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CN-122010938-A - Pyrido [1, 2-a ] pyrimidine mesoionic derivative containing five-membered heterocyclic structure, and preparation and application thereof

CN122010938ACN 122010938 ACN122010938 ACN 122010938ACN-122010938-A

Abstract

The invention relates to a pyrido [1,2-a ] pyrimidine mesoionic derivative containing a five-membered heterocyclic structure, a preparation method and application thereof. The compound is shown as a general formula (I), wherein R 1 represents cyanoalkyl, aryl or heterocyclic group, E, G, M, Q respectively and independently represents O, S, N or CR 3 ;R 2 、R 3 represents hydrogen, alkyl, nitro, cyano, halogen and the like. The compound has excellent insecticidal activity on green pea aphis, spodoptera frugiperda, corn borer, asparagus caterpillar, brown planthopper, chilo suppressalis, alfalfa aphid and the like. (I)。

Inventors

  • SONG BAOAN
  • WU SHANG
  • Song Runjiang
  • HU DEYU
  • MA QINGQING
  • WANG JIAN
  • Li Jianzhuan

Assignees

  • 贵州大学

Dates

Publication Date
20260512
Application Date
20260129

Claims (10)

  1. 1. Pyrido [1, 2-a ] pyrimidine medium ion compound or salt thereof containing five-membered heterocyclic ring structure, which is characterized in that the compound is shown as a general formula (I): (I) Wherein R 1 represents cyanoalkyl, aryl or heterocyclyl; E. g, M, Q each independently represents O, S, N or CR 3 ; R 2 、R 3 independently represents hydrogen, nitro, cyano, halogen, hydroxy, mercapto, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, formyl, alkylcarbonyl, alkylsulfanyl, alkylsulfonyl, amino substituted by alkyl, cycloalkyl, aryl or heterocyclyl; The foregoing "cycloalkyl" is optionally substituted with at least one group selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted with alkyl, or cycloalkylalkyl; The foregoing "heterocyclyl" or "aryl" is optionally aryl or heterocyclyl substituted with at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted with alkyl, cycloalkylalkyl, unsubstituted or substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.
  2. 2. The pyrido [1, 2-a ] pyrimidine-based mesoionic compound having a five-membered heterocyclic structure according to claim 1, or a salt thereof, wherein: r 1 represents cyano C 1 -C 8 alkyl, aryl or heterocyclyl; R 2 、R 3 independently represents hydrogen, nitro, cyano, halogen, hydroxy, mercapto, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, halogenated C 1 -C 8 alkyl, halogenated C 2 -C 8 alkenyl, halogenated C 2 -C 8 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkylthio, formyl, C 1 -C 8 alkylcarbonyl, C 1 -C 8 alkylsulfoxide, C 1 -C 8 alkylsulfonyl, amino substituted by C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, aryl or heterocyclyl; The foregoing "C 3 -C 8 cycloalkyl" is optionally substituted with at least one group selected from halogen, cyano, nitro, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, halogenated C 1 -C 8 alkyl, halogenated C 2 -C 8 alkenyl, halogenated C 2 -C 8 alkynyl, halogenated C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted with C 1 -C 8 alkyl, or C 3 -C 8 cycloalkyl C 1 -C 8 alkyl; The foregoing "heterocyclyl" or "aryl" is optionally substituted with a moiety selected from oxo, halo, cyano, nitro, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, halo C 1 -C 8 alkyl, halo C 2 -C 8 alkenyl, halo C 2 -C 8 alkynyl, halo C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted with C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl C 1 -C 8 alkyl, unsubstituted or substituted with a moiety selected from halo, C, Cyano, nitro, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkylthio, Aryl or heterocyclic substituted by at least one of C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy or halogenated C 1 -C 8 alkoxy.
