Preparation method for co-production of aryl acyl chloride and alkyl acyl chloride

Abstract

The invention discloses a co-production preparation method of aryl acyl chloride and alkyl acyl chloride, which comprises the following steps: in a solvent or solvent-free condition, carrying out condensation reaction on trichloromethyl aromatic hydrocarbon or a mixture of trichloromethyl aromatic hydrocarbon and aryl carboxylic acid and alkyl carboxylic acid under the action of a catalyst, and carrying out rectification separation to obtain target products aryl acyl chloride and alkyl acyl chloride. The synthesis method is short in reaction step and convenient to operate, aryl carboxylic acid can be recycled at the same time to prepare corresponding aryl acyl chloride, the synthesis method has the advantages of being small in investment, few in by-product and low in cost, meanwhile, it is avoided that a large number of reagents such as thionyl chloride and oxalyl chloride are additionally used in acyl chloride production, pollution is reduced, and industrial production is quite facilitated.

Description

Technical Field

[0001] The present invention belongs to the field of chemical synthesis, and particularly relates to a co-production preparation method of aryl acyl chloride and alkyl acyl chloride. Background Art

[0002] Aryl acyl chlorides are mainly used in organic synthesis. They can undergo condensation reactions with alcohols and amines and can be used as raw materials for preparing organic peroxides (such as dibenzoyl peroxide and tert-butyl peroxybenzoate), pesticides, vat dyes, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, rubber antioxidants, gel fracturing fluids, pharmaceuticals, etc. They have a wide range of applications and large demand. Among alkyl acyl chlorides, acetyl chloride can be used as a raw material for pesticides and pharmaceuticals and is also an intermediate for manufacturing the water treatment agent ethyldiphosphonic acid, and is also used for manufacturing new electroplating complexing agents.

[0003] Currently, there are multiple routes for synthesizing aryl acyl chlorides and alkyl acyl chlorides, and most of them are for separate synthesis. For example, Chinese invention patents CN115181016A and CN111909024A provide a route for synthesizing benzoyl chloride using thionyl chloride and benzoic acid as raw materials and toluene as a solvent. This method causes serious pollution, has cumbersome post-treatment, and thionyl chloride has strong corrosiveness to equipment, which does not meet the requirements of current sustainable development.

[0004] Chinese invention patents CN1552693A and invention patent WO2006013048A1 provide a route for synthesizing benzoyl chloride using oxalyl chloride and benzoic acid as raw materials, dimethylformamide as a solvent, and under the action of a Lewis acid catalyst. The oxalyl chloride used in this method has high requirements for equipment, and the post-treatment of solvent recovery is relatively cumbersome.

[0005] Chinese invention patent CN109956863A provides a route for hydrolyzing benzotrichloride to prepare benzoyl chloride under the action of a zinc chloride catalyst. This method generates a large amount of hydrogen chloride gas, has high requirements for equipment, and increases the cost of tail gas separation and recovery.

[0006] Chinese invention patent CN115073286A provides a route for co-producing acetyl chloride and nitric acid using acetic acid and nitryl chloride as raw materials and water as a solvent. The nitryl chloride used in this method is highly harmful to the environment, is easily decomposed by light, is difficult to store and use, and is prone to safety hazards.

[0007] Chinese invention patent CN116332786A provides a route for synthesizing acetyl chloride by oxidizing ethanol with chromium trioxide and then reacting with thionyl chloride. This method has a wide range of raw material sources and low prices, but chromium trioxide is highly toxic and is also prone to safety hazards. Summary of the Invention

[0008] In order to overcome the problems existing in the prior art, the purpose of the present invention is to provide a simple, efficient, green and environment-friendly co-production method of aryl acyl chloride and alkyl acyl chloride to meet the increasing demand for the above products in the industrial field.

[0009] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0010] The present invention provides a co-production method of aryl acyl chloride and alkyl acyl chloride. Under the condition of solvent or solvent-free, the trichloromethylarene shown in Formula I or its mixture with the aryl carboxylic acid shown in Formula II reacts with the alkyl carboxylic acid shown in Formula III under the action of a catalyst to carry out a condensation reaction, and the aryl acyl chloride shown in Formula IV and the alkyl acyl chloride shown in Formula V are obtained through rectification separation. The synthesis reaction formula is as follows:

[0011]

[0012] Among them,

[0013] R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from any one of H, halogen, alkyl, alkoxy, nitro, cyano, acetyl, phenyl, and methanesulfonyl.

