Process for the catalytic preparation of m-phenoxybenzaldehyde using a copper catalyst

Abstract

The present application relates to a kind of copper catalyst catalytic preparation method of m-phenoxybenzaldehyde. With m-bromobenzaldehyde and phenol as raw material, under the action of copper catalyst, by adding base activation catalyst to prepare m-phenoxybenzaldehyde. The copper catalyst prepared by this method is stable, and can be recycled. The m-phenoxybenzaldehyde prepared by coupling m-bromobenzaldehyde and phenol has high efficiency, high selectivity, and the catalyst is easy to recover. Product separation has good process application prospect.

Description

Technical Field

[0001] This invention relates to a method for preparing m-phenoxybenzaldehyde using a copper catalyst, and more particularly to the preparation of a copper catalyst and its coupling reaction for preparing m-phenoxybenzaldehyde. Background Technology

[0002] With increasing public concern for food and environmental safety, research on pesticides and insecticides used in agriculture has gradually focused on issues such as high activity, low biotoxicity, and low residue. Pyrethroid pesticides and insecticides have slowly become a mainstream class in the market. As the most important raw material in the production of pyrethroid insecticides, the production of cypermethrin, deltamethrin, and other similar products relies heavily on m-phenoxybenzaldehyde. The synthesis of high-purity m-phenoxybenzaldehyde is of great significance to the development of agriculture and forestry. Due to my country's vast territory and the large area occupied by farms and forest farms, there is a huge demand for insecticides. Domestically, more than 4,000 tons of m-phenoxybenzaldehyde are consumed annually, hence research on m-phenoxybenzaldehyde has never ceased.

[0003] In 2017, Yuntong Zhai et al. found that N,N′-dicarboxamide ligand-supported copper catalysts exhibited good performance in the coupling of phenol with (hetero)aryl bromides and iodine. This reaction, using DMF as a solvent for 24 hours, achieved satisfactory conversion, but the time required was too long for industrial applications. Furthermore, DMF is expensive and its use can have adverse environmental impacts. (J.Org.Chem.2017,82,4964-4969)

[0004] In 2016, Mengyang Fan et al. discovered that CuI catalysts supported on N-aryl-N'-alkyl-substituted phthalamide ligands could effectively promote the coupling between (hetero)aryl chlorides and phenols. DMSO was the optimal solvent for this reaction; however, DMSO poses a risk of explosion, is too expensive to produce, and is difficult to recover and separate, thus limiting its industrial application. (Angew. Chem. Int. Ed. 2016, 55, 6211–6215)

[0005] In 2018, Ebrahim et al. prepared m-phenoxybenzaldehyde using a primary alcohol oxidation method. They used m-phenoxybenzyl alcohol as a raw material, hydrogen peroxide aqueous solution as the oxidant, and Fe3O4@SiO2~urea / MgBr2 nanoparticles as the catalyst. The reaction was carried out at 60℃ for 1–2 hours. Although this method has mild operating conditions, the preparation costs of the raw materials and catalyst are high, and it is difficult to carry out large-scale production. (Applied Organometallic Chemistry, 2018, 32(2))

[0006] In 2021, Fereshteh et al. used hydrogen peroxide as a green oxidant and imidazole tungstate as a heterogeneous catalytic system to oxidize toluenemethoxybenzyl alcohol to prepare m-phenoxybenzaldehyde. While this method is simple, it is costly and not conducive to industrial production. (Advanced Synthesis & Catalysis, 2021, 355:1591-1600.)

[0007] Chinese patent document CN1322705A discloses a method for preparing m-phenoxybenzaldehyde via gas-phase catalytic hydrogenation of m-phenoxybenzoic acid. The catalyst used is a Mn-based catalyst, with its main components being one or more of MnO, Al2O3, Zr, Zn, Ti, Hf, and Nb. The reaction temperature is 350–430℃ for gas-phase hydrogenation synthesis of m-phenoxybenzaldehyde. This method uses hydrogen gas, which is flammable and explosive, posing a significant safety hazard. Furthermore, the high reaction temperature required by this method makes the catalyst prone to sintering, increasing the risk of explosion and causing environmental pollution.

