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CN104557963B - Dialdehyde-constructed nitrogenous or heterocyclic oxygen compound with insecticidal activity and preparation method thereof - Google Patents

Dialdehyde-constructed nitrogenous or heterocyclic oxygen compound with insecticidal activity and preparation method thereof Download PDF

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CN104557963B
CN104557963B CN201410690772.2A CN201410690772A CN104557963B CN 104557963 B CN104557963 B CN 104557963B CN 201410690772 A CN201410690772 A CN 201410690772A CN 104557963 B CN104557963 B CN 104557963B
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compound
alkyl
group
acceptable salt
pharmaceutically acceptable
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CN104557963A (en
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李忠
钱旭红
邵旭升
徐晓勇
陶黎明
宋恭华
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/08—Bridged systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/18—Bridged systems

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

Abstract

The invention relates to a dialdehyde-constructed nitrogenous or heterocyclic oxygen compound with insecticidal activity, and preparation and application thereof, and provides a compound disclosed as Formula (A), (B), (C) or (D), or an optical isomer, cis-trans-isomer or insecticidally acceptable salt thereof. The invention also relates to an agricultural composition comprising the compound or the optical isomer, cis-trans-isomer or insecticidally acceptable salt thereof, application of the agricultural composition, and a preparation method of the compound or the optical isomer, cis-trans-isomer or insecticidally acceptable salt thereof. The compound and derivatives thereof have high insecticidal activity for Homoptera, Lepidoptera and other pests in agriculture and forestry, such as aphids, planthoppers, aleyrodids, leafhoppers, thrips, cotton bollworms, cabbage worms, cabbage moths, tobacco caterpillars, armyworms and the like.

Description

Dialdehyde-constructed nitrogen-containing or oxygen-containing heterocyclic compound with insecticidal activity and preparation method thereof
the application is a divisional application of an invention patent application with the application date of 2008-12-19 and the application number of 201310398752.3, and the invention name of the invention is 'dialdehyde-constructed nitrogen-containing or oxygen-containing heterocyclic compound with insecticidal activity and a preparation method thereof'.
The application with the application number of 201310398752.3 is a divisional application of an invention patent application with the application date of 2008-19.12. 200810207355.2 and the invention name of 'dialdehyde-constructed nitrogen-containing or oxygen-containing heterocyclic compound with insecticidal activity and a preparation method thereof'.
Technical Field
The invention relates to a novel neonicotinoid insecticide, a preparation method and application thereof.
Background
Neonicotinoid insecticides represented by imidacloprid have high insecticidal activity, a wide insecticidal spectrum, low toxicity to mammals and aquatic animals, good system physical properties, appropriate field stability and environmental friendliness, and become an important hotspot field for creating new pesticides. Subsequently, a series of nicotine insecticides such as thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram and dinotefuran have been developed (see european patents 247477, 296453, 685477, 235725, 235725, 315826, 192060, 244777, 0386565, 580553 and 1031566, and japanese patents 62292765, 8259568, 8291171 and 7242633).
However, due to the serious resistance problem caused by the excessive and frequent use of imidacloprid and the cross resistance between the neonicotinoid insecticides caused by the structural similarity, the application of the compounds is limited to a certain extent, the development of the compounds is restricted, meanwhile, the neonicotinoid insecticides are mainly high-efficiency to homoptera and coleoptera pests, and the relatively narrow insecticidal spectrum also limits the drug selectivity in the aspect of pest control.
Therefore, how to modify the structure of the nitromethylene compound with high activity to generate a new and more effective pesticide, solve the resistance problem of the neonicotinoid pesticide, expand the insecticidal spectrum, and make the application of the nitromethylene compound in the pesticide composition become the technical problem which needs to be solved urgently in the field.
Disclosure of Invention
The invention provides a new and more effective pesticide, solves the resistance problem of the neonicotinoid insecticides, expands the insecticidal spectrum and solves the problems in the prior art.
The invention aims to provide a compound for efficiently preventing and controlling pests and a preparation method thereof.
It is another object of the present invention to provide protection for growing and harvested crops from insect attack and infestation.
In one aspect, the present invention provides a compound having a structure represented by formula (a), (B), (C) or (D), or an optical isomer, cis-trans isomer or agriculturally pharmaceutically acceptable salt of said compound:
in the formula:
R1is a five-membered or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a halogenated five-membered or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group, wherein the substituent is one or more selected from the following groups: halogen, C1–4Haloalkyl or C1–4A chloroalkoxy group;
R2is H, C1-C8Saturated or unsaturated alkyl, halogenated C1-8Saturated or unsaturated alkyl, -CH2CH2OCH2CH3，-CH2CH2OCH3，C1-8Saturated or unsaturated alkoxy, phenyl, benzyl, C1–4Alkyl-carbonyl or C1–4An alkyl-sulfonyl group;
R3and R4Each independently is H, C1-6Alkyl, allyl, benzyl, C1–4alkoxy-C1–4Alkyl radical, C1–4Alkoxy-carbonyl, phenoxycarbonyl, C2–6Alkynyl-carbonyl, C2–3Alkenyl-carbonyl, C3–6Cycloalkyl-carbonyl, benzoyl, or substituted by one or more radicals selected from halogen, C1–4Alkyl radical, C1–4Haloalkyl, C1–4Alkoxy and C1–4Benzoyl, furancarbonyl or N, N-dimethylcarbonyl substituted by a substituent of alkyl-carbonyl, or R3And R4Together form-CH2-CH2-，-CH2-CH2-CH2-or CH2-XR-CH2-, where X is a heteroatom such as N, O, S, R is a substituent on the heteroatom and is selected from H and C1-6Alkyl, allyl, benzyl,phenyl radical, C1–4alkoxy-C1–4Alkyl radical, C1–4Alkoxy-carbonyl, phenoxycarbonyl, C2–6Alkynyl-carbonyl, C2–3Alkenyl-carbonyl, C3–6Cycloalkyl-carbonyl, benzoyl, or substituted by one or more radicals selected from halogen, C1–4Haloalkyl, C1-8Saturated or unsaturated alkyl or alkoxy and C1–4Benzoyl, furancarbonyl or N, N-dimethylcarbonyl substituted with a substituent of alkyl-carbonyl;
R5，R6，R7，R8and R9Is H, saturated or unsaturated C1-4Alkyl, halogen, C1-8Saturated or unsaturated alkoxy, halogeno C1-4Saturated or unsaturated alkoxy radicals, C1–4Alkyl-carbonyl, C1–8Alkyl-ester group, C1–4Alkyl-sulfonate, phenyl or benzyl;
y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl.
In a preferred embodiment, R1Selected from: pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, oxazolyl, or a halide thereof.
In a preferred embodiment, R is preferred1Is a halogenated pyridyl, halogenated thiazolyl, halogenated pyrimidinyl, halogenated tetrahydrofuranyl, or halogenated oxazolyl, more preferably the halide is chloride.
In another preferred embodiment, R1Is composed ofOr
In another preferred embodiment, R2Is H, C1-4Saturated or unsaturated alkyl, halogenated C1-C4Saturated or unsaturated alkyl radicals, C1–4Alkyl-carbonyl, substituted or unsubstituted benzyl, wherein the substituents are one or more selected from the group consisting of: halogen, C1–4Haloalkyl or C1–4A chloroalkoxy group.
In a preferred embodiment, R2Is hydrogen or C1-3Alkyl, preferably hydrogen or methyl.
