CN105130920A - Method for recycling formic acid in 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine - Google Patents
Method for recycling formic acid in 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine Download PDFInfo
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- CN105130920A CN105130920A CN201510579081.XA CN201510579081A CN105130920A CN 105130920 A CN105130920 A CN 105130920A CN 201510579081 A CN201510579081 A CN 201510579081A CN 105130920 A CN105130920 A CN 105130920A
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- C07—ORGANIC CHEMISTRY
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- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
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Abstract
The invention aims at providing a method for recycling formic acid in 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine, which adopts a formic acid recycling application technology to optimize a synthetic method of 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine. The method specifically comprises the following steps: taking methyl nitroguanidine and paraformaldehyde as reaction raw materials, taking methanesulfonic acid as a catalyst and formic acid as solvent, and reacting to obtain 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine; after the reaction is ended, lowering the temperature, carrying out the decompression concentration, and recycling the formic acid; adjusting the pH value of a reaction solution after the reaction to weak acid, then increasing the temperature to 50 to 80 DEG C, preserving the heat for 0.5h to 2h, cooling to the room temperature, filtering and separating after the crystallization, repeatedly washing a filter cake, and centrifuging and drying to obtain a product. By adopting the method, not only is the cost saved, but also the environmental pollution is reduced, and the mass production and application popularization of the product can be facilitated.
Description
Technical field
The invention belongs to nicotinic insecticide preparation field, be specifically related to the circulation utilization method of formic acid in the production of a kind of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine.
Background technology
3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine is the intermediate of synthesis Diacloden, Diacloden is a kind of s-generation nicotinic insecticide of brand new, can not only have tag, stomach toxicity, systemic activity, and than Provado, there is higher activity, better security, wider insecticidal spectrum, faster speed of action, longer validity period.
The synthesis technique of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine and crystallization processes are the important and difficult issues of research.From the studies in China document published, the synthesis technology of this product, product crystallization technique and synthesis yield all await further raising, more allow people regrettably about 3-methyl-4-nitro-imine tetrahydrochysene-1,3, the impurity existed in the impurity produced in 5-oxadiazine building-up process and product, its source with production control method all without bibliographical information, but the scale operation promote the use of the key that insecticides thiamethoxam succeeds exactly of this problem.Obtainable 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine sample on China market, its quality is also always uneven.Domestic existing production technology and quality control process are unfavorable for the further raising of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine production level.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine reclaims the circulation utilization method of formic acid in producing, adopt recovery formic acid to apply mechanically technology to 3-methyl-4-nitro-imine tetrahydrochysene-1, the synthetic method of 3,5-oxadiazine is optimized.
In the technical study exploitation of He Cheng oxadiazine, we solve the select permeability (adopting formic acid to be solvent better effects if) of solvent species, solvent strength and solvent load, and market is recognized the price of formic acid is higher, in order to the cost-saving recovery that have employed formic acid; Solve the select permeability (adopting methylsulfonic acid better effects if) of catalyst acid kind and consumption; Total yield of products reaches 85% even more than 85%.
The concrete technical scheme of the present invention is: with methyl nitroguanidine and paraformaldehyde for reaction raw materials, take methylsulfonic acid as catalyzer, formic acid is solvent, be obtained by reacting 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine; Reaction terminates rear cooling, carries out concentrating under reduced pressure, reclaims formic acid; Reacted reaction solution adjust ph is to slightly acidic, and cool to room temperature again after then temperature being risen to 50 ~ 80 DEG C of insulation 0.5h ~ 2h, crystallization and filtration is separated, and filter cake repetitive scrubbing, obtains product after centrifugal oven dry.
In said process, the mol ratio of methyl nitroguanidine and paraformaldehyde is 1:3.0 ~ 5.0, preferred 1:3.0 ~ 4.0; The mol ratio of methyl nitroguanidine and methylsulfonic acid is 15 ~ 18:1.
