CN111471042A - Pyrazole compound containing substituted phenyl oxadiazole structure and preparation method and application thereof - Google Patents
Pyrazole compound containing substituted phenyl oxadiazole structure and preparation method and application thereof Download PDFInfo
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- CN111471042A CN111471042A CN202010463819.7A CN202010463819A CN111471042A CN 111471042 A CN111471042 A CN 111471042A CN 202010463819 A CN202010463819 A CN 202010463819A CN 111471042 A CN111471042 A CN 111471042A
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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
- A01N43/82—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 three ring hetero atoms
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Abstract
The invention relates to a pyrazole compound (I) containing a substituted phenyl oxadiazole structure, and a preparation method and application thereof. Is obtained by condensing substituted pyrazole acyl chloride (II) and substituted phenyl oxadiazole methylamine (III). The pyrazole compound containing the substituted phenyl oxadiazole structure has a good control effect on harmful insects, and can be 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, in particular to a pyrazole compound containing a substituted phenyl oxadiazole structure, and a preparation method and application thereof.
Background
The pest control is always the core field of pesticide science research, and the use of pesticides enables most pests to be effectively controlled. However, with the increasing application range of pesticides, the problem of drug resistance of traditional pesticides is increasingly revealed, which requires vast pesticide scientists to develop novel efficient and low-toxicity pesticides.
The pyrazole compounds are important nitrogen-containing heterocyclic compounds and have wide application in the field of agricultural production, such as pyrazole insecticides, fipronil and tebufenpyrad.
Oxadiazole derivatives play an important role in plant protection in recent years as important nitrogen-containing heterocycles.
Therefore, in order to further search for a new compound with a better insecticidal effect from pyrazole compounds and reasonably combine a pyrazole unit and an oxadiazole structure, the invention discloses a pyrazole compound containing a substituted phenyl oxadiazole structure and having an agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole compound containing a substituted phenyl oxadiazole structure, which has a good control effect on pests such as armyworm and the like, is efficient and environment-friendly, and meets the requirement of crop protection on efficient pesticides.
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 pyrazole compound containing a substituted phenyl oxadiazole structure, which has a structure shown in a general formula I,
preferably, the pyrazole compound containing the substituted phenyl oxadiazole structure has the following structure:
preferably, the preparation method of the pyrazole compound containing the substituted phenyl oxadiazole structure comprises the following steps:
wherein, the substituted pyrazole acyl chloride intermediate is prepared by the method of reference literature (J.Agric.food chem.2013,61, 8730-8736); substituted phenyl oxadiazole methylamine intermediate reference (Chemical Reagents 2004,26, 99-100).
The compound of the general formula I has good insecticidal effect on insects such as armyworm and the like, so that the compound can be used for preparing insecticides and further protecting plants such as 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 use of the insecticide of the present invention, a commonly used application method such as stem and leaf spray, water surface application, soil treatment, seed treatment and the like can be selected, for example, when stem and leaf spray is employed, an aqueous emulsion, suspension, water-dispersible granule, emulsifiable concentrate of the compound represented by the general formula I as an active ingredient can be used in a concentration range of 1 to 1000 μ g/m L, preferably in a concentration of 1 to 500 μ g/m L.
The pyrazole compound containing the substituted phenyl oxadiazole structure disclosed by the invention has an excellent control effect on pest armyworms, so that the pyrazole compound 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. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present 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:
adding 10mmol of compound IIIa, 50mmol of triethylamine and 30m of L dichloromethane into a reaction bottle, adding 12mmol of intermediate II into the reaction bottle under the ice bath condition, reacting for 8 hours at room temperature after adding, stopping the reaction, and reactingConcentrating the solution to be dry, and carrying out column chromatography separation on the obtained crude product to obtain a target compound Ia;1H NMR(CDCl3,400MHz):8.46(d,J＝4.0Hz,1H,Py-H),7.94(s,1H,Pyrazole-H),7.87～7.89(m,1H,Py-H),7.83(d,J＝8.4Hz,2H,Ar-H),7.76(d,J＝8.0Hz,3H,Pyrazole-H and Ar-H),7.71(d,J＝8.0Hz,2H,Ar-H),7.54(d,J＝8.0Hz,2H,Ar-H),7.36～7.39(m,1H,Py-H),7.20(s,1H,NH),6.49(s,1H,Pyrazole-H),6.37(s,1H,Pyrazole-H),5.34(s,2H,CH2),4.78(d,J＝4.0Hz,2H,CH2).
example 2:
adding 10mmol of a compound IIIb, 30mmol of sodium bicarbonate and 30m L of trichloromethane into a reaction bottle, adding 9mmol of an intermediate II under an ice bath condition, heating and refluxing for reaction for 12 hours after adding, stopping the reaction, concentrating the reaction liquid to be dry, and separating the obtained crude product by column chromatography to obtain a target compound Ib;1H NMR(CDCl3,400MHz):8.46～8.48(m,1H,Py-H),7.88～8.03(m,4H,Pyrazole-H,Py-H and Ar-H),7.68～7.73(m,3H,Ar-H andPyrazole-H),7.53(d,J＝8.4Hz,2H,Ar-H),7.36～7.49(m,3H,Py-H,Ar-H and NH),6.47(s,1H,Pyrazole-H),6.37(s,1H,Pyrazole-H),5.33(s,2H,CH2),4.76(d,J＝4.8Hz,2H,CH2).
