CN112500411A - Preparation method of 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt - Google Patents
Preparation method of 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt Download PDFInfo
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Abstract
The invention discloses a preparation method of 1,1' -ethylene-2, 2' -bipyridyl dichloride salt, which comprises the steps of taking 2,2' -bipyridyl and dichloroethane as raw materials, taking a solvent A or a solvent B as a solvent, and carrying out cyclization reaction at a reaction temperature of 120-300 ℃ to obtain the 1,1' -ethylene-2, 2' -bipyridyl dichloride salt; wherein, the solvent A is selected from dichloroethane; the solvent B satisfies the following conditions: firstly, chemical reaction is not carried out between the raw materials or the reaction products; ② the raw materials of dichloroethane and 2,2' -bipyridyl can be dissolved. Compared with the prior art, the method has the advantages of simple process, short reaction route and low cost, and is suitable for industrial production. And the catalyst is added into the reaction system, so that the reaction rate can be remarkably accelerated, and the conversion rate of raw materials and the selectivity of target products are improved.
Description
Technical Field
The invention belongs to the field of chemical synthesis, relates to a preparation method of 1,1' -ethylene-2, 2' -bipyridyl dichloride (diquat dichloride), and particularly relates to a method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride by using 2,2' -bipyridyl and dichloroethane as raw materials.
Background
1,1 '-ethylene-2, 2' -bipyridyl dibromide, that is, diquat dibromide, was originally developed by Imperial Chemical Industries, Inc., a predecessor of Ministry, England, and is an excellent contact desiccant and herbicide with systemic properties, and is one of the most widely used biocidal herbicide products in the world, and the global sales and usage are second only to glyphosate, paraquat and glufosinate.
Patents US2823987, GB815348 indicate diquat anions (C1)-,Br-,I-,SO4 2-) Does not destroy its herbicidal activity. The literature (The dipyridylium herbicides, paraquat and diquat, P99; J.Sci.food Agric.,1960,309-315) reports that The active ingredients of diuron and The like herbicides are cationic moieties, that The anionic species have no effect on their herbicidal activity, and that The effect of these ions on equimolar amounts of substrate is equal.
Bromine is a precious resource, chlorine is cheap, and the development of a method for preparing the diquat dichloride salt to replace the diquat dibromide salt has important economic significance. The preparation method of the diquat dichloride salt reported at present mainly comprises the following steps:
1. ion exchange process
For example, U.S. Pat. No. 5,2823987 discloses a method for preparing a dichlorodiurethane solution by reacting a dibromodiurethane solution with silver chloride under stirring, and filtering out silver bromide to obtain a dichlorodiurethane solution. The method uses expensive silver chloride as chlorine exchanger, and has high cost and no industrial significance.
There is also a literature (Brit.J.induster.Med., 1966,23,133) that diquat dichloride can be obtained by ion exchange with ion exchange resins, and there is no industrial significance.
Patent US3803147 uses alkyl-bis-pyridinium bromide (ethylene-bis-pyridinium bromide) to couple with sodium amalgam in solvent, and then the generated 1,1 '-ethylene-2, 2' -bipyridyl dibromide is oxidized in diluted hydrochloric acid and air atmosphere to obtain 1,1 '-ethylene-2, 2' -bipyridyl dichloride. The method has long reaction steps and complex operation process, and flammable and explosive sodium and highly toxic mercury are used in the reaction process.
Chinese patent CN107573342A generates 1,1 '-ethylene-2, 2' -dipyridyl dibromide salt through the reaction of dipyridyl and dibromoethane, then 1,1 '-ethylene-2, 2' -dipyridyl dibromide salt water solution is used as raw material, and 1,1 '-ethylene-2, 2' -dipyridyl dibromide salt mother liquor and bromination by-products with cation content of 20-30% are obtained through a series of post-treatments such as hydrogen peroxide oxidation, bromine absorption, liquid separation and the like. The method has an industrial application prospect, but the 1,1 '-ethylene-2, 2' -dipyridyl dichloride salt parent drug is obtained by preparing diquat dibromide salt, oxidizing, brominating and carrying out multi-step post-treatment, and the method has long steps and complex operation.
