CN114573561B - Triazinone compound containing benzyl or heterocycle substituted as well as preparation method and application thereof - Google Patents

Triazinone compound containing benzyl or heterocycle substituted as well as preparation method and application thereof Download PDF

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CN114573561B
CN114573561B CN202210277448.2A CN202210277448A CN114573561B CN 114573561 B CN114573561 B CN 114573561B CN 202210277448 A CN202210277448 A CN 202210277448A CN 114573561 B CN114573561 B CN 114573561B
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formula
compound
phenyl
preparation
aphids
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CN114573561A (en
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凌云
路星星
杨新玲
张莉
段红霞
徐欢
林誉凡
张晓鸣
孙腾达
王长凯
石发胜
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China Agricultural University
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China Agricultural University
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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
    • C07D401/12—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 chain containing hetero atoms as chain links
    • 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
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses a medicine containingA triazinone compound substituted by benzyl or heterocycle, its preparation method and application are provided. The compounds containing the formula I can be prepared according to the following method: reacting aminotriazinone (II) with different benzyl chlorides (II) to obtain a compound I; the compound is applied to preventing and controlling agricultural pests as pesticides for agricultural pest aphids, plutella xylostella, white flies, black leafhoppers and the like; the invention has novel structure, simple operation, easily obtained raw materials and no harmful byproducts; the insecticidal composition has good insecticidal activity, particularly has obvious killing activity on aphids, and can be used as a potential insecticide for agricultural pests and used for controlling the agricultural pests such as aphids, plutella xylostella, white flies, black leafhoppers and the like.

