CN112500411B - 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' -dipyridyl dichloride salt, which takes 2,2' -dipyridyl and dichloroethane as raw materials and solvent A or solvent B as solvents to carry out cyclization reaction at the reaction temperature of 120-300 ℃ to obtain the 1,1' -ethylene-2, 2' -dipyridyl dichloride salt; wherein, the solvent A is selected from dichloroethane; the solvent B satisfies the following conditions: (1) does not chemically react with the reaction raw materials or the reaction products; (2) can dissolve the dichloroethane and 2,2' -bipyridine serving as reaction raw materials. 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, i.e., diquat dibromide, was originally developed by Imperial Chemical Industries, a predecessor of Ministry, england, inc. (Imperial Chemical Industries, abbreviated as ICI), is an excellent contact desiccant and herbicide with systemic property, is also one of the most widely used biocidal herbicide products in the world at present, and is second to glyphosate, paraquat and glufosinate in global sales and use amount.
Patents US2823987, GB815348 indicate diquat anion (C1) - ,Br - ,I - ,SO 4 2- ) Without destroying 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 type has no effect on their herbicidal activity, and that The effect of these ions on equimolar amounts of substrate is equivalent.
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 a chlorine exchanger, 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.
U.S. Pat. No. 3,3803147 uses alkyl-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 by reacting dipyridyl and dibromoethane, then uses 1,1 '-ethylene-2, 2' -dipyridyl dibromide salt aqueous solution as raw material, and obtains 1,1 '-ethylene-2, 2' -dipyridyl dibromide salt mother liquor and bromination by-product with cation content of 20-30% by 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' -bipyridyl dichloride 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 heated together to 130-170 ℃ to prepare 1,1' -ethylene-2, 2' -bipyridine dichloride salt and a byproduct of ethylene 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 and high cost, and no better industrial preparation method exists at present.
Dibromoethane is the main raw material for synthesizing 1,1 '-ethylene-2, 2' -bipyridine dibromo salt, the market price of dibromoethane is more than ten times of that of dichloroethane, and the molecular weight of dibromoethane is close to 2 times of that of 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 found.
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' -dipyridyl dichloride salt takes 2,2' -dipyridyl and dichloroethane as reaction raw materials, takes a solvent A or a solvent B as a solvent, and carries out cyclization reaction at the reaction temperature of 120-300 ℃ to obtain the 1,1' -ethylene-2, 2' -dipyridyl dichloride salt; wherein, the solvent A is selected from dichloroethane; the solvent B satisfies the following conditions: (1) does not chemically react with the reaction raw materials or the reaction products; (2) can dissolve the dichloroethane and 2,2' -bipyridine serving as reaction raw materials.
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 is 0.01 to 1, preferably 0.5 to 10, and more preferably 2 to 6.
As another technical scheme of the method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride of the present invention, when the solvent B is used as a solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl is 0.01 to 99, preferably 1 to 10; the mass ratio of the solvent to the 2,2' -bipyridine is 0.1-30, preferably 4-6.
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 to 260 ℃ and more preferably 180 to 210 ℃.
The inventors have found that the pressure does not greatly affect the result of the cyclization reaction, and the pressure of the cyclization reaction is generally 0.3 to 6.0MPa, preferably 0.6 to 3.0MPa.
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 normal condition, the catalyst is added, and under the condition of shortening the reaction time by 20-90%, the conversion rate of 2,2' -dipyridine is improved by 0.8-4 times, and the selectivity of 1,1' -ethylene-2, 2' -dipyridine dichloride is improved by 3-8%. Therefore, as a preferred embodiment of the method for preparing the 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to the present invention, the 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' -bipyridyl, 6' -dimethyl-2, 2' -bipyridyl, 2- (2-pyridyl) -1, 2-dihydropyridine (CAS number: 64534-28-7), 1H,1' H-2,2' -bipyridyl 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' -bipyridine is 0.00005-0.05, preferably 0.0002-0.01.
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 following beneficial effects:
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 and low cost, and is suitable for industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
360g of 2,2' -bipyridine and 3600g 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 130 ℃, the reaction pressure is raised to 0.3MPa, the temperature is maintained at 130 ℃ for 48h, and the reaction is stopped. 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
360g of 2,2' -bipyridine and 3600g 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 250 ℃, the reaction pressure is increased to 2.8MPa, the temperature is kept at 250 ℃ for 20h, and the reaction is stopped. Sampling analysis shows that the conversion rate of the 2,2' -bipyridine is 58.2 percent, and the selectivity of the product 1,1' -ethylene-2, 2' -bipyridine dichloride salt is 89.3 percent.
