CN109369578A - A kind of succinic acid furfural dibasic acid esters insecticides and its preparation method and application - Google Patents

Abstract

It is that the effective component being extracted from plants is modified the present invention relates to a kind of succinic acid furfural dibasic acid esters insecticides, is easier to the characteristics of being decomposed into innocuous substance, no pollution to the environment after remaining application.After modification, this insecticide has preferable control efficiency to insect, nematode, can especially prevent and treat prodenia litura, aphid and root-knot nematode well.Simultaneously, the insecticide toxicity is lower, residual in crops is few, it is small to the harmfulness of people, animal, it solves existing insecticide very well to be more toxic, the more problem of the residual in crop improves the safety of agricultural production, pest will not generate antibody to insecticide of the invention in a long time, therefore have good insecticidal effect.

Description

A kind of succinic acid furfural dibasic acid esters insecticides and its preparation method and application

Technical field

The present invention relates to pesticide fields, in particular it relates to a kind of succinic acid furfural dibasic acid esters insecticides, Yi Jiqi Preparation method and for preventing and treating the animal pest in agricultural, especially crop, the purposes of the insect in plant, nematode.

Background technique

China is a large agricultural country, and plant pest is endangering always the agricultures such as China vegetables, grain and industrial crops Product.This becomes one of the main reason for restricting the production estimations such as vegetables, corn and soybean, cotton, wheat, when of a serious nature Even result in crops total crop failure.

While traditional chemical insecticide plays effective positive effect in preventing and treating pest and disease damage, also to environment and the mankind with Serious side effect is carried out.Usually there is certain deficiency in chemical insecticide itself, along with the long-term improper use of the mankind, Cause to have seriously polluted the environment, compromise human health, destroys the ecological balance of nature.In addition, disease pest mistake herein Also drug resistance is generally produced in journey, is prevented and treated the problems such as being increasingly difficult to and is shown especially out.Therefore, chemical pesticide, which is no longer appropriate for people, makes With.

In recent years, " green pesticide " is all being advocated energetically in countries in the world, thus quality and standard proposition to insecticide More strict requirements must have selectivity good, the features such as with environmental-friendly, nuisanceless, mechanism of action novel and unique. Plant insecticide is the insecticides for being processed into the extract of plant or plant, degradable since it has low toxicity, The advantages of Environmental compatibility is good, is not likely to produce drug resistance to pest, the toast that these advantages become the research of plant insecticide Hand can warm.

Summary of the invention

The present invention existing insecticide there are aiming at the problem that, provide a kind of novel succinic acid furfural di esters desinsection Agent, the insecticide have good control efficiency to animal pest such as insect, nematode, but to person poultry harmless.In other words, described Insecticide is effective to animal pest, safe to non-target organism, in addition, it is easily decomposed and decomposition product is harmless to environment, because This and environment high are harmonious.

Yet another object of the invention is that providing a kind of for preventing and treating the composition of the animal pest in agricultural, contain The succinic acid furfural dibasic acid esters insecticides are as active constituent.

Yet another object of the invention is that it is dynamic in prevention and treatment agricultural to provide the succinic acid furfural dibasic acid esters insecticides The purposes of insect, nematode in object pest, especially crop, plant.

Yet another object of the invention is that providing the succinic acid furfural dibasic acid esters insecticides in preparation crop or plant Application in protective agent, the crop or plant protection product are used to prevent and treat animal pest in agricultural, especially crop, in plant Insect, nematode.

Yet another object of the invention is that providing the succinic acid furfural di esters method for producing insecticide.

Specifically, the present invention provides a kind of compound of formula I or its salt:

Wherein, R₁、R₂It is each independently halogen or NO₂；

R₃For C1-C6 alkyl, C3-C8 naphthenic base, C6-C14 aryl or C6-C14 aryl C1-C6 alkyl, wherein the C1- C6 alkyl, C3-C8 naphthenic base, C6-C14 aryl, C6-C14 aryl C1-C6 alkyl are optionally by one or more selected from following Substituent group replace: halogen, C1-4 alkyl, C1-4 alkoxy, OH, NO₂Or CN.

In a preferred embodiment, R₁Selected from halogen or nitro, it is preferable that R₁For F, Cl or NO₂。

In a preferred embodiment, R₂Selected from halogen, it is preferable that R₂For F or Cl.

In a preferred embodiment, R₃Selected from C1-C6 alkyl, optionally by one or more selected from following Substituent group replace: halogen, C1-4 alkoxy or OH, it is preferable that R₃For methyl, ethyl, propyl, isopropyl, butyl or 2- hydroxyl Base ethyl, it is highly preferred that R₃For methyl, ethyl, propyl or 2- hydroxyethyl.

In a preferred embodiment, R₁=F, R₂=Cl, R₃=CH₃, compound of formula I indicates by Formulas I a:

In a preferred embodiment, R₁=NO₂, R₂=Cl, R₃=CH₂CH₃, compound of formula I indicates by Formulas I b:

In a preferred embodiment, R₁=Cl, R₂=F, R₃=CH₂CH₂OH, compound of formula I are indicated by Formulas I c:

In a preferred embodiment, R₁=Cl, R₂=F, R₃=CH₂CH₂CH₃, compound of formula I indicates by Formulas I d:

Specific embodiment

It hereafter will be described in detail the present invention.

Unless otherwise defined, all technical and scientific terms used in this application have and fields technology people of the present invention Member is generally understood identical meaning.All patents and publications that the application refers to is incorporated herein by reference.

In the present invention, term " halogen " indicates fluorine, chlorine, bromine or iodine.

In the present invention, term " alkyl " (including when being used alone and including in other groups) means to include 1~12 The branch of a carbon atom and the radical of saturated aliphatic alkyl of straight chain, preferably 1~6 carbon atom, more preferable 1~4 carbon atom, such as first Base, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, isobutyl group, amyl, hexyl, heptyl, octyl, nonyl, decyl, 4,4- Dimethyl amyl group, 2,2,4- tri-methyl-amyls, undecyl, dodecyl and their various isomers etc..

In the present invention, term " naphthenic base " (when including being used alone and include in other groups) includes the packet of saturation Cyclic hydrocarbon groups containing 1-3 ring comprising monocycle alkyl, bicyclic alkyl and tricyclic alkyl, it includes 3-8 to form The carbon of ring, such as: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl.

In the present invention, term " aryl " refer to it is any it is stable have 6-20 carbon atom, preferably 6-14 carbon atom, More preferable 6-10 carbon atom, it may be up to the monocycle or bicyclic carbocyclic of 7 atoms in each ring, wherein at least one ring is Aromatic rings.The example of above-mentioned aryl unit includes phenyl, naphthalene, tetralyl, indanyl, xenyl, phenanthryl, anthracene Base or acenaphthenyl.

Those skilled in the art recognizes, since the salt of in the environment and in physiological conditions compound is corresponding to them Salt-independent shape be in balance, therefore salt share salt-independent shape Purificatiou.Therefore, the salt of a variety of compound of formula I can be used for Prevent and treat animal pest.The salt of compound of formula I includes the acid-addition salts with inorganic acid or organic acid, the acid such as hydrobromic acid, salt Acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, winestone Acid, 4- toluenesulfonic acid or valeric acid.When compound of formula I includes acidic moiety such as carboxylic acid or phenol, salt further includes and organic base Or inorganic base those of is formed, the alkali such as pyridine, triethylamine or ammonia or sodium, potassium, lithium, calcium, magnesium or barium amide, hydrogen Compound, hydroxide or carbonate.

