EP0000388B1 - Pyridazinon(thiono)-phosphoric acid esters, process for their preparation and their use as insecticides and acaricides - Google Patents
Pyridazinon(thiono)-phosphoric acid esters, process for their preparation and their use as insecticides and acaricides Download PDFInfo
- Publication number
- EP0000388B1 EP0000388B1 EP78100345A EP78100345A EP0000388B1 EP 0000388 B1 EP0000388 B1 EP 0000388B1 EP 78100345 A EP78100345 A EP 78100345A EP 78100345 A EP78100345 A EP 78100345A EP 0000388 B1 EP0000388 B1 EP 0000388B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- spp
- thiono
- butyl
- preparation
- propyl
- 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
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241001065719 Tetranychus ludeni Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000254086 Tribolium <beetle> Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 244000000054 animal parasite Species 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MVEKXQBZICSLMC-UHFFFAOYSA-N butan-2-yl ethoxy hydrogen phosphate Chemical compound C(C)OOP(OC(C)CC)(O)=O MVEKXQBZICSLMC-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 244000078703 ectoparasite Species 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N methyl iso-propyl ketone Natural products CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- PECRFPZAFZIMEN-UHFFFAOYSA-N propan-2-ylhydrazine;sulfuric acid Chemical compound CC(C)NN.OS(O)(=O)=O PECRFPZAFZIMEN-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650905—Six-membered rings having the nitrogen atoms in the positions 1 and 2
Definitions
- the present invention relates to new pyridazinone (thiono) phosphoric acid esters, a process for their preparation and their use as insecticides and acaricides.
- O, O-dialkyl-O-pyridazinyl thionophosphoric acid esters e.g. O, O-diethyl-0- (1-phenyl-1,6-di-hydro-pyridaz (6) on (3) yl) -thionophosphoric acid esters are characterized by insecticidal and acaricidal activity (see US Pat. No. 2,759,937).
- Japanese patent application 74 12 702 0.0-dialkyl-0-3 (N-methyl-6-pyridazinonyl) (thiono) phosphoric acid ester with insecticidal properties is known.
- the pyridazinone (thiono) phosphoric acid esters mentioned at the beginning and described in more detail below are, as shown by comparative experiments, unexpectedly superior to the known structurally similar phosphoric acid esters as insecticides and acaricides.
- the pyridazinone (thiono) phosphoric acid esters (I) according to the invention have better insecticidal and acaricidal activity than the previously known compounds of analogous constitution and the same direction of action.
- the products according to the present invention thus represent a real enrichment of the technology.
- the 1,6-dihydro-3-hydroxy-1-iso-propyl-pyridazin (6) on (III) which is also to be used as the starting material can also be prepared by processes known from the literature.
- the process for the preparation of the compounds according to the invention is preferably carried out using suitable solvents or diluents.
- suitable solvents or diluents include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ether, e.g. Diethyl and dibutyl ether, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, and also nitriles, such as aceto and propionitrile.
- chlorinated hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ether, e.g. Diethyl
- All customary acid binders can be used as acid acceptors.
- Alkali carbonates and alcoholates such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.
- the reaction temperature can be varied within a wide range. Generally one works between 0 and 100 ° C, preferably at 20 to 60 ° C.
- the reaction is generally allowed to proceed at normal pressure.
- the starting components are preferably used in equivalent ratios.
- An excess of one or the other component has no significant advantages.
- the reaction components are generally combined in one of the specified solvents and are usually stirred at elevated temperature for one or more hours to complete the reaction. Then an organic solvent is added, e.g. Toiuol, and works up the organic phase as usual by washing, drying and distilling off the solvent.
- the new compounds are obtained in the form of oils, which usually cannot be distilled without decomposing, but by so-called “distillation", i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way.
- the refractive index is used to characterize them.
