CN1184190C - cyclopropane carboxylic ester compound - Google Patents
cyclopropane carboxylic ester compound Download PDFInfo
- Publication number
- CN1184190C CN1184190C CNB001011553A CN00101155A CN1184190C CN 1184190 C CN1184190 C CN 1184190C CN B001011553 A CNB001011553 A CN B001011553A CN 00101155 A CN00101155 A CN 00101155A CN 1184190 C CN1184190 C CN 1184190C
- Authority
- CN
- China
- Prior art keywords
- compound
- methyl
- carboxylic acid
- phenyl
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The (2, 3, 5, 6-tetrafluoro-4-methoxyphenyl) methyl trans-3-(2, 2-dichlorovinyl)-2, 2-dimethyl cyclopropane carboxylate of the present invention can be used as the active component of a pesticide composition with excellent pesticidal activity.
Description
The present invention relates to ester cpds and contain the pesticide composition of this compound as activeconstituents.
Prospectus by EP-31199A is known, the benzyl ester that the fluoro-of some halogenated alkenyl cyclopropane-carboxylic acids replaces has insecticidal activity, and in these compounds, wherein the activity of those isomer that are transconfiguration at the 1-position and the substituting group on the 3-position of cyclopropane ring of the ratios of the isomers that is cis-configuration at the 1-position and the substituting group on the 3-position of cyclopropane ring is higher.Moreover the prospectus of EP-378026A discloses the cyclopropanecarboxylcompound with insecticidal effect.
Yet in pesticide composition, prevention effect and security all are important, therefore, in some use, from the angle of safety, use these compounds to be restricted usually.Pesticide composition especially for the prevailing disease control usually is to use in the restriceted envelope of living environment, and therefore, these compositions not only need desinsection or repellent activity, but also will comprise people, livestock and pet low toxicity to Mammals.
Under above-mentioned background, the present inventor has carried out deep research, finds (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl anti--3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester shows the excellent insecticidal activity, and very safe to Mammals.Based on this discovery, finished the present invention.
Therefore, the invention provides (2,3,5, the 6-tetrafluoro-4-p-methoxy-phenyl) methyl shown in the formula (I) trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester (hereinafter being called The compounds of this invention):
Wherein, the steric configuration between the substituting group on the 1-position of cyclopropane ring and 3 is trans, and contains the pesticide composition of described compound as activeconstituents.
For example, can be by making the hereinafter trans-3-shown in the formula (II) (2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid or its active derivative
Produce The compounds of this invention with (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl alcohol or its active derivatives reaction shown in the formula (III) hereinafter
Reaction above-mentioned usually in organic solvent, choose wantonly in the presence of the reaction auxiliary, and if necessary, undertaken by removal by product from reaction system.
Usually the reaction times is between 5 minutes-72 hours; And the temperature range of reaction is usually between between the boiling temperature of-80 ℃ of used solvents to the reaction or 200 ℃.
As for the active derivative of formula (II) carboxylic acid cpd, that can mention has its carboxylic acid halides, acid anhydrides, a C
1-C
4Alkyl ester etc.
As for the active derivative of formula (III) alkylol cpd, that can mention has its halogenide, sulphonate, a quaternary ammonium salt etc.
Although the alkylol cpd of the carboxylic acid cpd of formula (II) or its active derivative and formula (II) or the mol ratio of its active derivative can not be subjected to anyly restrictedly to select, preferably with etc. mole or use these reactants to react near 1: 1 mol ratio.
The reaction auxiliary comprises tertiary amine such as triethylamine, 4-Dimethylamino pyridine, diisopropyl ethyl amine etc.; Nitrogenous aromatic substance such as pyridine etc.; Alkali metal alcoholates such as sodium methylate, potassium tert.-butoxide etc.; Mineral alkali such as sodium hydroxide, salt of wormwood, sodium hydride etc.; Protonic acid such as tosic acid, sulfuric acid etc.; Lewis acid such as phenoxide titanium (IV); With combination of other reagent such as dicyclohexyl carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride, triphenylphosphine and azo-2-carboxylic acid's diethyl ester or azo-2-carboxylic acid's diisopropyl ester etc.
Can be pursuant to formula (II) or its active derivative or formula (III) alkylol cpd or its active derivative, from above-mentioned auxiliary, suitably select auxiliary, and their amount can suitably be determined according to the mode of reaction.
The solvent that can be used in the reaction comprises hydro carbons such as benzene,toluene,xylene etc.; Ethers such as ether, tetrahydrofuran (THF) etc.; Halohydrocarbon such as methylene dichloride, 1,2-ethylene dichloride etc.; Amides such as dimethyl formamide etc.; Ketone such as acetone etc.; Organosulfur type solution such as dimethyl sulfoxide (DMSO) etc.; And composition thereof.
After reaction is finished, liquid reaction mixture is carried out conventional aftertreatment, as with organic solvent extraction, concentrate etc., can obtain The compounds of this invention thus.And, if desired, can pass through operation purifying The compounds of this invention such as chromatogram, distillation, recrystallization.
Carboxylic acid cpd shown in the formula (II) can be according to the method preparation of describing among " pesticide science " [Pestic.Sci.] 5.791 (1974); And the alkylol cpd shown in the formula (III) can be according to the method preparation that is described among the EP-31199A.
In The compounds of this invention, the 1-position of cyclopropane ring and the substituting group on the 3-position are the transconfiguration relation each other.Yet it must be essentially no cis type compound that The compounds of this invention is not necessarily wanted, and it also can be cis and trans mixture, as long as it is rich in the transconfiguration isomer.For example, it can be that wherein trans body is 80% or more cis and transconfiguration mixture of isomers.