Composition/preparation

The present invention also provides a kind of composition, the composition includes compound of formula I or its salt as active constituent, and Preferably comprise agriculturally suitable auxiliary agent, solvent, carrier, surfactant or filler.The composition also optionally also wraps Containing at least one additional biologically active cpds or reagent.

Suitable organic solvent includes the institute's polarized and non-polar organic solvent commonly used in preparation purpose.It is preferred molten Agent is selected from: ketone, such as methyl iso-butyl ketone (MIBK) and cyclohexyl ketone；Amides, such as dimethylformamide；Alkanoic acid amide Class, such as spectrasolv DMDA and N, N- dimethyloctanamide and cyclic solvent, such as N-Methyl pyrrolidone, N- Octylpyrrolidone, N-dodecylpyrrolidone, N- Octylcaprolactam, N- dodecyl caprolactam and butyrolactone；With And intensive polar solvent, such as dimethyl sulfoxide；And arene, such as dimethylbenzene；Mineral oils, such as white spirit, stone Oil, alkylbenzene and bobbin oil；And esters, such as propylene glycol methyl ether acetate, dibutyl adipate, hexyl acetate, acetic acid Heptyl ester, tri-n-butyl citrate and n-butyl phthalate；And alcohols, such as benzylalcohol and 1- methoxy-2-propanol.

According to the present invention, carrier is natural or synthesis, organic or inorganic substance, is mixed with reactive compound Or it combines to obtain better adaptability, the especially application to plant or plant parts or seed.(it can be solid to the carrier Body or liquid) it is usually inert and shall apply to agricultural use.

Available solid or liquid-carrier include: such as ammonium salt and natural rock dust (such as kaolin, clay, cunning Stone, chalk, quartz, attapulgite, montmorillonite or diatomite), synthesis rock dust (such as high degree of dispersion silica, Aluminium oxide and natural or synthetic silicate), resin, wax, solid fertilizer, water, alcohol (especially butanol), organic solvent, mineral Oil and vegetable oil and its derivative.The mixture of these carriers can also be used.

Suitable solid packing and carrier include inorganic particle, such as 0.005-20 μm of average grain diameter, preferably 0.02-10 μm Carbonate, silicate, sulfate and oxide, such as ammonium sulfate, ammonium phosphate, urea, calcium carbonate, calcium sulfate, magnesium sulfate, oxygen Change magnesium, aluminium oxide, silica, so-called fine-particle silicon dioxide, silica gel, natural or synthetic silicate and alumino-silicate, And plant product such as grain flour, wood powder/sawdust and cellulose powder.

Useful solid carrier for granule includes: the natural rock for for example crushing and being classified, such as calcite, big Fibrous gypsum, float stone, sepiolite, dolomite, and synthesis inorganic and organic dust particle and organic material such as sawdust, The particle of coconut husk, corncob and tobacco stem.

Useful liquefied gaseous state filler or carrier are that those are gaseous liquid under normal temperature and normal pressure, Such as aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.

In the preparation, usable tackifier (such as carboxymethyl cellulose) and powder, particle or latex form Natural and synthesis polymer (such as gum arabic, polyvinyl alcohol and polyvinyl acetate) or natural phospholipid (such as brain phosphorus Rouge and lecithin) and synthetic phospholipid.Other additives can be mineral oil and vegetable oil.

If filler used is water, also it can be used such as organic solvent as secondary solvent.Useful liquid solvent Mainly are as follows: aromatic compound such as dimethylbenzene, toluene or alkylnaphthalene；Chlorinated aromatic compound and chloro fat race hydrocarbon, such as Chlorobenzene, vinyl chloride or methylene chloride；Aliphatic hydrocarbon, such as hexamethylene or paraffin, such as mineral oil fractions, mineral oil and vegetable oil； Alcohol (such as butanol or ethylene glycol) and its ether and ester；Ketone, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or cyclohexanone；By force Polar solvent such as dimethylformamide and dimethyl sulfoxide；And water.

Suitable surfactant (adjuvant, emulsifier, dispersing agent, protective colloid, wetting agent and adhesive) includes institute There are common ion and nonionic, such as the nonyl phenol of ethoxylation, the polyalkylene glycol ethers of linear chain or branched chain alcohol, alkane Base phenol and the reaction product of ethylene oxide and/or propylene oxide, fatty acid amine and ethylene oxide and/or propylene oxide react production Object and aliphatic ester, alkylsulfonate, alkyl sulfate, alkyl ether sulfate, alkyl ether phosphate, aryl-sulfate, second The aryl alkyl phenol (such as triphenylethylene base-phenol-ethoxylate) of oxygroup and ethoxylation and propenoxylated virtue Aryl alkyl phenol-the ethoxylate and ethyoxyl and propoxylate of base alkyl phenol such as sulphation and phosphorylation.Other examples It forms sediment for natural and synthesis water-soluble polymer, such as lignosulphonates, gelatin, Arabic gum, phosphatide, starch, hydrophobically modified Powder and cellulose derivative, especially cellulose esters and cellulose ether and polyvinyl alcohol, polyvinyl acetate, polyvinyl The copolymer of pyrrolidones, polyacrylic acid, polymethylacrylic acid and (methyl) acrylic acid and (methyl) acrylate, and by The copolymer of methacrylic acid and methacrylate that alkali metal hydroxide neutralizes, and the naphthalene sulfonate that optionally replaces with The condensation product of formaldehyde.If one of described active constituent and/or one of the inert carrier it is not soluble in water and application in water into When row, then the presence of surfactant is needed.In the present composition, the ratio of surfactant is 5-40 weight %.

Dyestuff such as inorganic pigment can be used, such as iron oxide, titanium oxide and Prussian blue；And organic dyestuff, such as alizarin Dyestuff, azo dyes and metallized phthalocyanine dye；And micronutrient, such as molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt And zinc salt.

The defoaming agent that may be present in the preparation includes such as alcohols of silicone emulsion, long-chain, fatty acid and its salt, with And organic fluorocompound and its mixture.

The example of thickener is polysaccharide such as xanthan gum or aluminium-magnesium silicate；Silicate, such as attapulgite, montmorillonite or thin Grain silica.

If appropriate, also may be present other additional components, for example, protective colloid, adhesive, sticker, thickener, Thixotroping substance, bleeding agent, stabilizer, sequestering agent, complexing agent.In general, the active constituent can be usually used in preparation mesh Any solid or liquid additive combination.