The mol ratio of methyl nitroguanidine and solvent formic acid is: 1:2.5 ~ 6.0; Described formic acid mass concentration is 60% ~ 98%.
In said process, temperature of reaction is 70 ~ 75 DEG C, and the reaction times is 8h ~ 20h, preferred 14h.
After reaction terminates, cool the temperature to room temperature, concentrating under reduced pressure, the formic acid of recovery can directly as the solvent reacted next time.Its concentration is about 85% ~ 65%.
The formic acid reclaimed is applied mechanically more than at least twice repeatedly, and when formic acid concn is reduced to 65%, adopting the formic acid (such as concentration is the formic acid of 98%) adding high density to be again formulated to concentration is 75% ~ 85%, again recycles.
Find in research, add if methyl nitroguanidine is disposable, reaction can produce solidification phenomenon and especially can cause when large-scale reaction stirring difficulty when starting, if methyl nitroguanidine equal portions are dropped in batches, solidification phenomenon would not clearly be conducive to reaction and carries out, therefore, it preferably adds by we in batches.
For reacted reaction solution in said process, when to control its temperature be 40 DEG C ~ 55 DEG C, with alkali metal hydroxide or alkali metal sulfates adjust pH for 6 ~ 7, weak acid partial neutral system is more of value to the carrying out of reaction.Then temperature is risen to 50 ~ 80 DEG C insulation 0.5h ~ 2h after cool to room temperature again, this process in order to better by the magazins' layout in reactant.Filtering separation after crystallization 2h ~ 8h, filter cake repetitive scrubbing, obtains product after centrifugal oven dry.
Beneficial effect: oxadiazine as a kind of important intermediate of s-generation nicotinic insecticide of brand new, during production, select suitable raw material and processing step extremely important, especially the choosing of solvent.The present invention adopts formic acid to be solvent, and provides the circulation utilization method of formic acid in production process, can accomplish not only cost-saving but also reduce environmental pollution, is conducive to scale operation and the application of this product.
Embodiment:
Embodiment 1
The paraformaldehyde of formic acid 45g and 45g of 98% is added in reactor, starts to stir, add catalyst methanesulfonic acid 5g simultaneously, then methyl nitroguanidine 60g gradation is dropped into reactor, persistently overheating to 70-75 DEG C, reaction 14h.
Reaction terminates rear cooling and concentrating under reduced pressure reclaims formic acid, and the formic acid concn now reclaimed after testing is 85%.After reaction, mother liquor adds 65g water and controls interior temperature at 40-50 DEG C, and the sodium hydroxide solution adjust ph with 50% is by strongly-acid to slightly acidic, and dripping quantity is 36.06g.Then room temperature is cooled to again, crystallization 4h filtering separation after temperature being risen to 70 DEG C of insulation 1h.By filter cake repetitive scrubbing several times, weight 59.9g after this product drying is obtained.
As calculated, the yield of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine prepared by the present invention is 83.11%, and content is 99.47%.
Embodiment 2
Add after the formic acid 130g of reclaim in embodiment 1 85% and process water 10g is mixed, then paraformaldehyde 45g is added in reactor, start to stir, add catalyst methanesulfonic acid 5g simultaneously, then methyl nitroguanidine 60g gradation is dropped into reactor, persistently overheating to 70 ~ 75 DEG C, reaction 14h.
Reaction terminates rear cooling and concentrating under reduced pressure reclaims formic acid, and the formic acid concn now reclaimed after testing is 75%.After reaction, mother liquor adds 65g process water and controls interior temperature at 40-50 DEG C, and the sodium hydroxide solution adjust ph with 50% is by strongly-acid to slightly acidic, and dripping quantity is 30-50g.Then room temperature is cooled to again, crystallization 4h filtering separation after temperature being risen to 70 DEG C of insulation 1h.By filter cake repetitive scrubbing several times, weight 65g after this product drying is obtained.
