CN102731453B - A kind of production control method of 98% content carbofuran - Google Patents
A kind of production control method of 98% content carbofuran Download PDFInfo
- Publication number
- CN102731453B CN102731453B CN201210234906.0A CN201210234906A CN102731453B CN 102731453 B CN102731453 B CN 102731453B CN 201210234906 A CN201210234906 A CN 201210234906A CN 102731453 B CN102731453 B CN 102731453B
- Authority
- CN
- China
- Prior art keywords
- carbofuran
- solvent
- benzofuranol
- methyl isocyanate
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
A kind of 98% content carbofuran production control method, adopt 1,2-ethylene dichloride or 1,2-propylene dichloride is reaction, recrystallisation solvent, solvent load is 2 ~ 4 times of benzofuranol quality, and the mol ratio of benzofuranol and methyl isocyanate, triethylamine is 1:1.05:0.01, drips methyl isocyanate under reflux temperature, cooling, crystallization, filtration are finished in reaction, and filtration cakes torrefaction obtains mass content 98.0 ~ 98.9% major product; Filtrate isolates 10 ~ 15% of quality at every turn, uses after supplementing the novel solvent merging of equal quality as lower batch reaction mother liquor simultaneously; Each isolated filtrate distillation, recovered solvent does fresh solvent and uses, and obtain the carbofuran byproduct of mass content 84.1 ~ 92.7%, total recovery is 99.0 ~ 99.8% (in benzofuranols) simultaneously.The present invention can avoid recrystallization operation, and major product carbofuran mass content Absorbable organic halogens controls 98.0% ~ 98.9%, and solvent recuperation amount is little; The carbofuran product of by-product mass content 84.1 ~ 92.7%, as 3% carbofuran granule raw material.
Description
Technical field
The present invention relates to a kind of production control method of 98% content carbofuran.
Background technology
Carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuryl methylamino-manthanoate) is broad spectrum insecticide, nematocides, molecular structural formula:
Be applicable to the control of various pests in paddy rice, cotton, tobacco, Soybean and Other Crops, also can be used as seed treatment agent specially.
US5387702 discloses a kind of preparation method of carbofuran, and it adopts the aprotic solvent such as benzene or toluene, and under Trimethylamine 99 or Triethylamine catalyst exist, benzofuranol and methyl isocyanate react, and filtration drying obtains carbofuran, yield 95%.
GB1265255 discloses a kind of preparation method of carbofuran, it adopts benzene, hexanaphthene, methylcyclohexane, heptane, hexane, methylene dichloride, trichloromethane, tetracol phenixin or methyl-isobutyl ether equal solvent, under Triethylamine catalyst exists, benzofuranol and methyl isocyanate generation continuous processing are reacted, and filtration drying obtains the carbofuran product of mass content 96.8%.
It is solvent that current domestic enterprise produces many employing toluene, and under Triethylamine catalyst exists, benzofuranol (99%) and methyl isocyanate (99.5%) react, and reaction terminates rear cooling, crystallization is filtered, oven dry obtains carbofuran, product content 97 ~ 98%.Reaction solvent can only apply mechanically 1 time.Because major impurity in benzofuranol is pyrocatechol, 1 mole of pyrocatechol can be created on the two methylene dicarbamate of phenyl-1,2-of more indissoluble in toluene with 2 moles isocyanate reactions, causes product content obviously to reduce.Because toluene belongs to weak polar solvent, to the solvability extreme difference of carboxylamine aromatic ester, carboxylamine aromatic ester forms solid and separates out together with product; Simultaneously methyl isocyanate reacts with the water in solvent and air that the dimethyl urea produced is same is insoluble in toluene, and the quality product content that result in carbofuran is difficult to control more than 98%, and the high-grade-goods rate of product is very low.
CN98112498 discloses a kind of process for purification of carbofuran, and adopt the binary solvents such as alcohol/water to carry out to crude product the carbofuran that recrystallization obtains high-content, the method need increase recrystallization operation and cost.
Along with riskiest pesticide is progressively forbidden, be that the low market of poisoning product benfuracarb and carbosulfan of development of raw materials progressively expands and finally can replace carbofuran with carbofuran, and the mass content of producing benfuracarb and carbosulfan requirement raw material carbofuran more than 98%, therefore must need a kind of stable, effective production control method when production 98% content carbofuran.
Summary of the invention
The object of this invention is to provide a kind of production control method of 98% content carbofuran.