As for carboxylic acid cpd shown in the formula (II) or its active derivative, for example can mention following compounds:
Trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl-cyclopropane-carboxylic acid,
Trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl-cyclopropane carboxylic acid acyl chlorides.
The carboxylic acid cpd of transconfiguration isomer or its active derivative can obtain being rich in the transconfiguration isomer as carboxylic acid cpd above-mentioned or its active derivative The compounds of this invention are rich in use.
As for the alkylol cpd shown in the formula (III) or its active derivative, for example can mention following compounds:
(2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl alcohol,
1-chloromethyl-2,3,5,6-tetrafluoro-4-anisole,
1-brooethyl-2,3,5,6-tetrafluoro-4-anisole.
The compounds of this invention is following arthropods to its specific examples with insect of prevention effect, as insect and acarine:
Hemiptera
Delphacidae (plant hopper) is as Laodelphax striatellus (small brown rice planthopper), Nilaparvatalugens (brown paddy plant hopper) and Sogatella furcifera (white backed planthopper); Angle top Cicadidae (leafhopper) is as Nephotettix cincticeps (rice green leafhopper) and Nephotettixvirescens (nephotettix bipunctatus); Aphidiadae (aphid); Pentatomiddae (stinkbug); Aleyrodidae (aleyrodid); A red-spotted lizard section (scale insect); Tingidae (lace bug); Psyllidae (wood louse) or the like.
Lepidopteran
Pyralidae (snout moth) is as Chilo suppressalis (striped rice borer), Cnaphalosrocismedinalis (Cnaphalocrocis medinali(rice leaf roller)) and Plodia interpunctella (Indian meal moth); Noctuidae is as Spodoptera litura (prodenia litura), Pseudaletia separata (rice leaf noctuid) and Mamestra brassicae (lopper worm); Sulfur butterfly is as Pieris rapaecrucivora (small white Japan subspecies); Tortricidae (volume moth) is as each kind (Adoxophyes spp.) of Adoxophyes spp genus; Moth fruit moth section; Lyonetid section (lyonetid); Lymantriidae (poison moth); Ground each kind (Antoarapha spp.) of Noctua; Asrotis spp. (each of Agrotis kind) is as Agrothis segetum (yellow cutworm) and Aarothis ipsilon (black cutworm); Helicoverpa.spp; Each of Heliothis kind of (Heliothis spp.); Plutella xylostella (small cabbage moth); Parnara guttata (rice plant skipper); Tineapellionella (bag rain moth); Tineola bisselliella (curtain rain moth) or the like.
Diptera
Culex is as Culex pipiens pallens (culex pipiens pollens) and Culextritaeniorhvnchus (Culex tritaeniorhynchus); Aedes is as Aedes aegypei (Aedes aegypti) and Aedes albopictus (Aedes albopictus); Anopheles is as Anoppelessinensis (Anopheles sinensis); Chironomidae (midge); Nuscidae is as Musca domestica (housefly), Muscina stabulans (false stable fly) and Fannia canicularis (little housefly); Calliphoridae; Flesh flies; Anthomyiidae (flowerfly) is as Delia platura (delia platura) and Deliaantiqua (fly is planted on green onion ground); Tephritidae (trypetid); Drosophilidae (little fruit bat, drosophila yellow gorilla); Moth files (moth fly, sand fly subfamily); Phoridae; Simulidae (blackfly); Tabanidae; Sting Nuscidae (stable fly); Midge or the like.
Coleoptera
Attagenus unicolor (monochromatic fur moth); Anthrenus verbasci (roundlet khapra beetle); Corn root leaf A is as Diabrotica virgifera (corn young shoot root is chrysomelid) and Diabrotica undecimpunctaca howardi (cucumber 11 asterophyllite first); Scarabaeidae (chafer) is as Anomala cuprea (bronze different beetle) and Anomalarufocuprea (soybean chafer); Curculionidae (weevil) is as Sitophilus zeamais (sitophilus zea-mais), Lissorhoptrus oryzophilus (rice root weevil), Anthonomus grandisgrandis (cotton boll resembles) and Callosobruchus chinensis (Callosobruchus chinensis); TRenebrionidae (intending ground beetle) is as Tenebrio molitor (tenebrio molitor) and Tribolium castaneum (red flour beetle); Chrysomelidae (Zea mays root snout moth's larva) is as Oulema oryzae (rice leaf beetles), Phyllotretastriolata (Phyllotreta striolata) and Aulacophora femoralis (aulacophora femoralis); Anobiidae; Epilachna spp. (each of epilachna genus kind) is as Henosepilachnavigintioctopunctata (potato potato ladybug); Lyctidae (European bamboo powder moth); Bostrichidae (pseudo-powder moth); Cerambycidae; Paederus fuscipes (Paederus fuscipes Curtis) or the like.
Neuroptera (Dictyoptera)
Blattella germanica (blatta germanica), Periplaneta fuliainosa (smoke Perilpaneta americana), Periplaneta americana (periplaneta americana), Periplaneta brunnea (periplaneta brunnea), Blatta orientalis (oriental cockroach) or the like.
Thysanoptera (thrips)
Thrips palmi (pale brown thrips), Frankliniella occidentalis (alfalfa thrips), Thrips hawaiiensis (flower thrips) or the like.
Hymenoptera
Formicidae (ant); Vespidae (hornet); Bethylidae (swollen leg honeybee); Tenthredinidae (sawfly) is as yellow-winged cabbage sawfly [Athalia rosae ruficornis] (wild cabbage sawfly) or the like.
Orthoptera
Gryllotalpidae (mole cricket), locust section (locust) or the like.
