Method for preparing m-phenoxybenzaldehyde under catalysis of copper catalyst

Abstract

The invention relates to a method for preparing m-phenoxybenzaldehyde through catalysis of a copper catalyst. According to the method, m-bromobenzaldehyde and phenol are used as raw materials, and under the action of a copper catalyst, an alkali activation catalyst is added to prepare m-phenoxybenzaldehyde. The copper catalyst prepared by the method is stable and recoverable. The reaction process for preparing m-phenoxybenzaldehyde by coupling m-bromobenzaldehyde and phenol is efficient and high in selectivity, the catalyst is easy to recover, and product separation has good process application prospects.

Description

Technical Field

[0001] The invention relates to a method for preparing m-phenoxybenzaldehyde by using a copper catalyst, in particular to the preparation of a copper catalyst and a coupling reaction of the copper catalyst for preparing m-phenoxybenzaldehyde by using the copper catalyst. Background Art

[0002] As people pay more and more attention to food safety and environmental safety, the research on pesticides and insecticides used in agriculture has gradually focused on high activity, low biotoxicity and low residue. Pyrethroid pesticides or insecticides have gradually become the mainstream type of pesticides and insecticides on the market. As the most important raw material in the production of pyrethroid insecticides, the production of cypermethrin, cypermethrin, etc. cannot be separated from 3-phenoxybenzaldehyde. The synthesis of high-purity 3-phenoxybenzaldehyde is of great significance to the development of agriculture and forestry. Due to the vast territory of my country, the large area of ​​farms and forests, there is a huge demand for insecticides. More than 4,000 tons of 3-phenoxybenzaldehyde are consumed in China every year, so the research on 3-phenoxybenzaldehyde has never stopped.

[0003] In 2017, Yuntong Zhai et al. found that N, N′-dimethylamide ligand-supported copper catalyst has good performance in the process of coupling phenol with (hetero)aryl bromide and iodine. The reaction uses DMF as solvent for 24 hours. Although the conversion effect is good, the time period is too long for industrial use. DMF is a solvent with high price and will also have adverse effects on the environment during use. (J.Org.Chem.2017,82,4964-4969)

[0004] In 2016, Mengyang Fan et al. found that CuI-loaded N-aryl-N'alkyl-substituted phthalamide ligand catalysts can effectively promote the coupling between (hetero)aryl chlorides and phenols. This reaction uses DMSO as the best solvent for the process, but DMSO is prone to explosion risks, and the production cost is too high. It is not easy to recycle and separate, and its use in industry will be limited. (Angew. Chem. Int. Ed. 2016, 55, 6211–6215)

[0005] In 2018, Ebrahim et al. used the primary alcohol oxidation method to prepare m-phenoxybenzaldehyde, using m-phenoxybenzyl alcohol as the raw material, aqueous hydrogen peroxide as the oxidant, and Fe3O4@SiO2~urea / MgBr2 nanoparticles as the catalyst, and reacted at 60°C for 1 to 2 hours. Although the operating conditions of this method are mild, the preparation cost of the raw materials and catalysts is 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 skeleton tungstate as a heterogeneous catalytic system to oxidize toluene methoxybenzyl alcohol to prepare m-phenoxybenzaldehyde. Although 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 reports a method: m-phenoxybenzoic acid is used to prepare m-phenoxybenzaldehyde through gas phase catalytic hydrogenation, the catalyst used is a Mn-based catalyst, the main components of the catalyst are MnO, Al2O3 and one or more of Zr, Zn, Ti, Hf, Nb, and the reaction temperature is 350-430°C for gas phase hydrogenation to synthesize m-phenoxybenzaldehyde. This method uses hydrogen, which is flammable and explosive, extremely harmful, and has great safety hazards. In addition, this method requires a high reaction temperature, the catalyst is easy to sinter, the explosion risk is greater, and it is easy to cause environmental pollution.

[0008] Chinese patent document CN111689841A reports a method: using water as a reaction solvent, in the presence of hydrogen peroxide, transition metal salt, activated carbon catalysis, oxygen is passed through for oxidation reaction, the reaction temperature is 20-70°C, the reaction solution is filtered, pH is adjusted, and layers are separated, and simple distillation is performed to obtain refined m-phenoxybenzaldehyde. This method uses hydrogen peroxide, which is highly corrosive and oxidizing, and has certain hazards to the environment and human body, and is easy to cause air pollution. Summary of the invention

[0009] The purpose of the present invention is to improve the deficiencies of the prior art and provide a method for preparing m-phenoxybenzaldehyde by using a copper catalyst. A simple and efficient copper catalyst is firstly prepared, and then the copper catalyst is used to prepare m-phenoxybenzaldehyde.

[0010] The technical scheme of the present invention is: a method for preparing m-phenoxybenzaldehyde by catalyzing a copper catalyst, and the specific steps are as follows: A. preparing the copper catalyst: putting diaminonaphthalene, acyl chloride, alkali and a copper compound into a ball mill, adding grinding balls for ball milling, washing and drying to obtain a copper polymer catalyst; B. preparing m-phenoxybenzaldehyde: adding m-bromobenzaldehyde, phenol, alkali, solvent and the catalyst prepared in step A into a container, heating and reacting to obtain m-phenoxybenzaldehyde.

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

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

[0013] Preferably, in step A, the ball mass ratio during ball milling is 1:(1-2); the rotation speed of the ball mill is 145-160 r / min; and the ball milling time is 12-16 h.

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

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

[0016] Preferably, the added mass of the catalyst in step B is 25% to 60% of m-bromobenzaldehyde.

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

[0018] Preferably, the reaction temperature in step B is 110-125° C. and the reaction time is 3-12 h.

