CN111689909A - Preparation method of herbicide pyrithiobac-sodium - Google Patents
Preparation method of herbicide pyrithiobac-sodium Download PDFInfo
- Publication number
- CN111689909A CN111689909A CN202010595127.8A CN202010595127A CN111689909A CN 111689909 A CN111689909 A CN 111689909A CN 202010595127 A CN202010595127 A CN 202010595127A CN 111689909 A CN111689909 A CN 111689909A
- Authority
- CN
- China
- Prior art keywords
- sodium
- pyrithiobac
- preparation
- sulfinate
- herbicide
- 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.)
- Pending
Links
- CNILNQMBAHKMFS-UHFFFAOYSA-M Pyrithiobac-sodium Chemical compound [Na+].COC1=CC(OC)=NC(SC=2C(=C(Cl)C=CC=2)C([O-])=O)=N1 CNILNQMBAHKMFS-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 15
- 239000004009 herbicide Substances 0.000 title claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- PBEKEFWBLFBSGQ-UHFFFAOYSA-N 2-chloro-4,6-dimethoxypyrimidine Chemical compound COC1=CC(OC)=NC(Cl)=N1 PBEKEFWBLFBSGQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 4
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 claims abstract description 4
- LYPGDCWPTHTUDO-UHFFFAOYSA-M sodium;methanesulfinate Chemical compound [Na+].CS([O-])=O LYPGDCWPTHTUDO-UHFFFAOYSA-M 0.000 claims abstract description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- AQKPOJRMYFQSLX-UHFFFAOYSA-N 2-chloro-6-sulfanylbenzoic acid Chemical compound OC(=O)C1=C(S)C=CC=C1Cl AQKPOJRMYFQSLX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 abstract description 2
- SIXNTGDWLSRMIC-UHFFFAOYSA-N sodium;toluene Chemical compound [Na].CC1=CC=CC=C1 SIXNTGDWLSRMIC-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PCVRHOZHSQQRMC-UHFFFAOYSA-N 4,6-dimethoxy-1h-pyrimidine-2-thione Chemical compound COC1=CC(OC)=NC(S)=N1 PCVRHOZHSQQRMC-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- SZCPTRGBOVXVCA-UHFFFAOYSA-N 2-amino-6-chlorobenzoic acid Chemical compound NC1=CC=CC(Cl)=C1C(O)=O SZCPTRGBOVXVCA-UHFFFAOYSA-N 0.000 description 1
- -1 2-chloro-6-mercaptobenzoic acid sodium salt Chemical compound 0.000 description 1
- XCSNRORTQRKCHB-UHFFFAOYSA-N 2-chloro-6-nitrotoluene Chemical compound CC1=C(Cl)C=CC=C1[N+]([O-])=O XCSNRORTQRKCHB-UHFFFAOYSA-N 0.000 description 1
- ITDVJJVNAASTRS-UHFFFAOYSA-N 4,6-dimethoxy-2-methylsulfonylpyrimidine Chemical compound COC1=CC(OC)=NC(S(C)(=O)=O)=N1 ITDVJJVNAASTRS-UHFFFAOYSA-N 0.000 description 1
- AMATXUCYHHHHHB-UHFFFAOYSA-N 5,5-dibromo-1,3-diazinane-2,4,6-trione Chemical compound BrC1(Br)C(=O)NC(=O)NC1=O AMATXUCYHHHHHB-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/60—Three or more oxygen or sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method of herbicide pyrithiobac-sodium in the field of plant protection, which takes 2-chloro-4, 6-dimethoxypyrimidine as a raw material to directly react with 2-chloro-6-mercaptobenzoic acid under the action of a solvent, inorganic base and an alkyl sodium sulfinate catalyst to prepare the pyrithiobac-sodium. The sodium alkyl sulfinate is one of sodium trifluoromethyl sulfinate, sodium methyl sulfinate, sodium benzene sulfinate and sodium p-methyl benzene sulfinate. The solvent is one or more of toluene, chlorobenzene, acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and 1, 4-dioxane. The inorganic base is one of potassium carbonate, sodium carbonate and cesium carbonate. The invention realizes the preparation of the pyrithiobac-sodium by adopting a clean process technology, and has the characteristics of high reaction yield, simple process and the like.
