CN108084173B - Pyrazole compound containing isoxazole structure and preparation method and application thereof - Google Patents
Pyrazole compound containing isoxazole structure and preparation method and application thereof Download PDFInfo
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- 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
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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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Abstract
The invention provides a pyrazole compound containing an isoxazole structure, and a preparation method and application thereof, and belongs to the technical field of organic synthesis. The structure of the compound is shown as I:
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a pyrazole compound containing an isoxazole structure, and a preparation method and application thereof.
Background
Isoxazoles are an important five-membered heterocyclic structure, the skeleton of which is widely present in many compound molecules with broad-spectrum pharmacological and biological activities. Many bioactive compounds having an isoxazole structure have been developed into various agricultural chemicals such as bactericides, herbicides, insecticides, and the like. Such as oxazaphosphorine (Isoxathion), is a broad spectrum contact insecticide; hymexazol is a systemic fungicide with high efficiency, low toxicity and environmental protection.
The pyrazole compounds are nitrogen-containing heterocyclic compounds with broad-spectrum biological activity, and have high efficiency and low toxicity, so that a plurality of compounds containing pyrazole groups have good weeding, insecticidal and bactericidal activities, and are widely applied to the field of pesticides. Such as insecticides: fipronil (Fipronil), Tolfenpyrad (tolfenpyrd), Pyraclofos (Pyraclofos), Tebufenpyrad (fenpropyrid), Fenpyroximate (Fenpyroximate), etc.; and (3) bactericide: fluxapyroxad (Fluxapyroxad), Penthiopyrad (Penthiopyrad), Pyraoxystrobin (Pyraoxystrobin), Bixafen (Bixafen |), and the like.
Therefore, in order to find a new compound with high-efficiency broad-spectrum bioactivity, isoxazolyl and pyrazolyl are reasonably introduced into the same molecule by adopting a substructure connection method, so that a new compound with insecticidal and bactericidal activities is expected to be obtained from the isoxazolyl and the pyrazolyl, and the new compound has very wide research and development prospects.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a pyrazole compound containing an isoxazole structure, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
a pyrazole compound containing an isoxazole structure has a chemical structure shown in formula I:
wherein Ar in the chemical structural formula I is an aromatic group.
In the pyrazole compound containing an isoxazole structure as described above, preferably, the aromatic group is selected from one of the following groups: phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-tert-butylphenyl, 1-naphthyl and 2-furyl.
A preparation method of the pyrazole compound containing the isoxazole structure, which comprises the following steps:
preparation of pyrazole compounds containing isoxazole structures shown in formula I:
(1) adding 5-pyrazolone shown in a formula II and 5-arylalkenyl-3-methyl-4-nitroisoxazole shown in a formula III into a reactor, and adding a solvent for dissolving; adding organic base after dissolving, stirring and reacting for a period of time at room temperature, and detecting whether complete reaction is achieved;
(2) and (2) after the reaction in the step (1) is completed, adding an acetylation reagent into the reaction system, continuously stirring at room temperature for reaction, and after the reaction is completed, washing, extracting, separating, performing rotary evaporation and purifying to obtain the target product pyrazole compound containing the isoxazole structure.
In the preparation method as described above, preferably, in the step (1), it is checked whether or not the reaction has been completed by thin layer chromatography.
In the production method as described above, preferably, in the step (1), the solvent is dichloromethane, toluene, tetrahydrofuran, diethyl ether, chloroform, ethanol or acetonitrile; the organic base is triethylamine, pyridine, diisopropylethylamine or 1, 8-diazabicycloundec-7-ene.
In the production method as described above, preferably, in the step (2), the acetylating reagent is acetyl chloride or acetic anhydride.
In the above-mentioned preparation method, preferably, the molar ratio of the 5-pyrazolone, the 5-aralkenyl-3-methyl-4-nitroisoxazole, the organic base and the acetylating agent are added in the following proportion: the ratio of 5-pyrazolone to 5-aralkenyl-3-methyl-4-nitroisoxazole to organic base to acetylating agent is 1: 1-1.2: 1-1.5: 1-1.2.
In the preparation method, preferably, the amount of the solvent is 20-30 times of the mass of the 5-pyrazolone;
preferably, the reaction time in the step (1) is 11 to 13 hours under stirring at room temperature; still preferably, the reaction time is 12h at room temperature with stirring;
preferably, the reaction time of the step (2) is continuously stirred at room temperature for 1 to 3 hours; more preferably, the reaction time is continued for 2h at room temperature with stirring.