Siphonaptera
Ctenocephalides canis (ctenocephalides canis), Ctenocephalides felis (ctenocephalides felis), Pulex irritans (Pulex irritans) or the like.
Anoplura
Humanlice (Pediculus humanus), crab louse (Phthirus pubis), head louse (Pediculus humanus var.Capitis), body louse (Pediculus humanus var.Corporis) or the like.
Isoptera (termite)
Reticulitermes speratus (eastern subterranean termite), Coptotermesformosanus (Coptotermes formosanus Shtrari) or the like.
Acarina (mite and tick)
Pyroglyphidae is as Dermatophagoides farinae (America dermatophagoides pteronyssinus) and Dermatophagoides pteronyssinus (European tame peronium mite); Mite section is as Tyrophagus putrescentiae Schrank (tyrophagus putrescentiae) and Aleuroglyophusovatus Troupeau (oval baking soda mite); Eat sweet mite section, as Glycyphagusprivatus (the sweet mite of concealed food), Glycyphagus domesticus (the sweet mite of family's food) and Glycyphagus destructor Schrank (destroy and eat sweet mite); Cheyletidae is as Cheyletus malaccensis (Malacca cheyletid mite) and Cheyletus moorei; Tarsonemidae; Chrtoglyphus; First mite section (Oribatei); Tetranychidae (tetranychid) is as Tetranychus urticae (T.urticae Koch), Tetranychus kanzawai (kamisawa tetranychus), Panonychus citri (tangerine Panonychus citri) and Panonychus ulmi (elm Panonychus citri); Hard tick section is as Haemaphysalis longicornis (haemaphysalis longicornis) or the like.
Moreover The compounds of this invention also can be prevented and treated the insect that existing sterilant and miticide is had resistance effectively.
Pesticide composition of the present invention is used to kill the purpose with the repellent insect.
When The compounds of this invention is used as the activeconstituents of pesticide composition, normally with solid carrier, liquid vehicle, carrier gas or bait, and choose wantonly and mix with processing aid such as tensio-active agent etc., be mixed with various preparations such as finish, missible oil, wettable powder, suspension agent (as aqueous suspension, aqueous emulsion etc.), granule, pulvis, aerosol, ULV preparation, toxicity bait etc. afterwards.
These preparations contain The compounds of this invention by weight 0.001-95% usually as activeconstituents.
The solid carrier that uses in the preparation comprises, for example, the fine powder of clay and particle (for example kaolinton, diatomite, synthetic hydrated SiO 2, wilkinite, fubasami clay and acid clay), talcum, potter's clay, other inorganic mineral (for example sericite, quartz, sulphur, activated carbon, lime carbonate and hydrated SiO 2) and chemical fertilizer (as: ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride).Said liquid carrier comprises, water for example, alcohols (for example methyl alcohol and ethanol), ketone (for example acetone and methylethylketone), aromatic hydrocarbons (benzene for example, toluene, dimethylbenzene, ethylbenzene and methylnaphthalene), aliphatic hydrocarbon (hexane for example, hexanaphthene, kerosene and lightweight oil), ester class (for example ethyl acetate and butylacetate), nitrile (for example acetonitrile and isopropyl cyanide), ethers (for example diisopropyl ether is with diox), acid amides (N for example, dinethylformamide and N, the N-N,N-DIMETHYLACETAMIDE), halogenated hydrocarbon (methylene dichloride for example, trichloroethane and tetracol phenixin), methyl-sulphoxide and vegetables oil (for example soybean oil and Oleum Gossypii semen).Said carrier gas (being the volatilizer of so-called aerosol) comprises, for example CFC gas, butagas, LPG (liquefied petroleum gas (LPG)), dme and carbonic acid gas.
Said tensio-active agent comprises, for example alkyl-sulphate, alkylsulfonate, alkylaryl sulphonate, alkyl aryl ether and their polyoxyethylene product, polyglycol ether, polyol ester and sugar alcohol derivant.
The auxiliary agent of preparation (as tackiness agent and dispersion agent) comprises, for example casein, gelatin, polysaccharide (for example starch, Sudan Gum-arabic, derivatived cellulose and alginic acid), lignin derivative, wilkinite, sugar and synthetic water-soluble polymers [as poly-(vinyl alcohol), poly-(vinyl pyrrolidone) and gather (vinylformic acid)].Stablizer comprises, for example PAP (acid phosphatase isopropyl ester), BHT (2,6-two-tertiary butyl-4-methylphenol), BHA (mixture of the 2-tertiary butyl-4-methoxyphenol and the 3-tertiary butyl-4-methoxyphenol), vegetables oil, mineral oil, tensio-active agent and lipid acid or their ester.
The matrix material that is used for poison bait comprises, for example bait component (such as grain powder, vegetables oil, sugar and crystalline cellulose), oxidation inhibitor (for example butylated hydroxytoluene and nordihydroguaiaretic acid), sanitas (for example dehydroacetic acid (DHA)), prevent reagent (for example paprika powder) and attractive substance (for example cheese spices, onion spice and peanut oil) that child and pet are eaten by mistake.
Suspension agent (flowable concentrate) (aqueous suspension or aqueous emulsion) normally obtains by 1 to 75% The compounds of this invention being scattered in the water that contains 0.5 to 15% dispersion agent, 0.1 to 10% suspension aids (for example protective colloid or can transmit the compound of thixotropic behavior), 0 to 10% suitable auxiliary substance (for example defoamer, rust-preventive agent, stablizer, spreader-sticker, penetrant, antifreezing agent, bactericide, mycocide).Also can replace water, form oil suspension with the insoluble basically oil of The compounds of this invention.
Protective colloid comprises, for example gelatin, casein, natural gum, ether of cellulose and polyvinyl alcohol.
