CN111909145B - Preparation and application of 2-substituent-1, 3-thiazolidine containing pyridine bi-substituted phenoxy unit - Google Patents
Preparation and application of 2-substituent-1, 3-thiazolidine containing pyridine bi-substituted phenoxy unit Download PDFInfo
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- CN111909145B CN111909145B CN202010972041.2A CN202010972041A CN111909145B CN 111909145 B CN111909145 B CN 111909145B CN 202010972041 A CN202010972041 A CN 202010972041A CN 111909145 B CN111909145 B CN 111909145B
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- thiazolidine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
Abstract
The invention relates to preparation and application of 2-substituent-1, 3-thiazolidine containing pyridine bi-substituted phenoxy unit. Formed by condensing 2-substituent-1, 3-thiazolidine and pyridine bi-substituted phenoxy compound. The 2-substituent-1, 3-thiazolidine containing the pyridine bi-substituted phenoxy unit has better insecticidal activity on harmful insects, and the compound 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 2-substituent-1, 3-thiazolidine containing pyridine-substituted phenoxy units.
Background
The control of pests is one of the hot spots in the research of the field of plant protection, and the use of pesticides allows the pests to be effectively controlled. With the widespread use of insecticides, some pests have developed resistance to traditional insecticides in recent years. This requires the agrochemical chemist to develop new highly effective pesticides.
The pyridine ring is used as a common pesticide molecule active fragment, and has the functions of killing insects, inhibiting bacteria and the like in the field of pesticides.
The 2-substituent-1, 3-thiazolidine ring is an important nitrogen heterocyclic ring and has wide application in the aspect of plant protection.
In order to continuously search out a compound with good insecticidal activity from 2-substituent-1, 3-thiazolidine derivatives, a pyridine bi-substituted phenoxy unit and a 2-substituent-1, 3-thiazolidine group are linked together, and the invention discloses 2-substituent-1, 3-thiazolidine containing the pyridine bi-substituted phenoxy unit, which has agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide 2-substituent-1, 3-thiazolidine containing pyridine bi-substituted phenoxy units, which has excellent insecticidal effect on pests such as armyworm, aphid and the like, 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.
In order to solve the above technical problems, the present invention provides, in a first aspect, a 2-substituent-1, 3-thiazolidine containing a pyridinylphenoxy unit, having a structure of the general formula I:
preferably, the 2-substituent-1, 3-thiazolidine containing the pyridine bi-substituted phenoxy unit has the following structure:
the second aspect of the present invention provides a process for preparing the above-mentioned 2-substituent-1, 3-thiazolidine containing a pyrido-substituted phenoxy unit, which comprises the following reaction steps:
the compound of the general formula I has better insecticidal effect on armyworm, aphid and other pests, so that the compound can be used for preparing insecticide and further protecting 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 present invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, it can be used alone or in the form of an insecticidal composition, such as an aqueous emulsion, a suspension, a water-dispersible granule, an emulsion and the like, prepared by using the formula I as an active ingredient, together with an agricultural chemical adjuvant 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 within the range of 0.1% to 99.5%, and the appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous creams contain from 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably from 10% to 40%; the active ingredient is present in the suspension in an amount of 5% to 50%, 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 2-substituent-1, 3-thiazolidine containing the pyridine disubstituted phenoxy unit has good insecticidal effect on armyworm, aphid and other pests, so that the 2-substituent-1, 3-thiazolidine 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 conditions used in routine experiments.
Example 1:
10mmol of intermediate II a were dissolved in 50ml of DMF and 30mmol of potassium carbonate were added, followed by 13mmol of intermediate III. The reaction solution was heated to 80 ℃ and stirred for 13 hours. Removing the solvent to obtain a crude product, and performing column chromatography separation to obtain a target compound Ia;1H NMR(400MHz,CDCl3):δ8.07(d,J＝2.0Hz,1H,Py-H),7.70～7.73(m,1H,Py-H),7.37(d,J＝8.8Hz,2H,Ar-H),7.08(d,J＝8.8Hz,2H,Ar-H),6.96(d,J＝8.4Hz,1H,Py-H),4.58(s,2H,CH2),3.80(t,J＝7.6Hz,2H,CH2),3.38(t,J＝7.6Hz,2H,CH2).
example 2:
10mmol of intermediate IIb are dissolved in 60mL of acetonitrile, 22mmol of cesium carbonate are added, followed by 11mmol of intermediate III. The reaction mixture was heated under reflux for 10 hours. Separating the crude product obtained by removing the solvent by column chromatography to obtain a target object Ib;1H NMR(400MHz,CDCl3):δ8.06(d,J＝2.4Hz,1H,Py-H),7.70～7.73(m,1H,Py-H),7.51(d,J＝8.8Hz,2H,Ar-H),7.03(d,J＝8.8Hz,2H,Ar-H),6.96(d,J＝8.4Hz,1H,Py-H),4.58(s,2H,CH2),3.80(t,J＝7.6Hz,2H,CH2),3.38(t,J＝7.6Hz,2H,CH2).
