN108745389A reports a method for preparing p-hydroxybenzonitrile, comprising the following steps: 1) adding a phosphorus source to water at 50°C to 85°C, stirring and dissolving, and adding a sieved calcium source in batches; after filtering and washing, drying at 120°C to 180°C, crushing and sieving to obtain a precursor powder; 2) adding an auxiliary agent to the sieved precursor powder and mixing evenly, then adding deionized water, extruding and forming, obtaining a shaped catalyst precursor, and drying to constant weight; wherein the mass ratio of precursor powder: auxiliary agent: deionized water is 50 to 75:4 to 10:24 to 40; 3) placing the shaped catalyst precursor in a muffle furnace, heating to 550°C to 700°C at a heating rate of 4°C to 8°C / min and keeping warm for 2 to 5h to synthesize a catalyst for p-hydroxybenzonitrile. However, this method requires a high temperature and has complex steps. Summary of the invention

[0005] The purpose of the present invention is to improve the deficiencies of the prior art and provide a method for catalyzing the synthesis of p-hydroxybenzonitrile using a copper polymer catalyst.

[0006] The technical scheme of the present invention is: a method for synthesizing p-hydroxybenzonitrile catalyzed by a copper polymer catalyst, and the specific steps are as follows: a) preparation of the copper polymer catalyst: the acylation reaction of benzyl diamine and acyl chloride is promoted by a base to obtain an amide polymer, and a copper compound is combined to form a copper polymer catalyst; b) preparation of p-hydroxybenzonitrile: p-chlorobenzonitrile is placed in a hydrothermal kettle, a hydroxide and a solvent are added, and the copper polymer catalyst prepared in step a) is added to heat and react for a certain period of time to generate p-hydroxybenzonitrile. As shown in Formula 1.

[0007]

[0008] Formula 1. Preparation of p-hydroxybenzonitrile catalyzed by copper polymer catalyst

[0009] The copper polymer catalyst is obtained by a solution method, wherein alkali and dichloromethane are placed in a container, diphenyl diamine is added, and then acyl chloride is added to stir the reaction, and then a copper compound is added, and the stirring is continued and then the copper polymer catalyst is washed with water to obtain the copper polymer catalyst.

[0010] Preferably, the base is potassium carbonate, sodium carbonate or potassium phosphate; the copper compound is cupric acetate, cuprous iodide, cupric chloride, cupric bromide or cuprous oxide; the diphenyl diammonium is tetramethylbenzyl diamine or dihydroxybenzyl diamine; and the acyl chloride is oxalyl chloride or chloroacetyl chloride.

[0011] Preferably, the molar ratio of the diphenylenediamine to the acyl chloride is 1:(0.5-1.5); the molar ratio of the diphenylenediamine to the base is 1:(1-2); and the molar ratio of the diphenylenediamine to the copper compound is 1:(0.5-1).

[0012] Preferably, the added mass of the copper polymer catalyst is 0.14%-10% of the mass of p-chlorobenzonitrile; the molar ratio of p-chlorobenzonitrile to hydroxide is 1:(2-8); and the added amount of the solvent is (0.7-4.3) times the mass of p-chlorobenzonitrile.

[0013] Preferably, the hydroxide is potassium hydroxide or sodium hydroxide; and the solvent is water, dimethyl sulfoxide or DMF.

[0014] Preferably, the heating reaction temperature in step b) is 70-100° C. and the reaction time is 3-10 h.

[0015] Beneficial effects:

[0016] The invention provides a preparation method of a copper polymer catalyst and a method for preparing p-hydroxybenzonitrile. The method avoids the use of harmful products, reduces production risks and harm to the environment. The catalyst is stable, efficient and easy to separate. The process is simple and efficient, the conditions are mild, the selectivity is high, the danger is low, and the product is easy to separate. The process has low requirements on equipment, low cost and price, and is suitable for industrial production. DETAILED DESCRIPTION

[0017] Embodiment 1: Preparation of copper polymer catalyst A. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slowly adding 1.27 g (10 mmol) of oxalyl chloride and stirring for 2 hours. 0.91 g (5 mmol) of copper acetate was added, stirred for 5 hours, washed with water, and dried to obtain copper polymer catalyst A.

