CN114591294A - Triazolone compound containing chloropyridine methylene as well as preparation method and application thereof - Google Patents
Triazolone compound containing chloropyridine methylene as well as preparation method and application thereof Download PDFInfo
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- CN114591294A CN114591294A CN202210275818.9A CN202210275818A CN114591294A CN 114591294 A CN114591294 A CN 114591294A CN 202210275818 A CN202210275818 A CN 202210275818A CN 114591294 A CN114591294 A CN 114591294A
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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
- C07D401/02—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 two hetero rings
- C07D401/06—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 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
- A01N43/64—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
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a triazolone compound containing chloropyridine methylene and a preparation method and application thereof, wherein the structural general formula of the compound is shown as a formula I. The compound containing the formula I can be prepared by the following method: reacting 4-amino-2- ((6-chloropyridin-3-yl) methyl) -5-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one (I-01) with different acyl chlorides (II) to obtain a formula I; the compound of the invention is applied to control agricultural pests; the invention has novel structure, simple operation of the preparation method, easily obtained raw materials and no generation of harmful by-products; and the insecticidal composition has good insecticidal activity, especially has obvious killing activity on aphids, and can be used as a potentialThe pesticide is used for controlling the agricultural pests.
Description
Technical Field
The invention belongs to the technical field of pesticides, and relates to a triazolone compound containing chloropyridine methylene, a preparation method thereof and application thereof in the aspect of insect disinfestation.
Background
Aphids have large-scale damage in fields and gardening, wherein soybean aphids, peach aphids, pea aphids and the like are representative aphid types with strong damage. At present, the control of aphids mainly depends on chemical agents, chemical pesticides for controlling the aphids mainly comprise pyrethroids, bisamides, neonicotinoids and the like, and the neonicotinoid insecticides have been applied for nearly thirty years since the advent, but are still one of the most important insecticides in the world. The main structure of the neonicotinoid insecticide is that heterocyclic groups (6-chloro-3-pyridine, 2-chloro-5-thiazole, tetrahydrofuran ring and five-membered or six-membered nitrogen heterocyclic groups are connected by a methylene group, the research of related neonicotinoid insecticides using triazolone as five-membered nitrogen heterocyclic groups is not available, and along with the resistance of commercial agents and the increasing importance on environmental protection all over the world, the synthesis of high-efficiency, low-toxicity and environment-friendly neonicotinoid insecticides with different structural segments is a priority in the current agricultural production.
In the prior art, the triazolone compound containing chloropyridine methylene, the structure of which is shown as the general formula I, is not reported.
Disclosure of Invention
The invention aims to provide triazolone compounds containing chloropyridine methylene and a preparation method thereof.
The structural formula of the triazolone compound containing chloropyridine methylene provided by the invention is shown as the formula I:
in formula I:
r is selected from H or
Wherein R is1Represents hydrogen, halogen, hydroxyl, amino, cyano, nitro, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 carbon cycloalkyl, C1-C12 alkylamino, halogenated C1-C12 alkylamino, C2-C12 alkenyl, C2-C12 alkynyl, C2-C12 alkenyloxy, halogenated C2-C12 alkenyloxy, C2-C12 alkynyloxy, halogenated C2-C12 alkynyloxy, 3-6 carbon nitrogen-containing heterocycle, 3-5 carbon sulfur-containing heterocycle, substituted phenyl;
the substituent on the substituted phenyl group can be one or more of hydrogen, hydroxyl, halogen atoms (fluorine, chlorine, bromine and iodine), dichloro (fluorine and bromine) methyl, trichloro (fluorine and bromine) methyl, cyano, nitro, trifluoromethyl, trifluoromethoxy, 1-4 carbonamide, 1-5 carbon hydrocarbyl, 1-6 carbon alkoxy, 1-4 carbon alkyl carbonyl oxy and 1-4 carbon alkoxy carbonyl oxy.
Further, the compound of formula i may be specifically selected from the following compounds: r is selected from H or
R1Is selected from CH3、CH2Cl、CHCl2、CCl3、CHF2、CF3、CH(CH3)Cl、C(CH3)2CH2Cl、CH(Br)CH2Br、CH＝CH2、CH(CH3)2、C(CH3)＝CH2、CH2CH2CH3、CH＝CHCH3、CH＝C(CH3)2、C(CH3)3Cyclopropyl, cyclopentyl, cyclohexyl, 2-thiophene, 2-F-phenyl, 3-F-phenyl, 4-F-phenyl, 3-Cl-phenyl, 4-Br-phenyl, 2-OCH3-phenyl, 3-OCH3-phenyl, 4-OCH3-phenyl, 2-CH3-phenyl, 3-CH3-phenyl, 4-CH3-phenyl, 2-CF3-phenyl, 3-CF3-phenyl, 4-NO2-phenyl.