Example 3
360g of 2,2' -bipyridine and 3600g 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 290 ℃, the reaction pressure is increased to 3.3MPa, the temperature is maintained at 290 ℃ for 1h, and the reaction is stopped. 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
360g of 2,2' -bipyridine and 3600g 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 160 ℃, the reaction pressure is increased to 0.6MPa, the temperature is maintained at 160 ℃ for 48h, and the reaction is stopped. 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
360g of 2,2' -bipyridine, 3600g of dichloroethane and 1.5g of tetrabutylammonium bromide serving as a catalyst are added into a dry 5L reaction kettle, stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly increased to 160 ℃, the reaction pressure is increased to 0.6MPa, the temperature is maintained at 160 ℃ for 20h, and the reaction is stopped. 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, and the temperature is kept at 200 ℃ for 20 hours, so that 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
550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.2g of 2- (2-pyridyl) -1, 2-dihydropyridine 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 raised to 200 ℃, the reaction pressure is raised to 1.3MPa, the temperature is kept at 200 ℃ for 8 hours, and the reaction is stopped. 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 charged 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.2g of catalyst 1H,1' H-2,2' -bipyridinoethylene. 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 maintained at 200 ℃ for 8 hours, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 93.6%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 97.8%.
Example 9
To a dry 5L reactor were charged 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' -bipyridinylethylene. 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 maintained at 200 ℃ for 8 hours, and the reaction is stopped. 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 maintained 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. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 73.0%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 96.9%.
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. 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 8 hours, and the reaction is stopped. 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 was charged 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.03g of 2-cyanopyridine as a catalyst. 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 maintained at 200 ℃ for 8 hours, and the reaction is stopped. 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 was charged 550g of 2,2' -bipyridine, 3300g of dichloroethane, and 0.3g of 2-cyanopyridine as a catalyst. 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 maintained at 200 ℃ for 8 hours, and the reaction is stopped. 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' -bipyridyl 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 raised to 240 ℃, the reaction pressure is raised to 2.4MPa, the temperature is maintained at 240 ℃ for 10 hours, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 30.3%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 91.0%.
Example 15
1000g of 2,2' -bipyridyl, 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 maintained at 240 ℃ for 3h, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 54.6%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 94.3%.
Example 16
A dry 5L reactor was charged with 500g of 2,2' -bipyridine, 1000g of dichloroethane (reaction material), and 2500g of nitrobenzene (solvent). Stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly increased to 190 ℃, the reaction pressure is increased to 1.0MPa, the temperature is maintained at 190 ℃ for 20h, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 32.6%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 92.2%.
Example 17
A dry 5L reactor was charged with 500g of 2,2 '-bipyridine, 1000g of dichloroethane, 2500g of nitrobenzene, and 0.2g of 6-methyl-2, 2' -bipyridine as a catalyst. Stirring is started, nitrogen in the reaction kettle is replaced, the temperature is slowly increased to 190 ℃, the reaction pressure is increased to 1.0MPa, the temperature is maintained at 190 ℃ for 12 hours, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 70.8%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 97.5%.
Example 18
360g of 2,2' -bipyridine and 3600g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen is replaced in the reaction kettle, the temperature is slowly increased to 160 ℃, the reaction pressure is increased to 0.6MPa, nitrogen is filled into the system until the reaction pressure is 3.0MPa, the temperature is kept at 160 ℃ for 48 hours, and the reaction is stopped. 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
360g of 2,2' -bipyridine and 3600g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen is replaced in the reaction kettle, the temperature is slowly increased to 160 ℃, the reaction pressure is increased to 0.6MPa, nitrogen is filled into the system until the reaction pressure is 6.0MPa, the temperature is kept at 160 ℃ for 48 hours, and the reaction is stopped. 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.
It is clear from examples 4, 18 and 19 that the pressure does not greatly affect the reaction results.
Example 20
360g of 2,2' -bipyridine and 3600g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen replacement is carried out on the reaction kettle, the temperature is slowly raised to 160 ℃, the reaction pressure is raised to 0.6MPa, nitrogen is filled into the system until the reaction pressure is 5.0MPa, heat preservation is carried out for 10 hours at 160 ℃, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 10.2%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 92.4%.
Example 21
360g of 2,2' -bipyridine and 3600g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen is replaced in the reaction kettle, the temperature is slowly increased to 180 ℃, the reaction pressure is increased to 0.9MPa, nitrogen is filled into the system until the reaction pressure is 5.0MPa, the temperature is kept at 180 ℃ for 10 hours, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 16.3%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 92.3%.
