CN108892671B - Preparation method of pyroxsulam - Google Patents
Preparation method of pyroxsulam Download PDFInfo
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- CN108892671B CN108892671B CN201810947826.7A CN201810947826A CN108892671B CN 108892671 B CN108892671 B CN 108892671B CN 201810947826 A CN201810947826 A CN 201810947826A CN 108892671 B CN108892671 B CN 108892671B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The invention provides a preparation method of pyroxsulam, and belongs to the technical field of herbicide preparation. The pyroxsulam is prepared by the condensation reaction of 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine in an organic solvent and 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride in the presence of an organic base. The condensation reaction is carried out under the catalysis of 4-dimethylamino pyridine. The preparation method of pyroxsulam provided by the invention has the advantages of high yield, simple operation and high safety, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of herbicide preparation, and particularly relates to a preparation method of pyroxsulam.
Background
Pyrithiobac-sodium is a triazolopyrimidine sulfonamide herbicide developed by Yinong Dow, USA under CAS registry number 422556-08-9, with the generic name pyroxsulam, and with the chemical name N- (5, 7-dimethoxy [1,2,4] triazolo [1, 5-alpha ] pyrimidin-2-yl) -2-methoxy-4- (trifluoromethyl) -3-pyridinesulfonamide. The pyroxsulam is a sulfonamide systemic conduction type selective post-seedling herbicide for winter wheat fields, and has the advantages of wide herbicidal spectrum, high herbicidal activity and quick drug action. The herbicide is absorbed by leaves, sheaths, stems or roots of weeds, accumulates at growing points, inhibits acetolactate synthase, cannot synthesize branched-chain amino acids, further influences protein synthesis, influences cell division of the weeds, and causes the weeds to stop growing, yellow and then die.
Chinese patent document CN1930164A discloses an improved process for the preparation of N- ([1,2,4] triazolopyrimidin-2-yl) arylsulfonamides by condensation of 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine and 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride under the catalysis of a homemade N-arylthioimine catalyst. The method has the following defects: the preparation of the N-aryl sulfimide catalyst requires dimethyl sulfide, the reagent is inflammable, explosive, highly toxic and malodorous, chlorine gas is required to be introduced, and the preparation method has the advantages of complex operation, difficult control, low safety, high corrosivity on production equipment, high operation difficulty and no contribution to industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method of pyroxsulam, which has the advantages of high yield, simple operation, high safety and low production cost and is suitable for industrial production.
The technical scheme for realizing the above purpose of the invention is as follows: the pyroxsulam is prepared through the condensation reaction of 2-amino-5, 7-dimethoxy- [1,2,4] triazolo [1,5-a ] pyrimidine and 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride in organic solvent in the presence of organic alkali, and the condensation reaction is catalyzed by 4-dimethylamino pyridine.
Preferably, the organic solvent is acetonitrile, dichloromethane, tetrahydrofuran or toluene.
Preferably, the weight ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the organic solvent is 1: 1-1: 10; further, the weight ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the organic solvent is 1: 5-1: 10.
Preferably, the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine is 1: 1-1: 3; further, the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine is 1: 1-1: 1.3.
Preferably, the organic base is triethylamine, N-diisopropylethylamine or 1, 8-diazabicyclo [5.4.0] undec-7-ene.
Preferably, the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the organic base is 1: 1-1: 3; further, the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the organic base is 1: 1-1: 1.3
Preferably, the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the 4-dimethylaminopyridine is 1: 0.0001-1: 0.01; further, the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the 4-dimethylaminopyridine is 1: 0.0005-1: 0.002.
Preferably, the condensation reaction temperature is 10-40 ℃.
The invention has the following beneficial effects: (1) the method has the advantages of simple operation, simple process conditions, high safety, greatly reduced organic alkali consumption, low production cost and suitability for industrial production. (2) For the condensation reaction, a small amount of 4-dimethylamino pyridine is added to obtain a good catalytic effect, so that a high yield of more than 92% can be obtained, the reaction time is greatly shortened, and the production energy consumption is reduced.