- the pyridazinone (thiono) phosphoric acid esters according to the invention are notable for excellent insecticidal and acaricidal activity. They act not only against plant, hygiene and storage pests, but also in the veterinary medical sector against animal parasites (ectoparasites), such as parasitic fly larvae. With low phytoxicity, the compounds have both a good action against sucking and eating insects and mites.
- the compounds according to the invention can be successfully used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.
- the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.
- customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc.,
- formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
- extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- organic solvents can, for example, also be used as auxiliary solvents.
- liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and the like Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
- Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers; natural rock powders, such as
- Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
- Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
- the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
- the active compounds according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.
- the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
- the active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.
- the application takes place in a customary manner adapted to the application forms.
- the active ingredients When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
- Emulsifier 1 part by weight of alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
- Cabbage plants (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are sprayed to runoff point with the active substance preparation.
- the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
- Emulsifier 1 part by weight of alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
- Bean plants Phaseolus vulgaris which are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are sprayed to runoff point with the preparation of active compound.
- the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
- the 1-isopropyl-1,6-dihydro-3-hydroxy-6-oxopyridazine to be used as the starting material can be prepared, for example, as follows:
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Die vorliegende Erfindung betrifft neue Pyridazinon(thiono)-phosphorsäureester, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Insektizide und Akarizide.The present invention relates to new pyridazinone (thiono) phosphoric acid esters, a process for their preparation and their use as insecticides and acaricides.
Es ist bereits bekannt, daß O,O-Dialkyl-O-pyridazinyl thiono-phosphorsäureester, z.B. O,O-Diäthyl-0-(1-phenyl-1,6-di-hydro-pyridaz(6) on (3)yl)-thionophosphorsäureester, sich durch insektizide und akarizide Wirksamkeit auszeichnen (vergleiche US-Patentschrift 2759 937).It is already known that O, O-dialkyl-O-pyridazinyl thionophosphoric acid esters, e.g. O, O-diethyl-0- (1-phenyl-1,6-di-hydro-pyridaz (6) on (3) yl) -thionophosphoric acid esters are characterized by insecticidal and acaricidal activity (see US Pat. No. 2,759,937).
Außerdem sind aus der japanischen Patentanmeldung 74 12 702 0,0-Dialkyl-0-3 (N-methyl-6-pyridazinonyl) (thiono)phosphorsäureester mit insektiziden Eigenschaften bekannt. Die eingangs erwähnten und unten näher beschriebenen Pyridazinon(thiono)phosphorsäureester sind wie durch Vergleichsversuche gezeigt werden konnte den bekannten strukturell ähnlich aufgebauten Phosphorsäureestern in ihrer Wirkung als Insektizide und Akarizide unerwartet überlegen.In addition, Japanese patent application 74 12 702 0.0-dialkyl-0-3 (N-methyl-6-pyridazinonyl) (thiono) phosphoric acid ester with insecticidal properties is known. The pyridazinone (thiono) phosphoric acid esters mentioned at the beginning and described in more detail below are, as shown by comparative experiments, unexpectedly superior to the known structurally similar phosphoric acid esters as insecticides and acaricides.
Es wurden nun die neuen Pyridazinon(thiono)-phosphor-säureester der Formel
worin
- R und R' fĂĽr gleiches oder verschiedenes Alkyl und
- X fĂĽr Sauerstoff oder Schwefel stehen.
wherein
- R and R 'for the same or different alkyl and
- X stands for oxygen or sulfur.
Diese neuen Verbindungen zeichnen sich durch starke insektizide und akarizide Eigenschaften aus.These new compounds are characterized by strong insecticidal and acaricidal properties.
