CN110845478B - Preparation and use of pyrazole formyloxime derivatives containing 1-substituted pyridyl-3-trifluoromethylpyrazole units - Google Patents
Preparation and use of pyrazole formyloxime derivatives containing 1-substituted pyridyl-3-trifluoromethylpyrazole units Download PDFInfo
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- CN110845478B CN110845478B CN201911165396.4A CN201911165396A CN110845478B CN 110845478 B CN110845478 B CN 110845478B CN 201911165396 A CN201911165396 A CN 201911165396A CN 110845478 B CN110845478 B CN 110845478B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention relates to the preparation and use of pyrazole formyloxime derivatives (I) containing 1-substituted pyridyl-3-trifluoromethylpyrazole units. Obtained by reacting pyrazole oxime (II) with 1-substituted pyridyl-3-trifluoromethylpyrazole-4-formyl chloride (III). The pyrazole formyloxime derivative containing the 1-substituted pyridyl-3-trifluoromethyl pyrazole unit has 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 preparation and application of a pyrazole formyl oxime derivative containing a 1-substituted pyridyl-3-trifluoromethyl pyrazole unit.
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 heterocyclic compound is widely applied in the aspect of agricultural production, and the pyrazole formyloxime derivative has good insecticidal activity as an important heterocyclic compound, wherein a typical compound is fenpyroximate and plays an important role in the field of pesticides.
Substituted pyrazole rings as important heterocyclic units are often introduced into the molecular structure of pesticide compounds, such as pyrazole insecticides, tolfenpyrad, chlorantraniliprole and the like, and also show excellent insecticidal effects.
Therefore, in order to continuously search and find compounds with excellent insecticidal activity from pyrazole formyloxime compounds and reasonably combine a substituted pyrazole unit with a pyrazole oxime fragment, the invention discloses a pyrazole formyloxime derivative containing a 1-substituted pyridyl-3-trifluoromethyl pyrazole unit, which has agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole formyl oxime derivative containing a 1-substituted pyridyl-3-trifluoromethyl pyrazole unit, which has excellent control effect on various pests such as armyworm, aphid and the like, is efficient, safe and environment-friendly, and meets the requirement 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 above technical problems, the present invention provides in a first aspect a pyrazole formyloxime derivative containing a 1-substituted pyridyl-3-trifluoromethylpyrazole unit having the structure of formula I,
wherein, X is H,4-Cl,4-Br,2,4-F2
I。
Preferably, the pyrazole formyloxime derivative containing the 1-substituted pyridyl-3-trifluoromethylpyrazole unit has the following structure:
the second aspect of the present invention provides a process for producing the above-mentioned pyrazole formyloxime derivative containing a 1-substituted pyridyl-3-trifluoromethylpyrazole unit, which comprises the steps of:
dissolving a compound II in an organic solvent, adding an acid-binding agent, dropwise adding a mixed solution of an intermediate III and a small amount of solvent, reacting for a period of time after dropwise adding, concentrating mother liquor under reduced pressure, separating and purifying an obtained crude product to obtain a target compound,
preferably, the preparation method of the pyrazole formyloxime derivative containing the 1-substituted pyridyl-3-trifluoromethylpyrazole unit comprises the following steps:
among them, 1-substituted pyridyl-3-trifluoromethylpyrazole-4-carbonyl chloride was synthesized by a conventional method (organic chemistry, 2011,31, 1943-; the synthesis of the pyrazole oxime intermediates is referred to the conventional methods reported in the literature (J.Agric.food chem.2008,56, 10805-10810).
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 armyworms, aphids 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 present invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, it can be used alone or in the form of an insecticidal composition, such as an aqueous emulsion, a suspension, a water-dispersible granule, an emulsion and the like, prepared by using the formula I as an active ingredient, together with an agricultural chemical adjuvant 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 formyloxime derivative containing the 1-substituted pyridyl-3-trifluoromethyl pyrazole unit disclosed by the invention has excellent control effect on harmful insects such as armyworms, aphids and the like, and 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:
a reaction flask was charged with 5mmol IIa, 20mmol pyridine and 30mL DMF. While stirring in an ice bath, a mixed solution of 7mmol of intermediate III and 2mL of DMF was slowly dropped thereinto. After dropping, the mixture was heated to 90 ℃ and stirred for 20 hours. Removing the solvent under reduced pressure, and separating the obtained crude product by column chromatography to obtain a target compound Ia;1H NMR(400MHz,CDCl3)δ:8.52～8.54(m,1H,Py-H),8.22(s,1H,Pyrazole-H),8.10(s,1H,CH＝N),7.96～7.98(m,1H,Py-H),7.49～7.52(m,1H,Py-H),7.35～7.39(m,2H,Ar-H),7.15～7.18(m,1H,Ar-H),6.97(d,J＝7.6Hz,2H,Ar-H),3.64(s,3H,CH3),2.55(s,3H,CH3).
