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WO2000078739A1 - Derives de tetrazine a effet pesticide - Google Patents

Derives de tetrazine a effet pesticide Download PDF

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Publication number
WO2000078739A1
WO2000078739A1 PCT/EP2000/005627 EP0005627W WO0078739A1 WO 2000078739 A1 WO2000078739 A1 WO 2000078739A1 EP 0005627 W EP0005627 W EP 0005627W WO 0078739 A1 WO0078739 A1 WO 0078739A1
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WO
WIPO (PCT)
Prior art keywords
och
alkyl
formula
och3
cycloalkyl
Prior art date
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PCT/EP2000/005627
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English (en)
Inventor
Werner Zambach
Rudolf Naef
Stephan Trah
André Jeanguenat
Martin Eberle
Arthur Steiger
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Syngenta Participations Ag
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Publication date
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to EP00938800A priority Critical patent/EP1187818A1/fr
Priority to AU54056/00A priority patent/AU5405600A/en
Priority to JP2001504905A priority patent/JP2003502413A/ja
Publication of WO2000078739A1 publication Critical patent/WO2000078739A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/08—Six-membered rings

Definitions

  • Pesticidally active tetrazine derivatives are:
  • the present invention relates to compounds of formula
  • X 2 and X 3 are each independently of the other H or F ⁇ ,
  • Ri is halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-dhaloalkyl, C 3 -C 8 halocycloalkyl d-C 6 alkoxy, C 3 -C 8 cycloalkoxy, d-C 6 haloalkoxy, C 3 -C 8 halocycloalkoxy, d-C 6 alkylth ⁇ o,
  • An is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , C C 6 alkyl, C 3 -C 8 cycloalkyl, d-Cealkyl-d-C ⁇ cycloalkyl, C 3 -C 8 cycloalkyl-d-C 6 alkyl, CrC 6 haloalkyl, C 3 -C 8 halocycloalkyl,
  • Ar 2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 alkyl-C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-d-C 6 alkyl, Ci-Cehaloalkyl, C 3 -C 8 halocycloalkyl,
  • A is a single bond, d-d_.alky.ene, O, O(C C 12 alkylene), S(O) n ,
  • Z is O, NR 4 , NNR 4 R 5 or NOR 4 ;
  • R 2 is H, C ⁇ -C 6 alkyl or C 3 -C 8 cycloalkyl
  • R 9 ⁇ - (CH 2 )m R 3 is Q ⁇ Q ;
  • R 4 and R 5 are each independently of the other H, d-C 6 alkyl or d-C 6 haloalkyl;
  • R 6 is H, d-C 6 alkyl, C 3 -C 8 cycloalkyl, CrC 6 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl- d-C 6 alkyl, (CH 2 ) p C(O)R 7 or d-C 6 alkoxy-C 2 -C 6 alkyl;
  • R 7 is H, C ⁇ -C 6 alkyl, C 3 -C 8 cycloalkyl, C C 6 haloalkyl, d-C 6 alkoxy, N(R 8 ) 2 or d-C 6 alkoxy-C 2 -C 6 alkyl;
  • R 8 is H, d-C 6 alkyl, C 3 -C 8 cycloalkyl, C C 6 haloalkyl or aryl-C C 6 alkyl;
  • R 9 and R 10 are each independently of the other H or d-C 6 alkyl; m is 1 , 2, 3 or 4; n is O, 1 or 2; p is 0, 1 , 2, 3, 4, 5 or 6; and
  • Q is O or S; with the proviso, that when T-V is -NH-NH-, Xi is halogen, X 2 and X 3 are both hydrogen, Ari and Ar 2 are both phenyl which may be unsubstituted or substituted, A is not a single bond; or, where applicable, a possible E/Z isomer, mixture of E/Z isomers and/or tautomer thereof, in each case in free form or in salt form, to a process for the preparation of those compounds and to the use thereof, to pesticidal compositions in which the active ingredient is selected from those compounds, in each case in free form or in agrochemically acceptable salt form, and to a process for the manufacture of those compositions and to their use.
  • 1,2,4,5-triazine derivatives are proposed in the literature as active ingredients in compositions for controlling pests on domestic animals and productive livestock and in crops of useful plants.
  • the biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, that problem being solved according to the invention by the provision of the present compounds of formula (I).