[0018] Embodiment 2: Preparation of copper polymer catalyst B. 2.12 g of sodium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slowly adding 1.27 g (10 mmol) of oxalyl chloride, and stirring for 2 hours. 0.91 g (5 mmol) of copper acetate was added, stirred for 5 hours, washed with water, and dried to obtain copper polymer catalyst B.

[0019] Embodiment 3: Preparation of copper polymer catalyst C. 4.246 g of potassium phosphate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride, and stirred for 2 hours. 1.82 g (10 mmol) of copper acetate was added, stirred for 5 hours, washed with water, and dried to obtain copper polymer catalyst C.

[0020] Embodiment 4: Preparation of copper polymer catalyst D. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride, stirring for 2 hours, adding 0.95 g (5 mmol) of cuprous iodide, stirring for 5 hours, washing with water, and drying to obtain copper polymer catalyst D.

[0021] Embodiment 5: Preparation of copper polymer catalyst E. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride, stirring for 2 hours, washing with 0.6725 g (5 mmol) of cupric chloride, and drying to obtain copper polymer catalyst E.

[0022] Embodiment 6: Preparation of copper polymer catalyst F. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride, and stirred for 2 hours. 1.117 g (5 mmol) of copper bromide was added, stirred for 5 hours, washed with water, and dried to obtain copper polymer catalyst F.

[0023] Embodiment 7: Preparation of copper polymer catalyst G. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slowly adding 1.27 g (10 mmol) of oxalyl chloride, stirring for 2 hours, and then adding 0.715 g (5 mmol) of cuprous oxide, stirring for 5 hours, washing with water, and drying to obtain copper polymer catalyst G.

[0024] Embodiment 8: Preparation of copper polymer catalyst H. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slow addition of 0.635 g of oxalyl chloride (5 mmol), stirred for 2 hours, and then 0.715 g (5 mmol) of cuprous oxide was added, stirred for 5 hours, washed with water, and dried to obtain copper polymer catalyst H.

[0025] Embodiment 9: Preparation of copper polymer catalyst I. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.40 g (10 mmol) of tetramethylbenzenediamine was added, followed by slowly adding 2.26 g (20 mmol) of chloroacetyl chloride, stirring for 2 hours, and then adding 0.715 g of cuprous oxide, stirring for 5 hours, washing with water, and drying to obtain copper polymer catalyst I.

[0026] Embodiment 10: Preparation of copper polymer catalyst J. 2.76 g of potassium carbonate and 10 ml of dichloromethane were placed in a flask, and 2.16 g (10 mmol) of dihydroxybenzenediamine was added, followed by slowly adding 2.26 g (20 mmol) of chloroacetyl chloride, stirring for 2 hours, and then adding 0.715 g of cuprous oxide, stirring for 5 hours, washing with water, and drying to obtain copper polymer catalyst J.

