CN110092783B - Preparation method of thiamethoxam - Google Patents
Preparation method of thiamethoxam Download PDFInfo
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Abstract
The invention discloses a preparation method of thiamethoxam, which comprises the steps of using 2-chloro-5-chloromethyl thiazole and 3-methyl-4-nitro imino perhydro-1, 3,5-
Description
Technical Field
The invention relates to the field of compound synthesis, in particular to a preparation method of a pesticide thiamethoxam.
Background
The new class of nicotinoids is the fourth generation following organophosphates, carbamates and pyrethroids. The mechanism of action is the binding to nicotinic acetylcholine receptors of the postsynaptic membrane of the insect nervous system. The pesticide has the characteristics of low toxicity, unique target, various application methods and the like, has become a pesticide with wide application in agricultural production, and has attracted wide attention of pesticide researchers.
Thiamethoxam is a novel class of nicotinic insecticides developed by syngenta corporation. As an important strategic species of antecedent, thiamethoxam 2016 reaches $ 12 billion worldwide in sales, and the listed insecticides are ranked second in the global sales line. Thiamethoxam has been registered for use in crops in over 115 countries around the world as an insecticide and seed treatment.
The preparation routes of thiamethoxam reported at home and abroad at present comprise four routes:
route 1: 2-chloro-5-chloromethylthiazole and 3-methyl-4-nitroimino perhydro-1, 3,5-
And carrying out diazine reaction to prepare the thiamethoxam.
Route 2: 2-benzylthio-5-chloromethylthiazole and 3-methyl-4-nitroimino perhydro-1, 3,5-
After the diazine reaction, the thiamethoxam is prepared by chlorination.
Route 3: 2-phenylthio-5-chloromethylthiazole and 3-methyl-4-nitroimino perhydro-1, 3,5-
After the diazine reaction, the thiamethoxam is prepared by chlorination.
Route 4: 2-cyclohexylmethyl-5-chloromethylthiazole and 3-methyl-4-nitroimino perhydro-1, 3,5-
After the diazine reaction, the thiamethoxam is prepared by chlorination.
Scheme 1 above is 2-chloro-5-chloromethylthiazole and 3-methyl-4-nitroimino perhydro-1, 3,5-
And (3) carrying out diazine reaction, and preparing the thiamethoxam under the action of a catalyst and an acid-binding agent. The route is a classical route for synthesizing thiamethoxam and is also a route for industrial production reported in China.
CN108164522A reports a method for preparing thiamethoxam by the above route 1, wherein the method comprises the following steps of washing with water, adjusting PH with hydrochloric acid, desolventizing, cooling, crystallizing and the like after the reaction is finished, so as to obtain a thiamethoxam original drug. However, the method has the problems of low yield, more three wastes, high wastewater treatment difficulty and the like.
Dabaixiong and the like report (CN108822098A) that aiming at the solubility of thiamethoxam raw drug at different temperatures, pure white thiamethoxam raw drug is obtained through operations of dropwise adding 2-chloro-5-chloromethylthiazole, filtering at high temperature, cooling for crystallization, eluting the raw drug with methanol and the like, the method has the advantages that the operations of water washing, extraction, solvent evaporation and the like are omitted, the catalyst needs to be added, the yield of the first-batch synthesis thiamethoxam raw drug is very low (about 10 percent), and a large amount of products are dissolved in a reaction solvent. The content of thiamethoxam raw medicine is not high, and is only about 98%. Meanwhile, the method adopts a mode of dripping 2-chloro-5-chloromethyl thiazole, the dripping speed is slow, and certain difficulties and risks exist in industrial operation due to the low freezing point (solidification below 30 ℃) of the 2-chloro-5-chloromethyl thiazole; moreover, the reaction mother liquor needs to be treated in a centralized way, and the operation is more complex.