Weiterhin wurde gefunden, daß die neuen Pyridazinon(thiono)-phosphorsäureester der Formel (I) erhalten werden, wenn man (Thiono)Phosphorsäurediesterhalogenide der Formel
- R, R' und X die oben angegebene Bedeutung haben und
- Hal fĂĽr Halogen, vorzugsweise Chlor, steht, mit 1,6-Di-hydro-3-hydroxy-1-isopropyl-pyridazin(6)on der Formel
- R, R 'and X have the meaning given above and
- Hal represents halogen, preferably chlorine, with 1,6-di-hydro-3-hydroxy-1-isopropyl-pyridazine (6) one of the formula
Überraschenderweise zeigen die erfindungsgemäßen Pyridazinon-(thiono)-phosphorsäureester (I) eine bessere insektizide und akarizide Wirkung als die vorbekannten Verbindungen analoger Konstitution und gleicher Wirkungsrichtung. Die Produkte gemäß vorliegender Erfindung stellen somit eine echte Bereicherung der Technik dar.Surprisingly, the pyridazinone (thiono) phosphoric acid esters (I) according to the invention have better insecticidal and acaricidal activity than the previously known compounds of analogous constitution and the same direction of action. The products according to the present invention thus represent a real enrichment of the technology.
Verwendet man beispielsweise O-Äthyl-O-sek.-butyl-phosphor-säurediesterchlorid und 1,6-Dihydro-3-hydroxy-1-isopropyl-pyridazin(6)on als Ausgangsmaterialien, so kann der Reaktionsverlauf durch das folgende Formelschema wiedergegeben werden:
- R und R'
unabhängig voneinanderfürgeradkettigesoder verzweigtes Atkyi mit 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen und - X für Schwefel.
- R and R '
independently for straight-chain or branched Atkyi with 1 to 8, in particular 1 to 4, carbon atoms and - X for sulfur.
Die als Ausgangsstoffe zu verwendenden (Thiono)Phosphorsäurediesterhalogenide (11) sind bekannt und nach literaturbekannten Verfahren auch technisch gut herstellbar. Als Beispiele dafür seien im einzelnen genannt:
- O,O-Dimethyl-, O,O-Diäthyl-, O,O-Di-n-propyl-, O,O-Di-isopropyl-, 0,0-DI-n-butyl-, O,O-Di-iso-butyl-, O,O-Di-sek.-butyl-, O-Methyl-O-äthyl-, O-Methyl-O-n-propyl-, O-Methyl-O-iso-propyl-, O-Methyl-O-n-butyl-, O-Methyi-O-iso-butyl-, O-Methyl-O-sek.-butyl-, 0-Athyl-O-n-propyl-, 0-Äthyl-O-isopropyl-, O-Äthyl-O-n-butyl, O-Äthyl-O-iso-butyl-, O-Äthyl-O-sek.-butyl-, O-n-Propyl-O-iso-propyl-, 0-n-Propyl-O-n-butyl-, O-n-Propyl-O-iso-butyl-, 0-n-Propyl-O-sek.-butyl-, O-iso-Propyl-O-n-butyl-, O-iso-Propyl-O-iso-butyl-, O-iso-Propyl-O-sek.-butylphosphorsäurediesterchlorid und die entsprechenden Thionoanalogen.
- O, O-dimethyl, O, O-diethyl, O, O-di-n-propyl, O, O-di-isopropyl, 0.0-DI-n-butyl, O, O-Di -iso-butyl-, O, O-di-sec.-butyl-, O-methyl-O-ethyl-, O-methyl-on-propyl-, O-methyl-O-iso-propyl-, O-methyl -On-butyl-, O-methyl-O-iso-butyl-, O-methyl-O-sec-butyl-, 0-ethyl-on-propyl-, 0-ethyl-O-isopropyl-, O-ethyl -On-butyl, O-ethyl-O-iso-butyl-, O-ethyl-O-sec-butyl-, on-propyl-O-iso-propyl-, 0-n-propyl-on-butyl-, On-propyl-O-iso-butyl-, 0-n-propyl-O-sec-butyl-, O-iso-propyl-on-butyl-, O-iso-propyl-O-iso-butyl-, O -iso-propyl-O-sec.-butylphosphoric diester chloride and the corresponding thiono analogues.