[0027] Embodiment 11: 0.7g (5mmol) of p-chlorobenzonitrile, 0.4g of sodium hydroxide (10mmol), 3g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 100°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.536g of p-hydroxybenzonitrile, with a yield of 90%. Embodiment 12: 0.7g (5mmol) of p-chlorobenzonitrile, 0.4g of sodium hydroxide (10mmol), 2g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 100°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.548g of p-hydroxybenzonitrile, with a yield of 92%. Embodiment 13: 0.7g (5mmol) of p-chlorobenzonitrile, 0.4g of sodium hydroxide (10mmol), 1g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred for reaction at 100°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was filtered and separated. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.566g of p-hydroxybenzonitrile, with a yield of 95%. Embodiment 14: 0.7g (5mmol) of p-chlorobenzonitrile, 0.4g of sodium hydroxide (10mmol), 1g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred for reaction at 90°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was filtered and separated. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.542g of p-hydroxybenzonitrile, with a yield of 91%. Embodiment 15: 0.7g (5mmol) of p-chlorobenzonitrile, 0.4g of sodium hydroxide (10mmol), 1g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 90°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.554g of p-hydroxybenzonitrile, with a yield of 93%. Embodiment 16: 0.7g (5mmol) of p-chlorobenzonitrile, 0.4g of sodium hydroxide (10mmol), 1g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 85°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.548g of p-hydroxybenzonitrile, with a yield of 92%.Embodiment 17: 1.38g (10mmol) of p-chlorobenzonitrile, 0.8g of sodium hydroxide (20mmol), 1g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 80°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.566g of p-hydroxybenzonitrile, with a yield of 95%. Embodiment 18: 1.38g (10mmol) of p-chlorobenzonitrile, 0.8g of sodium hydroxide (20mmol), 1g of water, and 0.1g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 80°C for 5h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.554g of p-hydroxybenzonitrile, with a yield of 93%. Embodiment 19: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 75°C for 5 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.554 g of p-hydroxybenzonitrile, with a yield of 93%. Embodiment 20: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 80°C for 5 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.589 g of p-hydroxybenzonitrile, with a yield of 99%. Embodiment 21: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 70°C for 3 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.536 g of p-hydroxybenzonitrile, with a yield of 90%. Embodiment 22: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 80°C for 5 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 0.589 g of p-hydroxybenzonitrile, with a yield of 99%.Embodiment 23: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.589 g of p-hydroxybenzonitrile, with a yield of 99%.

[0028] Embodiment 24: 5.0 g (36 mmol) of p-chlorobenzonitrile, 3.36 g of potassium hydroxide (60 mmol), 5 g of water, and 0.5 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 80° C. for 5 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 4.286 g of p-hydroxybenzonitrile, with a yield of 99%. Embodiment 25: 5.0 g (36 mmol) of p-chlorobenzonitrile, 3.36 g of potassium hydroxide (60 mmol), 5 g of water, and 0.25 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was stirred at 80° C. for 5 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain about 4.113 g of p-hydroxybenzonitrile, with a yield of 95%.

[0029] Embodiment 26: 0.7 g (5 mmol) of p-chlorobenzonitrile, 3.36 g of potassium hydroxide (60 mmol), 3 g of water, and 0.1 g of copper polymer catalyst B were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.536 g of p-hydroxybenzonitrile, with a yield of 90%.

[0030] Embodiment 27: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst C were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.511 g of p-hydroxybenzonitrile, with a yield of 86%.

[0031] Embodiment 28: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst D were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.506 g of p-hydroxybenzonitrile, with a yield of 85%.

[0032] Embodiment 29: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst E were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.506 g of p-hydroxybenzonitrile, with a yield of 85%.

[0033] Embodiment 30: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst F were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.589 g of p-hydroxybenzonitrile, with a yield of 99%.

[0034] Embodiment 31: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst G were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.565 g of p-hydroxybenzonitrile, with a yield of 95%.

[0035] Embodiment 32: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 3 g of water, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 15 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.511 g of p-hydroxybenzonitrile, with a yield of 86%.

[0036] Embodiment 33: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of dimethyl sulfoxide, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.589 g of p-hydroxybenzonitrile, with a yield of 99%.

[0037] Embodiment 34: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of DMF, and 0.1 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.526 g of p-hydroxybenzonitrile, with a yield of 87%.

[0038] Embodiment 35: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst H were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.526 g of p-hydroxybenzonitrile, with a yield of 87%.

[0039] Embodiment 36: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst I were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.550 g of p-hydroxybenzonitrile, with a yield of 91%.

[0040] Embodiment 37: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.1 g of copper polymer catalyst J were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.562 g of p-hydroxybenzonitrile, with a yield of 93%.