The additional biologically active cpds of at least one or reagent are selected from the group consisting of: Abamectin, accephate, acequinocyl, Acetamiprid, acrinathrin, pyridine mutter cyclopropyl worm ester, sulfanilamide (SN) mite ester, Amitraz, avermectin, Nimbin, azinphos-methyl, Benfuracard micro, bensultap, Biphenthrin, Bifenazate, bistrifluron, borate, Buprofezin, west Denapon, carbofuran, cartap, Carzol, Rynaxypyr, chlorfenapyr, UC 62644, chlopyrifos, chlorpyrifos-methyl, ring worm Hydrazides, mite dead net, clothianidin, cyanogen insect amide, cycloprothrin, cycloxaprid, cyflumetofen, cyfloxylate, β-cyfluthrin chrysanthemum Ester, Cyhalothrin, γ-Cyhalothrin, λ-Cyhalothrin, cypermethrin, α-cypermethrin, ζ-chlorine cyanogen chrysanthemum Ester, cyromazine, decis, diafenthiuron, basudin, dieldrite, diflubenzuron, dimefluthrin, dimehypo, Rogor, furan worm Amine, difenolan, emaricin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, esfenvalerate, ethiprole, Etofenprox, etoxazole, fenbutatin oxide, fenifrothion, benzene Sulphur prestige, fenoxycarb, Fenpropathrin, fenvalerate, Fipronil, flonicamid, Flubendiamide, flucythrinate, phonetic worm amine, fluorine Worm urea, fluorine bacterium mite ester, fluorine thiophene worm sulfone, fluopyram, fluorine pyrrole furanone, taufluvalinate, τ-taufluvalinate, worm sulphur Phosphorus, Carzol, lythidathion, chlorine tebufenozide, flubenzuron, Hexythiazox, hydramethylnon, imidacloprid, indoxacarb, desinsection soap, isofenphos, lice Mite urea, malathion, fluorine chlorine ether pyrethroids, metaflumizone, Halizan, acephatemet, methidathion, first thiodicarb, methomyl, methoxy are general It is woods, methoxychlor, metofluthrin, Azodrin, methoxyfenozide, Nitenpyram, nithiazide, Rimon, more Fluorine urea, oxamoyl, parathion, parathion-methyl, Permethrin, thimet, Phosalone, phosmet, phosphamidon, Aphox, Profenofos, the third Flumethrin, propargite, propyl benzene hydrocarbon pyrethroids, pymetrozine, pyrazine Fipronil, pyrethrins, pyridaben, pyridalyl, New quinazoline (metadiazine) insecticides, pyriminostrobin, pyridine Fipronil, pyriproxyfen, rotenone, ryanodine, fluorine silicon chrysanthemum Ester, ethyl pleocidin, pleocidin, Envidor, Spiromesifen, spiral shell worm ethyl ester, sulprofos, the pyridine of sulfone worm, tebufenozide, pyrrole mite Amine, diflubenzuron, Tefluthrin, Terbufos, Ravap, tetramethrin, etrafluorine ethofenprox, thiacloprid, Diacloden, thiodicarb, desinsection Double, Tolfenpyrad, tralomethrin, triaguron, metrifonate, triflumuron, all bacterial strains, the Insect Pathogenic of bacillus thuringiensis are thin Bacterium, all bacterial strains of nuclear polyhedrosis virus, Insect Pathogenic virus and insect pathogenic fungus.

According to its specific physical and/or chemical characteristic, active constituent of the invention or composition can be with its dosage forms Or use form application prepared therefrom, the administration form such as aerosol, capsule suspension, harl concentrating agents, hot mistiness Contracting agent, encapsulated granule, fine grained agent, the mobility concentrating agents for seed treatment, instant solution, can dusting powder Agent, emulsifiable concentrating agents, oil in water emulsion, water-in-oil emulsion, bulky grain agent, fine granule, oil-dispersing property powder agent, oil are mixed Dissolubility flowing concentrating agents, oily forming ionisable polymer, gas agent (under stress), production gas product, foaming agent, paste, insecticide are coated Seed, suspension concentrating agents, outstanding newborn concentrating agents, soluble concentrating agents, suspension, wettable powder, soluble powder, pulvis and Granula, the granule of water solubility and water dispersible or tablet, water solubility or water-dispersible powder for seed treatment, wettable Microcapsules in pulvis, natural products and synthetic and polymer and seed coat material through active material dipping, with And ULV harl and hot mist preparation.

Composition of the invention not only includes instant and the preparation that can be administered to by appropriate device on plant or seed, It further include the commercially available concentrating agents that must be diluted with water before the use.Common usage is sprinkling gained spray after for example diluting in water Spray film body, dilute in the oil after application, without dilution directly application, with granule treatment seed or soil application.

Composition and preparation of the invention usually contains 0.05 to 99 weight %, 0.01 to 98 weight %, preferably 0.1 to 95 The active constituent of weight %, more preferable 0.5 to 90 weight %, most preferably 10 to 70 weight %.For special applications, such as timber With the protection of derivative Wood products, composition of the invention and preparation usually contain 0.0001 to 95 weight %, preferably 0.001 To the active constituent of 60 weight %.

It can be changed in a wide range by the content of the active constituent in the administration form of commercial preparation preparation.In administration form The concentration of active constituent be usually 0.000001 to 95 weight %, preferably 0.0001 to 2 weight %.

Above-mentioned preparation can be prepared with method known per se, such as by by active constituent and at least one Conventional filler Agent, solvent or diluent, adjuvant, emulsifier, dispersing agent and/or adhesive or fixative, wetting agent, hydrophobing agent, if appropriate, Desiccant and UV stabilizer, and if appropriate, dyestuff and pigment, defoaming agent, preservative, inorganic and organic thickening agent, adhesion Agent, gibberellin and other processing aids and water mixing.Other procedure of processings are needed according to type of preparation to be prepared, it is such as wet Method grinding, dry grinding and granulation.

Carrying out processing of the invention to plant and plant parts using active constituent or composition directly can carry out or pass through Conventional treatment method acts on its ambient enviroment, habitat or memory space and carries out, and the conventional treatment method is for example to pass through leaching Stain, spraying, irrigation, evaporation, dusting, atomizing, broadcasts sowing, foams, smearing, being coated with, watering (pouring), instiling at sprinkling, in breeding material In the case where material, especially for seed, it can also pass through dry seed treatment, wet seed treatment, slurries processing, Surface hardened layer, packet Be coated by one or more layers etc..Also soil can be injected by ultra-low volume method or by active agent preparation or active constituent itself In efficiently use active constituent.

Plant/crop protection

The invention further relates to animal pest of the succinic acid furfural dibasic acid esters insecticides in prevention and treatment agricultural, especially make The purposes of insect, nematode in object or plant.

The animal pest includes:

Insect, such as:

Isopoda (Isopoda), for example, comb beach louse (Oniscus asellus), pillworm (Armadillidium Vulgare), ball pillworm (Porcellio scaber).

Sufficient mesh (Diplopoda) again, for example, Blaniulus guttulatus.

Lip foot mesh (Chilopoda), for example, Geophilus carpophagus, common house centipede belong to (Scutigera spp.).

Comprehensive mesh (Symphyla), for example, kahikatea worm (Scutigerella immaculata).

Thysanoptera (Thysanura), for example, silverfish (Lepisma saccharina).

Collembola (Collembola), for example, arms Onychiurus arcticus (Onychiurus armatus).

Orthoptera (Orthoptera), for example, family Xi (Acheta domesticus), Gryllotalpa spp (Gryllotalpa Spp.), African migratory locust (Locusta migratoria migratorioides), black locust category (Melanoplus spp.), sand Unconcerned locust (Schistocerca gregaria).

Blattaria (Blattaria), for example, oriental cockroach (Blatta orientalis), American cockroach (Periplaneta americana), leucophaea maderae (Leucophaea maderae), blatta germanica (Blattella germ anica)。

Dermaptera (Dermaptera), for example, European ball sister-in-law (Forficula auricularia).

Isoptera (Isoptera), for example, Reticulitermes (Reticulitermes spp.).

Anoplura (Phthiraptera), for example, body louse (Pediculus humanus corporis), Haematopinus (Haematopinus spp.), Linognathus (Linognathus spp.), Trichodectes (Trichodectes spp.), Damalinia (Damalinia spp.)。

Thysanoptera (Thysanoptera), for example, greenhouse hedge thrips (Hercinothripsfemoralis), onion thrips (Thrips tabaci), palm thrips (Thrips palmi), Frankliniella occidentalis (Frankliniella occidentalis).

Heteroptera (Heteroptera), for example, Eurygasterspp category (Eurygaster spp.), Dysdercusintermedius, square butt stinkbug (Piesma quadrata), bed bug (Cimex lectularius), length It is red to hunt stinkbug (Rhodnius prolixus), cone Toona (Triatoma spp.).

