CN1122810A - Process for prodn. of oxy-thiophosphate - Google Patents
Process for prodn. of oxy-thiophosphate Download PDFInfo
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Abstract
In condition of no bais change of raw materials and no major change of process equipment, and by optimizing various catalysts and technological conditions, the yield of oxy-sulfur phosphatide is increased by about 15 percent, and its impurity content decreased by about 8%. Advantages: low cost, stable product quality, simple technology, and little wastes.
Description
The present invention belongs to the field of organophosphorus pesticide.
The invention relates to a new process for producing O, O-dimethyl-S- (methylamino formyl methyl) sulfur phosphate (I), and the compound is a pesticide with wide insecticidal spectrum, strong systemic property, high insecticidal activity and small resistance. The general name of the derivative is Omethoate (Omethonate) and the chemical structural formula is
In sixty to eighty years, a plurality of technical data (including patents) report the synthesis method of omethoate at home and abroad, and the main method comprises the following steps: preamine method (chloracetamide method), methyl isocyanate method, Bunte salt method, and post-amine method. The omethoate crude oil synthesized by adopting the pre-ammonolysis method and the Bunte method generates a large amount of inorganic salt waste residues in the production process, which causes great loss of omethoate in the extraction process, while the omethoate crude oil synthesized by adopting the methyl isocyanate method has the defects of difficult control of process conditions, great influence on the purity of omethoate, large toxicity of raw materials, high cost and serious corrosion to equipment, thus being difficult to popularize and apply in production because the omethoate crude oil is prepared by adopting the solid-liquid heterogeneous reaction.
The post-amination method has the advantages of easily obtainedraw materials, simple process operation and convenient post-treatment, and is a currently and generally adopted omethoate production method in China. Phosphorus trichloride is taken as an initial raw material, and the method comprises the following four steps: general production process of dimethyl (mono) phosphite
The reaction formula is as follows:
the production process comprises the following steps:
and sequentially putting methanol and toluene into a reaction kettle, slowly dripping phosphorus trichloride for about 15 minutes under the conditions that the temperature is less than or equal to 30 ℃ and the vacuum degree is more than or equal to 67kPa, and rapidly deacidifying under the conditions that the temperature is controlled to be 60-70 ℃ and the vacuum degree is more than or equal to 67kPa after the dripping of the phosphorus trichloride is finished to obtain the toluene solution of dimethyl phosphite. General production process of ammonium (di) thiophosphoryl salt
The reaction formula is as follows:
the production process comprises the following steps:
and (3) sequentially putting the obtained toluene solution of dimethyl phosphite and sulfur powder into a reaction kettle, then slowly introducing liquid ammonia into the reaction kettle, controlling the ammonia introduction reaction temperature to be 25-35 ℃, keeping the temperature for reaction for 1 hour after ammonia introduction is finished, and adding water. Standing and layering to obtain the ammonium salt water solution of sulfur and phosphorus. General production process of (tri) oxysulfuryl phosphate
The reaction formula is as follows:
the production process comprises the following steps:
and (3) sequentially putting the obtained ammonium sulfate phosphate aqueous solution (with the pH value adjusted to 7-8) and methyl chloroacetate into a reaction kettle, reacting at the temperature of 58-64 ℃ for 2 hours, standing for layering after the reaction is finished, and performing reduced pressure desolventization on the crude ester to obtain the thiophosphate. General Process for producing omethoate (75 years reported in German patent Ger.110883)
The reaction formula is as follows:
the production process comprises the following steps:
and sequentially putting the obtained oxyphosphate and chloroform into a reaction kettle, precooling to-18 ℃, then slowly dripping methylamine (40%) at the temperature of less than or equal to-8 ℃, keeping the temperature for 40 minutes after finishing dripping, adding hydrochloric acid for neutralizing until the pH value is 6-7 after the reaction is finished, standing for layering, extracting the crude product for three times by using chloroform, and then carrying out decompression desolventizing, wherein the desolventizing end point temperature is 112 ℃, thus obtaining the omethoate crude oil.