[0008] Chinese patent document CN111689841A reports a method in which water is used as the reaction solvent, and an oxidation reaction is carried out under the catalytic conditions of hydrogen peroxide, transition metal salts, and activated carbon, with oxygen flowing through the solution. The reaction temperature is 20-70℃. The reaction solution is filtered, the pH is adjusted to separate the layers, and purified m-phenoxybenzaldehyde is obtained by simple evaporation. This method uses hydrogen peroxide, which is highly corrosive and oxidizing, posing certain hazards to the environment and human health, and easily causing air pollution. Summary of the Invention

[0009] The purpose of this invention is to provide a method for preparing m-phenoxybenzaldehyde by using a copper catalyst to overcome the shortcomings of the prior art. First, a simple and efficient copper catalyst is prepared, and then the m-phenoxybenzaldehyde is prepared using the copper catalyst.

[0010] The technical solution of the present invention is as follows: a method for preparing m-phenoxybenzaldehyde by copper catalyst, the specific steps of which are as follows: A. Preparation of copper catalyst: diaminonaphthalene, acyl chloride, base and copper compound are placed in a ball mill, grinding balls are added for ball milling, and the mixture is washed and dried to obtain a copper polymer catalyst; B. Preparation of m-phenoxybenzaldehyde, the method is as follows: m-bromobenzaldehyde, phenol, base, solvent and the catalyst prepared in step A are added to a container, and the mixture is heated to react and obtain m-phenoxybenzaldehyde.

[0011] Preferably, the diaminonaphthalene mentioned in step A is 1,5-diaminonaphthalene or 1,8-diaminonaphthalene; the acyl chloride is oxalyl chloride or chloroacetyl chloride; the alkaline salt is potassium carbonate, sodium carbonate or potassium phosphate; and the copper compound is copper acetate, cuprous iodide or copper bromide.

[0012] The preferred molar ratio of diaminonaphthalene to acyl chloride in step A is 1:(0.5-1.5); the molar ratio of diaminonaphthalene to alkali is 1:(1-2); and the molar ratio of diaminonaphthalene to copper compound is 1:(0.5-1).

[0013] In step A, the preferred ball milling ratio is 1:(1-2); the milling speed is 145-160 r / min; and the milling time is 12-16 h.

[0014] The preferred molar amount of phenol added in step B is 1 to 2 times that of m-bromobenzaldehyde.

[0015] Preferably, the alkali mentioned in step B is cesium carbonate or potassium phosphate, and the molar amount of the alkali added is 1.5 to 2 times that of m-bromobenzaldehyde.

[0016] The preferred step B involves adding a catalyst at a mass of 25% to 60% of m-bromobenzaldehyde.

[0017] The solvent mentioned in step B is preferably dioxane or DMF; the mass of the solvent added is 2 to 4 times the mass of m-bromobenzaldehyde.

[0018] The preferred reaction temperature in step B is 110–125°C; the reaction time is 3–12 h.

[0019] The principle of this invention is shown in Equation 1:

[0020]

[0021] Formula 1. Method for coupling m-bromobenzaldehyde and phenol to generate m-phenoxybenzaldehyde

[0022] Beneficial effects:

[0023] This invention provides a method for preparing a copper catalyst and a method for preparing m-phenoxybenzaldehyde from m-bromobenzaldehyde and phenol. This method avoids the use of hydrogen peroxide, reducing production risks and environmental hazards. The catalyst is stable, efficient, and easy to separate. The process is simple, efficient, and operates under mild conditions with high selectivity, low risk, and easy product separation. The process requires minimal equipment, is inexpensive, and is suitable for industrial production. Detailed implementation method:

[0024] Implementation Method 1: Preparation of Catalyst A. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 12.6 g (100 mmol) of oxalyl chloride, 27.6 g (200 mmol) of potassium carbonate, and 9.1 g (50 mmol) of copper acetate were added to a planetary ball mill jar. 65.1 g of grinding balls were placed inside, and the mixture was ball-milled at 145 r / min for 12 h. After ball milling, the mixture was washed and dried in an oven to obtain copper polymer catalyst A.