[0014] Preferably, R1, R2, R3, R4, R5 are each selected from any one of the substituent combinations shown in Table A, and R6, R7, R8 are each selected from any one of the substituent combinations shown in Table B.

[0015] Table A

[0016]

[0017]

[0018] Table B

[0019]

[0020]

[0021] Preferably, the molar ratio of the trichloromethylarene shown in Formula I or its mixture with the aryl carboxylic acid shown in Formula II to the alkyl carboxylic acid shown in Formula III is 1: (0.5 - 2); in the mixture, the molar ratio of the trichloromethylarene shown in Formula I to the aryl carboxylic acid shown in Formula II is 1: (0 - 0.25).

[0022] Preferably, in the condensation reaction, the molar ratio of the catalyst to the alkyl carboxylic acid shown in Formula III is 0.0005 - 1.2:1; the reaction temperature is 50 - 170 °C, more preferably 80 - 100 °C; the reaction time is 0.5 - 6 hours, more preferably 2 - 3 hours.

[0023] Preferably, the catalyst is selected from one or more of Lewis acids, metal oxides, inorganic acids, organic acids, acidic ionic liquids, molecular sieves, and zeolites.

[0024] Preferably, the Lewis acid is at least one of AlCl3, ZnCl2, FeCl2, FeCl3, BF3, and SnCl4; the metal oxide is at least one of Al2O3, ZnO2, FeO, Fe2O3, Fe3O4, SnO, and SnO2.

[0025] Preferably, the catalyst is AlCl3 and / or FeCl3.

[0026] Preferably, the solvent is selected from one or more of substituted or unsubstituted aromatic hydrocarbons containing 1-24 carbons, substituted or unsubstituted straight-chain or branched aliphatic hydrocarbons, ethers, ketones, nitriles, ionic liquids, and supercritical carbon dioxide.

[0027] Preferably, the solvent is selected from one or more of nitrobenzene, toluene, xylene, mesitylene, pseudocumene, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, diglyme, and triglyme.

[0028] Preferably, the mass ratio of the solvent to the alkyl carboxylic acid shown in Formula III is (10-1):1, more preferably (4-2):1.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] In the present invention, a trichloromethylarene or a mixture of a trichloromethylarene and an aryl carboxylic acid is subjected to a condensation reaction with an alkyl carboxylic acid, and then the target products aryl acyl chloride and alkyl acyl chloride are obtained by rectification separation. The synthesis method of the present invention has short reaction steps, convenient operation, and can simultaneously recycle the aryl carboxylic acid to prepare the corresponding aryl acyl chloride. It has the advantages of less investment, fewer by-products, and low cost. At the same time, it avoids the additional use of a large amount of reagents such as thionyl chloride and oxalyl chloride in the production of acyl chloride, reduces pollution, and is very beneficial to industrial production. Detailed Description of the Invention

[0031] The following provides a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only for the purpose of illustrating and explaining the present invention, and are not intended to limit the present invention.

[0032] In the preparation method of the present invention, the compound raw materials having the structures shown in Formula I, Formula II, and Formula III can be commercially obtained or prepared by conventional reactions in the art. Both cases are within the protection scope of the present invention.

[0033] Synthesis of Compounds of Formula IV and V:

[0034] Example 1

[0035] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 161 g of nitrobenzene. The mixture was stirred and heated to 140 °C for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 37.1 g of p-chlorobenzoyl chloride with a yield of 84.7%; and 17.9 g of fluoroacetyl chloride with a yield of 74.6%.

[0036] Example 2

[0037] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 3.3 g (0.025 mol) of AlCl3 were added to 161 g of nitrobenzene. The mixture was stirred and heated to 140 °C for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 33.4 g of p-chlorobenzoyl chloride with a yield of 76.2%; and 16.7 g of fluoroacetyl chloride with a yield of 69.3%.