The compound that can transmit thixotropic nature comprises, for example wilkinite, aluminium magensium silicate, xanthan gum and polyacrylic acid.
Thus obtained composition directly or use behind dilute with water.Also the present composition and other sterilant, miticide, nematocides, soil pests control agent, mycocide, weedicide, plant-growth regulator, repellent, synergistic agent, fertilizer or soil improvement agent can be combined use.
As for these sterilants, nematicide, miticide and soil pests control agent, can mention:
Organo phosphorous compounds, as fenitrothion 95 [O, O-dimethyl O-(3-methyl-4-nitrophenyl) phosphorothionate], Tiguvon [O, O-dimethyl O-(3-methyl-4-(methylthio group) phenyl)-phosphorothionate], diazinon [O, O-diethyl O-2-sec.-propyl-6-methylpyrimidine-4-base phosphorothionate], Chlorpyrifos 94 [O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate], acephate [O, S-dimethyl ethanoyl thio-phosphamide ester], methidathion [S-2,3-dihydro-5-methoxyl group-2-oxo-1,3,4-thiadiazoles-3-ylmethyl O, O-Methyl disulfide substituted phosphate], thiodemeton [O, O-diethyl S-2-ethylmercapto group diethyldithioposphoric acid ester], SD-1750 [2,2-dichlorovinyl dimethyl phosphate], Toyodan [O-ethyl O-4-(methylthio group) phenyl-S-propyl disulfide substituted phosphate], cynock [O-4-cyano-phenyl O, O-dimethyl sulphide phosphorothioate], dioxabenzofos [2-methoxyl group-4H-1,3,2-benzo two oxa-s phosphorus-2-sulfide], Rogor [O, O-dimethyl S-(N-methylamino formyl radical methyl) phosphorodithioate], Tsidial [2-dimethoxy sulfo-phosphono-sulphur (phenyl) ethyl acetate], Malathion [(dimethoxy sulfo-phosphono sulfenyl) diethyl succinate], Trichlorphon [2,2,2-three chloro-1-hydroxyethyl dimethyl phosphates], azinphos-methyl [S-3,4-dihydro-4-oxo-1,2,3-phentriazine-3-ylmethyl O, O-Methyl disulfide substituted phosphate], monocrotophos [dimethyl (E)-1-methyl-2-(methylamino formyl radical) vinyl phosphate] and Nialate [O, O, O ', O '-tetraethyl-S, S '-methylene-bis-(phosphorodithioate)];
Amino formate compounds, as fenobucarb [2-2-phenylbutane ylmethyl carbamate], benfuracarb [N-[2,3-dihydro-2,2-dimethyl benzofuran-amino the sulfenyl of 7-base oxygen carbonyl (methyl)]-N-sec.-propyl-Beta-alanine ethyl ester], Propoxur [2-isopropyl phenyl N-methyl carbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furyl N-dibutylamino sulfenyl-N-methyl carbamate], carbaryl [1-naphthyl N-methyl carbamate], methomyl [S-methyl-N-[(methyl-carbamyl) the oxygen base] the thioacetyl imido-ester], ethiofencarb [2-(ethylmercapto group methyl) phenol methylcarbamate], aldicarb [2-methyl-2-(methylthio group) propionic aldehyde O-methyl-carbamyl oxime], oxamyl [N, N-dimethyl-2-methylamino methanoyl imino--2-(methylthio group) ethanamide] and fenothiocarb [(S-4-phenoxy group butyl)-N, N-dimethyl thiocarbamate];
Pyrethroid compound, as ether chrysanthemum ester [2-(4-ethoxyl phenenyl)-2-methyl-propyl-3-phenoxy benzyl ether], fenvalerate [(RS)-alpha-cyano-3-phenoxy benzyl (RS)-2-(4-chloro-phenyl-)-3 Methylbutanoic acid ester], esfenvalerate [(S)-alpha-cyano-3-phenoxy benzyl (S)-2-(4-chloro-phenyl-)-3 Methylbutanoic acid ester], Fenvalerate [(RS)-alpha-cyano-3-phenoxy benzyl 2,2,3,3-4-methyl cyclopropane carboxylic acid ester], Cypermethrin [(RS)-alpha-cyano-3-phenoxy benzyl (1RS)-cis, trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester], permethrin [3-phenoxy benzyl (1RS)-cis, trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester], cyhalothrin [(RS)-alpha-cyano-3-phenoxy benzyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoropropyl-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester], Deltamethrin [(S)-alpha-cyano-3-phenoxy benzyl (1R)-cis-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester], cycloprothrin [(RS)-alpha-cyano-3-phenoxy benzyl (RS)-2,2-two chloro-1-(4-ethoxyl phenenyl) cyclopropanecarboxylcompound], taufluvalinate [alpha-cyano-3-phenoxy benzyl N-(2-chloro-α, α, α-three fluoro-p-methylphenyl)-the D-L-valine ester], bifenthrin [(2-methyl diphenyl-3-ylmethyl) (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoropropyl-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester], halfenprox [2-(4-bromine difluoro-methoxy phenyl) 2-methyl isophthalic acid-(3-phenoxy group-benzyloxy)-propane, tralomethrin [(S)-alpha-cyano-3-phenoxy benzyl (1R-cis)-3-{ (1RS)-(1,2,2,2-tetrabromo ethyl) }-2,2-dimethyl cyclopropane