CN112778179A - Synthesis method of thiodicarb - Google Patents
Synthesis method of thiodicarb Download PDFInfo
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- CN112778179A CN112778179A CN202110130319.6A CN202110130319A CN112778179A CN 112778179 A CN112778179 A CN 112778179A CN 202110130319 A CN202110130319 A CN 202110130319A CN 112778179 A CN112778179 A CN 112778179A
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- thiodicarb
- sulfur dichloride
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/06—Compounds containing sulfur atoms only bound to two nitrogen atoms
- C07C381/08—Compounds containing sulfur atoms only bound to two nitrogen atoms having at least one of the nitrogen atoms acylated
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Abstract
The invention discloses a method for synthesizing thiodicarb, which comprises the following steps: (1) dividing the solvent into two parts, and dissolving methomyl in one part to obtain methomyl solution; dissolving 18-crown-6 in another part to obtain 18-crown-6 solution; (2) under the closed condition, firstly dropwise adding part of sulfur dichloride into a solution of 18-crown ether-6; and after the dropwise addition is finished, dropwise adding the residual sulfur dichloride and the methomyl solution for reaction, and after the dropwise addition is finished, continuing the heat preservation reaction to obtain the thiodicarb. The method has the advantages of high reaction selectivity, reduction of by-product generation, high purity of the obtained product, high yield and capability of effectively improving the problem of pipeline blockage in the production process. The method has simple process operation and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of synthesis of pesticide compounds, and particularly relates to a synthesis method of thiodicarb.
Background
Thiobimethoate (called thiodicarb for short), which is also called thiodicarb and lavine, is a second-generation carbamate pesticide, which is one of low-toxicity derivatives obtained by further improving on the basis of methoate, namely, two methoate molecules are connected through a thioether chain to form a dicate, the toxicity is only about one tenth of that of methoate, and the thiodicate is a high-efficiency, broad-spectrum, low-toxicity and systemic stomach toxicity pesticide. The product was developed by Unico, USA, and Ciba-Jia, Switzerland in 1977, and was put into operation in 1984. To date, they have been registered in thirty countries throughout the world with annual sales of thousands of tons. The pesticide is widely used for crops such as cotton, vegetables, fruit trees, tea, tobacco, forest, wheat and the like, is particularly effective for larvae of pests such as lepidoptera, homoptera, hymenoptera, diptera, coleoptera and the like, and is a domestic excellent variety for preventing and controlling resistant cotton bollworms at present.
Thiodicarb is generally synthesized by the following route:
the pure thiodicarb is a white crystal, the original drug is a light tan crystal, the melting point is 173-174 ℃, the relative density is 1.442(20 ℃), and the solubility (25 ℃) is as follows: 150g/kg of dichloromethane, 8g/kg of acetone, 5g/kg of methanol, 3g/kg of xylene and 35mg/kg of water. Stable under neutral condition, slow hydrolysis under acidic condition (half-life period is 9 days when pH value is 3), quick hydrolysis under alkaline condition, stable at 60 deg.C, easy decomposition of aqueous suspension due to sunlight, and half-life period in bioactive soil is less than 2 days.
Carbamate pesticides and organophosphorus and pyrethroid are used as main pesticides due to excellent insecticidal activity, but the pesticides (such as methomyl, carbofuran and aldicarb) have high toxicity to mammals, so that the application of a plurality of varieties is limited to a certain extent, and particularly, the development trend of restricting or forbidding high-toxicity pesticide varieties at home and abroad in recent years is to develop and produce high-quality, high-efficiency and low-toxicity pesticide varieties, which is also the research focus of the pesticides in the world at present. The thiodicarb has high control effect on resistant cotton bollworms, is quick in biodegradation, low in toxicity and free of phytotoxicity on crops, so that the thiodicarb becomes a low-toxicity pesticide variety which is developed quickly at home and abroad in recent years, and the sales volume is also increased continuously.
