CN110950826B - Preparation method of carbosulfan - Google Patents
Preparation method of carbosulfan Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
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Abstract
The invention provides a preparation method of carbosulfan, which comprises the following steps: (1) dissolving carbofuran in an organic solvent, adding triethylamine as an acid-binding agent I, uniformly stirring and mixing, then dropwise adding sulfur dichloride, and carrying out heat preservation reaction after dropwise adding is finished to prepare a sulfide solution; (2) adding di-n-butylamine, 4-dimethylaminopyridine and triethylamine serving as an acid-binding agent II into the obtained sulfide solution, and carrying out heat preservation reaction after the addition is finished to obtain carbosulfan reaction liquid; (3) washing the carbosulfan reaction liquid until the reaction liquid is neutral, separating out an organic phase, and carrying out decompression and desolventization to obtain the carbosulfan with the content of more than or equal to 96 percent, the yield of more than or equal to 98 percent and harmful impurity carbosulfan in the carbosulfan of less than or equal to 0.1 percent. The method has the advantages of simple and convenient operation, easily obtained raw materials and low cost, and the prepared carbosulfan has low content of main harmful impurities and high yield and purity of target products.
Description
Technical Field
The invention belongs to the technical field of pesticide preparation, and particularly relates to a preparation method of carbosulfan.
Background
Carbosulfan is a carbamate insecticide, a low-toxicity derivative of carbosulfan developed by FMC corporation of america. Carbofuran has a high toxicity, so that the development of low-toxicity carbofuran derivatives is widely expected due to the fact that carbofuran has high toxicity, and the toxicity of carbofuran is only one-twelfth of that of carbofuran as a very important carbofuran low-toxicity derivative variety (Zenzez et al, "chemical synthesis of carbosulfan", "pesticides", volume 34, No.6(1995) P12 to 16).
The preparation method of carbosulfan reported at home and abroad at present mainly comprises the following three methods:
(1) di-n-butylamine reacts with sulfur monochloride to prepare di-n-butylamino sulfur chloride, and then reacts with methylamino formyl fluoride and furan phenol to prepare carbosulfan (DE3215256A 1).
(2) Di-n-butylamine reacts with sulfur monochloride to prepare di-n-butylamino sulfur chloride, and then reacts with carbofuran to prepare carbosulfan (US4329293, CN 102786503B).
(3) Carbofuran is directly reacted with sulfur dichloride to prepare chloride, and then reacted with di-n-butylamine to prepare carbosulfan (JP58026878, US 4413005).
The first and second methods both use sulfur monochloride as a starting material, have many reaction steps, long route and complicated post-treatment, use sulfuryl chloride as a raw material, strictly control the moisture content in the reaction, have small operation flexibility, generate a large amount of sulfur dioxide in the tail gas, and have high tail gas treatment cost. In addition, US4329293 adopts N-hexane as a reaction solvent, the N-hexane is very volatile, so that the safety risk exists, CN102786503A utilizes cosolvent N-methylpyrrolidone or dimethyl amide to improve the solubility of carbofuran in the reaction liquid, but the recovery loss rate of the cosolvent is high, the wastewater treatment difficulty is high, and the production cost is high.
In the third method, the yield reported in JP58026878 is 79.8%, the product yield reported in US4413005 is 76.6%, the yields are both low, the preparation cost is high, and the obtained carbosulfan product contains unreacted raw carbosulfan. The carbofuran has high toxicity, can be absorbed by plant roots, has high toxicity to fishes, quails, wild ducks and the like, is forbidden in the countries of the United states, Thailand, Kenya and the like, and strictly limits the content of the carbofuran which is a main harmful impurity in carbofuran to be less than 0.1 percent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of carbosulfan, which has the advantages of simple and convenient operation, low content of main harmful impurities, high yield and purity of target products, easily obtained raw materials and low cost.
In order to solve the technical problems, the invention adopts the following technical scheme.
A preparation method of carbosulfan comprises the following steps:
(1) dissolving carbofuran in an organic solvent, adding triethylamine as an acid-binding agent I, uniformly stirring and mixing, then dropwise adding sulfur dichloride, and carrying out heat preservation reaction after dropwise adding is finished to prepare a sulfide solution;
(2) adding di-n-butylamine, a catalyst 4-dimethylaminopyridine and an acid-binding agent II triethylamine into a sulfide solution, and after the addition is finished, carrying out a heat preservation reaction to obtain carbosulfan reaction liquid;
(3) washing the carbosulfan reaction liquid until the reaction liquid is neutral, separating out an organic phase, and carrying out decompression and desolventization to obtain the carbosulfan with the content of more than or equal to 96 percent, the yield of more than or equal to 98 percent and harmful impurity carbosulfan in the carbosulfan of less than or equal to 0.1 percent.
