CN111592526B - Preparation and application of 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing azole heterocyclic structure - Google Patents
Preparation and application of 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing azole heterocyclic structure Download PDFInfo
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- CN111592526B CN111592526B CN202010570509.5A CN202010570509A CN111592526B CN 111592526 B CN111592526 B CN 111592526B CN 202010570509 A CN202010570509 A CN 202010570509A CN 111592526 B CN111592526 B CN 111592526B
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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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- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
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Abstract
The invention relates to a preparation method and application of 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing azole heterocyclic structure. The compound is prepared by reacting azole heterocyclic aromatic methylamine (II) with 3- (chloropyridine methoxy aryl) -1-methylpyrazole acyl chloride (III). The 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing the azole heterocyclic structure shows good insecticidal effect on harmful insects, and can be used for preparing insecticides 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 a 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing an azole heterocyclic structure.
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 2-chloro-5-chloromethyl pyridine is a key intermediate of pesticides such as imidacloprid and acetamiprid and has important application in agricultural production.
Azole heterocyclic compounds are widely applied in agricultural production, wherein pyrazole compounds have excellent insecticidal and acaricidal activities, and pyrazole heterocycles are widely introduced into pesticide compound molecules and have excellent killing activities on mites, aphids and the like. The 1,2, 3-triazole is also an important nitrogen-containing heterocycle and plays an important role in the aspect of insecticidal in the field of pesticides.
Therefore, in order to further search a lead compound with good insecticidal activity from pyrazole compounds, an active group splicing method is adopted to reasonably link a pyrazole skeleton containing a 2-chloro-5-chloromethylpyridine unit with substituted pyrazole and a 1,2, 3-triazo unit respectively, and the invention discloses a 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing an azole heterocyclic structure with agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing an azole heterocyclic structure, which has an excellent control effect on various pests, 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 technical problems, the invention provides a 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing an azole heterocyclic structure, which has a structure shown in a general formula I,
preferably, the 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing the azole heterocyclic structure has the following structure:
the second aspect of the present invention provides a preparation method of the above azole heterocyclic structure-containing 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound, which comprises the following steps:
dissolving a compound II in an organic solvent, adding an acid-binding agent, then adding an intermediate III, reacting for a period of time, concentrating mother liquor, separating and purifying a crude product to obtain a target product,
preferably, the preparation method of the 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing the azole heterocyclic structure comprises the following steps:
wherein, the intermediate II is prepared by the method of reference document (J.Med.chem.1998,41,2390); intermediate III was prepared synthetically by the method of the reference document (j.agric.food chem.2013,61,8730).
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 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing the azole heterocyclic structure disclosed by the invention has a good control effect on harmful insects, so that the compound 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:
a reaction flask was charged with 5mmol of compound IIa, 20mmol of sodium carbonate and 30mL of DMF. To this was added 8mmol of intermediate III under ice-bath conditions. The reaction solution was heated to 90 ℃ and reacted for 19 hours. Stopping the reaction, removing the solvent under reduced pressure, and performing column chromatography separation on the obtained crude product to obtain the target compound Ia.1H NMR(400MHz,CDCl3):δ8.46(s,1H,Pyridine-H),7.92(s,1H,Pyrazole-H),7.74～7.77(m,1H,Pyridine-H),7.67～7.73(m,5H,Pyrazole-H andAr-H),7.44(d,J＝8.4Hz,2H,Ar-H),7.36(d,J＝8.0Hz,1H,Pyridine-H),6.97(d,J＝8.8Hz,2H,Ar-H),6.80(s,1H,Pyrazole-H),6.68(s,1H,NH),6.48(s,1H,Pyrazole-H),5.07(s,2H,CH2),4.64(d,J＝5.6Hz,2H,CH2),4.24(s,3H,CH3).
Example 2:
a reaction flask was charged with 8mmol of compound IIb, 50mmol of triethylamine and 30mL of dichloromethane. 15mmol of intermediate III was added thereto under ice-bath conditions, followed by stirring at room temperature for 13 hours. Removing solvent under reduced pressure, and separating the obtained crude product by column chromatography to obtain target compound Ib。1H NMR(400MHz,CDCl3):δ8.46(s,1H,Pyridine-H),8.08(d,J＝8.4Hz,2H,Ar-H),7.82(s,2H,Triazole-H),7.75～7.77(m,1H,Pyridine-H),7.70(d,J＝8.8Hz,2H,Ar-H),7.48(d,J＝8.4Hz,2H,Ar-H),7.36(d,J＝8.0Hz,1H,Pyridine-H),6.98(d,J＝8.8Hz,2H,Ar-H),6.76(s,1H,Pyrazole-H),6.51(s,1H,NH),5.08(s,2H,CH2),4.67(d,J＝5.6Hz,2H,CH2),4.24(s,3H,CH3).
Example 3:
insecticidal activity screening of samples against armyworm
Leaf dipping method proposed by International Resistance Action Committee (IRAC) was used: the test object is armyworm, a proper amount of corn leaves are soaked in prepared liquid medicine and naturally dried in the shade, then 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 cultured in an observation room at 24-27 ℃, and the experimental 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 assay concentration was 500. mu.g/mL.
The insecticidal activity data of the targets are listed in table 1. As can be seen from the activity data in Table 1, both targets Ia and Ib exhibit excellent insecticidal action against armyworm. At the test concentration of 500. mu.g/mL, the insecticidal effects of the target substances Ia and Ib on armyworms were 100% and 100%, respectively.
TABLE 1 preliminary insecticidal Activity data of Ia-Ib
The test data show that the novel pyrazole compound obtained by reasonably linking the pyrazole skeleton containing the 2-chloro-5-chloromethylpyridine unit with the substituted pyrazole and the 1,2, 3-triazo unit respectively shows excellent insecticidal activity.
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. A3- (chloropyridine methoxyaryl) -1-methylpyrazole compound I containing an azole heterocyclic structure is characterized by having a structure as follows:
2. the preparation method of the 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound I containing the azole heterocyclic structure according to claim 1 is characterized by comprising the following steps:
3. the use of 3- (chloropyridine methoxyaryl) -1-methylpyrazole compounds I containing azole heterocyclic structures according to claim 1 for the preparation of insecticides, 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 use of 3- (chloropyridine methoxyaryl) -1-methylpyrazole compounds I containing azole heterocyclic structures according to claim 3 for the preparation of insecticides, characterized in that: when compound 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%.
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| CN109678845A (en) * | 2018-12-05 | 2019-04-26 | 南通大学 | Pyrazole amide analog derivative of the structure containing benzotriazole and its preparation method and application |
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