The invention provides a preparation method of a compound (R ═ H) shown as a formula I, which comprises the following steps:
reacting a compound shown as a formula III with a compound shown as a formula IV to obtain a compound shown as a formula I-01;
the above reaction is carried out in the presence of an acid-binding agent, which may be selected from at least one of: sodium carbonate, potassium carbonate, cesium carbonate; the above reaction is carried out in a solvent which may be selected from at least one of the following: acetonitrile, dimethyl sulfoxide, N-dimethylformamide; the reaction conditions of the above reaction are: the reaction temperature is 70 ℃ to 100 ℃; the reaction time is 0.5-24 hours; in the above reaction, the initial molar ratio of the compound of formula iii to the compound of formula iv is 1: (1-2).
The compounds of formula III used in the following examples can be synthesized with reference to the following references: kahvecci, Battery et al, chemistry of Heterocyclic Compounds,51, (5), 447-.
The invention provides a compound shown as a formula I (R is
) The preparation method comprises the following steps:
reacting 4-amino-2- ((6-chloropyridin-3-yl) methyl) -5-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one (I-01) with different acyl chlorides shown in formula II to obtain a compound shown in formula I; wherein, in the formula I,R1the definition of (A) is the same as that of formula I.
The reaction is carried out in the presence of an acid-binding agent, wherein the acid-binding agent can be at least one selected from the following group: triethylamine, pyridine; the above reaction is carried out in a solvent, which may be selected from at least one of the following: dichloromethane, pyridine; the reaction conditions of the above reaction are: the reaction temperature is 0 ℃ to 35 ℃; the reaction time is 0.5-24 hours, preferably 1-6 hours; in the above reaction, the initial molar ratio of the compound represented by formula I-01 to the compound represented by formula II is 1: (1.2-2).
The invention also provides application of the compound shown in the formula I.
The application of the compound shown in the formula I is the application of the compound in preventing and controlling pests which cause harm to agricultural production or the application in preparing pesticides.
The pests comprise aphids (such as soybean aphids), diamondback moths, whiteflies, leafhoppers and the like.
The compound shown in the formula I is used for preventing and controlling pests harmful to agricultural production, shows good aphid killing activity, and the compounds I-17-I-36 show good soybean aphid insecticidal activity at 200 ppm.
The invention also protects a pesticide.
The active ingredients of the pesticide comprise compounds shown in formula I.
The invention discloses a triazolone compound containing chloropyridine methylene. The compound can be applied to control agricultural pests such as aphids, diamondback moths, whiteflies, leafhoppers and the like; the compound provided by the invention has a novel structure, the preparation method is simple to operate, raw materials are easy to obtain, and no harmful by-product is generated; and the insecticidal composition has good insecticidal activity, especially has obvious killing activity on aphids, and can be used as an insecticide for preventing and controlling agricultural pests such as aphids, diamond back moths, whiteflies, leafhoppers and the like.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The compounds of formula III used in the following examples can be synthesized with reference to the following references: kahvecci, Baihitin et al, Chemary of Heterocyclic Compounds,51, (5),447-456(2015).
Example 1: synthesis of 4-amino-2- ((6-chloropyridin-3-yl) methyl) -5-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one (I-01)
In a 100mL single neck flask, aminotriazolone (1.14g, 10mmol) and acetonitrile (40mL) were added and dissolved with stirring, potassium carbonate (2.76g, 20mmol) and an appropriate amount of sodium iodide were added and after stirring for 15min, 2-chloro 5- (chloromethyl) pyridine (1.78g, 11mmol) was added and stirred under reflux for 6h, and the reaction was monitored by TLC for completion. The reaction solution was added to water, extracted with ethyl acetate, washed twice with saturated sodium chloride solution, dried over sodium sulfate, and then subjected to silica gel column chromatography using methylene chloride/methanol (150: 1-100: 1) to give 1.23g of a pale yellow solid, a yield of 51.43%, a melting point of 129.6-131.0 ℃.1H NMR(500MHz,Chloroform-d)δ8.40(d,1H),7.67(dd,J＝8.2,2.5Hz,1H),7.30(d,J＝8.2Hz,1H),4.89(s,2H),4.28(s,2H),2.23(s,3H).