The pyrazole compound containing the isoxazole structure is applied to control of plant harmful insects or plant pathogenic fungi.
The pyrazole compound containing the isoxazole structure is applied to control of plant harmful insects or plant pathogenic fungi, wherein the insects comprise Lepidoptera noctuidae armyworm, Homoptera cicadae Nephotettix cincticeps and Homoptera aphid; the fungi include Rhizoctonia cerealis, Colletotrichum cucumerinum and Magnaporthe grisea. The present invention is not limited to the kinds of harmful insects and fungi, and is within the scope of application of the present invention as long as the pyrazole compound containing an isoxazole structure prepared in the present invention is used for disinsection and sterilization.
Compared with the closest prior art, the technical scheme provided by the invention has the following beneficial effects:
1. the pyrazole compound containing the isoxazole structure, which is shown in the general formula I and has a novel structure, is obtained by introducing isoxazolyl and pyrazolyl into the same molecule by adopting a substructure connection method.
2. The preparation method has the advantages of simple and convenient operation, mild condition, high yield, relatively easy post-treatment and suitability for large-scale preparation.
3. The pyrazole compound containing the isoxazole structure has insecticidal and bactericidal activity, and can be used as an insecticide and a bactericide for preventing and treating plant harmful insects and plant pathogenic fungi.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The specific embodiment of the invention provides a pyrazole compound containing an isoxazole structure, and a preparation method and application thereof.
The pyrazole compound containing the isoxazole structure has a chemical structure shown in a formula I:
wherein Ar in the chemical structural formula I is an aromatic group;
further preferably, the aromatic group is selected from one of the following: phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-tert-butylphenyl, 1-naphthyl or 2-furyl.
The preparation method of the pyrazole compound containing the isoxazole structure in the specific embodiment of the invention comprises the following steps:
preparation of pyrazole compounds containing isoxazole structures shown in formula I:
(1) adding 5-pyrazolone shown in a formula II and 5-arylalkenyl-3-methyl-4-nitroisoxazole shown in a formula III into a reactor, and adding a solvent for dissolving; adding organic base after dissolving, stirring and reacting for a period of time at room temperature, and detecting whether complete reaction is achieved;
(2) and (2) after the reaction in the step (1) is completed, adding an acetylation reagent into the reaction system, continuously stirring at room temperature for reaction, and after the reaction is completed, washing, extracting, separating, performing rotary evaporation and purifying to obtain the target product pyrazole compound containing the isoxazole structure.
Further preferably, thin layer chromatography is used to detect whether the reaction has been completed.
Further preferably, in step (1), the solvent is dichloromethane, toluene, tetrahydrofuran, diethyl ether, chloroform, ethanol or acetonitrile. The organic base is triethylamine, pyridine, diisopropylethylamine or 1, 8-diazabicycloundec-7-ene. In the step (2), the acetylating reagent is acetyl chloride or acetic anhydride.
In the preparation method of the specific embodiment of the invention, 5-pyrazolone, 5-arylalkenyl-3-methyl-4-nitroisoxazole, organic base and acetylating agent are added according to the following molar ratio:
5-pyrazolone, 5-aralkenyl-3-methyl-4-nitroisoxazole, organic base and acetylating agent are 1: 1-1.2 (such as 1.1, 1.13, 1.15, 1.16, 1.18, 1.19) to 1-1.5 (such as 1.1, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45) to 1-1.2 (such as 1.1, 1.13, 1.15, 1.16, 1.18, 1.19).
More preferably, the amount of the solvent is 20 to 30 times (e.g., 21 times, 22 times, 23 times, 24 times, 25 times, 26 times, 27 times, 28 times, 29 times) the mass of the 5-pyrazolone.
Preferably, the reaction time in step (1) is 11-13h (e.g. 11.1h, 11.5h, 12h, 12.3h, 12.5h, 12.8h) with stirring at room temperature; still preferably, the reaction time is 12h at room temperature with stirring;
preferably, the reaction time in step (2) is continued to be stirred at room temperature for 1 to 3h (e.g. 1.1h, 1.5h, 2h, 2.3h, 2.5h, 2.8 h); more preferably, the reaction time is continued for 2h at room temperature with stirring.