carboxylic acid ester], salifluofen [4-phenelyl { 3-(4-fluoro-3-phenoxy phenyl) propyl group } dimethylsilane], d-phenothrin [3-phenoxy benzyl (1R-cis, trans)-chrysanthemum monocarboxylate], cyphenothrin [(RS)-alpha-cyano-3-phenoxy benzyl (1R-cis, trans)-chrysanthemum monocarboxylate], d-resmethrin [5-phenmethyl-3-furylmethyl (1R-cis, trans)-chrysanthemum monocarboxylate], fluorine ester chrysanthemum ester [(S)-alpha-cyano-3-phenoxy benzyl (1R-cis (Z))-(2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoro propoxy-) propenyl } cyclopropanecarboxylcompound], cyfloxylate [(RS)-alpha-cyano-4-fluoro-3-phenoxy benzyl 3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester], tefluthrin [2,3,5,6-tetrafluoro-4-methyl-benzyl (1RS-cis (Z))-3-(2-chloro-3,3,3-trifluoropropyl-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester], transfluthrin [2,3,5,6-ptfe benzyl (1R-is trans)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester], Tetramethrin [3,4,5,6-tetrahydrochysene phthaloyl iminomethyl (1RS)-cis, trans-chrysanthemum monocarboxylate], esbiothrin [(RS)-3-allyl group-2-methyl-4-oxo ring penta-2-thiazolinyl (1RS)-cis, trans-chrysanthemum monocarboxylate], prallethrin [(S)-2-methyl-4-oxo-3-(2-propynyl) encircles penta-2-thiazolinyl (1R)-cis, and is trans-chrysanthemum monocarboxylate], Prallethrin [(RS)-1-ethynyl-2-methyl-pentenyl (1R)-cis, trans-chrysanthemum monocarboxylate], imidazoles chrysanthemum ester [2,5-dioxo-3-(Propargyl) imidazolidine-1-ylmethyl (1R)-cis, trans-2,2-dimethyl-3-(2-methyl-prop-1-thiazolinyl) cyclopropanecarboxylcompound], d-PH [5-(2-propynyl) furfuryl group (1R)-cis, trans-chrysanthemum monocarboxylate] and 5-(2-propynyl)-furfuryl group-2,2,3, the 3-4-methyl cyclopropane carboxylic acid ester];
Thiadiazine derivatives such as Buprofezin [uncle's 2-fourth imino--3-sec.-propyl-5-phenyl-1,3,5-thiadiazine-4-ketone;
N-nitroimidazole derivatives;
Clam worm poison derivative is as cartap [S, S '-(2-dimethylamino trimethylene)-two (thiocarbamates)], thiocyclam [N, N-dimethyl-1,2,3-three thias oneself-5-base amine] and bensultap [S, S '-2-dimethylamino trimethylene-two (thio phenyl sulphonate)];
Chlorinated hydrocarbon, as 5a,6,9,9a-hexahydro-6,9-methano-2,4 [6,7,8,9,10,10-chlordene-1,5,5a, 6,9,9a-six hydrogen-6,9-methylene-2,4,3-benzo sulphur dioxide heptan-3-oxide compound], γ-phenyl-hexachloride [1,2,3,4,5, the 6-HEXACHLOROBUTADIENE] and kelthane 1, two (4-the chloro-phenyl-)-trichloro-ethyl alcohol of 1-;
The benzoylphenylurea compounds, [1-(3 as UC 62644,5-two chloro-4-(3-chloro-5-5-flumethiazine-2-base oxygen base) phenyl)-3-(2, the 6-difluoro benzoyl) urea], [1-(3 for Teflubenzuron, 5-two chloro-2, the 4-difluorophenyl)-3-(2, the 6-difluoro benzoyl) urea] and flufenoxuron [1-[4-(2-chloro-4-4-trifluoromethylphenopendant)-2-fluorophenyl)-3-(2, the 6-difluoro benzoyl) urea]; With different flufenoxuron { 1-[3-(2-chloro-4-4-trifluoromethylphenopendant)-2]-fluorophenyl }-3-(2, the 6-difluoro benzoyl) urea;
Thiourea derivative is as methamidophos [N-(2,6-di-isopropyl-4-Phenoxyphenyl)-N '-tertiary butyl thiocarbamide];
The compound of N-phenylpyrazole type; Evil worm ketone [5-methoxyl group-3-(2-p-methoxy-phenyl)-1,3,4-oxadiazole-2-(3H)-ketone], bromopropylate [4,4 '-two bromo benzilic acid isopropyl esters], tetradifon [4-chloro-phenyl-2,4,5-trichlorophenyl sulfone], chinomethionate [S, S-6-methyl-quinoxaline-2,3-two basic dithiocarbonates], alkynes mite spy [2-(4-tertiary butyl phenoxy group)-cyclohexyl third-2-base sulfite], fenbutatin oxide [two { three (2-methyl-2-phenyl propyl) tin } oxide compound], hexythiazox [(4RS, 5RS)-5-(4-chloro-phenyl-)-N-chlorine hexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxylic acid amides], four mite piperazines [3, two (the 2-chloro-phenyl-s)-1 of 6-, 2,4,5-tetrazine], pyridaben [the 2-tertiary butyl-5-(4-tertiary butyl benzylthio-)-4-chlorine pyridazine-3 (2H)-ketone], azoles mite ester [(E)-4-[(1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl] t-butyl perbenzoate], tebufenpyrad [N-4-tert.-butylbenzene methyl)-4-chloro-3-ethyl-1-methyl-5-pyrazoles carboxylic acid amides, polynactin mixture [tetranactin, dinactin and trinactin], pyrimidifen [5-chloro-N-[2-{4-(2-ethoxyethyl group)-2,3-dimethyl phenoxy } ethyl]-6-ethyl-pyrimidine-4-amine], rice is that mycin (Milbemectin) doubly, avermectin (Abamectin), ivermectin (ivermectin), nimbin [AZAD] or the like.