Example 2: synthesis of N- (1- ((6-chloropyridin-3-yl) methyl) -3-methyl-5-oxo-1, 5-dihydro-4H-1, 2, 4-triazol-4-yl) -2,2, 2-trifluoroacetamide (I-02)
In a 50mL single neck flask, I-01(0.48g, 2mmol) and methylene chloride (20mL) were added and dissolved with stirring, pyridine (0.25g, 3mmol) was added, and trifluoromethylacyl chloride (0.42g, 2mmol) was added and stirred overnight at room temperature and the reaction was monitored by TLC for completion. Adding hydrochloric acid waterThe solution (10%) was extracted with dichloromethane, washed twice with saturated sodium chloride solution, dried over sodium sulfate and then chromatographed on silica gel using ethyl acetate/n-hexane (1: 1) to give 0.54g of a white solid in 85.07% yield and mp 138.2-139.4 ℃.1H NMR(500MHz,DMSO-d6)δ8.32(d,1H),7.72(d,J＝10.7Hz,1H),7.51(d,J＝8.2Hz,1H),4.86(s,2H),1.92(s,3H).
Compounds I-03-I-36 were prepared by repeating the procedure of I-02.
The appearance, melting point and yield of some of the compounds of general formula I of the present invention are shown in Table 1,1the H NMR data are shown in Table 2.
Table 1: melting Point, appearance and yield of the partial Compounds of formula I
Table 2: nuclear magnetic hydrogen spectrum data of partial compound of formula I
Example 3: insecticidal activity of compounds of formula i against soybean aphid:
the test insects are normal colony of soybean aphid (Aph I gycol I nes Matsumura) fed by soybean leaves in a laboratory. Weighing the medicines, adding 1mL of dimethyl sulfoxide to dissolve the medicines, adding two drops of Tween-20 emulsifier, adding a certain amount of distilled water, and uniformly stirring to prepare the liquid medicine with the required concentration. The leaves of soybeans with aphids (about 20) were immersed in the drug for 10 seconds, taken out and gently spun, the excess drug was blotted with filter paper, and then the leaves were put into a twelve-well plate with condensed agar liquid (2%) at the bottom and sealed with rice paper, and the results were examined for 48 hours, and each compound was repeated 3 times. The control was prepared by adding the emulsifier and solvent to distilled water and stirring the mixture uniformly.
The larvae were considered dead if they were not induced to move normally when contacted with a brush.
Calculating mortality
Calculating mortality and correcting mortality
Wherein P1 is the mortality rate of the treatment, K is the number of dead insects, and N is the total number of insects treated.
Where P2 is corrected mortality, P1 is treatment mortality, and P0 is blank control mortality.
TABLE 3 Soybean aphid-killing Activity of part of the Compounds of formula I and of the commercial insecticides at 200mg/L test results (48h)
As can be seen from Table 3, some of the compounds of formula I provided by the present invention have some insecticidal activity against the soybean aphid tested. At a concentration of 200mg/L, the lethality of most compounds to soybean aphid is over 80%. Wherein, the compounds I-17 to I-36 have better insecticidal activity on soybean aphids, which proves that the structure of the compound in the formula I can be a potential insecticide structure and is worthy of further modification and research.
Claims (10)
1. A compound having the structural formula I:
in formula I:
r is selected from H or
Wherein R is1Represents hydrogen, halogen, hydroxyl, amino, cyano, nitro, C1-C12 alkyl, halogenated C1-C12 alkyl, C1-C12 alkoxy, halogenated C1-C12 alkoxy, C3-C12 carbon cycloalkyl, C1-C12 alkylamino, halogenated C1-C12 alkylamino, C2-C12 alkenyl, C2-C12 alkynyl, C2-C12 alkenyloxy, halogenated C2-C12 alkenyloxy, C2-C12 alkynyloxy, halogenated C2-C12 alkynyloxy, 3-6 carbon nitrogen-containing heterocycle, 3-5 carbon sulfur-containing heterocycle and substituted phenyl.
2. The compound of claim 1, wherein: the substituents on the substituted phenyl are selected from: one or more of hydrogen, hydroxyl, halogen atoms (fluorine, chlorine, bromine and iodine), dichloro (fluorine and bromine) methyl, trichloro (fluorine and bromine) methyl, cyano, nitro, trifluoromethyl, trifluoromethoxy, 1-4 carbonamide, 1-5 carbon hydrocarbon group, 1-6 carbon alkoxy, 1-4 carbon alkyl carbonyl oxygen and 1-4 carbon alkoxy carbonyl oxygen.
