CN110407828B - Pyrazole-5-amide derivative containing oxazole structure and preparation method and application thereof - Google Patents
Pyrazole-5-amide derivative containing oxazole structure and preparation method and application thereof Download PDFInfo
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- CN110407828B CN110407828B CN201910763701.3A CN201910763701A CN110407828B CN 110407828 B CN110407828 B CN 110407828B CN 201910763701 A CN201910763701 A CN 201910763701A CN 110407828 B CN110407828 B CN 110407828B
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- pyrazole
- amide derivative
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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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- 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
Abstract
The invention relates to a pyrazole-5-amide derivative (I) containing an oxazole structure, and a preparation method and application thereof. Obtained by condensing pyrazole formyl chloride (II) and oxazole methylamine (III). The pyrazole-5-amide derivative containing the oxazole structure has an effective 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, and particularly relates to a pyrazole-5-amide derivative containing an oxazole structure, and a preparation method and application thereof.
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 drug resistance of the traditional pesticide varieties becomes more and more prominent, and the continuous research and development of new pesticides become necessary choices due to the continuous emergence of new plant diseases and insect pests.
The substituted pyrazole ring is widely applied in agricultural production, the pyrazole compound has excellent insecticidal and acaricidal activity, and the pyrazole heterocycle is widely introduced into pesticide compound molecules, such as pyraclostrobin, tebufenpyrad and tolfenpyrad, and has excellent killing activity on mites, aphids and the like.
Oxazole rings are also important nitrogen-containing heterocycles, oxazole derivatives play an important role in the field of pesticides, and in recent years, many researches report that oxazole derivatives have good insecticidal activity.
Therefore, in order to further search for a compound with excellent biological activity from the pyrazole amide derivatives, the pyrazole amide skeleton and an oxazole unit are reasonably and organically linked together by adopting an active group splicing method, and the invention discloses a pyrazole-5-amide derivative containing an oxazole structure with agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole amide compound containing an oxazole structure, which has excellent control effect on various pests, is efficient, safe 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-5-amide derivative containing an oxazole structure, which has a structure shown in a general formula I,
preferably, the pyrazole-5-amide derivative containing the oxazole structure has the following structure:
the second aspect of the present invention provides a preparation method of the above pyrazole-5-amide derivative containing an oxazole structure, which comprises the following steps:
dissolving a compound III in an organic solvent, adding an acid-binding agent, adding an intermediate II, 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 an obtained residue to obtain a target compound,
preferably, the acid scavenger is selected from pyridine, triethylamine and N, N-Diisopropylethylamine (DIPEA), and the solvent is selected from N, N-Dimethylformamide (DMF), dichloromethane and chloroform. The heating reaction temperature is 0-80 ℃, and the reaction time is 9-20 hours.
Preferably, the preparation method of the pyrazole-5-amide derivative containing the oxazole structure comprises the following steps:
among them, 2-aryloxazol-4-methylamine intermediate III can be synthesized by a method described in reference to literature (chi. chem. lett.2015,26,672); pyrazole formyl chloride intermediates II were synthesized according to the methods described in J.Agric.food chem.2013,61, 8730-8736.
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. The insects comprise lepidoptera pests such as cotton bollworms, asparagus caterpillars, diamond back moths, cabbage caterpillars, rice leaf rollers, chilo suppressalis and the like; homoptera pests such as leafhopper, plant hopper, vermin, whitefly, coccid of psyllidae, etc.; dipteran pests such as houseflies, leaf miner, mosquitoes, etc.; locusts of the order orthoptera, pests of the order Coleoptera, longicorn beetles, scarab beetles, weevils, and the like; stinkbugs of the order hemiptera, 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-5-amide derivative containing the oxazole structure disclosed by the invention has an excellent control effect on harmful insects, so that the pyrazole-5-amide derivative can be used for preparing insecticides 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:
4mmol of compound IIIa are dissolved in 30mL of chloroform, followed by addition of 20mmol of pyridine and subsequent addition of 6mmol of intermediate IIa thereto under ice-bath conditions. After the addition, the ice-bath reaction was continued for 9 hours. Stopping the reaction, carrying out reduced pressure rotary evaporation on the reaction liquid until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain a target compound Ia;1H NMR(400MHz,CDCl3):δ8.46～8.47(m,1H,Py-H),8.03～8.08(m,2H,Ar-H),7.93(d,J＝8.8Hz,2H,Ar-H),7.86～7.88(m,1H,Py-H),7.77(s,1H,Oxazole-H),7.61(s,1H,Oxazole-H),7.45(d,J＝8.8Hz,2H,Ar-H),7.34-7.39(m,1H,Py-H),7.12-7.17(m,2H,Ar-H),6.96(s,1H,NH),6.29(s,1H,Pyrazole-H),5.29(s,2H,CH2),4.45(d,J＝5.2Hz,2H,CH2).