Table 1 is product index
Table 1
| Project | Index % |
| Moisture≤ | 0.3 |
| 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine peak area (this product) >= | 98.0 |
| Single impurity peak area≤ | 0.1 |
This product produced 85% formic acid used once in table 2 has been done eight batches of results respectively and has been contrasted
Table 2
As calculated, the average yield of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine prepared by the present invention is 87.81%, and content is 99.68%.
Embodiment 3
The formic acid 160g of 75% of the recovery in embodiment 2 and paraformaldehyde 40g is added in reactor, starts to stir, add catalyst methanesulfonic acid 5g simultaneously, then methyl nitroguanidine 60g gradation is dropped into reactor, persistently overheating to 70-75 DEG C, reaction 14h.
Reaction terminates rear cooling and concentrating under reduced pressure reclaims formic acid, and the formic acid concn now reclaimed after testing is 65%.After reaction, mother liquor adds 65g process water and controls interior temperature at 40-50 DEG C, and the sodium hydroxide solution adjust ph with 50% is by strongly-acid to slightly acidic, and dripping quantity is 30-50g.Then room temperature is cooled to again, crystallization 4h filtering separation after temperature being risen to 70 DEG C of insulation 1h.By filter cake repetitive scrubbing several times, weight 62.74g after this product drying is obtained.
Do five batches of results respectively to this product using 75% formic acid of twice to produce in table 3 to contrast
Table 3
As calculated, the average yield of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine prepared by the present invention is 87.06%, and content is 99.59%.
Embodiment 4
The formic acid 180g of reclaim in embodiment 3 65% and paraformaldehyde 50g is added in reactor, starts to stir, add catalyst methanesulfonic acid 5g simultaneously, then methyl nitroguanidine 60g gradation is dropped into reactor, persistently overheating to 70-75 DEG C, reaction 14h.
Reaction terminates rear cooling and concentrating under reduced pressure reclaims formic acid, and the formic acid concn now reclaimed after testing is 50%.After reaction, mother liquor adds 65g process water and controls interior temperature at 40-50 DEG C, and the sodium hydroxide solution adjust ph with 50% is by strongly-acid to slightly acidic, and dripping quantity is 30-50g.Then room temperature is cooled to again, crystallization 4h filtering separation after temperature being risen to 70 DEG C of insulation 1h.By filter cake repetitive scrubbing several times, weight 54.44g after this product drying is obtained.
Do five batches of results respectively to this product using 65% formic acid of three times to produce in table 4 to contrast.
Table 4
As calculated, the average yield of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine prepared by the present invention is 75.44%, and content is 99.51%.
Embodiment 5:
Reaction yield aobvious downtrending when formic acid concn drops to 65%, now we add to 65% formic acid the formic acid that 98% formic acid adjusts to 75% and are analyzing, and experimental result sees the following form.
Table 5
| Material | Quality (g) |
| 65% formic acid (after using for three times) | 220 |
| Add 98% formic acid | 87 |
| Paraformaldehyde (technical grade) | 50 |
| Methylsulfonic acid | 5 |
| Methyl nitroguanidine (dry product) | 60 |
| Process water | 65 |
| 50% sodium hydroxide | 30-50 |
| Washing process water | 119 |
| This product wet product | 61 |
| This product dry product | 54.44 |
Five batches of results that table 6 pair embodiment 5 is produced contrast
Table 6
As calculated, the average yield of 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine prepared by the present invention is 87.06%, and content is 99.56%.
Can be found out by above five embodiments, formic acid is applied mechanically more than at least twice repeatedly, and concentration is best when 75%-85% scope.The formic acid concn repeatedly applied mechanically several times can also adopt the formic acid adding high density to be again formulated to optimum concentration range when being reduced to about 65% and reuse.This product reaction after yield all about 85%, content all more than 99%, on domestic industry level.
Above several embodiments of the present invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should belong within patent covering scope of the present invention.