example 2:
a reaction flask was charged with 6mmol IIb, 30mmol triethylamine and 20mL tetrahydrofuran. While stirring in an ice bath, a mixed solution of 8mmol of intermediate III and 3mL of tetrahydrofuran was slowly dropped thereinto. After dropping, stirring in ice bath was continued for 12 hours. Removing the solvent under reduced pressure, and separating the obtained crude product by column chromatography to obtain a target compound Ib;1H NMR(400MHz,CDCl3)δ:8.52～8.54(m,1H,Py-H),8.23(s,1H,Pyrazole-H),8.11(s,1H,CH＝N),7.96～7.98(m,1H,Py-H),7.50～7.53(m,1H,Py-H),7.33(d,J＝8.8Hz,2H,Ar-H),6.92(d,J＝8.8Hz,2H,Ar-H),3.64(s,3H,CH3),2.53(s,3H,CH3).
example 3:
a reaction flask was charged with 8mmol IIc, 20mmol sodium carbonate and 20mL chloroform. To this was slowly dropped a mixed solution of 10mmol of intermediate III and 5mL of chloroform with stirring at room temperature. After dropping, the reaction was heated under reflux for 18 hours. ReducingRemoving the solvent under pressure, and separating the obtained crude product by column chromatography to obtain a target compound Ic;1H NMR(400MHz,CDCl3)δ:8.52～8.54(m,1H,Py-H),8.23(s,1H,Pyrazole-H),8.11(s,1H,CH＝N),7.96～7.98(m,1H,Py-H),7.46～7.52(m,3H,Py-H and Ar-H),6.85～6.87(m,2H,Ar-H),3.63(s,3H,CH3),2.52(s,3H,CH3).
example 4:
a reaction flask was charged with 10mmol IId, 22mmol sodium acetate and 30mL dichloromethane. While stirring in an ice bath, a mixture of 9mmol of III and 5mL of dichloromethane was slowly dropped thereinto. After the completion of the dropwise addition, stirring was continued at room temperature for 15 hours. After the solvent is removed, the obtained crude product is separated by column chromatography to obtain a target object Id;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.24(s,1H,Pyrazole-H),8.08(s,1H,CH＝N),7.97～8.00(m,1H,Py-H),7.51～7.54(m,1H,Py-H),6.82～7.02(m,3H,Ar-H),3.72(s,3H,CH3),2.49(s,3H,CH3).
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 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 for culture at 24-27 ℃, and the result is investigated after 2 d. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The assay concentration was 500. mu.g/mL.
Example 6:
screening of insecticidal Activity of samples against aphids
The spray method proposed by the International Resistance Action Committee (IRAC) was used: the test target is aphid, namely broad bean leaves connected with the aphid are sprayed under a Potter spray tower, the processed aphid is cultured in an observation room at 20-22 ℃, 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 shows that the target substances Ia, Ib, ic and id have good insecticidal action on armyworms and aphids. At a test concentration of 500. mu.g/mL (Table 1), the insecticidal rates of the target substances Ia, Ib, ic and id against armyworm were 100%, 100%, 100% and 100%, respectively; the insecticidal rates of the target substances Ia, Ib, ic and id on aphids were 100%, 100%, 100% and 100%, respectively.
TABLE 1 Primary pesticidal Activity data for Ia-Id
The experimental data show that the novel pyrazole oxime compound obtained by combining the substituted pyrazole unit and the pyrazole oxime skeleton has good insecticidal activity, and valuable experimental data are provided for further research on the novel pyrazole oxime compound 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, and that the foregoing examples and descriptions are merely illustrative of the principles of the invention, and that various changes and modifications can be made without departing from the spirit and scope of the invention, which is intended to be within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A pyrazole formyloxime derivative I containing a 1-substituted pyridyl-3-trifluoromethylpyrazole unit, characterized by having the following structure:
2. a process for the preparation of pyrazole formyloxime derivatives I containing 1-substituted pyridyl-3-trifluoromethylpyrazole units as claimed in claim 1, characterized by the following steps:
3. use of pyrazole formyloxime derivative I containing a 1-substituted pyridyl-3-trifluoromethylpyrazole unit according to claim 1 for the preparation of a mythicide.
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