CN111560015B - Preparation and application of 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole unit - Google Patents
Preparation and application of 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole unit Download PDFInfo
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- CN111560015B CN111560015B CN202010462479.6A CN202010462479A CN111560015B CN 111560015 B CN111560015 B CN 111560015B CN 202010462479 A CN202010462479 A CN 202010462479A CN 111560015 B CN111560015 B CN 111560015B
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- 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
- A01N43/82—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
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Abstract
The invention relates to a preparation method and application of 1,2,3-triazole benzyloxy pyrazole derivative (I) containing 1,2,4-oxadiazole unit. Obtained by the reaction of oxadiazole methylamine (II) and 1,2,3-triazole benzyloxy pyrazole acyl chloride (III). The 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole 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, and in particular relates to preparation and application of 1,2,3-triazole benzyloxy pyrazole derivatives containing 1,2,4-oxadiazole units.
Background
The control of pests has been a core area of pesticide science research, and the widespread use of insecticides has led to effective control of many pests. However, with the continuous expansion of the application scale of the pesticide, the problem of drug resistance of the traditional pesticide varieties is increasingly highlighted, and the continuous emergence of new insect pests makes the research and development of novel pesticides an inevitable choice.
1,2,4-oxadiazole ring is an important heterocyclic group and has wide application in agricultural production, such as pyrazole insecticide tolfenpyrad and tebufenpyrad.
1,2,3-triazole is also an important heterocycle, and 1,2,3-triazole derivatives play an important role in the field of pesticides.
Pyrazole derivatives are also important heterocyclic skeletons and play an important role in the field of plant protection, such as pesticides fenpyroximate and tolfenpyrad.
Therefore, in order to continuously find compounds with good biological activity from pyrazole derivatives, 1,2,4-oxadiazole, 1,2,3-triazole and a pyrazole skeleton structure are combined together, and the invention discloses 1,2,3-triazole benzyloxy pyrazole derivatives containing 1,2,4-oxadiazole units, which have agricultural insecticidal application values.
Disclosure of Invention
The invention aims to provide a 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole units, which has a good insecticidal 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 first aspect of the invention provides a 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole unit, which has a structure shown in a general formula I:
preferably, the 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole units has the following structure:
the second aspect of the invention provides a preparation method of the 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole unit, which comprises the following steps:
dissolving a compound II in an organic solvent, adding an acid-binding agent, then adding an intermediate III, after reacting for a period of time, carrying out suction filtration on a reaction solution, carrying out reduced pressure concentration on a mother solution, separating and purifying obtained residues to obtain a target,
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, tetrahydrofuran and acetonitrile.
Preferably, the preparation method of the 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole unit comprises the following steps:
wherein, the aryl oxadiazole methylamine intermediate II can be synthesized by the method of reference literature (Chemical Reagents 2004,26,99-100); the chloro-pyridine bipyrazole acyl chloride intermediate III is synthesized by the method of a reference literature (J.Agric.food chem.2013,61, 8730-8736).
The compound of the general formula I has excellent control activity on armyworm and the like, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture 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 1,2,3-triazole benzyloxy pyrazole derivative containing 1,2,4-oxadiazole unit disclosed by the invention has an excellent control effect on armyworm and the like, and therefore, can be used for preparing insecticides for 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 IIa was dissolved in 30mL1, 4-dioxane, 30mmol of pyridine was added, and 8mmol of intermediate III was added thereto under ice bath conditions. After addition, the reaction was carried out at room temperature for 19 hours. Stopping the reaction, removing the solvent under reduced pressure, and purifying the obtained residue by column chromatography to obtain a compound Ia; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.48(m,1H,Py-H),8.10(d,J＝8.8Hz,2H,Ar-H),7.88～7.93(m,3H,Py-H and Ar-H),7.82(s,2H,Triazole-H),7.56～7.63(m,4H,Ar-H),7.36～7.39(m,1H,Py-H),7.10(s,1H,NH),6.38(s,1H,Pyrazole-H),5.37(s,2H,CH 2 ),4.79(d,J＝5.6Hz,2H,CH 2 ).
example 2:
8mmol of the compound IIb was dissolved in 35mL of dichloromethane, 50mmol of triethylamine was added, and 9mmol of the intermediate III was added thereto under ice bath conditions. After addition, the mixture was stirred at room temperature for 12 hours. Stopping the reaction, removing the solvent under reduced pressure, and purifying the obtained residue by column chromatography to obtain a compound Ib; 1 H NMR(CDCl 3 ,400MHz)δ:8.47(s,1H,Py-H),8.09(d,J＝8.4Hz,2H,Ar-H),8.03～8.06(m,2H,Ar-H),7.89(d,J＝7.6Hz,1H,Py-H),7.82(s,2H,Triazole-H),7.57(d,J＝8.0Hz,2H,Ar-H),7.36～7.38(m,1H,Py-H),7.14～7.18(m,3H,Ar-H and NH),6.37(s,1H,Pyrazole-H),5.36(s,2H,CH 2 ),4.78(s,2H,CH 2 ).