Through the deep knowledge and a large amount of experiments of the prior post-amination production process, the following results are found: the reaction system of ammonium sulfate phosphate is a solid-liquid-gas heterogeneous system, and uneven and insufficient reaction is easily caused between materials. In the general process, the ammonia reaction temperature is too high and the ammonia concentration is too high locally, so that the by-products are increased, and the content and the yield of ammonium sulfate phosphate are influenced; the reaction system of the oxygen thiophosphate is a liquid-liquid heterogeneous system, materials are difficult to be fully mixed, the reaction temperature of the general process is too high, the reaction time is too long, so that the increase of by-products is caused, and the content and the yield of the oxygen thiophosphate are influenced; the omethoate aminolysis reaction system is also a liquid-liquid heterogeneous system, and the whole reaction process is relatively complex. The general process has too short reaction time, incomplete reaction, great loss of raw materials, too high reaction temperature, increased by-products and incomplete water removal during final desolventizing, which easily causes product decomposition and influences the purity and yield of omethoate.
The factors cause the low total yield (about 40 percent more) of the current domestic omethoate production and unstable crude oil content (less than 70 percent more).
The invention provides a scheme for optimizing various process conditions of the existing post-amination method production process on the basis of the existing post-amination method production process, and invents a new process capable of greatly improving the total yield of omethoate production and stabilizing the crude oil content.
The invention has the following changed processes for each step of synthesis: 1. in the existing synthesis reaction process of sulfur-phosphorus ammonium salt:
① the ammonia introduction and reaction temperature are reduced, and the ammonia introduction and reaction time is shortened;
② changing the ammonia introduction mode, 2, in the existing synthesis reaction process of the oxygen sulfur phosphorus ester:
① shortening the reaction time and reducing the reaction temperature;
② adding catalyst into the reaction system;
③, changing the desolventizing condition and the desolventizing mode of the crude product, 3, in the existing omethoate aminolysis reaction process:
① use a homogeneous reaction system without solvent or a quasi-homogeneous reaction system with small amount of solvent
Is a step of;
② changing the reaction temperature and prolonging the reaction time;
③ changing the concentration of the raw material methylamine;
④ the desolventizing condition and the desolventizing mode of the crude product are changed.
The conditions for optimizing the process in each step are as follows: firstly, producing sulfur-phosphorus ammonium salt: 1. the ammonia introduction and reaction temperature is controlled to be 5-25 ℃, and the ammonia introduction and reaction time is controlled to be 3-6 hours; 2. the ammonia introducing pipe is changed into a multi-hole pipe or a multi-hole coil pipe. Secondly, producing the oxygen sulfur phosphorus ester: 1. the reaction temperature is controlled to be 50-60 ℃, and the reaction time is controlled to be 60-150 minutes, which is suitable; 2. adding a phase transfer catalyst into a reaction system, controlling the reaction temperature to be 40-60 ℃, and controlling the reaction time to be 40-80 minutes, wherein the reaction system is suitable; 3. the catalyst can be selected from aliphatic and aromatic quaternary ammonium salts and quaternary phosphonium salts with the total carbon number of 10-28, and their compounds, such as transfer catalysts of benzyl trimethyl ammonium halide, tetrabutyl ammonium halide, dodecyl triethyl ammonium halide, trioctyl methyl ammonium halide, etc., and their compounds (the halide ion can be chlorine, bromine, iodine anion, etc.); 4. the dosage of the catalyst is 1-5% of the pure amount of the ammonium salt; 5. adding a proper amount of water-containing solvent of toluene or sec-butyl alcohol into the crude product of the thiophosphate, and carrying out decompression desolventizing 6. when the crude product of the thiophosphate is purified, a distillation kettle with a swing disc and a stirrer connected is adopted for carrying out decompression desolventizing. Thirdly, producing omethoate crude oil: 1. a solvent-free homogeneous reaction system is adopted, and a quasi-homogeneous reaction system taking chloroform or water as a solvent in about one fifth of the original process can also be added; 2. the concentration of the raw material methylamine is appropriate to be 20-40%; 3. the reaction temperature is controlled to be-10 to-20 ℃, and the reaction time is controlled to be 40 to 90 minutes, which is suitable; 4. adding a proper amount of benzene or toluene solvent with water into the crude product, and performing desolventizing under reduced pressure, wherein the final temperature of desolventizing is proper and is 70-100 ℃; 5. and during the purification of the crude product, a distillation kettle with a throwing disc and a stirrer connected is adopted for decompression and desolventizing.