Reaction formula is as follows:
Realizing technical scheme of the present invention is:
Adopt the stronger inert solvent of polarity for reaction, recrystallisation solvent, triethylamine is catalyzer, and benzofuranol and methyl isocyanate are obtained by reacting carbofuran.The by product phenyl-1,2-two methylene dicarbamate, the dimethyl urea etc. that produce in reaction process dissolve in a solvent, and reaction terminates rear cold filtration, and filtration cakes torrefaction obtains the carbofuran that mass percentage is greater than 98%; Filtrate isolates certain volume at every turn, part by product is removed system with filtrate, react as lower batch reaction mother liquor after supplementing the fresh solvent merging of isodose simultaneously, make by product in lower batch reaction solvent not reach its saturation concentration like this, the by product major part that lower batch reaction generates is still in reaction mother liquor; Each isolated filtrate distillation, recovered solvent can do fresh solvent and use, and also obtains the lower carbofuran of a small amount of mass content as 3% content carbofuran granule raw material.
The stronger inert solvent of polarity of the present invention refers to 1,2-ethylene dichloride, 1,2-propylene dichloride, solvent load is 2 ~ 4 times of benzofuranol quality, the mol ratio of benzofuranol and methyl isocyanate, triethylamine is 1:1.05:0.01, is heated to reflux temperature, drips methyl isocyanate in 1 hour.Cooling, crystallization, filtration are finished in reaction, and filtration cakes torrefaction obtains mass percentage and is greater than 98.0% major product carbofuran; Filtrate is isolated 10 ~ 15% at every turn, remaining filtrate uses as lower batch reaction solvent after supplementing the fresh solvent merging of isodose simultaneously, each isolated filtrate is distilled, recovered solvent does fresh solvent and uses, by-product mass percentage is the carbofuran byproduct of 84.1 ~ 92.7% simultaneously, and this product is used as the raw material of 3% carbofuran granule.The weight of carbofuran byproduct is 1 ~ 3% of carbofuran major product gross weight, and total recovery is greater than 99.0%.
Several primary inert solvent to the solvability of carbofuran and major impurity, in table 1.
Table 1 solubility experiment data (at remarks room temperature 30 DEG C, the solubleness of 100mL solvent)
| Toluene | 1,2-propylene dichloride | 1,2-ethylene dichloride | |
| Carbofuran/g | 5.1 | 9.1 | 14.0 |
| Dimethyl urea/g | 0.06 | 5.3 | 6.3 |
| Two methylene dicarbamate/the g of phenyl-1,2- | 0.08 | 0.8 | 1.2 |
Compared with other synthetic methods, the present invention has the following advantages:
1) recrystallization operation can be avoided, owing to upgrading a certain amount of mother liquor at every turn, by-product concentration in every batch reaction mother liquor is made to control at a lower level, there is not accumulation, therefore the major product carbofuran content often criticizing synthesis is high, carbofuran mass content can stability contorting in 98.0% ~ 98.9%(liquid chromatography, external standard);
2) yield is high, total recovery 99.0 ~ 99.8% (in benzofuranol);
3) solvent recuperation amount is few, due to every batch of only recycling small portion solvent, is equivalent to solvent and applies mechanically after more than 6 times just complete process 1 batch of reaction solvent, more traditional recrystallization method, and whole solvent energy consumption is distilled in crystallization after filtering low;
4) isolated filtrate distillation, recovered solvent does fresh solvent and uses, simultaneously the carbofuran product of by-product mass content 84.1 ~ 92.7%, as 3% carbofuran granule raw material.
Embodiment
Embodiment 1
66g industrial goods benzofuranol (99%), 264g1 is added with in the 500mL there-necked flask of cooling tube, dropping funnel, thermometer, stirring, 2-ethylene dichloride and 0.4g triethylamine, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, and centrifuging also uses 20g1,2-ethylene dichloride washing leaching cake, filter cake oven-dried weight 68.3g, liquid spectrum external standard method analyzes carbofuran mass content 98.9%.
The heavy 285.7g of filtrate, the filtrate weighing up 10% replenishes fresh 1, the 2-ethylene dichloride of equal quality simultaneously, and mixed filtrate is applied mechanically as the solution circulated of lower batch reaction.The 10% filtrate Distillation recovery 24.5g1 weighed up, 2-ethylene dichloride and 2.1g white solid (carbofuran mass content 90.8%).