[0038] Example 3

[0039] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 3.4 g (0.025 mol) of ZnCl2 were added to 161 g of nitrobenzene. The mixture was stirred and heated to 140 °C for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 24.2 g of p-chlorobenzoyl chloride with a yield of 55.2%; and 12.2 g of fluoroacetyl chloride with a yield of 50.4%.

[0040] Example 4

[0041] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 2.55 g (0.025 mol) of Al2O3 were added to 161 g of nitrobenzene. The mixture was stirred and heated to 140 °C for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 20.6 g of p-chlorobenzoyl chloride with a yield of 47%; and 11 g of fluoroacetyl chloride with a yield of 45.4%.

[0042] Example 5

[0043] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 3.77 g (0.025 mol) of SnO2 were added to 161 g of nitrobenzene. The mixture was stirred and heated to 140 °C and reacted for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 26.3 g of p-chlorobenzoyl chloride with a yield of 60%; and 15 g of fluoroacetyl chloride with a yield of 62%.

[0044] Example 6

[0045] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 2.0 g (0.0125 mol) of FeCl3 were added to 161 g of xylene. The mixture was stirred and heated to 140 °C and reacted for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 27.3 g of p-chlorobenzoyl chloride with a yield of 62.3%; and 13.8 g of fluoroacetyl chloride with a yield of 56.9%.

[0046] Example 7

[0047] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 8.1 g (0.05 mol) of FeCl3 were added to 161 g of mesitylene. The mixture was stirred and heated to 140 °C and reacted for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 37.4 g of p-chlorobenzoyl chloride with a yield of 85.3%; and 18.8 g of fluoroacetyl chloride with a yield of 78.2%.

[0048] Example 8

[0049] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 161 g of dichlorobenzene. The mixture was stirred and heated to 140 °C and reacted for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 39 g of p-chlorobenzoyl chloride with a yield of 89.2%; and 20.4 g of fluoroacetyl chloride with a yield of 84.7%.

[0050] Example 9

[0051] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 161 g of xylene, and the mixture was stirred and heated to 140 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 27.8 g of p-chlorobenzoyl chloride with a yield of 63.4%; and 13.9 g of fluoroacetyl chloride with a yield of 57.7%.

[0052] Example 10

[0053] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 161 g of diglyme, and the mixture was stirred and heated to 140 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 30.9 g of p-chlorobenzoyl chloride with a yield of 70.5%; and 16.7 g of fluoroacetyl chloride with a yield of 69.3%.

[0054] Example 11

[0055] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 161 g of undecane, and the mixture was stirred and heated to 140 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 31.6 g of p-chlorobenzoyl chloride with a yield of 72.1%; and 17.2 g of fluoroacetyl chloride with a yield of 71.4%.

[0056] Example 12

[0057] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 161 g of 1-methylimidazolium tetrafluoroborate ionic liquid, and the mixture was stirred and heated to 140 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 32.9 g of p-chlorobenzoyl chloride with a yield of 75.1%; and 17.9 g of fluoroacetyl chloride with a yield of 74.3%.

[0058] Example 13

[0059] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 140 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 41.6 g of p-chlorobenzoyl chloride with a yield of 95.1%; and 22.2 g of fluoroacetyl chloride with a yield of 92.2%.

[0060] Example 14

[0061] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were stirred and heated to 140 °C for reaction for 6 h. The products were separated by rectification, obtaining 17.8 g of p-chlorobenzoyl chloride with a yield of 40.6%; and 8.2 g of fluoroacetyl chloride with a yield of 34.0%.

[0062] Example 15

[0063] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 9.75 g (0.125 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 140 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 21.2 g of p-chlorobenzoyl chloride with a yield of 48.3%; and 11.7 g of fluoroacetyl chloride with a yield of 96.5%.

[0064] Example 16

[0065] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 43.1 g of p-chlorobenzoyl chloride with a yield of 98.6%; and 23 g of fluoroacetyl chloride with a yield of 95.1%.

[0066] Example 17

[0067] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, and 2.85 g (0.025 mol) of trifluoroacetic acid were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 50 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 8.8 g of p-chlorobenzoyl chloride with a yield of 20.3%; and obtaining 4.1 g of fluoroacetyl chloride with a yield of 16.8%.