Said repellent comprises, for example 3, and 4-is alkane glycol, N all, the N-diethyl--toluamide, 1-methyl-propyl 2-(2-hydroxyethyl)-1-piperidine carboxylic acid ester, right-Meng alkane-3,8-two pure and mild essence oil from plant (as Hyssop oil).
Said synergistic agent comprises, for example two-(2,3,3,3-tetrachloro propyl group) ether (S-421), N-(2-ethylhexyl) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide (MGK-264) and α-[2-(2-butoxy oxyethyl group) oxyethyl group]-4,5-methylene-dioxy-2-propyltoluene (Piperonyl Butoxide).
When The compounds of this invention was used as the activeconstituents of agricultural pest control composition, its application dosage was normally in the scope of 5 to 500g/10 ares.When using behind the preparation dilute with water of missible oil, wettable powder or suspension agent form, the The compounds of this invention concentration in the dilution preparation is usually at 0.1-1, in the 000ppm scope.The preparation of granule and powder form can directly use, and need not dilution.When The compounds of this invention is used as domestic hygiene and prevailing disease control composition or animal pest control composition, the preparation of missible oil, wettable powder or suspension agent form normally is being diluted with water to 1-10, use behind the 000ppm, and the preparation of finish, aerosol, ULV preparation or toxicity bait form can directly use.
Can suitably increase or reduce the application dosage and the application concentration of above-mentioned preparation according to condition (as the kind of the method for application of the type of preparation, time of application, place, preparation, insect, destructiveness or the like).
Embodiment
Next, specify the present invention by following preparation embodiment, example of formulations and experimental example, it is restriction to scope of the present invention that these embodiment should not be construed as.
At first, for example understand the preparation of The compounds of this invention.
Preparation embodiment 1
Under ice-cooled temperature, (1R)-trans-3-(2 with 0.71g, the 2-dichloroethylene)-2,2-dimethylcyclopropane carboxyl acyl chloride solution in 5ml toluene joins (2 of 0.78g, 3,5,6-tetrafluoro-4-p-methoxy-phenyl) in the mixture of methyl alcohol, 15ml toluene and 0.5g pyridine, adds 0.04g 4-Dimethylamino pyridine afterwards again.After one day, in reaction mixture, add entry, it is extracted with t-butyl methyl ether.Organic layer is concentrating under reduced pressure after dried over sodium sulfate.The resistates that obtains uses hexane/ethyl acetate (20/1) mixture to carry out the column chromatography purifying as eluent, obtain 0.96g (productive rate: 80%) (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl (1R)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester (The compounds of this invention 1).
1H-NMR(CDCl
3，TMS)δ1.18(3H，s)，1.29(3H，s)，1.60(1H，d，J＝5.4Hz)，2.26(1H，dd，J＝8.3Hz，5.4Hz)，4.10(3H，t，J＝1.5Hz)，5.19(1H，t，J＝1.5Hz)，5.20(1H，t，J＝1.5Hz)，5.59(1H，d，J＝8.3Hz)
Specific rotation [α]
D 28=-20 ° of (C=1.4, CHCl
3)
Preparation embodiment 2
Under ice-cooled temperature, with the diisopropyl azo-2-carboxylic acid of 2.6g in toluene 40% solution and the mixture of 10ml tetrahydrofuran (THF) join 1.09g (1RS)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid, 1.05g (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl alcohol and 1.33g triphenylphosphine are in the 40ml tetrahydrofuran (THF) in the formed solution.After one day, with the reaction mixture concentrating under reduced pressure.The resistates that obtains uses hexane/ethyl acetate (10/1) mixture to carry out the column chromatography purifying as eluent, obtain 1.69g (productive rate: 84%) (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl (1RS)-trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester (The compounds of this invention 2).
1H-NMR(CDCl
3，TMS)δ1.18(3H，s)，1.29(3H，s)，1.60(1H，d，J＝5.4Hz)，2.26(1H，dd，J＝8.3Hz，5.4Hz)，4.10(3H，t，J＝1.5Hz)，5.19(1H，t，J＝1.6Hz)，5.20(1H，t，J＝1.6Hz)，5.59(1H，d，J＝8.3Hz)
Next, example of formulations and experimental example have been provided hereinafter.Umber all refers to weight part, except as otherwise noted.The compound 3 and 4 that uses among the embodiment hereinafter is the representative compounds of the present invention that are rich in transconfiguration.The ratio of (1RS)-trans body in the compound 3/(1RS)-cis body is 9/1, and the ratio of and (1RS)-trans body in the compound 4/(1RS)-cis body is 8/2.
Example of formulations 1: missible oil
With each compound dissolution of the present invention of 10 parts in 35 parts dimethylbenzene and 35 parts of dimethyl formamide mixtures, and to polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzene sulphonates of wherein adding 14 parts, and fully stir and mix the mixture of gained, prepare 10% missible oil of 1-4 of the present invention number each compound.
Example of formulations 2: wettable powder
Each compound of the present invention of 20 parts is joined in 4 parts of Sodium Lauryl Sulphate BP/USPs, 2 parts of calcium lignin sulphonates, 20 parts of synthetic hydrated silica fine powders and the 54 parts of diatomaceous mixtures, in fruit juice mixing tank (juice mixer), stir and mix the mixture of gained then, prepare 20% wettable powder of 1-4 of the present invention number each compound.
Example of formulations 3: granula
Each compound of the present invention of 5 parts is joined in the mixture of the fine powder of 5 parts of synthetic hydrated silicas, 5 parts of Sodium dodecylbenzene sulfonatees, 30 parts of wilkinites and 55 parts of clays; fully stir and mix the mixture of gained; again to wherein adding an amount of water; and restir mixture; with the mixture pelleting of tablets press with gained; and under airflow the dry particle that obtains, prepare 5% granule of 1-4 of the present invention number each compound.