Homoptera (Homoptera), for example, Aleurodes brassicae, Bemisia tabaci (Bemisiatabaci), greenhouse Aleyrodid (Trialeurodes vaporariorum), cotten aphid (Aphis gossypii), brevicoryne brassicae (Brevicoryne Brassicae), the hidden tumor aphid of tea Fischer (Cryptomyzus ribis), beans winged euonymus aphid (Aphis fabae), apple aphid (Aphis Pomi), apple aphid (Eriosomalanigerum), mealy plum aphid (Hyalopterus arundinis), Phylloxera Vastatrix, Pemphigus (Pemphigus spp.), grain aphid (Macrosiphum avenae), tumor aphid genus (Myzus Spp.), step wart aphid (Phorodon humuli), cereal excessive pipe aphid (Rhopalosiphumpadi), Empoasca flavescens are neglected (Empoasca spp.), Euscelis bilobatus, rice green leafhopper (Nephotettix cincticeps), Europe fruit heavily fortified point ball A red-spotted lizard (Lecanium corni), olive black bourch (Saissetia oleae), small brown rice planthopper (Laodelphax Striatellus), brown paddy plant hopper (Nilaparvatalugens), red kidney Aspidiotus (Aonidiella aurantii), ivy Aspidiotus (Aspidiotushederae), mealybug category (Pseudococcus spp.), Psylla spp (Psylla spp.).

Lepidoptera (Lepidoptera), for example, prodenia litura (Spodoptera litura), Pectinophora gossypiella (Pectinophora gossypiella), loose looper (Bupalus piniarius), winter geometrid moth (Cheimatobia Brumata), the thin moth of apple (Lithocolletis blancardella), apple ermine moth (Hyponomeuta padella), dish Moth (Plutella xylostella), malacosoma neustria (Malacosoma neustria), pornography and drug moth (Euproctis Chrysorrhoea), Euproctis (Lymantria spp.), cotton lyonetid (Bucculatrixthurberiella), tangerine lyonetid (Phyllocnistis citrella), Noctua (Agrotis spp.), cutworm category (Euxoa spp.), dirty cut noctuid Belong to (Feltia spp.), earias insulana (Eariasinsulana), Heliothis (Heliothis spp.), lopper worm (Mamestra brassicae), small noctuid (Panolis flammea), Spodoptera (Spodoptera spp.), powder Autographa spp (Trichoplusia ni), codling moth (Carpocapsa pomonella), Pieris spp (Pierisspp.), striped rice borer category (Chilo spp.), corn borer (Pyrausta nubilalis), Anagasta kuehniella (Ephestia kuehniella), greater wax moth (Galleria mellonella), Tineolabisselliella (Tineolabisselliella), bag casemaking clothes moth (Tinea pellionella), brown knit moth (Hofmannophilapseudospretella), flax Huang volume moth (Cacoecia podana), Capua reticulana, Spruce bunworm (Choristoneura fumiferana), grape codling moth (Clysia ambiguella) (Clysia ambiguella), Homonamagnanima (Homona magnanima), the green volume moth of oak (Tortrix viridana), Cnaphalocerus spp., Oulema oryzae (Oulema oryzae)。

Coleoptera (Coleoptera), for example, furniture death watch beetle (Anobium punctatum), lesser grain borer (Rhizopertha Dominica), a bean weevil (Bruchidius obtectus), acanthoscelides obtectus (Acanthoscelides obtectus), North America are disliked House longhorn beetle (Hylotrupes bajulus), poplar firefly chrysomelid (Agelastica alni), colorado potato bug (Leptinotarsa decemlineata), horseradish daikon leaf beetle (Phaedon cochleariae), Diabroticaspp (Diabrotica spp.), rape golden head flea beetle (Psylliodes chrysocephala), Epilachna Varivestis, Atomaria spp., saw-toothed grain beetle (Oryzaephilus surinamensis), flower genus (Anthonomus Spp.), Sitophilus (Sitophilus spp.), vine black ear beak as (Otiorrhynchus sulcatus), banana rootstock as (Cosmopolites sordidus), seed are as (Ceuthorrhynchus assimilis), alfalfa leaf are as (Hypera Postica), khapra beetle category (Dermestes spp.), spot khapra beetle category (Trogoderma spp.), Anthrenus (Anthrenus Spp.), fur moth category (Attagenusspp.), powder moth category (Lyctus spp.), pollen beetle (Meligethes Aeneus), Ptinus (Ptinus spp.), golden spider beetle (Niptus hololeucus), globose spider beetle (Gibbium Psylloides), Tribolium (Tribolium spp.), yellow meal worm (Tenebrio molitor), click beetle category (Agriotesspp.), wide chest Agriotes spp (Conoderus spp.), gill cockchafer (Melolontha melolontha), horse Bell potato gill cockchafer (Amphimallon solstitialis), brown New Zealand's rib wing Phyllophaga (Costelytra Zealandica), rice root weevil (Lissorhoptrus oryzophilus).

Hymenoptera (Hymenoptera), for example, Diprion (Diprion spp.), real tenthredinidae (Hoplocampa Spp.), hair ant category (Lasius spp.), Monomorium (Monomoriumpharaonis), Vespa (Vespa spp.).

Diptera (Diptera), for example, Aedes (Aedes spp.), Anopheles (Anophelesspp.), Culex It is (Culex spp.), Drosophila melanogaster, Musca (Muscaspp.), Fannia (Fannia spp.), red Head calliphorid (Calliphora erythrocephala), Lucilia (Lucilia spp.), Carysomyia (Chrysomyia Spp.), Cuterebra (Cuterebra spp.), Gasterophilus (Gastrophilus spp.), Hyppobosca spp., Genus Stomoxys (Stomoxys spp.), Oestrus (Oestrus spp.), Hypoderma (Hypoderma spp.), Gadfly (Tabanus Spp.), Tannia spp., garden march fly (Bibio hortulanus), Oscinella frit (Oscinella frit), grass seeds Fly category (Phorbia spp.), Chenopodiaceae spring fly (Pegomyia hyoscyami), Mediterranean fruitfly (Ceratitis capitata), The big trypetid of olive (Dacus oleae), European daddy-longlegs (Tipulapaludosa), Hylemyia (Hylemyia spp.), liriomyza bryoniae Belong to (Liriomyza spp.).

Siphonaptera (Siphonaptera), for example, Xanthopsyllacheopis (Xenopsylla cheopis), Ceratophyllus (Ceratophyllus spp.)。

Arachnoidea (Arachnida), for example, Middle East gold scorpion (Scorpio maurus), latrodectus mactans (Latrodectus mactans), Acarus siro (Acarus siro), Argas (Argasspp.), Ornithodoros (Ornithodoros spp.), Dermanyssus gallinae (Dermanyssus gallinae), Eriophyes ribis, tangerine rue rust mite (Phyllocoptruta oleivora), Boophilus (Boophilusspp.), Rhinpicephalus (Rhipicephalus spp.), Amblyomma (Amblyomma spp.), Hyalomma (Hyalomma spp.), Isodesspp (Ixodes spp.), Psoroptes (Psoroptes spp.), Chorioptes (Chorioptes spp.), Sarcoptesspp (Sarcoptes spp.), Tarsonemus (Tarsonemusspp.), Bryobia praetiosa (Bryobia praetiosa), Panonychus citri category (Panonychus spp.), Tetranychus (Tetranychus spp.), half Tarsonemus (Hemitarsonemus spp.), short whisker Acarapis (Brevipalpus spp.)。

