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CN-122010933-A - Pyrido [1,2-a ] pyrimidine mesoionic derivative containing alkynyl cyano structure, and preparation and application thereof

CN122010933ACN 122010933 ACN122010933 ACN 122010933ACN-122010933-A

Abstract

The invention relates to a pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl cyano structure, a preparation method and application thereof. The compound has the following formula [ I ] structure, has excellent insecticidal activity on spodoptera frugiperda, prodenia litura, asparagus caterpillar, corn borer, cutworm, plant hopper, green bean tail-trimming aphid and the like, and can be used for preparing medicines or medicaments for preventing and controlling pests such as spodoptera frugiperda, prodenia litura, asparagus caterpillar, corn borer, cutworm, plant hopper, green peach aphid and the like. The structure and the preparation process are simple, and the production cost is low.

Inventors

  • SONG BAOAN
  • WANG JIAN
  • Song Runjiang
  • HU DEYU
  • ZHANG JIAN
  • ZHANG LUOMAN
  • WANG QIAN

Assignees

  • 贵州大学

Dates

Publication Date
20260512
Application Date
20260107

Claims (10)

  1. 1. A pyrido [1,2-a ] pyrimidine mesogenic derivative containing an alkynyl cyano structure, which is characterized by comprising a compound shown in a general formula [ I ] or a stereoisomer, an N-oxide or a salt thereof: Wherein Q 1 、Q 2 independently represents O or S; X independently represents C or N; r 5 independently represents cyanoalkyl, halo or unsubstituted pyrimidinyl, halo or unsubstituted thiazolyl, halo or unsubstituted pyridinyl; r 1 -R 4 is independently selected from at least one of hydrogen, tritium, alkyl, halogen; R 6 is selected from hydrogen, tritium, alkyl, halogen, alkoxy, haloalkoxy, haloalkyl.
  2. 2. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl cyano structure according to claim 1, wherein: r 5 represents cyanoalkyl, halo or unsubstituted pyrimidinyl, halo or unsubstituted thiazolyl, halo or unsubstituted pyridinyl; R 1 -R 4 is independently selected from at least one of hydrogen, tritium, C 1 -C 8 alkyl, halogen; R 6 is selected from hydrogen, tritium, C 1 -C 8 alkyl, halogen, C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkyl.
  3. 3. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl cyano structure according to claim 1, wherein: r 5 represents cyanoalkyl, halo or unsubstituted pyrimidinyl, halo or unsubstituted thiazolyl, halo or unsubstituted pyridinyl; R 1 -R 4 is independently selected from at least one of hydrogen, tritium, C 1 -C 6 alkyl, halogen; R 6 is selected from hydrogen, tritium, C 1 -C 6 alkyl, halogen, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkyl.
  4. 4. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl cyano structure according to claim 1, wherein: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。
  5. 5. A process for the preparation of pyrido [1,2-a ] pyrimidine-based mesoionic derivatives containing alkynyl cyano structures according to any of claims 1 to 3, comprising the steps of: the compound shown in the general formula [ II ] is reacted with the compound shown in the general formula [ III ] to prepare the compound shown in the general formula [ I ], and the reaction equation is as follows: ; Wherein L 1 、L 2 independently represents halogen or-OH, -O-CH 3 、-O-CH 2 CH 3 , and the substituent X, Q 1 、Q 2 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 is as defined in any one of claims 1 to 3; Preferably, the reaction is carried out in the presence of a base selected from at least one of an inorganic base or an organic base and a solvent selected from at least one of DCM, diethyl ether, DMF, tetrahydrofuran, methyltetrahydrofuran, toluene, xylene, diphenyl ether or dioxane.
  6. 6. A composition is characterized by comprising the pyrido [1,2-a ] pyrimidine dielectric ion derivative containing alkynyl cyano structure and an agriculturally-available auxiliary agent according to any one of claims 1 to 4, wherein the formulation of the composition is selected from Emulsifiable Concentrates (EC), powders (DP), wettable Powders (WP), granules (GR), aqueous Solutions (AS), suspending agents (SC), ultra-low volume sprays (ULV), soluble Powders (SP), microcapsules (MC), fumigants (FU), aqueous Emulsions (EW) and water dispersible granules (WG).
  7. 7. The use of pyrido [1,2-a ] pyrimidine derivatives containing alkynyl cyano structures according to any one of claims 1 to 4, or the use of the composition according to claim 6 for the preparation of a medicament for controlling agricultural pests, which are lepidoptera pests and hemiptera pests, wherein the agricultural pests are spodoptera frugiperda, prodenia litura, spodoptera exigua, corn borer, black cutworm, plant hopper and myzus persicae.
  8. 8. A method for controlling agricultural pests, which are lepidoptera and hemiptera pests, characterized in that pyrido [1,2-a ] pyrimidine-based mesoionic derivatives containing alkynyl cyano structures according to any one of claims 1 to 4 or a composition according to claim 6 are allowed to act on pests or living environments thereof, and the agricultural pests are spodoptera frugiperda, prodenia litura, asparagus caterpillar, corn borer, cutworm, plant hopper and green peach aphid.
  9. 9. A method for protecting plants from agricultural pests comprising the method step wherein the pest is contacted with a pyrido [1,2-a ] pyrimidine-based mesogenic derivative containing an alkynyl cyano structure according to any of claims 1 to 4, or a composition according to claim 6.
  10. 10. An intermediate as shown in formula [ II ] of claim 5.