[0041] Embodiment 38: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.07 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.536 g of p-hydroxybenzonitrile, with a yield of 90%.

[0042] Embodiment 39: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.03 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.526 g of p-hydroxybenzonitrile, with a yield of 87%.

[0043] Embodiment 40: 0.7 g (5 mmol) of p-chlorobenzonitrile, 1.12 g of potassium hydroxide (20 mmol), 1 g of water, and 0.01 g of copper polymer catalyst A were added to a reaction vessel, and the mixture was placed in a hydrothermal kettle and stirred at 80° C. for 10 h. After the reaction, the pH was adjusted to acidic with hydrochloric acid, and the catalyst was separated by filtration. The solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain about 0.505 g of p-hydroxybenzonitrile, with a yield of 85%.

[0044] The catalyst washed and dried after the reaction in Implementation Example 2 is reused. The process flow is consistent with the implementation case, and the catalyst recovery and use are as shown in Table 1:

[0045] Table 1:

[0046] Recycling times Yield of p-hydroxybenzonitrile 1 99％ 2 96％ 3 94％ 4 93％ 5 95％

[0047] From the experimental results of catalyst recycling in Table 1, it can be seen that the copper polymer catalyst has good recyclability.

[0048] The catalyst after washing and drying after the reaction in Implementation Example 23 is reused. The process flow is consistent with the implementation case, and the catalyst recovery and use are as shown in Table 2:

[0049] Table 2:

[0050] Recycling times Yield of p-hydroxybenzonitrile 1 85％ 2 86％ 3 85％ 4 84％ 5 86％

[0051] From the experimental results of catalyst recycling in Table 2, it can be seen that the copper polymer catalyst has good recyclability.

Claims

1. A method for synthesizing p-hydroxybenzonitrile catalyzed by a copper polymer catalyst, the specific steps of which are as follows: a) preparation of the copper polymer catalyst: the acylation reaction of benzyl diamine and acyl chloride is promoted by a base to obtain an amide polymer, which is combined with a copper compound to form a copper polymer catalyst; b) preparation of p-hydroxybenzonitrile: p-chlorobenzonitrile is placed in a hydrothermal autoclave, a hydroxide and a solvent are added, and the copper polymer catalyst prepared in step a) is added and heated for a certain reaction time to generate p-hydroxybenzonitrile.

2. The method according to claim 1, characterized in that The copper polymer catalyst is obtained by a solution method, wherein an alkali and dichloromethane are placed in a container, diphenyl diamine is added, then acyl chloride is added and stirred for reaction, and then a copper compound is added, and the copper polymer catalyst is obtained by washing with water after continued stirring.

3. The method according to claim 2, characterized in that The base is potassium carbonate, sodium carbonate or potassium phosphate; the copper compound is cupric acetate, cuprous iodide, cupric chloride, cupric bromide or cuprous oxide; the diphenyl diammonium is tetramethyl diphenyl diamine or dihydroxy diphenyl diamine; and the acyl chloride is oxalyl chloride or chloroacetyl chloride.

4. The method according to claim 2, characterized in that The molar ratio of the diphenylenediamine to the acyl chloride is 1:(0.5-1.5); the molar ratio of the diphenylenediamine to the base is 1:(1-2); and the molar ratio of the diphenylenediamine to the copper compound is 1:(0.5-1).

5. The method according to claim 1, characterized in that The added mass of the copper polymer catalyst is 0.14%-10% of the mass of p-chlorobenzonitrile; the molar ratio of p-chlorobenzonitrile to hydroxide is 1:(2-8); and the added amount of the solvent is (0.7-4.3) times the mass of p-chlorobenzonitrile.

6. The method according to claim 1, characterized in that The hydroxide is potassium hydroxide or sodium hydroxide; the solvent is water, dimethyl sulfoxide or DMF.

7. The method according to claim 1, characterized in that Step b) The heating reaction temperature is 70-100° C. and the reaction time is 3-10 h.

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