Pengronggui et al report (CN107698578A) that polyethylene glycol 6000 and KI catalyst are added in the route (1), and after the reaction is finished, the thiamethoxam bulk drug with the content of more than 98% is obtained through operations of cooling, filtering and the like. Chenjianwei et al reported that (CN107501256A) the perhydrogenation of 2-chloro-5-chloromethylthiazole and 3-methyl-4-nitroimino-1, 3, 5-substituted benzene under the action of catalysts 4-dimethylaminopyridine and Me-DABCO
And (3) carrying out diazine reaction, namely filtering inorganic salt, adding a decolorizing agent into the filtrate, filtering again, desolventizing, cooling, crystallizing, filtering and the like to obtain the thiamethoxam with the purity of more than 99%. The two methods obtain products with higher purity, but the corresponding catalyst is added, so that the catalyst is not only expensive, but also the problem of high difficulty in catalyst recovery is solved, and the process time is long. Meanwhile, the yield of the original medicine prepared by the Pengronggui and other reported methods is low, the decoloring agents adopted by the Chenjiawei and other reported methods are active carbon, diatomite and adsorption resin, new three wastes are generated, and the problem that the decoloring agents cannot be recycled exists, so that the method is not suitable for green cleaning industryThe method has the advantages of long reaction time consumption, complex operation, long operation period and long operation period, and needs to be carried out by a series of operations such as salt residue filtration, filter cake leaching, solid decolorization, decolorizer filtration, desolventizing, heating dissolution, cooling crystallization and the like; the amount of three wastes is large, and the energy consumption is high; the catalyst not only uses 4-dimethylamino pyridine, Me-DABCO, but also uses an acid-binding agent, and has the problems of low price and high difficulty in catalyst recovery.
The reaction principles of the routes 2, 3 and 4 are basically consistent, all aromatic groups can be replaced by chlorine, and the method has the problems of unstable intermediate, long synthetic route, low yield and the like, and is not suitable for large-scale industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of thiamethoxam, which has the advantages of readily available raw materials, mild reaction conditions, less three wastes, simple and convenient operation, short time consumption, easy industrial production, high yield and high content.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of thiamethoxam comprises the following steps:
(1) perhydrogenation of 3-methyl-4-nitroimino-1, 3,5-
Adding diazine, 2-chloro-5-chloromethyl thiazole and an acid-binding agent into a reaction solvent, and carrying out condensation reaction to obtain a reaction solution; the acid-binding agent is N, N-diisopropylethylamine;
(2) adding a decoloring agent into the reaction liquid obtained in the step (1) for decoloring;
(3) and adding water into the decolorized reaction solution, cooling, crystallizing, filtering, and drying filter residues to obtain pure white thiamethoxam.
In the above method for preparing thiamethoxam, the reaction solvent is preferably dimethyl carbonate.
In the above preparation method of thiamethoxam, in the step (3), the molar ratio of the water to the 2-chloro-5-chloromethyl thiazole is preferably 5-10: 1.
In the above method for preparing thiamethoxam, preferably, in the step (2), the decolorizing agent is ozone.
In the above preparation method of thiamethoxam, preferably, the mass ratio of the ozone to the 2-chloro-5-chloromethyl thiazole is 0.05-0.1: 1.
In the above preparation method of thiamethoxam, preferably, in the step (3), the temperature for cooling and crystallizing the thiamethoxam is 0 ℃ to 10 ℃.
In the above method for preparing thiamethoxam, preferably, in the step (1), the 3-methyl-4-nitroimino perhydro-1, 3,5-
The ratio of the diazine, the 2-chloro-5-chloromethyl thiazole, the acid-binding agent and the reaction solvent is 0.2 mol: 100 g.
In the above method for preparing thiamethoxam, preferably, in the step (1), the temperature of the condensation reaction is 30 ℃ to 50 ℃.
Compared with the prior art, the invention has the advantages that:
1. the method overcomes the defects that the prior process needs complex purification operations such as filtration, desolventizing, control of the adding speed of reactants and the like, needs a single catalyst, has more three-waste treatment, or has low yield and content of prepared products and the like. The method of the invention not only shortens the reaction time, but also improves the reaction yield. The method has the advantages of mild process conditions, easy operation, easily obtained raw materials, less three wastes, lower production cost, good product quality, high content and the like, and is suitable for large-scale industrial clean production.