Nematode

In principle, the plant nematode of all kinds can all be prevented and treated with the compounds of this invention.It was found that the compounds of this invention It is particularly advantageous when preventing and treating nematode selected from the following: Meloidogyne (Meloidogyne spp.), such as Meloidogyne incognita (Meloidogyneincognita), javanese root knot nematode (Meloidogyne javanica), M hapla (Meloidogyne hapla), peanut root-knot nematode (Meloidogyne arenaria)；Ditylenchus (Ditylenchus Spp.), for example, fuller's teasel Ditylenchus dipsaci (Ditylenchus dipsaci), Potato Rot Nemotode (Ditylelenchus destructor)；Pratylenchus (Pratylenchus spp.), for example, Cobb root (Pratylenchus Penetrans), pseudo- Pratylenchidae (Pratylenchusfallax), coffee pot handle (Pratylenchus coffeae), Lu Si Pratylenchidae (Pratylenchus loosi), disability Pratylenchidae (Pratylenchus vulnus)；Ball golden nematode Belong to (Globodera spp.), for example, globodera rostochiensis (Globodera rostochiensis), globus pallidus golden nematode (Globodera pallida) etc.；Heterodera (Heterodera spp.), such as soybean cyst nematode (Heterodera Glycines), Heterodera shachtoii etc.；Aphelenchoides (Aphelenchoides spp.), such as LIPIDS OF DRY RICE EMBRYO point Nematode (Aphelenchoides besseyi), Aphelenchoides ritzema-bosi (Aphelenchoides ritzemabosi), strawberry Aphelenchoides (Aphelenchoides fragarieae)；Aphelenchus ssp., such as Aphelenchusavenae；It wears Hole Turbatrix (Radopholus spp.), such as Radopholus similis Throne (Radopholussimilis)；Tylenchulus Semipenetrans category (Tylenchulus spp.), such as Tylenchulus Semipenetrans (Tylenchulussemipenetrans)；Shallow bid spin line Eimeria (Rotylenchulus ssp.), such as kidney shape shallow bid spin line worm (Rotylenchulus reniformis)；Umbrella aphelenchoides Belong to (Bursaphelenchus spp.), such as Bursaphelenchus xylophilus (Bursaphelenchus xylophilus), Aphelenchoides (Aphelenchoidesspp.), minute hand Turbatrix (Longidorus spp.), Xiphinema (Xiphinema spp.), hair It pierces Turbatrix (Trichodorus spp.).

Crop

Crop to be protected only carried out description in wide in range mode, it is distinguished and is described in detail below.For example, just using In way, vegetables are understood to, for example, fruit vegetables and capitulum vegetables, such as carrot, green pepper, chilli, tomato, eggplant Son, cucumber, cucurbit, bush pumpkin, semen viciae fabae, scarlet runner bean, bush bean, pea, arithoke, corn；There are also leaf vegetables, such as lettuce Lettuce, witloof, hare's-lettuce, Chinese celery, rocket salad, cochlear dish leaf, iceberg lettuce, leek, spinach, Swiss chard；There are also tuberous vegetable, Root vegetables and stem vegetables, such as celeriac, beet root, carrot, summer and winter radish, horseradish, salsify, asparagus, table beet, palm Bud, bamboo shoots and bulb vegetable, such as onion, leek, fennel, garlic；There are also rape class vegetables, such as cauliflower, stem coconut palm Dish, kohlrabi, red cabbage, white cabbage, green cabbage, savoy, brussels sprout, Chinese cabbage.

In purposes, perennial crop is understood to mean that citrus fruit trees, for example, orange, grape fruit, citrus, lemon, Bitter orange, bigarabe, kumquat, tangerine；There are also the operatic circle, such as apple, Li He Wen Quince and drupe, for example, peach, nectarine, cherry, Lee, European Lee, apricot；There are also grape, hops, olive, tea, soybean, rape, cotton, sugarcane, beet, potato, tobacco and the torrid zones Crop, such as mango, papaya, fig, pineapple, nipa palm, banana, durian, persimmon, coconut, cocoa, coffee, avocado, litchi Branch, passionflower, guava, there are also almonds and nut, such as fibert, English walnut, pistachio, Jia such as to set nut, Bertholletia excelsa, beauty Continent hickory nut, butternut, chestnut, hickory nut, Queensland nut, peanut, there are also berries, such as currant, gooseberry, stirrup Son, blackberry, blueberry, strawberry, tooth pimple, Kiwi berry, cowberry.

Plant

In purposes, plant includes ornamental plant, it is thus understood that mean annual and perennial plant, such as cut-flower, Such as rose, carnation, gerbera, lily, crowndaisy chrysanthemum chrysanthemum, chrysanthemum, tulip, daffodil, pasqueflower, opium poppy, belladonna lily, big beautiful Flower, azalea, high mallow, however also include such as bed plant, potted plant and shrub, such as rose, marigold, heartsease, day Zhu Kui, fuchsia, the rose of Sharon, chrysanthemum, balsamine, cyclamen, African violet, sunflower, begonia, be planted in Ornamental turf, In golf lawn, also in cereal such as barley, wheat, rye, triticale, oat, rice, grain and sorghum, in corn. In addition, for example, dwarf thicket and coniferous tree, such as fig tree, azalea, dragon spruce, fir tree, pine tree, Japanese yew, juniper, anticipate greatly Sharp five-leaved pine, folder leaf of bamboo peach.

In purposes, plant includes that fragrance is understood to mean that annual and perennial plant, for example, foreign fennel, do it is peppery Green pepper, green pepper, pepper, vanilla, marjoram, thyme, cloves, Chinese juniper, cortex cinnamomi, tarragon, coriander, safflower, ginger.

According to the present invention it is possible to handle all plant and plant parts.Herein, plant is interpreted as referring to owning Plant and plant population, such as need and unwanted wild plant or crop plants (crop including Lock-in is planted Object).

Use form

The use form of the compounds of this invention or composition is unrestricted, may include foliage applying, soil generally Earth application and seed treatment.

Foliage applying is interpreted as direct by conventional treatment method or acts on its environment, habitat or storage space The present invention that plant and plant parts carry out is handled with active constituent, for example, by dipping, sprinkling, evaporation, be atomized, broadcast sowing, It smears and injects.The meaning of plant parts is interpreted as all positions and organ above and below the ground of plant, such as bud, leaf, flower And root, example include leaf, needle, stem, handle, flower, fructification, fruit, seed and root, stem tuber and rhizome.Plant parts are also wrapped Harvested material is included, there are also asexual and case of propagation material, such as rice shoot, stem tuber, rhizome, is transplanted and seed.

Soil application should be understood by the way that insecticide is poured soil, is doped into soil and in Irrigation System with liquid Method of application is dripped in using on soil, to prevent and treat insect and/or spider mite and/or nematode.Alternatively, active constituent knot of the invention Close object can introduced plant in solid form (such as in granular form) growth place.In the case where rice crop, this may be used also With by by inventive compound conjugate with the rice field of the metered waterflooding of solid administration forms (such as in granular form) In and realize.

In the present invention, composition of the invention is applied to seed individually or in the form of appropriate formulation.Preferably, into The seed of row processing should be at sufficiently stable and be not the state by any damage during processing.Generally, seed can With any time point processing between harvest and sowing.In general, the seed used is separated from plant, and remove cob, Shell, stem, epidermis, villus or pulp.It is, for example, possible to use harvested, clean and dried to water capacity less than 15 weights Measure the seed of %.Alternatively, also can be used it is dry after (such as with water) processed and then dry seed again.

When handling seed, it usually needs ensure the selected present composition for being applied to seed amount and/or its The amount of his additive is adversely affected the rudiment of seed not, and keeps the plant grown up to injury-free.Especially at certain This point is especially considered in the case where the active constituent that there may be phytotoxicity effect under a little rate of application.

