CN105924454A - Preparation method of azamethiphos intermediate 3H-oxazolo[4,5-b]pyridin-2-one - Google Patents
Preparation method of azamethiphos intermediate 3H-oxazolo[4,5-b]pyridin-2-one Download PDFInfo
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- CN105924454A CN105924454A CN201610296072.4A CN201610296072A CN105924454A CN 105924454 A CN105924454 A CN 105924454A CN 201610296072 A CN201610296072 A CN 201610296072A CN 105924454 A CN105924454 A CN 105924454A
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- pyridine
- ketone
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- triphosgene
- methylpyridine phosphorus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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Abstract
A preparation method of an azamethiphos intermediate 3H-oxazolo[4,5-b]pyridin-2-one includes the technological steps that 1, 2-amino-3-pyridinol is dissolved in a solvent; 2, alkali is added; 3, a triphosgene organic solution is dripped at -5-30 DEG C; 4, a reaction is carried out for 2-20 h at 40-90 DEG C; 5, solid-liquid separation is carried out after the temperature is cooled to 0-20 DEG C; 6, drying is carried out, and the azamethiphos intermediate 6-chloro-3H-oxazolo[4,5-b]pyridin-2-one is obtained. Compared with the prior art, according to the method, reaction steps are short, operation is easy, and reaction conditions are mild; besides, as triphosgene with low toxicity is used for replacing high-toxicity phosgene, the reaction yield reaches up to 85%, the organic solvent can be recycled and reused, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the production method of a kind of methylpyridine phosphorus, especially a kind of methylpyridine phosphorus intermediate azoles [4,
5-b] preparation method of pyridine-2 (3H) ketone.
Background technology
Methylpyridine phosphorus, chemical name S-6-chloro-2,3-dihydro-2-oxo-1,3-azoles [4,5-b] pyridin-3-yl-first
Base-0,0-dimethyl disulfide substituted phosphate；English name Azamethiphos, CAS No.:[35575-96-3], methylpyridine phosphorus
Being a kind of acaricide, have insecticidal activity concurrently, belong to stomach function regulating toxicant of tagging, lasting effect is good, and insecticidal spectrum is wide, can be used for Cotton Gossypii, fruit tree,
Vegetable and domestic animal, public health and family prevent and treat various acarids and stupid moth, aphid, leaf louse, Grapholita spp, colorado potato bug and grey
Fly, Blatta seu periplaneta etc., be to people and animals' low toxicity, is efficient, the resistant medicament of low toxicity, low-residual.The preparation of methylpyridine phosphorus is with azoles
[4,5-b] pyridine-2 (3H) ketone is raw material, obtains through reactions such as chlorination, methylolation, chloro, condensations；Currently available technology
The preparation method of azoles [4,5-b] pyridine-2 (3H) ketone has: BU11.Chen.Jpn.1987,60(5): 1,793 1799 reports
Under catalyst action, the reaction under high pressure of CO；CN1393448A document is disclosed, and with 2-amino-3,5-pyridone is raw material,
Prepare azoles [4,5-b] pyridine-2 (3H) thioketone and oxidation reaction through cyclisation respectively, generate azoles [4,5-b] pyridine-2 (3H) ketone
Method；Said method reactions steps is long, is difficult to operation, and reaction condition is high, and therefore, research is a kind of, and reactions steps is short, be prone to behaviour
The preparation method of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone that work, reaction condition are gentle is to have industry
Change meaning.
Summary of the invention
The technical problem to be solved is to provide that a kind of reactions steps is short, easily operated, reaction condition is gentle
The preparation method of methylpyridine phosphorus intermediate 6-chlorazol [4,5-b] pyridine-2 (3H) ketone.
The present invention solves the technical scheme of its technical scheme:
The preparation method of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone, its processing step is: 1. by 2-
Amino-3-pyridone dissolves in a solvent, 2. adds alkali, 3. drips triphosgene organic solution at a temperature of-5 30 DEG C, 4.