Detailed Description
The present invention will be further specifically described below with reference to examples, but is not limited thereto.
Example 1
2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine (25.4g,0.13mol) was added to 137g of dichloromethane, followed by stirring, addition of 4-dimethylaminopyridine (0.006g, 0.05mmol) and 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride (27.5g, 0.1mol), stirring for 30min, dropwise addition of triethylamine (13.1g,0.13mol) at room temperature, and finally heating to 35 ℃ for reaction for 3 h. The mixture was then treated with 4N HCl (60g), stirred at 25 ℃ for 1 hour, cooled to 10 ℃, filtered, washed with water, washed with methanol and dried to give pyroxsulam 40.8g, 94% yield, 98.5% purity (HPLC).
The products of the above examples were confirmed by nuclear magnetic and mass spectrometry.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference.
Claims (4)
1. The preparation method of pyroxsulam is characterized in that the pyroxsulam is prepared by condensation reaction of 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine and 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride in an organic solvent in the presence of organic base; the condensation reaction is carried out under the catalysis of 4-dimethylamino pyridine;
the organic solvent is dichloromethane;
the organic base is triethylamine;
the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the organic base is 1: 1-1: 1.3;
the molar ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the 4-dimethylaminopyridine is 1: 0.0001-1: 0.01;
the condensation reaction temperature is 10-40 ℃.
2. The preparation method of pyroxsulam according to claim 1, wherein the weight ratio of the 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to the organic solvent is 1: 1-1: 10.
3. The preparation method of pyroxsulam according to claim 1, characterized in that the molar ratio of 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine is 1: 1-1: 3.
4. The preparation method of pyroxsulam according to claim 3, characterized in that the molar ratio of 2-methoxy-4- (trifluoromethyl) -pyridine-3-sulfonyl chloride to 2-amino-5, 7-dimethoxy [1,2,4] triazolo [1,5-a ] pyrimidine is 1: 1-1: 1.3.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822404A (en) * | 1984-01-26 | 1989-04-18 | The Dow Chemical Company | Sulfonamides derived from substituted 2-amino-1,2,4-triazolo (1,5-a) pyrimidines and compositions and methods of controlling undesired vegetation |
| CN1930164A (en) * | 2004-03-26 | 2007-03-14 | 美国陶氏益农公司 | Process for the preparation of n-([1,2,4]triazolopyrimidin-2-yl)aryl sulfonamides |
| WO2014086856A1 (en) * | 2012-12-04 | 2014-06-12 | Basf Agro B.V., Arnhem (Nl) | Compositions comprising a quillay extract and a biopesticide |
| CN106588672A (en) * | 2016-12-31 | 2017-04-26 | 浙江建业化工股份有限公司 | Production method of diisopropylethylamine |
| CN108101844A (en) * | 2018-03-14 | 2018-06-01 | 常州沃腾化工科技有限公司 | The preparation method of 10,11- dihydros -10 oxo -5H- dibenzo [b, f] azepine * -5- formamides |
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2018
- 2018-08-20 CN CN201810947826.7A patent/CN108892671B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822404A (en) * | 1984-01-26 | 1989-04-18 | The Dow Chemical Company | Sulfonamides derived from substituted 2-amino-1,2,4-triazolo (1,5-a) pyrimidines and compositions and methods of controlling undesired vegetation |
| CN1930164A (en) * | 2004-03-26 | 2007-03-14 | 美国陶氏益农公司 | Process for the preparation of n-([1,2,4]triazolopyrimidin-2-yl)aryl sulfonamides |
| WO2014086856A1 (en) * | 2012-12-04 | 2014-06-12 | Basf Agro B.V., Arnhem (Nl) | Compositions comprising a quillay extract and a biopesticide |
| CN106588672A (en) * | 2016-12-31 | 2017-04-26 | 浙江建业化工股份有限公司 | Production method of diisopropylethylamine |
| CN108101844A (en) * | 2018-03-14 | 2018-06-01 | 常州沃腾化工科技有限公司 | The preparation method of 10,11- dihydros -10 oxo -5H- dibenzo [b, f] azepine * -5- formamides |
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