Preparation method

The present invention also provides the succinic acid furfural di esters method for producing insecticide, comprising the following steps:

Step 1: reacting Formula II compound with the first halogenating agent or nitrating agent with preparation formula III compound

Step 2: reacting formula III compound with preparation of compounds of formula I with the second halogenating agent or nitrating agent

And

Optional step 3: react compound of formula I with alcohol so that a kind of compound of formula I is changed into another Formulas I chemical combination Object；

Wherein, the R₁-R₃Definition it is as described herein.

The halogenating agent can be selected from SelectFluor or N- chlorosuccinimide, and the nitrating agent can be four oxygen Change phenodiazine.

For R₃For the Formula II compound (i.e. (5- Fonnyl-furan -2- base) methylsuccinic acid methyl esters) of methyl, can adopt It is prepared with following extracting method:

Will dry marigold crush after extracted with ethyl alcohol, extracting solution is concentrated to dryness, then with suitable quantity of water dissolved dilution, adds second Acetoacetic ester extraction, lower layer's aqueous add water-saturated n-butanol to extract, and extract liquor is concentrated to dryness to obtain n-butanol phase；

Above-mentioned n-butanol is mutually used into normal phase silica gel column chromatography crude separation, the component containing target compound again will be through glucan (5- Fonnyl-furan -2- base) methylsuccinic acid methyl esters that gel LH-20 pillar layer separation is purified.

In a preferred embodiment, the extracting method includes:

1. step crushes the dry herb G of marigold, ethyl alcohol heating and refluxing extraction is added, combined extract after filtering is dense It is reduced to dry (paste), then with suitable quantity of water dissolved dilution, dilution adds isometric ethyl acetate to extract, and acetic acid ethyl acetate extract subtracts Pressure is concentrated to dryness to obtain ethyl acetate phase G1；Lower layer's aqueous adds isometric water-saturated n-butanol to extract, butanol extraction liquid decompression It is concentrated to dryness to obtain n-butanol phase G2；

Step 2. by step 1. obtained in G2 with methylene chloride-methanol use normal phase silica gel column chromatography crude separation, utilize TLC inspection, which is known, merges the similar component of ingredient, obtains 8 part G2-1 → G2-8.

3. by step, 2. a small amount of methanol in the resulting part G2-8 dissolves step, through sephadex lh-20 column chromatography point From examining to know using TLC and merge the similar component of ingredient, obtain 5 part G2-8-1 → G2-8-5: wherein G2-8-2 (6.11mg) is title compound.

Beneficial effect

Succinic acid furfural dibasic acid esters insecticides of the invention are that the effective component being extracted from plants is modified, and are protected The characteristics of being decomposed into innocuous substance, no pollution to the environment are easier to after having stayed application.Also, after modification, succinic acid of the invention Furfural dibasic acid esters insecticides have preferable control efficiency to insect, nematode, can especially prevent and treat prodenia litura, aphid and root well Tie lines worm.Meanwhile succinic acid furfural dibasic acid esters insecticides toxicity of the invention is lower, the residual in crops is few, to people, animal Harmfulness it is small, solve existing insecticide very well and be more toxic, the more problem of residual in crop improves agricultural The safety of production, pest will not generate antibody to insecticide of the invention in a long time, therefore have good desinsection Effect.The present invention also provides the succinic acid furfural di esters method for producing insecticide, and technique is easily operated, are suitble to big rule The industrialized production of mould.

Embodiment

Extract embodiment

The extraction of (5- Fonnyl-furan -2- base) methylsuccinic acid methyl esters

1. step crushes marigold dry herb G (2.7kg), 95% ethyl alcohol is added and is heated to reflux, extracts 2 times, 2h/ Secondary, combined extract after filtering is concentrated to dryness (paste), then with suitable quantity of water dissolved dilution.Dilution adds isometric acetic acid second Ester extracts 2 times, and acetic acid ethyl acetate extract is concentrated to dryness to obtain ethyl acetate phase G1 (16.1g)；Lower layer's aqueous adds isometric Water-saturated n-butanol extracts 2 times, and butanol extraction liquid is concentrated to dryness to obtain n-butanol phase G2 (15.9g).

Step 2. by step 1. obtained in G2 with methylene chloride-methanol (50:1 to 20:1) use normal phase silicagel column (200-300 mesh) chromatography crude separation is examined using TLC and knows the similar component of merging ingredient, obtains 8 part G2-1 → G2- 8。

Step 3. by step, 2. partially dissolved with a small amount of methanol by resulting G2-8 (0.24g), through sephadex lh-20 column (internal diameter 1.5cm, pillar height 95cm) chromatographic isolation is examined using TLC and knows the similar component of merging ingredient, obtains 5 part G2- 8-1 → G2-8-5: wherein G2-8-2 (6.11mg) is title compound.

Structural characterization:

Molish reaction is negative, and shows the presence of not carbohydrate.

ESI-MS m/z:263 [M+Na]+, show that the compound molecular weight is 240.

?¹H-NMR(DMSO-d₆, 400MHz) in, δ: 9.55 (1H, s ,-CHO) are α, the aldehyde radical hydrogen on β unsaturation aldehyde radical Proton signal, 7.50 (1H, d, J=3.5Hz, 3-H), 6.60 (1H, d, J=3.5Hz, 4-H) belong to 2,5-, bis- substituted furan The Hydrogen Proton signal that ring is 3,4,4.51 (2H, s, 5-CH₂It O- is) methylol proton signal, the above are the hydrogen of 5 hydroxymethyl furfural Proton signal；In 3.58 (3H, s ,-OCH₃) it can be observed a methoxyl group Hydrogen Proton signal, 2.48 (2H, ddd, J=6.8,1.8, 0.9Hz), visible two methylene Hydrogen Proton signal at 2.42 (2H, ddd, J=6.8,1.8,0.9Hz).

?¹³In C-NMR (DMSO-d6,100MHz), δ: 177.9 (- CHO), 162.2 (C-5), 151.7 (C-2), 124.4 (C-3), 109.6 (C-4), 55.8 (- OCH₂) be 5 hydroxymethyl furfural parent nucleus carbon signal, 173.6 (C-7), 172.8 (C-10), 28.8 (C-8), 29.2 (C-9) are the carbon signal of double esterification succinic acid (succinic acid), 51.3 (- OCH₃) it is that esterification methyl carbon is believed Number.

In HMBC, it is related to 151.7 (C-2) that 9.55 (1H, s, 2-CHO) can be observed；7.50 (1H, d, J=3.5Hz, 3-H) with 162.2 (C-5), 151.7 (C-2), 109.6 (C-4) are related；6.60 (1H, d, J=3.5Hz, 4-H) and 162.2 (C- 5), 151.7 (C-2), 124.4 (C-3) are related；4.51(2H,s,5-CH₂O-) and 162.2 (C-5), 109.6 (C-3) are related； 3.58(3H,s,-OCH₃) related to 172.8 (C-10)；2.48 (2H, ddd, J=6.8,1.8,0.9Hz), 2.42 (2H, ddd, J =6.8,1.8,0.9Hz) with 173.6 (C-7), 172.8 (C-10) are related.