Because the global environment form is gradually severe, in order to further reduce the influence of chemical pesticides on the environment, produce high-quality pesticides, and reduce the content of non-effective components in the pesticides, the development direction of the pesticides at present is one of the directions, the patent CN108047106A improves the traditional process, reduces the isomer impurity of thiodicarb in the product thiodicarb, improves the product purity, but the impurity control of the thiodicarb is insufficient, influences the product quality, and is easy to block pipelines in the large-scale production process, so the process still needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of thiodicarb, which has high reaction selectivity, high purity of the obtained product and high yield.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method of thiodicarb comprises the following steps:
(1) dividing the solvent into two parts, and dissolving methomyl in one part to obtain methomyl solution; dissolving 18-crown-6 in another part to obtain 18-crown-6 solution;
(2) under the closed condition, firstly dropwise adding part of sulfur dichloride into a solution of 18-crown ether-6; and after the dropwise addition is finished, dropwise adding the residual sulfur dichloride and the methomyl solution for reaction, and after the dropwise addition is finished, continuing the heat preservation reaction to obtain the thiodicarb.
In the synthesis method of the thiodicarb, the dosage of the 18-crown ether-6 is preferably 0.05-0.5% of the mass of the thiodicarb.
Preferably, in the step (2), chlorine gas is introduced while the remaining sulfur dichloride and methomyl solution are added dropwise, and after the addition is completed, the introduction of chlorine gas is stopped.
In the above method for synthesizing thiodicarb, preferably, in step (2), the partial sulfur dichloride is firstly dripped at-5 to 5 ℃;
gradually heating to 15-25 ℃ in the process of dropwise adding the residual sulfur dichloride and the methomyl solution; the time for dripping the residual sulfur dichloride and the methomyl solution is 4-6 hours;
the temperature of the heat preservation reaction is 15-25 ℃; the time of the heat preservation reaction is 4-6 h.
In the above method for synthesizing thiodicarb, the molar ratio of the thiodicarb to total sulfur dichloride is preferably 1: 0.54-0.60;
the mass of the part of the sulfur dichloride dropwise added firstly is 1/3-1/2 of the total mass of the sulfur dichloride.
In the above method for synthesizing thiodicarb, the solvent is preferably pyridine.
In the above method for synthesizing thiodicarb, the mass of the solvent in the methomyl solution is preferably 1.5-2 times that of the methomyl.
In the above method for synthesizing thiodicarb, preferably, in step (1), the mass ratio of the methomyl to the total mass of the solvent is 1: 3-5.
In the above method for synthesizing thiodicarb, the amount of chlorine gas introduced is preferably 1-3% of the total mass of sulfur dichloride.
Preferably, after the heat preservation reaction is finished, adding methanol into the reaction liquid for quenching, controlling the temperature to be less than 30 ℃ in the quenching process, filtering, and drying to obtain the thiodicarb.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts low-temperature catalytic reaction to prepare the thiodicarb, and concretely, the thiodicarb and the sulfur dichloride are used as raw materials, 18-crown ether-6 is used as a catalyst, the raw materials are added into a solvent in a low-temperature double-dropping mode, and the synthetic reaction can be carried out at low temperature under the catalysis of the 18-crown ether-6 to generate the thiodicarb, so that the generation of byproducts is reduced, and the selectivity and the product quality of the thiodicarb are improved.
2. The method of the invention is favorable for further improving the selectivity of the sulfur double-methomyl and reducing the impurities of the sulfur double-methomyl in the product by introducing chlorine gas in the reaction process.
3. The content of the thiodicarb synthesized by the method is more than 97.8%, the product yield is more than 86% (calculated by the methomyl), the synthesized thiodicarb reaches the international advanced level, and the problem that pipelines are easy to block in the production process can be effectively solved. The method has simple process operation and is suitable for large-scale industrial production.
Detailed Description
Aiming at the defects that the impurity control in the thiodicarb in the prior art is still to be improved, the product quality is influenced, and a plunger pipeline is easy to carry out in the large-scale production process, the inventor finds that the thiodicarb is prepared by adopting low-temperature catalytic reaction, the thiodicarb and sulfur dichloride are used as raw materials, 18-crown ether-6 is used as a catalyst, the raw materials are added into a solvent in a low-temperature double-dropping mode, and the synthetic reaction can be carried out at low temperature under the catalysis of the 18-crown ether-6 to generate the thiodicarb, so that the generation of byproducts can be effectively reduced, and the selectivity and the product quality of the thiodicarb are improved; the inventor surprisingly finds that the scheme not only can effectively improve the purity of the product, but also can effectively improve the defects that the pipeline is easy to block in the production process and the like; furthermore, the selectivity of the sulfur double-methomyl can be further improved by introducing chlorine gas in the reaction process, and the impurities of the sulfur double-methomyl in the product are reduced. Through analysis, the inventors speculate that the scheme can greatly reduce the generation of impurities such as disulfide and polysulfide, and further can obtain the good effects.