  • the compounds of formula (I) may be in the form of salts or may form e.g. acid addition salts.
  • the latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxyiic acids, such as unsubstituted or substituted, e.g. halo-substituted, C 1 -C alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g.
  • compounds of formula (I) having at least one acid group may form salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g.
  • sodium, potassium or magnesium salts or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. Within the scope of the invention preference is given to agrochemically advantageous salts; also included, however, are other salts, which can be used, for example, for the isolation or purification of free compounds of formula (I) or the agrochemically acceptable salts thereof.
  • any reference to the free compounds of formula (I) or to their salts is to be understood as including also the corresponding salts or the free compounds of formula (I), respectively, as appropriate and expedient.
  • the free form is preferred.
  • carbon-containing groups and compounds each contain from 1 up to and including 6, preferably from 1 up to and including 4, especially 1 or 2, carbon atoms.
  • Aryl is phenyl or naphthyl, preferably phenyl.
  • Heteroaryl is pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or 1,2,4-triazinyl, especially pyridyl.
  • Halogen - as a group perse and as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
  • Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Cycloalkyl - as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl, cycloalkoxy and cycloalkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Alkenyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3- octadienyl, or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl.
  • straight- chained e.g. allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3- o
  • Alkynyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1 ,5- heptadien-3-ynyl, or branched, e.g. 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2- ynyl or 2-methylhept-3-ynyl.
  • straight- chained e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1
  • Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkoxy and haloalkylthio, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different.
  • haloalkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkoxy and haloalkylthio - are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 or CH(CF 3 ) 2 ; butyl or an
  • X 1 is Rf
  • X 2 and X 3 are each independently of the other H or R,;
  • Ri is halogen, CN, NO 2 , C ⁇ -C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 haloalkyl, C 3 -C 8 halocycloalkyl,
  • Ar ! is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 alkyl-C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 8 halocycloalkyl, d-C 6 alkoxy, C 3 -C 8 cycloalkoxy, d-C 6 haloalkoxy, C 3 -C 8 halocycloalkoxy, d-C 6 alkylthio,
  • Ar 2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-Cealkyl-d-C ⁇ cycloalkyl, C 3 -C 8 cycloalkyl-C ⁇ -C 6 alkyI, CrCehaloalkyl, C 3 -C 8 halocycloalkyl,
  • Z is O, NR 4 , NNR 4 R 5 or NOR.,
  • R 2 is H, C ⁇ -C 6 alkyl or C 3 -C 8 cycloalkyl;
  • R 3 is Q Q ;
  • R 4 and R 5 are each independently of the other H, d-C 6 alkyl or C C 6 haloalkyl;
  • R 6 is H, d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl- d-C ⁇ alkyl, (CH 2 ) p C(O)R 7 or d-C 6 alkoxy-C 2 -C 6 alkyl;
  • R 7 is H, d-C ⁇ alkyl, C 3 -C 8 cycloalkyl, C ⁇ -C 6 haloalkyl, d-C 6 alkoxy, N(R 8 ) 2 or C C 6 alkoxy-
  • R 8 is H, d-C 6 alkyl. C 3 -C 8 cycloalkyl, d-dhaloalkyl or aryl-d-C 6 alkyl;
  • R 9 and R 10 are each independently of the other H or d-C 6 alkyl; m is 1 , 2, 3 or 4; n is 0, 1 or 2; p is 0, 1 , 2, 3, 4, 5 or 6; and Q is O or S.
  • R is halogen, d-C alkyl, C 3 -C 6 cycloalkyl, d-C 4 haloalkyl, d-C 4 alkoxy, C -C 4 haloalkoxy, d-C 4 alkylthio or d-C haloalkylthio; especially halogen, d-C 2 alkyl, d-C 2 haloalkyl, d-C 2 - alkoxy or C C 2 haloalkoxy; more especially fluorine, chlorine, methyl, trifluoromethyl or methoxy;
  • the invention relates also to a process for the preparation of compounds of formula (I), in each case in free form or in salt form, which process comprises, for example, a) reacting a compound of formula
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof.
  • solvents and diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and di
  • Preferred leaving groups are halogens, tosylates, mesylates and triflates, especially halogens, more especially chlorine and bromine.