In another preferred embodiment, R3And R4Is hydrogen or C1-6Alkyl, or R3And R4Together form-CH2-CH2-or-CH2-CH2-CH2-。
In a preferred embodiment, R3And R4Is hydrogen or C1-3Alkyl, preferably hydrogen, methyl or ethyl, or R3And R4Together form-CH2-CH2-or-CH2-CH2-CH2-。
In another preferred embodiment, R5，R6，R7，R8And R9Is H, saturated or unsaturated C1-2Hydrocarbyl, halogen, C1-4Saturated or unsaturated alkoxy, halogeno C1-2Saturated or unsaturated alkoxy radicals, C1–4Alkyl-ester group (RCOO-), C1–2An alkyl-sulfonyl ester group or a trifluoromethanesulfonyl ester.
In a preferred embodiment, R5，R6，R7，R8And R9Is hydrogen, methyl, chlorine, bromine, methoxy or ethoxy, preferably hydrogen, methyl, methoxy.
In another preferred embodiment, Y is nitro or cyano.
In a preferred embodiment, Y is preferably nitro.
In another aspect, the present invention provides an agricultural composition comprising:
(a)0.001 to 99.99% by weight of the above compound, an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, or a combination thereof; and
(b) an agriculturally pharmaceutically acceptable carrier and/or excipient.
In a preferred embodiment, component (a) constitutes from 0.01 to 99.9% by weight, preferably from 0.05 to 90% by weight, of the agricultural composition.
In a preferred embodiment, the agricultural composition is used for killing or preventing pests selected from the group consisting of: coleopteran, lepidopteran, hemipteran, orthopteran, isopteran or dipteran insects.
In a preferred embodiment, the pests have piercing or rasping mouthparts.
In another preferred example, the pest is aphid, plant hopper, whitefly, leafhopper, thrips, cotton bollworm, cabbage caterpillar, diamond back moth, prodenia litura, or armyworm.
In another preferred embodiment, the agricultural composition further comprises an additional active substance selected from the group consisting of: an insecticide, a bait, a bactericide, an acaricide, a nematicide, a fungicide or a growth control agent.
In another aspect, the invention relates to the use of the agricultural composition for killing or preventing agricultural pests, hygiene pests and pests that are harmful to the health of animals; or as a pesticidal composition for killing or preventing agricultural pests, hygiene pests and animal health hazards.
In another aspect, the present invention provides a pesticidal and/or pesticidal method comprising applying an agricultural composition as described above to a plant suffering from or likely to suffer from a pest, the soil surrounding it or the environment.
In another aspect, the present invention relates to the use of a compound as described above, an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, or a combination thereof, in the preparation of a pesticidal composition.
In a further aspect, the present invention provides a process for the preparation of the above compound, an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt thereof, comprising the steps of:
reacting a compound of formula (a) with a compound of formula (B), (C) or (D) in the presence of a catalytic amount of an acid at 0-60 ℃ to produce a compound of formula (A), (B), (C) or (D), wherein R is2Is a hydrogen atom, and is,
in the formula, R1、R3、R4、R5、R6，R7，R8，R9And Y is as defined above, n is 0 or 1.
In a preferred embodiment, the reaction temperature is from 15 to 45 ℃ and preferably from 20 to 30 ℃.
In another preferred embodiment, the solvent used is selected from: acetonitrile or ethanol, preferably acetonitrile.
In another preferred embodiment, the catalytic amount of acid used is selected from: concentrated hydrochloric acid, concentrated sulfuric acid or benzoic acid, preferably concentrated hydrochloric acid.
In a preferred embodiment, the method comprises the steps of:
carrying out the following reaction in acetonitrile in the presence of a catalytic amount of an acid at 20-30 ℃ for 2-24 hours to obtain a compound of formula (A), wherein R2Is hydrogen:
carrying out the following reaction in acetonitrile in the presence of a catalytic amount of an acid at 20-30 ℃ for 2-24 hours to obtain a compound of formula (B):
carrying out the following reaction in acetonitrile in the presence of a catalytic amount of an acid at 10-50 ℃ for 2-24 hours to obtain a compound of formula (C):
carrying out the following reaction in acetonitrile in the presence of a catalytic amount of an acid at 10-50 ℃ for 2-24 hours to obtain a compound of formula (D):
Detailed Description
The inventor of the invention synthesizes a novel neonicotinoid compound through the reaction of dialdehyde and a nitromethylene compound based on the nitromethylene structure of the prior nitromethylene neonicotinoid insecticide for a long time and deep research, the insecticidal activity of the compound is obviously improved, and the compound has an expanded insecticidal spectrum. On this basis, the inventors have completed the present invention.
Radical definition
As used herein, the term "C1-6Alkyl "means a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The term "C1-6Alkoxy "means a straight or branched chain alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the likeAnd (4) clustering.
The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted with one or more of the above halogen atoms, which may be the same or different, such as trifluoromethyl, pentafluoroethyl, or the like.
The term "five-or six-membered heterocyclic group" means a five-or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, for example, pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuryl, or oxazolyl, etc.
Process for the preparation of the compounds of the invention
The compounds of the present invention may be synthesized by the reaction steps described above. The compounds of formula (a) in the reaction steps can be synthesized by the skilled person according to prior art literature, for example see WO 2006056108a1, WO2007101369a1 and PCT/CN 2008/071115.
In one embodiment of the present invention, the compound of formula (a) is synthesized as follows:
in one embodiment of the present invention, the compound of formula (B) is synthesized as follows:
in one embodiment of the present invention, the compound of formula (C) is synthesized as follows:
in one embodiment of the present invention, the compound of formula (C) is synthesized as follows:
in one embodiment of the present invention, the compound of formula (a) may be prepared by the following reaction:
(1) dripping acetonitrile solution of 2-chloro-5-chloromethylpyridine into 5-10 times molar weight of diamine solution, and reacting at 0-50 deg.C for 5-10 hr. And (3) after-treatment, removing diamine under reduced pressure, dissolving with ethyl acetate, and spin-drying the solvent to obtain a product: n is a radical of＊1＊- (6-chloro-3-methylpyridyl) -diamine;
(2)N＊1＊refluxing- (6-chloro-3-methylpyridyl) -diamine and 1, 1-dithiomethyl-2-nitroethylene with ethanol as a solvent for 4-8 hours to obtain a product: a nitromethylene compound;
(3) the compound (A) with the general formula is obtained by reacting a nitromethylene compound with glyoxal under the catalysis of acid (hydrochloric acid, sulfuric acid, heteropoly acid and the like).
In another embodiment, the compound of formula (B) may be prepared by the following reaction:
(1) adding a proper amount of acetonitrile into an ethylamine aqueous solution, dropwise adding acetonitrile dissolving solution of 6-chloro-3-chloromethylpyridine in an ice bath, tracking the reaction process by TLC, adding a large amount of water into the reaction mixed solution after the reaction is finished, extracting by dichloromethane, drying, carrying out suction filtration, and evaporating the solvent to obtain oily liquid N- (6-chloropyridine-3-methylene) ethylamine;
(2) refluxing N- (6-chloropyridine-3-methylene) ethylamine and 1, 1-dithiomethyl-2-nitroethylene with ethanol as a solvent for 4-8 hours, concentrating, and performing column chromatography separation to obtain a product N- (6-chloropyridine-3-methylene) -N-ethyl-1-thiomethyl-2-nitroethyleneamine;
(3) reacting N- (6-chloropyridine-3-methylene) -N-ethyl-1-thiomethyl-2-nitroethenylidene amine with a methylamine alcohol solution in the presence of ethanol as a solvent for 4-8 hours in an ice bath, concentrating, and performing column chromatography separation to obtain N- (6-chloropyridine-3-methylene) -N-ethyl-N' -methyl-2-nitroethenylidene diamine;
(4) n- (6-chloropyridine-3-methylene) -N-ethyl-N' -methyl-2-nitroethenediamine and malondialdehyde are catalyzed by acid (hydrochloric acid, sulfuric acid, heteropoly acid, etc.) to obtain the compound (B) of the formula.