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 synthesis method of thiodicarb, which comprises the following steps:
a1000 mL four-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel were charged with 244.00g of pyridine and 0.08g of 18-crown-6. Sealing a reaction system, cooling to-5 ℃, firstly dropwise adding 1/3 in 66.98g of sulfur dichloride (the mass content is calculated according to 83%), slowly introducing chlorine gas after the dropwise addition of the sulfur dichloride is finished, then gradually heating to 15 ℃, simultaneously dropwise adding a pyridine solution of methomyl (obtained by dissolving 162.20g of methomyl in 243.00g of pyridine) and the rest of the sulfur dichloride within 4 hours, stopping introducing the chlorine gas after the dropwise addition is finished, introducing 0.67g of chlorine gas into the reaction liquid, then carrying out heat preservation reaction at 15 ℃ for 4 hours, adding 285.00g of methanol into the reaction liquid after the reaction is finished for quenching, controlling the temperature to be less than 30 ℃ in the quenching process, stirring and washing for 30 minutes at room temperature, filtering, and drying the obtained filter cake at 50 ℃ to obtain the sulfur bismuticarb product.
Through detection, the product has the mass of 155.90g, the content of 97.80 percent and the yield of 86.05 percent.
Example 2:
the invention relates to a synthesis method of thiodicarb, which comprises the following steps:
a1000 mL four-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel having a constant pressure was charged with 487.00g of pyridine and 0.81g of 18-crown-6. Sealing the reaction system, cooling to 5 ℃, firstly dripping 1/2 of 74.43g of sulfur dichloride (the mass content is calculated according to 83%), starting to slowly introduce chlorine gas after the dripping of the sulfur dichloride is finished, then gradually heating to 25 ℃, simultaneously dripping the pyridine solution of methomyl (obtained by dissolving 162.20g of methomyl in 324.00g of pyridine) and the residual sulfur dichloride within 6 hours, stopping introducing the chlorine gas after the dripping is finished, introducing 2.23g of chlorine gas into the reaction liquid, then carrying out heat preservation reaction at 25 ℃ for 6 hours, adding 285.00g of methanol into the reaction liquid for quenching after the reaction is finished, controlling the temperature to be less than 30 ℃ in the quenching process, stirring and washing for 30 minutes at room temperature, filtering, and drying the obtained filter cake at 50 ℃ to obtain the sulfur bismethomyl product.
Through detection, the product has the mass of 156.20g, the content of 97.95 percent and the yield of 86.35 percent.
Example 3:
the invention relates to a synthesis method of thiodicarb, which comprises the following steps:
a1000 mL four-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel having a constant pressure was charged with 373.06g of pyridine and 0.65g of 18-crown-6. Sealing the reaction system, cooling to 5 ℃, firstly dripping 1/2 in 70.70g of sulfur dichloride (the mass content is calculated according to 83%), starting to slowly introduce chlorine gas after the dripping of the sulfur dichloride is finished, then gradually heating to 20 ℃, simultaneously dripping the pyridine solution of methomyl (obtained by dissolving 162.20g of methomyl in 275.74g of pyridine) and the residual sulfur dichloride within 5 hours, stopping introducing the chlorine gas after the dripping is finished, introducing 1.27g of chlorine gas into the reaction liquid, then preserving the temperature at 20 ℃ for reaction for 5 hours, adding 285.00g of methanol into the reaction liquid for quenching after the reaction is finished, controlling the temperature to be less than 30 ℃ in the quenching process, stirring and washing for 30 minutes at room temperature, filtering, and drying the obtained filter cake at 50 ℃ to obtain the sulfur bismethomyl product.
Through detection, the product has the mass of 156.42g, the content of 98.00 percent and the yield of 86.51 percent.