2. Chlorohydrin cyclization method
GB1087052 uses 2,2' -bipyridine and 1-chloro-2-ethanol to be co-heated to 130-170 ℃ to prepare 1,1' -ethylene-2, 2' -bipyridine dichloride salt and a byproduct glycol. The method has the advantages of high cost of chloroethanol as a raw material, and troublesome separation and purification of ethylene glycol as a byproduct.
In conclusion, the known ion exchange method, chlorohydrin method and the like for synthesizing the 1,1 '-ethylene-2, 2' -bipyridyl dichloride have long flow path and high cost, and no better industrial preparation method exists at present.
Dibromoethane is a main raw material for synthesizing 1,1 '-ethylene-2, 2' -dipyridyl dibromide, the market price of the dibromoethane is more than ten times of that of dichloroethane, and the molecular weight of the dibromoethane is close to 2 times of that of the dichloroethane. If a method for synthesizing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt by replacing dibromoethane with dichloroethane can be developed, the method has important significance for reducing the production cost of the herbicide diquat.
At present, detailed reports on the one-step synthesis of 1,1' -ethylene-2, 2' -bipyridyl dichloride salt by dichloroethane and 2,2' -bipyridyl are not available.
Disclosure of Invention
The invention provides a preparation method of 1,1 '-ethylidene-2, 2' -bipyridine dichloride salt, aiming at the defects of long reaction route, complex process, high cost and the like in the prior art for preparing diquat dichloride salt.
The purpose of the invention is realized by the following technical scheme:
a preparation method of 1,1' -ethylene-2, 2' -bipyridyl dichloride salt comprises the steps of taking 2,2' -bipyridyl and dichloroethane as reaction raw materials, taking a solvent A or a solvent B as a solvent, and carrying out cyclization reaction at the reaction temperature of 120-300 ℃ to obtain the 1,1' -ethylene-2, 2' -bipyridyl dichloride salt; wherein, the solvent A is selected from dichloroethane; the solvent B satisfies the following conditions: firstly, chemical reaction is not carried out between the raw materials or the reaction products; ② the raw materials of dichloroethane and 2,2' -bipyridyl can be dissolved.
In one embodiment of the method for producing a 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to the present invention, when the solvent a is used as the solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl to dichloroethane as the raw material to the total amount of dichloroethane and dichloroethane as the solvent is 0.01 to 99:1, preferably 0.5 to 10:1, and more preferably 2 to 6: 1.
In another technical scheme of the preparation method of the 1,1' -ethylene-2, 2' -bipyridyl dichloride salt, when the solvent B is used as a solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl is 0.01-99: 1, preferably 1-10: 1, and more preferably 1-3: 1; the mass ratio of the solvent to the 2,2' -bipyridine is 0.1-30: 1, and preferably 4-6: 1.
The solvent B is at least one of aromatic hydrocarbon, alcohol, ether, alcohol ether, nitrile and ester organic solvents. The solubility of the reaction raw materials in the solvent B is more than or equal to 0.001g/100g, which can meet the requirement; preferably, the solubility of the reaction raw material in the solvent B is 10g/100g or more.
Preferably, the solvent B is at least one of nitrobenzene, xylene, ethylene glycol, 2-methoxycyclohexanol, benzonitrile and butyl acetate.
Still more preferably, the solvent is dichloroethane or nitrobenzene.
Most preferably, the solvent is dichloroethane.
The cyclization reaction according to the present invention is preferably carried out under a nitrogen atmosphere or an inert gas atmosphere from the viewpoint of safety of the reaction.
The reaction temperature is too low and slow, the reaction rate is accelerated by increasing the reaction temperature, but the reaction temperature is too high and exceeds 260 ℃, side reactions are aggravated, the target product 1,1 '-ethylene-2, 2' -bipyridyl dichloride is decomposed, the product selectivity is reduced, and when the temperature is continuously increased, the decomposition of the product is aggravated, the selectivity is greatly reduced, and the waste of resources is caused. Therefore, the temperature of the cyclization reaction is preferably 160-260 ℃, and more preferably 180-210 ℃.
The research of the inventor shows that the pressure has little influence on the result of the cyclization reaction, and the pressure of the cyclization reaction is generally 0.3-6.0 MPa, and preferably 0.6-3.0 MPa.
