CN111253384B - Preparation and application of 3-isoxazole methoxy pyrazole-5-amide containing substituted phenyl isoxazole unit - Google Patents
Preparation and application of 3-isoxazole methoxy pyrazole-5-amide containing substituted phenyl isoxazole unit Download PDFInfo
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- CN111253384B CN111253384B CN202010248869.3A CN202010248869A CN111253384B CN 111253384 B CN111253384 B CN 111253384B CN 202010248869 A CN202010248869 A CN 202010248869A CN 111253384 B CN111253384 B CN 111253384B
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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
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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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
- A01N43/80—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 1,2
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention relates to a preparation method and application of 3-isoxazole methoxyl pyrazole-5-amide (I) containing substituted phenyl isoxazole unit. Obtained by condensation of 3-isoxazole methoxy pyrazole-5-acyl chloride (II) and substituted phenyl isoxazole methylamine (III). The 3-isoxazolyl methoxyl pyrazole-5-amide containing the substituted phenyl isoxazole unit has an effective prevention and control effect on harmful insects, and the compound can be used for preparing insecticides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, in particular to preparation and application of 3-isoxazole methoxyl pyrazole-5-amide containing substituted phenyl isoxazole units.
Background
The prevention and control of pests are always the core field of pesticide science research, and the wide use of pesticides enables most pests to be effectively treated. However, with the continuous expansion of the application scale of the pesticide, the problem of the drug resistance of the traditional pesticide varieties becomes more and more prominent, and the continuous research and development of new pesticides become a necessary choice in addition to the continuous emergence of new plant diseases and insect pests.
The pyrazole amide serving as an important nitrogen-containing heterocyclic compound has wide application in the field of plant protection, and typical representatives of pyrazole amide insecticides, namely tolfenpyrad and tebufenpyrad.
Isoxazole rings, which are important members of the family of nitrogen-containing heterocycles, have also played a very important role in recent years in the field of plant protection.
Therefore, in order to further search and discover compounds with excellent biological activity from pyrazole amide and reasonably combine pyrazole amide units and isoxazole structures, the invention discloses a 3-isoxazole methoxy pyrazole-5-amide containing substituted phenyl isoxazole units, which has agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide 3-isoxazole methoxyl pyrazole-5-amide containing substituted phenyl isoxazole units, which has excellent control effect on various pests, is efficient, safe and environment-friendly, and meets the requirement of the field of crop protection on high-efficiency insecticides.
It is a further object of the present invention to provide the use of the above compounds in the preparation of insecticides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
In order to solve the technical problems, the invention provides a 3-isoxazole methoxy pyrazole-5-amide containing a substituted phenyl isoxazole unit, which has a structure shown in a general formula I,
preferably, the 3-isoxazole methoxy pyrazole-5-amide containing the substituted phenyl isoxazole unit has the following structure:
a second aspect of the present invention provides a process for the preparation of 3-isoxazole methoxy pyrazole-5-amides containing substituted phenylisoxazole units as described above, which comprises the steps of:
dissolving the intermediate III in an organic solvent, adding an acid-binding agent, then adding the intermediate II, finally reacting for a period of time, carrying out suction filtration on a reaction solution, carrying out reduced pressure concentration on a mother solution, separating and purifying obtained residues to obtain a target substance I,
preferably, the 3-isoxazole methoxy pyrazole-5-amide containing the substituted phenyl isoxazole unit is prepared as follows:
wherein, the intermediate II is synthesized by the method of reference literature (J.Agric.food chem.2013,61, 8730-8736); intermediate III was synthesized according to the procedures described in the literature (J.Med.chem.1998, 41, 2390-2410).
The compound of the general formula I has excellent control activity on insects, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture 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 of the formula I as active ingredients can be used in the concentration range from 1 to 1000. Mu.g/mL in water emulsions, suspensions, water-dispersible granules, emulsifiable concentrates, preferably in concentrations from 1 to 500. Mu.g/mL.
The 3-isoxazole methoxyl pyrazole-5-amide containing the substituted phenyl isoxazole unit has good insecticidal effect on harmful insects, and can be used for preparing insecticides 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:
12mmol of intermediate IIIa were dissolved in 35mL of 1, 2-dichloroethane, 28mmol of DIPEA (N, N-diisopropylethylamine) was added, and 12mmol of intermediate IIa was added thereto under ice bath conditions. After the addition, the reaction was heated under reflux for 20 hours. Stopping the reaction, carrying out reduced pressure rotary evaporation on the reaction liquid until the reaction liquid is dried, and separating the obtained crude product through column chromatography to obtain a target compound Ia; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.48(m,1H,Py-H),7.88～7.91(m,1H,Py-H),7.57～7.63(m,6H,Ar-H),7.37～7.40(m,1H,Py-H),7.24(d,J＝8.0Hz,3H,Ar-H and NH),6.68(s,1H,Isoxazole-H),6.42(s,1H,Isoxazole-H),6.34(s,1H,Pyrazole-H),5.41(s,2H,CH 2 ),4.57(d,J＝6.0Hz,2H,CH 2 ),2.39(s,3H,CH 3 ).
