CN111925365B - Preparation method and application of pyridine derivative containing substituted 1,3, 5-oxadiazine unit - Google Patents
Preparation method and application of pyridine derivative containing substituted 1,3, 5-oxadiazine unit Download PDFInfo
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- CN111925365B CN111925365B CN202010925982.0A CN202010925982A CN111925365B CN 111925365 B CN111925365 B CN 111925365B CN 202010925982 A CN202010925982 A CN 202010925982A CN 111925365 B CN111925365 B CN 111925365B
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- oxadiazine
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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
- C07D413/06—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 carbon chain containing only aliphatic carbon atoms
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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
- A01N43/88—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 six-membered rings with three ring hetero atoms
Abstract
The invention relates to a preparation method and application of a pyridine derivative (I) containing a substituted 1,3, 5-oxadiazine unit. By reaction of a substituted 1,3, 5-oxadiazine with a pyridine compound. The pyridine derivative containing the substituted 1,3, 5-oxadiazine unit has excellent insecticidal action 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 a preparation method and application of a pyridine derivative containing a substituted 1,3, 5-oxadiazine unit.
Background
The prevention and control of pests is an important research content in the field of pesticides. The use of the pesticide allows better control of pests. However, some pests have developed resistance to traditional pesticides in recent years. Therefore, development of novel high-efficiency pesticides is required for researchers.
The oxadiazine ring is used as an active fragment of a common pesticide molecule, and has excellent insecticidal effects and the like in the field of pesticides, such as commercialized oxadiazine insecticide indoxacarb.
Pyridine rings are also important active fragments of drug molecules, and pyridine derivatives play an important role in plant protection.
Therefore, in order to continue to search for novel compounds having excellent insecticidal effects from among pyridine compounds and to rationally combine oxadiazines and substituted pyridine active backbones, the present invention discloses pyridine derivatives containing substituted 1,3, 5-oxadiazine units, which have agricultural insecticidal utility values.
Disclosure of Invention
The invention aims to provide a pyridine derivative which has good insecticidal action on pests such as armyworm and the like and contains substituted 1,3, 5-oxadiazine units with high efficiency so as to meet 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.
To solve the above technical problems, a first aspect of the present invention provides a pyridine derivative containing a substituted 1,3, 5-oxadiazine unit, having a structure of formula I:
preferably, the pyridine derivative containing a substituted 1,3, 5-oxadiazine unit has the following structure:
a second aspect of the present invention provides a process for producing the above-mentioned pyridine derivative containing a substituted 1,3, 5-oxadiazine unit, which comprises the following reaction steps:
the compound of the general formula I shows better insecticidal activity on armyworm and other pests, so that the compound can be used for preparing insecticides and further protecting agricultural, horticultural and other 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 pyridine derivative containing the substituted 1,3, 5-oxadiazine unit disclosed by the invention has a good insecticidal effect on armyworm and other pests, so that the pyridine derivative 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:
10mmol of intermediate IIa are dissolved in 35mL of acetonitrile, 20mmol of potassium carbonate are added, followed by intermediate III 9 mmol. The reaction mixture was heated under reflux for 13 hours. Stopping the reaction, removing the solvent, and performing column chromatography separation on the crude product to obtain a compound Ia; 1 H NMR(400MHz,CDCl 3 ):δ8.05(s,1H,Py-H),7.80(d,J＝8.4Hz,1H,Py-H),7.51(d,J＝8.8Hz,2H,Ar-H),7.03(d,J＝8.4Hz,2H,Ar-H),6.96(d,J＝8.4Hz,1H,Py-H),4.89(s,2H,CH 2 ),4.82(s,2H,CH 2 ),4.65(s,2H,CH 2 ),3.06(s,3H,CH 3 ).
Example 2:
6mmol of intermediate IIb are dissolved in 35mL of acetone, then 30mmol of 4-Dimethylaminopyridine (DMAP) are added, followed by 8mmol of intermediate III. The reaction solution was stirred for 10 hours at room temperature. Stopping the reaction, removing the solvent, and performing column chromatography separation on the crude product to obtain a target compound Ib; 1 H NMR(400MHz,CDCl 3 ):δ8.06(s,1H,Py-H),7.79-7.82(m,1H,Py-H),7.37(d,J＝8.4Hz,2H,Ar-H),7.08(d,J＝8.8Hz,2H,Ar-H),6.96(d,J＝8.4Hz,1H,Py-H),4.88(s,2H,CH 2 ),4.82(s,2H,CH 2 ),4.66(s,2H,CH 2 ),3.06(s,3H,CH 3 ).