Claims (10)
1. 3-methyl-4-nitro-imine tetrahydrochysene-1,3, a 5-oxadiazine produce in the circulation utilization method of formic acid, it is characterized in that comprising the following steps:
With methyl nitroguanidine and paraformaldehyde for reaction raw materials, take methylsulfonic acid as catalyzer, formic acid is solvent, be obtained by reacting 3-methyl-4-nitro-imine tetrahydrochysene-1,3,5-oxadiazine; Reaction terminates rear cooling, carries out concentrating under reduced pressure, reclaims formic acid;
Reacted reaction solution adjust ph is to slightly acidic, and cool to room temperature again after then temperature being risen to 50 ~ 80 DEG C of insulation 0.5h ~ 2h, crystallization and filtration is separated, and filter cake repetitive scrubbing, obtains product after centrifugal oven dry.
2. circulation utilization method as claimed in claim 1, is characterized in that the mol ratio of methyl nitroguanidine and paraformaldehyde is 1:3.0 ~ 5.0; The mol ratio of methyl nitroguanidine and methylsulfonic acid is 15 ~ 18:1.
3. circulation utilization method as claimed in claim 1, is characterized in that the mol ratio of methyl nitroguanidine and formic acid is: 1:2.5 ~ 6.0; Described formic acid concn is 60% ~ 98%.
4. circulation utilization method as claimed in claim 1, it is characterized in that temperature of reaction is 70 ~ 75 DEG C, the reaction times is 8h ~ 20h.
5. circulation utilization method as claimed in claim 1, is characterized in that the formic acid reclaimed can directly as the solvent reacted next time.
6. circulation utilization method as claimed in claim 5, is characterized in that formic acid is applied mechanically more than at least twice repeatedly, and when formic acid concn is reduced to 65%, adopting the formic acid adding high density to be again formulated to concentration is 75% ~ 85%, again recycles.
7. circulation utilization method as claimed in claim 1, is characterized in that described methyl nitroguanidine equal portions drop in batches.
8. circulation utilization method as claimed in claim 1, it is characterized in that reacted reaction solution controls its temperature is 40 DEG C ~ 55 DEG C, with alkali metal hydroxide or alkali metal sulfates adjust pH for 6 ~ 7.
9. circulation utilization method as claimed in claim 1, after it is characterized in that reaction solution adjust ph to slightly acidic, cools to room temperature after temperature being risen to 70 DEG C of insulation 1h again.
10. circulation utilization method as claimed in claim 1, it is characterized in that according to the mass fraction, formic acid input amount is 45 ~ 220 parts, and paraformaldehyde is 40 ~ 50 parts, and methyl nitroguanidine is 45 ~ 60 parts, and methylsulfonic acid is 1 ~ 5 part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510579081.XA CN105130920A (en) | 2015-09-14 | 2015-09-14 | Method for recycling formic acid in 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine |
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| CN201510579081.XA CN105130920A (en) | 2015-09-14 | 2015-09-14 | Method for recycling formic acid in 3-methyl-4-nitroimino-tetrahydro-1, 3, 5-oxadiazine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217765A (en) * | 2018-11-27 | 2020-06-02 | 宁夏东吴农化股份有限公司 | Synthesis process of 3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine |
| CN112225709A (en) * | 2020-10-26 | 2021-01-15 | 安徽海顺化工有限公司 | Synthesis method and synthesis device of 3-methyl-4-nitroimino-1, 3, 5-oxadiazine |
-
2015
- 2015-09-14 CN CN201510579081.XA patent/CN105130920A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 潘启玉 等: "噻虫嗪中间体3-甲基-4-硝基亚胺基四氢-1,3,5-噁二嗪的合成研究", 《安徽化工》 * |
| 陶贤鉴 等: "新一代烟碱类杀虫剂-噻虫嗪的合成研究", 《现代农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217765A (en) * | 2018-11-27 | 2020-06-02 | 宁夏东吴农化股份有限公司 | Synthesis process of 3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine |
| CN112225709A (en) * | 2020-10-26 | 2021-01-15 | 安徽海顺化工有限公司 | Synthesis method and synthesis device of 3-methyl-4-nitroimino-1, 3, 5-oxadiazine |
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Application publication date: 20151209 |