Process for the catalytic synthesis of p-hydroxybenzonitrile using a copper polymer catalyst

Abstract

The present application relates to a kind of copper polymer catalyst catalytic synthesis of p-hydroxybenzonitrile method.In the action of the copper polymer catalyst, using p-chlorobenzonitrile and hydroxide coupling preparation p-hydroxybenzonitrile.The copper polymer catalyst prepared by this method has high stability, and can be recycled multiple times.The synthesis method of the present application has mild reaction conditions and simple steps, and is more suitable for industrial production needs from the aspects of society, environment and economy.

Description

TECHNICAL FIELD

[0001] The present application relates to a novel synthesis method of p-hydroxybenzonitrile, and relates to a method for synthesizing p-hydroxybenzonitrile catalyzed by a copper polymer catalyst, in particular to a method for synthesizing p-hydroxybenzonitrile from p-chlorobenzonitrile catalyzed by a copper polymer catalyst in one step. BACKGROUND

[0002] P-hydroxybenzonitrile is an intermediate of organophosphorus insecticide cyanofenphos and bromophos, and is also an intermediate of herbicide bromoxynil, and is also an intermediate of liquid crystal materials, perfumes, etc. There are many synthesis routes. The early method is T. Sandmeyer method, but the synthesis method has many steps, harsh reaction conditions, uses cyanide as raw material, and equivalent CuCN as catalyst, which can cause serious pollution to the environment, and the production cost is high. These problems seriously restrict the industrial application, so people try to use other ways to realize the synthesis of p-hydroxybenzonitrile, so as to avoid the use of such toxic cyanide reagents. At present, the main method used in China is the amination of p-hydroxybenzoic acid ester, which uses p-hydroxybenzoic acid, urea, and a dehydrating agent to melt under heating, and then dehydrates under reduced pressure. Common dehydrating agents include phosphorus pentoxide, phosphorus oxychloride, thionyl chloride, etc. The use of dehydrating agents is a constraint to industrial production. The synthesis of p-hydroxybenzonitrile from p-hydroxybenzaldehyde and hydroxylamine hydrochloride in formic acid is a good method. The product is obtained by stirring and refluxing under heating, and then neutralizing with sodium hydroxide solution, filtering and washing with water. However, a large amount of formic acid and sodium hydroxide is used in the reaction, the reaction is carried out in two steps, and there are three waste problems, so there are not small constraints from the economic and operational aspects. Therefore, it is urgent for industrial production to avoid the use of toxic substances in the synthesis of p-hydroxybenzonitrile, simplify the reaction steps, reduce the process flow, and reduce the equipment requirements. For example, Daniel W. Widlicka (Org. Process Res. Dev. 2024, 28, 2732-2742) and others extended the application of pyridine amide scaffolds to copper-catalyzed hydroxylation of halogenated aromatic hydrocarbons to obtain high yield of hydroxylated products. However, the preparation process of the catalyst is complex, the corresponding branch needs to be prepared in advance, and the preparation conditions are complex, which cannot be mass-produced in industrial production. For example, hanghua Xia (J. Am. Chem. Soc. 2016, 138, 13493-13496 13496) and others provided a powerful catalytic system for the hydroxylation of halogenated (hetero) aromatic compounds by compounding Cu and N, N'-bis(4-hydroxy-2, 6-dimethylphenyl) acetamide (BHMPO), so that the hydroxylation reaction can be carried out smoothly. However, the method is complex in operation, although the reaction conditions are mild, but the cost of raw materials is high, which is not conducive to industrial production.

[0003] Chinese patent document CN102311364A reports a method: o-(p) halogenated benzonitrile as raw material, with anhydrous alcohol solution of alkali metal alcoholate solution concentration of 5-50%, under the conditions of the reaction molar ratio of the two is 1:2-5, the reaction temperature is 100-250℃, the reaction pressure is 0.5-6 MPa, the reaction time is 1-24 hours, after cooling, cooling, vacuum distillation desolventizing, adding hydrochloric acid to obtain o-(p) hydroxybenzonitrile solid. But this method needs high temperature, and the reaction time is long.