[0019] The principle of the present invention is shown in Formula 1:

[0020]

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

[0022] Beneficial effects:

[0023] The invention provides a preparation method of a copper catalyst and a method for preparing m-phenoxybenzaldehyde from m-bromobenzaldehyde and phenol. The method avoids the use of hydrogen peroxide, reduces production risks and environmental hazards. 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 equipment requirements, low cost and is suitable for industrial production. DETAILED DESCRIPTION

[0024] Embodiment 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, and grinding balls (65.1 g) were put in and the mixture was milled at a speed of 145 r / min for 12 h. After the milling, the mixture was washed and dried in an oven to obtain a copper polymer catalyst A.

[0025] Embodiment 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, and grinding balls (117.4 g) were added and ball milled at a speed of 150 r / min for 13 h. After the ball milling, the mixture was washed and dried in an oven to obtain a copper polymer catalyst B.

[0026] Embodiment 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, and grinding balls (73.6 g) were added and ball milled at a speed of 160 r / min for 16 hours. After the ball milling, the catalyst was washed and dried in an oven to obtain a copper polymer catalyst C.

[0027] Embodiment 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, and grinding balls (117.9 g) were added and ball milled at a speed of 160 r / min for 14 h. After the ball milling was completed, the catalyst was washed and dried in an oven to obtain a copper polymer catalyst D.

[0028] Embodiment 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, and grinding balls (67.2 g) were added and ball milled at a speed of 160 r / min for 15 h. After the ball milling was completed, the mixture was washed and dried in an oven to obtain the copper polymer catalyst E.

[0029] Embodiment 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, and grinding balls (60.6 g) were added and ball milled at a speed of 150 r / min for 15 h. After the ball milling was completed, the catalyst was washed and dried in an oven to obtain a copper polymer catalyst F.

[0030] Embodiment 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, and grinding balls (66.9 g) were added and ball milled at a speed of 150 r / min for 15 h. After the ball milling was completed, the mixture was washed and dried in an oven to obtain the copper polymer catalyst G.

[0031] Embodiment 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, and grinding balls (63.8 g) were added and ball milled at a speed of 160 r / min for 15 h. After the ball milling, the mixture was washed and dried in an oven to obtain the copper polymer catalyst H.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0046] Embodiment 24: 517 g of dioxane was replaced with 716 g of dioxane, and the remaining operations were carried out in accordance with Embodiment 9 to obtain 150 g of m-phenoxybenzaldehyde with a yield of 76%.

[0047] Embodiment 25: 517 g of dioxane was replaced with 490 g of DMF, and the remaining operations were carried out in accordance with those described in Embodiment 9 to obtain 156 g of m-phenoxybenzaldehyde with a yield of 79%.

[0048] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 184 g of m-phenoxybenzaldehyde, with a yield of 93%.

[0049] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 160 g of m-phenoxybenzaldehyde, with a yield of 81%.

[0050] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 174 g of m-phenoxybenzaldehyde, with a yield of 88%.

[0051] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 83%.

[0052] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 145 g of m-phenoxybenzaldehyde, with a yield of 73%.

[0053] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 83%.

[0054] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 81%.

[0055] Embodiment 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 stirred and reacted at 120 degrees Celsius for 12 hours. After the reaction was completed, the copper catalyst was separated by filtration, extracted with ethyl acetate, the organic phases were combined, and the solvent was evaporated under reduced pressure to obtain 164 g of m-phenoxybenzaldehyde, with a yield of 77%.

[0056] Embodiment 34: The catalyst washed and dried after the reaction in Embodiment 26 is 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 use are as follows:

[0059] Recycling times m-Phenoxybenzaldehyde 1 88％ 2 86％ 3 90％ 4 87％ 5 85％

[0060] Embodiment 35: The catalyst washed and dried after the reaction in Embodiment 30 is 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 use are as follows:

[0063] Recycling times m-Phenoxybenzaldehyde 1 71％ 2 69％ 3 70％ 4 71％ 5 67％

Claims

1. A method for preparing m-phenoxybenzaldehyde by using a copper catalyst, the specific steps of which are as follows: A. Preparation of the copper catalyst: putting diaminonaphthalene, acyl chloride, alkali and a 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, alkali, solvent and the catalyst obtained in step A into a container, heating the container for reaction to obtain m-phenoxybenzaldehyde.

2. The method according to claim 1, characterized in that: The diaminonaphthalene described in step A is 1,5-diaminonaphthalene or 1,8-diaminonaphthalene; the acyl chloride is oxalyl chloride or chloroacetyl chloride; the alkali salt is potassium carbonate, sodium carbonate or potassium phosphate; and the copper compound is cupric acetate, cuprous iodide or cupric bromide.

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

4. The method according to claim 1, characterized in that: In step A, the ball mass ratio during ball milling is 1:(1-2); the rotation speed of the ball mill is 145-160 r / min; and the ball milling time is 12-16 h.

5. The method according to claim 1, characterized in that: The added molar amount of phenol described in step B is 1 to 2 times that of m-bromobenzaldehyde.

6. The method according to claim 1, characterized in that: The base described in step B is cesium carbonate or potassium phosphate, and the molar amount of the base added is 1.5 to 2 times that of m-bromobenzaldehyde.

7. The method according to claim 1, characterized in that: The added mass of the catalyst described in step B is 25% to 60% of m-bromobenzaldehyde.

8. The method according to claim 1, characterized in that: The solvent described in step B is dioxane or DMF; the mass of the added solvent is 2 to 4 times the mass of m-bromobenzaldehyde.

9. The method according to claim 1, characterized in that: The reaction temperature in step B is 110-125° C.; the reaction time is 3-12 hours.

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