  3. 3. The pyrido [1, 2-a ] pyrimidine-based mesoionic compound having a five-membered heterocyclic structure according to claim 1, or a salt thereof, wherein: r 1 is independently selected from cyano C 1 -C 8 alkyl, 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ; R 2 、R 3 independently of one another represents hydrogen, nitro, cyano, halogen, hydroxy, mercapto, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogenated C 1 -C 6 alkyl, halogenated C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkylthio, formyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfoxide, C 1 -C 6 alkylsulfonyl, amino substituted by C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, aryl or heterocyclyl; The foregoing "C 3 -C 6 cycloalkyl" is optionally substituted with at least one group selected from halogen, cyano, nitro, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, halogenated C 1 -C 6 alkyl, halogenated C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkynyl, halogenated C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl substituted with C 1 -C 6 alkyl, or C 3 -C 6 cycloalkyl C 1 -C 6 alkyl; The foregoing "heterocyclyl" or "aryl" is optionally substituted with a moiety selected from oxo, halo, cyano, nitro, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, halo C 1 -C 6 alkyl, halo C 2 -C 6 alkenyl, halo C 2 -C 6 alkynyl, halo C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl substituted with C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl C 1 -C 6 alkyl, unsubstituted or substituted with a moiety selected from halo, C, Cyano, nitro, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, Aryl or heterocyclyl substituted with at least one of C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkoxy, or halo C 1 -C 6 alkoxy; the said Is that 、 、 、 、 、 、 、 、 、 、 。
  4. 4. The pyrido [1,2-a ] pyrimidine-based mesoionic compound having a five-membered heterocyclic structure according to claim 1, or a salt thereof, characterized by being selected from the following specific compounds: 。
  5. 5. The process for preparing pyrido [1, 2-a ] pyrimidine compounds containing five-membered heterocyclic structures or salts thereof according to any one of claims 1 to 4, which comprises the steps of reacting a compound of the general formula II with a compound of the general formula III to obtain a compound of the general formula I, wherein the reaction equation is as follows: wherein L 1 、L 2 each independently represents halogen or OH, and the substituents R 1 、R 2 and E, G, M, Q are as defined in any one of claims 1 to 4; Further comprises: wherein X is selected from iodine, bromine or chlorine, and the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride or bis (triphenylphosphine) palladium dichloride.
  6. 6. A composition characterized by comprising a compound or a salt thereof according to any one of claims 1-4 and an agriculturally acceptable adjuvant or fungicide, insecticide or herbicide, preferably in a dosage form selected from the group consisting of Emulsifiable Concentrates (EC), powders (DP), wettable Powders (WP), granules (GR), aqueous Solutions (AS), suspensions (SC), ultra low volume sprays (ULV), soluble Powders (SP), microcapsules (MC), smoke agents (FU), emulsions in water (EW), water dispersible granules (WG), microemulsions (ME).
  7. 7. Use of a compound according to any one of claims 1 to 4 or a salt thereof, or a composition according to claim 6, for the manufacture of a medicament for controlling agricultural pests, said agricultural pests being hemiptera and lepidoptera pests, said agricultural pests being green pea green tail aphid, spodoptera frugiperda and corn borer.
  8. 8. A method for controlling agricultural insect pests, which is characterized in that the compound, or a salt or a solvate thereof, or the composition of claim 6, according to any one of claims 1 to 4 is allowed to act on pests or living environments thereof, wherein the pests are hemiptera and lepidoptera pests, and the pests are green pea green house flies, spodoptera frugiperda and corn borers.
  9. 9. Compound S1 The application of the composition in preparing medicines for preventing and controlling corn borer, beet armyworm, chilo suppressalis, brown planthopper and alfalfa aphid.
  10. 10. An intermediate as shown in formula II or IV of claim 5.