In another embodiment, the compound of formula (C) may be prepared by the following reaction:
(1) dripping acetonitrile solution of 2-chloro-5-chloromethylpyridine into diamine solution with 5-10 times of molar weight, and reacting for 5-10 hours at 0-50 ℃; and (3) after-treatment, removing diamine under reduced pressure, dissolving with ethyl acetate, and spin-drying the solvent to obtain a product: n is a radical of＊1＊- (6-chloro-3-methylpyridyl) -diamine;
(2)N＊1＊refluxing- (6-chloro-3-methylpyridyl) -diamine and 1, 1-dithiomethyl-2-nitroethylene with ethanol as a solvent for 4-8 hours to obtain a product: a nitromethylene compound;
(3) the nitromethylene compound (2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine) and butanedialdehyde are catalyzed by acid (hydrochloric acid, sulfuric acid, heteropoly acid and the like) to obtain the compound (C) with the general formula.
In another embodiment, the compound of formula (D) may be prepared by the following reaction:
(1) dripping acetonitrile solution of 2-chloro-5-chloromethylpyridine into 5-10 times molar weight of diamine solution, and reacting at 0-50 deg.C for 5-10 hr. After-treatment, diamine is removed under reduced pressure, dissolved by ethyl acetate, and solvent is dried by spinning to obtain product N＊1＊- (6-chloro-3-methylpyridyl) -diamine;
(2)N＊1＊- (6-chloro-3-methylpyridyl) -diamine and 1, 1-dithiomethyl-2-nitroethylene in ethanol as solvent, and refluxing4-8 hours, obtaining the product: a nitromethylene compound;
(3) the nitromethylene compound (2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine) and glutaraldehyde are subjected to acid (hydrochloric acid, sulfuric acid, heteropolyacid and the like) catalysis to obtain the compound (D) with the general formula.
Insecticidal Activity of the active substances according to the invention
The term "active substance according to the invention" or "active compound according to the invention" means a compound according to the invention, an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt thereof, which has a significantly improved insecticidal activity, as well as an extended insecticidal spectrum.
The term "agriculturally pharmaceutically acceptable salt" means that the anion of the salt is known and acceptable in forming a pharmaceutically acceptable salt of a pesticide. The salt is preferably water soluble. Suitable acid addition salts formed by the compounds of formulae (A), (B), (C) and (D) include salts with inorganic acids, such as hydrochloride, phosphate, sulfate, nitrate; and salts comprising organic acids, such as acetates, benzoates.
The active substance of the present invention can be used for controlling and exterminating a wide range of agricultural and forestry plant pests, pests of stored cereals, public health pests, pests harmful to animal health, and the like. In the present specification, "pesticide" is a general term for a substance having an effect of controlling all the pests mentioned above. Examples of pests include, but are not limited to: coleopteran insects: elephant of maize (Sitophilus zeamais), Tribophytes castanea (Tribolium castaneum), Iris japonica (Henospora virginiana), Iris japonica (Henospora fragrans), Elaeis quinata (Agrioticus bisporus), Elaeis quinquefasciata (Agrioticus fusscialis), Rhynchophylla rubra (Anamala cuprina), Rhynchophylla quadrifara (Popilia quadrata), Dimocarpa arborvita (Monolepis hieroglytica), Sonchus aspera (Monochamus alternatus), Rhizoctonia oryzae (Echinocnemus squameus), Podosporus fortunei (Basidiota bigua), Anoplophorax tenuiensis (Anoplophora longis), Morus bombycis (Aprina germarii), bark beetle umbiliciformis (Scopolyspora sinensis), or Floricus andriperus androsaceus (Agileria punctiformis); lepidopteran insects: gypsy moth (Lymantria dispar), tenebrio molitor (malacomonas neustris tetacea), chrysomyia littoralis (Diaphania persicaria), gypsy moth (Clania vasica), yellow-biting moth (cnidocpa fiaugensis), masson pine moth (dendrolimus punctatus), ancient poisonous moth (orydia gonostica), poplar piercing moth (paragene tapeformis), prodenia litura (Spodoptera litura), Chilo suppressalis (Chilo supressalis), corn borer (ostrinia), pink spot moth (ephora caudatus), cotton roll moth (adoxyphoides orana), chestnut leaf roller (pyestria spodallas), Agrotis cutworm (Agrotis), ostrinia nubilalis), Galleria mellea (Galleria mellea), cabbage moth (ostrinia nubila, cabbage moth (ostrinia nubilalis), cabbage moth (ostrinia nubila (ostrinia, ostrinia nubila, ostrinia (ostrinia nubila), plusia (ostrinia, Plutella), Plutella (ostrinia) or cabbage moth (ostrinia Plutella); homopteran insects: leafhopper nigricans (Nephotettix cincticeps), nilaparvatales (nilaparvatalens), mealybugs (Pseudococcus comstocki), arrowhead (Unaspis yanonensis), green peach aphid (Myzus persicae), cotton aphid (Aphis gossypidii), radish aphid (Lipaphis erysipunculosis), triatoma pyriformis (stephanis nashi), or whitefly (beusia tabaci); orthoptera insects: german cockroach (Blattella germanica), american cockroach (Periplaneta americana), african mole cricket (Gryllotalpa africana), or locusta migratoria (Locus migratoria); insects of the order isoptera: invasion of Solenopsis invicta (Solenopsis invicta), or Hoptotermes formosanus (Coptotermes formosanus); insects of the order diptera: houseflies (Muscadomestica), Aedes aegypti (Aedes aegypti), seed flies (Delia platura), Culex (Culex sp.), or Anopheles sinensis (Anopheles sinensis). Pests which are detrimental to the health of animals include Boophilus microplus (Boophilus microplus), Haemaphysalis longicornis (Haemaphysalis longicornis), Hyalomma glaucoides (Hyalomma anaticum), Dermata bovis (Hypoderma spp.), Fasciola hepatica (Faciola hepatica), Monitazia bellina (Moneizabalanchakhard), Ostertagia ostertagi spp, Trypanosoma ena enansi, Babesiabiennina, and the like.
The compound of the invention has special effect on piercing-sucking and filing-sucking mouthpart pests, such as aphids, leafhoppers, plant hoppers, thrips, whiteflies and other agricultural and forestry pests.
Pesticide compositions containing active substances according to the invention
The active substances according to the invention can be prepared in a customary manner to give pesticide compositions. The active compounds can be formulated in the customary formulations, for example solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compositions for seeds, and formulations for use with combustion devices, such as smoking cartridges, smoking pots and smoking trays, and ULV Cold mist (Cold mist) and hot mist (warnmist) formulations.
These formulations can be produced by known methods, for example by mixing the active compounds with extenders, that is, liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, that is, emulsifiers and/or dispersants and/or foam formers. Organic solvents may also be used as adjuvants, for example when water is used as extender.
Liquid solvents are basically suitable as diluents or carriers, for example: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and lipids; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less commonly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. The diluent or carrier of the liquefied gas means a liquid which will become a gas at normal temperature and pressure, for example, aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
The solid carrier can be selected from the group consisting of naturally occurring minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and synthetic minerals, such as highly dispersed silicic acid, alumina, and silicates. Solid carriers for granules are ground and classified natural marble, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stalks, etc.
Nonionic and anionic emulsifying trains may be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.
Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations. Colorants such as inorganic dyes, e.g., iron oxide, cobalt oxide and prussian blue; organic dyes, such as organic dyes, e.g., azo dyes or metallotitanyl cyanine dyes; and with trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, and the like.
These active compounds of the present invention may be present in commercial formulations as a mixture with other active compounds including, but not limited to: insecticides, baits, bactericides, acaricides, nematicides, fungicides, growth control agents and the like. Insecticides include, for example, phosphates, carbamates, pyrethrins, chlorinated hydrocarbons, benzoylureas, nereistoxin and substances produced by microorganisms, such as avermectins.