Das weiterhin als Ausgangsstoff zu verwendende 1,6-Dihydro-3-hydroxy-1-iso-propyl-pyridazin(6)on (III) kann ebenfalls nach literaturbekannten Verfahren hergestellt werden.The 1,6-dihydro-3-hydroxy-1-iso-propyl-pyridazin (6) on (III) which is also to be used as the starting material can also be prepared by processes known from the literature.
Das Verfahren zur Herstellung der erfindungsgemäßen Verbindungen wird bevorzugt under Mitverwendung geeigneterLösungs-oderVerdünnungsmitteldurchgeführt.Alssolchekommenpraktischalle inerten organischen Solventien infrage. Hierzu gehören insbesondere aliphatisclie und aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Benzin, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, oder Äther, z.B. Diäthyl-und Dibutyläther, Dioxan, ferner Ketone, beispielsweise Aceton, Methyläthyl-, Methyl-isopropyl- und Methyl-isobutylketon, außerdem Nitrile, wie Aceto- und Propionitril.The process for the preparation of the compounds according to the invention is preferably carried out using suitable solvents or diluents. As such, practically all inert organic solvents can be used. These include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ether, e.g. Diethyl and dibutyl ether, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, and also nitriles, such as aceto and propionitrile.
Als Säureakzeptoren können alle üblichen Säurebindemittel Verwendung finden. Besonders bewährt haben sich Alkalicarbonate und -alkoholate, wie Natrium- und Katiumcarbonat, -methylat bzw. -äthylat, ferner aliphatische, aromatische oder heterocyclische Amine, beispielsweise Trimethylamin, Triäthylamin, Dimethylanilin, Dimethylbenzylamin und Pyridin.All customary acid binders can be used as acid acceptors. Alkali carbonates and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.
Die Reaktionstemperatur kann innerhalb eines größeren Berreiches variiert werden. Im allgemeinen arbeitet man zwischen 0 und 100°C, vorzugsweise bei 20 bis 60°C.The reaction temperature can be varied within a wide range. Generally one works between 0 and 100 ° C, preferably at 20 to 60 ° C.
Die Umsetzung läßt man in allgemeinen bei Normaldruck ablaufen.The reaction is generally allowed to proceed at normal pressure.
Zur Durchführung des Verfahrens setzt man die Ausgangskomponenten vorzugsweise in äquivalenten Verhältnissen ein. Ein Überschuß der einen oder anderen Komponente bringt keine wesentlichen Vorteile. Die Reaktionskomponenten werden im allgemeinen in einem der angegebenen Lösungsmittelzusammengegeben und meist bei erhöhterTemperaturzurVervollständigung der Reaktion ein oder mehrere Stunden gerührt. Danach gibt man ein organisches Lösungsmittel, z.B. Toiuol, zu und arbeitet die organische Phase wie üblich durch Waschen, Trocknen und Abdestillieren des Lösungsmittels auf.To carry out the process, the starting components are preferably used in equivalent ratios. An excess of one or the other component has no significant advantages. The reaction components are generally combined in one of the specified solvents and are usually stirred at elevated temperature for one or more hours to complete the reaction. Then an organic solvent is added, e.g. Toiuol, and works up the organic phase as usual by washing, drying and distilling off the solvent.
Die neuen Verbindungen fallen in Form von Ölen an, die sich meist nicht unzersetztdestillieren lassen, jedoch durch sogenanntes "Andestillieren", d.h. durch längeres Erhitzen unter vermindertem Druck auf mäßig erhöhte Temperaturen von den letzten flüchtigen Anteilen befreit und auf diese Weise gereinigt werden. Zu ihrer Charakterisierung dient der Brechungsindex.The new compounds are obtained in the form of oils, which usually cannot be distilled without decomposing, but by so-called "distillation", i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way. The refractive index is used to characterize them.