example 3:
5mmol of intermediate IIc were dissolved in 30mL of DMA, then 20mmol of cesium carbonate were added, followed by 7mmol of intermediate III. The reaction mixture was heated to 85 ℃ and reacted for 15 hours. Stopping the reaction, removing the solvent, and performing column chromatography separation on the obtained crude product to obtain a target compound Ic; 1 H NMR(400MHz,CDCl 3 ):δ8.02(d,J＝2.4Hz,1H,Py-H),7.82～7.84(m,1H,Py-H),6.98～7.12(m,4H,Ar-H and Py-H),4.88(s,2H,CH 2 ),4.81(s,2H,CH 2 ),4.66(s,2H,CH 2 ),3.06(s,3H,CH 3 ).
example 4:
5mmol of intermediate IId was dissolved in 35mL DMSO, followed by 20mmol of sodium bicarbonate, followed by 5mmol of intermediate III. The reaction mixture was heated to 85 ℃ and reacted for 19 hours. Stopping the reaction, removing the solvent, and performing column chromatography separation on the obtained crude product to obtain a target compound Id; 1 H NMR(400MHz,CDCl 3 ):δ8.00(d,J＝2.0Hz,1H,Py-H),7.81-7.84(m,1H,Py-H),7.48(d,J＝2.4Hz,1H,Ar-H),7.28-7.31(m,1H,Ar-H),7.15(d,J＝8.4Hz,1H,Ar-H),7.03(d,J＝8.4Hz,1H,Py-H),4.89(s,2H,CH 2 ),4.81(s,2H,CH 2 ),4.65(s,2H,CH 2 ),3.06(s,3H,CH 3 ).
example 5:
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, a proper amount of corn leaves are fully 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 placed into an observation room at 24-27 ℃ for culture, 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 insecticidal activity of the compounds Ia, Ib, ic and id was determined as shown in Table 1. The results show that the compounds Ia, Ib, ic and id all have excellent insecticidal action against armyworms at a concentration of 500. mu.g/mL, with insecticidal activity of 100%, 100%, 80% and 100%, respectively.
TABLE 1 pesticidal Activity data for Compounds Ia-Id
The test results show that the novel compound obtained by combining the oxadiazine and the substituted pyridine active skeleton has good insecticidal action.
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 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 pyridine derivative I containing a substituted 1,3, 5-oxadiazine unit is characterized by having a structure as follows:
2. a process for the preparation of pyridine derivatives I containing substituted 1,3, 5-oxadiazine units according to claim 1, characterized in that it comprises the following steps:
3. Use of the pyridine derivatives I containing substituted 1,3, 5-oxadiazine units according to claim 1 for the preparation of a medicament for combating armyworms.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678795A (en) * | 1984-04-13 | 1987-07-07 | Nihon Tokushu Noyaku Seizo K.K. | 1-pyridylmethyl-2-nitromethylene-1,3-diazacycloalkane insecticides |
| US5010068A (en) * | 1989-12-21 | 1991-04-23 | Uniroyal Chemical Company, Inc. | Oxadiazinyl organophosphorus pesticides |
| CN103833663A (en) * | 2014-02-27 | 2014-06-04 | 南通大学 | Tridemorph quaternary ammonium base as well as preparation method and application thereof |
| CN104119316A (en) * | 2014-06-25 | 2014-10-29 | 南通大学 | Pyridine phenyl ether compound as well as preparation and application of pyridine phenyl ether compound |
| CN111315743A (en) * | 2017-11-02 | 2020-06-19 | 江苏龙灯化学有限公司 | Method for preparing thiamethoxam |
-
2020
- 2020-09-07 CN CN202010925982.0A patent/CN111925365B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678795A (en) * | 1984-04-13 | 1987-07-07 | Nihon Tokushu Noyaku Seizo K.K. | 1-pyridylmethyl-2-nitromethylene-1,3-diazacycloalkane insecticides |
| US5010068A (en) * | 1989-12-21 | 1991-04-23 | Uniroyal Chemical Company, Inc. | Oxadiazinyl organophosphorus pesticides |
| CN103833663A (en) * | 2014-02-27 | 2014-06-04 | 南通大学 | Tridemorph quaternary ammonium base as well as preparation method and application thereof |
| CN104119316A (en) * | 2014-06-25 | 2014-10-29 | 南通大学 | Pyridine phenyl ether compound as well as preparation and application of pyridine phenyl ether compound |
| CN111315743A (en) * | 2017-11-02 | 2020-06-19 | 江苏龙灯化学有限公司 | Method for preparing thiamethoxam |
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