Furthermore, the active compounds according to the invention can also be formulated with synergists in a mixture in their commercial preparations in the use forms prepared from these preparations. The synergist is a compound which improves the action of the active compound, and the synergist is not required to be added because the active compound has activity.
These formulations generally contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight, of the active compounds according to the invention, based on the pesticide composition. The concentration of the active compound in the dosage form prepared from commercial preparations for use can vary within wide limits. The concentration of active compound in the dosage form to be used may be from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1%.
Examples
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight. Wherein r.t. represents room temperature.
Example 1: synthesis of 4- (1- ((6-chloropyridin-3-yl) methyl) -4, 5-dihydro-1H-imidazolidin-2-yl) -1- (1- ((6-chloropyridin-3-yl) methyl) imidazolidin-2-yl) -1, 4-dinitro-3-buten-2-ol (Compound 13)
2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine was prepared in 56% yield according to the methods described in WO 2006056108a1 and WO2007101369a1 starting from 0.03mol of 2-chloro-5-chloromethylpyridine; rf 0.46 (petroleum ether: ethyl acetate 1: 1); mp-156.9 deg.C-161.8 deg.C. GC MS (m/s)220(25), 126(100), 90 (9).
4- (1- ((6-chloropyridin-3-yl) methyl) -4, 5-dihydro-1H-imidazolidin-2-yl) -1- (1- ((6-chloropyridin- 3-yl) methyl) imidazolidin-2-yl) -1, 4-dinitro-3-buten-2-ol synthesis
1.27g (0.005mol) of 2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine, 30ml of anhydrous acetonitrile, 3ml of a 30% aqueous glyoxal solution are added to a 50ml round-bottomed flask, stirred for half an hour, then a catalytic amount of concentrated hydrochloric acid is added for catalysis, stirring is continued, TLC is carried out to follow the reaction until all the raw materials are reacted completely, and then suction filtration is carried out to obtain a white powdery solid. Recrystallization afforded pure compound 13 as a white powdery solid, 1.05g, in about 76% yield.
mp＝164.6-165.3℃；1H NMR(400Mz,DMSO-d6):9.01(s,1H),8.41(d,J＝2.0Hz,1H),8.38(d,J＝2.0Hz,1H),7.80-7.86(m,2H),7.51-7.54(m,2H),6.50(d,J＝7.2Hz,1H),5.34(d,J＝15.2Hz,1H),5.18(d,J＝15.2Hz,1H),4.84(dd,J1＝2.4Hz,J2＝7.2Hz,1H),4.77(d,J＝16.8Hz,1H),4.67(d,J＝16.8Hz,1H),3.98(d,J＝2.4Hz,1H),3.86-3.95(m,2H),3.61-3.80(m,5H),3.40-3.47(m,1H)ppm；13C NMR(100Mz,DMSO-d6) 162.7,158.7,148.3,148.2,148.0,147.7,138.1,137.7,130.9,130.2,123.1,123.0,102.5,101.4,81.4,53.8,52.6,49.4,48.8,46.4,41.2,41.0 ppm; HRMS (ES +) calcd for C22H23N8O5 35Cl2(M+H)+549.1168; measured value, 549.1178; calculated value C22H23N8O5 35Cl37Cl(M+H)+551.1139; measured value, 551.1152; calculated value C22H23N8O5 37Cl2(M+H)+553.1109; the measured value, 553.1108.
Example 2: synthesis of 2-chloro-5- ((-2- (-4- (1- ((6-chloropyridin-3-yl) methyl) -4, 5-dihydro-1H-imidazolidin-2-yl) -2-methoxy-1, 4-dinitro-3-butenyl) imidazolidin-1-yl) methyl) pyridine (Compound 14)
0.549g (0.001mol) of Compound 1 was charged into a 50ml round-bottom flask, and 10ml of methanol, 50ml of methylene chloride and a catalytic amount of concentrated hydrochloric acid were added thereto, followed by reflux and TLC. After the reaction is finished, the solvent is removed, and the pure product of yellow powder is obtained by column chromatography separation, wherein the yield is 62%.
mp＝151.6-153.1℃；1H NMR(400Mz,DMSO-d6):9.03(s,1H),8.38(d,J＝2.0Hz,1H),8.36(d,J＝2.0Hz,1H),7.81-7.85(m,2H),7.49-7.51(m,2H),6.50(d,J＝7.2Hz,1H),5.35(d,J＝15.2Hz,1H),5.19(d,J＝15.2Hz,1H),4.80(d,J1＝7.2Hz,1H),4.77(d,J＝16.8Hz,1H),4.69(d,J＝16.8Hz,1H),3.68(s,3H),3.88-3.95(m,2H),3.61-3.85(m,5H),3.38-3.41(m,1H)ppm；13C NMR(100Mz,DMSO-d6) 162.6,158.7,148.9,148.3,148.1,147.6,138.1,137.8,130.9,129.9,122.8,123.1,102.2,101.6,81.6,58.7,53.8,52.6,49.6,48.9,46.4,41.3,41.0 ppm; HRMS (ES +) calcd for C23H25N8O5 35Cl2(M+H)+563.1325; measured value, 563.1311 calculation C23H25N8O5 35Cl37Cl(M+H)+,565.1295。
Example 3: synthesis of N1, N7-bis ((6-chloropyridin-3-yl) methyl) N1, N7-diethyl-N '1, N' 7-dimethyl-2, 6-dinitro-2, 5-heptanediimine (Compound 37)
(1) Synthesis of N- (6-chloropyridine-3-methylene) ethylamine
A300 mL three-neck round-bottom flask with a constant pressure dropping funnel and a thermometer is added with 65-70% ethylamine aqueous solution (70g,1mol) and acetonitrile 50mL, stirred for 15 minutes in ice bath to stabilize the temperature of the solution at about 0 ℃, added with acetonitrile (25mL) solution of 6-chloro-3-chloromethylpyridine (16.10g, 0.10mol) in the constant pressure dropping funnel, the dropping speed is controlled at 3 drops/minute, the dropping time is controlled at 3.5 hours, and the reaction is finishedThen, water was added, and extraction was performed with methylene chloride to collect an organic phase, whereby 14g of N- (6-chloropyridine-3-methylene) ethylamine was obtained as an oily liquid in a yield of 70%. GC-MS M/z (%) 170([ M ]]+,20),155(80),126(100),114(10),90(12)。
(2) Synthesis of N- (6-chloropyridine-3-methylene) -N-ethyl-1-thiomethyl-2-nitrovinylamine
In a 100mL three-necked round-bottomed flask, N- (6-chloropyridine-3-methylene) ethylamine (17.0g,0.1mol), 1, 1-dithiomethyl-2-nitroethylene (15.0g,0.09mol) and absolute ethanol (50mL) were added and refluxed. After the reaction, the reaction mixture was cooled to room temperature, concentrated under reduced pressure to give a thick liquid, and separated by column chromatography to give N- (6-chloropyridine-3-methylene) -N-ethyl-1-thiomethyl-2-nitrovinylamine 5.3g, with a yield of 18.5%. GC-MS M/z (%) (242 ([ M)]+-46,53),227(15),213(100),169(45),155(28),141(29),126(91),90(12)。
(3) Synthesis of N- (6-chloropyridine-3-methylene) -N-ethyl-N' -methyl-2-nitroethylenediamine
To a 100mL single neck round bottom flask was added N- (6-chloropyridine-3-methylene) -N-ethyl-1-thiomethyl-2-nitroethenylideneamine (5g,0.017mol), methylamine alcohol solution (1.8g,0.017mol methylamine), anhydrous ethanol (30mL), stirred on ice to bring the temperature down to 0 deg.C, and the reaction was continued until complete. Then, the solvent was evaporated by rotation under reduced pressure, and the resulting solution was concentrated to give a slurry, which was dissolved in an appropriate amount of methylene chloride, and the resulting solution was subjected to column separation using silica gel as a filler and methylene chloride/ethanol 25:1 as a developing agent, to collect the product, and the product was concentrated to give 0.9g of N- (6-chloropyridine-3-methylene) -N-ethyl-N' -methyl-2-nitroethylenediamine with a yield of 19.1%. TLC, dichloromethane, acetone, 5:1, Rf, 0.23. Melting point: 78-80oC (lit [67 ]]79-81℃)GC-MS:m/z(％)＝236([M]+－34,32),207(49),169(52),126(49),110(20),90(16),67(100).16.65
(4) N1, N7-bis ((6-chloropyridin-3-yl) methyl) N1, N7-diethyl-N '1, N' 7-dimethyl-2, 6-dinitro Synthesis of 2, 5-heptanediimine (Compound 37)
1.35g (0.005mol) of N- (6-chloropyridine-3-methylene) -N-ethyl-N' -methyl-2-nitroethylenediamine, 30ml of anhydrous acetonitrile, 0.72g (0.01mol) of malondialdehyde and a catalytic amount of HCl were placed in a 50ml round-bottomed flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 56%.