Embodiment 2
Apply mechanically experiment: the whole mother liquors adding 66g industrial goods benzofuranol (99%), embodiment 1 in the 500mL there-necked flask of band cooling tube, dropping funnel, thermometer, stirring, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, 80 DEG C are continued reaction 1h, and reaction terminates crystallisation by cooling, and centrifuging is also with 20g fresh 1,2-ethylene dichloride washing leaching cake, filter cake is dried, and filtrate is by the method process of embodiment 1, and experimental result is in table 2.
Experimental result applied mechanically by table 2
| Batch | Major product/g | Mass content/% | Reclaim product/g | Mass content/% | Total recovery/% |
| Apply mechanically 1 time | 86.1 | 98.6 | 2.2 | 89.9 | 99.1 |
| Apply mechanically 2 times | 86.0 | 98.7 | 2.4 | 90.9 | 99.3 |
| Apply mechanically 3 times | 86.7 | 98.3 | 2.1 | 89.3 | 99.4 |
| Apply mechanically 4 times | 86.2 | 98.1 | 2.5 | 90.8 | 99.0 |
| Apply mechanically 5 times | 86.4 | 98.4 | 2.2 | 90.2 | 99.2 |
| Apply mechanically 6 times | 86.4 | 98.3 | 2.6 | 92.7 | 99.6 |
| Apply mechanically 7 times | 86.4 | 98.0 | 2.4 | 91.2 | 99.0 |
Embodiment 3
66g industrial goods benzofuranol (99%), 132g1 is added with in the 500mL there-necked flask of cooling tube, dropping funnel, thermometer, stirring, 2-ethylene dichloride and 0.4g triethylamine, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, and centrifuging also uses 20g1,2-ethylene dichloride washing leaching cake, filter cake oven-dried weight 78.8g, liquid spectrum external standard method analyzes carbofuran mass content 98.4%.
The heavy 143.6g of filtrate, the filtrate weighing up 15% replenishes fresh 1, the 2-ethylene dichloride of equal quality simultaneously, and mixed filtrate is applied mechanically as the solution circulated of lower batch reaction.The 15% filtrate Distillation recovery 19.1g1 weighed up, 2-ethylene dichloride and 1.6g white solid (carbofuran mass content 87.0%).
Embodiment 4
Apply mechanically experiment: the whole mother liquors adding 66g industrial goods benzofuranol (99%), embodiment 3 in the 500mL there-necked flask of band cooling tube, dropping funnel, thermometer, stirring, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, centrifuging also uses fresh 1, the 2-ethylene dichloride washing leaching cake of 20g, and filter cake is dried, filtrate is by the method process of embodiment 3, and experimental result is in table 3.
Experimental result applied mechanically by table 3
| Batch | Major product/g | Mass content/% | Reclaim product/g | Mass content/% | Total recovery/% |
| Apply mechanically 1 time | 87.0 | 98.2 | 1.8 | 88.3 | 99.3 |
| Apply mechanically 2 times | 87.1 | 98.1 | 1.6 | 87.1 | 99.0 |
| Apply mechanically 3 times | 86.5 | 98.4 | 2.2 | 84.2 | 99.2 |
| Apply mechanically 4 times | 87.0 | 98.2 | 1.7 | 87.0 | 99.1 |
| Apply mechanically 5 times | 86.8 | 98.0 | 2.0 | 88.4 | 99.1 |
| Apply mechanically 6 times | 86.9 | 98.2 | 2.1 | 88.8 | 99.5 |
| Apply mechanically 7 times | 86.7 | 98.0 | 2.4 | 88.4 | 99.3 |
Embodiment 5
66g industrial goods benzofuranol (99%), 198g1 is added with in the 500mL there-necked flask of cooling tube, dropping funnel, thermometer, stirring, 2-propylene dichloride and 0.4g triethylamine, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, and centrifuging also uses 20g1,2-propylene dichloride washing leaching cake, filter cake oven-dried weight 76.4g, liquid spectrum external standard method analyzes carbofuran mass content 98.6%.
The heavy 210.0g of filtrate, the filtrate weighing up 10% replenishes fresh 1, the 2-propylene dichloride of equal quality simultaneously, and mixed filtrate is applied mechanically as the solution circulated of lower batch reaction.The 10% filtrate Distillation recovery 19.0g1 weighed up, 2-propylene dichloride and 1.3g white solid (carbofuran mass content 91.5%).