[0004] Chinese patent document CN108745389A reports a preparation method of p-hydroxybenzonitrile, comprising the following steps: 1) stirring and dissolving the phosphorus source in water at 50-85℃, adding the sieved calcium source into it in batches; after filtering and washing, drying at 120-180℃, crushing and sieving to obtain precursor powder; 2) adding the auxiliary agent into the sieved precursor powder, mixing uniformly, then adding deionized water, and extruding into strips to obtain a shaped catalyst precursor, and drying to constant weight; wherein the mass ratio of the precursor powder: auxiliary agent: deionized water is 50-75:4-10:24-40; 3) placing the shaped catalyst precursor in a muffle furnace, heating to 550-700℃ at a heating rate of 4-8℃ / min, and keeping the temperature for 2-5h to synthesize the p-hydroxybenzonitrile catalyst. But this method needs high temperature, and the steps are complex. SUMMARY

[0005] The purpose of the present application is to improve the shortcomings of the prior art and provide a method for synthesizing p-hydroxybenzonitrile catalyzed by a copper polymer catalyst.

[0006] The technical scheme of the present application is as follows: a method for synthesizing p-hydroxybenzonitrile catalyzed by a copper polymer catalyst, the specific steps are as follows: a) preparation of a copper polymer catalyst: acylation reaction of biphenyl diamine and acyl chloride to obtain an amide polymer by alkali promotion, and combination of a copper compound to form a copper polymer catalyst; b) preparation of p-hydroxybenzonitrile: placing p-chlorobenzonitrile in an autoclave, adding hydroxide and solvent, adding the copper polymer catalyst prepared in step a) for heating reaction, and generating p-hydroxybenzonitrile after a certain reaction time. As shown in formula 1.

[0007]

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

[0009] The above-mentioned copper polymer catalyst is obtained by solution method, applying alkali and dichloromethane in a container, adding biphenyl diamine, then adding acyl chloride for stirring reaction, then adding copper compound, and obtaining copper polymer catalyst after continuous stirring and water washing.

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

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

[0012] Preferably, the amount of the copper polymer catalyst added is 0.14%-10% of the amount of p-chlorobenzonitrile; the molar ratio of p-chlorobenzonitrile to the hydroxide is 1:(2-8); and the amount of the solvent added is (0.7-4.3) times the amount 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 temperature of the heating reaction in step b) is 70-100°C; and the reaction time is 3-10h.

[0015] Advantages:

[0016] The present application provides a method for preparing a copper polymer catalyst and using the catalyst to prepare p-hydroxybenzonitrile. The method avoids the use of harmful products, reduces the risk of production and harm to the environment. The catalyst is stable and efficient, and easy to separate. The process is simple and efficient, with mild conditions, high selectivity, low risk, and easy separation of products. The process requires low equipment and has low cost, which is suitable for industrial production. DETAILED DESCRIPTION

[0017] Embodiment 1: Preparation of copper polymer catalyst A. 2.76g of potassium carbonate and 10ml of dichloromethane were placed in a flask, and 2.40g (10mmol) of tetramethyl diphenyl diamine was added, followed by the slow addition of 1.27g (10mmol) of oxalyl chloride, and stirring for 2 hours. Copper acetate 0.91g (5mmol) was added, and after stirring for 5 hours, water was washed, and dried to obtain copper polymer catalyst A.

[0018] Embodiment 2: Preparation of copper polymer catalyst B. 2.12g of sodium carbonate and 10ml of dichloromethane were placed in a flask, and 2.40g (10mmol) of tetramethyl diphenyl diamine was added, followed by the slow addition of 1.27g (10mmol) of oxalyl chloride, and stirring for 2 hours. Copper acetate 0.91g (5mmol) was added, and after stirring for 5 hours, water was washed, and dried to obtain copper polymer catalyst B.