mp＝117.3-118.7℃；1H NMR(400Mz,DMSO-d6):8.36(d,J＝2.4Hz,2H),7.88(dd,J1＝2.4Hz,J2＝8.4Hz,2H),7.51(d,J＝8.4Hz,2H),4.97(t,J＝2.8Hz,2H),4.86(d,J＝15.2Hz,2H),4.49(d,J＝15.2Hz,2H),3.95-3.99(m,4H),3.66-3.78(m,6H),3.12-3.21(m,2H),1.91-1.93(m,6H)ppm；13C NMR(100Mz,DMSO-d6) 156.3,148.5,148.1,137.3,131.9,122.5,104.8,49.2,48.9,48.0,48.5,28.1,20.2 ppm; HRMS (EI +) calculated value C25H30N8O4 35Cl2(M+) 576.1767; the measured value, 576.1751.
Example 4: synthesis of 1, 5-bis (1- ((6-chloropyridin-3-yl) methyl) -4, 5-dihydro-1H-imidazolidin-2-yl) -1, 5-dinitro-1, 4-pentadiene (Compound 39)
1.27g (0.005mol) 2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine, 30ml of anhydrous acetonitrile, 0.720g (0.01mol) of malondialdehyde and a catalytic amount of HCl were placed in a 50ml round-bottomed flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 52%.
mp＝136.5-137.8℃；1H NMR(400Mz,DMSO-d6):8.34(d,J＝2.4Hz,2H),7.82(dd,J1＝2.4Hz,J2＝8.4Hz,2H),7.47(d,J＝8.4Hz,2H),4.96(t,J＝2.8Hz,2H),4.81(d,J＝15.8Hz,2H),4.44(d,J＝15.8Hz,2H),3.92-3.97(m,4H),3.65-3.72(m,2H),3.49-3.56(m,2H),1.92-1.93(m,2H)ppm；13C NMR(100Mz,DMSO-d6) 155.3,147.9,147.8,138.0,130.9,122.7,104.8,50.2,48.9,48.5,48.5,28.1 ppm; HRMS (ES +) calcd for C23H23N8O4 35Cl2(M+H)+545.1219; the measured value, 545.1201. Calculated value C23H23N8O4 35Cl37Cl(M+H)+547.1190; measured value, 547.1178 calculation C23H23N8O4 37Cl2(M+H)+549.1160; the measured value, 549.1181.
Example 5: synthesis of 1, 5-bis (1- ((2-chlorothiazol-5-yl) methyl) -4, 5-dihydro-1H-imidazolidin-2-yl) -1, 5-dinitro-1, 4-pentadiene (Compound 41)
1- ((2-Chlorothiazol-5-yl) methyl) -2- (nitromethylene) -1-imidazolidine was prepared according to the method described in example 1, starting with 0.03mol of 2-chloro-5-chloromethylthiazole instead of 2-chloro-5-chloromethylpyridine, in a yield of 56%; GC MS (m/s)226(24), 132(100), 77 (9).
1, 5-bis (1- ((2-chlorothiazol-5-yl) methyl) -4, 5-dihydro-1H-imidazolidin-2-yl) -1, 5-dinitro-1, synthesis of 4-pentadiene
1.30g (0.005mol) of 1- ((2-chlorothiazol-5-yl) methyl) -2- (nitromethylene) -1-imidazolidine, 30ml of anhydrous acetonitrile, 0.720g (0.01mol) of malondialdehyde and a catalytic amount of HCl are placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 44%.
mp＝138.6-139.9℃；1H NMR(400Mz,DMSO-d6):7.63(s,1H),4.98(t,J＝2.8Hz,2H),4.85(d,J＝15.8Hz,2H),4.43(d,J＝15.8Hz,2H),3.96-3.99(m,4H),3.67-3.71(m,2H),3.51-3.56(m,2H),1.95-1.97(m,2H)ppm；13C NMR(100Mz,DMSO-d6) 157.6,149.3,138.3,105.8,50.6,48.9,48.4,48.1,29.1 ppm; HRMS (ES +) calcd for C19H19N8O4S2 35Cl2(M+H)+557.0348; measured value, 557.0363 calculation C19H19N8O4S2 35Cl37Cl(M+H)+559.0318; the measured value, 559.0620.
Example 6: synthesis of 1, 5-bis (1- ((6-chloropyridin-3-yl) methyl) -1,4,5, 6-tetrahydropyrimidin-2-yl) -1, 5-dinitro-1, 4-pentadiene (Compound 43)
1- (6-chloro-3-methylpyridyl) -2-nitromethylenehexahydropyrimidine was prepared in 56% yield according to the procedures described in WO 2006056108A1 and WO2007101369A1 starting from 2.42g (0.015mol) of p-chloropyridine; rf 0.19 (ethanol: dichloromethane 1: 1); mp is 175.7-182.6 deg.C. GC MS (m/s)225(100), 196(9), 154(10), 139(11), 126(31), 113(10), 90 (31).
1, 5-bis (1- ((6-chloropyridin-3-yl) methyl) -4, 5-dihydro-1H-imidazolidin 2-yl) -1, 5-dinitro-1, synthesis of 4-pentadiene
1.34g (0.005mol) of 1- (6-chloro-3-methylpyridyl) -2-nitromethylenehexahydropyrimidine, 30ml of anhydrous acetonitrile, 0.720g (0.01mol) of malondialdehyde, and a catalytic amount of HCl were placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 55%.
mp＝133.7-134.9℃；1H NMR(400Mz,DMSO-d6):8.32(d,J＝2.4Hz,2H),7.81(dd,J1＝2.4Hz,J2＝8.4Hz,2H),7.49(d,J＝8.4Hz,2H),4.93(t,J＝2.8Hz,2H),4.78(d,J＝15.8Hz,2H),4.40(d,J＝15.8Hz,2H),3.91-3.96(m,4H),3.63-3.71(m,2H),3.49-3.53(m,2H),2.32-2.37(m,2H),1.92-1.93(m,2H)ppm；13C NMR(100Mz,DMSO-d6) 155.6,148.3,147.9,138.0,130.7,122.7,105.1,50.2,48.8,48.5,48.1,36.2,28.0 ppm; HRMS (ES +) calcd for C25H27N8O4 35Cl2(M+H)+572.1454; the measured value, 572.1468. Calculated value C25H27N8O4 35Cl37Cl(M+H)+574.1425; the measured value, 574.1416.