It is compared in conjunction with DEPT spectrum and pertinent literature, can determine that isolated compound is (5- formoxyl-furan Mutter -2- base) methylsuccinic acid methyl esters, structure is as follows:

Synthetic example

Embodiment 1: the synthesis of Formulas I a compound

(5- Fonnyl-furan -2- base) methylsuccinic acid methyl esters (5.0 mMs) is dissolved in MeCN (80mL), is added SelectFluor (5.5 mMs, 1.1 equivalents) is added in water (40 milliliters), at room temperature then by the mixture room of formation Temperature stirring 1 hour, is monitored by TLC and is reacted, is extracted with ethyl acetate after the completion, extract liquor water, salt water washing and drying (Na₂SO₄), decompression situation removes solvent, and residue is dissolved in dry methylene chloride (50mL), in 0 DEG C of dropwise addition pyridine (4.0 millis Rise), acetic anhydride (1.0 milliliters) are then added dropwise again at such a temperature, then reaction mixture is stirred at room temperature, passes through TLC Monitoring reaction, adds methylene chloride (100 milliliters), with water, salt water washing and drying (Na after the completion₂SO₄), decompression boils off molten Agent obtains crude product；By crude product ethyl alcohol recrystallization, (the fluoro- 5- Fonnyl-furan -2- base of 4-) methylsuccinic acid methyl esters is obtained, Yield 63%.

By (the fluoro- 5- Fonnyl-furan -2- base of 4-) methylsuccinic acid methyl esters (2.0 mMs), N- chlorosuccinimide (2.0 mMs) are dissolved in tetrahydrofuran (50 milliliters) and the mixed solution of n,N-Dimethylformamide (5 milliliters), are warming up to 100 DEG C, sealing reaction 5h is monitored by TLC and is reacted, be cooled to room temperature after the completion, solvent is recovered under reduced pressure, residue is saturated Sodium bicarbonate aqueous solution is washed, and ethyl acetate extraction reaction 3 times, merges dry (Na after organic phase salt is washed 1 time₂SO₄).It depressurizes back Solvent is received, (petroleum ether: ethyl acetate=10:1 to 5:1) obtains title compound, yield 80% to silica gel column chromatography.

Embodiment 2: the synthesis of Formulas I b compound

(5- Fonnyl-furan -2- base) methylsuccinic acid methyl esters (5.0 mMs) is dissolved in ethyl acetate (50ml), - 15 DEG C are cooled to, is added dinitrogen tetroxide (5.0 mMs), mixture is stirred to react 2h at such a temperature, is monitored by TLC Reaction, pours into 100 grams of thin ice after the completion, separates organic phase after 3h, and organic phase is recovered under reduced pressure solvent, residue water and Ethanol washing obtains crude product；Crude product ethyl alcohol recrystallization obtains (5- formoxyl -4- nitro-furan -2- base) methylsuccinic acid first Ester, yield 45%.

By (5- formoxyl -4- nitro-furan -2- base) methylsuccinic acid methyl esters (2.0 mMs), N- chloro succinyl is sub- Amine (2.0 mMs) is dissolved in tetrahydrofuran (50 milliliters) and the mixed solution of n,N-Dimethylformamide (5 milliliters), is warming up to 100 DEG C, sealing reaction 6h is monitored by TLC and is reacted, be cooled to room temperature after the completion, solvent is recovered under reduced pressure, residue is saturated Sodium bicarbonate aqueous solution is washed, and ethyl acetate extraction reaction 3 times, merges dry (Na after organic phase salt is washed 1 time₂SO₄).It depressurizes back Solvent is received, (hexamethylene: ethyl acetate=30:1 to 4:1) obtains (chloro- furans -2- of 5- formoxyl -4- nitro -3- to silica gel column chromatography Base) methylsuccinic acid methyl esters, yield 82%.

(the chloro- furans -2- base of 5- formoxyl -4- nitro -3-) methylsuccinic acid methyl esters (1.0 mMs) is dissolved in MeCN It in (10 milliliters), is added saturated aqueous sodium carbonate (1 milliliter), ethyl alcohol (1 milliliter) then is added, be heated to 60 DEG C of reactions, lead to TLC monitoring reaction is crossed, uses water, salt water washing after the completion, decompression boils off solvent, and Gossypol recrystallized from chloroform obtains title compound, yield 91%.

Embodiment 3: the synthesis of Formulas I c compound

Method one: by (5- Fonnyl-furan -2- base) methylsuccinic acid methyl esters (5.0 mMs), N- chloro succinyl is sub- Amine (2.0 mMs) is dissolved in tetrahydrofuran (50 milliliters) and the mixed solution of n,N-Dimethylformamide (5 milliliters), is warming up to 100 DEG C, sealing reaction 4h is monitored by TLC and is reacted, be cooled to room temperature after the completion, solvent is recovered under reduced pressure, residue is saturated Sodium bicarbonate aqueous solution is washed, and ethyl acetate extraction reaction 3 times, merges dry (Na after organic phase salt is washed 1 time₂SO₄).It depressurizes back It receives solvent and obtains crude product, crude product ethyl alcohol recrystallization obtains (the chloro- 5- Fonnyl-furan -2- base of 4-) methylsuccinic acid methyl esters, receives Rate 75%.

(the chloro- 5- Fonnyl-furan -2- base of 4-) methylsuccinic acid methyl esters (2.0 mMs) is dissolved in MeCN (40mL), It is added SelectFluor (2.2 mMs, 1.1 equivalents), is added in water (20 milliliters) at room temperature, then by the mixing of formation Object is stirred at room temperature 1.5 hours, is monitored and is reacted by TLC, is extracted with ethyl acetate after the completion, extract liquor water, salt water washing are simultaneously Dry (Na₂SO₄), decompression situation removes solvent, and residue is dissolved in dry methylene chloride (20mL), in 0 DEG C of dropwise addition pyridine (2.0 milliliters) are then added dropwise acetic anhydride (0.5 milliliter) again at such a temperature, then reaction mixture are stirred at room temperature, and lead to TLC monitoring reaction is crossed, methylene chloride (40 milliliters) are added after the completion, with water, salt water washing and drying (Na₂SO₄), decompression is steamed Solvent is removed, (petroleum ether: ethyl acetate=50:1 to 10:1) obtains (the chloro- 5- Fonnyl-furan -2- of the chloro- 3- of 4- to silica gel column chromatography Base) methylsuccinic acid methyl esters, yield 52%.

(the chloro- 5- Fonnyl-furan -2- base of the chloro- 3- of 4-) methylsuccinic acid methyl esters (1.0 mMs) is dissolved in MeCN (10 Milliliter) in, it is added saturated aqueous sodium carbonate (1 milliliter), ethylene glycol (1 milliliter) then is added, be heated to 50 DEG C of reactions, pass through TLC monitoring reaction, uses water, salt water washing after the completion, and decompression boils off solvent, and re crystallization from toluene obtains title compound, yield 89%.

Method two: (5- Fonnyl-furan -2- base) is replaced with (5- Fonnyl-furan -2- base) methyl succinic tert-butyl acrylate Methylsuccinic acid methyl esters, repeats the above steps, through intermediate (the chloro- 5- Fonnyl-furan -2- base of 4-) methyl succinic tert-butyl acrylate (the chloro- 5- Fonnyl-furan -2- base of the chloro- 3- of 4-) methyl succinic tert-butyl acrylate, is finally made title compound, and three steps are always received Rate is 30%.

Embodiment 4: the synthesis of Formulas I d compound

Method one: (the chloro- 5- Fonnyl-furan -2- base of the chloro- 3- of 4-) methylsuccinic acid first that embodiment 3 is prepared Ester (1.0 mMs) is dissolved in MeCN (10 milliliters), is added saturated aqueous sodium carbonate (1 milliliter), and normal propyl alcohol (1 is then added Milliliter), 55 DEG C of reactions are heated to, is monitored and is reacted by TLC, use water, salt water washing after the completion, decompression boils off solvent, toluene weight Crystallization obtains title compound, yield 86%.