2. The method adopts an ozone decoloration mode, not only improves the quality of thiamethoxam, but also generates no three wastes, and the existing sodium hypochlorite and hydrogen peroxide decoloration generates new three wastes, and the solvent can be recycled and reused after treatment.
3. In the existing preparation process, kettle residues are generated by solvent desolventization when the solvent is recovered, but the invention has no desolventizing process and kettle residues; the N, N-diisopropylethylamine simultaneously plays a role of a catalyst and an acid-binding agent, the action mechanism of the acid-binding agent is that the N, N-diisopropylethylamine reacts with acid in the reaction to generate salt, the salt is dissolved by adding water, and the solvent can be directly used in a layered manner due to insolubility with water.
4. The method is favorable for obtaining products with higher yield and purity by controlling the parameters of the addition of water, an acid binding agent and a reaction solvent, crystallization temperature, condensation reaction temperature and the like, and in the method, the product yield is more than 91 percent, and the content can be more than 99 percent.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The preparation method of the thiamethoxam comprises the following steps:
(1) perhydrogenation of 3-methyl-4-nitroimino-1, 3,5-
Adding diazine, 2-chloro-5-chloromethyl thiazole and an acid-binding agent into a reaction solvent, and carrying out condensation reaction to obtain a reaction solution; the reaction solvent is dimethyl carbonate; the acid-binding agent is N, N-diisopropylethylamine;
(2) adding a decoloring agent into the reaction liquid obtained in the step (1) for decoloring;
(3) and adding water into the decolorized reaction solution, cooling, crystallizing, filtering, and drying filter residues to obtain pure white thiamethoxam.
In the step (3), the molar ratio of the water to the 2-chloro-5-chloromethylthiazole is 5-10: 1, preferably 7-10: 1, and further preferably 7: 1.
In the step (2), the decolorizing agent is ozone.
The mass ratio of the ozone to the 2-chloro-5-chloromethyl thiazole is 0.05-0.1: 1.
In the step (3), the temperature for cooling and crystallizing the thiamethoxam is 0-10 ℃.
In the step (1), the 3-methyl-4-nitroimino perhydro-1, 3,5-
The ratio of diazine, 2-chloro-5-chloromethylthiazole, acid-binding agent and reaction solvent is 0.2 mol: 100g, but is not limited to this value.
In the step (1), the condensation reaction temperature is 30-50 ℃.
In the invention, the condensation reaction is finished by using the standard that the content of 2-chloro-5-chloromethylthiazole tracked by high performance liquid chromatography is less than 1.0 percent, and the condensation reaction is usually within 1 hour.
The materials and equipment used in the following examples are commercially available.
Example 1
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. Directly introducing 2.4g of ozone into a reaction bottle, adding 25.2g of water after the ozone is introduced, cooling to 0 ℃ for crystallization, and filtering to obtain pure white thiamethoxam technical with the yield of 93.5% and the content of 99.5% (HPLC).
Example 2
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine at 30 ℃, the reaction is kept at the temperature for 1 hour, and the content of the 2-chloro-5-chloromethyl thiazole tracked by high performance liquid chromatography is less than1.0%, the reaction was stopped. 2.4g of ozone is directly introduced into a reaction bottle, 25.2g of water is added after the introduction, the temperature is reduced to 0 ℃ for crystallization, and the pure white thiamethoxam technical product is obtained after filtration, the yield is 92.1 percent, and the content is 99.1 percent (HPLC).
Example 3
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 50 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. 2.4g of ozone is directly introduced into a reaction bottle, 25.2g of water is added after the introduction, the temperature is reduced to 0 ℃ for crystallization, and the pure white thiamethoxam technical product is obtained after filtration, the yield is 92.6%, and the content is 99.3% (HPLC).
Example 4
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. 3.46g of ozone is directly introduced into a reaction bottle, 25.2g of water is added after the ozone is introduced, the temperature is reduced to 0 ℃ for crystallization, and the product is filtered to obtain pure white thiamethoxam raw drug with the yield of 93.6 percent and the content of 99.4 percent (HPLC).
