CN108864187B - Process for synthesizing important intermediate oxygen thiophosphate of omethoate - Google Patents
Process for synthesizing important intermediate oxygen thiophosphate of omethoate Download PDFInfo
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- CN108864187B CN108864187B CN201810887246.3A CN201810887246A CN108864187B CN 108864187 B CN108864187 B CN 108864187B CN 201810887246 A CN201810887246 A CN 201810887246A CN 108864187 B CN108864187 B CN 108864187B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); Derivatives thereof
- C07F9/4808—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
Abstract
The invention discloses a process for synthesizing an important intermediate of omethoate, which is mainly used for synthesizing the oxygen sulfur phospholipid by adopting an anhydrous system and drying crude ester of the oxygen sulfur phospholipid to prepare the oxygen sulfur phospholipid. The anhydrous reaction process technology improves the reaction environment to the maximum extent, improves the main reaction process, solves the adverse factors brought by solid-liquid reaction to the reaction, reduces hydrolysis, improves the reaction yield, and facilitates the post-treatment of the salt-containing compound. By using the process, the purity of the oxygen sulfur phosphorus ester can reach more than 89%, and the yield can reach more than 86%; the purity of the ammonium chloride can reach more than 99 percent, and the ammonium chloride can be directly sold as a first-grade product of a byproduct. Compared with the traditional process, the invention greatly improves the overall effect and has great social and economic benefits.
Description
Technical Field
The invention relates to a process for synthesizing an important omethoate intermediate, namely oxygen thiophosphate, and belongs to the technical field of intermediate synthesis.
Background
In the solid-liquid organic synthesis reaction, many side reactions exist, and the occurrence of the side reactions has more or less certain influence on the main reaction, such as: influence the progress of the main reaction, influence the content, yield and the like of the main product. The salt-containing by-products generated in the solid-liquid organic synthesis process are the most common, and how to solve the problem of the salt-containing by-products generated in the solid-liquid reaction process is a subject of continuous research by a plurality of organic synthesis researchers.
The oxygen thiophosphate reaction in the omethoate synthesis plays a role in starting and stopping in the whole process. The formation of ammonium chloride as a by-product in this reaction is also unavoidable. In the traditional process of the reaction, water needs to be added, the reaction is carried out at 65 ℃, the whole process environment is particularly favorable for dissolving ammonium chloride in a crude ester system, so that the system heat release is large, workers have difficulty in operating the temperature, the side reaction is increased, the chance of seeing main and side products is increased to a greater extent, and the yield of the step is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a process for synthesizing an important intermediate of omethoate, namely the oxygen thiophosphate, which has the advantages of more convenient temperature control, high product purity and high yield.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for synthesizing an important intermediate of omethoate, namely oxygen thiophosphate, and the synthesis of the oxygen thiophosphate adopts an anhydrous system.
The method for synthesizing the oxygen sulfur phosphorus ester comprises the following steps: the method comprises the steps of taking ammonium thiophosphate, methyl chloroacetate and a catalyst as raw materials, and reacting to obtain the thiophosphoryl ester.
The reaction temperature is 45-55 ℃ and the reaction time is 2-4 h.
Specifically, the method for synthesizing the oxygen sulfur phosphorus ester comprises the following steps: sequentially adding 1200kg of methyl chloroacetate, 500L of sulfur and phosphorus ammonium salt and 2-5kg of catalyst into a reaction kettle, starting a stirring and steam valve, closing the steam valve when the temperature rises to 45-55 ℃, preserving the heat at 45-55 ℃ for 2-4h, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 20-40 ℃, centrifugally separating ammonium chloride from the materials, drying and desolventizing the coarse oxygen and phosphorus sulfate ester to obtain fine oxygen and phosphorus sulfate ester; and drying the centrifuged ammonium chloride to obtain a byproduct for sale.
The preparation method of the ammonium thiophosphoryl salt comprises the following steps: pumping 600-plus 900L dimethyl phosphite into a reaction kettle, adding 80-150kg of sulfur powder, starting ammonia introduction when the temperature of the reaction kettle reaches below 5 ℃, stopping ammonia introduction when the ammonia introduction temperature is not more than 12 ℃, controlling the temperature to be 0-10 ℃ when the pH of reaction feed liquid is 6-7.5, preserving the temperature for 45-60min, and discharging.
The catalyst is one or a mixture of more of tributylamine, triethylamine, TEBA and hexadecyl trimethyl ammonium chloride.
The drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the oxygen-sulfur-phosphorus ester crude ester is 1: 2.
the desolventizing temperature is controlled to be 100 ℃ and 130 ℃, and the vacuum is controlled to be below-0.095 MPa.