The invention carries out all-round optimization on various process conditions for producing the omethoate by the amine hydrolysis method after the old process, and under the condition of basically not changing production raw materials and not greatly moving process equipment, the total yield of the omethoate production is improved by more than 20 percent, and the crude oil content is stabilized at about 80 percent. It has the advantages of less investment, quick effect, high benefit, less three wastes, etc.
To help better understand the present invention, experimental results under several process conditions, and examples and comparative examples of pilot and industrial tests are given below.
Table one: industrial test results for the Synthesis of ammonium Phosphothios
The test result shows that: the ammonium salt content of the ammonium salt synthesized by the new process is improved by 1.5 percent compared with the ammonium salt synthesized by the old process, and the yield is equivalent to be improved by 5.4 percent (compared with the batch numbers 32 and 34).
Table two: small test results for catalytic synthesis of oxathiophosphate
The experimental results show that: by adopting the new process (adding a certain amount of catalyst), the reaction time can be shortened (experiments 1, 2 and 3), the reaction temperature is reduced (experiment 3), the generation of by-products is reduced, the content of the oxygen sulfur phospholipid is greatly improved, and the average yield of the oxygen sulfur phospholipid is improved by about 15 percent compared with the prior process. Up to 21.4% (experiment 1 vs experiment 4).
Table three: test result for optimizing omethoate crude oil small test process condition
Experiment 1 shows that: the crude oil content is not obviously changed even if the concentration of the raw material methylamine is changed by adopting the old process reaction conditions.
Experiments 2, 3, 4, 5 show that: by adopting the new process reaction conditions and changing the concentration of the raw material methylamine, the average content of the crude oil can be improved by about 5 percent (compared with the experiment 6).
Experiments 2 and 5 show that: the reaction system, reaction conditions and post-treatment method of the old process are optimized in an all-round way, so that the content and yield of the crude oil are greatly improved. The average crude oil content is improved by 1.5 percent compared with experiments 3 and 4, improved by 7.2 percent compared with the prior art (experiment 1), and the average crude oil yield is improved by 4 percent compared with experiments 3 and 4 and improved by 9.45 percent compared with experiment 1.
Table four: industrial test results for omethoate solventless aminolysis reaction
The test result shows that: compared with the crude oil content of the old process, the new process can averagely improve the crude oil content by more than 5 percent.
The old technology (reaction time 120 minutes) and the new technology (reaction time 80 minutes) of the thiophosphate are respectively compared with the actual production of 35 batches, and the thiophosphate obtained by the new technology and the old technology is respectively used for the actual production of 70 batches of crude oil according to the crude oil synthesis method of the old technology. The statistical results show that: compared with the prior art (the reaction time is 120 minutes), the average content of the oxysulfide phosphate obtained by adopting the new process (the reaction time is 80 minutes) is increased by 1.9 percent, the average content of the crude oil is increased by 3.4 percent, the quality of the product is stable, and the content of the crude oil is basically stabilized to be more than 70 percent.
[ example 1]
Putting 1mol of 24.8% dimethyl phosphite toluene solution into a reaction bottle, then adding equimolar sulfur powder, precooling to 10 ℃ under stirring, starting to slowly introduce 1.4mol of ammonia gas, keeping the ammonia introduction temperature at about 15 ℃, introducing ammonia and reacting for 3 hours, then adding 175gof water, standing for layering, removing the upper layer of toluene, and measuring the content of the lower layer of ammonium salt aqueous solution to be 42.4%.
[ COMPARATIVE EXAMPLE 1]
The raw materials, the feeding amount and the experimental steps are the same as those of the example 1, but the ammonia introducing temperature is kept at about 30 ℃, the heat preservation time is 1 hour after the ammonia introducing is finished, and the content of the ammonium salt aqueous solution is finally obtained and is 40.3 percent.
[ Industrial example 1]
Putting 1350Kg of 23.8 percent dimethyl phosphite toluene solution into a reaction kettle, then adding 120Kg of sulfur powder, slowly introducing 100Kg of liquid ammonia under stirring, keeping the ammonia introduction temperature at about 15 ℃, introducing ammonia for reaction for 6 hours, adding 650Kg of water, standing and layering to obtain 1600Kg of ammonium salt aqueous solution with the content of 41.5 percent.