Example 5
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
Diazine 32.6g (0.2mol), 2-chloro-5-chloromethylthiazole 34.6g (0.2mol), N, N-diisopropyl26.0g (0.2mol) of ethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of 2-chloro-5-chloromethyl thiazole tracked by high performance liquid chromatography is less than 1.0 percent, and the reaction is stopped. Directly introducing 1.73g of ozone into a reaction bottle, completely adding 25.2g of water, cooling to 0 ℃ for crystallization, and filtering to obtain the white thiamethoxam technical product with the yield of 93.2 percent and the content of 99.3 percent (HPLC).
Example 6
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. Directly introducing 2.4g of ozone into a reaction bottle, completely adding 25.2g of water, cooling to 10 ℃ for crystallization, and filtering to obtain pure white thiamethoxam raw drug, wherein the yield is 91.4%, and the content is 99.3% (HPLC).
Example 7
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. Directly introducing 2.4g of ozone into a reaction bottle, completely adding 25.2g of water, cooling to 5 ℃ for crystallization, and filtering to obtain pure white thiamethoxam technical with the yield of 94.2% and the content of 99.4% (HPLC).
Example 8
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. Directly introducing 2.4g of ozone into a reaction bottle, completely adding 36g of water, cooling to 5 ℃ for crystallization, and filtering to obtain pure white thiamethoxam raw drug, wherein the yield is 94.3%, and the content is 99.5% (HPLC).
Example 9
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethyl thiazole and 26.0g (0.2mol) of N, N-diisopropylethylamine, the temperature is controlled at 40 ℃, the reaction is kept at the temperature for 1 hour, the content of the 2-chloro-5-chloromethyl thiazole is tracked by high performance liquid chromatography to be less than 1.0 percent, and the reaction is stopped. Directly introducing 2.4g of ozone into a reaction bottle, completely adding 18g of water, cooling to 5 ℃ for crystallization, and filtering to obtain pure white thiamethoxam raw drug, wherein the yield is 91.3%, and the content is 98.5% (HPLC).
Comparative example 1
Dimethyl carbonate (100g), 3-methyl-4-nitroimino perhydro-1, 3,5-
32.6g (0.2mol) of diazine, 34.6g (0.2mol) of 2-chloro-5-chloromethylthiazole and 14.0g (0.1mol) of potassium carbonate, controlling the temperature at 40 ℃, keeping the temperature at the temperature for 5 hours for reaction, tracking the content of the 2-chloro-5-chloromethylthiazole by high performance liquid chromatography to be less than 1.0 percent, and stopping the reaction. Directly introducing 2.4g of ozone into a reaction bottle, completely adding 21.6g of water, cooling to 5 ℃ for crystallization, and filtering to obtain pure white thiamethoxam technical with the yield of 88.3 percent and the content of 99 percent (HPLC).
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (3)
1. The preparation method of thiamethoxam is characterized by comprising the following steps:
(1) adding 3-methyl-4-nitroimino perhydro-1, 3, 5-oxadiazine, 2-chloro-5-chloromethyl thiazole and an acid-binding agent into a reaction solvent for condensation reaction to obtain a reaction solution; the acid-binding agent is N, N-diisopropylethylamine; the reaction solvent is dimethyl carbonate; the ratio of the 3-methyl-4-nitroimino perhydro-1, 3, 5-oxadiazine to the 2-chloro-5-chloromethyl thiazole to the acid-binding agent to the reaction solvent is 0.2 mol: 100 g;
(2) adding a decoloring agent into the reaction liquid obtained in the step (1) for decoloring; the decolorant is ozone; the mass ratio of the ozone to the 2-chloro-5-chloromethyl thiazole is 0.05-0.1: 1;
(3) adding water into the reaction solution after the decolorization treatment, cooling and crystallizing, filtering, and drying filter residues to obtain pure white thiamethoxam; the molar ratio of the water to the 2-chloro-5-chloromethylthiazole is 5-10: 1.
2. The preparation method of thiamethoxam according to claim 1, wherein in the step (3), the temperature for cooling and crystallizing the thiamethoxam is 0-10 ℃.
3. A method for preparing thiamethoxam according to claim 1, wherein the condensation reaction is performed at a temperature of 30 ℃ to 50 ℃ in step (1).
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