Example 22
360g of 2,2' -bipyridine and 3600g of dichloroethane are added into a dry 5L reaction kettle, stirring is started, nitrogen is replaced in the reaction kettle, the temperature is slowly increased to 200 ℃, the reaction pressure is increased to 1.3MPa, nitrogen is filled into the system until the reaction pressure is 5.0MPa, the temperature is kept at 200 ℃ for 10 hours, and the reaction is stopped. A sample was taken for analysis, and the conversion of 2,2' -bipyridine was 22.6%, and the selectivity of the product, 1' -ethylene-2, 2' -bipyridine dichloride salt, was 92.3%.
From examples 20 to 22, it is understood that at a more preferable temperature, the reaction rate can be remarkably increased and the conversion rate of the raw material can be improved as the temperature is increased.
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 gas in the reaction kettle is replaced, 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 gas in the reaction kettle is replaced, the temperature is slowly raised to 200 ℃, the reaction pressure is raised 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 (17)
1. A preparation method of 1,1' -ethylene-2, 2' -dipyridyl dichloride is characterized in that 2,2' -dipyridyl and dichloroethane are used as reaction raw materials, a solvent A or a solvent B is used as a solvent, and a cyclization reaction is carried out at a reaction temperature of 120-300 ℃ in the presence of a catalyst to obtain the 1,1' -ethylene-2, 2' -dipyridyl dichloride; wherein, the solvent A is selected from dichloroethane; the solvent B satisfies the following conditions: (1) does not chemically react with the reaction raw materials or the reaction products; (2) the dichloroethane and the 2,2' -bipyridyl serving as reaction raw materials can be dissolved; 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, 6,6' -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 mass ratio of the catalyst to the 2,2' -bipyridyl is 0.00005-0.05.
2. The process according to claim 1, wherein the mass ratio of dichloroethane to 2,2' -bipyridine is 0.01 to 99, based on the total amount of dichloroethane as the raw material and dichloroethane as the solvent, when the solvent A is used as the solvent.
3. The process according to claim 2, wherein the mass ratio of dichloroethane to 2,2' -bipyridine is 0.5 to 10, based on the total amount of dichloroethane as the raw material and dichloroethane as the solvent, when the solvent A is used as the solvent.
4. The process according to claim 3, wherein the mass ratio of dichloroethane and 2,2' -bipyridine to the total amount of dichloroethane as the raw material and dichloroethane as the solvent is 2 to 6.
5. The method for producing 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein when the solvent B is used as a solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl is 0.01 to 99; the mass ratio of the solvent to the 2,2' -bipyridine is 0.1-30.
6. The method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride according to claim 5, wherein when the solvent B is used as a solvent, the mass ratio of dichloroethane to 2,2' -bipyridyl is 1 to 10.
7. The method for producing 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 6, wherein the mass ratio of said dichloroethane to 2,2' -bipyridyl is 1 to 3.
8. The method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride according to claim 5, wherein when the solvent B is used as the solvent, the mass ratio of the solvent to the 2,2' -bipyridyl is 4 to 6.
9. 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.
10. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, characterized in that said solvent B is at least one of nitrobenzene, xylene, ethylene glycol, 2-methoxycyclohexanol, benzonitrile, butyl acetate.
11. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, characterized in that said solvent is dichloroethane or nitrobenzene.
12. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, characterized in that the temperature of said cyclization reaction is 160-260 ℃.
13. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 12, wherein said temperature of said cyclization reaction is 180-210 ℃.
14. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride according to claim 1, wherein the catalyst is at least one selected from 2- (2-pyridyl) -1, 2-dihydropyridine, and 1H,1'H-2,2' -bipyridyl vinyl.
15. The method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, characterized in that the mass ratio of the catalyst to 2,2' -bipyridyl is 0.0002 to 0.01.
16. The method for preparing 1,1' -ethylene-2, 2' -bipyridyl dichloride salt according to claim 15, wherein the mass ratio of the catalyst to the 2,2' -bipyridyl is 0.0002 to 0.0005.
17. The method for preparing 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt according to claim 1, wherein said cyclization reaction is in the form of a batch reaction or a continuous reaction.
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| CN108752289A (en) * | 2018-09-10 | 2018-11-06 | 南京艾普特生物医药有限公司 | 2,2 '-hydrazines-bis-（3- ethyl benzo thiazole phenanthroline -6- sulfonic acid）The synthetic method of diamine salts |
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| CN109020918A (en) * | 2018-08-14 | 2018-12-18 | 南京艾普特生物医药有限公司 | The synthetic method of 3- methyl-2-benzothiazolinone hydrazone hydrochloride and its hydrate |
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