  • Suitable basic catalysts are tertiary amines and aza-aromatic compounds, preferably trialkylamines and substituted pyridines, especially triethylamine and 4-dimethylamino- pyridine.
  • Suitable chlorinating agents are (COCI) 2 , SOCI 2 , SO 2 CI 2 , PCI 3 , POCI 3 and PCI 5 , preferably PCI 5 .
  • Suitable oxidising agents are halogens, O 2 and nitrite salts, preferably sodium nitrite.
  • the reactions are advantageously effected in a temperature range of from about 0°C to about +120°C, preferably from about 0°C to about +80°C.
  • a compound of formula (Ila) is reacted with a compound of formula (III) at from about 0° to about 30°, preferably about 10°, in a halogenated hydrocarbon, preferably methylene chloride, in the presence of a basic catalyst mixture, preferably a mixture of triethylamine and 4-dimethylaminopyridine; the resulting product is isolated, reacted with a chlorinating agent, preferably PCI 5 , at from about 80° to about 120°, preferably about 110°, in a halogenated hydrocarbon, preferably chlorobenzene, and the resulting chlorination product is then isolated again and reacted with hydrazine at about from 0° to 40°, preferably 20°, in an ether, preferably tetrahydrofuran; the resulting dihydro- tetrazine derivative is isolated and reacted with an oxidising agent, preferably sodium nitrite, at from about 0° to about
  • an oxidising agent preferably
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. Examples of solvents and diluents are given in variant a).
  • Suitable leaving groups, basic catalysts, chlorinating agents and oxidising agents are those mentioned in variant a).
  • Suitable catalysts for the reaction with a compound of formula (V) are palladium complexes, e.g. tetrakis(triphenylphosphine)palladium.
  • a tetrazine derivative is first prepared in accordance with variant a) and is then reacted with a compound of formula (V) at about from 0° to 80°, preferably 50°, in an ether, preferably dimethoxyethane, in the presence of a catalyst, preferably tetrakis(triphenylphosphine)palladium.
  • Salts of compounds of formula (I) can be prepared in a manner known per se. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I); for example, acid addition salts can be converted into other acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt that forms, for example silver chloride, is insoluble and thus precipitates out from the reaction mixture.
  • a salt of an inorganic acid such as a hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I) that have salt-forming properties may be obtained in free form or in the form of salts.
  • the compounds of formula (I) may also be obtained in the form of their hydrates and/or may include other solvents, for example solvents used for the crystallisation of compounds in solid form.
  • the invention relates to all those forms of the process in which a compound obtainable as starting compound or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out or a starting material is used in the form of a derivative or salt or, especially, is formed under the reaction conditions.
  • the invention relates especially to the processes described in the Preparation Examples.
  • the invention relates also to novel starting materials and intermediates, in each case in free form or in salt form, used according to the invention for the preparation of the compounds of formula (I) and their salts, to the use of those novel starting materials and intermediates and to processes for their preparation.
  • the invention relates especially also to compounds of formula
  • the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warmblooded animals, fish and plants.
  • the active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina.
  • the insecticidal, ovicidal and/or acaricidal activity of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • the said animal pests include, for example, those mentioned in European Patent Application EP-A-736 252, page 5, line 55, to page 6, line 55.
  • the pests listed therein are therefore included by reference in the subject matter of the present invention.
  • the compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
  • Target crops include both natural crops and crops that have been modified by breeding or genetic methods, especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • strawberries, raspberries and blackberries leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
  • the compounds according to the invention are especially suitable for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, citrus, maize, soybean, rape and vegetable crops.
  • plant-destructive feeding insects such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae
  • spider mites such as Tetranychus spp., in cotton, fruit, citrus, maize, soybean, rape and vegetable crops.
  • compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruits, tubers or grains, or plant cuttings, against fungal infections and animal pests.
  • the propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • Further areas of use of the compounds according to the invention are the protection of stored goods and storerooms and the protection of raw materials, and also in the hygiene sector, especially in the protection of warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, foxes, chinchillas, rabbits and the like, and also domestic animals and pets, such as cats and dogs, and even human beings, against pests of the mentioned type.
  • farm animals such as cows, pigs, sheep and goats
  • poultry such as hens, turkeys and geese
  • animals bred for their fur such as mink, foxes, chinchillas, rabbits and the like
  • domestic animals and pets such as cats and dogs, and even human beings, against pests of the mentioned type.