The pyrazole compound containing the isoxazole structure has insecticidal and bactericidal activities, can be used as an insecticide and a bactericide for preventing and treating plant harmful insects and plant pathogenic fungi, and can be applied to the field of pesticides.
The compound of the present invention is suitable for controlling plant harmful insects including armyworm of the Lepidoptera family, leafhopper of the Homoptera family, aphid of the Homoptera family and the like. Of course, the plant pests which can be controlled by the compounds according to the invention are not limited to the above-mentioned exemplary ranges, which are not limiting for the invention.
The compounds of the present invention are suitable for the control of phytopathogenic fungi, including Rhizoctonia cerealis, Colletotrichum cucumerinum and Pyricularia oryzae, among others. The phytopathogenic fungi which can be controlled by the compounds according to the invention are, of course, not limited to the scope of the examples given above, and are not to be regarded as limiting the invention.
Preparation examples:
example 1:
adding 5-pyrazolone shown in formula II (1.74g, 10.0mmol) and 5-phenylalkenyl-3-methyl-4-nitroisoxazole shown in formula IIIa (2.76g, 12.0mmol) and 30mL of dichloromethane into a 100mL round-bottomed bottle, then adding triethylamine (2.0mL, 15.0mmol), stirring at room temperature for 12h, and detecting by TLC after the reaction is complete; subsequently, acetyl chloride (0.85mL, 12.0mmol) was added dropwise to the reaction system, the reaction was continued for 2 hours under stirring at room temperature, 50mL of water was added to the reaction system, liquid separation was performed, the aqueous phase was extracted with methylene chloride (30mLx2), the organic phases were combined, and anhydrous MgSO was added4Drying, rotary evaporation and concentration, column chromatography of the residue (eluent: petroleum ether/ethyl acetate 10/1) gave 4.15g of the corresponding target product shown in formula I a as a white solid in 93% yield and a melting point of 40-41 ℃.
1H NMR(400MHz，CDCl3)δ2.11(s，3H)，2.16(s，3H)，2.48(s，3H)，3.88(dd，J＝14.4Hz，8.8Hz，1H)，3.96(dd，J＝14.8Hz，8.0Hz，1H)，4.60(t，J＝8.0Hz，1H)，7.19-7.24(m，1H)，7.25-7.34(m，5H)，7.35-7.46(m，4H)；13C NMR(100MHz，CDCl3)δ172.6，167.2，155.5，147.3，141.4，140.1，137.6，130.5，129.1，128.6，127.3，127.2，127.0，122.7，109.0，37.1，31.5，20.0，13.3，11.5。
Example 2:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone of formula II, 5-p-tolylenyl-3-methyl-4-nitroisoxazole of formula IIIb, triethylamine and acetyl chloride charged was 1: 1.2: 1.5: 1.2, to give 4.19g of the target product of formula Ib as a white solid in 91% yield and 56-57 ℃ melting point.
1H NMR(400MHz，CDCl3)δ2.12(s，3H)，2.17(s，3H)，2.30(s，3H)，2.48(s，3H)，3.88(dd，J＝14.4Hz，8.8Hz，1H)，3.96(dd，J＝14.8Hz，7.6Hz，1H)，4.57(t，J＝7.6Hz，1H)，7.11(d，J＝6.4Hz，2H)，7.19(d，J＝6.8Hz，2H)，7.24-7.34(m，1H)，7.35-7.47(m，4H)；13C NMR(100MHz，CDCl3)δ172.7，167.3，155.5，147.3，141.4，137.6，137.1，136.6，130.4，129.2，128.0，127.3，127.1，122.7，109.1，36.8，31.7，20.9，20.1，13.4，11.5。
Example 3:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone shown in formula II, 5-p-methoxyphenylalkenyl-3-methyl-4-nitroisoxazole shown in formula IIIc, triethylamine and acetyl chloride charged was 1: 1.2: 1.5: 1.2, to give 4.29g of the target product shown in formula I c, as a white solid, in 90% yield and 55-56 ℃ melting point.
