CN110467599B - Preparation and application of pyrazole amide containing substituted pyridine unit - Google Patents
Preparation and application of pyrazole amide containing substituted pyridine unit Download PDFInfo
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- CN110467599B CN110467599B CN201910782020.1A CN201910782020A CN110467599B CN 110467599 B CN110467599 B CN 110467599B CN 201910782020 A CN201910782020 A CN 201910782020A CN 110467599 B CN110467599 B CN 110467599B
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- substituted pyridine
- pyrazole
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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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- 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
- C07D401/02—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 two hetero rings
- C07D401/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention relates to preparation and application of pyrazole amide containing a substituted pyridine unit. Is obtained by condensing pyrazole acyl chloride intermediate and substituent pyridine methyl amine. The pyrazole amide containing the substituted pyridine unit shows effective control effect on harmful insects, and the compound 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 preparation and application of pyrazole amide containing a substituted pyridine 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.
Pyrazole rings are widely used in agricultural production, pyrazole compounds have excellent insecticidal and acaricidal activities, and pyrazole heterocycles are widely introduced into pesticide compound molecules, such as the pyrazole amide insecticide tolfenpyrad, and have excellent killing activity against armyworms and the like (Biochim. Biophys. acta 1998,1364, 236-244).
The nitrogen-containing heterocyclic compounds are widely applied in agricultural production, and the substituted pyridine compounds have excellent insecticidal activity and the like as an important nitrogen-containing heterocyclic compound, wherein the typical substituted pyridine compound has sulfoxaflor and plays an important role in the insecticidal aspect in the field of pesticides (US 20080108667).
Therefore, in order to find compounds having better biological activity, pyrazole units and substituted pyridine groups are reasonably spliced together, and a novel compound having insecticidal activity is expected to be obtained.
Disclosure of Invention
The invention aims to provide pyrazole amide containing substituted pyridine units, 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.
Another object of the present invention is to provide a process for the preparation of the above compounds.
It is a further object of the present invention to provide the use of the above compounds in the preparation of armyworm and aphid killing agents.
In order to solve the above technical problems, a first aspect of the present invention provides a pyrazole amide containing a substituted pyridine unit, having the following structure:
the invention provides a preparation method of the pyrazole amide containing the substituted pyridine unit, which is characterized by comprising the following steps:
wherein, the intermediate pyrazole formyl chloride can be synthesized by the method of reference literature (J.Agric.food chem.2013,61, 8730-8736); synthesis of intermediate substituent picolylamines is according to the conventional methods reported in the literature (Chemical Reagents 2004,26, 99-100).
The compound of the general formula I has excellent control activity on armyworm and aphid, so that the compound can be used for preparing agents for killing the armyworm and the aphid and further protecting plants in agriculture, horticulture and the like.
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 amide containing the substituted pyridine unit disclosed by the invention has excellent control effect on armyworm and aphid, so that the pyrazole amide 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:
3mmol of compound IIIa are dissolved in 15mL of tetrahydrofuran and 12mmol of pyridine are added. 5mmol of intermediate IIa was added thereto under ice-bath conditions, and stirring was continued at room temperature for 12 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,DMSO-d6):δ8.94(s,1H,NH),8.06(d,J＝2.0Hz,1H,Py-H),7.84～7.87(m,1H,Py-H),7.13～7.45(m,4H,Py-H and Ar-H),4.44(d,J＝6.0Hz,2H,CH2),3.82(s,3H,N-CH3),2.13(s,3H,CH3).
example 2:
6mmol of the compound IIIa is dissolved in 30mL of acetonitrile, 10mmol of the intermediate IIb and 18mmol of sodium carbonate are added thereto at room temperature, and after the addition, the reaction is heated under reflux for 16 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,DMSO-d6):δ8.93(s,1H,NH),8.07(d,J＝2.0Hz,1H,Py-H),7.84～7.87(m,1H,Py-H),7.12～7.46(m,4H,Py-H and Ar-H),
4.44(d,J＝6.0Hz,2H,CH2),3.83(s,3H,N-CH3),2.55(q,J＝8.0Hz,2H,CH2),1.16(t,J＝7.6Hz,3H,CH3).
example 3:
8mmol of the compound IIIb was dissolved in 30mL of 1, 2-dichloroethane, and 7mmol of the intermediate IIb and 16mmol of sodium hydrogencarbonate were added thereto at room temperature, and the mixture 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 carrying out column chromatography separation and purification on the obtained residue to obtain a target compound Ic;1H NMR(400MHz,DMSO-d6):δ8.92(s,1H,NH),8.11(d,J＝2.0Hz,1H,Py-H),7.82～7.84(m,1H,Py-H),7.02～7.26(m,5H,Py-H and Ar-H),4.44(d,J＝6.0Hz,2H,CH2),3.83(s,3H,N-CH3),2.55(q,J＝7.2Hz,2H,CH2),1.16(t,J＝7.6Hz,3H,CH3).
example 4:
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 respectively 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).
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 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 better insecticidal activity. At the tested concentration of 500 mug/mL (Table 1), the killing effect of the compounds Ia to IC on aphids is 100%, 100% and 100% respectively; the insecticidal activity of the compounds Ia to ic on armyworms is 100%, 100% and 100% respectively. The killing effect of the compounds Ia and Ib on aphids is 100 percent and 100 percent respectively when the tested concentration is 100 mu g/mL; compounds Ia and Ib exhibited 100% and 90% killing activity against armyworm at the tested concentration of 100. mu.g/mL, respectively. In addition, compounds Ia and Ib also exhibited excellent insecticidal effects on aphids at the tested concentrations reduced to 20. mu.g/mL, with kill rates of 100% and 90%, respectively.
TABLE 1 insecticidal Activity data of Ia-Ic
"-" means not determined
The experimental data show that the novel compound obtained by organically linking the substituted pyridine group and the pyrazole skeleton shows excellent insecticidal activity, and the compound can be selected as an insecticidal precursor to be further used for structural derivation and biological activity research.
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 amide I containing a substituted pyridine unit is characterized by having the structure:
2. a process for the preparation of pyrazole amides I containing substituted pyridine units according to claim 1, characterized in that the process comprises the following steps:
3. use of a pyrazole amide I containing substituted pyridine units according to claim 1 for the preparation of an aphicidal medicament.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88102427A (en) * | 1987-04-24 | 1988-11-09 | 三菱化成工业株式会社 | Pyrazole derivatives and insecticidal or acaricidal compositions containing them |
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN103081916A (en) * | 2011-11-02 | 2013-05-08 | 中国中化股份有限公司 | Application of pyrazole amide compound as agricultural bactericide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88102427A (en) * | 1987-04-24 | 1988-11-09 | 三菱化成工业株式会社 | Pyrazole derivatives and insecticidal or acaricidal compositions containing them |
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN103081916A (en) * | 2011-11-02 | 2013-05-08 | 中国中化股份有限公司 | Application of pyrazole amide compound as agricultural bactericide |
Non-Patent Citations (1)
| Title |
|---|
| 生物电子等排及其在新农药创制中的应用;刘长令;《农药》;19981231;第37卷(第2期);1-7 * |
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