Example 7: n- ((6-chloropyridin-3-yl) methyl) -N-ethyl-2-methyl-4-nitro-8-oxa-2-azabicyclo [3,2,1 ] s]Synthesis of oct-3-en-3-amine (Compound 46)
1.35g (0.005mol) of N- (6-chloropyridine-3-methylene) -N-ethyl-N' -methyl-2-nitroethylenediamine, 30ml of anhydrous acetonitrile, 0.860g (0.01mol) of succinaldehyde and a catalytic amount of HCl were placed in a 50ml round-bottomed flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, removing the solvent, and performing column chromatography separation to obtain a light yellow powdery pure product with the yield of 40%.
mp＝125.3-125.7℃；1H NMR(400Mz,DMSO-d6):8.72(s,1H),8.27(d,J＝2.4Hz,1H),7.75(dd,J1＝2.4Hz,J2＝8.4Hz,1H),7.58(d,J＝8.4Hz,1H),5.25-5.30(s,2H),4.41-4.50(m,2H),2.96-3.26(m,2H),2.86(s,3H),2.36-2.41(m,2H),1.81-1.5(m,4H),1.16-1.26(m,3H)ppm；13C NMR (100Mz, DMSO-d6) 158.5,154.4,151.6,150.8,148.1,139.3,137.1,107.8,89.5,65.8,49.8,46.9,40.6,21.9,20.3 ppm; HRMS (EI +) calculated value C15H21N4O3 35Cl(M+) 339.1224; the measured value, 339.1257. Calculated value C15H21N4O3 37Cl(M+) 341.1194; the measured value, 341.1213.
Example 8: 9- ((6-Chloropyridin-3-yl) methyl) -4-nitro-8-oxa-10, 11-dihydroimidazo [2,3-a]Bicyclo [3,2,1 ]]Synthesis of oct-3-ene (Compound 52)
1.27g (0.005mol) 2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine, 30ml of anhydrous acetonitrile, 0.860g (0.01mol) of succinaldehyde, and a catalytic amount of HCl were placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product with the yield of 71 percent.
mp＝149.0-150.0℃；1H NMR(400Mz,DMSO-d6):8.35(d,J＝2.4Hz,1H),7.81(dd,J1＝2.4Hz,J2＝8.4Hz,1H),7.51(d,J＝8.4Hz,1H),5.36-5.39(s,2H),5.00(d,J＝15.6Hz,1H),4.68(d,J＝15.6Hz,1H),3.57-3.73(m,4H),1.94-2.04(m,4H)ppm；13C NMR(100Mz,DMSO-d6) 155.6,149.7,149.6,139.7,132.6,124.5,109.6,87.0,75.1,51.2,50.3,46.6,31.9 and 31.7 ppm; HRMS (ES +) calcd for C14H16N4O3 35Cl(M+H)+323.0911; the measured value, 323.0912. Calculated value C14H16N4O3 37Cl(M+H)+325.0811; the measured value, 325.0895. Calculated value C14H15N4O3 35ClNa(M+Na)+345.0730; the measured value, 345.0722. Calculated value C14H15N4O3 37ClNa(M+Na)++347.0701; the measured value, 347.0692.
Example 9: 9- ((2-Chlorothiazol-5-yl) methyl) -4-nitro-8-oxa-10, 11-dihydroimidazo [2,3-a]Bicyclo [3,2,1 ]]Synthesis of oct-3-ene (Compound 53)
1.30g (0.005mol) 2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine, 30ml of anhydrous acetonitrile, 0.860g (0.01mol) of succinaldehyde, and a catalytic amount of HCl were placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, removing the solvent, and performing column chromatography separation to obtain a light yellow powdery pure product with the yield of 63%.
mp＝151.7-152.1℃；1H NMR(400Mz,DMSO-d6):7.65(s,1H),5.33-5.37(s,2H),5.01(d,J＝15.6Hz,1H),4.69(d,J＝15.6Hz,1H),3.52-3.70(m,4H),1.90-2.01(m,4H)ppm；13C NMR(100Mz,DMSO-d6) 155.2,149.6,139.1,124.5,110.6,87.1,75.6,51.3,50.6,46.9,31.9,31.2 ppm; HRMS (ES +) calcd for C12H15N4O3S35Cl(M+H)+329.0475; measured value, 329.0412 calculation C12H15N4O3S37Cl(M+H)+331.0446; measured out ofValue, 331.0423.
Example 10: 9- ((6-Chloropyridin-3-yl) methyl) -4-nitro-8-oxa-10, 11, 12-trihydropyrimido [2, 3-a)]Bicyclo [3,2,1 ]]Synthesis of oct-3-ene (Compound 61)
1.34g (0.005mol) of 1- (6-chloro-3-methylpyridyl) -2-nitromethylenehexahydropyrimidine, 30ml of anhydrous acetonitrile, 0.860g (0.01mol) of succinaldehyde, and a catalytic amount of HCl were placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 38%.
mp＝143.2-144.9℃；1H NMR(400Mz,DMSO-d6):8.33(d,J＝2.4Hz,1H),7.80(dd,J1＝2.4Hz,J2＝8.4Hz,1H),7.49(d,J＝8.4Hz,1H),5.32-5.35(s,2H),5.00(d,J＝15.6Hz,1H),4.66(d,J＝15.6Hz,1H),3.51-3.68(m,4H),2.33-2.41(m,2H),1.89-2.00(m,4H)ppm；13C NMR(100Mz,DMSO-d6) 155.5,149.6,149.3,139.7,132.6,124.1,109.3,86.6,75.1,51.2,50.7,46.6,32.1,31.7,26.9 ppm; HRMS (ES +) calcd for C15H19N4O3 35Cl(M+H)+337.1067; the measured value, 337.1015. Calculated value C15H19N4O3 37Cl(M+H)+339.1038; the measured value, 339.0995.
Example 11: 9- ((6-Chloropyridin-3-yl) methyl) -4-cyano-8-oxa-10, 11-dihydroimidazo [2,3-a]Bicyclo [3,2,1 ]]Synthesis of oct-3-ene (Compound 64)
1.17g (0.005mol) 2-chloro-5- (2-cyanomethylene-imidazolidin-1-ylmethyl) -pyridine, 30ml of anhydrous acetonitrile, 0.860g (0.01mol) of succinaldehyde, and a catalytic amount of HCl were placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 66%.
mp＝125.1-126.8℃；1H NMR(400Mz,DMSO-d6):8.34(d,J＝2.4Hz,1H),7.82(dd,J1＝2.4Hz,J2＝8.4Hz,1H),7.55(d,J＝8.4Hz,1H),5.33(s,1H),5.25(s,1H),5.00(d,J＝15.6Hz,1H),4.78(d,J＝15.6Hz,1H),3.56-3.78(m,4H),1.91-2.00(m,4H)ppm；13C NMR(100Mz,DMSO-d6) 153.6,149.0,148.6,139.7,132.3,121.5,99.6,87.3,75.7,51.3,50.2,46.6,31.5,29.7 ppm; HRMS (ES +) calcd for C15H16N4O35Cl(M+H)+303.1013; the measured value, 303.0992. Calculated value C15H16N4O37Cl(M+H)+305.0983; the measured value, 305.0957.