Example 4:
the invention relates to a synthesis method of thiodicarb, which comprises the following steps:
a1000 mL four-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel having a constant pressure was charged with 356.84g of pyridine and 0.32g of 18-crown-6. Sealing the reaction system, cooling to 0 ℃, firstly dripping 2/5 in 68.22g of sulfur dichloride (the mass content is calculated according to 83%), starting to slowly introduce chlorine gas after the dripping of the sulfur dichloride is finished, then gradually heating to 20 ℃, simultaneously dripping the pyridine solution of methomyl (obtained by dissolving 162.20g of methomyl in 291.96g of pyridine) and the residual sulfur dichloride within 5 hours, stopping introducing the chlorine gas after the dripping is finished, introducing 1.02g of chlorine gas into the reaction liquid, then preserving the temperature at 20 ℃ for reaction for 5 hours, adding 285.00g of methanol into the reaction liquid for quenching after the reaction is finished, controlling the temperature to be less than 30 ℃ in the quenching process, stirring and washing for 30 minutes at room temperature, filtering, and drying the obtained filter cake at 50 ℃ to obtain the sulfur bismethomyl product.
Through detection, the product has the mass of 156.23g, the content of 97.90 percent and the yield of 86.32 percent.
Example 5:
the invention relates to a synthesis method of thiodicarb, which comprises the following steps:
a1000 mL four-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel having a constant pressure was charged with 519.04g of pyridine and 0.57g of 18-crown-6. Sealing the reaction system, cooling to 0 ℃, firstly dripping 2/5 in 71.94g of sulfur dichloride (the mass content is calculated according to 83%), starting to slowly introduce chlorine gas after the dripping of the sulfur dichloride is finished, then gradually heating to 17 ℃, simultaneously dripping the pyridine solution of methomyl (obtained by dissolving 162.20g of methomyl in 291.96g of pyridine) and the residual sulfur dichloride within 5 hours, stopping introducing the chlorine gas after the dripping is finished, introducing 1.08g of chlorine gas into the reaction liquid, then carrying out heat preservation reaction at 17 ℃ for 6 hours, adding 285.00g of methanol into the reaction liquid after the reaction is finished for quenching, controlling the temperature to be less than 30 ℃ in the quenching process, stirring and washing for 30 minutes at room temperature, filtering, and drying the obtained filter cake at 50 ℃ to obtain the sulfur bismethomyl product.
Through detection, the product has the mass of 156.48g, the content of 98.10 percent and the yield of 86.63 percent.
Comparative example 1:
the synthesis process of thiodicarb differs from that in example 5 only in that 18-crown-6 is not added into the reaction system.
Through detection, the product has the mass of 152.21g, the content of 96.21 percent and the yield of 82.65 percent.
Comparative example 2:
the synthesis process of thiodicarb as shown in example 5 differs from that of example 5 only in that 18-crown ether-6 is not added into the reaction system and no chlorine gas is introduced during the dropwise addition of the rest of sulfur dichloride.
Through detection, the product has the mass of 146.24g, the content of 95.70 percent and the yield of 78.98 percent.
Comparative example 3:
the synthesis process of thiodicarb as shown in example 5 differs from that of example 5 only in that 1.62g of 4-dimethylamino pyridine is used as catalyst to replace 18-crown ether-6 and no chlorine is introduced during the dropwise addition of the rest of sulfur dichloride.
Through detection, the product has the mass of 155.40g, the content of 97.30 percent and the yield of 85.33 percent.
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 (10)
1. A synthetic method of thiodicarb is characterized by comprising the following steps:
(1) dividing the solvent into two parts, and dissolving methomyl in one part to obtain methomyl solution; dissolving 18-crown-6 in another part to obtain 18-crown-6 solution;
(2) under the closed condition, firstly dropwise adding part of sulfur dichloride into a solution of 18-crown ether-6; and after the dropwise addition is finished, dropwise adding the residual sulfur dichloride and the methomyl solution for reaction, and after the dropwise addition is finished, continuing the heat preservation reaction to obtain the thiodicarb.
2. The method for synthesizing thiodicarb as claimed in claim 1, wherein the amount of 18-crown-6 is 0.05-0.5% by mass of the thiodicarb.
3. The method for synthesizing thiodicarb as claimed in claim 1, wherein step (2) further comprises introducing chlorine gas while adding dropwise the remaining sulfur dichloride and methomyl solution, and stopping introducing chlorine gas after the addition is completed.