3. The compound of claim 1 or 2, wherein: the compound of formula i is selected from the following compounds: r is selected from H or
R1Is selected from CH3、CH2Cl、CHCl2、CCl3、CHF2、CF3、CH(CH3)Cl、C(CH3)2CH2Cl、CH(Br)CH2Br、CH＝CH2、CH(CH3)2、C(CH3)＝CH2、CH2CH2CH3、CH＝CHCH3、CH＝C(CH3)2、C(CH3)3Cyclopropyl, cyclopentyl, cyclohexyl, 2-thiophene, 2-F-phenyl, 3-F-phenyl, 4-F-phenyl, 3-Cl-phenyl, 4-Br-phenyl, 2-OCH3-phenyl, 3-OCH3-phenyl, 4-OCH3-phenyl, 2-CH3-phenyl, 3-CH3-phenyl, 4-CH3-phenyl, 2-CF3-phenyl, 3-CF3-phenyl, 4-NO2-phenyl.
4. A process for the preparation of a compound of formula i as defined in claim 1, wherein R ═ H comprises the steps of: reacting a compound shown as a formula III with a compound shown as a formula IV to obtain a compound shown as a formula I, wherein R is H;
5. the method of claim 1, wherein:
the reaction is carried out in the presence of an acid-binding agent selected from at least one of: sodium carbonate, potassium carbonate, cesium carbonate; the reaction is carried out in a solvent selected from at least one of: acetonitrile, dimethyl sulfoxide, N-dimethylformamide; the reaction conditions of the reaction are as follows: the reaction temperature is 70 ℃ to 100 ℃; the reaction time is 0.5-24 hours; in the reaction, the initial molar ratio of the compound shown in the formula III to the compound shown in the formula IV is 1: (1-2).
6. A compound of formula I as claimed in claim 1 wherein R is
The process for the preparation of a compound of (1), comprising the steps of:
reacting a compound of formula I (formula I-01) wherein R is H with a compound of formula II to give R is
A compound of formula I;
wherein in formula I, R1The definition of (D) is the same as that of formula I.
7. The method of claim 6, wherein: the reaction is carried out in the presence of an acid-binding agent selected from at least one of: triethylamine, pyridine; the reaction is carried out in a solvent selected from at least one of: dichloromethane and pyridine; the reaction conditions of the reaction are as follows: the reaction temperature is 0 ℃ to 35 ℃; the reaction time is 0.5-24 hours, preferably 1-6 hours; in the reaction, the initial molar ratio of the compound represented by formula I-01 to the compound represented by formula II is 1: (1.2-2).
8. Use of a compound according to any one of claims 1 to 3 for controlling pests which are harmful to agricultural production, or for producing pesticides.
9. Use according to claim 8, characterized in that:
the pests comprise aphids, diamondback moths, whiteflies and leafhoppers;
the pesticide is used for killing any of the following pests: aphids, diamondback moths, whiteflies and leafhoppers.
10. A pesticide whose active ingredient comprises a compound as claimed in any one of claims 1 to 3.
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| CN202210275818.9A CN114591294B (en) | 2022-03-21 | 2022-03-21 | Triazolone compound containing chloropyridine methylene and preparation method and application thereof |
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| CN202210275818.9A CN114591294B (en) | 2022-03-21 | 2022-03-21 | Triazolone compound containing chloropyridine methylene and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000010984A1 (en) * | 1998-08-19 | 2000-03-02 | Hokko Chemical Industry Co., Ltd. | Triazolinone derivatives and herbicide compositions |
| JP2012077078A (en) * | 2010-09-10 | 2012-04-19 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Novel triazolone derivative and pest control agent containing the same as active constituent |
| CN102993189A (en) * | 2011-09-15 | 2013-03-27 | 中国中化股份有限公司 | Hydrazone-containing triazolinone compounds and uses thereof |
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- 2022-03-21 CN CN202210275818.9A patent/CN114591294B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000010984A1 (en) * | 1998-08-19 | 2000-03-02 | Hokko Chemical Industry Co., Ltd. | Triazolinone derivatives and herbicide compositions |
| JP2012077078A (en) * | 2010-09-10 | 2012-04-19 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Novel triazolone derivative and pest control agent containing the same as active constituent |
| CN102993189A (en) * | 2011-09-15 | 2013-03-27 | 中国中化股份有限公司 | Hydrazone-containing triazolinone compounds and uses thereof |
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