1H NMR(400MHz，CDCl3)δ2.07(s，3H)，2.08(s，3H)，2.42(s，3H)，3.69(s，3H)，3.76(dd，J＝14.4Hz，8.0Hz，1H)，3.87(dd，J＝14.8Hz，8.0Hz，1H)，4.47(t，J＝7.6Hz，1H)，6.75(d，J＝7.2Hz，2H)，7.14(d，J＝7.6Hz，2H)，7.18-7.26(m，1H)，7.29-7.39(m，4H)；13C NMR(100MHz，CDCl3)δ172.7，167.4，158.4，155.5，147.3，141.4，137.7，132.2，130.5，129.1，128.3，127.3，122.8，113.9，109.3，55.1，36.5，31.8，20.1，13.4，11.5。
Example 4:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone represented by formula II, 5-p-fluorophenylalkenyl-3-methyl-4-nitroisoxazole represented by formula IIId, triethylamine and acetyl chloride fed was 1: 1.2: 1.5: 1.2, to give 4.37g of the target product represented by formula Id, as a white solid, in a yield of 94%, a melting point of 101-.
1H NMR(400MHz，CDCl3)δ2.06(s，6H)，2.42(s，3H)，3.78(dd，J＝13.6Hz，8.0Hz，1H)，3.86(dd，J＝14.8Hz，7.6Hz，1H)，4.50(t，J＝7.6Hz，1H)，6.91(t，J＝7.6Hz，2H)，7.12-7.27(m，3H)，7.28-7.41(m，4H)；13C NMR(100MHz，CDCl3)δ172.4，167.3，161.6(d，JC-F＝244.6Hz)，155.5，147.2，141.4，137.6，136.0(d，JC-F＝3.0Hz)，130.5，129.1，128.9(d，JC-F＝8.0Hz)，127.4，122.8，115.4(d，JC-F＝21.2Hz)，108.8，36.6，31.7，20.1，13.4，11.5。
Example 5:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone represented by formula II, 5-p-chlorophenylalkenyl-3-methyl-4-nitroisoxazole represented by formula IIIe, triethylamine and acetyl chloride charged was 1: 1.2: 1.5: 1.2, to give 4.42g of the target product represented by formula Ie, as a white solid, in 92% yield and 112 ℃ melting point and 113 ℃.
1H NMR(400MHz，CDCl3)δ2.07(s，6H)，2.42(s，3H)，3.77(dd，J＝13.2Hz，8.0Hz，1H)，3.85(dd，J＝14.4Hz，7.6Hz，1H)，4.49(t，J＝7.6Hz，1H)，7.10-7.27(m，5H)，7.27-7.40(m，4H)；13C NMR(100MHz，CDCl3)δ172.2，167.3，155.5，147.2，141.4，138.7，137.5，132.8，130.5，129.1，128.8，128.7，127.4，122.8，108.6，36.6，31.5，20.1，13.4，11.5。
Example 6:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone represented by formula II, 5-p-bromophenenyl-3-methyl-4-nitroisoxazole represented by formula IIIf, triethylamine and acetyl chloride charged was 1: 1.2: 1.5: 1.2, to give 4.73g of the target product represented by formula If, as a white solid, a yield of 90%, a melting point of 109-.
1H NMR(400MHz，CDCl3)δ2.14(s，3H)，2.15(s，3H)，2.50(s，3H)，3.84(dd，J＝14.8Hz，8.4Hz，1H)，3.93(dd，J＝14.8Hz，8.0Hz，1H)，4.55(t，J＝8.0Hz，1H)，7.18(d，J＝8.0Hz，2H)，7.27-7.34(m，1H)，7.35-7.69(m，6H)；13C NMR(100MHz，CDCl3)δ172.2，167.3，155.6，147.2，141.4，139.3，137.5，131.7，130.5，129.1，129.0，127.5，122.8，121.0，108.5，36.7，31.5，20.1，13.4，11.5。
Example 7:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone shown in formula II, 5-naphthalenyl-3-methyl-4-nitroisoxazole in formula IIIg, triethylamine and acetyl chloride charged was 1: 1.2: 1.5: 1.2, to give 4.22g of the target product shown in formula I g, a colorless oily liquid, a yield of 85%, and a melting point of 45-46 ℃.