React 2 to 20 hours at a temperature of 40 90 DEG C, after 5. cooling to 0 20 DEG C, solid-liquid separation, 6. dry in methylpyridine phosphorus
Mesosome 6-chlorazol [4,5-b] pyridine-2 (3H) ketone.
As a preferred embodiment of the present invention, dissolving the solvent of 2-amino-3-pyridone is water, methanol, ethanol, different
One of which in acetone, acetone, DMF, dichloromethane, dichloroethanes, chloroform or several mixture.
As a preferred embodiment of the present invention, described triphosgene organic solution for triphosgene is dissolved in dimethanol,
One of which in ethanol, isopropyl acetone, toluene, dimethylbenzene, stupid, dichloromethane, dichloroethanes, chloroform or several mixture structures
The organic solution made in the organic solvent become, the consumption of organic solvent is 36 times of triphosgene quality.
As a preferred embodiment of the present invention, triphosgene is 0.5 3 times with the mass ratio of 2-amino-3-pyridone.
As a preferred embodiment of the present invention, described alkali be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, three
Ethamine or dimethylamine.
As a preferred embodiment of the present invention, alkali is 3 30:1 with the mass ratio of 2-amino-3-pyridone.
Compared with prior art, the inventive method not only reactions steps is short, easily operated, reaction condition temperature, and due to
The relatively low triphosgene of toxicity replaces the phosgene that toxicity is higher, reaction recovery rate to be up to 85%, and organic solvent is recyclable to be applied mechanically, and is suitable to
Industrialized production.
Detailed description of the invention
The preparation method of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone, its processing step is: 1.
2-amino-3-pyridone is dissolved in a solvent, 2. adds alkali, at a temperature of-5 30 DEG C, 3. drip triphosgene organic molten
Liquid, 4. reacts 2 to 20 hours at a temperature of 40 90 DEG C, after 5. cooling to 0 20 DEG C, and solid-liquid separation, 6. dry to obtain methyl pyrrole
Pyridine phosphorus intermediate 6-chlorazol [4,5-b] pyridine-2 (3H) ketone.
Embodiment 1
Addition 480g30% sodium hydrate aqueous solution and 66g2-amino-3-pyridone in 2L there-necked flask, stirring and dissolving, will
192g triphosgene is dissolved in 400mL toluene makes solution；After there-necked flask is heated slowly to 80 DEG C, the toluene of dropping triphosgene is molten
Liquid, reaction temperature controls between 75 90 DEG C, insulation reaction 6 hours after completion of dropwise addition；Cool to 20 30 DEG C, with hydrochloric acid or
Sodium hydroxide regulation reactant liquor pH value is neutrality, continues to cool to less than 10 DEG C, filters, and filter cake is washed once, dries white
Solid azoles [4,5-b] pyridine-2 (3H) ketone 54.6g, yield 85.8%, after filtrate separates, dried recovered toluene.
Embodiment 2
Addition 810g30% sodium hydrate aqueous solution and 110g2-amino-3-pyridone in 2L there-necked flask, stirring and dissolving, will
340g triphosgene is dissolved in 600mL toluene and 300mL chloroform makes solution；After there-necked flask is heated slowly to 80 DEG C, drip three light
The toluene of gas and chloroformic solution, reaction temperature controls between 74 88 DEG C, insulation reaction 8 hours after completion of dropwise addition；Cool to
20 30 DEG C, regulating reactant liquor pH value with hydrochloric acid or sodium hydroxide is neutrality, continues to cool to less than 10 DEG C, filters, filter cake water
Wash once, dry to obtain white solid azoles [4,5-b] pyridine-2 (3H) ketone 91.4g, yield 86.2%, after filtrate separates, be dried back
Receive toluene and chloroform.
Claims (6)
1. the preparation method of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone, it is characterised in that its technique
Step is: is 1. dissolved in a solvent by 2-amino-3-pyridone, 2. adds alkali, 3. drip three light at a temperature of-5 30 DEG C
Gas organic solution, 4. reacts 2 to 20 hours at a temperature of 40 90 DEG C, after 5. cooling to 0 20 DEG C, and solid-liquid separation, 6. dry
Obtain methylpyridine phosphorus intermediate 6-chlorazol [4,5-b] pyridine-2 (3H) ketone.