Wie bereits mehrfach erwähnt, zeichnen sich die erfindungsgemäßen Pyridazinon(thiono)-phosphorsäureester durch eine hervorragende insektizide und akarizide Wirksamkeit aus. Sie wirken nicht nur gegen Pflanzen-, Hygiene- und Vorratsschädlinge, sondern auch auf dem veterinär-medizinischen Sektor gegen tierische Parasiten (Ektoparasiten), wie parasitierende Fliegenlarven. Die Verbindungen besitzen bei geringer Phytoxizität sowohl eine gute Wirkung gegen saugende als auch fressende Insekten und Milben.As already mentioned several times, the pyridazinone (thiono) phosphoric acid esters according to the invention are notable for excellent insecticidal and acaricidal activity. They act not only against plant, hygiene and storage pests, but also in the veterinary medical sector against animal parasites (ectoparasites), such as parasitic fly larvae. With low phytoxicity, the compounds have both a good action against sucking and eating insects and mites.
Aus diesem Grunde können die erfindungsgemäßen Verbindungen mit Erfolg im Pflanzenschutz sowie auf dem Hygiene-, Vorratsschutz- und Veterinärsektor als Schädlingsbekämpfungsmittel eingesetzt werden.For this reason, the compounds according to the invention can be successfully used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.
Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten und Spinnentieren die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistante Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:
- Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
- Aus der ordnung der Kiplopoda z.B. Blaniulus guttulatus.
- Aus der Ordnung der Chilopoda z.B. Geophilus carpophagus, Scutigera spec.
- Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.
- Aus der Ordnung der Thysanura z.B. Lepisma saccharina.
- Aus der Ordnung der Collembola z.B. Onychiurus armatus.
- Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
- Aus der Ordnung der Dermaptera z.B. Forficula auricularia.
- Aus der Ordnung der Isoptera z.B. Reticulitermes spp..
- Aus der Ordnung der Anoplura z.B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
- Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.
- Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.
- Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
- Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
- Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
- Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Orzyaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp.,Anthrenusspp.,Attagenusspp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
- Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
- Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp..
- Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
- Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ceratophyllus spp..
- Aus der Ordnung der Arachnida z.B. Scopio maurus, Latrodectus mactans.
- Aus der Ordnung der Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chlorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp..
- From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
- From the order of the Kiplopoda, for example, Blaniulus guttulatus.
- From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
- From the order of the Symphyla, for example, Scutigerella immaculata.
- From the order of the Thysanura, for example Lepisma saccharina.
- From the order of the Collembola, for example Onychiurus armatus.
- From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
- From the order of the Dermaptera, for example, Forficula auricularia.
- From the order of the Isoptera, for example Reticulitermes spp ..
- From the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
- From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.
- From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci.
- From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
- From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Phusoponosum., Myzus sppas spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
- From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Buccotisitriapp. , Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuacoellaellaellaellaellaellaellaellaellaellaellaellaella reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
- From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrisoamisilamisppas, Atomic spp. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenusspp., Lyctus spp., Meligethes aeneus, Ptiptus sppol., Pt ., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
- From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
- From the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp ..
- Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
- From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp ..
- From the order of the Arachnida, for example Scopio maurus, Latrodectus mactans.
- From the order of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes, Chlorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Schäume, Pasten, lösliche Pulver, Granulate, Aerosole, Suspensions-Emulsionskonzentrate, Saatgutpuder, Wirkstoff-imprägnierte Natur- und synthetische Stoffe, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut,ferner in Formulierungen mit Brennsätzen, wie Räucherpatronen, -dosen, -spiralen u.ä, sowie ULV-Kalt- und Warmnebel-Formulierungen.The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm mist formulations.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehender verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, oderAlkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Parafine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyl-äthylketon, Methylisobutylketon oderCyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normalerTemperatur und unterNormaldruckgasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe; natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; alsfeste TrägerstoffefürGranulate: gebrochene undfraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehle, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol- Äther, z.B. Alkylaryl-polyglykol-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z.B. Lignin-Sulfitablaugen und Methylcellulose.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and the like Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers; natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifiers and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents: eg lignin sulfite liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat.Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo-Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90%.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die Anwendung der erfindungsgemäßen Wirkstoffe erfolgt in Form ihrer handelsüblichen Formulierungen und/oder den aus diesen Formulierungen bereiteten Anwendungsformen.The active compounds according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.