The cyclization reaction is carried out in the absence of a catalyst or in the presence of a catalyst. When the cyclization reaction is carried out under the condition without a catalyst, under the preferable reaction condition, the conversion rate of the raw material 2,2' -bipyridyl is more than or equal to 30 percent, the selectivity of the 1,1' -ethylene-2, 2' -bipyridyl dichloride is maintained at about 90 percent, and the conversion rate of the raw material is further improved along with the increase of the reaction time. A small amount of catalyst is added into a reaction system, so that the reaction rate can be remarkably accelerated, and the conversion rate of raw materials and the selectivity of target products are improved. Under the common condition, the catalyst is added, under the condition that the reaction time is shortened by 20-90%, the conversion rate of 2,2' -bipyridyl is improved by 0.8-4 times, and the selectivity of 1,1' -ethylene-2, 2' -bipyridyl dichloride is improved by 3-8%. Therefore, as a preferred embodiment of the method for producing a 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to the present invention, a cyclization reaction is carried out in the presence of a catalyst.
The catalyst is selected from organic amine, quaternary ammonium salt and amide; the organic amine is selected from at least one of 6-methyl-2, 2' -bipyridine, 6' -dimethyl-2, 2' -bipyridine, 2- (2-pyridyl) -1, 2-dihydropyridine (CAS number: 64534-28-7), 1H,1' H-2,2' -bipyridine ethylene (1H, 1' H- [2, 2' ] bipyridinylidine; CAS number: 64429-07-8) and 2-cyanopyridine; the quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride and dodecyltrimethylammonium chloride, and is preferably tetrabutylammonium bromide; the amide is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide, and is preferably N, N-dimethylformamide.
Most preferably, the catalyst is selected from at least one of 2- (2-pyridyl) -1, 2-dihydropyridine, 1H,1'H-2,2' -bipyridyl ethylene.
The mass ratio of the catalyst to the 2,2' -bipyridyl is 0.00005-0.05: 1, preferably 0.0002-0.01: 1, and most preferably 0.0002-0.0005: 1.
The cyclization reaction of the present invention can take various forms, and suitable reaction forms include, but are not limited to, batch reaction and continuous reaction.
Compared with the prior art, the invention has the beneficial effects that:
the invention overcomes the defects of long reaction route, complex process, high cost and the like in the prior art; the method has the advantages of simple process, short reaction route, obvious reduction of cost and suitability for industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 130 ℃, increasing the reaction pressure to 0.3MPa, keeping the temperature at 130 ℃ for 48 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 4.1 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 93.0 percent.
Example 2
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 250 ℃, increasing the reaction pressure to 2.8MPa, preserving the heat at 250 ℃ for 20 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 58.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 89.3 percent.
Example 3
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 290 ℃, increasing the reaction pressure to 3.3MPa, keeping the temperature at 290 ℃ for 1h, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 30.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 76.3 percent.
Example 4
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 160 ℃, increasing the reaction pressure to 0.6MPa, keeping the temperature at 160 ℃ for 48 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 32 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.1 percent.
Example 5
Adding 360g of 2,2' -bipyridine, 3600g of dichloroethane and 1.5g of tetrabutylammonium bromide serving as a catalyst into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 160 ℃, increasing the reaction pressure to 0.6MPa, keeping the temperature at 160 ℃ for 20h, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 58.4 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 98.2 percent.
Example 6
550g of 2,2' -bipyridine and 3300g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly raised to 200 ℃, the reaction pressure is raised to 1.3MPa, the temperature is kept at 200 ℃ for 20h, and the reaction is stopped. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 35.1 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 91.2 percent.
Example 7
To a dry 5L reactor, 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.2g of catalyst 2- (2-pyridyl) -1, 2-dihydropyridine were added. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, keeping the temperature at 200 ℃ for 8 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 92.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 97.4 percent.
Example 8
To a dry 5L reactor was added 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.2g of catalyst 1H,1' H-2,2' -bipyridinoethylene. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, keeping the temperature at 200 ℃ for 8 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 93.6 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 97.8 percent.
Example 9
To a dry 5L reactor, 550g of 2,2' -bipyridine, 3300g of dichloroethane, 0.1g of catalyst 2- (2-pyridyl) -1, 2-dihydropyridine, and 0.1g of 1H,1' H-2,2' -bipyridinoethylene were charged. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, keeping the temperature at 200 ℃ for 8 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 94.5 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 97.6 percent.