Embodiment 6
Apply mechanically experiment: the whole mother liquors adding 66g industrial goods benzofuranol (99%), embodiment 5 in the 500mL there-necked flask of band cooling tube, dropping funnel, thermometer, stirring, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, centrifuging also uses fresh 1, the 2-propylene dichloride washing leaching cake of 20g, and filter cake is dried, filtrate is by the method process of embodiment 5, and experimental result is in table 4.
Experimental result applied mechanically by table 4
| Batch | Major product/g | Mass content/% | Reclaim product/g | Mass content/% | Total recovery/% |
| Apply mechanically 1 time | 87.4 | 98.3 | 1.6 | 85.0 | 99.5 |
| Apply mechanically 2 times | 86.9 | 98.4 | 1.6 | 85.1 | 99.1 |
| Apply mechanically 3 times | 87.4 | 98.3 | 1.5 | 84.8 | 99.4 |
| Apply mechanically 4 times | 86.7 | 98.5 | 1.9 | 84.1 | 99.2 |
| Apply mechanically 5 times | 87.0 | 98.2 | 1.8 | 86.4 | 99.2 |
| Apply mechanically 6 times | 87.2 | 98.2 | 2.1 | 85.3 | 99.7 |
| Apply mechanically 7 times | 87.1 | 98.1 | 1.5 | 85.7 | 99.0 |
Embodiment 7
66g industrial goods benzofuranol (99%), 132g1 is added with in the 500mL there-necked flask of cooling tube, dropping funnel, thermometer, stirring, 2-propylene dichloride and 0.4g triethylamine, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, and centrifuging also uses 20g1,2-propylene dichloride washing leaching cake, filter cake oven-dried weight 80.1g, liquid spectrum external standard method analyzes carbofuran mass content 98.3%.
The heavy 141.7g of filtrate, the filtrate weighing up 15% replenishes fresh 1, the 2-propylene dichloride of equal quality simultaneously, and mixed filtrate is applied mechanically as the solution circulated of lower batch reaction.The 15% filtrate Distillation recovery 18.7g1 weighed up, 2-propylene dichloride and 1.4g white solid (carbofuran mass content 88.6%).
Embodiment 8
Apply mechanically experiment: the whole mother liquors adding 66g industrial goods benzofuranol (99%), embodiment 7 in the 500mL there-necked flask of band cooling tube, dropping funnel, thermometer, stirring, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, centrifuging also uses fresh 1, the 2-propylene dichloride washing leaching cake of 20g, and filter cake is dried, filtrate is by the method process of embodiment 7, and experimental result is in table 5
Experimental result applied mechanically by table 5
| Batch | Major product/g | Mass content/% | Reclaim product/g | Mass content/% | Total recovery/% |
| Apply mechanically 1 time | 87.3 | 98.2 | 1.6 | 87.4 | 99.4 |
| Apply mechanically 2 times | 87.4 | 98.1 | 1.7 | 86.9 | 99.5 |
| Apply mechanically 3 times | 87.3 | 98.1 | 1.7 | 86.8 | 99.4 |
| Apply mechanically 4 times | 86.9 | 98.1 | 1.9 | 88.0 | 99.2 |
| Apply mechanically 5 times | 86.8 | 98.2 | 2.2 | 87.7 | 99.4 |
| Apply mechanically 6 times | 87.2 | 98.1 | 2.1 | 87.2 | 99.7 |
Embodiment 9
66g industrial goods benzofuranol (99%), 264g1 is added with in the 500mL there-necked flask of cooling tube, dropping funnel, thermometer, stirring, 2-propylene dichloride and 0.4g triethylamine, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, and centrifuging also uses 20g1,2-propylene dichloride washing leaching cake, filter cake oven-dried weight 72.7g, liquid spectrum external standard method analyzes carbofuran mass content 98.8%.
The heavy 280.2g of filtrate, the filtrate weighing up 10% replenishes fresh 1, the 2-propylene dichloride of equal quality simultaneously, and mixed filtrate is applied mechanically as the solution circulated of lower batch reaction.The 10% filtrate Distillation recovery 25.1g1 weighed up, 2-propylene dichloride and 1.7g white solid (carbofuran mass content 90.0%).
Embodiment 10
Apply mechanically experiment: the whole mother liquors adding 66g industrial goods benzofuranol (99%), embodiment 9 in the 500mL there-necked flask of band cooling tube, dropping funnel, thermometer, stirring, be heated to reflux temperature start to drip methyl isocyanate, 0.42mol methyl isocyanate is added in 1 hour, reaction terminates crystallisation by cooling, centrifuging also uses fresh 1, the 2-propylene dichloride washing leaching cake of 20g, and filter cake is dried, filtrate is by the method process of embodiment 9, and experimental result is in table 6.