Example of formulations 4: pulvis
With 1 part of 1-4 of the present invention number each compound dissolution in an amount of acetone, to the fine powder that wherein adds 5 parts of synthetic hydrated silicas, 0.3 part of PAP and 93.7 parts of clays, stir and mix the mixture of gained by the fruit juice mixing device, and steam and remove acetone, prepare 1% pulvis of 1-4 of the present invention number each compound.
Example of formulations 5: suspension agent
With 20 parts of 1-4 of the present invention number each compound and 28.5 parts of aqueous solution that contain 1.5 part of three oleic acid sorbitan esters and 2 parts of polyvinyl alcohol.The gained mixture is ground to particle diameter less than 3 μ m or littler with sand milling.Afterwards, 40 parts of aqueous solution that contain 0.05 part of xanthan gum and 1.0 parts of aluminium magensium silicates are added wherein.Stir and mixing, thereby thus obtained mixture obtains compound 20% suspension.
Example of formulations 6: finish
Each compound dissolution of the present invention of 0.1 part in 10 parts methylene dichloride, and is mixed the solution of gained with 89.9 parts of deodorized kerosines, obtain 0.1% finish of 1-4 of the present invention number each compound.
Example of formulations 7: oil base aerosol
Each compound of the present invention of 1 part, 5 parts methylene dichloride and 34 parts of deodorized kerosines are mixed, obtain a kind of solution, the solution of gained is packed in the aerosol container, this container connection is gone up valve part, then under pressurized conditions, 60 parts propellents (liquefied petroleum gas (LPG)) are compressed in this container through valve part, thereby have obtained the oil base aerosol of 1-4 of the present invention number each compound.
Example of formulations 8: water base aerosol
The emulsifying agent { Atmos300 (trade name of registration with each compound of the present invention of 0.6 part, 5 parts dimethylbenzene, 3.4 parts of deodorized kerosines and 1 part, Atlas chemical company) } mix, obtain a kind of solution, the pure water of the solution of gained and 50 parts is packed in the aerosol container, this container connection is gone up valve part, under pressurized conditions, 40 parts propellents (liquefied petroleum gas (LPG)) are compressed in this container through valve part then, thereby have obtained the water base aerosol of 1-4 of the present invention number each compound.
Example of formulations 9: poison bait
With each compound dissolution of the present invention of 10mg in the acetone of 0.5ml, solution-treated 5g solid animal-feed powder (solid feed powder CE-2 (the Solid FeedPowder CE-2 that is used to bring up with gained, Cler Japan, Inc. trade name)), uniform mixing, and dry air, remove the acetone in the mixture, obtain 0.2% poison bait of 1-4 compound of the present invention.
Example of formulations 10: acarid control sheet
With each compound dissolution of the present invention in an amount of acetone, the drips of solution of gained is added on the non-woven fabrics, makes this non-woven fabrics impregnated, afterwards this non-woven fabrics of wind with the ratio of every square metre of non-woven fabrics of 1g solution, remove acetone, obtain the acarid control sheet of 1-4 compound of the present invention.
Example of formulations 11: microcapsule
The mixture of 10 parts of each compounds of the present invention, 10 parts of phenyl xylyl ethane and 0.5 part of SumidurL-75 (tolylene diisocyanate that Sumitomo Bayer Urethane company limited produces) joined in 20 part 10% the gum arabic aqueous solution.The gained mixture stirs in homogenizer, to obtain the emulsion that average particle size particle size is 20 μ m.Then 2 parts ethylene glycol is joined in this emulsion, the gained mixture reacted 24 hours under 60 ℃ heating bath condition, obtained the micro-capsule slurry.On the other hand, 0.2 part of xanthan gum and 1.0 parts of Veegum R (aluminium magensium silicate that Sanyo chemical industry company limited produces) are dispersed in 56.3 parts the ion exchanged water, obtain thickener soln.
With micro-capsule slurry prepared above 42.5 parts and above 57.5 parts prepared thickener soln mix, obtain 10% microcapsule of The compounds of this invention.
The experimental example that hereinafter provides is used and is described in (2 among the EP-31199A, 3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl [(1RS)-cis-(2, the 2-dichloroethylene)-2, describe in the specification sheets of 2-dimethyl cyclopropane carboxylic acid ester (hereinafter being called control compound A) and EP-378026A (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl [(1R)-trans-(2-is fluoride-based for the 2-chloro-)-2,2-dimethyl cyclopropane carboxylic acid ester (hereinafter being called control compound B) is compound in contrast.
Experimental example 1
＜to the insecticidal activity of housefly 〉
The compounds of this invention 1 is dissolved in the acetone, and compound concentration is 80,40,20 and a series of diluents of 10ppm.On the other hand, The compounds of this invention 2 and control compound A also are dissolved in respectively in the acetone, compound concentration is 160,80,40 and the diluent of 20ppm.In addition, compound 3 and 4 also is dissolved in respectively in the acetone, makes concentration respectively and be 100,50,25 and the diluent of 12.5ppm.Thus obtained each diluent of 0.5 μ l part is coated onto on the backboard of female adult housefly.Feed to these examination worms afterwards and raise water and bait.Behind the twenty four hours, the insect number that counting is dead calculates mortality ratio thus.Calculate LD from mortality ratio
50(mg/kg).
＜to the toxicity of rat 〉
The compounds of this invention 1-4 and control compound A are diluted to predetermined concentration with Semen Maydis oil.With the solution of each dilution with the dosage of 10ml/kg to the male rat administration.Give rat feeding water and feed.After seven days, count that live and rat number that die, calculate LD by mortality ratio
50(mg/kg).