1H NMR(400MHz，CDCl3)δ2.05(s，3H)，2.19(s，3H)，2.49(s，3H)，3.98(dd，J＝14.8Hz，8.4Hz，1H)，4.11(dd，J＝14.4Hz，8.0Hz，1H)，4.78(t，J＝8.0Hz，1H)，7.30(t，J＝6.0Hz，1H)，7.36-7.52(m，7H)，7.72-7.85(m，4H)；13C NMR(100MHz，CDCl3)δ172.6，167.3，155.6，147.4，141.6，137.6，137.5，133.1，132.3，130.6，129.1，128.5，127.7，127.5，127.4，126.3，126.1，126.0，125.1，122.8，108.8，37.3，31.5，20.0，13.4，11.5。
Example 8:
the same procedure as in example 1 was followed, and the molar ratio of 5-pyrazolone shown in formula II, 5-furenyl-3-methyl-4-nitroisoxazole shown in formula IIIh, triethylamine and acetyl chloride charged was 1: 1.2: 1.5: 1.2, to give 3.84g of the target product shown in formula I h, as a white solid, 88% yield and 52-53 ℃ melting point.
1H NMR(400MHz，CDCl3)δ2.12(s，3H)，2.18(s，3H)，2.49(s，3H)，3.88(dd，J＝14.4Hz，8.8Hz，1H)，3.96(dd，J＝14.8Hz，8.0Hz，1H)，7.19-7.24(m，2H)，7.25-7.34(m，5H)，7.38(d，J＝4.0Hz，1H)；13C NMR(100MHz，CDCl3)δ172.6，167.2，155.5，147.3，141.4，140.1，137.6，130.5，129.1，128.6，127.3，127.2，127.0，122.7，109.0，37.1，31.5，20.0，13.3，11.5。
The application example is as follows:
example 9:
in this example, the insecticidal activity against plant harmful insects was measured for pyrazoles having an isoxazole structure.
The insecticidal activity test of armyworm (Mythimna sepata) was performed on the compounds I a to I h synthesized in the above examples 1 to 8 by a Potter spray method, and the use concentration was 500 mg/L; the insecticidal activity test of broad bean aphid (Aphis fabae) is carried out on the synthesized compound by adopting a leaf worm simultaneous leaching method, and the using concentration is 500 mg/L; the insecticidal activity of rice leafhopper (Nephotettix bipunctatus) was tested by the dipping plant method for the synthesized compound at a concentration of 500 mg/L.
The results of the insecticidal activity test of the compounds synthesized in examples 1 to 8 are shown in Table 1:
TABLE 1 preliminary insecticidal Activity data for Compounds I a-I h of examples 1-8
The insecticidal activity test results in table 1 show that all pyrazole compounds containing isoxazole structures show certain insecticidal activity. The insecticidal activity of the compounds I d, I e and I f on armyworm, aphid and leafhopper is relatively good, and especially the insecticidal activity of the compound I d is relatively high.
Example 10: in the embodiment, the pyrazole compound containing an isoxazole structure is tested for bactericidal activity against plant pathogenic fungi.
The compounds synthesized in the above examples 1 to 8 were tested for bactericidal activity against Rhizoctonia cerealis (Rhizoctonia cerealis) by the in vitro leaf virus-containing potato agar medium method, and the use concentration was 100 mg/L; the bactericidal activity of cucumber Colletotrichum orbiculosum (Colletotrichum orbicular) was tested on the synthesized compound by hypha growth inhibition method, and the use concentration was 100 mg/L.
The results of the bactericidal activity test of the plant pathogenic fungi on the compounds synthesized in examples 1 to 8 are shown in table 2:
TABLE 2 preliminary bactericidal activity data for compounds I a-I h synthesized in examples 1-8
The bactericidal activity test results in table 2 show that the pyrazole compound containing an isoxazole structure has certain bactericidal activity on two tested fungi. The compounds I d, I e and I f have relatively good inhibitory activity against Rhizoctonia cerealis and Colletotrichum cucumerinum, and particularly the compound I d has relatively high bactericidal activity.
The experimental data show that the isoxazolyl and the pyrazolyl are introduced into the same molecule by adopting a substructure connection method, so that the obtained novel compound shows good biological activity, and the experimental data also provide certain theoretical guidance for the molecular design, synthesis and biological activity research of novel pyrazole compounds containing an isoxazole structure in the future.
In summary, the invention has the following beneficial technical effects:
1. the pyrazole compound containing the isoxazole structure, which is shown in the general formula I and has a novel structure, is obtained by introducing isoxazolyl and pyrazolyl into the same molecule by adopting a substructure connection method.
2. The preparation method has the advantages of simple and convenient operation, mild condition, high yield, relatively easy post-treatment and suitability for large-scale preparation.