Experimental result applied mechanically by table 6
| Batch | Major product/g | Mass content/% | Reclaim product/g | Mass content/% | Total recovery/% |
| Apply mechanically 1 time | 87.0 | 98.4 | 2.1 | 87.9 | 99.7 |
| Apply mechanically 2 times | 87.1 | 98.2 | 2.2 | 87.3 | 99.8 |
| Apply mechanically 3 times | 87.0 | 98.3 | 2.3 | 86.1 | 99.8 |
| Apply mechanically 4 times | 86.7 | 98.2 | 2.4 | 85.3 | 99.4 |
| Apply mechanically 5 times | 86.8 | 98.1 | 2.3 | 85.7 | 99.4 |
| Apply mechanically 6 times | 86.8 | 98.3 | 2.5 | 85.1 | 99.8 |
Claims (2)
1. a production control method for carbofuran, is characterized in that following steps: 1. adopt the one of inert polar solvents 1,2-ethylene dichloride or 1,2-propylene dichloride for reaction, recrystallisation solvent; 2. triethylamine is catalyzer, and benzofuranol and methyl isocyanate are obtained by reacting carbofuran; 3. cooling, crystallization, filtration are finished in reaction, and filtration cakes torrefaction obtains the carbofuran major product of mass percentage >=98%; 4. filtrate isolates 10 ~ 15% of gross weight at every turn, uses after supplementing the novel solvent merging of equivalent weight as lower batch reaction solvent simultaneously; 5. each isolated filtrate distillation, distill the solvent be recycled and do novel solvent use, the carbofuran byproduct of by-product mass percentage 84.1 ~ 92.7% simultaneously, as 3% carbofuran granule raw material;
Reaction formula is as follows:
Described inert polar solvents consumption is 2 ~ 4 times of benzofuranol quality, and the mol ratio of benzofuranol and methyl isocyanate, triethylamine is 1:1.05:0.01, is heated to reflux temperature and starts to drip methyl isocyanate, in 1 hour, add methyl isocyanate.
2. the production control method of a kind of carbofuran according to claim 1, it is characterized in that the weight of carbofuran byproduct is 1.7 ~ 3.0% of carbofuran major product gross weight, total recovery counts 99.0 ~ 99.8% with benzofuranol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210234906.0A CN102731453B (en) | 2012-07-09 | 2012-07-09 | A kind of production control method of 98% content carbofuran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210234906.0A CN102731453B (en) | 2012-07-09 | 2012-07-09 | A kind of production control method of 98% content carbofuran |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102731453A CN102731453A (en) | 2012-10-17 |
| CN102731453B true CN102731453B (en) | 2015-12-02 |
Family
ID=46987835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210234906.0A Active CN102731453B (en) | 2012-07-09 | 2012-07-09 | A kind of production control method of 98% content carbofuran |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102731453B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529963A (en) * | 2014-12-25 | 2015-04-22 | 湖北沙隆达股份有限公司 | Production method for increasing yield of carbofuran (active pharmaceutical ingredient) to 98% |
| CN114276318B (en) * | 2021-12-09 | 2023-06-20 | 湖南海利化工股份有限公司 | Method for recovering high-quality carbofuran from carbofuran production mother liquor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1265255A (en) * | 1969-07-30 | 1972-03-01 | ||
| US4463184A (en) * | 1981-07-31 | 1984-07-31 | Union Carbide Corporation | Process for the preparation of carbofuran |
| CN1048217A (en) * | 1990-08-17 | 1991-01-02 | 刘新进 | 2,3-dihydroxyl-2, a kind of preparation method of 2-dimethyl-7-benzofuran phenol |
| US5387702A (en) * | 1993-09-29 | 1995-02-07 | Council Of Scientific And Industrial Research | Process for the preparation of cabofuran |
| CN101323561A (en) * | 2008-07-30 | 2008-12-17 | 国家农药创制工程技术研究中心 | Extraction fractional distillation for separating pyrocatechol in furanol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61130282A (en) * | 1984-11-29 | 1986-06-18 | Mitsubishi Chem Ind Ltd | Production of benzofuranyl carbamate |
-
2012
- 2012-07-09 CN CN201210234906.0A patent/CN102731453B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1265255A (en) * | 1969-07-30 | 1972-03-01 | ||