The preparation side of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone the most according to claim 1
Method, it is characterised in that the solvent dissolving 2-amino-3-pyridone is water, methanol, ethanol, isopropyl acetone, acetone, DMF, dichloro
One of which in methane, dichloroethanes, chloroform or several mixture.
The preparation side of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone the most according to claim 1
Method, it is characterised in that described triphosgene organic solution for being dissolved in methanol, ethanol, isopropanol, toluene, diformazan by triphosgene
The organic solvent that one of which in benzene, stupid, dichloromethane, dichloroethanes, chloroform or several mixture are constituted is made
Organic solution, the consumption of organic solvent is 36 times of triphosgene quality.
The preparation side of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone the most according to claim 3
Method, it is characterised in that triphosgene is 0.5 3 times with the mass ratio of 2-amino-3-pyridone.
The preparation side of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone the most according to claim 1
Method, it is characterised in that described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine or dimethylamine.
The preparation side of a kind of methylpyridine phosphorus intermediate azoles [4,5-b] pyridine-2 (3H) ketone the most according to claim 5
Method, it is characterised in that alkali is 3 30:1 with the mass ratio of 2-amino-3-pyridone.
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| CN201610296072.4A CN105924454A (en) | 2016-05-08 | 2016-05-08 | Preparation method of azamethiphos intermediate 3H-oxazolo[4,5-b]pyridin-2-one |
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| CN201610296072.4A CN105924454A (en) | 2016-05-08 | 2016-05-08 | Preparation method of azamethiphos intermediate 3H-oxazolo[4,5-b]pyridin-2-one |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3575305A1 (en) | 2018-05-31 | 2019-12-04 | Biocidal Alternative Solutions | Method for producing compounds comprising an oxazolopyridinone functional group |
| CN110950888A (en) * | 2019-11-11 | 2020-04-03 | 山东省科学院菏泽分院 | Preparation method of chlorooxanone with Vilsmeier reagent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1803802A (en) * | 2005-01-12 | 2006-07-19 | 中国科学院福建物质结构研究所 | Method for synthesizing oxazole pyridone compound |
| WO2010021797A1 (en) * | 2008-08-22 | 2010-02-25 | Memory Pharmaceuticals Corporation | Condensed heterocyclic compounds having 5-ht6 receptor affinity |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803802A (en) * | 2005-01-12 | 2006-07-19 | 中国科学院福建物质结构研究所 | Method for synthesizing oxazole pyridone compound |
| WO2010021797A1 (en) * | 2008-08-22 | 2010-02-25 | Memory Pharmaceuticals Corporation | Condensed heterocyclic compounds having 5-ht6 receptor affinity |
Non-Patent Citations (2)
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| JIAN-QIANG QIAN等: "A novel approach for the synthesis of Crizotinib through the key chiral alcohol intermediate by asymmetric hydrogenation using highly active Ir-Spiro-PAP catalyst", 《TETRAHEDRON LETTERS》 * |
| 孟纪文等: "噁唑[4,5-b]吡啶-2-(3H)酮的合成", 《精细化工中间体》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3575305A1 (en) | 2018-05-31 | 2019-12-04 | Biocidal Alternative Solutions | Method for producing compounds comprising an oxazolopyridinone functional group |
| WO2019229141A1 (en) | 2018-05-31 | 2019-12-05 | Biocidal Alternative Solutions | Process for producing compounds containing an oxazolopyridinone functional group |
| CN110950888A (en) * | 2019-11-11 | 2020-04-03 | 山东省科学院菏泽分院 | Preparation method of chlorooxanone with Vilsmeier reagent |
| CN110950888B (en) * | 2019-11-11 | 2022-05-20 | 山东省科学院菏泽分院 | Preparation method of chlorooxanone with Vilsmeier reagent |
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