example 2:
15mmol of intermediate IIIb were dissolved in 50mL of N, N-Dimethylformamide (DMF), and 30mmol of sodium carbonate were added, followed by addition of 20mmol of intermediate IIa thereto under ice bath conditions. After the addition, the mixture was heated to 90 ℃ and reacted for 15 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and separating the obtained crude product by column chromatography to obtain a target object Ib; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.47(m,1H,Py-H),7.89～7.91(m,1H,Py-H),7.58～7.66(m,6H,Ar-H),7.38～7.43(m,3H,Ar-H and Py-H),7.15(s,1H,NH),6.68(s,1H,Isoxazole-H),6.47(s,1H,Isoxazole-H),6.34(s,1H,Pyrazole-H),5.42(s,2H,CH 2 ),4.59(d,J＝5.6Hz,2H,CH 2 ).
example 3:
5mmol of the compound IIIc are dissolved in 25mL of dichloromethane, 20mmol of pyridine are then added, and 8mmol of the intermediate IIa are subsequently added thereto under ice-bath conditions. After addition, stirring was continued at room temperature for 16 hours. Stopping the reaction, carrying out reduced pressure rotary evaporation on the reaction liquid until the reaction liquid is dried, and separating the obtained crude product through column chromatography to obtain a target Ic; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.48(m,1H,Py-H),7.88～7.91(m,1H,Py-H),7.57～7.66(m,6H,Ar-H),7.37～7.40(m,1H,Py-H),7.23(s,1H,NH),6.94(d,J＝8.8Hz,2H,Ar-H),6.68(s,1H,Isoxazole-H),6.34(s,2H,Isoxazole-H and Pyrazole-H),5.41(s,2H,CH 2 ),4.57(d,J＝5.6Hz,2H,CH 2 ),3.84(s,3H,OCH 3 ).
example 4:
insecticidal activity screening of samples against armyworm
The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the target for testing is armyworm, namely, a proper amount of corn leaves are fully soaked in prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed in a culture dish filled with filter paper, 10 heads/dish of larvae in the 3-instar middle period of the armyworm are connected, the corn leaves are placed in an observation room at 24-27 ℃ for culture, and the result is investigated after 48 hours. If the body of the insect is touched by a writing brush, the dead insect is determined to be no response. The test concentration was 500. Mu.g/mL (other concentrations of drug solution could be diluted with 500. Mu.g/mL).
The results of the insecticidal activity test showed that at the tested concentration of 500. Mu.g/mL (Table 1), the compounds Ia, ib and ic all exhibited good insecticidal activity against armyworm with 100%,100% and 100% insecticidal effect, respectively.
Preliminary insecticidal Activity data of Ia-Ic
The experimental data show that the novel compound obtained by reasonably splicing the isoxazole heterocyclic structural unit and the pyrazole amide skeleton shows good biological activity.
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. A3-isoxazole methoxy pyrazole-5-amide (I) containing a substituted phenylisoxazole unit is characterized by having the structure:
2. a process for the preparation of 3-isoxazolemethoxypyrazole-5-amides (I) containing substituted phenylisoxazole units according to claim 1, characterized by the following steps:
3. use of 3-isoxazolemethoxypyrazole-5-carboxamide containing substituted phenylisoxazole units (I) according to claim 1 for the preparation of a medicament against armyworms, characterized in that: the compound is used alone; or in the form of insecticidal compositions, i.e. aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates, formulated with the compound (I) according to claim 1 as the active ingredient, together with customary agrochemical adjuvants in the art.
4. Use of 3-isoxazolemethoxypyrazole-5-carboxamide containing substituted phenylisoxazole units (I) according to claim 3 for the preparation of a medicament against armyworms, characterized in that: when the compound (I) of claim 1 is used as an active ingredient of an anti-mythimnic agent, the content in the anti-mythimnic agent 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 |
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| CN110407828A (en) * | 2019-08-19 | 2019-11-05 | 南通大学 | A kind of pyrazoles -5- amide derivatives of the structure containing oxazole and its preparation method and application |
| CN110845488A (en) * | 2019-11-19 | 2020-02-28 | 南通大学 | Preparation method and application of 3- (benzotriazole benzyloxy) pyrazole derivative containing aryl isoxazole |
| CN110845487A (en) * | 2019-11-19 | 2020-02-28 | 南通大学 | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof |
| CN110922397A (en) * | 2019-11-19 | 2020-03-27 | 南通大学 | Preparation method and application of 3- (pyrazolylbiphenylmethoxy) pyrazole derivative containing substituted isoxazole unit |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407828A (en) * | 2019-08-19 | 2019-11-05 | 南通大学 | A kind of pyrazoles -5- amide derivatives of the structure containing oxazole and its preparation method and application |
| CN110845488A (en) * | 2019-11-19 | 2020-02-28 | 南通大学 | Preparation method and application of 3- (benzotriazole benzyloxy) pyrazole derivative containing aryl isoxazole |
| CN110845487A (en) * | 2019-11-19 | 2020-02-28 | 南通大学 | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof |
| CN110922397A (en) * | 2019-11-19 | 2020-03-27 | 南通大学 | Preparation method and application of 3- (pyrazolylbiphenylmethoxy) pyrazole derivative containing substituted isoxazole unit |
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