[ Industrial comparative example 1]
The raw materials, the feeding amount and the experimental steps are the same as those of the industrial example 1, but the ammonia introducing temperature is kept at about 30 ℃, the heat preservation time is 1 hour after the ammonia introducing is finished, and 1550kg of ammonium salt aqueous solution with the content of 40.4 percent is obtained.
[ example 2]
Placing 0.5mol of 40.1% ammonium salt aqueous solution into a reaction bottle, then adding 2.25mol of methyl chloroacetate, stirring, controlling the temperature to be 55-60 ℃, reacting for 60 minutes, standing for layering after the reaction is finished, removing a water layer, carrying out reduced pressure distillation on the obtained crude ester, and recoveringexcessive methyl chloroacetate, wherein the amount of refined ester (namely the phosphorothioate) is 100.0g, the chromatographic content is 84.2%, and the yield is 78.7%.
[ example 3]
The raw materials, the feeding amount and the experimental steps are the same as those of the example 2, but the reaction time is 80 minutes, the final obtained refined ester amount is 98.0g, the chromatographic content is 89.6 percent, and the yield is 81.7 percent.
[ example 4]
386.0g of 41.0% ammonium salt aqueous solution and 488.0g of methyl chloroacetate are respectively placed in a reaction bottle, 6.4g of tetrabutylammonium iodide is added, the temperature is controlled to be about 55 ℃ under stirring, the reaction is carried out for 60 minutes, the following steps are carried out in the same way as the example 2, and finally the amount of the obtained refined ester is 200.7g, the chromatographic content is 94.4%, and the yield is 90.2%.
[ example 5]
The raw materials, the feeding amount and the experimental steps are the same as those of example 4, but the catalyst is changed into benzyl tributyl ammonium chloride, the final refined ester amount is 200.8g, the chromatographic content is 90.9%, and the yield is 85.3%.
[ comparative example 2]
The raw materials, the feeding amount and the experimental steps are the same as those of example 4, but the reaction temperature is controlled to be 58-62 ℃, the reaction time is 2 hours, the final obtained refined ester amount is 193.0g, the chromatographic content is 83.0 percent, and the yield is 76.3 percent.
[ Industrial example 2]
1300Kg of 40.4 percent ammonium salt aqueous solution and 1600Kg of methylchloroacetate are sequentially put into a reaction kettle, stirred, the temperature is controlled to be 58-60 ℃, the reaction is carried out for 80 minutes, standing and layering are carried out, the obtained crude ester is subjected to reduced pressure distillation, the yield of the thiophosphate is 700Kg, the chromatographic content is 83.2 percent, and the yield is 82.7 percent.
[ Industrial control example 2]
The raw materials, the feeding amount and the experimental steps are the same as those of the industrial example 2, but the reaction temperature is controlled to be 58-62 ℃, the reaction time is 2 hours, 680Kg of phosphorothioate is obtained, the chromatographic content is 79.4 percent, and the yield is 76.3 percent.
[ example 6]
Putting 270.0g of 79% oxathiophosphate in a reaction bottle, stirring, precooling to-15 ℃, starting to dropwise add 165.0g of methylamine (40%), controlling the temperature to be below-11 ℃, keeping the temperature for reaction for 60 minutes after dropwise addition, neutralizing with hydrochloric acid until the pH value is 6-7, extracting with chloroform, adding 50g of toluene into the crude product, and performing decompression desolventizing at the final desolventizing temperature of 95 ℃. The amount of omethoate crude oil obtained was 251.1g, the content by thin layer analysis was 70.0%, and the yield was 82.5%.
[ example 7]
The raw materials, the feeding amount and the experimental steps are the same as those of example 6, but the concentration of methylamine is 30%, the obtained omethoate crude oil amount is 266.6g, the content is 73.5%, and the yield is 92.0%.
[ control example 3]
The raw materials, the material loading and the experimental steps are the same as those in example 6, however, 338g of chloroform solvent is added into the reaction system, the concentration of methylamine is 30%, the reaction temperature is below-8 ℃, the heat preservation time is 40 minutes, the crude product is directly desolventized without adding toluene to obtain 248.1g of omethoate crude oil, the content of thin layer analysis is 65.8%, and the yield is 82.3%.