Description
Technical Field
The invention relates to a preparation method of herbicide pyrithiobac-sodium in the field of plant protection, in particular to a preparation method of herbicidal pyrithiobac-sodium.
Technical Field
The pyrithiobac-sodium is developed by a Japanese combined chemical company, the dibromin company and the U.S. Dupont company are jointly developed, and the herbicide for the new-generation broad-spectrum cotton field which is marketed in the 90 th century can effectively prevent and kill annual and perennial gramineous weeds and most of broadleaf weeds and also has good preventing and killing effect on weeds difficult to kill.
Through the literature search of the prior art, some preparation methods of pyrithiobac-sodium have been reported in the prior art. For example, U.S. patent No. 4932999 and european patent No. EP315889 report that 3-chloro-2-methyl nitrobenzene is used as raw material, and through oxidation and reduction, 2-chloro-6-aminobenzoic acid is obtained, and then diazotization is carried out to form salt, and condensation with 2-mercapto-4, 6-dimethoxy pyrimidine is carried out at low temperature. The process needs diazotization reaction, generates a large amount of waste water containing odor, has large pollution, and the raw material of the 2-mercapto-4, 6-dimethoxy pyrimidine is expensive. Another preparation method is, for example, a preparation method of 2-chloro-6- (4, 6-dimethoxypyrimidine-2-ylthio) benzoic acid sodium salt reported in Chinese invention patent (CN1065862A) and U.S. invention patents (US4932999 and US 5149357), wherein a 2-methanesulfonyl-4, 6-dimethoxypyrimidine intermediate is prepared by taking diethyl malonate and thiourea as synthetic starting materials, dimethyl sulfate is required to be used as a methylating reagent in the reaction process, a large amount of waste water containing a bad smell is generated, and the synthetic steps are long and have great pollution. Therefore, the development of a synthesis route of the pyrithiobac-sodium, which has the advantages of short reaction route, simple industrial process, safety and low cost, is very necessary for the market promotion of the novel green cotton field herbicide pyrithiobac-sodium.
OBJECT OF THE INVENTION
The invention aims to provide a preparation method of herbicide pyrithiobac-sodium aiming at the defects of the prior art, so that the preparation of the herbicide pyrithiobac-sodium is realized by adopting a clean process technology, and the preparation method has the characteristics of high reaction yield and simple process.
The invention is realized by the following technical scheme that 2-chloro-4, 6-dimethoxy pyrimidine is used as a raw material to directly react with 2-chloro-6-mercapto sodium benzoate under the action of a solvent, inorganic base and an alkyl sodium sulfinate catalyst to prepare the pyrithiobac-sodium. The process does not produce odor and a large amount of waste water, and can realize clean production.
In the preparation method, the catalyst is sodium alkyl sulfinate, such as sodium trifluoromethyl sulfinate, sodium methyl sulfinate, sodium benzene sulfinate, sodium p-methyl benzene sulfinate and the like, the reaction temperature is 60-150 ℃, and the optimal reaction temperature is 100-120 ℃.
The solvent is one or more of toluene, chlorobenzene, acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and 1, 4-dioxane.
The inorganic base is one of potassium carbonate, sodium carbonate and cesium carbonate.
The reaction route of the preparation method of the invention is as follows:
the technology of the invention has short synthesis steps (one step), high synthesis yield (yield is more than 80 percent), does not generate waste water containing smelly odor, and solves the problem of high pollution. Compared with the second method in the prior art reported in the background technology, the method has the advantages of long steps (6 steps), low total synthesis yield (16%), adoption of highly toxic reagents dimethyl sulfate and phosphorus oxychloride in the process, generation of waste water containing smelly odor, and great pollution.