  • flea infestation in domestic animals and pets is a problem for the animal owner for which there is still no adequate solution.
  • none of the known methods of controlling fleas is totally satisfactory, especially since most of the known methods are aimed principally at controlling the fully grown fleas in the coat and take no account at all of the various juvenile stages of the fleas, which live not only in the animal's coat, but also on the floor, on carpets, on the animal's sleeping place, on chairs, in the garden and in all the other places with which the infested animal comes into contact.
  • Flea treatment is generally expensive and must be continued for prolonged periods, success generally being achieved only when the treatment is applied not only to the affected animal, e.g. the dog or cat, but also simultaneously to all the places frequented by the affected animal.
  • the compounds of formula (I) according to the invention can be used alone or in combination with other biocides.
  • biocides for example, in order to enhance the effect they can be combined with pesticides having the same direction of action or in order to broaden the spectrum of activity they can be combined with substances having a different direction of action.
  • the compounds of formula (I) are advantageously combined with substances having endoparasiticidal properties. They can, of course, also be used in combination with anti-bacterial agents.
  • Especially suitable mixing partners are, for example: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau- fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl;
  • the good pesticidal activity of the compounds of formula (I) according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.
  • the methods of applying the crop protection agents i.e. the methods for controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention.
  • Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm.
  • the compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances and the invention relates also thereto.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula (I), or a combination of that active ingredient with other agrochemical active ingredients and, as appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants) and the invention relates also thereto.
  • auxiliaries there are used, for example, solid carriers, solvents, stabilisers, "slow release” auxiliaries, dyes and optionally surface-active substances (surfactants).
  • Suitable carriers and auxiliaries include all those substances customarily used in crop protection products.
  • Suitable auxiliaries such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries in the compositions used according to the invention, include e.g. those described in EP-A-736 252, page 7, line 51 to page 8, line 39; they are included by reference in the subject matter of the present invention.
  • Suitable anionic surfactants include both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurine salts as surfactants.
  • the compounds of formula (I) are distinguished inter alia also by excellent activity against fleas, not only adult fleas being rapidly killed but also, by a circuitous route, the juvenile stages of the fleas. Flea larvae hatching out from the flea eggs feed substantially on the excreta of the adult fleas. Since the compounds of formula (I) according to the invention kill the adult fleas very rapidly, the necessary excreta are absent and the juvenile stages are deprived of nutrient medium, so that they perish before reaching the adult stage.
  • the present invention therefore relates preferably to a method of controlling parasites on human beings, domestic animals, productive livestock and pets, wherein an effective amount of a composition comprising at least one compound of formula (I), or a physiologically tolerable salt thereof, is administered systemically or, preferably, topically to the warmblooded animal.
  • the long-term action is achieved by the compounds of formula (I) according to the invention with various forms of administration, for example by administering the active ingredient in a formulated form externally or internally to the animal to be treated.
  • "Formulated" in this case means, for example, in the form of a powder, a tablet or granules, in liposomes or a capsule, in the form of an emulsion, a foam or a spray, in microencapsulated form or in pour-on or spot-on form.
  • all orally administrable compositions comprise, in addition to customary formulation substances, further additives that encourage the host animal to take the composition orally voluntarily, e.g. suitable odorants and flavourings.
  • Percutaneous administration e.g. by subcutaneous or intramuscular injection or as a depot preparation in the form of an implant, and topical application, for example in pour-on or spot- on form, represent preferred subjects of this invention on account of their being easy to carry out.
  • a further mode of administration is oral administration, e.g. in the form of a tablet.
  • Percutaneous and topical forms of administration are of particular interest and give excellent results.
  • Percutaneous forms of administration include, for example, subcutaneous, intramuscular and even intravenous administration of injectable forms.
  • customary syringes with needles it is also possible to use needle-less high-pressure syringe devices.
  • pour-on and spot-on formulations are especially preferred forms of topical administration, but administration in the form of sprays, ointments, solutions or powders may also be expedient.
  • a suitable formulation it is possible to enhance the ability of the active ingredients to penetrate the living tissue of the host animal and/or to maintain their availability. That is important when, for example, more sparingly soluble active ingredients are used, the low solubility of which requires means for enhancing solubility, since in such cases the animal's body fluid is capable of dissolving only small amounts of active ingredients at a time.