[ Industrial example 3]
Putting 400Kg of thiophosphate (79.2%) into a reaction kettle, precooling to-15 ℃ under stirring, beginning to dropwise add 180Kg of 40% methylamine, controlling the temperature below-10 ℃, keeping the temperature for reaction for 60 minutes after the dropwise addition is finished, then neutralizing with hydrochloric acid until the pH value is 6-7, extracting with chloroform, adding 50Kg of toluene into the crude product, and carrying out decompression desolventizing at the final desolventizing temperature of 95 ℃. The crude oil of the omethoate is 360Kg, the content of the TLC is 72.7 percent, and the yield is 82.6 percent.
[ Industrial example 4]
Putting 420Kg of thiophosphate (79.8%) into a reaction kettle, stirring, precooling to-15 ℃, adding 60Kg of water, beginning to dropwise add 190Kg of 40% methylamine, controlling the temperature below-11 ℃, keeping the temperature for 60 minutes after dropwise addition, then neutralizing with hydrochloric acid until the pH value is 6-7, extracting with chloroform, decompressing and desolventizing, wherein the desolventizing end point temperature is 112 ℃. The crude oil of the omethoate is 380Kg, the content of the TLC is 77.6 percent, and the yield is 88.3 percent.
[ Industrial example 5]
Putting 420Kg of thiophosphate (79.2%) into a reaction kettle, stirring, precooling to-15 ℃, adding 100Kg of chloroform, beginning to dropwise add 180Kg of 40% methylamine, controlling the temperature below-10 ℃, keeping the temperature for 60 minutes after dropwise addition, then neutralizing with hydrochloric acid until the pH value is 6-7, extracting with chloroform, decompressing and desolventizing, wherein the desolventizing end point temperature is 110 ℃. The crude oil amount of the omethoate is 355Kg, the content of the TLC is 72.3 percent, and the yield is 81.4 percent.
[ Industrial example 6]
Putting 420Kg of thiophosphate (81.0%) into a reaction kettle, precooling to-15 ℃ under stirring, beginning to dropwise add 189Kg of 30% methylamine, controlling the temperature below-10 ℃, keeping the temperature for reaction for 60 minutes after dropwise addition, then neutralizing with hydrochloric acid until the pH value is 6-7, extracting with chloroform, and carrying out decompression and exsolution. The crude oil amount of the omethoate is 390Kg, the content of the thin layer analysis is 79.3 percent, and the yield is 91.3 percent.
[ Industrial control example 3]
The raw materials, the feeding amount and the experimental steps are the same as those of the industrial example 3, however, 500Kg of chloroform solvent is added before the reaction, the heat preservation time is 40 minutes, the crude product is directly desolventized without adding toluene to obtain 350Kg of omethoate crude oil, the content of the thin layer analysis is 67.8 percent, and the yield is 75.3 percent.
