CN112010848B - Preparation method and application of 1,3, 4-oxadiazole compound containing trifluoromethyl pyridine biaryloxy structure - Google Patents
Preparation method and application of 1,3, 4-oxadiazole compound containing trifluoromethyl pyridine biaryloxy structure Download PDFInfo
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- CN112010848B CN112010848B CN202011047901.8A CN202011047901A CN112010848B CN 112010848 B CN112010848 B CN 112010848B CN 202011047901 A CN202011047901 A CN 202011047901A CN 112010848 B CN112010848 B CN 112010848B
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- biaryloxy
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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
- C07D413/02—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
- C07D413/12—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 linked by a chain containing hetero atoms as chain links
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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
- A01N43/82—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 three ring hetero atoms
Abstract
The invention relates to a preparation method and application of a 1,3, 4-oxadiazole compound (I) containing a trifluoromethyl pyridine biaryl oxy structure. Formed by the reaction of a trifluoromethyl pyridine biaryloxy compound (II) and 2-mercapto-5-aryl-1, 3, 4-oxadiazole (III). The 1,3, 4-oxadiazole compound containing the trifluoromethyl pyridine biaryl oxy structure has a good 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 preparation method and application of a 1,3, 4-oxadiazole compound containing a trifluoromethyl pyridine biaryloxy structure.
Background
Pest control has been one of the fields of agricultural chemical research, and most of pests are being effectively controlled by the use of insecticides. In recent years, some pests have developed resistance to traditional pesticide species. This requires the development of new, highly effective insecticides.
Pyridine structures are widely applied in agricultural production, and the compounds have excellent insecticidal and acaricidal activities, so that pyridine rings are widely introduced into pesticide compound molecules.
1,3, 4-oxadiazole is also an important nitrogen-containing heterocycle and plays an important role in the aspect of killing insects in the field of pesticides.
Therefore, in order to further search for a compound with excellent biological activity from the 1,3, 4-oxadiazole compounds, an active group splicing method is adopted to reasonably link a trifluoromethyl pyridine biaryloxy skeleton and a substituent 1,3, 4-oxadiazole together, and the invention discloses a class of 1,3, 4-oxadiazole compounds containing a trifluoromethyl pyridine biaryloxy structure and having agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a 1,3, 4-oxadiazole compound containing a trifluoromethyl pyridine biaryl oxy structure, which shows an excellent insecticidal effect on various pests and is efficient, safe and environment-friendly, so as to meet the requirement of crop protection on efficient 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 1,3, 4-oxadiazole compound containing a trifluoromethyl pyridine biaryl oxy structure, which has a structure shown in a general formula I,
preferably, the 1,3, 4-oxadiazole compound containing the trifluoromethyl pyridine biaryl structure has the following structure:
the second aspect of the present invention provides a preparation method of the above 1,3, 4-oxadiazole compound containing a trifluoromethylpyridine biaryloxy structure, which comprises the following steps:
the compound of the general formula I has better insecticidal effect on armyworm and other pests, so that the compound can be used for preparing insecticides 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 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 1,3, 4-oxadiazole compound containing the trifluoromethyl pyridine biaryl oxy structure disclosed by the invention has good control activity on harmful insects such as armyworm and the like, and therefore, the 1,3, 4-oxadiazole 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:
6mmol of compound IIIa are dissolved in 20mL of acetonitrile, followed by addition of 30mmol of potassium carbonate. Adding 8mmol of intermediate IIa at room temperature, and heating and refluxing for reaction for 12 hours after the addition is finished. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation on the obtained residue to obtain the target compound Ia.1H NMR(400MHz,CDCl3):δ8.39(s,1H,Pyridine-H),7.87～8.00(m,3H,Ar-H and Pyridine-H),7.42～7.52(m,2H,Ar-H),7.16(s,1H,Ar-H),7.11(s,2H,Ar-H),7.03(d,J＝8.8Hz,1H,Pyridine-H),4.56(s,2H,CH2),3.77(s,3H,OCH3).
Example 2:
10mmol of compound IIIb are dissolved in 30mL of acetone, followed by addition of 30mmol of triethylamine. 13mmol of intermediate IIa is added thereto at room temperature, and stirring is continued at room temperature for 15 hours after the addition is completed. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation on the obtained residue to obtain a target compound Ib.1H NMR(400MHz,CDCl3):δ8.38(s,1H,Pyridine-H),8.14(d,J＝8.0Hz,2H,Ar-H),7.88～7.90(m,1H,Pyridine-H),7.77(d,J＝8.4Hz,2H,Ar-H),7.17(s,1H,Ar-H),7.12(s,2H,Ar-H),7.04(d,J＝8.8Hz,1H,Pyridine-H),4.58(s,2H,CH2),3.77(s,3H,OCH3).
Example 3:
8mmol of compound IIIc are dissolved in 30mL of DMF, followed by addition of 20mmol of sodium carbonate. 10mmol of intermediate IIb was added thereto at room temperature, and after the addition, the reaction mixture was heated to 80 ℃ and stirred for 16 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography on the obtained residue to obtain the target compound Ic.1H NMR(400MHz,CDCl3):δ8.36(s,1H,Pyridine-H),7.87(d,J＝8.4Hz,3H,Ar-H and Pyridine-H),7.27～7.37(m,4H,Ar-H),7.02(d,J＝8.8Hz,1H,Pyridine-H),6.98(d,J＝8.4Hz,1H,Ar-H),4.49(s,2H,CH2),3.75(s,3H,OCH3),2.41(s,3H,CH3).
Example 4:
screening of insecticidal Activity of Compounds against armyworm
The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the test object is armyworm. Soaking appropriate amount of corn leaf in the prepared medicinal liquid, naturally drying in the shade, placing into a culture dish filled with filter paper, inoculating 10 heads/dish of 3-year-old mid-stage larva of armyworm, culturing in an observation room at 24-27 deg.C, and investigating the result after 48 hr. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration is 500. mu.g/mL (other concentrations of the drug solution can be obtained by diluting 500. mu.g/mL of the drug solution).
The insecticidal activity test data show that the compounds Ia-ic all show good effect of killing armyworms. At the tested concentration of 500. mu.g/mL (Table 1), the lethality of compounds Ia-IC to armyworm was 80%, 70% and 80%, respectively.
TABLE 1 preliminary insecticidal Activity data for Ia-Ic
The experimental data show that the new compound obtained by linking the trifluoromethyl pyridine biaryl skeleton and the substituent 1,3, 4-oxadiazole has better insecticidal effect.
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. A1, 3, 4-oxadiazole compound I containing a trifluoromethyl pyridine biaryl oxy structure is characterized by having the following structure:
2. the preparation method of the 1,3, 4-oxadiazole compound I containing a trifluoromethylpyridine biaryloxy structure as claimed in claim 1, is characterized by comprising the following steps:
3. the use of the 1,3, 4-oxadiazole compound I containing a trifluoromethylpyridine biaryloxy structure according to claim 1 for preparing a pesticide.
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