  • a compound of formula (I) according to the invention may also be present in a matrix formulation which physically prevents the active ingredient from being released and excreted prematurely and maintains the bioavailability of the active ingredient.
  • a matrix formulation is injected into the body, e.g. intramuscularly or subcutaneously, and remains there as a form of depot from which the active ingredient is released continuously.
  • matrix formulations are known to the person skilled in the art. They are generally wax-like, semi-solid substances, for example vegetable waxes and polyethylene glycols having a high molecular weight, or solid polymer formulations, for example so-called microspheres.
  • the rate of release of the active ingredient from the implant and thus the period of time over which the implant exhibits an action is generally determined by the accuracy with which the implant has been calibrated (amount of active ingredient in the implant), the environment around the implant and the polymer formulation from which the implant has been made.
  • premix in which the active ingredient is dispersed in a liquid or is in finely divided form in solid carriers.
  • That premix can normally comprise about 1 to 800 mg of compound per kg of premix, depending on the desired final concentration in the feed.
  • the compounds of formula (I) according to the invention may be hydrolysed by the constituents of the feed, they should be formulated in a protective matrix, for example in gelatin, before being added to the premix.
  • the present invention accordingly relates also to the aspect of controlling parasites by administering to the host animal with its food a compound of formula (I) that has been protected against hydrolysis.
  • a compound of formula (I) according to the invention is advantageously administered in a dose of from 0.01 to 800 mg/kg, preferably from 0.1 to 200 mg/kg, especially from 0.5 to 30 mg/kg, body weight, based on the host animal.
  • a good dose that can be routinely administered to the host animal is from 0.5 to 100 mg/kg, especially from 0.1 to 40 mg/kg, body weight.
  • the administration is effected at suitable intervals in dependence upon the mode of administration and body weight.
  • the total dose may vary from one species of animal to another and also within a species of animal for the same active ingredient, since it depends inter alia on the weight, age and constitution of the host animal.
  • the compound of formula (I) according to the invention will normally be administered not in pure form but, preferably, in the form of a composition that comprises, in addition to the active ingredient, constituents that assist administration, suitable constituents being those which are tolerated by the host animal. It is of course possible, in addition to controlling the adult parasites in accordance with the invention, also to use conventional methods to control the juvenile stages of the fleas, although the latter is not absolutely essential.
  • compositions to be administered in accordance with the invention generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound of formula (I) according to the invention and from 99.9 to 1 % by weight, especially from 99.9 to 5 % by weight, of a solid or liquid, physiologically tolerable carrier, including from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a non-toxic dispersant.
  • Such formulations may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
  • auxiliaries such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
  • physiologically tolerable carriers known from veterinary medicinal practice for oral, percutaneous and topical administration can be used as formulation auxiliaries. Some examples are given below.
  • Suitable carriers are especially fillers, such as sugars, e.g. lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, for example tricalcium phosphate or calcium hydrogen phosphate, and binders, such as starch pastes using, for example, maize, wheat, rice or potato starch, gelatin, tragacanth, methylcellulose and/or, if desired, disintegrators, such as the above-mentioned starches, also carboxymethyl starch, cross- linked polyvinylpyrrolidone, agar, alginic acid or a salt thereof, such as sodium alginate.
  • fillers such as sugars, e.g. lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, for example tricalcium phosphate or calcium hydrogen phosphate
  • binders such as starch pastes using, for example, maize, wheat
  • Adjuvants are especially flow conditioners and lubricants, for example silicic acid, talc, stearic acid or salts thereof, such as magnesium or calcium stearate, and/or polyethylene glycol.
  • Dragee cores can be provided with suitable, optionally enteric, coatings, there being used inter alia concentrated sugar solutions which may comprise gum arabic, talc, polyvinylpyrrolidone, polyethylene glycol and/or titanium dioxide, or coating solutions in suitable organic solvents or solvent mixtures, or, for the preparation of enteric coatings, solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethyl- cellulose phthalate. Dyes, flavourings or pigments may be added to the tablets or dragee coatings, for example for identification purposes or to indicate different doses of active ingredient.
  • hard gelatin capsules and also soft sealed capsules made of gelatin and a plasticiser, such as glycerol or sorbitol.