The invention has the beneficial effects that:
1. the invention develops an anhydrous reaction according to the characteristics of ammonium chloride (dissolution in water and precipitation at low temperature), namely, in the solid-liquid organic reaction generated by ammonium chloride as a side reaction, the water is prevented from entering, so that the whole system is in an anhydrous reaction state. Once the reaction system has no water, the ammonium chloride exists in the system in a solid state, and the overall process advantage is obvious according to the process improvement of the following three aspects:
(1) the amount of solvent is increased. The invention increases the proportion of the solvent (methyl chloroacetate), thereby increasing hot melting, and operators can better control the reaction temperature, thereby improving the reaction rate of reactants, increasing the generation of main products, reducing the molecular collision chance of byproducts and main products, and reducing the generation of side reactions.
(2) The reaction temperature was lowered. Because the system does not contain water, the reaction temperature is reduced compared with the reaction temperature when water exists, thereby reducing the reaction condition. In addition, the reduction of the reaction temperature not only can reduce the generation of side reactions, but also can improve the content of main products and the yield of the whole reaction.
(3) And adding a centrifugal and drying device. And after the ammonium chloride is separated out, centrifuging and drying the ammonium chloride to collect the ammonium chloride, recovering the filtrate as a solvent, and selling the dried ammonium chloride. The system does not add water, reduces the discharge of waste water, promotes the clean production of the company, increases the income of byproducts for the company, and achieves multiple purposes.
2. The invention dries the coarse ester of the oxygen sulfur phosphorus ester, so that the whole system is anhydrous, and the hydrolysis in the desolventizing process of the organic compound can be effectively reduced, thereby improving the purity and the yield of the oxygen sulfur phosphorus ester. The invention repeatedly screens the drying agent of the liquid organic compound: (1) the drying of liquid organic compounds, generally by adding a drying agent to the liquid organic compound, must be carried out without chemical or catalytic interaction with the organic compound. (2) The drying agent should be insoluble in the liquid organic compound. (3) When selecting a desiccant that combines with water to form a hydrate, the water absorption capacity and drying effectiveness of the desiccant must be considered. Therefore, the 3A molecular sieve is finally selected as the drying agent to dry the coarse ester of the oxygen sulfur phospholipid, so that the hydrolysis of the oxygen sulfur phospholipid in the desolventizing process can be effectively reduced.
3. By using the process, the purity of the oxygen sulfur phosphorus ester can reach more than 89%, and the yield can reach more than 86%; the purity of the ammonium chloride can reach more than 99 percent, and the ammonium chloride can be directly sold as a first-grade product of a byproduct. Compared with the traditional process, the overall effect of the invention is greatly improved.
4. The anhydrous reaction process technology of the invention improves the reaction environment to the maximum extent, improves the process of the main reaction, solves the adverse factors brought by the solid-liquid reaction to the reaction, improves the reaction yield, and ensures that the post-treatment of the salt-containing compound is more convenient and has huge social and economic benefits.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
The preparation method of the ammonium thiophosphoryl salt comprises the following steps: pumping 700L dimethyl phosphite into a reaction kettle, adding 100kg of sulfur powder, starting ammonia introduction when the temperature of the reaction kettle reaches below 3 ℃, stopping ammonia introduction when the temperature in the reaction kettle is not more than 12 ℃ when the ammonia introduction is carried out, controlling the temperature to be 5 ℃, preserving the temperature for 50min when the pH of reaction feed liquid is 7.2, and discharging.
Example 1
A process for synthesizing an important intermediate of omethoate, namely oxygen thiophosphate, comprises the following steps: putting 900kg of methyl chloroacetate, 500L of ammonium thiophosphate and 2.5kg of triethylamine into a reaction kettle in sequence, starting a stirring and steam valve, closing the steam valve when the temperature rises to 45 ℃, preserving the heat at 45 ℃ for 3h, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 30 ℃, carrying out centrifugal separation on the ammonium chloride on the materials, obtaining the thrown filtrate, namely the coarse thiophosphate ester, carrying out three-stage drying and desolventizing on the coarse thiophosphate ester, controlling the desolventizing temperature to be 130 ℃, controlling the vacuum to be below-0.095 MPa, and removing the methyl chloroacetate to obtain the refined thiophosphate ester; and drying the centrifuged ammonium chloride to obtain a byproduct for sale.
The drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the oxygen-sulfur-phosphorus ester crude ester is 1: 2.
the purity of the phosphorothioates obtained in this example was 89.78%, the yield was 85.89%, and the purity of ammonium chloride was 99.07%.
Example 2
A process for synthesizing an important intermediate of omethoate, namely oxygen thiophosphate, comprises the following steps: putting 1200kg of methyl chloroacetate, 900L of ammonium thiophosphate and 3.5kg of triethylamine into a reaction kettle in sequence, starting a stirring and steam valve, closing the steam valve when the temperature rises to 55 ℃, preserving the heat at 55 ℃ for 3h, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 30 ℃, carrying out centrifugal separation on the ammonium chloride on the materials, obtaining the thrown filtrate, namely the coarse thiophosphate ester, carrying out three-stage drying and desolventizing on the coarse thiophosphate ester, controlling the desolventizing temperature to be 130 ℃, controlling the vacuum to be below-0.095 MPa, and removing the methyl chloroacetate to obtain the refined thiophosphate ester; and drying the centrifuged ammonium chloride to obtain a byproduct for sale.
The drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the oxygen-sulfur-phosphorus ester crude ester is 1: 2.
the purity of the phosphorothioates obtained in this example was 89.91%, the yield was 86.08%, and the purity of ammonium chloride was 99.17%.
Example 3
A process for synthesizing an important intermediate of omethoate, namely oxygen thiophosphate, comprises the following steps: putting 1000kg of methyl chloroacetate, 700L of ammonium thiophosphate and 4kg of triethylamine into a reaction kettle in sequence, starting a stirring valve and a steam valve, closing the steam valve when the temperature rises to 50 ℃, preserving the heat for 3h at 50 ℃, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 30 ℃, carrying out centrifugal separation on the ammonium chloride on the materials, obtaining a thrown filtrate, namely coarse thiophosphate ester, carrying out three-stage drying and desolventizing on the coarse thiophosphate ester, controlling the desolventizing temperature to be 130 ℃, controlling the vacuum to be below-0.095 MPa, removing the methyl chloroacetate, and obtaining the refined thiophosphate ester; and drying the centrifuged ammonium chloride to obtain a byproduct for sale.
The drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the oxygen-sulfur-phosphorus ester crude ester is 1: 2.
the purity of the phosphorothioates obtained in this example was 90.14%, the yield was 86.28%, and the purity of ammonium chloride was 99.26%.
Comparative example
The traditional process (water system) for synthesizing the important intermediate of the omethoate is as follows: adding 600kg of methyl chloroacetate, 700L of ammonium thiophosphate, 300kg of water and 4kg of triethylamine into a reaction kettle in sequence, starting a stirring valve and a steam valve, closing the steam valve when the temperature rises to 65 ℃, preserving the heat at 65 ℃ for 3h, standing in a water separation tank for 3h after the heat preservation is finished, and filtering and desolventizing a lower-layer crude product in a metering tank to obtain the thiophosphoryl ester.
The purity of the phosphorothioate obtained in the comparative example was 87.56%, the yield was 83.76%, and the purity of the ammonium chloride was 96.64%.
The foregoing description is only a preferred embodiment of the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A process for synthesizing an important intermediate of omethoate is characterized in that an anhydrous system is adopted for synthesizing the oxygen thiophosphate; the specific method for synthesizing the oxygen sulfur phosphorus ester comprises the following steps: sequentially adding 1200kg of methyl chloroacetate, 500 kg of 900L of ammonium thiophosphate and 2-5kg of triethylamine serving as a catalyst into a reaction kettle, starting a stirring and steam valve, closing the steam valve when the temperature rises to 45-55 ℃, preserving the heat at 45-55 ℃ for 2-4h, opening a cooling water valve after the heat preservation is finished to cool materials, discharging the materials when the temperature is reduced to 20-40 ℃, centrifugally separating ammonium chloride from the materials, drying and desolventizing the coarse ester of oxygen sulfur phosphorus ester to obtain the refined ester of oxygen sulfur phosphorus ester; drying the centrifuged ammonium chloride and selling a byproduct; the drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the oxygen-sulfur-phosphorus ester crude ester is 1: 2.
2. the process of claim 1, wherein the ammonium thiophosphoryl salt is prepared by: pumping 600-plus 900L dimethyl phosphite into a reaction kettle, adding 80-150kg of sulfur powder, starting ammonia introduction when the temperature of the reaction kettle reaches below 5 ℃, stopping ammonia introduction when the ammonia introduction temperature is not more than 12 ℃, controlling the temperature to be 0-10 ℃ when the pH of reaction feed liquid is 6-7.5, preserving the temperature for 45-60min, and discharging.
3. The process as claimed in claim 1, wherein the desolventizing temperature is controlled at 100 ℃ and 130 ℃ and the vacuum is controlled below-0.095 MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122810A (en) * | 1994-11-08 | 1996-05-22 | 清华紫光(集团)总公司 | Process for prodn. of oxy-thiophosphate |
| CN1702074A (en) * | 2004-05-24 | 2005-11-30 | 姚文刚 | Process for synthesizing dimethoate |
| WO2009083131A2 (en) * | 2007-12-21 | 2009-07-09 | Clariant International Ltd | Cosmetic, pharmaceutical or dermatological compositions having a high content of water-soluble care components |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6838452B2 (en) * | 2000-11-24 | 2005-01-04 | Vascular Biogenics Ltd. | Methods employing and compositions containing defined oxidized phospholipids for prevention and treatment of atherosclerosis |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122810A (en) * | 1994-11-08 | 1996-05-22 | 清华紫光(集团)总公司 | Process for prodn. of oxy-thiophosphate |
| CN1702074A (en) * | 2004-05-24 | 2005-11-30 | 姚文刚 | Process for synthesizing dimethoate |
| WO2009083131A2 (en) * | 2007-12-21 | 2009-07-09 | Clariant International Ltd | Cosmetic, pharmaceutical or dermatological compositions having a high content of water-soluble care components |
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