[0025] Implementation Method 2: Preparation of Catalyst B. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 12.6 g (100 mmol) of oxalyl chloride, 21.2 g (200 mmol) of sodium carbonate, and 9.1 g (50 mmol) of copper acetate were added to a planetary ball mill jar. 117.4 g of grinding balls were placed inside, and the mixture was ball-milled at 150 r / min for 13 h. After ball milling, the mixture was washed and dried in an oven to obtain copper polymer catalyst B.

[0026] Implementation Method 3: Preparation of Catalyst C. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 6.3 g (50 mmol) of oxalyl chloride, 42.4 g (200 mmol) of potassium phosphate, and 9.1 g (50 mmol) of copper acetate were added to a planetary ball mill jar. 73.6 g of grinding balls were placed inside, and the mixture was ball-milled at 160 r / min for 16 hours. After ball milling, the mixture was washed and dried in an oven to obtain copper polymer catalyst C.

[0027] Implementation Method 4: Preparation of Catalyst D. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 12.6 g (100 mmol) of oxalyl chloride, 27.6 g (100 mmol) of potassium carbonate, and 9.5 g (50 mmol) of cuprous iodide were added to a planetary ball mill jar. 117.9 g of grinding balls were placed inside, and the mixture was ball-milled at 160 r / min for 14 h. After ball milling, the mixture was washed and dried in an oven to obtain copper polymer catalyst D.

[0028] Implementation Method 5: Preparation of Catalyst E. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 12.6 g (100 mmol) of oxalyl chloride, 27.6 g (200 mmol) of potassium carbonate, and 11.2 g (50 mmol) of copper bromide were added to a planetary ball mill jar. 67.2 g of grinding balls were placed inside, and the mixture was ball-milled at 160 r / min for 15 h. After ball milling, the mixture was washed and dried in an oven to obtain copper polymer catalyst E.

[0029] Implementation Method 6: Preparation of Catalyst F. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 12.6 g (100 mmol) of oxalyl chloride, 27.6 g (200 mmol) of potassium carbonate, and 1.82 g (100 mmol) of copper acetate were added to a planetary ball mill jar. 60.6 g of grinding balls were placed inside, and the mixture was ball-milled at 150 r / min for 15 h. After ball milling, the mixture was washed and dried in an oven to obtain copper polymer catalyst F.

[0030] Implementation Method 7: Preparation of Catalyst G. 15.8 g (100 mmol) of 1,8-diaminonaphthalene, 17 g (150 mmol) of chloroacetyl chloride, 27.6 g (200 mmol) of potassium carbonate, and 4.56 g (50 mmol) of copper acetate were added to a planetary ball mill jar. 66.9 g of grinding balls were placed inside, and the mixture was ball-milled at 150 r / min for 15 h. After ball milling, the mixture was washed and dried in an oven to obtain the copper polymer catalyst G.

[0031] Implementation Method 8: Preparation of Catalyst H. 15.8 g (100 mmol) of 1,5-diaminonaphthalene, 11.3 g (100 mmol) of chloroacetyl chloride, 27.6 g (200 mmol) of potassium carbonate, and 9.1 g (100 mmol) of copper acetate were added to a planetary ball mill jar. 63.8 g of grinding balls were placed inside, and the mixture was ball-milled at 160 r / min for 15 h. After ball milling, the mixture was washed and dried in an oven to obtain the copper polymer catalyst H.

[0032] Example 9: 185 g (1 mol) of m-bromobenzaldehyde, 103 g (1.1 mol) of phenol, 488 g (1.5 mol) of cesium carbonate, 517 g of dioxane, and 50 g of the copper polymer catalyst A prepared according to Example 1 were added to a reaction vessel and stirred at 120°C for 5 hours. After the reaction, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 155 g of m-phenoxybenzaldehyde, with a yield of 78.5%. Example 10: The reaction time was changed to 3 hours, and the remaining operations were performed as described in Example 9, yielding 139 g of m-phenoxybenzaldehyde, with a yield of 70%.