Example 10
550g of 2,2 '-bipyridine, 3300g of dichloroethane, and 0.3g of 6-methyl-2, 2' -bipyridine as a catalyst were charged in a dry 5-L reactor. Stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly increased to 200 ℃, the reaction pressure is increased to 1.3MPa, the temperature is kept at 200 ℃, the reaction is stopped after 8 hours, and the reaction product 1,1 '-ethylene-2, 2' -bipyridyl dichloride is gradually separated out from the reaction liquid in the reaction process. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 73.0 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 96.9 percent.
Example 11
550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.3g of catalyst 6,6' -dimethyl-2, 2' -bipyridine were charged into a dry 5-L reactor. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, keeping the temperature at 200 ℃ for 8 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of 2,2' -bipyridine is 68.3 percent, and the salt selectivity of the product 1,1' -ethylene-2, 2' -bipyridine dichloride is 96.6 percent.
Example 12
To a dry 5L reactor, 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.03g of 2-cyanopyridine as a catalyst were charged. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, keeping the temperature at 200 ℃ for 8 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 72.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 97.1 percent.
Example 13
To a dry 5L reactor, 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.3g of 2-cyanopyridine as a catalyst were charged. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, keeping the temperature at 200 ℃ for 8 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 78.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 96.6 percent.
Example 14
1000g of 2,2' -bipyridine and 3000g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly increased to 240 ℃, the reaction pressure is increased to 2.4MPa, the temperature is maintained at 240 ℃ for 10 hours, and the reaction is stopped. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 30.3 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 91.0 percent.
Example 15
1000g of 2,2' -bipyridine, 3000g of dichloroethane and 10g of catalyst N, N-dimethylformamide are added into a dry 5L reaction kettle, stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly raised to 240 ℃, the reaction pressure is raised to 2.4MPa, the temperature is kept at 240 ℃ for 3h, and the reaction is stopped. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 54.6 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 94.3 percent.
Example 16
To a dry 5L reactor, 500g of 2,2' -bipyridine, 1000g of dichloroethane (reaction material) and 2500g of nitrobenzene (solvent) were charged. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 190 ℃, increasing the reaction pressure to 1.0MPa, keeping the temperature at 190 ℃ for 20 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 32.6 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.2 percent.
Example 17
A5L dry reactor was charged with 500g of 2,2 '-bipyridine, 1000g of dichloroethane, 2500g of nitrobenzene, and 0.2g of catalyst 6-methyl-2, 2' -bipyridine. Starting stirring, replacing nitrogen in the reaction kettle, slowly heating to 190 ℃, increasing the reaction pressure to 1.0MPa, keeping the temperature at 190 ℃ for 12 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 70.8 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 97.5 percent.
Example 18
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 160 ℃, increasing the reaction pressure to 0.6MPa, filling nitrogen into the system until the reaction pressure is 3.0MPa, preserving the heat at 160 ℃ for 48 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 32.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.0 percent.
Example 19
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 160 ℃, increasing the reaction pressure to 0.6MPa, filling nitrogen into the system until the reaction pressure is 6.0MPa, preserving the heat at 160 ℃ for 48 hours, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 32.4 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.2 percent.
From examples 4, 18 and 19, it is clear that the pressure does not greatly affect the reaction results.
Example 20
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 160 ℃, increasing the reaction pressure to 0.6MPa, filling nitrogen into the system until the reaction pressure is 5.0MPa, preserving the heat at 160 ℃ for 10h, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 10.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.4 percent.
Example 21
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 180 ℃, increasing the reaction pressure to 0.9MPa, filling nitrogen into the system until the reaction pressure is 5.0MPa, preserving the heat at 180 ℃ for 10h, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 16.3 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.3 percent.
Example 22
Adding 360g of 2,2' -bipyridine and 3600g of dichloroethane into a dry 5L reaction kettle, starting stirring, replacing the reaction kettle with nitrogen, slowly heating to 200 ℃, increasing the reaction pressure to 1.3MPa, filling nitrogen into the system until the reaction pressure is 5.0MPa, preserving the heat at 200 ℃ for 10h, and stopping the reaction. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 22.6 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 92.3 percent.