Description

Pyrido [1, 2-a ] pyrimidine mesoionic derivative containing five-membered heterocyclic structure, and preparation and application thereof Technical Field The invention relates to the field of chemical industry and pesticides, in particular to a pyrido [1, 2-a ] pyrimidine medium ion derivative containing five-membered heterocyclic units, a preparation method thereof and application of the pyrido [1, 2-a ] pyrimidine medium ion derivative containing five-membered heterocyclic units in medicines for preventing and controlling pests such as green pea green-tail aphids, spodoptera frugiperda, corn borers, beet armyworms, brown planthoppers, chilo suppressalis and alfalfa aphids. Background In order to cope with the problems of progressive reduction of cultivated land and the like caused by the increasing world population and the increasing urban rate, the grain yield must be continuously increased. Insect pests are one of the main factors threatening the safe production of grains. Pesticides play a key role in protecting crops from insect pests and ensuring grain safety. However, due to the long-term, large-scale and irregular use of conventional pesticides, pests have developed serious resistance thereto. For example, brown planthoppers (NILAPARVATA LUGENS) have developed varying degrees of resistance to 36 effective pesticides, with a fold resistance to imidacloprid generally exceeding 1000 times, based on the data of the Arthropod Pesticide Resistance Database (APRD). A spodoptera exigua (Spodoptera exigua) population collected from the Zhejiang province in 2019 exhibited a multiple of resistance to chlorantraniliprole of over 2000. The group of Chilo suppressalis (Chilo suppressalis) in 2024 shows high level resistance to chlorantraniliprole, and the resistance multiple is 160-1698 times. Thus, there is an urgent need to develop novel efficient pesticides to alleviate the increasingly serious resistance problem. The mesoionic pesticide trifluoro-phenylpyrimidine and dicloromezotiaz developed by kedi Hua (original DuPont company) has novel structure, unique action mechanism and no cross resistance with the existing pesticide. Therefore, the research of the novel-structure mesoionic pesticide is developed by taking the trifluoro-phenylpyrimidine and dicloromezotiaz as the leads, and the novel-structure mesoionic pesticide becomes a hot spot direction for the research of domestic and foreign pesticide creation. A number of mesogenic compounds derived from the 1-and 3-positions of the pyrido [1,2-a ] pyrimidine ring are disclosed in WO2011017342A2, WO2012106495A1, WO2016171053A1 and WO2021151034 Al. Meanwhile, the research team also proves that the five-membered heterocycle has excellent insecticidal activity in the substitution of the 3-position of the pyrido [1,2-a ] pyrimidine ring in the patent CN113651811B and the patent CN 117720535B. Therefore, the 1-position of the pyrido [1, 2-a ] pyrimidine ring retains the common active groups in the neonicotinoid insecticide, and the thiazole, thiophene, furan and oxazole structures with wide biological activity are introduced into the 3-position of the pyrido [1, 2-a ] pyrimidine ring, so that the efficient and broad-spectrum insecticidal compound is hopefully created. Summary of the invention. The invention provides a pyrido [1, 2-a ] pyrimidine medium ion derivative containing a five-membered heterocyclic structure and a preparation method thereof. It is still another object of the present invention to provide a composition comprising the above compound or a salt thereof. It is a further object of the present invention to provide the use of the above compound or a salt thereof, or the composition. It is another object of the present invention to provide a method for controlling agricultural insect pests using the above-mentioned compound or a salt thereof, or the composition. The structural general formula (I) of the pyrido [1, 2-a ] pyrimidine mesoionic derivative containing the five-membered heterocyclic ring structure is as follows: In order to achieve the above purpose, the present invention adopts the following technical scheme: (I) R 1 is independently selected from cyanoalkyl, aryl or heterocyclyl, more preferably R 1 is selected from cyanoC 1-C8 alkyl, 、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、; E. g, M, Q each independently represents O, S, N or CR 3; R 2、R3 independently represents hydrogen, nitro, cyano, halogen, hydroxy, mercapto, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, formyl, alkylcarbonyl, alkylsulfanyl, alkylsulfonyl, amino substituted by alkyl, cycloalkyl, aryl or heterocyclyl; preferably, R 2、R3 independently represents hydrogen, Nitro, cyano, halogen, hydroxy, mercapto, C 1-C8 alkyl, C 2-C8 alkenyl, C 2-C8 alkynyl, halogenated C 1-C8 alkyl, Halogenated C 2-C8 alkenyl, halogenated C 2-C8 alkynyl, C 1-C8 alkoxy, C 1-C8 alkylthio, halogenated C 1-C8 alkoxy, Halogenated C 1-C8 alk