example 3:
adding 8mmol of a compound IIIc, 50mmol of N, N-Diisopropylethylamine (DIPEA) and 35m L DMF into a reaction bottle, adding 13mmol of an intermediate II into the reaction bottle under an ice bath condition, stirring the mixture at room temperature for 15 hours, stopping the reaction, concentrating the reaction solution to dryness, and separating the obtained crude product by column chromatography to obtain a target compound Ic;1H NMR(CDCl3,400MHz):8.46～8.48(m,1H,Py-H),7.98～8.03(m,1H,Ar-H),7.93(d,J＝2.0Hz,1H,Pyrazole-H),7.87～7.89(m,1H,Py-H),7.74(s,1H,Pyrazole-H),7.69(d,J＝8.4Hz,2H,Ar-H),7.52(d,J＝8.4Hz,2H,Ar-H),7.35～7.38(m,2H,Py-H and NH),6.95～7.03(m,2H,Ar-H),6.48(s,1H,Pyrazole-H),6.35(s,1H,Pyrazole-H),5.32(s,2H,CH2),4.78(d,J＝5.2Hz,2H,CH2).
example 4:
adding 9mmol of a compound IIId, 35mmol of triethylamine and 30m L DMSO into a reaction bottle, adding 18mmol of an intermediate II under an ice bath condition, stirring at room temperature for 10 hours after adding, stopping the reaction, concentrating the reaction solution to dryness, and separating the obtained crude product by column chromatography to obtain a target object Id;1H NMR(CDCl3,400MHz):8.46～8.48(m,1H,Py-H),7.92(d,J＝8.0Hz,3H,Ar-H and Pyrazole-H),7.87～7.90(m,1H,Py-H),7.69～7.73(m,3H,Ar-H and Pyrazole-H),7.54(d,J＝8.4Hz,2H,Ar-H),7.35～7.38(m,1H,Py-H),7.28(d,J＝8.0Hz,2H,Ar-H),7.16(s,1H,NH),6.47～6.48(m,1H,Pyrazole-H),6.37(s,1H,Pyrazole-H),5.34(s,2H,CH2),4.77(d,J＝5.2Hz,2H,CH2),2.42(s,3H,CH3).
example 5:
adding 12mmol of a compound IIIe, 30mmol of pyridine and 35m L2-butanone into a reaction bottle, adding 20mmol of an intermediate II into the reaction bottle under an ice bath condition, heating and refluxing the reaction liquid for 26 hours after the addition, stopping the reaction, concentrating the reaction liquid to be dry, and separating the obtained crude product by column chromatography to obtain a target product Ie;1H NMR(CDCl3,400MHz):8.47(d,J＝3.6Hz,1H,Py-H),8.16(d,J＝8.0Hz,2H,Ar-H),7.93(s,1H,Pyrazole-H),7.88～7.90(m,1H,Py-H),7.70～7.75(m,5H,Ar-H and Pyrazole-H),7.54(d,J＝8.4Hz,2H,Ar-H),7.36～7.39(m,1H,Py-H),7.22(s,1H,NH),6.48(s,1H,Pyrazole-H),6.37(s,1H,Pyrazole-H),5.34(s,2H,CH2),4.80(d,J＝4.8Hz,2H,CH2).
example 6:
insecticidal activity screening of samples against armyworm
The method comprises soaking corn leaves in prepared medicinal liquid, naturally drying in the shade, placing into a culture dish filled with filter paper, inoculating 10 heads/dish of 3-year-old middle-stage larva of armyworm, culturing at 24-27 deg.C in an observation room, and examining the result after 48 hr, wherein the larva is touched with a writing brush and has no response, and the test dosage is 500 μ g/m L (other medicinal liquid is diluted with 500 μ g/m L).
The insecticidal activity test data of the objects Ia to ie are shown in Table 1. the objects Ia to ie showed good control of armyworm at the test dose of 500. mu.g/m L, and the insecticidal activities were 100%, 100%, 100%, 100% and 100%, respectively.
TABLE 1 Primary insecticidal Activity data for Ia-Ie
The experimental data show that the novel compound formed by combining the pyrazole unit and the oxadiazole structure has good insecticidal 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 (3)
1. A pyrazole compound I containing a substituted phenyl oxadiazole structure is characterized by having a structure as follows:
2. the process for preparing pyrazole compounds I containing substituted phenyl oxadiazole structure according to claim 1, characterized by the following steps:
3. the use of the pyrazole compound I containing a substituted phenyl oxadiazole structure according to claim 1 for preparing insecticides.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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