The calculating of＜safety coefficient 〉
From to the insecticidal activity of housefly with to the toxicity of rat, according to following formula, the computationally secure coefficient.The results are shown in the table 1.
Safety coefficient=to the toxicity (LD of rat
50)/to the insecticidal activity (LD of housefly
50)
Table 1
| Compound | Insecticidal activity (LD to housefly 50) | Toxicity (LD to rat 50) | Safety coefficient |
| Compound 1 | 0.54 | 300 | 560 |
| Compound 2 | 0.93 | Be higher than 300 | Be higher than 320 |
| Compound 3 | 1.0 | 100-300 | 100-300 |
| Compound 4 | 1.0 | 100-300 | 100-300 |
| Control compound A | 2.4 | 30 | 13 |
Experimental example 2
With the acetone soln of compound 1 and control compound B be coated in 10 female houseflies (
Musca Domestica) regio pectoris, back (activeconstituents: housefly of 0.04 μ g/), feed to housefly and to raise water and feed.After 24 hours, determine mortality ratio (three repetitions).The results are shown in the table 2.
Table 2
| Compound | Mortality ratio (%) |
| Compound 1 | 100.0 |
| Control compound B | 21.4 |
Shown in above-mentioned embodiment, The compounds of this invention has fabulous pest controling effect and to mammalian safe, can be used as the very useful active ingredient of the pest control agent that prevents localized epidemics's disease.
Claims (7)
- (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) methyl shown in the following formula trans-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester:
- 2. according to the compound of claim 1, the 1-position of cyclopropane ring is the R-configuration in the wherein said chemical formula.
- 3. be rich in (2,3,5,6-tetrafluoro-4-p-methoxy-phenyl) the methyl 3-(2, the 2-dichloroethylene)-2 of trans body, 2-dimethyl cyclopropane carboxylic acid ester.
- 4. according to the compound of claim 3, it contains 80% or more trans body.
- 5. pesticide composition, it contains as the compound of the claim 1 of activeconstituents and carrier.
- 6. the method for a pest control, it comprises that the place that insect or insect are perched uses the compound according to claim 1 of significant quantity.
- 7. according to the application of compound on pest control of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001011553A CN1184190C (en) | 2000-01-26 | 2000-01-26 | cyclopropane carboxylic ester compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001011553A CN1184190C (en) | 2000-01-26 | 2000-01-26 | cyclopropane carboxylic ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1306958A CN1306958A (en) | 2001-08-08 |
| CN1184190C true CN1184190C (en) | 2005-01-12 |
Family
ID=4575782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001011553A Expired - Fee Related CN1184190C (en) | 2000-01-26 | 2000-01-26 | cyclopropane carboxylic ester compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1184190C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101473842B (en) * | 2009-01-23 | 2012-06-06 | 江苏扬农化工股份有限公司 | Insecticidal composition |
| CN102020564A (en) * | 2009-09-17 | 2011-04-20 | 上海生农生化制品有限公司 | Fluoro-containing cyclopropane carboxylate with acetylenic bond and preparation method and use thereof |
| CN102277744B (en) * | 2011-06-10 | 2013-10-09 | 东华大学 | Antibiotic and anti-asthma finishing liquid, preparation method thereof and application thereof on fabrics |
-
2000
- 2000-01-26 CN CNB001011553A patent/CN1184190C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1306958A (en) | 2001-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1249023C (en) | Ester compound and use thereof | |
| CN1092490C (en) | Pyrethroid compound and composition containing said compound for preventing and killing pests | |
| CN1228315C (en) | Cyclopropanecarboxylic acid esters and pest controllers containing the same | |
| CN1910169A (en) | Pyrethroid pesticide | |
| CN101668733B (en) | Cyclopropane carboxylic compounds and their use in pest control | |
| CN101516855B (en) | Ester compound and its use as pesticide | |
| EP0926129B1 (en) | Ester compound and pesticide containing it | |
| CN101636382B (en) | Cyclopropane carboxylic acid ester compound and its use in pest control | |
| CN1184190C (en) | cyclopropane carboxylic ester compound | |
| CN1236772A (en) | Pyrethroid compound and composition for controlling pest containing the same | |
| CN1177797C (en) | Pyrethroid compound and composition for controlling pest containing the same as active ingredient | |
| CN1203063C (en) | Easter compound, method for preventing and controlling injurious insect and use of said ester compound | |
| CN1215051C (en) | Ester compounds | |
| KR100638133B1 (en) | Cyclopropanecarboxylic ester compounds | |
| CN1117043A (en) | Ester compound, agent for controlling noxious organisms containing the same as active ingredient, and production | |
| KR20100110333A (en) | Cyclopropanecarboxylate and pest controlling composition containing the same | |
| CN1200936C (en) | Pyrone compounds and their use | |
| MXPA00001035A (en) | Ester cyclopropanecarboxylic compounds. | |
| MXPA99009958A (en) | Piretroid compositions and composition containing them to control pla | |
| FR2802527A1 (en) | Ester of trans 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid with (2,3,5,6-tetrafluoro-4-methoxyphenyl) methanol having insecticidal and acaricidal properties with low mammalian toxicity | |
| ITRM990799A1 (en) | CYCLOPROPANCARBOXYL ESTER COMPOUNDS. | |
| CN1377577A (en) | Composition for controlling tardigvada | |
| MXPA99004663A (en) | Composite piretroid and composition for controlling powers containing the same as an ingredient | |
| MXPA99005460A (en) | Compounds of pesticide esters | |
| TW201035019A (en) | Ester compound and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050112 Termination date: 20170126 |