Detailed Description
The following examples illustrate the invention in detail: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
EXAMPLE 1 preparation of pyrithiobac-sodium
2-chloro-4, 6-dimethoxypyrimidine (4.38g, 25.0mmol), 2-chloro-6-mercaptobenzoic acid sodium salt (4.69g, 25mmol), sodium methylsulfinate (0.66g, 6.3mmol), potassium carbonate (5.18g, 37.5mmol), 30ml of toluene and 5ml of N, N-dimethylformamide were added to a reaction flask, and the mixture was refluxed for 14 hours, cooled, filtered, the filter cake was washed with toluene, the filtrate was recovered, the filter cake was dried in vacuum, dissolved in 35ml of water, adjusted to pH 1-2 with 10% hydrochloric acid, filtered, washed with water, and dried to obtain 6.65g of pyrithiobac-sodium as a yellow solid with a yield of 81.6%, melting point: 232.8-234.8 ℃.1HNMR(300MHz,DMSO)，(ppm) ＝7.56(d,J＝2.1Hz,1H),7.47(dd,J＝9.4,6.5Hz,2H),5.42(s,1H),3.81(s,6H).
EXAMPLE 2 preparation of pyrithiobac-sodium
2-chloro-4, 6-dimethoxypyrimidine (4.38g, 25.0mmol), 2-chloro-6-mercaptobenzoic acid (4.69g, 25mmol), sodium benzene sulfinate (1.07g, 6.5mmol), sodium carbonate (5.30g, 50.0mmol), N-methylpyrrolidone (40ml) were added to a reaction flask, and the reaction was allowed to proceed for 10 hours at 100 ℃ to 120 ℃, followed by cooling, filtration, washing of the filter cake with N-methylpyrrolidone, recovery of the filtrate, drying of the filter cake in vacuo, dissolving with 30ml of water, adjusting the pH to 1-2 with 10% hydrochloric acid, washing of the filtrate, and drying to obtain 6.48g of pyrithiobac-sodium as a yellow solid, yield 80.9%, melting point: 232.5-234.6 ℃.
EXAMPLE 3 preparation of pyrithiobac-sodium
2-chloro-4, 6-dimethoxypyrimidine (8.76g, 50.0mmol), 2-chloro-6-mercaptobenzoic acid (10.34g, 55mmol), sodium trifluoromethanesulfonate (2.34g, 15mmol), cesium carbonate (16.3g, 50mmol), toluene (80ml), N-dimethylacetamide acetonitrile (20ml) were added to a reaction flask, reacted at 110 ℃ for 10 hours, cooled and filtered, the filter cake was washed with toluene, the filtrate was recovered, the filter cake was dried in vacuo, dissolved in 70ml of water, adjusted to PH 1-2 with 10% hydrochloric acid, filtered, washed with water and dried to obtain 13.5g of pyrithiobac-sodium as a yellow solid in a yield of 82.6%, melting point: 232.1-234.3 ℃.
EXAMPLE 4 preparation of pyrithiobac-sodium
In a reaction flask, 2-chloro-4, 6-dimethoxypyrimidine (8.76g, 50.0mmol), 2-chloro-6-mercaptobenzoic acid (9.45g, 50mmol), sodium p-toluenesulfinate (2.67g, 15mmol), sodium carbonate (9.75 g, 75mmol), acetonitrile (80ml) were added, reacted at 80 ℃ for 24 hours, the reaction was cooled and filtered, the filter cake was washed with acetonitrile, the filtrate was recovered, the filter cake was dried in vacuo, dissolved in 80ml of water, adjusted to PH 1-2 with 10% hydrochloric acid, filtered, washed with water and dried to obtain 13.2g of pyrithiobac-sodium as a yellow solid, yield 80.2%, melting point: 232.2-234.6 ℃.
Claims (6)
1. A preparation method of herbicide pyrithiobac-sodium is characterized in that 2-chloro-4, 6-dimethoxy pyrimidine is used as a raw material to directly react with 2-chloro-4, 6-dimethoxy pyrimidine under the action of a solvent, inorganic base and a sodium alkyl sulfinate catalyst to prepare the pyrithiobac-sodium.
2. The process for preparing a herbicidal pyrithiobac-sodium as claimed in claim 1, wherein the sodium alkylsulfinate is one of sodium trifluoromethanesulfonate, sodium methanesulfinate, sodium benzenesulfinate and sodium p-toluenesulfinate.