  • the hard gelatin capsules may comprise the active ingredient in the form of granules, for example in admixture with fillers, such as lactose, binders, such as starches, and/or glidants, such as talc or magnesium stearate, and, if desired, stabilisers.
  • the active ingredient is preferably dissolved or suspended in suitable liquids, such as fatty oils, paraffin oil or liquid polyethylene glycols, to which stabilisers may likewise have been added. Preference is given inter alia to capsules that may either easily be bitten through or swallowed without being chewed.
  • the pour-on or spot-on method comprises applying the compound of formula (I) to a locally defined area of the skin or coat, advantageously on the back of the neck or the backbone of the animal. This is carried out, for example, by applying a swab or spray of the pour-on or spot-on formulation to a relatively small area of the coat from where the active ingredient becomes distributed over a wide area of the coat almost automatically as a result of the spreading constituents of the formulation assisted by the movements of the animal.
  • Pour-on and spot-on formulations advantageously comprise carriers that promote rapid distribution over the surface of the skin or in the coat of the host animal and are generally termed spreading oils.
  • suitable oils for example, oily solutions; alcoholic and iso- propanolic solutions, e.g.
  • solutions of 2-octyl dodecanol or oleyl alcohol solutions in esters of monocarboxylic acids, such as isopropyl myristate, isopropyl palmitate, lauric acid oxalic ester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, decyl oleate, capric acid esters of saturated fatty alcohols of chain length C 12 -C ⁇ 8 ; solutions of esters of dicarboxylic acids, such as dibutyl phthalate, diisopropyl isophthalate, adipic acid diisopropyl ester, di-n-butyl adipate or solutions of esters of aliphatic acids, e.g.
  • glycols It may be advantageous for a dispersant known from the pharmaceutical or cosmetic industry also to be present.
  • a dispersant known from the pharmaceutical or cosmetic industry also to be present. Examples are pyrrolidin-2-one, N-alkylpyrrolidin-2-one, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.
  • the oily solutions include e.g. vegetable oils, such as olive oil, groundnut oil, sesame oil, pine oil, linseed oil and castor oil.
  • vegetable oils may also be in epoxidised form. It is also possible to use paraffins and silicone oils.
  • a pour-on or spot-on formulation will contain from 1 to 20 % by weight of a compound of formula (I), from 0.1 to 50 % by weight dispersant and from 45 to 98.9 % by weight solvent.
  • the pour-on or spot-on method can be used especially advantageously for herd animals, such as cattle, horses, sheep and pigs, where it is difficult or time-consuming to treat all the animals orally or via injection.
  • this method can of course also be used for all other animals, including individual domestic animals and pets, and is very popular with the keepers of the animals because it can often be carried out without the expert assistance of a veterinary surgeon.
  • Suitable for parenteral and percutaneous administration are oily injection solutions or suspensions, there being used suitable lipophilic solvents or vehicles, such as fatty oils, for example sesame oil, or synthetic fatty acid esters, for example ethyl oleate, or triglycerides, or aqueous injection solutions or suspensions that comprise viscosity-increasing substances, for example sodium carboxymethylcellulose, sorbitol and/or dextran, and, optionally, stabilisers.
  • suitable lipophilic solvents or vehicles such as fatty oils, for example sesame oil, or synthetic fatty acid esters, for example ethyl oleate, or triglycerides
  • aqueous injection solutions or suspensions that comprise viscosity-increasing substances, for example sodium carboxymethylcellulose, sorbitol and/or dextran, and, optionally, stabilisers.
  • preparations of the present invention can be prepared in a manner known perse, for example by means of conventional mixing, granulating, confectioning, dissolving or lyophi- lising processes.
  • pharmaceutical preparations for oral administration can be obtained by combining the active ingredient with solid carriers, optionally granulating the resulting mixture, and processing the mixture or granules, if desired or necessary after the addition of suitable excipients, to form tablets or dragee cores.
