CN111635398B - Preparation and application of pyrazole derivative containing oxazole methoxy biaryl unit - Google Patents
Preparation and application of pyrazole derivative containing oxazole methoxy biaryl unit Download PDFInfo
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- CN111635398B CN111635398B CN202010595170.4A CN202010595170A CN111635398B CN 111635398 B CN111635398 B CN 111635398B CN 202010595170 A CN202010595170 A CN 202010595170A CN 111635398 B CN111635398 B CN 111635398B
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- methoxy
- pyrazole derivative
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to preparation and application of a pyrazole derivative (I) containing an oxazole methoxy biaryl unit. Is obtained by condensing oxazole methoxyl biaryl compound (II) and pyrazole oxime (III). The pyrazole derivative containing the oxazole methoxy biaryl unit has excellent control effect on harmful insects, and is used for preparing pesticides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, and particularly relates to preparation and application of a pyrazole derivative containing an oxazole methoxy biaryl unit.
Background
The prevention and control and the inhibition of insect pests are important contents in the field of pesticide science research. The widespread use of various types of insecticides has kept insect pests under control at all times. With the increasing application scale of traditional pesticides, a variety of pests gradually develop resistance to traditional pesticides. Therefore, there is a need for agrochemical chemists to develop new highly effective, low toxicity pesticides.
The nitrogen-containing heterocyclic ring has wide application in agricultural production, and the pyrazole as an important member plays an important role in the field of plant protection in recent years, such as pyrazole insecticides like tebufenpyrad and chlorantraniliprole.
Substituted oxazole rings, which are also important nitrogen-containing heterocycles, are often incorporated into the molecules of pesticidal compounds and exhibit excellent pesticidal activity.
Therefore, in order to continuously search for novel compounds with good insecticidal activity from pyrazole compounds, oxazole methoxy biaryl units and pyrazole frameworks are organically connected together, and the invention discloses pyrazole derivatives containing the oxazole methoxy biaryl units, which have agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole derivative containing oxazole methoxy biaryl units, which has excellent control effect on various pests, is efficient, safe and environment-friendly, and meets the requirement of crop protection on efficient pesticides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
It is a further object of the present invention to provide the use of the above compounds in the preparation of insecticides.
In order to solve the technical problems, the invention provides a pyrazole derivative containing an oxazole methoxy biaryl unit, which has a structure shown in a general formula I,
preferably, the pyrazole derivative containing the oxazole methoxy biaryl unit has the following structure:
the second aspect of the present invention provides a preparation method of the pyrazole derivative containing an oxazole methoxy biaryl unit, which is characterized by comprising the following steps:
dissolving a compound III and an acid-binding agent in an organic solvent, adding a compound II, filtering and removing the solvent after the reaction is finished, separating the obtained residue by column chromatography to obtain a target compound,
preferably, the preparation method of the pyrazole derivative containing the oxazole methoxy biaryl unit comprises the following steps:
the intermediate II was prepared by the method of reference (j.med.chem.1998,41,2390) and the intermediate III was prepared by the method of reference (bioorg.med.chem.lett.2016,26,3818).
The compound of the general formula I has excellent control effect on insects, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture and the like. The insects comprise aphids and the like. Of course, the pests which the compounds of the invention can control are not limited to the above exemplified ranges.
When the compound of the invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, the compound can be used alone or in the form of an insecticidal composition, for example, the compound is prepared into an aqueous emulsion, a suspending agent, a water dispersible granule, an emulsion and the like by taking the formula I as an active ingredient and adding pesticide auxiliaries commonly used in the field.
Commonly used pesticide adjuvants include liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; common surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention represented by the general formula I is used as an active ingredient in an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the suspension concentrate contains 5% to 50% of active ingredient, preferably 5% to 40%.
For the use of the insecticide of the present invention, a commonly used application method such as stem and leaf spraying, water surface application, soil treatment, seed treatment, and the like can be selected. For example, when spray application from stems and leaves is employed, the compounds represented by the general formula I as active ingredients can be used in the form of aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates in the concentration range of 1 to 1000. mu.g/mL, preferably in the concentration range of 1 to 500. mu.g/mL.
The pyrazole derivative containing the oxazole methoxy biaryl unit disclosed by the invention has a good control effect on harmful insects, and therefore, the pyrazole derivative can be used for preparing pesticides used in the fields of agriculture, horticulture and the like.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1:
in a reaction flask, 15mmol of compound IIIa, 50mmol of triethylamine and 50mL of DMF were added, and 20mmol of compound IIa was added thereto with stirring at room temperature. After the addition, the reaction solution was heated to 95 ℃ and reacted for 22 hours. After the reaction is finished, removing the solvent under reduced pressure, and separating the obtained residue by column chromatography to obtain a target compound Ia; 1 H NMR(400MHz,CDCl 3 ):δ7.98(d,J＝8.4Hz,2H,Ar-H),7.77(s,1H,CH＝N),7.73(s,1H,Oxazole-H),7.43(d,J＝8.4Hz,2H,Ar-H),7.23(d,J＝8.4Hz,2H,Ar-H),6.82～7.01(m,6H,Ar-H),5.06(s,2H,CH 2 ),4.93(s,2H,CH 2 ),3.61(s,3H,CH 3 ),2.37(s,3H,CH 3 ).
