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CN-122011051-A - Pyrido [1,2-a ] pyrimidine mesoionic derivative containing alkynyl ferrocene structure, and preparation and application thereof

CN122011051ACN 122011051 ACN122011051 ACN 122011051ACN-122011051-A

Abstract

The invention relates to a pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl ferrocene structure, and a preparation method and application thereof. The compound has the following structure of the formula [ I ] and has excellent insecticidal activity on spodoptera frugiperda, corn borer, cutworm, plant hopper, horsebean tail-trimming aphid and the like, and can be used for preparing medicines or medicaments for preventing and controlling pests such as spodoptera frugiperda, corn borer, cutworm, white back planthopper, brown planthopper, horsebean tail-trimming 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. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl ferrocene structure shown in the general formula [ I ] is characterized by comprising a compound shown in the 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; m independently represents Fe, co, ni, mg; 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, haloalkyl, halogen; R 6 is selected from hydrogen, tritium, alkyl, halogen, alkoxy, haloalkoxy, haloalkyl, alkynyl substituted or unsubstituted with at least one of ferrocenyl or cycloalkyl.
  2. 2. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl ferrocene structure according to claim 1, wherein: R 5 represents cyano C 1 -C 8 alkyl, 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, haloalkyl, 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, alkynyl substituted or unsubstituted with at least one of ferrocenyl or C 3 -C 8 cycloalkyl; R 7 each independently represents hydrogen, deuterium, alkyl, haloalkyl, phenyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkanoyl, alkoxy, or haloalkoxy.
  3. 3. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl ferrocene structure according to claim 1, wherein: R 5 represents cyano C 1 -C 6 alkyl, 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, haloalkyl, 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, alkynyl substituted or unsubstituted with at least one of ferrocenyl or C 3 -C 6 cycloalkyl.
  4. 4. The pyrido [1,2-a ] pyrimidine mesoionic derivative containing an alkynyl ferrocene structure according to claim 1, wherein: compound 1:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 2:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 3:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 4:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 5:R 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 6:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =CH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 7:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =CH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 8:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =CH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 9:R 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =CH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 10:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =CH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 11:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =Cl,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 12:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =Cl,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 13:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =Cl,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 14:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =Cl,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 15:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =Cl,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 16:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCF 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 17:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCF 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 18:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCF 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 19:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCF 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 20:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =OCF 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 21:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 22:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 23:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 24:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =OCH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 25:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =OCH 3 ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 26:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 27:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 28:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 29:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 30:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 31:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 32:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 33:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 34:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 35:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 36:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 37:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 38:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 39:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 40:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 = ,Q 1 =O,Q 2 =O,X=C,M=Fe; Compound 41:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Co; Compound 42:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Co; Compound 43:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Co; Compound 44:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Co; Compound 45:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Co; Compound 46:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Ni; Compound 47:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Ni; Compound 48:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Ni; Compound 49:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Ni; Compound 50:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Ni; Compound 51:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Mg; Compound 52:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Mg; Compound 53:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Mg; Compound 54:r 1 =H、R 2 =H、R 3 =H、R 4 =H、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Mg; Compound 55:r 1 =H、R 2 =H、R 3 =H、R 4 =CH 3 、R 5 = ,R 6 =H,Q 1 =O,Q 2 =O,X=C,M=Mg。
  5. 5. A method for preparing pyrido [1,2-a ] pyrimidine mesoionic derivatives containing alkynyl ferrocene structure according to any one of claims 1 to 4, 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 represents halogen or-OH, -O-CH 3 、-O-CH 2 CH 3 , respectively, and the substituents X, M, Q 1 、Q 2 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 are 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 an alkynyl ferrocene structure and an agriculturally-available auxiliary agent, wherein the formulation of the composition is selected from Emulsifiable Concentrates (EC), powders (DP), wettable Powders (WP), granules (GR), water Aqua (AS), suspending agents (SC), ultra-low volume sprays (ULV), soluble Powders (SP), microcapsules (MC), smoke agents (FU), emulsion in water (EW) and water dispersible granules (WG).
  7. 7. Use of pyrido [1,2-a ] pyrimidine mesoionic derivatives containing alkynyl ferrocene structures according to any one of claims 1 to 4, or of the composition according to claim 6 for the preparation of a medicament for controlling agricultural pests, such as spodoptera frugiperda, corn borer, cutworm, fava bean tail aphid, sogatella furcifera and brown planthopper.
  8. 8. A method for preventing and controlling agricultural insect pests, which is characterized in that pyrido [1,2-a ] pyrimidine medium ion derivatives containing alkynyl ferrocene structures of any one of claims 1-4 or the composition of claim 6 are caused to act on harmful pests or living environments thereof, wherein the agricultural insect pests are spodoptera frugiperda, corn borer, cutworm, broad bean tail-trimming aphid, sogatella furcifera and brown planthopper.
  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 ferrocene 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 ferrocene 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 ferrocene structure, a preparation method thereof and application of the pyrido [1,2-a ] pyrimidine dielectric ion derivative containing the alkynyl ferrocene structure in preparation of medicines for preventing and treating spodoptera frugiperda, corn borer, small cutworm, fava bean tail-repair aphid, sogatella furcifera and brown planthopper. 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. Such as hemiptera insect plant hoppers, aphids, lepidoptera insect spodoptera and the like are important insect pest groups in agricultural production, and are the insect pests with the strongest drug resistance. Plant hoppers (NILAPARVATA LUGENS) are pests on asian rice crops that occur throughout the year and are severely disaster-producing. It can not only interfere with rice growth by sucking phloem juice and spawning, but also spread plant viruses. In the retransmission and tight-send area, the rice planthoppers can be effectively prevented and controlled if not, and the comprehensive hazard is enough to lead the paddy field to be reduced in large area and even be out of harvest. Spodoptera frugiperda (Spodoptera frugiperd) is an important pest for corn, rice, sorghum, sugarcane, peanut, soybean and other non-food crops such as cotton. Can be propagated throughout the year, and becomes 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. Agrotis ypilon is an important soil pest for corn, cotton, sorghum, tobacco, wheat, sesame, beans and various vegetable seedlings. The damage has the characteristics of concealment, binge eating and destruction, often causes serious consequences of 'lack of seedlings and broken ridges', and is one of pests which need to be monitored and controlled in the agricultural production. Corn borers (Ostrinia furnacalis, asian corn borers) are boring pests for important crops such as corn, sorghum, millet, cotton, sugarcane, potato, sunflower and a variety of weeds. The hazard extends through the whole growth period of the corn. According to the arthropod resistance database APRD, corn borers have developed varying degrees of resistance to a variety of insecticidal actives (including organophosphates, pyrethroids, etc.) worldwide. The broad bean tail trimming aphid (Megoura japonica) is an important piercing-sucking pest for leguminous crops such as broad beans, peas, alfalfa, common vetch and the like. It can be propagated for multiple generations and can also be moved on hosts in winter. The plant can directly produce harm through piercing and sucking host juice to cause leaf rolling, yellowing, damaged growing points and dwarf plants. The virus diseases can also be transmitted to cause harm indirectly, and the broad bean tail repair aphid is a key transmission medium of leguminous plant virus diseases such as broad bean wilt virus and the like. The loss caused by the toxin transmission is often far greater than the harm of direct ingestion. The damage characteristic of the broad bean tail-trimming aphid is that the cluster is a tender part and the virus is efficiently transmitted, and in agricultural production, the aphid prevention strategy is often adopted for prevention and control. In view of the foregoing, there is a need to develop pesticides with novel structures, high efficiency, low risk and unique mechanisms of action. 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