  • Preferred formulations have especially the following composition (throughout, percentages are by weight):
  • Emulsifiable concentrates active ingredient: 1 to 90 %, preferably 5 to 20 % surface-active agent: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Injection solution active ingredient: 0.1 to 10 %, preferably 0.5 to 5 % non-ionic surfactant: 0.1 to 30 %, preferably 0.5 to 10 % mixture of ethanol and propylene glycol: 60 to 99 %, preferably 85 to 90 %
  • Injection suspension aqueous or oily: active ingredient: 0.1 to 20 %, preferably 1 to 10 % non-ionic surfactant: 0.1 to 20 %, preferably 1 to 10 % water or vegetable oil: 60 to 99 %, preferably 85 to 95 %
  • compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil)
  • anti- foams e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
  • Example 1 3-(4'-Chlorobiphenyl-4-yl)-6-(2,6-difluorophenyl)-1 ,2-dihvdro ⁇ ,2,4.51tetrazine a) 6.1 g of 4-bromobenzoic acid ethyl ester and 1.84 g of tetrakis(triphenylphosphine)- palladium are stirred in 140 ml of dimethoxyethane at room temperature for 1 h. 140 ml of 2M sodium carbonate solution and 5.0 g of 4-chlorophenylboronic acid are then added.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne des composés représentés par la formule générale (I), où T-V désigne -N=N- ou -NH-NH- ; X1 désigne R1 ; X2 et X3 représentent chacun indépendamment H ou R1 ; R1 désigne par exemple halogène, CN, NO2, C1-C6alkyle, C3-C8cycloalkyle, C1-C6haloalkyle, C3-C8halocycloalkyle, C1-C6alcoxy, C3-C8cycloalcoxy ou C1-C6haloalcoxy ; Ar1 représente un aryle ou hétéroaryle non substitué ou substitué en positions mono à tétra ; Ar2 représente un aryle ou hétéroaryle non substitué ou susbtitué en positions mono à penta ; A désigne une liaison simple, C1-C12alkylène, O, O(C1-C12alkylène), S(O)n, S(O)n(C1-C12alkylène), C2-C8alcénylène, C2-C8alkynylène; NR6, NR6(C1-C12alkylène) ou C(=Z) ; Z représente O, NR4, NNR4R5 ou NOR4 ; R2 désigne H, C1-C6alkyle ou C3-C8cycloalkyle ; R4 et R5 représentent chacun indépendamment H, C1-C6alkyle ou C1-C6haloalkyle ; R6 désigne H, C1-C6alkyle, C3-C8cycloalkyle, C1-C6haloalkyle, C2-C8alcényle, C2-C8alkynyle, aryl-C1-C6alkyle, (CH2)pC(O)R7 ou C1-C6alcoxy-C2-C6alkyle ; R7 représente H, C1-C6alkyle, C3-C8cycloalkyle, C1-C6haloalkyle, C1-C6alcoxy, N(R8)2 ou C1-C6alcoxy-C2-C6alkyle ; R8 désigne H, C1-C6alkyle, C3-C8cycloalkyle, C1-C6haloalkyle ou aryl-C1-C6alkyle ; n est égal à 0, 1 ou 2 ; p est égal à 0, 1, 2, 3, 4, 5, ou 6 ; et Q désigne O ou S. L'invention concerne également un procédé de préparation desdits composés et leur utilisation ; des pesticides dont le principe actif est choisi par ces composés ; un procédé de préparation de ces compositions et leur utilisation ; les produits intermédiaires obtenus au cours de la préparation de ces composés ; et un procédé de préparation desdits intermédiaires et leur utilisation.