example 2:
in a reaction flask, 12mmol of compound IIIb, 30mmol of potassium carbonate and 60mL of acetonitrile were added, to which 16mmol of compound IIb was added with stirring at room temperature. After the addition, the reaction mixture was heated under reflux for 16 hours. After the reaction is finished, removing the solvent under reduced pressure, and carrying out column chromatography separation on the obtained residue to obtain a target compound Ib; 1 H NMR(400MHz,CDCl 3 ):δ8.02～8.06(m,2H,Ar-H),7.78(s,1H,CH＝N),7.77(s,1H,Oxazole-H),6.76～7.42(m,9H,Ar-H),5.15(s,2H,CH 2 ),4.88(s,2H,CH 2 ),3.60(s,3H,CH 3 ),2.35(s,3H,CH 3 ).
example 3:
screening of insecticidal Activity of samples against aphids
The spray method proposed by the International Resistance Action Committee (IRAC) was used: the tested object is aphid, namely broad bean leaves connected with the aphid are sprayed under a Potter spray tower, the processed aphid is cultured in an observation room at the temperature of 20-22 ℃, and the result is investigated after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The assay concentration was 500. mu.g/mL.
The insecticidal activity data of the target are shown in table 1. As can be seen from Table 1, both targets Ia and Ib have excellent insecticidal effects on aphids. At the concentration tested, 500. mu.g/mL, the insecticidal activity of the targets Ia and Ib on aphids was 100% and 100%, respectively.
TABLE 1 preliminary insecticidal Activity data of Ia-Ib
The test results show that the novel pyrazole compound obtained by connecting the oxazole methoxy biaryl unit and the pyrazole active fragment has good insecticidal effect.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A pyrazole derivative I containing oxazole methoxy biaryl unit is characterized in that the structure is as follows:
2. the preparation method of the pyrazole derivative I containing oxazole methoxy biaryl unit according to claim 1, which is characterized by comprising the following steps:
3. the use of the pyrazole derivative I containing oxazole methoxy biaryl unit according to claim 1 in the preparation of pesticides, wherein: the compound is used alone; or in the form of insecticidal compositions, namely, the compound I in claim 1 is used as an active ingredient, and is added with pesticide auxiliary agents commonly used in the field to be processed into aqueous emulsions, suspending agents, water dispersible granules and emulsifiable concentrates.
4. The use of the pyrazole derivative I containing oxazole methoxy biaryl unit according to claim 3 in the preparation of pesticides, wherein: when the compound I as claimed in claim 1 is used as an active ingredient of an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117728A (en) * | 1993-02-12 | 1996-02-28 | 拜尔公司 | Substituted oxazoles |
| CN104151309A (en) * | 2014-07-03 | 2014-11-19 | 南通大学 | Preparation and application of compound containing 1,3,4-thiadiazole parazole oxime ether |
| CN104193727A (en) * | 2014-08-04 | 2014-12-10 | 南通大学 | Preparation and application of pyrazole oxime ether compound containing trifluoro methyl pyridine |
| CN104961728A (en) * | 2015-05-22 | 2015-10-07 | 南通大学 | Preparation method and application of pyridinyl methoxybiphenyl structure-containing pyrazole oxime ester compound |
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2020
- 2020-06-23 CN CN202010595170.4A patent/CN111635398B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117728A (en) * | 1993-02-12 | 1996-02-28 | 拜尔公司 | Substituted oxazoles |
| CN104151309A (en) * | 2014-07-03 | 2014-11-19 | 南通大学 | Preparation and application of compound containing 1,3,4-thiadiazole parazole oxime ether |
| CN104193727A (en) * | 2014-08-04 | 2014-12-10 | 南通大学 | Preparation and application of pyrazole oxime ether compound containing trifluoro methyl pyridine |
| CN104961728A (en) * | 2015-05-22 | 2015-10-07 | 南通大学 | Preparation method and application of pyridinyl methoxybiphenyl structure-containing pyrazole oxime ester compound |
Non-Patent Citations (5)
| Title |
|---|
| Hong Dai 等.Synthesis and Bioactivities ofNovel Pyrazole Oxime Derivatives Containing a 5-Trifluoromethylpyridyl Moiety.《Molecules》.2016,第21卷1-12. * |
| Hong Dai 等.The thiazoylmethoxy modification on pyrazole oximes: Synthesis and insecticidal biological evaluation beyond acaricidal activity.《Chinese Chemical Letters》.2014,1014–1016. * |
| 戴红 等.新型含取代吡啶环的取代吡唑甲醛肟的合成及生物活性测定.《有机化学》.2015,第35卷2399～2404. * |
| 戴红 等.新型含取代噁二唑结构的吡唑肟类化合物的合成与生物活性研究.《有机化学》.2018,第38卷1755～1762. * |
| 戴红 等.新型含取代噻二唑环结构的吡唑肟类化合物的合成及生物活性研究.《2617～2603》.2015,第35卷2617～2603. * |
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