[0033] Implementation Method 11: The reaction time was changed to 7 hours, and the remaining operations were performed as described in Implementation Method 9, to obtain 168g of m-phenoxybenzaldehyde, with a yield of 85%.

[0034] Implementation Method 12: The reaction time was changed to 12 hours, and the remaining operations were performed as described in Implementation Method 9, to obtain 176g of m-phenoxybenzaldehyde, with a yield of 89%.

[0035] Implementation Method 13: The amount of phenol added was changed to 94g (1mol), and the remaining operations were carried out as described in Implementation Method 9, to obtain 149g of m-phenoxybenzaldehyde, with a yield of 75%.

[0036] Implementation Method 14: The amount of phenol added was changed to 141g (1.5mol), and the remaining operations were carried out as described in Implementation Method 9, to obtain 176g of m-phenoxybenzaldehyde, with a yield of 89%.

[0037] Implementation Method 15: The amount of phenol added was changed to 188g (2mol), and the remaining operations were carried out as described in Implementation Method 9, to obtain 164g of m-phenoxybenzaldehyde, with a yield of 83%.

[0038] Implementation Method 16: 488g (1.5mol) of cesium carbonate was replaced with 399g (1.5mol) of potassium phosphate, and the remaining operations were performed as described in Implementation Method 9, to obtain 149g of m-phenoxybenzaldehyde, with a yield of 75%.

[0039] Implementation Method 17: The amount of cesium carbonate added was changed to 390g (1.8mol), and the remaining operations were carried out as described in Implementation Method 9, to obtain 164g of m-phenoxybenzaldehyde, with a yield of 83%.

[0040] Implementation Method 18: The amount of cesium carbonate added was changed to 650g (2mol), and the remaining operations were carried out as described in Implementation Method 9, to obtain 168g of m-phenoxybenzaldehyde, with a yield of 85%.

[0041] Implementation Method 19: The amount of catalyst added was changed to 47g (25% of the substrate), and the remaining operations were carried out as described in Implementation Method 9, to obtain 150g of m-phenoxybenzaldehyde, with a yield of 76%.

[0042] Implementation Method 20: The amount of catalyst added was changed to 100g (55% of the substrate), and the remaining operations were carried out as described in Implementation Method 9, to obtain 156g of m-phenoxybenzaldehyde, with a yield of 79%.

[0043] Implementation Method 21: The amount of catalyst added was changed to 111g (60% of the substrate), and the remaining operations were carried out as described in Implementation Method 9, to obtain 160g of m-phenoxybenzaldehyde, with a yield of 81%.

[0044] Implementation Method 22: The reaction temperature was changed to 110 degrees Celsius, and the remaining operations were carried out as described in Implementation Method 9, to obtain 150g of m-phenoxybenzaldehyde, with a yield of 76%.

[0045] Implementation Method 23: The reaction temperature was changed to 125 degrees Celsius, and the remaining operations were carried out as described in Implementation Method 9, to obtain 146g of m-phenoxybenzaldehyde, with a yield of 74%.

[0046] Implementation Method 24: Replace 517g of dioxane with 716g of dioxane, and perform the remaining operations as described in Implementation Method 9 to obtain 150g of m-phenoxybenzaldehyde, with a yield of 76%.

[0047] Implementation Method 25: Replace 517g of dioxane with 490g of DMF, and perform the remaining operations as described in Implementation Method 9 to obtain 156g of m-phenoxybenzaldehyde, with a yield of 79%.

[0048] Implementation Method 26: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst A were reacted at 120°C with stirring for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 184 g of m-phenoxybenzaldehyde, with a yield of 93%.

[0049] Implementation Method 27: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst B were reacted at 120°C with stirring for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 160 g of m-phenoxybenzaldehyde, with a yield of 81%.