PCT/EP2000/005627 1999-06-21 2000-06-19 Derives de tetrazine a effet pesticide WO2000078739A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP00938800A EP1187818A1 (fr) 1999-06-21 2000-06-19 Derives de tetrazine a effet pesticide
AU54056/00A AU5405600A (en) 1999-06-21 2000-06-19 Pesticidally active tetrazine derivatives
JP2001504905A JP2003502413A (ja) 1999-06-21 2000-06-19 農薬活性テトラジン誘導体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH114899 1999-06-21
CH1148/99 1999-06-21

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WO2000078739A1 true WO2000078739A1 (fr) 2000-12-28

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EP (1) EP1187818A1 (fr)
JP (1) JP2003502413A (fr)
AU (1) AU5405600A (fr)
CO (1) CO5160333A1 (fr)
EG (1) EG22089A (fr)
WO (1) WO2000078739A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702122A (zh) * 2012-05-16 2012-10-03 南通大学 由二氢四嗪氧化制备四嗪的方法
CN105037329A (zh) * 2015-09-06 2015-11-11 青岛科技大学 一种含氟四嗪吡唑类杀螨剂
CN105061399A (zh) * 2015-09-06 2015-11-18 青岛科技大学 一种含氟四嗪吡啶类化合物及其用途
CN105104407A (zh) * 2012-03-10 2015-12-02 陕西韦尔奇作物保护有限公司 一种高效杀虫组合物
CN105130962A (zh) * 2015-09-06 2015-12-09 青岛科技大学 一种四嗪吡唑类杀螨剂
US11078192B2 (en) 2016-07-05 2021-08-03 Guangzhou Maxinovel Pharmaceuticals Co., Ltd. Aromatic acetylene or aromatic ethylene compound, intermediate, preparation method, pharmaceutical composition and use thereof
US11384048B2 (en) 2017-12-29 2022-07-12 Guangzhou Maxinovel Pharmaceuticals Co., Ltd. Aromatic vinyl or aromatic ethyl derivative, preparation method therefor, intermediate, pharmaceutical composition, and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005912A1 (fr) * 1978-05-25 1979-12-12 Fbc Limited Tétrazines acaricides, larvicides et ovicides, compositions les contenant, procédé pour leur préparation et leur utilisation
EP0029657A2 (fr) * 1979-11-16 1981-06-03 Fbc Limited Dérivés de tétrazines pesticides, leur utilisation et leurs compositions, procédés pour leur préparation ainsi que leurs intermédiaires de préparation
US4414221A (en) * 1980-03-22 1983-11-08 Fbc Limited Pesticidal 1,2,4-triazole compounds
EP0635499A2 (fr) * 1993-07-21 1995-01-25 CHINOIN Gyogyszer és Vegyészeti Termékek Gyára RT. Dérivés de tétrazine actifs comme acaricides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005912A1 (fr) * 1978-05-25 1979-12-12 Fbc Limited Tétrazines acaricides, larvicides et ovicides, compositions les contenant, procédé pour leur préparation et leur utilisation
EP0029657A2 (fr) * 1979-11-16 1981-06-03 Fbc Limited Dérivés de tétrazines pesticides, leur utilisation et leurs compositions, procédés pour leur préparation ainsi que leurs intermédiaires de préparation
US4414221A (en) * 1980-03-22 1983-11-08 Fbc Limited Pesticidal 1,2,4-triazole compounds
EP0635499A2 (fr) * 1993-07-21 1995-01-25 CHINOIN Gyogyszer és Vegyészeti Termékek Gyára RT. Dérivés de tétrazine actifs comme acaricides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105104407A (zh) * 2012-03-10 2015-12-02 陕西韦尔奇作物保护有限公司 一种高效杀虫组合物
CN105104407B (zh) * 2012-03-10 2017-06-16 陕西韦尔奇作物保护有限公司 一种高效杀虫组合物
CN102702122A (zh) * 2012-05-16 2012-10-03 南通大学 由二氢四嗪氧化制备四嗪的方法
CN105037329A (zh) * 2015-09-06 2015-11-11 青岛科技大学 一种含氟四嗪吡唑类杀螨剂
CN105061399A (zh) * 2015-09-06 2015-11-18 青岛科技大学 一种含氟四嗪吡啶类化合物及其用途
CN105130962A (zh) * 2015-09-06 2015-12-09 青岛科技大学 一种四嗪吡唑类杀螨剂
CN105061399B (zh) * 2015-09-06 2017-03-22 青岛科技大学 一种含氟四嗪吡啶类化合物及其用途
WO2017036427A3 (fr) * 2015-09-06 2017-04-13 浙江博仕达作物科技有限公司 Acaricide de pyrazole de tétrazine
US11078192B2 (en) 2016-07-05 2021-08-03 Guangzhou Maxinovel Pharmaceuticals Co., Ltd. Aromatic acetylene or aromatic ethylene compound, intermediate, preparation method, pharmaceutical composition and use thereof
US11384048B2 (en) 2017-12-29 2022-07-12 Guangzhou Maxinovel Pharmaceuticals Co., Ltd. Aromatic vinyl or aromatic ethyl derivative, preparation method therefor, intermediate, pharmaceutical composition, and application

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EG22089A (en) 2002-07-31
CO5160333A1 (es) 2002-05-30
AU5405600A (en) 2001-01-09
EP1187818A1 (fr) 2002-03-20

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