[0019] Example 3: Preparation of Copper Polymer Catalyst C. Place 4.246 g of potassium phosphate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl- diphenyl diamine followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride and stir for 2 hours. Add copper acetate 1.82 g (10 mmol) and stir for 5 hours, wash with water and dry to obtain copper polymer catalyst C.

[0020] Example 4: Preparation of Copper Polymer Catalyst D. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl-diphenyl diamine followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride and stir for 2 hours. Add 0.95 g (5 mmol) of cuprous iodide and continue stirring for 5 hours, wash with water and dry to obtain copper polymer catalyst D.

[0021] Example 5: Preparation of Copper Polymer Catalyst E. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl-diphenyl diamine followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride and stir for 2 hours. Add 0.6725 g (5 mmol) of copper chloride and wash with water and dry to obtain copper polymer catalyst E.

[0022] Example 6: Preparation of Copper Polymer Catalyst F. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl-diphenyl diamine followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride and stir for 2 hours. Add 1.117 g (5 mmol) of copper bromide and stir for 5 hours, wash with water and dry to obtain copper polymer catalyst F.

[0023] Example 7: Preparation of Copper Polymer Catalyst G. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl-diphenyl diamine followed by slow addition of 1.27 g (10 mmol) of oxalyl chloride and stir for 2 hours. Add 0.715 g (5 mmol) of cuprous oxide and stir for 5 hours, wash with water and dry to obtain copper polymer catalyst G.

[0024] Example 8: Preparation of Copper Polymer Catalyst H. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl-diphenyl diamine followed by slow addition of 0.635 g of oxalyl chloride (5 mmol) and stir for 2 hours. Add 0.715 g (5 mmol) of cuprous oxide and stir for 5 hours, wash with water and dry to obtain copper polymer catalyst H.

[0025] Preparation of Copper Polymer Catalyst I. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.40 g (10 mmol) of tetramethyl- diphenyl diamine, followed by slow addition of 2.26 g (20 mmol) of chloroacetyl chloride, stir for 2 hours and then add cuprous oxide 0.715 g, stir for 5 hours, wash with water and dry to obtain copper polymer catalyst I.

[0026] Preparation of Copper Polymer Catalyst J. Place 2.76 g of potassium carbonate and 10 ml of dichloromethane in a flask and add 2.16 g (10 mmol) of dihydroxy- diphenyl diamine, followed by slow addition of 2.26 g (20 mmol) of chloroacetyl chloride, stir for 2 hours and then add cuprous oxide 0.715 g, stir for 5 hours, wash with water and dry to obtain copper polymer catalyst J.

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

[0028] Example 24: In a reaction vessel, 5.0 g (36 mmol) of p-chlorobenzonitrile and 3.36 g of potassium hydroxide (60 mmol) and 5 g of water were added, respectively, and 0.5 g of copper polymer catalyst A was placed in an autoclave and stirred at 80 °C for 5 h. After the reaction was completed, the catalyst was separated by filtration after adjusting the pH to be acidic with hydrochloric acid, and the solution was extracted with ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain about 4.286 g of p-hydroxybenzonitrile with a yield of 99%.

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

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

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

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

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

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

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

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

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

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

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

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

[0041] Embodiment 38: In a reaction vessel, 0.7 g (5 mmol) of p-chlorobenzonitrile and 1.12 g of potassium hydroxide (20 mmol) and 1 g of water were added, respectively, and 0.07 g of copper polymer catalyst A was added, and the reaction was stirred at 80°C for 10 h in an autoclave. After the reaction was completed, the catalyst was separated by filtration after adjusting the pH to be acidic with hydrochloric acid, and the solution was extracted with ethyl acetate, and the organic phase was combined, and the solvent was distilled off under reduced pressure to obtain about 0.536 g of p-hydroxybenzonitrile with a yield of 90%.