Der Wirkstoffgehalt der aus den handelsĂĽblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Gew.- Wirkstoff, vorzugsweise zwischen 0,01 und 10 Gew.- liegen.The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.
Die Anwendung geschieht in einer den Anwendungsformen angepaĂźten ĂĽblichen Weise.The application takes place in a customary manner adapted to the application forms.
Bei der Anwendung gegen Hygiene- und Vorratsschädlinge zeichnen sich die Wirkstoffe durch eine hervorragende Residualwirkung auf Holz und Ton sowie durch eine gute Alkalistabilität auf gekälkten Unterlagen aus.When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegeben Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Mit derWirkstoffzubereitung werden Kohlpflanzen (Brassica oleracea), welche stark von der Pfirsichblattlaus (Myzus persicae) befallen sind, tropfnaĂź besprĂĽht.Cabbage plants (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are sprayed to runoff point with the active substance preparation.
Nach den angegebenen Zeiten wird die Abtötung in % bestimmt. Dabei bedeutet 100%, daß alle Blattläuse agetötet wurden; 0% bedeutet, daß keine Blattläuse abgetötet wurden.After the specified times, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle A hervor:
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Mit der Wirkstoffzubereitung werden Bohnenpflanzen (Phaseolus vulgaris), die stark von allen Entwicklungsstadien der gemeinen Spinnmilbe oder Bohnenspinnmilbe (Tetranychus urticae) befallen sind, tropfnaĂź besprĂĽht.Bean plants (Phaseolus vulgaris) which are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are sprayed to runoff point with the preparation of active compound.
Nach den angegebenen Zeiten wird die Abtötung in % bestimmt. Dabei bedeutet 100%, daß alle Spinnmilben abgetötet wurden; 0% bedeutet, daß keine Spinnmilben abgetötet wurden.After the specified times, the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle B hervor:
Ein Gemisch aus 15,4 g (0,1 Mol) 1 - Isopropyl - 1,6 - dihydro - 3 - hydroxy - 6 - oxo - pyridazin, 20,7 g (0,15 Mol) Kaliumcarbonat, 300 ml Acetonitril und 18,9 g (0,1 Mol) O,O - Diäthylthionophosphorsäurediesterchlorid wird 5 Stunden bei 45°C gerührt. Dann gibt man 400 ml Toluol zu und schüttelt das Reaktions-gemisch 2 mal mit je 300 ml Wasser. Die organische Phase wird über Natriumsulfat getrocknet, dann destilliert man das Lösungsmittel im Vakuum ab. Der Rückstand wird bei ca. 80°C andestilliert. Man erhält auf diese Weise 25,3 g (76% der Theorie) O,O - Diäthyl - O - [1 - iso - propyl - 1,6 - dihydro- 6 - oxo - pyridazin(3)yl] - thionophosphorsäureester in Form eines hellbraunen Öles mit dem.Brechungsindex .A mixture of 15.4 g (0.1 mol) of 1 - isopropyl - 1,6 - dihydro - 3 - hydroxy - 6 - oxo - pyridazine, 20.7 g (0.15 mol) of potassium carbonate, 300 ml of acetonitrile and 18 , 9 g (0.1 mol) of O, O - diethylthionophosphoric diester chloride is stirred at 45 ° C. for 5 hours. Then 400 ml of toluene are added and the reaction mixture is shaken twice with 300 ml of water each time. The organic phase is dried over sodium sulfate, then the solvent is distilled off in vacuo. The residue is distilled at approx. 80 ° C. In this way, 25.3 g (76% of theory) of O, O - diethyl - O - [1 - iso - propyl - 1,6 - dihydro-6 - oxo - pyridazin (3) yl] - thionophosphoric acid ester are obtained in the form of a light brown oil with the refractive index .
