CN108069853B

CN108069853B - Synthetic method of 3, 5-dichlorobenzoyl chloride

Info

Publication number: CN108069853B
Application number: CN201711421533.7A
Authority: CN
Inventors: 吴美宁; 王农跃; 茅晓晖; 郑建霖; 程小霞; 聂孝文; 郑土才
Original assignee: Jiangxi Jixiang Pharmaceutical Co ltd
Current assignee: Jiangxi Jixiang Pharmaceutical Co ltd
Priority date: 2017-12-25
Filing date: 2017-12-25
Publication date: 2020-12-22
Anticipated expiration: 2037-12-25
Also published as: CN108069853A

Abstract

The invention discloses a method for synthesizing 3, 5-dichlorobenzoyl chloride, which takes trimesoyl chloride as a raw material and directly removes two carbon monoxide under the action of a nickel or nickel-based catalyst to obtain the 3, 5-dichlorobenzoyl chloride. Compared with the existing preparation method, the method has the characteristics of short reaction flow, low catalyst price, less three wastes, no need of recycling a large amount of dangerous byproducts, lower production cost and the like, and is suitable for industrial production.

Description

Synthetic method of 3, 5-dichlorobenzoyl chloride

Technical Field

The invention relates to a method for synthesizing 3, 5-dichlorobenzoyl chloride, belonging to the field of fine organic chemical industry.

Background

3, 5-dichlorobenzoyl chloride is an important organic synthesis intermediate, and is widely used as an intermediate of medicines, pesticides and the like, such as the herbicide propyzamide.

The synthesis routes of 3, 5-dichlorobenzoyl chloride mainly comprise the following steps:

1. U.S. Pat. No. 4, 3931300, the advance of chemical industry (2002,21 (10), 756-757), German patent DE 2659147, etc. report that anthranilic acid, p-aminobenzoic acid or a mixture of both are chlorinated by a chlorinating agent to obtain 3, 5-dichloro-anthranilic acid, 3, 5-dichloro-p-aminobenzoic acid or a mixture of both, then diazotized and reduced to eliminate amino groups to obtain 3, 5-dichlorobenzoic acid, and finally chlorinated by a chlorinating agent to obtain 3, 5-dichlorobenzoyl chloride. The method has the advantages of multiple reaction steps, low total yield, high raw material price, high pollution and poor safety.

2. Journal of American Chemical Society (1951, 73,455-456) reported that 3, 5-dichlorotoluene was chlorinated to produce 3, 5-dichlorotrichloromethylbenzene and controlled hydrolyzed to produce 3, 5-dichlorobenzoyl chloride; U.S. Pat. No. 3,5, 2999879 reports the oxidation of 3, 5-dichloroethylbenzene to 3, 5-dichlorobenzoic acid, followed by chlorination to 3, 5-dichlorobenzoyl chloride. The 3, 5-dichlorotoluene can also be oxidized into 3, 5-dichlorobenzoic acid and then chlorinated to prepare the 3, 5-dichlorobenzoyl chloride. The raw materials of the route are not easy to obtain, and the method is lack of industrial value.

3. The catalytic chlorination of isophthaloyl dichloride reported in US 3869510, Japanese JP 57193434, etc. to produce 5-chloroisophthaloyl dichloride in PdCl₂、Pd/BaSO₄、Pd/Al₂O₃And the 3, 5-dichlorobenzoyl chloride is obtained by heating to 245 ℃ or above in the presence of the catalyst, the raw materials of the route are high in price, the decarbonylation catalyst is expensive, and the reaction temperature requirement is high.

4. Chemical reagents (2015, 37 (2), 176-₂O₃The 3, 5-dichlorobenzoyl chloride is obtained by catalyzing and decarbonylating at 290 ℃, and the catalyst of the route has high price and high requirements on reaction conditions.

5. U.S. Pat. No. 5, 3689546 reports that 5-chloroformylm-benzenedisulfonyl chloride is chlorinated at elevated temperatures with removal of sulfur dioxide by passing chlorine gas to give 3, 5-dichlorobenzoyl chloride in yields of up to 94%, and that the starting material 5-chloroformylm-benzenedisulfonyl chloride can be synthesized by known methods, for example by sulfonation with sulfur trioxide or oleum starting from benzoyl chloride and chlorination with a chlorinating agent such as phosphorus pentachloride or phosphorus oxychloride. The method has the advantages of few reaction steps, cheap and easily obtained raw materials, high sulfonation yield and the like, but phosphorus pentachloride is a monitored dangerous chemical, has large molecular weight and high unit consumption, and meanwhile, the byproduct, namely the monitored dangerous chemical, namely phosphorus oxychloride, has the same molar weight and needs to be recycled or treated. In addition, the density and boiling point of the byproduct phosphorus oxychloride are high, and the byproduct phosphorus oxychloride is difficult to completely separate and remove from the product, so that the yield and the product content of the third step of sulfur dioxide removal chlorination reaction are reduced. In addition, the process also has the problems of serious three wastes and equipment corrosion, poor production safety and the like.

Since the above-described processes for preparing 3, 5-dichlorobenzoyl chloride still suffer from such disadvantages or drawbacks, improvements in the process for preparing 3, 5-dichlorobenzoyl chloride are still of great interest.

