CN111303140B - Pyrazole derivative containing substituted isoxazole unit and preparation method and application thereof - Google Patents
Pyrazole derivative containing substituted isoxazole unit and preparation method and application thereof Download PDFInfo
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- CN111303140B CN111303140B CN202010248868.9A CN202010248868A CN111303140B CN 111303140 B CN111303140 B CN 111303140B CN 202010248868 A CN202010248868 A CN 202010248868A CN 111303140 B CN111303140 B CN 111303140B
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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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Abstract
The invention relates to a pyrazole derivative (I) containing a substituted isoxazole unit, and a preparation method and application thereof. Obtained by the reaction of isoxazolemethylamine (II) with pyrazolecarbonyl chloride (III). The pyrazole derivative containing the substituted isoxazole unit 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, in particular to a pyrazole derivative containing a substituted isoxazole unit, 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 is increasingly prominent, the influence on non-target organisms and the huge pollution to the environment are ignored, and the continuous occurrence of new plant diseases and insect pests makes the continuous research and development of new pesticides an inevitable choice.
The pyrazole derivatives are important nitrogen-containing heterocyclic compounds and have wide application in agricultural production, such as pyrazole insecticide tolfenpyrad and pyrazole acaricide fenpyroximate.
Isoxazole compounds are also important nitrogen-containing heterocyclic compounds and play an important role in the field of pesticides.
Therefore, in order to further search for a compound with good biological activity from pyrazole compounds, a pyrazole skeleton and an isoxazole unit are organically combined together, and the invention discloses a pyrazole derivative containing a substituted isoxazole unit and having agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole derivative containing a substituted isoxazole unit, which has excellent control effect on various pests and is efficient, safe and environment-friendly so as to meet the requirement of crop protection on efficient pesticides.
The invention also aims to provide the application of the compound in preparing pesticides.
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 derivative containing a substituted isoxazole unit, which has a structure shown in a general formula I,
preferably, the pyrazole derivative containing the substituted isoxazole unit has the following structure:
the second aspect of the present invention provides a method for preparing pyrazole derivatives containing substituted isoxazole units, which comprises the following steps:
dissolving the compound II in an organic solvent, adding an acid-binding agent, adding the intermediate III, reacting for a period of time, filtering the reaction solution, concentrating the mother liquor under reduced pressure, separating and purifying the obtained residue to obtain the target compound,
preferably, the acid scavenger is selected from pyridine, triethylamine, 4-Dimethylaminopyridine (DMAP) and sodium carbonate, and the solvent is selected from 1,4-dioxane, dichloromethane, acetone and acetonitrile.
Preferably, a pyrazole derivative containing a substituted isoxazole unit is prepared as follows:
the intermediate II can be synthesized by a method described in the literature (Chemical Reagents 2004,26,99-100); intermediate III was synthesized according to the methods described in the literature (j.agric.food chem.2013,61, 8730-8736).
The compound of the general formula I has excellent control effect on armyworm, aphid, diamondback moth and other insects, so that the compound can be used for preparing pesticides to protect agricultural and horticultural plants. 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 creams contain from 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably from 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 substituted isoxazole unit disclosed by the invention has an excellent control effect on harmful insects, and therefore, 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:
8mmol of compound IIa was dissolved in 30mL1, 4-dioxane, followed by addition of 30mmol of pyridine, and then intermediate IIIa 9mmol was added thereto under ice-bath conditions. After the addition, the reaction was heated under reflux for 13 hours. Stopping the reaction, carrying out reduced pressure rotary evaporation on the reaction liquid until the reaction liquid is dry,separating the obtained crude product by column chromatography to obtain a target compound Ia; 1 H NMR(CDCl 3 ,400MHz)δ:8.47～8.48(m,1H,Py-H),7.89～7.92(m,1H,Py-H),7.50～7.84(m,4H,Ar-H),7.35～7.43(m,3H,Ar-H and Py-H),7.23(s,1H,NH),7.12～7.16(m,2H,Ar-H),6.62(s,1H,Isoxazole-H),6.48(s,1H,Isoxazole-H),6.34(s,1H,Pyrazole-H),5.41(s,2H,CH 2 ),4.58～4.63(m,2H,CH 2 ).