[0050] Implementation Method 28: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst C were reacted at 120°C with stirring for 12 hours. After the reaction, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 174 g of m-phenoxybenzaldehyde, with a yield of 88%.

[0051] Implementation Method 29: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst D were reacted at 120°C with stirring for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 83%.

[0052] Example 30: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst E were reacted at 120°C with stirring for 12 hours. After the reaction, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 145 g of m-phenoxybenzaldehyde, with a yield of 73%.

[0053] Implementation Method 31: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst F were reacted at 120°C with stirring for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 83%.

[0054] Example 32: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst G were reacted at 120°C with stirring for 12 hours. After the reaction, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 81%.

[0055] Implementation Method 33: 185 g (1 mol) of m-bromobenzaldehyde, 141 g (1.5 mol) of phenol, 650 g (2 mol) of cesium carbonate, 517 g of dioxane, and 110 g of copper polymer catalyst H were reacted at 120°C with stirring for 12 hours. After the reaction, the copper catalyst was separated by filtration, extracted with ethyl acetate, and the organic phases were combined. The solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 77%.

[0056] Implementation Method 34: The catalyst washed and dried after the reaction in Implementation Method 26 was reused. The results are shown in Table 1.

[0057] Table 1:

[0058] The process flow is consistent with the implementation case, and the catalyst recovery and utilization are shown in the table below:

[0059] Number of recyclings m-Phenoxybenzaldehyde 1 88％ 2 86％ 3 90％ 4 87％ 5 85％

[0060] Implementation Method 35: The catalyst washed and dried after the reaction in Implementation Method 30 was reused. The results are shown in Table 2.

[0061] Table 2:

[0062] The process flow is consistent with the implementation case, and the catalyst recovery and utilization are shown in the table below:

[0063] Number of recyclings m-Phenoxybenzaldehyde 1 71％ 2 69％ 3 70％ 4 71％ 5 67％

Claims

1. A method for preparing m-phenoxybenzaldehyde catalyzed by a copper catalyst, comprising the following steps: A. Preparation of the copper catalyst: placing diamino naphthalene, acyl chloride, base and copper compound into a ball mill, adding grinding balls for ball milling, washing and drying to obtain a copper polymer catalyst; B. Preparation of m-phenoxybenzaldehyde: adding m-bromobenzaldehyde, phenol, base, solvent and the catalyst prepared in step A into a container, heating to obtain m-phenoxybenzaldehyde; wherein the diamino naphthalene in step A is 1,5-diamino naphthalene or 1,8-diamino naphthalene; the acyl chloride is oxalyl chloride or chloroacetyl chloride; the base is potassium carbonate, sodium carbonate or potassium phosphate; and the copper compound is copper acetate, cuprous iodide or copper bromide.

2. The method of claim 1, wherein: In step A, the molar ratio of diamino naphthalene to acyl chloride is 1:(0.5-1.5); the molar ratio of diamino naphthalene to base is 1:(1-2); and the molar ratio of diamino naphthalene to copper compound is 1:(0.5-1).

3. The method of claim 1, wherein: In step A, the mass ratio of the material to the grinding balls is 1:(1-2) during ball milling; the rotation speed of the ball mill is 145-160 r / min; and the ball milling time is 12-16 h.

4. The method of claim 1, wherein: In step B, the molar amount of phenol added is 1-2 times that of m-bromobenzaldehyde.

5. The method of claim 1, wherein: In step B, the base is cesium carbonate or potassium phosphate, and the molar amount of base added is 1.5-2 times that of m-bromobenzaldehyde.

6. The method of claim 1, wherein: In step B, the mass of the catalyst added is 25%-60% of that of m-bromobenzaldehyde.

7. The method of claim 1, wherein: In step B, the solvent is dioxane or DMF, and the mass of the solvent added is 2-4 times that of m-bromobenzaldehyde.

8. The method of claim 1, wherein: In step B, the reaction temperature is 110-125℃, and the reaction time is 3-12 h.

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