Das als Ausgangsmaterial zu verwendende 1-Isopropyl-1,6-dihydro-3-hydroxy-6-oxo-pyridazin kann zum Beispiel wie folgt hergestellt werden:
Zu einer Lösung von 73,8 g (0,6 Mol) Isopropylhydrazinsulfat in 180 ml Wasser und 10 mi konzentrierter Salzsäure gibt man bei 60°C 58,8 g (0,6 Mol) Maleinsäureanhydrid. Dan wird das Gemisch 3 Stunden unter Rückfluß gekocht und anschließend auf 0°C abgekühlt. Nach einer halben Stunden saugt man das ausgefallene Produkt ab. Man erhält so 59 g (64% der Theorie) 1 -isopropy)-1,6-dihydro-3-hydroxy-6-oxo-pyridazin in Form fabloser Kristalle mit dem Schmelzpunkt 148°C.58.8 g (0.6 mol) of maleic anhydride are added at 60 ° C. to a solution of 73.8 g (0.6 mol) of isopropyl hydrazine sulfate in 180 ml of water and 10 ml of concentrated hydrochloric acid. The mixture is then refluxed for 3 hours and then cooled to 0 ° C. After half an hour, the precipitated product is suctioned off. 59 g (64% of theory) of 1-isopropy) -1,6-dihydro-3-hydroxy-6-oxopyridazine are thus obtained in the form of fabulous crystals with a melting point of 148 ° C.
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2732101 | 1977-07-15 | ||
DE19772732101 DE2732101A1 (en) | 1977-07-15 | 1977-07-15 | PYRIDAZINONE (THIONO) PHOSPHORIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000388A1 EP0000388A1 (en) | 1979-01-24 |
EP0000388B1 true EP0000388B1 (en) | 1980-11-26 |
Family
ID=6014045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100345A Expired EP0000388B1 (en) | 1977-07-15 | 1978-07-11 | Pyridazinon(thiono)-phosphoric acid esters, process for their preparation and their use as insecticides and acaricides |
Country Status (19)
Country | Link |
---|---|
US (1) | US4219546A (en) |
EP (1) | EP0000388B1 (en) |
JP (1) | JPS5419988A (en) |
AR (1) | AR218924A1 (en) |
AT (1) | AT354812B (en) |
AU (1) | AU514922B2 (en) |
BR (1) | BR7804540A (en) |
CA (1) | CA1099270A (en) |
CS (1) | CS207631B2 (en) |
DE (2) | DE2732101A1 (en) |
DK (1) | DK318478A (en) |
EG (1) | EG13407A (en) |
ES (1) | ES471749A1 (en) |
IL (1) | IL55123A (en) |
IT (1) | IT7825663A0 (en) |
NZ (1) | NZ187841A (en) |
PT (1) | PT68271A (en) |
TR (1) | TR19756A (en) |
ZA (1) | ZA784027B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4571397A (en) * | 1982-03-05 | 1986-02-18 | Nissan Chemical Industries | Pyridazinone derivatives, preparation thereof, and agricultural and horticultural fungicidal, insecticidal, acaricidal, nematicidal compositions containing said derivatives |
JPH0350221U (en) * | 1989-09-22 | 1991-05-16 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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NL93954C (en) * | 1955-03-21 | 1900-01-01 | ||
US3100206A (en) * | 1961-05-05 | 1963-08-06 | Dow Chemical Co | O-(1,6-dihydro-6-oxo - 3 - pyridazinyl) o - alkyl phosphoramidate and phosphoramidothioate |