Disclosure of Invention

In order to overcome the defects of serious three-waste and corrosion, large treatment capacity of hazardous chemicals, low production safety, high cost, low product content and the like in the existing 3, 5-dichlorobenzoyl chloride preparation technology, the invention provides a synthesis method of 3, 5-dichlorobenzoyl chloride.

The invention provides a method for synthesizing 3, 5-dichlorobenzoyl chloride, which takes trimesoyl chloride as a raw material to directly prepare the 3, 5-dichlorobenzoyl chloride through a reaction of removing two carbon monoxide by catalysis.

The synthetic route of the invention is as follows:

the invention relates to a method for synthesizing 3, 5-dichlorobenzoyl chloride, which is characterized by comprising the following steps: taking trimesoyl chloride as a raw material, and directly removing two carbon monoxide at the temperature of 180 ℃ and 250 ℃ under the catalysis of a nickel or nickel-based catalyst to prepare the 3, 5-dichlorobenzoyl chloride. The nickel or nickel-based catalyst is preferably Ni/Al₂O₃、Ni/SiO₂、Ni/TiO₂、Ni-Cu/Al₂O₃And Ni-Co/Al₂O₃Particularly preferred is Ni/Al₂O₃、Ni/SiO₂And Ni-Cu/Al₂O₃. The weight ratio of catalyst to trimesoyl chloride is preferably 0.01-0.06: 1.0. The reaction temperature for removing carbon monoxide is preferably 180-250 ℃, particularly preferably 200-230 ℃.

The method takes trimesoyl chloride as a raw material, prepares the 3, 5-dichlorobenzoyl chloride through direct one-step catalytic decarbonylation reaction, has simple synthesis process, easily obtained raw materials, low catalyst price and high product yield, avoids reclaiming or treating a large amount of dangerous chemicals, has high production safety and has higher industrial value.

Detailed Description

The starting materials and the like used in the following examples are all technical grade products and were not further purified. The content determination was performed using High Performance Liquid Chromatography (HPLC) normalization.

Example 13 Synthesis of 5, 5-Dichlorobenzoyl chloride

A500 mL four-necked flask was charged with 265.5 g (1.0 mole) of trimesoyl chloride, and 2.7 g of Ni-Co/Al₂O₃The catalyst is heated to 180 ℃ under stirring, the temperature is kept for reaction for 32h, reduced pressure distillation is carried out, and 125-128 ℃ fractions (1.73 kPa) are collected to obtain 187.7g of 3, 5-dichlorobenzoyl chloride, the yield is 89.6 percent, and the content is 98.37 percent.

Example Synthesis of 5, 5-Dichlorobenzoyl chloride

A500 mL four-necked flask was charged with 228.3 g (0.86 mol) of trimesoyl chloride, and 6.8 g of Ni/Al₂O₃The catalyst is heated to 220 ℃ under stirring, the reaction is carried out for 18h under the condition of heat preservation, reduced pressure distillation is carried out, and the fraction (1.73 kPa) at the temperature of 125-128 ℃ is collected to obtain 164.5g of 3, 5-dichlorobenzoyl chloride, the yield is 91.3 percent, and the content is 98.13 percent.

EXAMPLE 33 Synthesis of 5-Dichlorobenzoyl chloride

A500 mL four-necked flask was charged with 318.6 g (1.2 moles) of trimesoyl chloride, and 10.5 g of Ni-Cu/Al₂O₃The catalyst is heated to 200 ℃ under stirring, the reaction is carried out for 22h under the condition of heat preservation, reduced pressure distillation is carried out, and fractions with the temperature of 125-128 ℃ (1.73 kPa) are collected to obtain 233.8g of 3, 5-dichlorobenzoyl chloride, the yield is 93.0 percent, and the content is 98.27 percent.

EXAMPLE 43 Synthesis of 5-Dichlorobenzoyl chloride

A500 mL four-necked flask was charged with 265.5 g (1.0 mol) of trimesoyl chloride, and 4.5g of Ni/SiO₂The catalyst is heated to 250 ℃ under stirring, the reaction is carried out for 18h under the condition of heat preservation, reduced pressure distillation is carried out, and the 125-128 ℃ fraction (1.73 kPa) is collected to obtain 185.4g of 3, 5-dichlorobenzoyl chloride, the yield is 88.5 percent, and the content is 98.36 percent.

It is to be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the foregoing embodiments and descriptions are merely illustrative of the principles of the invention. Various changes and modifications can be made without departing from the spirit and scope of the invention, and these are within the scope of the invention as claimed.

Claims

1. A method for synthesizing 3, 5-dichlorobenzoyl chloride is characterized by comprising the following steps: with trimesoyl chlorideDirectly removing two carbon monoxide at 180-220 ℃ under the catalysis of a nickel or nickel-based catalyst to prepare 3, 5-dichlorobenzoyl chloride; the nickel or nickel-based catalyst is Ni/Al₂O₃、Ni/SiO₂、Ni-Cu/Al₂O₃And Ni-Co/Al₂O₃(ii) a The weight ratio of the catalyst to the trimesoyl chloride is 0.01-0.06: 1.0.