The chemical reaction formula is as follows:
preferably, the carbosulfan preparation method comprises the steps of mixing the carbosulfan acid binding agent I, the sulfur dichloride, the di-n-butylamine, the 4-dimethylamino pyridine and the acid binding agent II at a molar ratio of 1.00: 1.10-1.50: 1.05-1.10: 1.00-1.10: 0.03-0.05: 1.10-1.50, and obtaining a better reaction effect and better target product yield and purity.
In the preparation method of carbosulfan, preferably, in the step (1), the volume ratio of the organic solvent to carbosulfan is 10-15: 1.
In the above preparation method of carbosulfan, preferably, in step (1), the organic solvent is any one of dichloroethane, dichloromethane, toluene, and chlorobenzene.
In the preparation method of carbosulfan, preferably, in the step (1), the dripping temperature of the sulfur dichloride is 0-10 ℃, and the dripping time is 1-1.5 hours;
before dropwise adding sulfur dichloride, the method also comprises the step of regulating the temperature of the mixed solution obtained after uniformly stirring and mixing to 0-10 ℃.
In the preparation method of carbosulfan, preferably, in the step (1), the temperature of the heat preservation reaction is 0-20 ℃, and the time of the heat preservation reaction is 2-3 hours.
Preferably, in the step (2), the preparation method of carbosulfan further comprises the step of cooling the sulfide solution to 0-10 ℃ and then adding each reaction raw material;
when reaction raw materials of di-n-butylamine, a catalyst 4-dimethylaminopyridine and an acid-binding agent II triethylamine are added, the temperature of a reaction system is ensured to be 0-10 ℃.
In the preparation method of carbosulfan, preferably, in the step (2), the temperature of the heat preservation reaction is 0-25 ℃ and the time is 1-2 hours.
Preferably, in the above preparation method of carbosulfan, in step (3), the step of washing the reaction solution of carbosulfan until the reaction solution is neutral specifically includes: and sequentially washing, pickling and washing the carbosulfan reaction solution until the reaction solution is neutral.
In the preparation method of carbosulfan, preferably, the acid adopted by the acid cleaning is hydrochloric acid or sulfuric acid, and the mass fraction of the acid is 5-20%
The innovation of the invention is that:
the applicant finds that in the process of preparing carbosulfan by using sulfur dichloride, carbosulfan and di-n-butylamine as reaction raw materials, the carbosulfan has poor solubility in most organic solvents and is difficult to completely dissolve, and the phenomenon that part of carbosulfan solid is wrapped by sulfur dichloride is found when the carbosulfan is reacted with the sulfur dichloride, so that the carbosulfan cannot completely react, and the content of high-toxicity carbosulfan in a product exceeds 2 percent. Aiming at the problem, through a great deal of research, the applicant dissolves the carbofuran in the organic solvent by changing the feeding sequence and mode, adds the acid-binding agent, uniformly mixes the materials and then adds the sulfur dichloride in a dropwise manner, thereby effectively solving the problem that the carbofuran is wrapped and enters the product, greatly improving the thorough reaction degree of the carbofuran, reducing the content of the carbofuran in the final product and effectively improving the yield of the product.
By adding 4-dimethylamino pyridine into a reaction system of sulfide solution and di-n-butylamine, the reaction time of sulfide and di-n-butylamine can be greatly shortened from 12h to 2h in the original process, the problem of incomplete reaction of intermediate sulfide is solved, and the product content and yield are further greatly improved.
Compared with the prior art, the invention has the advantages that:
1. compared with the method using sulfur monochloride as the raw material, the process provided by the invention is a two-step reaction, and solves the problems of long synthesis route and complex post-treatment; compared with the similar method using sulfur dichloride as a raw material, the method disclosed by the invention finds out the reasons of low product yield and high impurity caused by the method using sulfur dichloride as a raw material through a large amount of researches, optimizes a vulcanization reaction feeding mode after the large amount of researches, mixes carbofuran, an organic solvent and acid-binding agent triethylamine, and then slowly drops the sulfur dichloride for reaction to prepare an intermediate sulfide, thereby solving the technical problems of the existing method using sulfur dichloride as a raw material.
2. In the preparation method of carbosulfan, the 4-dimethylaminopyridine is used, so that the synthesis period is greatly shortened, and the reaction efficiency, the product yield and the product purity are further improved.