example 3:
9mmol of Compound IIc was dissolved in 20mL of acetone, and 20mmol of 4-Dimethylaminopyridine (DMAP) was added thereto, and 9mmol of intermediate III was added thereto under ice-bath conditions. After the addition, the reaction solution was heated under reflux for 20 hours. Stopping the reaction, removing the solvent under reduced pressure, and purifying the obtained residue by column chromatography to obtain a compound Ic; 1 H NMR(CDCl 3 ,400MHz)δ:8.39(d,J＝4.4Hz,1H,Py-H),7.74～8.03(m,5H,Py-H,Triazole-H and Ar-H),7.28～7.66(m,7H,Py-H and Ar-H),6.30(s,1H,Pyrazole-H),5.28(s,2H,CH 2 ),4.69(d,J＝4.4Hz,2H,CH 2 ).
example 4:
6mmol of the compound IId was dissolved in 25mL of tetrahydrofuran, 20mmol of triethylamine was added, and 6mmol of the intermediate III was added thereto under ice bath conditions. After the addition, the reaction mixture was heated under reflux for 16 hours. Stopping the reaction, removing the solvent under reduced pressure, and purifying the obtained residue by column chromatography to obtain a compound Id; 1 H NMR(CDCl 3 ,400MHz)δ:8.46～8.48(m,1H,Py-H),8.09(d,J＝8.8Hz,2H,Ar-H),7.92(d,J＝8.0Hz,2H,Ar-H),7.87～7.89(m,1H,Py-H),7.82(s,2H,Triazole-H),7.57(d,J＝8.8Hz,2H,Ar-H),7.35～7.38(m,1H,Py-H),7.28(d,J＝8.0Hz,2H,Ar-H),7.20(s,1H,NH),6.38(s,1H,Pyrazole-H),5.36(s,2H,CH 2 ),4.77(d,J＝5.6Hz,2H,CH 2 ),2.41(s,3H,CH 3 ).
example 5:
5mmol of the compound IIe were dissolved in 20mL of acetonitrile, 20mmol of sodium carbonate were added, and intermediate III 9mmol were added thereto under ice-bath conditions. After the addition, the reaction mixture was heated under reflux for 15 hours. Stopping the reaction, removing the solvent under reduced pressure, and purifying the obtained residue by column chromatography to obtain a compound Ie; 1 H NMR(CDCl 3 ,400MHz)δ:8.47～8.48(m,1H,Py-H),8.09(d,J＝8.0Hz,2H,Ar-H),7.99～8.05(m,1H,Ar-H),7.88～7.90(m,1H,Py-H),7.81(s,2H,Triazole-H),7.56(d,J＝8.8Hz,2H,Ar-H),7.36～7.39(m,1H,Py-H),7.22(s,1H,NH),6.96～7.04(m,2H,Ar-H),6.37(s,1H,Pyrazole-H),5.36(s,2H,CH 2 ),4.80(d,J＝5.2Hz,2H,CH 2 ).
example 6:
insecticidal activity screening of samples against armyworm
The leaf dipping method proposed by the International Resistance Action Committee (IRAC) is utilized: 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 compounds Ia to ie all exhibit excellent insecticidal activity against armyworm at the tested concentration of 500. Mu.g/mL, with insecticidal effects of 100%,100%,100% and 100%, respectively.
TABLE 1 Primary insecticidal Activity data for Ia-Ie
The test results show that the 1,2,4-oxadiazole, 1,2,3-triazole and the pyrazole skeleton structure are combined together, the obtained novel pyrazole derivative has an excellent insecticidal effect, and meanwhile, a certain structural mode selection is provided for the follow-up 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 merely to illustrate 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 to be protected by the following claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A1,2,3-triazole benzyloxy pyrazole derivative (I) containing 1,2,4-oxadiazole unit is characterized in that the structure is as follows:
2. the preparation method of the 1,2,3-triazole benzyloxy pyrazole derivative (I) containing 1,2,4-oxadiazole unit according to claim 1, which is characterized by comprising the following steps:
3. the use of the 1,2,3-triazole benzyloxy pyrazole derivative (I) containing 1,2,4-oxadiazole unit according to claim 1 in the preparation of a pesticide.
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| 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 |
| CN110845487A (en) * | 2019-11-19 | 2020-02-28 | 南通大学 | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof |
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| 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 |
| CN110845487A (en) * | 2019-11-19 | 2020-02-28 | 南通大学 | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof |
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