example 2:
6mmol of the compound IIb was dissolved in 25mL of dichloromethane, followed by the addition of 30mmol of triethylamine, and then the intermediate IIIa 8mmol was added thereto under ice-bath conditions. After the addition, stirring in ice bath was continued for 10 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 on the obtained crude product to obtain a target object Ib; 1 H NMR(CDCl 3 ,400MHz)δ:8.48(d,J＝3.6Hz,1H,Py-H),7.90(d,J＝7.6Hz,1H,Py-H),7.74～7.77(m,2H,Ar-H),7.61(d,J＝8.0Hz,2H,Ar-H),7.38～7.41(m,1H,Py-H),7.12～7.26(m,5H,Ar-H and NH),6.63(s,1H,Isoxazole-H),6.42(s,1H,Isoxazole-H),6.34(s,1H,Pyrazole-H),5.42(s,2H,CH 2 ),4.59(d,J＝4.0Hz,2H,CH 2 ),2.39(s,3H,CH 3 ).
example 3:
8mmol of Compound IIc was dissolved in 20mL of acetone, followed by addition of 20mmol of 4-Dimethylaminopyridine (DMAP), and then 8mmol of intermediate III 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 Ic; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.48(m,1H,Py-H),7.89～7.91(m,1H,Py-H),7.69～7.76(m,4H,Ar-H),7.38～7.41(m,1H,Py-H),7.23(s,1H,NH),7.11～7.16(m,4H,Ar-H),6.62(s,1H,Isoxazole-H),6.43(s,1H,Isoxazole-H),6.33(s,1H,Pyrazole-H),5.41(s,2H,CH 2 ),4.58(d,J＝6.0Hz,2H,CH 2 ).
example 4:
20mmol of compound IId were dissolved in 35mL of acetonitrile, followed by addition of 30mmol of sodium carbonate, followed by addition of 30mmol of intermediate IIIa thereto under ice-bath conditions. After the addition, the reaction was heated under reflux for 18 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 on the obtained crude product to obtain a target object Id; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.48(m,1H,Py-H),7.88～7.90(m,1H,Py-H),7.70～7.76(m,4H,Ar-H),7.42～7.44(m,3H,Ar-H),7.37～7.40(m,1H,Py-H),7.34(s,1H,NH),7.11～7.16(m,2H,Ar-H),6.62(s,1H,Isoxazole-H),6.46(s,1H,Isoxazole-H),6.36(s,1H,Pyrazole-H),5.41(s,2H,CH 2 ),4.59(d,J＝6.0Hz,2H,CH 2 ).
example 5:
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 48 hours. 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 results of the insecticidal activity tests (Table 1) show that the target compounds Ia, ib, ic and id all exhibited excellent insecticidal effects against armyworm at the tested concentration of 500. Mu.g/mL, and the insecticidal activities thereof were 100%,100%,100% and 100%, respectively.
Preliminary insecticidal Activity data for Ia-Id
The experimental results show that the pyrazole skeleton and the substituted isoxazole unit are connected together to obtain the novel pyrazole derivative with excellent insecticidal effect, and valuable experimental data are provided for further carrying out synthesis and biological activity research of novel pyrazole compounds 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 (3)
1. A pyrazole derivative I containing a substituted isoxazole unit is characterized by having the structure:
2. a process for the preparation of pyrazole derivatives I containing substituted isoxazole units according to claim 1, characterized in that it comprises the following steps:
3. the use of a pyrazole derivative I containing a substituted isoxazole unit according to claim 1 for the preparation of a myxocide.
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Citations (3)
| 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 |
| 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 (3)
| 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 |
| 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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