example 2:
3mmol of compound IIIa are dissolved in 30mL of dichloromethane, followed by addition of 2mL of triethylamine and subsequently 5mmol of intermediate IIb are added thereto under ice-bath conditions. After the addition, the reaction was heated under reflux for 15 hours. Stopping the reaction, carrying out reduced pressure rotary evaporation on the reaction liquid until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain a target compound Ib;1H NMR(400MHz,CDCl3):δ8.46～8.47(m,1H,Py-H),7.86～7.97(m,5H,Py-H,Ar-H and Oxazole-H),7.61(s,1H,Oxazole-H),7.51(d,J＝2.0Hz,1H,Ar-H),7.45(d,J＝8.4Hz,2H,Ar-H),7.32-7.38(m,2H,Py-H and Ar-H),6.99(s,1H,NH),6.30(s,1H,Pyrazole-H),5.32(s,2H,CH2),4.45(d,J＝5.6Hz,2H,CH2).
example 3:
6mmol of compound IIIb are dissolved in 30mL of DMF, followed by addition of 15mmol of DIPEA and subsequent addition of 7mmol of intermediate IIa thereto under ice-bath conditions. After the addition, the mixture is heated to 80 ℃ for reaction for 20 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ic.1H NMR(400MHz,CDCl3):δ8.46～8.48(m,1H,Py-H),8.01～8.05(m,2H,Ar-H),7.87～7.89(m,1H,Py-H),7.72～7.82(m,3H,Ar-H and Oxazole-H),7.59(s,1H,Oxazole-H),7.35～7.38(m,1H,Py-H),7.21～7.26(m,1H,Ar-H),7.09～7.15(m,3H,Ar-H and NH),6.29(s,1H,Pyrazole-H),5.28(s,2H,CH2),4.45(d,J＝5.6Hz,2H,CH2).
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 into a culture dish filled with filter paper, 10 heads/dish of armyworm larvae in the 3-instar middle stage are connected, the corn leaves are placed into an observation room for culture at 24-27 ℃, and the result is investigated after 2 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration was 500. mu.g/mL (other concentrations of drug solution could be diluted with 500. mu.g/mL).
The insecticidal activity test result shows that all the compounds have insecticidal activity. At the tested dose of 500. mu.g/mL (Table 1), the insecticidal activity of compounds Ia, Ib and ic against armyworm was all better, with killing rates of 100%, 100% and 90%, respectively.
TABLE 1 preliminary insecticidal Activity data for Ia-Ic
The experimental data show that the novel compound obtained by reasonably combining the substituted oxazole structure and the pyrazole amide active units shows good biological activity, and the experimental data also provide important structure selection modes and theoretical bases for continuing to carry out molecular design, synthesis and biological activity research of novel pyrazole amide derivatives in the future.
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-5-amide derivative I containing an oxazole structure is characterized by having a structure as follows:
2. the preparation method of pyrazole-5-amide derivatives I containing oxazole structure as claimed in claim 1, characterized by the following steps:
3. the application of the pyrazole-5-amide derivative I containing the oxazole structure in preparing the armyworm killing medicament according to claim 1, which is characterized in that: the compound is used alone; or in the form of an insecticidal composition, namely the compound I is used as an active ingredient and is added with pesticide auxiliaries commonly used in the field to be processed into an aqueous emulsion, a suspending agent, a water dispersible granule and an emulsifiable concentrate.
4. The application of the pyrazole-5-amide derivative I containing the oxazole structure in preparing the armyworm killing medicament according to claim 3, wherein the pyrazole-5-amide derivative I comprises the following components in percentage by weight: when compound I is used as an active ingredient of an anti-myxocidal drug, the content in the anti-myxocidal drug is selected in the range of 0.1% to 99.5%.
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| CN110922397B (en) * | 2019-11-19 | 2022-12-23 | 南通大学 | Preparation method and application of 3- (pyrazole biphenyl methoxy) pyrazole derivative containing substituted isoxazole unit |
| CN110845487B (en) * | 2019-11-19 | 2022-12-09 | 南通大学 | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof |
| CN110845488B (en) * | 2019-11-19 | 2022-12-27 | 南通大学 | Preparation method and application of 3- (benzotriazole benzyloxy) pyrazole derivative containing aryl isoxazole |
| CN111253384B (en) * | 2020-04-01 | 2023-04-07 | 南通大学 | Preparation and application of 3-isoxazole methoxy pyrazole-5-amide containing substituted phenyl isoxazole unit |
| CN111285864B (en) * | 2020-04-01 | 2022-10-11 | 南通大学 | Preparation and application of p-chlorophenyl isoxazole methoxy pyrazole derivative containing isoxazole heterocyclic unit |
| CN111303140B (en) * | 2020-04-01 | 2022-10-14 | 南通大学 | Pyrazole derivative containing substituted isoxazole unit and preparation method and application thereof |
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| CN109879868A (en) * | 2019-03-07 | 2019-06-14 | 南通大学 | The preparation and application of the pyrazol acid amide compounds of the oxazole structure of aryl containing 2- |
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| CN109879868A (en) * | 2019-03-07 | 2019-06-14 | 南通大学 | The preparation and application of the pyrazol acid amide compounds of the oxazole structure of aryl containing 2- |
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