3. According to the invention, by improving the feeding mode and sequence and adding 4-dimethylaminopyridine in the reaction process of the intermediate product sulfide solution and di-n-butylamine, the content of the final product in the whole process is not less than 96%, the yield is not less than 98%, carbofuran, a harmful impurity in the product, is controlled to be not more than 0.1%, the amount of three wastes generated is small, a large amount of sulfur dioxide tail gas generated by using raw material sulfuryl chloride can be avoided, the method has the characteristics of green process and wide popularization and application prospect.
4. In the method, the raw materials are further optimized and controlled, so that a better reaction effect is obtained, and better yield and purity of the target product are obtained.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloroethane into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 5 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction for 2h at 20 ℃ to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 25 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 193.6g of a reddish brown oily substance, wherein the content is 96.2 percent, the yield is 98.0 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.04 percent through quantitative analysis of high performance liquid chromatography.
Example 2
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloromethane into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 5 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction at 20 ℃ for 2h to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 0 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 0 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 194.1g of a reddish brown oily substance, wherein the content is 96.1 percent, the yield is 98.2 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.06 percent through quantitative analysis of high performance liquid chromatography.
Example 3
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of toluene into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 0 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction at 10 ℃ for 3h to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 25 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 193.7g of a reddish brown oily substance, wherein the content is 96.5 percent, the yield is 98.4 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.05 percent through quantitative analysis of high performance liquid chromatography.
Example 4
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of chlorobenzene into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 5 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction for 2h at 20 ℃ to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 20 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% sulfuric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, the reaction solution is decompressed and desolventized to obtain 193.9g of a reddish brown oily substance, the content is 96.0 percent through quantitative analysis of high performance liquid chromatography, the yield is 98.0 percent (calculated by carbofuran), and the content of a main harmful impurity carbofuran is 0.05 percent.
Example 5
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloroethane into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 5 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.0h, and carrying out heat preservation reaction at 15 ℃ for 2h to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 25 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 194.2g of a reddish brown oily substance, wherein the content is 96.1 percent, the yield is 98.2 percent (calculated by carbofuran) and the content of main harmful impurity carbofuran is 0.05 percent through quantitative analysis of high performance liquid chromatography.
Example 6
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloroethane into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 5 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction at 10 ℃ for 3h to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 10 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 194.3g of a reddish brown oily substance, wherein the content is 96.2 percent, the yield is 98.3 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.06 percent through quantitative analysis of high performance liquid chromatography.
Example 7
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloroethane into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 55.6g (0.55mol) of triethylamine, stirring and mixing uniformly, cooling to 0 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction at 0 ℃ for 3h to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 10 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 193.8g of a reddish brown oily substance, wherein the content is 96.1 percent, the yield is 98.0 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.05 percent through quantitative analysis of high performance liquid chromatography.
Example 8
The invention relates to a preparation method of carbosulfan, which comprises the following steps:
(1) adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloroethane into a 2L reaction bottle with a stirrer, after the carbofuran is dissolved, adding 60.6g (0.6mol) of triethylamine, stirring and mixing uniformly, cooling to 0 ℃, stirring and dropwise adding 54.6g (0.53mol) of sulfur dichloride, finishing dropping within 1.5h, and carrying out heat preservation reaction at 0 ℃ for 3h to obtain a sulfide solution;
(2) after the heat preservation reaction is finished, cooling the sulfide solution to 5 ℃, sequentially adding 70.9g (0.55mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine, and carrying out heat preservation reaction at 25 ℃ for 2 hours;
(3) after the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 193.4g of a reddish brown oily substance, wherein the content is 96.5 percent, the yield is 98.2 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.05 percent through quantitative analysis of high performance liquid chromatography.
Comparative example 1
The preparation method of carbosulfan comprises the following steps:
110.5g (0.5mol) of carbofuran and 1.0L of dichloroethane are added into a 2L reaction bottle with a stirrer, 60.6g (0.6mol) of triethylamine is added after the carbofuran is dissolved, the mixture is stirred and mixed evenly, and the temperature is reduced to 5 ℃. Stirring and dripping 54.6g (0.53mol) of sulfur dichloride for 1.5h, then heating to 20 ℃ and reacting for 2h under the condition of heat preservation. After the heat preservation reaction is finished, the temperature is reduced to 5 ℃, 64.5g (0.5mol) of di-n-butylamine and 75.8g (0.75mol) of triethylamine are sequentially added, and the heat preservation reaction is carried out for 12 hours at the temperature of 25 ℃. After the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 184.9g of a reddish brown oily substance, wherein the content is 86.5 percent, the yield is 84.2 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 0.07 percent through quantitative analysis of high performance liquid chromatography.