Method two: (the chloro- 5- Fonnyl-furan -2- base of the chloro- 3- of 4-) the methylsuccinic acid uncle being prepared with embodiment 3 Butyl ester replaces (the chloro- 5- Fonnyl-furan -2- base of the chloro- 3- of 4-) methylsuccinic acid methyl esters, repeats the above steps, is made titled Close object, yield 83%.

Wherein, the structural characterization parameter of compound Ia~Id is as follows:

Table 1: the structural characterization analytical table of compound Ia~Id

Effect example

Embodiment 1: the compounds of this invention is to 3 instar larvae biological activity determination of prodenia litura

It is 1,2,4,8,16,32,64 μ g/ that compound Ia~Id is aseptically configured to mass concentration gradient respectively L for reagent liquid, be control with clear water, every processing sets 3 repetitions, and every processing borer population is 30.When test, by prodenia litura 3 Instar larvae impregnates 5s in each compound medical fluid, swashes in toilet paper dry, is put in 24 holes culture box, is fed with fresh feed It, be put into illumination constant incubator culture (27 DEG C of temperature, relative humidity 75%, photoperiod L: D=14: 10).Upon administration Polypide death toll is checked for 24 hours, and calculates the death rate and corrected mortality.Death standard: polypide tail portion is touched with pulling needle, motionless person is It is dead.

Calculation method: virulence is calculated by regress analysis method with the logarithm of concentration and the probit value of corrected mortality Regression equation and the lethal concentration of 50 (LC₅₀)。

The death rate (%)=(dead borer population/total borer population) × 100

Corrected mortality (%)=[(the processing death rate-control death rate)/(1- compares the death rate)] × 100

The result of test is as shown in table 2 below:

Table 2: lethality measurement result of the compounds of this invention to 3 instar larvae of twill children moth

By the data in table 2 it is found that the compounds of this invention has good control efficiency to twill children's moth larvae.

Embodiment 2: killing aphids experiment

Using infusion process, compound Ia~Id is configured to mass concentration gradient respectively is 1,2,4,8,16,32,64 by lower μ g/L for reagent liquid, by the taro blade with worm, every leaf has 30~50 aphids, immerses medical fluid about 5s, then places training Support in ware, in insulating box (25 ± 1) DEG C, investigate the death rate of each processing test worm afterwards for 24 hours.3 repetitions of every kind of processing.Blank pair According to for clear water.

Calculation method: virulence is calculated by regress analysis method with the logarithm of concentration and the probit value of corrected mortality Regression equation and the lethal concentration of 50 (LC₅₀)。

The death rate (%)=(dead borer population/total borer population) × 100

Corrected mortality (%)=[(the processing death rate-control death rate)/(1- compares the death rate)] × 100

The result of test is as shown in table 3 below:

Table 3: lethality measurement result of the compounds of this invention to aphid

By the data in table 3 it is found that the compounds of this invention has good control efficiency to aphid.

Embodiment 3: the compounds of this invention is to two age root-knot nematode biological activity determinations

The test of inhibition plant pathogeny line insect is carried out using dip method to the compound of above-mentioned Formulas I a~Id, more than measurement Compound is to the activity of two age root-knot nematodes, and referring concurrently to NY/T 1154.5-2006, (Part V: ovicidal activity test impregnates Method) the above compound is tested to the inhibitory activity of root-knot nematode egg hatch, as a result as shown in table 4 and table 5:

Table 4: the compounds of this invention is to two age root-knot nematode lethality measurement results

Table 5: the compounds of this invention is to root-knot nematode worm's ovum lethality measurement result

By the data in table 4,5 it is found that the compounds of this invention has very well two age root-knot nematodes and root-knot nematode worm's ovum Control efficiency.

Embodiment 4: toxicity test

According to the earthworm toxicity test and edaphon toxicity test in chemical pesticide environmental safety assessment test rule The step of, earthworm toxicity test and edaphon toxicity test are carried out to compound Ia~Id in the present invention, wherein soil The pesticide usual amounts simulated in microbiological test be 40ppm, two test the result is as follows:

Table 6: the toxicity test result of the compounds of this invention

By the data in table 6 it is found that the compounds of this invention is low to toxicity biological in soil environment.

Generally speaking, the compounds of this invention has excellent kill for animal pest especially prodenia litura, aphid, nematode Worm activity, and there is very low toxicity for biological in soil environment.Therefore, the compounds of this invention be especially suitable for The insecticide of animal pest especially crop, the insect in plant, nematode.

The foregoing describe the preferred embodiment for the present invention, and however, it is not to limit the invention.Those skilled in the art couple Embodiment disclosed herein can carry out the improvements and changes without departing from scope and spirit.

Claims (10)

1. a kind of compound of formula I or its salt:

Wherein, R₁、R₂It is each independently halogen or NO₂；

R₃For C1-C6 alkyl, C3-C8 naphthenic base, C6-C14 aryl or C6-C14 aryl C1-C6 alkyl, wherein the C1-C6 alkane Base, C3-C8 naphthenic base, C6-C14 aryl, C6-C14 aryl C1-C6 alkyl optionally selected from the following are taken by one or more Replace for base: halogen, C1-4 alkyl, C1-4 alkoxy, OH, NO₂Or CN.

2. compound according to claim 1, which is characterized in that the R₁Selected from halogen or nitro, it is preferable that R₁For F, Cl or NO₂。

3. compound according to claim 1, which is characterized in that the R₂Selected from halogen, it is preferable that R₂For F or Cl.

4. compound according to claim 1, which is characterized in that the R₃Selected from C1-C6 alkyl, optionally by one Or more substituent group selected from the following replace: halogen, C1-4 alkoxy or OH, it is preferable that R₃For methyl, ethyl, propyl, different Propyl, butyl or 2- hydroxyethyl, it is highly preferred that R₃For methyl, ethyl, propyl or 2- hydroxyethyl.

5. compound according to claim 1, is selected from:

Ia:

Ib:

Ic:

Id:

6. a kind of for preventing and treating the composition of animal pest, it includes compound according to claim 1-5 works For active constituent, and preferably comprise agriculturally suitable auxiliary agent, solvent, carrier, surfactant or filler.

7. animal pest of the compound according to claim 1-5 in prevention and treatment agricultural, especially insect, nematode In purposes.

8. application of the compound according to claim 1-5 in preparation crop or plant protection product, the work Object or plant protection product are used to prevent and treat the animal pest in agricultural, especially insect, nematode.

9. a kind of method for preparing compound of formula I according to claim 1, it includes following steps:

Step 1: reacting Formula II compound with the first halogenating agent or nitrating agent with preparation formula III compound

Step 2: reacting formula III compound with preparation of compounds of formula I with the second halogenating agent or nitrating agent

And

Optional step 3: react compound of formula I with alcohol so that a kind of compound of formula I is changed into another compound of formula I；

Wherein, the R₁-R₃Definition as described in the appended claim 1；

The halogenating agent is selected from SelectFluor or N- chlorosuccinimide, and the nitrating agent is dinitrogen tetroxide.

10. according to the method described in claim 9, it is characterized in that, working as R₃For CH₃When, the method also includes R₃For methyl The extraction of Formula II compound:

Will dry marigold crush after extracted with ethyl alcohol, extracting solution is concentrated to dryness, then with suitable quantity of water dissolved dilution, adds acetic acid second Ester extraction, lower layer's aqueous add water-saturated n-butanol to extract, and extract liquor is concentrated to dryness to obtain n-butanol phase；

Above-mentioned n-butanol is mutually used into normal phase silica gel column chromatography crude separation, the component containing target compound again will be through sephadex The R that LH-20 pillar layer separation is purified₃For CH₃Formula II compound.