3. The pyrazole compound containing the isoxazole structure has insecticidal and bactericidal activity, and can be used as an insecticide and a bactericide for preventing and treating plant harmful insects and plant pathogenic fungi.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (11)
1. The pyrazole compound containing the isoxazole structure is characterized in that the chemical structure of the pyrazole compound containing the isoxazole structure is shown as a formula I:
wherein Ar in the chemical structural formula I is an aromatic group;
the aromatic group is selected from one of the following: phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-tert-butylphenyl, 1-naphthyl and 2-furyl.
2. The process for preparing pyrazole compounds having an isoxazole structure according to claim 1, which comprises the steps of:
preparation of pyrazole compounds containing isoxazole structures shown in formula I:
(1) adding 5-pyrazolone shown in a formula II and 5-arylalkenyl-3-methyl-4-nitroisoxazole shown in a formula III into a reactor, and adding a solvent for dissolving; adding organic base after dissolving, stirring and reacting for a period of time at room temperature, and detecting whether complete reaction is achieved;
(2) after the reaction in the step (1) is completed, adding an acetylation reagent into the reaction system, continuously stirring at room temperature for reaction, and after the reaction is completed, washing, extracting, separating, performing rotary evaporation and purifying to obtain a target product pyrazole compound containing an isoxazole structure;
in the step (1), the solvent is dichloromethane, toluene, tetrahydrofuran, diethyl ether, chloroform, ethanol or acetonitrile;
the organic base is triethylamine, pyridine, diisopropylethylamine or 1, 8-diazabicycloundec-7-ene;
the preparation method comprises the following steps of adding 5-pyrazolone, 5-arylalkenyl-3-methyl-4-nitroisoxazole, organic base and an acetylation reagent according to the following molar ratio: 5-pyrazolone: 5-aralkenyl-3-methyl-4-nitroisoxazole: organic base: the acetylating reagent is 1: 1-1.2: 1-1.5: 1 to 1.2.
3. The method according to claim 2, wherein in the step (1), it is determined whether or not the reaction has been completed by thin layer chromatography.
4. The method according to claim 2, wherein in the step (2), the acetylating reagent is acetyl chloride or acetic anhydride.
5. The method according to claim 2, wherein the amount of the solvent is 20 to 30 times the mass of the 5-pyrazolone.
6. The method according to claim 2, wherein the reaction time in step (1) is 11 to 13 hours at room temperature with stirring.
7. The method according to claim 2, wherein the reaction time in step (1) is 12 hours at room temperature with stirring.
8. The method of claim 2, wherein the reaction time in step (2) is 1 to 3 hours with continued stirring at room temperature.
9. The method according to claim 2, wherein the reaction time in step (2) is 2 hours while stirring at room temperature.
10. Use of the pyrazole compounds containing the isoxazole structure prepared according to the preparation process as claimed in any of claims 2 to 9 for controlling plant harmful insects or phytopathogenic fungi.
11. The use of pyrazole compounds containing an isoxazole structure according to claim 10 for controlling plant harmful insects or phytopathogenic fungi, such insects being myxomyxozoa of the family noctuidae of the order lepidoptera, leafhopper of the family cicadae of the order homoptera and aphids of the family aphidae of the order homoptera;
the fungi are Rhizoctonia cerealis, Colletotrichum cucumerinum and Magnaporthe grisea.
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| CN1189823A (en) * | 1995-04-20 | 1998-08-05 | G·D·瑟尔公司 | Cyclic amidino agents useful as nitric oxide synthase inhibitors |
| CN1216530A (en) * | 1996-04-25 | 1999-05-12 | 日产化学工业株式会社 | Ethylene derivatives and pest controlling agents |
| JP3216673B2 (en) * | 1993-11-26 | 2001-10-09 | 宇部興産株式会社 | Method for producing 3-hydroxyisoxazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3216673B2 (en) * | 1993-11-26 | 2001-10-09 | 宇部興産株式会社 | Method for producing 3-hydroxyisoxazole |
| CN1189823A (en) * | 1995-04-20 | 1998-08-05 | G·D·瑟尔公司 | Cyclic amidino agents useful as nitric oxide synthase inhibitors |
| CN1216530A (en) * | 1996-04-25 | 1999-05-12 | 日产化学工业株式会社 | Ethylene derivatives and pest controlling agents |
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