4. The method for synthesizing thiodicarb as claimed in claim 1, wherein in step (2), the partial sulfur dichloride is firstly added dropwise at-5 to 5 ℃;
gradually heating to 15-25 ℃ in the process of dropwise adding the residual sulfur dichloride and the methomyl solution; the time for dripping the residual sulfur dichloride and the methomyl solution is 4-6 hours;
the temperature of the heat preservation reaction is 15-25 ℃; the time of the heat preservation reaction is 4-6 h.
5. The method for synthesizing thiodicarb according to any one of claims 1 to 4, wherein the molar ratio of the thiodicarb to total sulfur dichloride is 1: 0.54-0.60;
the mass of the part of the sulfur dichloride dropwise added firstly is 1/3-1/2 of the total mass of the sulfur dichloride.
6. The method for synthesizing thiodicarb according to any one of claims 1 to 4, wherein the solvent is pyridine.
7. The method for synthesizing thiodicarb according to any one of claims 1 to 4, wherein the mass of the solvent in the solution of thiodicarb is 1.5 to 2 times the mass of thiodicarb.
8. The method for synthesizing thiodicarb according to any one of claims 1 to 4, wherein in step (1), the ratio of the mass of the thiodicarb to the total mass of the solvent is 1: 3 to 5.
9. The method for synthesizing thiodicarb according to any one of claims 1 to 4, wherein the amount of chlorine gas introduced is 1 to 3% by mass of the total amount of sulfur dichloride.
10. The synthesis method of thiodicarb according to any one of claims 1 to 4, wherein after the reaction is completed with heat preservation, methanol is added into the reaction solution for quenching, and the temperature is controlled to be less than 30 ℃ during the quenching process, and the thiodicarb is obtained by filtering and drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114031533A (en) * | 2021-11-15 | 2022-02-11 | 山东华阳农药化工集团有限公司 | Preparation method of high-content thiodicarb |
| CN114213321A (en) * | 2021-12-14 | 2022-03-22 | 山东第一医科大学(山东省医学科学院) | Synthetic method of 2-pyridyl thioether |
| CN114249688A (en) * | 2021-12-14 | 2022-03-29 | 烟台中科荣达新材料有限公司 | Synthetic method of 2,2' -dipyridyl disulfide |
| CN115626886A (en) * | 2022-11-02 | 2023-01-20 | 山东第一医科大学(山东省医学科学院) | Green thiodicarb synthesis process capable of reducing wastewater generation amount |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114031533A (en) * | 2021-11-15 | 2022-02-11 | 山东华阳农药化工集团有限公司 | Preparation method of high-content thiodicarb |
| CN114031533B (en) * | 2021-11-15 | 2024-01-12 | 山东华阳农药化工集团有限公司 | Preparation method of high-content thiodicarb |
| CN114213321A (en) * | 2021-12-14 | 2022-03-22 | 山东第一医科大学(山东省医学科学院) | Synthetic method of 2-pyridyl thioether |
| CN114249688A (en) * | 2021-12-14 | 2022-03-29 | 烟台中科荣达新材料有限公司 | Synthetic method of 2,2' -dipyridyl disulfide |
| CN114213321B (en) * | 2021-12-14 | 2023-10-10 | 山东第一医科大学(山东省医学科学院) | Synthesis method of 2-pyridyl thioether |
| CN114249688B (en) * | 2021-12-14 | 2023-12-05 | 烟台中科荣达新材料有限公司 | Synthesis method of 2,2' -bipyridine disulfide |
| CN115626886A (en) * | 2022-11-02 | 2023-01-20 | 山东第一医科大学(山东省医学科学院) | Green thiodicarb synthesis process capable of reducing wastewater generation amount |
| CN115626886B (en) * | 2022-11-02 | 2024-04-26 | 山东第一医科大学(山东省医学科学院) | Thiodicarb green synthesis process for reducing wastewater production |
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Application publication date: 20210511 Assignee: Ningxia Haili Technology Co.,Ltd. Assignor: HUNAN HAILI CHANGDE PESTICIDE & CHEMICAL INDUSTRY CO.,LTD. Contract record no.: X2023980037360 Denomination of invention: A synthetic method of thiobis Methomyl Granted publication date: 20221104 License type: Common License Record date: 20230703 |