example 3:
13mmol of intermediate IIc were dissolved in 30mL of N, N-Dimethylacetamide (DMA), 30mmol of sodium bicarbonate was added, followed by 16mmol of intermediate III, and the reaction was heated to 90 ℃ and stirred for 18 hours. Removing the solvent to obtain a crude product, and performing column chromatography separation to obtain a target object Ic;1H NMR(400MHz,CDCl3):δ8.02(d,J＝2.0Hz,1H,Py-H),7.72～7.75(m,1H,Py-H),7.48(d,J＝2.4Hz,1H,Ar-H),7.29～7.31(m,1H,Ar-H),7.15(d,J＝8.8Hz,1H,Ar-H),7.03(d,J＝8.4Hz,1H,Py-H),4.58(s,2H,CH2),3.79(t,J＝7.6Hz,2H,CH2),3.38(t,J＝7.6Hz,2H,CH2).
example 4:
10mmol of the intermediate IId was dissolved in 30mL of acetonitrile, 20mmol of potassium carbonate was added, followed by 12mmol of the intermediate III, and the reaction mixture was heated under reflux for 9 hours. Removing the solvent to obtain a crude product, and performing column chromatography separation to obtain a target object Id;1H NMR(400MHz,CDCl3):δ8.08(d,J＝2.0Hz,1H,Py-H),7.68～7.70(m,1H,Py-H),7.40～7.44(m,2H,Ar-H),7.21～7.25(m,1H,Ar-H),7.13(d,J＝8.0Hz,2H,Ar-H),6.93(d,J＝8.4Hz,1H,Py-H),4.57(s,2H,CH2),3.79(t,J＝7.6Hz,2H,CH2),3.37(t,J＝7.6Hz,2H,CH2).
example 5:
6mmol of intermediate IIe was dissolved in 30mL of 2-butanone, 20mmol of triethylamine and then 5mmol of intermediate III were added, and the reaction mixture was heated under reflux for 22 hours. Removing the solvent to obtain a crude product, and performing column chromatography separation to obtain a target object Ie;1H NMR(400MHz,CDCl3):δ8.07(d,J＝2.0Hz,1H,Py-H),7.70～7.72(m,1H,Py-H),7.09～7.11(m,4H,Ar-H),6.94(d,J＝8.8Hz,1H,Py-H),4.58(s,2H,CH2),3.78(t,J＝7.6Hz,2H,CH2),3.38(t,J＝7.6Hz,2H,CH2).
example 6:
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 the prepared liquid medicine and then 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 writing brush, the dead insect is determined to be no response. The test concentration was 500. mu.g/mL (the drug solution of other concentration can be diluted with 500. mu.g/mL).
Example 7:
screening of insecticidal Activity of Compounds on aphids
The spray method proposed by the International Resistance Action Committee (IRAC) was used: and (3) spraying the broad bean leaves connected with the aphids under a Potter spraying tower, culturing the treated aphids in an observation room at 20-22 ℃, and investigating the result after 48 hours. If the body of the insect is touched by a writing brush, the dead insect is determined to be no response. The test concentration was 500. mu.g/mL (the drug solution of other concentration can be diluted with 500. mu.g/mL).
The insecticidal activity test results show that (table 1), when the test concentration is 500 mu g/mL, the insecticidal effects of the compounds Ia to ie on armyworms are 100%, 100%, 100%, 70% and 80% respectively; the insecticidal activity of compounds id and ie against aphids was 100% and 80%, respectively.
TABLE 1 insecticidal Activity data of Ia-Ie
"-" indicates not determined
The test structure shows that the pyridine bi-substituted phenoxy unit and the 2-substituent-1, 3-thiazolidinyl group are linked together, and the obtained new compound shows excellent insecticidal action.
The foregoing shows and describes the general principles, principal 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, and that the foregoing examples and descriptions are merely illustrative of 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 intended to be 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. A2-substituent-1, 3-thiazolidine (I) containing pyridine bi-substituted phenoxy unit is characterized by having the structure:
2. the process for producing 2-substituent-1, 3-thiazolidine (I) containing a pyrido-substituted phenoxy unit according to claim 1, comprising the steps of:
3. use of a 2-substituent-1, 3-thiazolidine (I) containing a pyrido-substituted phenoxy unit according to claim 1 for the preparation of a aphicide.
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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 |
| WO2002096872A1 (en) * | 2001-05-29 | 2002-12-05 | Bayer Cropscience Ag | Substituted imidates as pesticidal agents |
| 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 |
| CN111548347A (en) * | 2020-06-20 | 2020-08-18 | 南通大学 | Pyrazole compound containing 2-cyanoimino-1, 3-thiazolidine heterocycle and preparation method and application thereof |
| CN111635397A (en) * | 2020-06-23 | 2020-09-08 | 南通大学 | Preparation and application of 3- (4-trifluoromethylphenyl) -1,2, 4-oxadiazole derivative containing five-membered nitrogen heterocycle |
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2020
- 2020-09-16 CN CN202010972041.2A patent/CN111909145B/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 |
| WO2002096872A1 (en) * | 2001-05-29 | 2002-12-05 | Bayer Cropscience Ag | Substituted imidates as pesticidal agents |
| 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 |
| CN111548347A (en) * | 2020-06-20 | 2020-08-18 | 南通大学 | Pyrazole compound containing 2-cyanoimino-1, 3-thiazolidine heterocycle and preparation method and application thereof |
| CN111635397A (en) * | 2020-06-23 | 2020-09-08 | 南通大学 | Preparation and application of 3- (4-trifluoromethylphenyl) -1,2, 4-oxadiazole derivative containing five-membered nitrogen heterocycle |
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