Partial industrial test results (table one) for synthesis of ammonium sulfate phosphate reaction materials and amounts: 450Kg of dimethyl phosphite, 120Kg of sulfur powder and 100Kg of ammonia gas as solvent: toluene 900Kg
| Test of Batch number | Phosphorous acid dimethyl ester | Introducing ammonia and reaction temperature (℃) | Chemical analysis of plant | Phosphorus Spectrum analysis (%) | Remarks for note | ||
| Feed amount | Content (wt.) | Ammonium salt content | Ammonium salts | Impurities and by-products | |||
| 23 | 1350 | 23.8 | 14～16 | 41.51 | 87.0 | 13.0 | New process |
| 32 | 1350 | 23.1 | 18～22 | 41.98 | 88.0 | 12.0 | New process |
| 34 | 1350 | 28～32 | 40.44 | 85.0 | 15.0 | Old process | |
Partial small-test results (table two) of catalytic synthesis of oxathiophosphate reaction materials and amounts: 386.0g of ammonium salt and 488.0g of methyl chloroacetate
| Serial number | Catalyst and process for preparing same | Amount of catalyst (g) | Temperature of heat preservation (℃) | Time of heat preservation (min) | Amount of crude ester (g) | Amount of essential ester (g) | Chromatographic content (％) | Phosphorus spectrum content (%) | Yield of (％) | Ammonium salt concentration (Subdivision) (％) | |
| Thiophosphoryl ester | By-products | ||||||||||
| 1 | YFR-1 | 4.8 | 58～60 | 60 | 538.7 | 224.7 | 92.99 | 92.0 | 8.0 | 97.7 | 41.17 |
| 2 | YFR-2 | 6.4 | " | " | 540.6 | 200.8 | 90.87 | 92.4 | 7.6 | 85.3 | " |
| 3 | YFR-3 | 6.4 | 55 | " | 554.2 | 200.7 | 94.39 | 94.7 | 5.3 | 90.2 | " |
| 4 | / | / | 58～62 | 120 | 550.4 | 193.0 | 83.04 | 91.2 | 8.8 | 76.3 | " |
Note: YFR-1 is trinonyl methyl ammonium iodide, YFR-2 is benzyl tributyl chloride, YFR-3 is tetrabutyl ammonium iodide
Partial test results (table three) of the omethoate crude oil pilot plant process condition optimization reaction materials and amounts: thiophosphate 270.0g, methylamine 1.25mol solvent: chloroform
| Serial number | Variation and optimization of the respective process conditions | After desolventizing Crude oil quantity (g) | Phosphorus spectrum content (%) | Sheet metal Chromatography Content (wt.) | Harvesting machine Rate of change (％) | Thiophosphoryl ester Chromatographic content (％) | ||||||
| Reaction system | Concentration of methylamine | Reaction temperature | Reaction time | Adding benzene for desolventizing | Crude oil | Thiophosphoric acid esters | By-products | |||||
| 1 | 340g chloroform | 30％ | ＜-8℃ | 40min | 248.1 | 79.0 | 7.0 | 14.0 | 65.8 | 82.3 | 73.80 | |
| 2 | Solvent-free | " | ＜-11℃ | 60min | 80g of benzene | 266.6 | 91.0 | 0.9 | 8.1 | 73.5 | 92.0 | 79.27 |
| 3 | " | " | " | " | 257.0 | 95.0 | 0.5 | 4.5 | 72.7 | 87.7 | " | |
| 4 | " | " | " | " | 246.3 | 85.3 | 0.9 | 13.8 | 70.7 | 87.8 | 73.80 | |
| 5 | " | " | " | " | 80g of benzene | 250.3 | 83.0 | 0.5 | 16.5 | 72.5 | 91.5 | " |
| 6 | " | 40％ | -10℃ | " | 80g of benzene | 251.1 | 88.0 | 0.7 | 11.3 | 70.0 | 82.5 | 79.27 |
Omethoate solventless aminolysis reaction partial industrial test results (table tetra) oxathiophosphates: 400Kg, methylamine: 180Kg, solvent: chloroform 27 days 6 to 12 days 7 in 1994
| Sequence of steps Number (C) | Date of experiment | Batch number of factory | Thiophosphoryl ester (％) | Selection of the Process | Results of plant analysis | Results of phosphorus spectrum analysis | Reference batch number | Content phase difference% | ||||
| Crude oil content | Acidity of the solution | Water content | Sulfur driving | Triesters and the like | Refined esters | |||||||
| 1 | 6.28 white | 449 | 96.06 | New process | 70.57 | 0.16 | 0.86 | 78.0 | 13.0 | 5.0 | 452 | +7.37 |
| 2 | 6.28 white | 451 | 96.06 | New process | 68.20 | 0.15 | 0.86 | / | / | / | 452 | +5.0 |
| 3 | 6.28 white | 452 | 96.06 | Old process | 63.20 | 0.12 | 0.50 | 73.5 | 13.0 | 12 | 449，451 | |
| 4 | 6.29 white | 1 | 93.18 | New process | 66.19 | 0.12 | 0.42 | / | / | / | 2 | +4.76 |
| 5 | 6.29 white | 4 | 93.18 | New process | 66.09 | 0.18 | 1.25 | / | / | / | 2 | +4.66 |
| 6 | 6.29 white | 2 | 93.18 | Old process | 61.63 | 0.12 | 0.46 | / | / | / | 1，4 | |
Claims (8)
1. An improved process for the synthesis of ammonium thiophosphate and thiophosphate ester includes the steps of
(1) Synthesizing ammonium thiophosphate by taking dimethyl phosphite, sulfur powder and liquid ammonia as raw materials;
(2) the thiophosphoryl ester is synthesized by taking thiophosphoryl ammonium salt and methyl chloroacetate as raw materials.