| US4463184A (en) * | 1981-07-31 | 1984-07-31 | Union Carbide Corporation | Process for the preparation of carbofuran |
| CN1048217A (en) * | 1990-08-17 | 1991-01-02 | 刘新进 | 2,3-dihydroxyl-2, a kind of preparation method of 2-dimethyl-7-benzofuran phenol |
| US5387702A (en) * | 1993-09-29 | 1995-02-07 | Council Of Scientific And Industrial Research | Process for the preparation of cabofuran |
| CN101323561A (en) * | 2008-07-30 | 2008-12-17 | 国家农药创制工程技术研究中心 | Extraction fractional distillation for separating pyrocatechol in furanol |
Non-Patent Citations (2)
| Title |
|---|
| Daniel A. Bachovchin，等.Superfamily-wide portrait of serine hydrolase inhibition achieved by library-versus-library screening.《PNAS》.2010,第107卷(第49期), * |
| 徐汉生，等.呋喃丹生产中的技术进展.《湖北化工》.1996,(第S1期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102731453A (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262285A (en) | Method for synthesizing intermediate of agricultural insecticide indoxacarb | |
| CN102731453B (en) | A kind of production control method of 98% content carbofuran | |
| CN111116591A (en) | Method for preparing sildenafil citrate | |
| EP3476838B1 (en) | Method for preparing azoxystrobin | |
| CN108033903B (en) | Synthesis process for water-borne esterification of DL-p-methylsulfonylphenylserine ethyl ester | |
| CN105585539B (en) | The method of one pot process cefotaxime side chain acetoacetic ester | |
| CN108997229B (en) | 1,2,3, 4-tetrahydroquinoxaline-6-carboxylic acid methyl ester and preparation method thereof | |
| CN103724203A (en) | Preparation method of o-methyl hydroxyphenylacetate | |
| CN101747284A (en) | Method for preparing antioxidant | |
| CN107629009B (en) | Synthesis method of integrated system 2-amino-4, 6-dimethoxypyrimidine | |
| CN110272451B (en) | Preparation method of tetraphenylphenol phosphonium salt | |
| CN113387844B (en) | Preparation method of dialkyl azodicarbonate | |
| CN111269149B (en) | Production process of 5- (3,3-dimethylguanidino) -2-oxopentanoic acid | |
| CN109836344B (en) | Method for producing glycine by organic solvent | |
| CN102718740B (en) | Trioxymethylene crystallization method | |
| CN101560238A (en) | Intermediates of betamethasone products-3, 20-double ethylene glycol production process | |
| CN110452165B (en) | Preparation method of 2-methylpyridine-4-formic acid | |
| Xu et al. | A high-yield and cost-effective synthesis of spirotetramat | |
| CN108373415A (en) | A kind of preparation method of two (bis- chloro- 5- nitrobenzophenones of 2,4-) carbonic esters | |
| CN112940062B (en) | Preparation method of 16-dehydroprogesterone | |
| CN114276318B (en) | Method for recovering high-quality carbofuran from carbofuran production mother liquor | |
| CN109651432B (en) | Method for preparing O, O-dimethyl-S- (N-methyl carbamoylmethyl) thiophosphate | |
| RU2633525C1 (en) | Method for produing 3,3'-dichloro-4,4'-diaminodiphenylmethane | |
| CN117946027A (en) | Preparation method of AE active ester | |
| CN107522763B (en) | Preparation method of (2'R) -2' -deoxy-2 '-fluoro-2' -methyluridine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Xiaoguang Inventor after: Liu Weidong Inventor after: Yin Lin Inventor after: Wang Yu Inventor after: Pang Huailin Inventor after: Mao Chunhui Inventor after: Zang Yangling Inventor after: Li Ping Inventor after: Chen Ming Inventor before: Wang Xiaoguang Inventor before: Wang Yu Inventor before: Pang Huailin Inventor before: Mao Chunhui Inventor before: Zang Yangling Inventor before: Li Ping Inventor before: Chen Ming |
|
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Xiaoguang Inventor after: Wang Yu Inventor after: Pang Huailin Inventor after: Mao Chunhui Inventor after: Zang Yangling Inventor after: Li Ping Inventor after: Chen Ming Inventor before: Wang Xiaoguang Inventor before: Liu Weidong Inventor before: Yin Lin Inventor before: Wang Yu Inventor before: Pang Huailin Inventor before: Mao Chunhui Inventor before: Zang Yangling Inventor before: Li Ping Inventor before: Chen Ming |
|
| CB03 | Change of inventor or designer information |