[0042] Embodiment 39: In a reaction vessel, 0.7 g (5 mmol) of p-chlorobenzonitrile and 1.12 g of potassium hydroxide (20 mmol) and 1 g of water were added, respectively, and 0.03 g of copper polymer catalyst A was added, and the reaction was stirred at 80°C for 10 h in an autoclave. After the reaction was completed, the catalyst was separated by filtration after adjusting the pH to be acidic with hydrochloric acid, and the solution was extracted with ethyl acetate, and the organic phase was combined, and the solvent was distilled off under reduced pressure to obtain about 0.526 g of p-hydroxybenzonitrile with a yield of 87%.

[0043] Embodiment 40: In a reaction vessel, 0.7 g (5 mmol) of p-chlorobenzonitrile and 1.12 g of potassium hydroxide (20 mmol) and 1 g of water were added, respectively, and 0.01 g of copper polymer catalyst A was added, and the reaction was stirred at 80°C for 10 h in an autoclave. After the reaction was completed, the catalyst was separated by filtration after adjusting the pH to be acidic with hydrochloric acid, and the solution was extracted with ethyl acetate, and the organic phase was combined, and the solvent was distilled off under reduced pressure to obtain about 0.505 g of p-hydroxybenzonitrile with a yield of 85%.

[0044] The washed and dried catalyst after reaction in embodiment 2 was reused. The process flow was consistent with the implementation case, and the catalyst recycling use condition was as shown in Table 1:

[0045] Table 1:

[0046] Number of recoveries p-Hydroxybenzonitrile yield 1 99％ 2 96％ 3 94％ 4 93％ 5 95％

[0047] From the experimental results of catalyst reuse in Table 1, the copper polymer catalyst has good reusability characteristics.

[0048] The washed and dried catalyst after reaction in embodiment 23 was reused. The process flow was consistent with the implementation case, and the catalyst recycling use condition was as shown in Table 2:

[0049] Table 2:

[0050] Number of recoveries p-Hydroxybenzonitrile yield 1 85％ 2 86％ 3 85％ 4 84％ 5 86％

[0051] From the experimental results of catalyst reuse in Table 2, the copper polymer catalyst has good reusability characteristics.

Claims

1. A method for synthesizing p-hydroxybenzonitrile catalyzed by a copper polymer catalyst, comprising the following steps: a) preparation of the copper polymer catalyst: a diamine of biphenyl is acylated by an acyl chloride to obtain an amide polymer by alkaline promotion, and the copper polymer catalyst is formed by complexing a copper compound; b) preparation of p-hydroxybenzonitrile: p-chlorobenzonitrile is placed in an autoclave, a hydroxide and a solvent are added, the copper polymer catalyst prepared in step a) is added, and heated reaction is carried out for a certain time to obtain p-hydroxybenzonitrile; wherein the diamine of biphenyl is tetramethyl diamine of biphenyl or dihydroxy diamine of biphenyl; and the acyl chloride is oxalyl chloride or chloroacetyl chloride.

2. The method of claim 1, wherein The copper polymer catalyst is obtained by a solution method, in which a base and dichloromethane are placed in a container, the diamine of biphenyl is added, then the acyl chloride is added and stirred, then the copper compound is added, and the copper polymer catalyst is obtained after water washing after continuous stirring.

3. The method of claim 2, wherein The base is potassium carbonate, sodium carbonate or potassium phosphate; and the copper compound is copper acetate, cuprous iodide, copper chloride, copper bromide or cuprous oxide.

4. The method of claim 2, wherein The molar ratio of the diamine of biphenyl to the acyl chloride is 1: (0.5-1.5); the molar ratio of the diamine of biphenyl to the base is 1: (1-2); and the molar ratio of the diamine of biphenyl to the copper compound is 1: (0.5-1).

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

6. The method of claim 1, wherein The hydroxide is potassium hydroxide or sodium hydroxide; and the solvent is water, dimethyl sulfoxide or DMF.

7. The method of claim 1, wherein The heating temperature in step b) is 70-100℃; and the reaction time is 3-10h.

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