The method is characterized in that: in the step (1), ammonia is introduced and the reaction temperature is controlled to be 5-25 ℃,
introducing ammonia and reacting for 3-6 hours. In the step (2), the reaction temperature is controlled to 50
The reaction time is 50-150 minutes at 60 ℃.
2. A method according to claim 1, characterized in that: in step (1), a porous material is used
The multi-pipe or multi-hole coil pipe is filled with ammonia.
3. A method according to claim 1, characterized in that: in step (2), in the reaction body
In this system, a phase transfer catalyst is added.
4. The process according to claim 3, wherein the catalyst has a total carbon number of 10 to 28
Aliphatic and aromatic quaternary ammonium salts, quaternary phosphonium salts, and combinations thereof, e.g. benzyl
Trimethyl ammonium halide, tetrabutylammonium halide, dodecyl triethyl ammonium halide, trioctyl
Methyl ammonium halide isophase transfer catalyst and their compound (the halide ion can be chlorine, bromine, etc.),
Bromine, iodine anions, etc.).
5. The method according to claim 3, wherein the amount of the catalyst is 1 to 5% of the pure amount of the ammonium salt.
6. A process as claimed in claim 3, wherein the reaction temperature is controlled to 40 to 60 ℃ and the reaction is carried out
The reaction time is controlled to be 20-80 minutes.
7. A method according to claim 1, characterized in that: in step (2), an oxathiophosphoryl ester
Adding a proper amount of water-containing solvent of toluene or sec-butyl alcohol into the crude product, and performing decompression desolventizing.
8. A method according to claim 1, characterized in that: in step (2), an oxathiophosphoryl ester
The crude product is purified by a distillation still with a throwing disc and a stirrer connected for decompression desolventizing
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| CN94117723A CN1039914C (en) | 1994-11-08 | 1994-11-08 | Process for prodn. of oxy-thiophosphate |
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| CN1039914C CN1039914C (en) | 1998-09-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193781A (en) * | 2014-09-09 | 2014-12-10 | 湘潭大学 | Synthetic method for thiophosphate |
| CN108864187A (en) * | 2018-08-06 | 2018-11-23 | 兰博尔开封科技有限公司 | A kind of new process synthesizing omethoate important intermediate oxy-thiophosphate |
| CN108997418A (en) * | 2018-08-06 | 2018-12-14 | 兰博尔开封科技有限公司 | A kind of improvement technique synthesizing omethoate |
| CN111393472A (en) * | 2019-12-27 | 2020-07-10 | 安道麦股份有限公司 | Method for recycling by-products in production process of spermine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD89107A (en) * | ||||
| DD110883A1 (en) * | 1974-02-15 | 1975-01-12 |
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1994
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193781A (en) * | 2014-09-09 | 2014-12-10 | 湘潭大学 | Synthetic method for thiophosphate |
| CN104193781B (en) * | 2014-09-09 | 2016-06-15 | 湘潭大学 | A kind of synthetic method of sulfur phosphide |
| CN108864187A (en) * | 2018-08-06 | 2018-11-23 | 兰博尔开封科技有限公司 | A kind of new process synthesizing omethoate important intermediate oxy-thiophosphate |
| CN108997418A (en) * | 2018-08-06 | 2018-12-14 | 兰博尔开封科技有限公司 | A kind of improvement technique synthesizing omethoate |
| CN108864187B (en) * | 2018-08-06 | 2020-12-25 | 兰博尔开封科技有限公司 | Process for synthesizing important intermediate oxygen thiophosphate of omethoate |
| CN108997418B (en) * | 2018-08-06 | 2021-06-18 | 兰博尔开封科技有限公司 | Improved technology for synthesizing omethoate |
| CN111393472A (en) * | 2019-12-27 | 2020-07-10 | 安道麦股份有限公司 | Method for recycling by-products in production process of spermine |
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| CN1039914C (en) | 1998-09-23 |
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