[0068] Example 18

[0069] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, 1.25 mL (0.025 mol) of 80% aqueous HNO3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 3 h. The solvent was distilled off by rectification to separate the products, obtaining 42 g of p-chlorobenzoyl chloride with a yield of 95.9%; and obtaining 22.5 g of fluoroacetyl chloride with a yield of 93.2%.

[0070] Example 19

[0071] In a 500 mL three-necked flask, a mixture of 52.9 g (0.23 mol) of p-chlorobenzotrichloride and 3.1 g (0.02 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, 1.5 g of zeolite were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 0.5 h. The solvent was distilled off by rectification to separate the products, obtaining 20.8 g of p-chlorobenzoyl chloride with a yield of 47.6%; and obtaining 9.2 g of fluoroacetyl chloride with a yield of 38.1%.

[0072] Example 20

[0073] In a 500 mL three-necked flask, a mixture of 46 g (0.2 mol) of p-chlorobenzotrichloride and 7.75 g (0.05 mol) of p-chlorobenzoic acid, 19.5 g (0.25 mol) of fluoroacetic acid, 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 3 h. The solvent was distilled off by rectification to separate the products, obtaining 41.2 g of p-chlorobenzoyl chloride with a yield of 94.1%; and obtaining 21 g of fluoroacetyl chloride with a yield of 87%.

[0074] Example 21

[0075] In a 500 mL three-necked flask, a mixture of 48.2 g (0.23 mol) of p-methylbenzotrichloride and 2.8 g (0.02 mol) of p-methylbenzoic acid, 22.5 g (0.25 mol) of methoxyacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of chlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 35.2 g of p-methylbenzoyl chloride with a yield of 91.2%; and obtaining 25.6 g of methoxyacetyl chloride with a yield of 94.3%.

[0076] Example 22

[0077] In a 500 mL three-necked flask, a mixture of 50.7 g (0.23 mol) of p-cyanobenzotrichloride and 3 g (0.02 mol) of p-cyanobenzoic acid, 21.3 g (0.25 mol) of α-cyanoacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of anisole. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 35.6 g of p-cyanobenzoyl chloride with a yield of 86.0%; and obtaining 21.3 g of α-cyanoacetyl chloride with a yield of 82.5%.

[0078] Example 23

[0079] In a 500 mL three-necked flask, a mixture of 59.8 g (0.23 mol) of 2-methoxy-4-chlorobenzotrichloride and 3.8 g (0.02 mol) of 2-methoxy-4-chlorobenzoic acid, 26.3 g (0.25 mol) of α-nitroacetic acid II, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 44.6 g of 2-methoxy-4-chlorobenzoyl chloride with a yield of 87.1%; and obtaining 22.5 g of α-nitroacetyl chloride with a yield of 85.5%.

[0080] Example 24

[0081] In a 500 mL three-necked flask, a mixture of 55.3 g (0.23 mol) of 3-nitrobenzotrichloride and 3.4 g (0.02 mol) of 3-nitrobenzoic acid, 53.1 g (0.25 mol) of diphenylacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 34.9 g of 3-nitrobenzoyl chloride with a yield of 75.2%; and obtaining 44.8 g of diphenylacetyl chloride with a yield of 77.4%.

[0082] Example 25

[0083] In a 500 mL three-necked flask, a mixture of 64.9 g (0.23 mol) of 2,4-dichloro-5-fluorobenzotrichloride and 4.2 g (0.02 mol) of 2,4-dichloro-5-fluorobenzoic acid, 32.2 g (0.25 mol) of dichloroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 43.3 g of 2,4-dichloro-5-fluorobenzoyl chloride with a yield of 76.2%; and obtaining 25.2 g of dichloroacetyl chloride with a yield of 69.3%.

[0084] Example 26

[0085] In a 500 mL three-necked flask, a mixture of 55.3 g (0.23 mol) of p-nitrobenzotrichloride and 3.4 g (0.02 mol) of p-nitrobenzoic acid, 38.2 g (0.25 mol) of 2-bromopropionic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 38 g of p-nitrobenzoyl chloride with a yield of 81.9%; and obtaining 32 g of 2-bromopropionyl chloride with a yield of 74.6%.