Description

Triazinone compound containing benzyl or heterocycle substituted as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and in particular relates to a triazinone compound containing benzyl or heterocycle substitution, a preparation method thereof and application thereof in the aspect of insect killing.
Background
Among 4000 kinds of aphids, about 250 kinds of aphids are the most damaging cultivated plant pests, and the aphids have the advantages of rapid propagation, various species, capability of surviving at any part of plants and consuming a large amount of nutrients of the plants, and also can transmit more than 200 kinds of viral diseases, and generate factors such as resistance to a plurality of pesticides, thus becoming the extraordinary agricultural, forestry and gardening pests. Pymetrozine (Pymetrozine) is a novel heterocyclic pesticide discovered by Ciba-Ge Igy company in 1988, has the characteristics of unique action mode, high selectivity, no interactive resistance with the traditional pesticide, environmental safety and the like, and has unique control effect on sucking mouthparts pests, especially aphids. Therefore, the pymetrozine has been widely applied to farmland crops and ornamental plants for preventing and controlling pests such as aphids, whiteflies, black leafhoppers and the like. The triazinone in pymetrozine is connected with the pyridine part by a carbon-nitrogen double bond, the triazinone and the pyridine part are taken as important active fragments, and no product is formed by connecting the triazinone ring and the pyridine part in a methylene form. With the increasing emphasis on environmental protection worldwide, the development of efficient, low-toxicity and environment-friendly pesticides of triazinones has been an urgent need in the current agricultural production.
In the prior art, the triazinone compound with a structure shown as the general formula I and containing benzyl or heterocycle substitution is not reported.
Disclosure of Invention
The invention aims to provide a triazinone compound containing a benzyl or heterocyclic substituted triazinone compound and a preparation method thereof.
The structural formula of the triazinone compound containing benzyl or heterocycle substitution provided by the invention is shown as formula I:
in the formula I, the compound of the formula I,
r is selected from any of the following groups: phenyl, substituted phenyl, 3-6 carbon heterocycle, substituted 3-6 carbon heterocycle; the heteroatom in the carbon heterocycle may be selected from at least one of the following: n, O and S.
Wherein the substituents in the substituted phenyl and substituted 3-6 carbon heterocycle are each selected from one or more of the following groups: hydroxy, halogen atom (fluorine, chlorine, bromine, iodine), dichloro (fluorine, bromine) methyl, trichloro (fluorine, bromine) methyl, cyano, nitro, trifluoromethyl, trifluoromethoxy, 1-4 carbonamido, 1-5 carbon hydrocarbon group (such as methyl), 1-6 carbon alkoxy (such as methoxy), 1-4 carbon alkyl carbonyl, 1-4 carbon alkoxy carbonyl.
Further, the carbon heterocycle in the 3-6 carbon heterocycle or substituted 3-6 carbon heterocycle is selected from any of the following: furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrimidine, pyrazine, quinoline, and the like.
Further, the compounds of formula I may be selected from the following compounds: r is selected from chloropyridyl (such as 2-chloropyridyl), chlorothiophene, chlorothiazolyl (such as 2-chlorothiazolyl), 2-fluoro-phenyl, 2-chloro-phenyl, 2-methyl-phenyl, 2-cyano-phenyl, 2-trifluoromethyl-phenyl, 3-fluoro-phenyl, 3-chloro-phenyl, 3-methyl-phenyl, 3-cyano-phenyl, 3-methoxy-phenyl, 3-trifluoromethyl-phenyl, 3-nitro-phenyl, 4-fluoro-phenyl, 4-chloro-phenyl, 4-methyl-phenyl, 4-cyano-phenyl, 4-trifluoromethyl-phenyl, 4-nitro-phenyl, 3, 4-dichlorophenyl.
The preparation method of the compound shown in the formula I provided by the invention comprises the following steps:
reacting amino triazinone shown in formula II with a compound shown in formula III to obtain a compound shown in formula I; wherein, in the formula II, R is defined as the formula I.
The above reaction is carried out in the presence of an acid-binding agent which may be selected from at least one of the following: 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 to 24 hours, preferably 12 to 18 hours; in the above reaction, the initial molar ratio of aminotriazine ketone represented by formula II to the compound represented by formula III is 1: (1.2-2).
In the present invention, the compounds of formula II can be synthesized by reference to the following documents: anhui agronomic notification 2013, 19 (04): 76-77; pesticide science and management 2015, 36 (9): 25-29.
The invention also provides application of the compound shown in the formula I.
The application of the compound shown in the formula I provided by the invention 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 include aphids (such as soybean aphids and peach aphids), plutella xylostella, white flies, black tail leafhoppers and the like.
The compound shown in the formula I shows good aphid killing activity when being used for preventing and controlling pests which cause harm to agricultural production, wherein the compounds I-01 and I-20 show similar insecticidal activity as pymetrozine.
The invention also provides an insecticide.
The active ingredient of the pesticide disclosed by the invention comprises a compound shown as a formula I.
The invention discloses a triazinone compound containing benzyl or heterocycle substituted; the compound can be applied to preventing and controlling agricultural insect aphids, plutella xylostella, white flies, black leafhoppers and the like; the compound provided by the invention has novel structure, the preparation method is simple to operate, raw materials are easy to obtain, and no harmful byproducts are generated; the insecticidal composition has good insecticidal activity, particularly has obvious killing activity on aphids, and can be used as an insecticide for controlling agricultural pests such as aphids, plutella xylostella, white flies, black leafhoppers and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified.
The compounds of formula II used in the examples below can be synthesized by reference to the following documents: anhui agronomic notification 2013, 19 (04): 76-77; pesticide science and management 2015, 36 (9): 25-29.
Example 1: synthesis of 4- ((6-chloropyridin-3-yl) methyl) amino) -6-methyl-4, 5-dihydro-1, 2, 4-triazin-3 (2H) -one (I-01)
In a 100mL single-necked flask, aminotriazine (1.28 g,10 mmol) and acetonitrile (40 mL) were added and dissolved under stirring, potassium carbonate (2.76 g,20 mmol) and a proper amount of sodium iodide were added, and after stirring for 15min, 2-chloro 5- (chloromethyl) pyridine (1.78 g,11 mmol) was added and stirred under reflux for 6h, and TLC was monitored to complete the reaction. The reaction mixture was added with water, extracted with ethyl acetate, washed twice with saturated sodium chloride solution, dried over sodium sulfate, and then subjected to silica gel column chromatography with methylene chloride/methanol (150:1-100:1) to give 0.86g of a yellow solid, yield 33.99%, melting point 137.1-137.4 ℃. 1 H NMR(500MHz,DMSO-d 6 )δ9.64(s,1H),8.36(d,J＝2.5Hz,1H),7.85(dd,J＝8.2,2.5Hz,1H),7.47(d,J＝8.1Hz,1H),5.82(t,J＝5.4Hz,1H),3.99(d,J＝5.4Hz,2H),3.88(s,2H),1.79(s,3H).
The procedure for the compound I-02-I-23 with reference to I-01 is completed by simply substituting 2-chloro-5- (chloromethyl) pyridine in the corresponding manner.
The appearance, melting point and yield of some of the compounds of the general formula I according to the invention are shown in Table 1, 1 the 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 2: insecticidal Activity of Compounds of formula I against agricultural pests
Aphid killing Activity test
The soybean aphid killing activity is determined as follows: the test insects were soybean aphids (AphIs glyci nes Matsumura), a normal population of soybean leaves raised in the laboratory. Weighing the medicine, adding 1mL of dimethyl sulfoxide for dissolution, adding two drops of Tween-20 emulsifier, adding a certain amount of distilled water, and stirring uniformly to prepare the medicine liquid with the required concentration. The leaf of soybean with aphid (about 20) was immersed in the preparation for 10 seconds, removed and dried gently, the excess preparation was sucked with filter paper, then the leaf of soybean was placed in a twelve-well plate with condensed agar (2%) at the bottom and sealed with rice paper, and the results were checked for 48 hours, and each compound was repeated 3 times. The control was prepared by adding only the emulsifier and solvent to distilled water and stirring well.
The method for measuring the activity of killing the green peach aphids comprises the following steps: the test insects were normal populations of green peach aphids (Myzus pers i cae (Sulzer)), and laboratory radish leaves. Weighing the medicine, adding 1mL of dimethyl sulfoxide for dissolution, adding two drops of Tween-20 emulsifier, adding a certain amount of distilled water, and stirring uniformly to prepare the medicine liquid with the required concentration. The leaf of the radish with aphid (about 20) was immersed in the preparation for 10 seconds, removed and dried gently, the excess preparation was blotted with filter paper, and then the leaf of the radish was placed in a 3cm dish with filter paper at the bottom and agar liquid (2%) after condensation, and the results were checked for 48 hours and each compound was repeated 3 times. The control was prepared by adding only the emulsifier and solvent to distilled water and stirring well.
The criterion is that normal movement cannot be induced when contacted with a brush, and larvae are considered dead.
Calculating mortality
Calculating mortality and correcting mortality
Wherein P1 is the mortality rate of treatment, K is the number of dead insects, and N is the total number of treatment.
Where P2 is the corrected mortality, P1 is the treated mortality, and P0 is the placebo mortality.
Table 3 results of the test for the soybean aphid killing Activity of the partial Compound of formula I and commercial insecticide at 200mg/L (48 h)
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 aphids tested. At a concentration of 200mg/L, the mortality rate of a plurality of compounds to soybean aphids exceeds 80%.
Testing of concentration Activity in death of Aphis sojae and Aphis persicae
The method for testing the activity of killing the soybean aphids in the middle concentration in killing process is the same as the common screening method
TABLE 4 lethal Medium concentration LC of partial Compounds of formula I against Aphis sojae 50 (48h)
TABLE 5 Medium concentration LC lethal to Aphis persicae of partial Compound of formula I 50 (48h)
As can be seen from tables 4 and 5, most of the compounds are relatively largeThe bean aphids and the peach aphids show obvious lethal activity. Wherein the concentration of the compounds I-01, I-12, I-13, I-19, I-20 and I-22 in killing soybean aphids is below 10mg/L, and especially the concentration of the compounds I-01, I-19 and I-22 in killing soybean aphids is better than that of the commercial control agent pymetrozine (LC 50 = 4.668 mg/L); wherein the concentration of the compound I-01 in killing the myzus persicae is below 10mg/L, which is superior to the commercial control medicament pymetrozine (LC 50 = 9.864 mg/L). The compound I-01 has better insecticidal activity on soybean aphids and peach aphids, and is a potential insecticide.