Example 12: 10- ((6-Chloropyridin-3-yl) methyl) -4-nitro-9-oxa-11, 12-dihydroimidazo [2,3-a]Bicyclo [3,3,1 ]]Synthesis of non-3-ene (Compound 77)
1.27g (0.005mol) of 2-chloro-5- (2-nitromethylene-imidazolidin-1-ylmethyl) -pyridine, 30ml of anhydrous acetonitrile, 3ml of a 25% aqueous solution of glutaraldehyde and a catalytic amount of HCl are placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, the solvent is removed, and column chromatography separation is carried out to obtain a light yellow powdery pure product, wherein the yield is 86%.
mp＝174.7-175.4℃；1H NMR(400Mz,DMSO-d6):8.38(dd,J1＝0.6Hz,J2＝2.4Hz,1H),7.84(dd,J1＝2.4Hz,J2＝8.4Hz,1H),7.52(dd,J1＝0.6Hz,J2＝8.4Hz,1H),5.12(s,1H),5.04-5.05(m,1H),4.97(d,J＝15.6Hz,1H),4.71(d,J＝15.6Hz,1H),3.62-3.74(m,4H),1.66-1.81(m,4H),1.51-1.55(m,1H),1.32-1.44(m,1H)ppm；13C NMR(100Mz,DMSO-d6) 156.6,149.7,149.6,139.7,132.9,124.5,105.8,81.7,68.9,51.7,50.0,46.3,28.8,27.2,14.8 ppm; HRMS (EI +) calculated value C15H17N4O3 35Cl(M+) 336.0989; the measured value, 336.0988. Calculated value C15H17N4O3 37Cl(M+) 338.0960; the measured value, 338.0968.
Example 13: 10- ((tetrahydrofuran-3-yl) methyl) -4-nitro-9-oxa-11, 12-dihydroimidazo [2,3-a [)]Bicyclo [3,3,1 ]]Synthesis of non-3-ene (Compound 80)
1- ((tetrahydrofuran-3-yl) methyl) -2- (-nitromethylene) -1-imidazoline was prepared according to the procedure described in example 1 starting from 0.2mol of 3-chloromethyltetrahydrofuran instead of 2-chloro-5-chloromethylpyridine, in 51% yield; GC MS (m/s)177(29), 99(100), 56 (9).
10- ((tetrahydrofuran-3-yl) methyl) -4-nitro-9-oxa-11, 12-dihydroimidazo [2,3-a [)]The ring structure of the bicyclic ring [3, 3,1]non-3-ene
1.065g (0.005mol) of 1- ((tetrahydrofuran-3-yl) methyl) -2- (-nitromethylene) -1-imidazoline, 3ml of a 25% aqueous glutaraldehyde solution, and a catalytic amount of HCl were placed in a 50ml round-bottom flask. Stirring at normal temperature, and tracking the reaction by TLC. After the reaction is finished, removing the solvent, and performing column chromatography separation to obtain a light yellow powdery pure product with the yield of 36%.
mp＝115.3-116.9℃；1H NMR(400Mz,DMSO-d6):5.11(s,1H),5.00-5.03(m,1H),4.18(d,J＝3.2Hz,2H),4.05-4.25(m,2H),3.85-3.96(m,4H),2.25(m,1H),1.66-1.81(m,4H),1.63-1.64(m,2H),1.57-1.59(m,2H),1.51-1.55(m,1H),1.32-1.44(m,1H)ppm；13C NMR(100Mz,DMSO-d6) 81.7,80.6,78.5,68.9,50.0,49.7,46.9,44.6,36.8,33.9,28.8,27.2,17.8,14.8 ppm; HRMS (EI +) calculated value C14H21N3O4(M+) 295.1532; the measured value, 295.1598.
Example 14: insecticidal Activity test of Compounds of the present invention
(1) Insecticidal Activity against aphids
The aphid belongs to homoptera pests, has a sucking mouth device and is a common crop pest. Aphis fabae (Aphisscarcivora) is taken as a test object and tested by adopting a dipping method.
The operation process is as follows: accurately weighing each sample, adding N, N-dimethylformamide to prepare 10g/L mother liquor, and diluting the mother liquor to a concentration of 500ppm by using an aqueous solution containing 0.2mL/L Triton X-100 during an experiment. After the wingless adult aphids are stably sucked on the bean sprouts, the wingless adult aphids and the bean sprouts are immersed into the liquid medicine with the concentration of 500ppm, the wingless adult aphids and the bean sprouts are taken out after 5 seconds, the surplus liquid medicine is sucked by using water absorption paper, and the wingless adult aphids are moved into a clean vessel to be raised at the constant temperature of 23 ℃. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.2mL/L Triton X-100. After 24 hours of treatment, the number of dead aphids tested was counted and the mortality (%) was calculated according to the formula: mortality (%) - (number of control live insects-number of treated live insects)/number of control live insects × 100%. The results are shown in tables 1-4 below.
(2) Insecticidal activity against plant hoppers
The plant hopper belongs to homoptera pests, has a sucking device, and is a common crop pest. Brown planthopper (Nilaparvata lugens) was used as a test object and tested by a spray method.
The operation process is as follows: the test compound is accurately prepared into 500, 250, 100, 50, 25, 12.5, 6.25, 3.13, 1.57 and 0.79ppm solutions by taking acetone as a solvent, and treated by an aqueous solution of acetone to be used as a blank control. Each treatment was repeated 3 cups (i.e. 3 times). 2ml of the solution was evenly sprayed into each cup using a small hand sprayer. 10 rice planthoppers are inoculated in each pot 6 hours before pesticide application. A total of 3 batches of the test were run sequentially. After 24 hours of treatment, the number of dead insects of the test insects was counted, and the mortality (%) was calculated (formula above). The results are shown in tables 1-4 below.
(3) Insecticidal activity against armyworm
The method of feeding the tea leaves by dipping the tea leaves is adopted. The compound to be tested is accurately prepared into 500, 250, 100, 50, 25, 12.5, 6.25, 3.13 and 1.57ppm solutions by taking acetone as a solvent, and is treated by an aqueous solution of acetone to be used as a blank control. Fresh corn leaves are soaked in the solution for 3 seconds, then dried at room temperature, taken for test insects, and inspected and the mortality rate of the test insects (%, formula is the same as above) is calculated after 24 hours, 10 test insects are used for each treatment, and 3 times of repetition is set. . The results are shown in tables 1-4.
(4) Insecticidal activity against diamondback moth
The method of feeding the tea leaves by dipping the tea leaves is adopted. Fresh cabbage leaves are soaked in the solution for 3 seconds, then dried at room temperature, taken by test insects, inspected 24 hours later and the mortality rate of the test insects (%, formula is the same as above) is calculated, 10 test insects are used for each treatment, and the process is repeated for 3 times. The blank was treated with clear water. The results are shown in tables 1-4 below.
Table 1: pesticidal activity of the compound of formula (A)
Table 2: pesticidal activity of the compound of formula (B)
Table 3: insecticidal Activity of Compounds of formula (C)
Table 4: pesticidal activity of the compound of formula (D)
Example 15: preparation of insecticide compositions containing the Compounds of the invention
(a) Oily suspensions
Preparing the following components in proportion: 25% (by weight, the same applies hereinafter) of any one of the compounds 1 to 73; 5% polyoxyethylene sorbitol hexaoleate; 70% of higher aliphatic hydrocarbon oil. The components were ground together in a sand mill until the solid particles fell below about 5 microns. The resulting viscous suspension can be used as such, but it can also be emulsified in water.
(b) Aqueous suspension
Preparing the following components in proportion: 25% of any one of compounds 1-73; 3% hydrated attapulgite (hydrateattataphyllit); 10% calcium lignosulfonate; 0.5% sodium dihydrogen phosphate; 61.5% water. The components are ground together in a ball mill until the solid particles fall below about 10 microns. The aqueous suspension can be used as such.