3. A process for the preparation of a herbicidal pyrithiobac-sodium as claimed in claim 1, wherein the solvent is one or more of toluene, chlorobenzene, acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, 1, 4-dioxane.
4. A process for the preparation of a herbicide pyrithiobac-sodium as claimed in claim 1, wherein the solvent inorganic base is one of potassium carbonate, sodium carbonate and cesium carbonate.
5. A process for the preparation of the herbicide pyrithiobac-sodium as claimed in claim 1, wherein the temperature of the reaction is 60 ℃ to 150 ℃.
6. A process for the preparation of the herbicide pyrithiobac-sodium as claimed in claim 1 or 5, wherein the optimum reaction temperature is from 100 ℃ to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010595127.8A CN111689909A (en) | 2020-06-28 | 2020-06-28 | Preparation method of herbicide pyrithiobac-sodium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010595127.8A CN111689909A (en) | 2020-06-28 | 2020-06-28 | Preparation method of herbicide pyrithiobac-sodium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111689909A true CN111689909A (en) | 2020-09-22 |
Family
ID=72484121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010595127.8A Pending CN111689909A (en) | 2020-06-28 | 2020-06-28 | Preparation method of herbicide pyrithiobac-sodium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111689909A (en) |
-
2020
- 2020-06-28 CN CN202010595127.8A patent/CN111689909A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NO147903B (en) | GASSAVFUKTINGSAPPARAT. | |
| PL173021B1 (en) | Pesticidal pyrimidinic compounds | |
| CA1134833A (en) | Trifluoromethyl-2-(thio)pyridone compounds and process for the preparation of the same | |
| KR20170016894A (en) | Methods for the preparation of 1,3-benzodioxole heterocyclic compounds | |
| CN113372283B (en) | Synthetic method of 2-methylamino-4-methoxy-6-methyl-1, 3, 5-triazine | |
| JP2017534637A (en) | Preparation method of revaprazan hydrochloride | |
| CN111689909A (en) | Preparation method of herbicide pyrithiobac-sodium | |
| CN101265235A (en) | Method for preparing herbicide bispyribac-sodium | |
| CN106588796B (en) | A kind of s-triazine structure containing triaryl and the armaticity binary primary amine of ehter bond and preparation method thereof | |
| CN103380125A (en) | Method for producing triazinyl-substituted oxindoles | |
| CN111807997B (en) | Synthesis method of N- (4-methoxycarbonyl-3-aminosulfonylbenzyl) methanesulfonamide | |
| US4115652A (en) | Process for the preparation of amino-nitrophenols | |
| CN103319421A (en) | Preparation method of pyribenzoxim belonging to pyrimidinylthiobenzoate herbicide | |
| DK169673B1 (en) | Process for the preparation of 4,6-bis (difluoromethoxy) pyrimidines | |
| CN105859559A (en) | Production method of 3-ethoxy-4-nitrophenol | |
| JPS5910353B2 (en) | 6-TERT-butyl-3-mercapto-4-amino-1 2 4-triazine-5 (4H)-onno seizouhouhou | |
| JPH0782268A (en) | Production of benzothiadiazole derivative | |
| CN106349168A (en) | Preparation method of foramsulfuron intermediate of sulfonylurea herbicide | |
| CN111018782A (en) | Preparation method of 9-aminoacridine and derivatives thereof | |
| KR20090064456A (en) | Process for the preparation of trifluoroethoxytoluenes | |
| JP6046827B2 (en) | 4- (5-Amino-6-hydroxybenzoxazol-2-yl) ammonium benzoate and its production and use | |
| CN111943818B (en) | Method for preparing 4,4' -bis (trifluoromethyl) diphenyl ether | |
| US5210287A (en) | 2,5-dichlorophenylthioglycolic acid derivative and method for its production | |
| CN112624930A (en) | Preparation method of 2, 2-bis (4-aminophenyl) hexafluoropropane | |
| CN115947675A (en) | Rasagiline intermediate and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200922 |
|
| WD01 | Invention patent application deemed withdrawn after publication |