Comparative example 2
The preparation method of carbosulfan comprises the following steps:
adding 110.5g (0.50mol) of carbofuran and 1.0L of dichloroethane into a 2L reaction bottle with a stirrer, adding 54.6g (0.53mol) of sulfur dichloride after the carbofuran is dissolved, stirring and mixing uniformly, cooling to 5 ℃, stirring, dropwise adding 60.6g (0.60mol) of triethylamine, finishing dropping for 1.5h, heating to 20 ℃, and carrying out heat preservation reaction for 2 h. After the reaction is finished, the temperature is reduced to 5 ℃, 64.5g (0.5mol) of di-n-butylamine, 2.5g (0.02mol) of 4-dimethylaminopyridine and 75.8g (0.75mol) of triethylamine are sequentially added, and the reaction is carried out for 2 hours at the temperature of 25 ℃. After the reaction is finished, the reaction solution is respectively washed by water, 10 w.t.% of hydrochloric acid and water until the reaction solution is neutral, the reaction solution is kept stand for layering, an organic phase is separated, and the reaction solution is decompressed and desolventized to obtain 187.7g of a reddish brown oily substance, wherein the content is 90.3 percent and the yield is 89.2 percent (calculated by carbofuran) and the content of main harmful impurities of the carbofuran is 2.6 percent through quantitative analysis of high performance liquid chromatography.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. The preparation method of carbosulfan is characterized by comprising the following steps of:
(1) dissolving carbofuran in an organic solvent, adding triethylamine as an acid-binding agent I, uniformly stirring and mixing, then dropwise adding sulfur dichloride, and carrying out heat preservation reaction after dropwise adding is finished to prepare a sulfide solution;
(2) adding di-n-butylamine, 4-dimethylaminopyridine and triethylamine serving as an acid-binding agent II into the sulfide solution, and carrying out heat preservation reaction after the addition is finished to obtain carbosulfan reaction liquid;
(3) washing the carbosulfan reaction liquid until the reaction liquid is neutral, separating out an organic phase, and carrying out decompression and desolventization to obtain the carbosulfan with the content of more than or equal to 96 percent, the yield of more than or equal to 98 percent and harmful impurity carbosulfan in the carbosulfan of less than or equal to 0.1 percent.
2. The method of claim 1, wherein the carbosulfan acid binding agent I sulfur dichloride di-n-butylamine I4-dimethylaminopyridine acid binding agent II is 1.00: 1.10-1.50: 1.05-1.10: 1.00-1.10: 0.03-0.05: 1.10-1.50 in terms of a molar ratio.
3. The method of claim 1, wherein in step (1), the volume ratio of the organic solvent to carbofuran is 10-15: 1.
4. The method for preparing carbosulfan according to any one of claims 1 to 3, wherein in the step (1), the organic solvent is any one of dichloroethane, dichloromethane, toluene and chlorobenzene.
5. The method for preparing carbosulfan according to any one of claims 1 to 3, wherein in step (1), the dripping temperature of the sulfur dichloride is 0 to 10 ℃, and the dripping time is 1 to 1.5 hours;
before dropwise adding sulfur dichloride, the method also comprises the step of regulating the temperature of the mixed solution obtained after uniformly stirring and mixing to 0-10 ℃.
6. The method for preparing carbosulfan according to any one of claims 1 to 3, wherein in step (1), the temperature of the incubation reaction is 0 to 20 ℃ and the time of the incubation reaction is 2 to 3 hours.
7. The method for preparing carbosulfan according to any one of claims 1 to 3, further comprising the step of cooling the sulfide solution to 0 to 10 ℃ and adding each reaction raw material in step (2);
when reaction raw materials of di-n-butylamine, 4-dimethylaminopyridine and acid-binding agent II triethylamine are added, the temperature of a reaction system is ensured to be 0-10 ℃.
8. The method for preparing carbosulfan according to any one of claims 1 to 3, wherein in the step (2), the temperature of the incubation reaction is 0 to 25 ℃ and the incubation reaction time is 1 to 2 hours.
9. The method for preparing carbosulfan according to any one of claims 1 to 3, wherein in the step (3), the step of washing the carbosulfan reaction solution until the reaction solution is neutral specifically comprises: and sequentially washing, pickling and washing the carbosulfan reaction solution until the reaction solution is neutral.
10. The method for preparing carbosulfan according to claim 9, wherein the acid used for acid washing is hydrochloric acid or sulfuric acid, and the mass fraction is 5-20%.
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| CN111574415B (en) * | 2020-05-27 | 2021-12-14 | 山东阳谷华泰化工股份有限公司 | Synthetic method of perchloromethylmercaptan |
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| US4413005A (en) * | 1981-06-02 | 1983-11-01 | Otsuka Kagaku Yakuhin Kabushiki Kaisha | Carbamate derivatives and insecticidal, miticidal or nematocidal compositions containing the same |
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