(c) Bait agent
Preparing the following components in proportion: 0.1-10% of any one of compounds 1-73; 80% wheat flour; 19.9-10% of molasses. These components are thoroughly mixed to form a bait shape as desired. Edible baits can be dispersed to a locus infested by sanitary pests, for example a domestic or industrial locus, such as a kitchen, hospital or store or outdoor area, to control pests by oral ingestion.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (28)

1. A compound having a structure represented by formula (D):
in the formula:
R1is a five-membered or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a halogenated five-membered or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group, wherein the substituent is selected fromOne or more of the group of: halogen, C1–4Haloalkyl or C1–4A chloroalkoxy group;
R3and R4Each independently is H, C1-6Alkyl, allyl, benzyl, C1–4alkoxy-C1–4Alkyl radical, C1–4Alkoxy-carbonyl, phenoxycarbonyl, C2–6Alkynyl-carbonyl, C2–3Alkenyl-carbonyl, C3–6Cycloalkyl-carbonyl, benzoyl, or substituted by one or more radicals selected from halogen, C1–4Alkyl radical, C1–4Haloalkyl, C1–4Alkoxy and C1–4Benzoyl, furancarbonyl or N, N-dimethylaminocarbonyl substituted by alkyl-carbonyl substituents, or R3And R4Together form-CH2-CH2-，-CH2-CH2-CH2-or-CH2-XR-CH2-, where X is a heteroatom N and R is a substituent on the heteroatom selected from H and C1-6Alkyl, allyl, benzyl, phenyl, C1–4alkoxy-C1–4Alkyl radical, C1–4Alkoxy-carbonyl, phenoxycarbonyl, C2–6Alkynyl-carbonyl, C2–3Alkenyl-carbonyl, C3–6Cycloalkyl-carbonyl, benzoyl, or substituted by one or more radicals selected from halogen, C1–4Haloalkyl, C1-8Saturated or unsaturated alkyl or alkoxy and C1–4Benzoyl, furancarbonyl or N, N-dimethylaminocarbonyl substituted with a substituent of alkyl-carbonyl;
R7，R8and R9Is H, saturated or unsaturated C1-4Alkyl, halogen, C1-8Saturated or unsaturated alkoxy, halogeno C1-4Saturated or unsaturated alkoxy radicals, C1–4Alkyl-carbonyl, C1–8Alkyl-ester group, C1–4Alkyl-sulfonate, phenyl or benzyl;
y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl.
2. The compound according to claim 1 or a pesticide thereofA pharmaceutically acceptable salt, wherein R is1Selected from: pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, oxazolyl, or a halide thereof.
3. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R1Is a halogenated pyridyl group, a halogenated thiazolyl group, a halogenated pyrimidinyl group, a halogenated tetrahydrofuranyl group, or a halogenated oxazolyl group.
4. The compound of claim 2, or an agriculturally pharmaceutically acceptable salt thereof, wherein the halide is chloride.
5. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R1Is composed of
6. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R3And R4Is hydrogen or C1-6Alkyl, or R3And R4Together form-CH2-CH2-or-CH2-CH2-CH2-。
7. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R3And R4Is hydrogen or C1-3Alkyl, or R3And R4Together form-CH2-CH2-or-CH2-CH2-CH2-。
8. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R7，R8And R9Is H, saturated or unsaturated C1-2Alkyl, halogen, C1-4Saturated or unsaturated alkoxy, halogeno C1-2Saturated or unsaturated alkoxy radicals, C1–4Alkyl-ester group, C1–2An alkyl-sulfonyl ester group or a trifluoromethanesulfonyl ester.
9. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R7，R8And R9Is hydrogen, methyl, chlorine, bromine, methoxy or ethoxy.
10. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein R7，R8And R9Hydrogen, methyl, methoxy.
11. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein Y is nitro or cyano.
12. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt thereof, wherein Y is nitro.
13. An agricultural composition comprising:
(a) 0.001-99.99% by weight of a compound of any one of claims 1-12 or an agriculturally pharmaceutically acceptable salt thereof, or a combination thereof; and
(b) an agriculturally pharmaceutically acceptable carrier and/or excipient.
14. An agricultural composition as claimed in claim 13, wherein component (a) comprises from 0.01 to 99.9% by weight of the agricultural composition.
15. An agricultural composition as claimed in claim 13, wherein the agricultural composition is for use in killing or preventing pests selected from the group consisting of: coleopteran, lepidopteran, hemipteran, orthopteran, isopteran or dipteran insects.
16. An agricultural composition of claim 15, wherein the pests have piercing or rasping mouthparts.
17. An agricultural composition as claimed in claim 15, wherein the pest is aphid, plant hopper, whitefly, leafhopper, thrips, cotton bollworm, cabbage worm, diamond back moth, prodenia litura, or armyworm.
18. An agricultural composition of claim 13, further comprising (c) an additional active compound selected from the group consisting of: insecticides, baits, bactericides, acaricides, nematicides, fungicides, growth control agents.
19. The agricultural composition of claim 13,
the agricultural composition is a solution, an emulsion, a suspension, a powder, a foaming agent, a paste and a granule; aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compositions for seeds, formulations for use with combustion devices, ULV cold or hot fogging formulations.
20. An agricultural composition of claim 18, wherein the pesticide comprises: phosphates, carbamates, pyrethroids, chlorinated hydrocarbons, benzoylureas, nereistoxin and substances produced by microorganisms.
21. An agricultural composition of claim 20, wherein the substance produced by the microorganism is abamectin.
22. Use of an agricultural composition as defined in claim 13 for killing or preventing agricultural pests, sanitary pests; or as a pesticide composition for killing or preventing agricultural pests and sanitary pests.
23. A compound selected from the group consisting of the compounds shown below;
wherein,
R1is composed ofR3Is C2H5，R4Is CH3，R7、R8、R9Is H, Y is NO2；
R1Is composed ofR3Is H, R4Is CH3，R7、R8、R9Is H, Y is NO2；
R1Is composed ofR3，R4Together form-CH2-CH2-，R7、R8、R9Is H, Y is NO2；
R1Is composed ofR3，R4Together form-CH2-CH2-，R7、R8、R9Is H, Y is CN;
R1is composed ofR3，R4Together form-CH2-CH2-，R7、R8、R9Is H, Y is NO2；
R1Is composed ofR3，R4Together form-CH2-CH2-，R7、R8、R9Is H, Y is NO2；
R1Is composed ofR3，R4Together form-CH2-CH2-CH2-，R7、R8、R9Is H, Y is NO2。
24. A process for the preparation of a compound according to claim 1, or an agriculturally pharmaceutically acceptable salt thereof, said process comprising the steps of:
reacting a compound of formula (a) with a compound of formula (D) in the presence of a catalytic amount of an acid at 0-60 ℃ to produce a compound having formula (D),
in the formula, R1、R3、R4、R7，R8，R9And Y is as defined in claim 1.
25. The method of claim 24, wherein the reaction temperature is 15-45 ℃.
26. The method of claim 24, wherein the solvent used is selected from the group consisting of: acetonitrile or ethanol.
27. The process of claim 24, wherein the catalytic amount of acid used is selected from the group consisting of: concentrated hydrochloric acid, concentrated sulfuric acid or benzoic acid.
28. The method of claim 24, wherein the method comprises the steps of:
carrying out the following reaction in acetonitrile in the presence of a catalytic amount of an acid at 10-50 ℃ for 2-24 hours to obtain a compound of formula (D):
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1631887A (en) * 2004-11-23 2005-06-29 华东理工大学 Nitryl methylene derivatives and uses thereof
CN101016277A (en) * 2007-02-12 2007-08-15 江苏天容集团股份有限公司 Second anabasine insecticide JT-L001 and chemical synthesis method thereof
EP1997820A1 (en) * 2006-03-09 2008-12-03 East China University of Science and Technology Preparation method and use of compounds having high biocidal activities

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1631887A (en) * 2004-11-23 2005-06-29 华东理工大学 Nitryl methylene derivatives and uses thereof
EP1997820A1 (en) * 2006-03-09 2008-12-03 East China University of Science and Technology Preparation method and use of compounds having high biocidal activities
CN101016277A (en) * 2007-02-12 2007-08-15 江苏天容集团股份有限公司 Second anabasine insecticide JT-L001 and chemical synthesis method thereof

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