From examples 20 to 22, it is understood that the reaction rate can be remarkably increased and the conversion rate of the raw material can be improved as the temperature is increased at a more preferable temperature.
Comparative example 1
550g of 2,2' -bipyridine, 3300g of dichloroethane and 55g of sodium chloride are added into a dry 5L reaction kettle, stirring is started, nitrogen replacement is carried out on the reaction kettle, the temperature is slowly increased to 200 ℃, the reaction pressure is increased to 1.3MPa, the temperature is maintained at 200 ℃ for 20h, and the reaction is stopped. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 34.9 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 91.0 percent.
Comparative example 2
550g of 2,2' -bipyridine, 3300g of dichloroethane and 55g of glass fiber are added into a dry 5L reaction kettle, stirring is started, nitrogen replacement is carried out in the reaction kettle, the temperature is slowly increased to 200 ℃, the reaction pressure is increased to 1.3MPa, the temperature is maintained at 200 ℃ for 20h, and the reaction is stopped. Sampling analysis shows that the conversion rate of the 2,2' -bipyridyl is 35.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridyl dichloride salt is 91.2 percent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of 1,1' -ethylene-2, 2' -bipyridyl dichloride is characterized in that 2,2' -bipyridyl and dichloroethane are used as reaction raw materials, a solvent A or a solvent B is used as a solvent, and cyclization reaction is carried out at the reaction temperature of 120-300 ℃ to obtain the 1,1' -ethylene-2, 2' -bipyridyl dichloride; wherein, the solvent A is selected from dichloroethane; the solvent B satisfies the following conditions: firstly, chemical reaction is not carried out between the raw materials or the reaction products; ② the raw materials of dichloroethane and 2,2' -bipyridyl can be dissolved.
2. The method for producing a 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein when the solvent A is used as the solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl to the total amount of dichloroethane as the raw material and dichloroethane as the solvent is 0.01 to 99:1, preferably 0.5 to 10:1, and more preferably 2 to 6: 1.
3. The method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein when the solvent B is used as the solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl is 0.01-99: 1, preferably 1-10: 1, and more preferably 1-3: 1; the mass ratio of the solvent to the 2,2' -bipyridine is 0.1-30: 1, and preferably 4-6: 1.
4. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein said solvent B is at least one of aromatic hydrocarbon, alcohol, ether, alcohol ether, nitrile, ester organic solvent, preferably at least one of nitrobenzene, xylene, ethylene glycol, 2-methoxycyclohexanol, benzonitrile, butyl acetate.
5. The method of claim 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt, characterized in that the solvent is dichloroethane or nitrobenzene.
6. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein the temperature of the cyclization reaction is 160-260 ℃, preferably 180-210 ℃.
7. The method for producing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein the cyclization reaction is carried out in the absence of a catalyst or in the presence of a catalyst.
8. The method of claim 7, wherein the catalyst is selected from the group consisting of organic amines, quaternary ammonium salts, amides; the organic amine is selected from at least one of 6-methyl-2, 2' -bipyridine, 6' -dimethyl-2, 2' -bipyridine, 2- (2-pyridyl) -1, 2-dihydropyridine, 1H,1' H-2,2' -bipyridine ethylene and 2-cyanopyridine; the quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride and dodecyltrimethylammonium chloride; the amide is at least one selected from N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide; the catalyst is at least one selected from 2- (2-pyridyl) -1, 2-dihydropyridine and 1H,1'H-2,2' -bipyridyl ethylene.
9. The method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 7, wherein the mass ratio of the catalyst to the 2,2' -bipyridyl is 0.00005-0.05: 1, preferably 0.0002-0.01: 1, and most preferably 0.0002-0.0005: 1.
10. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 7, wherein said cyclization reaction is in the form of a batch reaction or a continuous reaction.
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| CN113214258A (en) * | 2021-05-14 | 2021-08-06 | 安徽国星生物化学有限公司 | Method and device for synthesizing diquat dichloride |
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| CN116120321A (en) * | 2022-12-30 | 2023-05-16 | 重庆华歌生物化学有限公司 | Synthesis method of diquat dichloride |
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