Claims (9)

1. A compound of formula i:
in the formula I, R is selected from any of the following groups: 2-chloropyridyl, 3-cyano-phenyl, 3-trifluoromethyl-phenyl, 3-nitro-phenyl, 4-nitro-phenyl, 3, 4-dichlorophenyl and 2-cyano-phenyl.
2. A process for the preparation of a compound as claimed in claim 1 comprising the steps of:
reacting amino triazinone shown in formula II with a compound shown in formula III to obtain a compound shown in formula I;
wherein in the formula II, R is as defined in claim 1.
3. The preparation method according to claim 2, characterized in that:
the reaction is carried out in the presence of an acid-binding agent selected from at least one of the following: sodium carbonate, potassium carbonate, cesium carbonate; the said process is carried out in a solvent selected from at least one of the following: acetonitrile, dimethyl sulfoxide, N-dimethylformamide.
4. A method of preparation according to claim 2 or 3, characterized in that: 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 aminotriazine ketone shown in the formula II to the compound shown in the formula III is 1: (1.2-2).
5. The method of manufacturing according to claim 4, wherein: the reaction time is 12-18 hours.
6. The use of a compound according to claim 1 for controlling pests which are harmful to agricultural production.
7. Use of a compound according to claim 1 for the preparation of a pesticide.
8. Use according to claim 6 or 7, characterized in that:
the pests comprise aphids, plutella xylostella, whiteflies and black tail leafhoppers;
the pesticide is used for killing any of the following pests: aphids, plutella xylostella, whiteflies and black tail leafhoppers.
9. An insecticide whose active ingredient comprises the compound of claim 1.
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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0314615B1 (en) * 1987-10-16 1995-04-26 Ciba-Geigy Ag Pesticides
DE4011740A1 (en) * 1989-04-14 1990-10-18 Ciba Geigy Ag New 4-heterocyclyl-imino or-amino-1,2,4-triazin-3-one derivs. - useful as contact and systemic insecticides and acaricides
US5384403A (en) * 1993-03-31 1995-01-24 Ciba-Geigy Corporation Process for the preparation of aminotriazine derivatives

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