[0086] Example 27

[0087] In a 500 mL three-necked flask, 57.5 g (0.25 mol) of p-chlorobenzotrichloride, 19.5 g (0.25 mol) of fluoroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 36.4 g of p-chlorobenzoyl chloride with a yield of 83.1%; and obtaining 18.1 g of fluoroacetyl chloride with a yield of 75.4%.

[0088] Example 28

[0089] In a 500 mL three-necked flask, 65 g (0.25 mol) of 2-methoxy-4-chlorobenzotrichloride, 26.3 g (0.25 mol) of α-nitroacetic acid, and 4.1 g (0.025 mol) of FeCl3 were added to 80.5 g of dichlorobenzene. The mixture was stirred and heated to 90 °C for reaction for 6 h. The solvent was distilled off by rectification to separate the products, obtaining 45.1 g of 2-methoxy-4-chlorobenzoyl chloride with a yield of 88.1%; and obtaining 22.1 g of α-nitroacetyl chloride with a yield of 84.0%.

[0090] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0091] In addition, it should be noted that, in the above specific embodiments, the various specific technical features described can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not separately describe various possible combination manners.

[0092] Furthermore, any combinations can be made among the various different embodiments of the present invention as long as they do not violate the idea of the present invention, and they should also be regarded as the content disclosed by the present invention.

Claims

1. A co-production preparation method of aryl acyl chloride and alkyl acyl chloride, characterized in that, The method is to carry out a condensation reaction on the trichloromethylarene shown in Formula I or a mixture thereof with the aryl carboxylic acid shown in Formula II and the alkyl carboxylic acid shown in Formula III under solvent or solvent-free conditions under the action of a catalyst, and obtain the aryl acyl chloride shown in Formula IV and the alkyl acyl chloride shown in Formula V through rectification separation. The synthesis reaction formula is as follows: Wherein, R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from any one of H, halogen, alkyl, alkoxy, nitro, cyano, acetyl, phenyl, and methanesulfonyl.

2. The co-production preparation method according to claim 1, characterized in that, The R1, R2, R3, R4, R5 are selected from any one of the substituent combinations shown in Table A, and the R6, R7, R8 are selected from any one of the substituent combinations shown in Table B. Table A Table B 3. The co-production preparation method according to claim 1, wherein The molar ratio of the trichloromethylarene shown in Formula I or a mixture thereof with the aryl carboxylic acid shown in Formula II to the alkyl carboxylic acid shown in Formula III is 1:(0.5 - 2); in the mixture, the molar ratio of the trichloromethylarene shown in Formula I to the aryl carboxylic acid shown in Formula II is 1:(0 - 0.25).

4. The co-production preparation method according to claim 1, characterized in that, In the condensation reaction, the molar ratio of the catalyst to the alkyl carboxylic acid shown in Formula III is 0.0005 - 1.2:1; the reaction temperature is 50 - 170 °C, and the reaction time is 0.5 - 6 hours.

5. The co-production preparation method according to claim 1, wherein The catalyst is selected from one or more of Lewis acids, metal oxides, inorganic acids, organic acids, acidic ionic liquids, molecular sieves, and zeolites.

6. The co-production preparation method according to claim 5, characterized in that, The Lewis acid is at least one of AlCl3, ZnCl2, FeCl2, FeCl3, BF3, and SnCl4; the metal oxide is at least one of Al2O3, ZnO2, FeO, Fe2O3, Fe3O4, SnO, and SnO2.

7. The co-production preparation method according to claim 5 or 6, characterized in that, The catalyst is AlCl3 and / or FeCl3.

8. The co-production preparation method according to claim 1, wherein The solvent is selected from one or more of substituted or unsubstituted aromatic hydrocarbons containing 1 - 24 carbons, substituted or unsubstituted straight-chain or branched aliphatic hydrocarbons, ethers, ketones, nitriles, ionic liquids, and supercritical carbon dioxide.

9. The co-production preparation method according to claim 8, characterized in that, The solvent is selected from one or more of nitrobenzene, toluene, xylene, mesitylene, durene, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, diglyme, and triglyme.

10. The co-production preparation method according to claim 1, characterized in that, The mass ratio of the solvent to the alkyl carboxylic acid shown in Formula III is (10 - 1):1.

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