Description

Pyrido [1,2-a ] pyrimidine mesoionic derivative containing alkynyl cyano 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 dielectric ion derivative containing an alkynyl cyano structure, a preparation method thereof and application of the pyrido [1,2-a ] pyrimidine dielectric ion derivative containing the alkynyl cyano structure in preparing medicines for preventing and controlling pests such as spodoptera frugiperda, prodenia litura, asparagus caterpillar, corn borer, cutworm, plant hopper, green peach aphid, fava bean tail repair aphid and the like. Background In recent years, as chemical pesticides are used for years, pest resistance multiples have increased dramatically, resulting in serious resistance to existing commonly used pesticides. For example, hemiptera pests such as plant hoppers, aphids and lepidoptera pests such as chilo suppressalis, plutella xylostella, spodoptera frugiperda and the like are important pest groups in agricultural production, are also the most resistant pests, and pesticide resistance has become a great challenge for global pest control. Rice is one of the staple food of Chinese, the world of planting area is second, the world of output is first, the crowd taking rice as staple food accounts for more than 70% of the total population. In recent years, due to the increasing prominence of the problems of climate factors, change of cultivation system, lack of resistance of rice varieties, deterioration of ecological conditions, increase of pesticide resistance and the like, rice planthoppers (NILAPARVATA LUGENS) are the most serious insect pests in world rice production, and are one of important biological factors for limiting rice production. The main application of the traditional neonicotinoid insecticide is about 25% of the whole insecticide market, and the problems of resistance and bee toxicity are outstanding due to the excessive frequent use of the traditional neonicotinoid insecticide, so that the pesticide application amount is increased, and the environment protection is not facilitated, so that the development of a novel insecticide which has no interactive resistance with the traditional insecticide, novel action mode and low toxicity to beneficial insects such as bees is urgently needed. Spodoptera frugiperda (Spodoptera frugiperd) is a global major agricultural invasive pest, which can be harmful to corn, rice, sorghum, sugarcane, peanut, soybean and other non-food crops, and is listed in the "a list of crop diseases and insect pests" in China. Since the invasion of 2018 in 12 months into China, spodoptera frugiperda rapidly spreads to major areas of various large agriculture, and serious threat is caused to the safe production of important grain crops such as corn in China. The regions of south China, taiwan, south of Tibet, southwest of Yunnan, most of Guangxi, guangdong, fujian, zhejiang, jiangxi and southeast of Hunan are highly suitable regions for spodoptera frugiperda, so that annual reproduction can be carried out, seasonal south-north flier is formed in China, and the pest is a common pest. According to the arthropod resistance Database (Arthropod PESTICIDE RESISTANCE Database, APRD), spodoptera frugiperda has developed resistance to 47 insecticidal active ingredients worldwide. In summary, with the increasing and increasing of the consumption caused by the increasing of the resistance problem of the crop major insect pests in China, the practical problems of the crop major insect pest control agent variety and formulation aging, the aggravation of drug resistance, the shortage of new formulation and the like in China are solved, and the development of the pesticide with novel structure, high efficiency, low risk and unique action mechanism is needed. The Holyoke et al of original DuPont (Kedi Hua company) in 2009 in patent WO2009099929A1 discloses the synthesis and insecticidal activity of pyrido [1,2-a ] pyrimidine medium ion compounds for the first time, and the compounds have the characteristics of novel structure, no interactive resistance with the existing medicament, low toxicity to beneficial insects such as bees and the like, and have remarkable effects on plutella xylostella, green peach aphid, cotton aphid and rice brown planthopper. The structure-activity relationship shows that the activity of the pyrido [1,2-a ] pyrimidine parent ring is better than that of thiazole or imidazopyrimidine ring, and the 3-position benzene ring and the 3-position derivatization are helpful for maintaining high activity. In 2011, holyoke et al disclosed in patent WO2011017342A 2a class of mesoionic compounds, some of which have a mortality rate of 100% for plutella xylostella, fall armyworm and cotton aphid at 10 mg/L, wherein dithiapirimidine (dicloromezotiaz) is also successfully commercialized. Researches show that the activit