CH507304A (en) * | 1968-03-27 | 1971-05-15 | Bayer Ag | Process for the preparation of thionophosphonic acid esters |
JPS4912702B1 (en) * | 1970-09-11 | 1974-03-26 | ||
DE2343741A1 (en) * | 1973-08-30 | 1975-03-20 | Bayer Ag | 0-AETHYL-S-0- SQUARE CLAMP ON PYRIDAZ- (3) -ON- (6) -YL SQUARE CLIP ON -THIONOTHIOLPHOSPHORIC ACID, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES |
DE2531340A1 (en) * | 1975-07-12 | 1977-01-27 | Bayer Ag | O-AETHYL-O-PYRIDAZINYLTHIONOBENZENE PHOSPHONIC ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES |
DE2603993A1 (en) * | 1976-02-03 | 1977-08-04 | Bayer Ag | (THIONO) (THIOL) PYRIDAZINE PHOSPHORUS (PHOSPHONE) -AEUREESTER OR. -ESTERAMIDE, THE METHOD OF MANUFACTURING THEM AND THEIR USE AS INSECTICIDES AND ACARICIDES |
-
1977
- 1977-07-15 DE DE19772732101 patent/DE2732101A1/en not_active Withdrawn
-
1978
- 1978-06-29 US US05/920,506 patent/US4219546A/en not_active Expired - Lifetime
- 1978-07-10 PT PT68271A patent/PT68271A/en unknown
- 1978-07-11 DE DE7878100345T patent/DE2860340D1/en not_active Expired
- 1978-07-11 CS CS784647A patent/CS207631B2/en unknown
- 1978-07-11 EP EP78100345A patent/EP0000388B1/en not_active Expired
- 1978-07-12 TR TR19756A patent/TR19756A/en unknown
- 1978-07-12 AU AU37959/78A patent/AU514922B2/en not_active Expired
- 1978-07-12 IL IL55123A patent/IL55123A/en unknown
- 1978-07-12 NZ NZ187841A patent/NZ187841A/en unknown
- 1978-07-13 JP JP8460378A patent/JPS5419988A/en active Pending
- 1978-07-13 IT IT7825663A patent/IT7825663A0/en unknown
- 1978-07-13 CA CA307,314A patent/CA1099270A/en not_active Expired
- 1978-07-14 AT AT510578A patent/AT354812B/en not_active IP Right Cessation
- 1978-07-14 ES ES471749A patent/ES471749A1/en not_active Expired
- 1978-07-14 DK DK783184A patent/DK318478A/en unknown
- 1978-07-14 BR BR7804540A patent/BR7804540A/en unknown
- 1978-07-14 AR AR272959A patent/AR218924A1/en active
- 1978-07-14 ZA ZA00784027A patent/ZA784027B/en unknown
- 1978-07-15 EG EG441/78A patent/EG13407A/en active
Also Published As
Publication number | Publication date |
---|---|
AT354812B (en) | 1979-01-25 |
ES471749A1 (en) | 1979-02-01 |
DE2732101A1 (en) | 1979-01-25 |
AU3795978A (en) | 1980-01-17 |
JPS5419988A (en) | 1979-02-15 |
CA1099270A (en) | 1981-04-14 |
ZA784027B (en) | 1979-07-25 |
DE2860340D1 (en) | 1981-02-12 |
IT7825663A0 (en) | 1978-07-13 |
NZ187841A (en) | 1980-04-28 |
DK318478A (en) | 1979-01-16 |
BR7804540A (en) | 1979-03-06 |
EG13407A (en) | 1982-03-31 |
CS207631B2 (en) | 1981-08-31 |
PT68271A (en) | 1978-08-01 |
AR218924A1 (en) | 1980-07-15 |
US4219546A (en) | 1980-08-26 |
IL55123A0 (en) | 1978-09-29 |
AU514922B2 (en) | 1981-03-05 |
EP0000388A1 (en) | 1979-01-24 |
ATA510578A (en) | 1979-06-15 |
IL55123A (en) | 1982-05-31 |
TR19756A (en) | 1979-11-30 |
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