EP0000388A1 - 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 PDF

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Publication number
EP0000388A1
EP0000388A1 EP78100345A EP78100345A EP0000388A1 EP 0000388 A1 EP0000388 A1 EP 0000388A1 EP 78100345 A EP78100345 A EP 78100345A EP 78100345 A EP78100345 A EP 78100345A EP 0000388 A1 EP0000388 A1 EP 0000388A1
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Prior art keywords
spp
thiono
butyl
propyl
phosphoric acid
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German (de)
French (fr)
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EP0000388B1 (en
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Fritz Dr. Maurer
Ingeborg Dr. Hammann
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Bayer AG
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    • 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.
  • the pyridazinone (thiono) phosphoric acid esters (I) according to the invention have a better insecticidal and acaricidal action 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 Practically all inert organic solvents can be considered as such.
  • 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.
  • chlorinated hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlor
  • Alkali carbonates have proven particularly useful and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, furthermore aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine.
  • the reaction temperature can be varied within a wide range. In general, 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.
  • An organic solvent e.g. Toluene, and work 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 can usually not 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 not only work against plant, hygiene and storage pests, but also in the veterinary medical sector against animal parasites (ectoparasites), such as parasitic fly larvae. With low phytotoxicity, 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.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Dysdercus intermedius Piesma auadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Bemisia tabaci Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalobpouscillusphypsophile spp.
  • Cacoecia podana Capua reticulana, Choristonewra fumiferana, Clysia ambiguella, Homona magnanimn, Tortrix viridana.
  • Psylliodes chryaocephala Epilachna varivestis, Atomaria spp., Oryzttphilus surinamensis, Anthonomua spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assiailis, Hypera postica, Spp., Spp., Spp spp., Meligethes aeneus, Ptinua spp., Niptus hololeucus, Gibbiun psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderua spp., Melolontha melolontha, Aaphimallon solatitialis,
  • Bibio hortulanus Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Assblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spptes, ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • 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 fog 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. as well 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.
  • Solvent 3 parts by weight of acetone 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 preparation of active compound.
  • the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • Solvent 3 parts by weight of acetone 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:

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  • 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)

Abstract

Beschrieben sind Pyridazinon(thiono)-phosphorsäureester der Formel <IMAGE> worin R und R' für gleiches oder verschiedenes Alkyl und X für Sauerstoff oder Schwefel stehen. Diese Verbindungen zeigen eine insektizide und akarizide Wirkung und werden als Schädlingsbekämpfungsmittel verwendet. Man erhält diese Verbindungen, wenn man (Thiono)- phosphorsäure-diester-halogenide mit 1,6-Dihydro-3-hydroxy-1-isopropyl-pyridazin(6)on umsetzt.Pyridazinone (thiono) -phosphoric acid esters of the formula <IMAGE> are described in which R and R 'represent the same or different alkyl and X represents oxygen or sulfur. These compounds have an insecticidal and acaricidal activity and are used as pesticides. These compounds are obtained if (thiono) phosphoric acid diester halides are reacted with 1,6-dihydro-3-hydroxy-1-isopropylpyridazine (6) one.

Description

Die vorliegende Erfindung betrifft neue Pyridazinon(thiono)-phosphorsäureester, ein Verf.-hren 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 0,0-Dialkyl-O-pyridazinyl-thionophosphorsäureester, z.B. 0,0-Diäthyl-0-(1-phenyl-1,6-di- hydro-pyridaz(6)on(3)yl)-thionophosphorsäureester, sich durch insektizide und akarizide Wirksamkeit auszeichnen (vergleiche US-Patentschrift 2 759 937).It is already known that 0.0-dialkyl-O-pyridazinyl-thionophosphoric acid esters, e.g. 0,0-diethyl-0- (1-phenyl-1,6-di-hydro-pyridaz (6) on (3) yl) -thionophosphoric acid esters, which are distinguished by insecticidal and acaricidal activity (compare US Pat. No. 2,759,937) .

Es wurden nun die neuen Pyridazinon(thiono)-phosphorsäureester der Formel

Figure imgb0001
synthetisiert, worin

  • R und R' für gleiches oder verschiedenes Alkyl und
  • X für Sauerstoff oder Schwefel stehen.
There were now the new pyridazinone (thiono) phosphoric acid esters of the formula
Figure imgb0001
 synthesized in which
  • 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. Weiterhin wurde gefunden, daß die neuen Pyridazinon(thiono)-phosphorsäureester der Formel (I) erhalten werden, wenn man (Thiono)Phosphorsäurediesterhalogenide der Formel

Figure imgb0002
in welcher R,R' und X die oben angegebene Bedeutung haben und Hal für Halogen, vorzugsweise Chlor, steht, mit 1,6-Di- hydro-3-hydroxy-1-isopropyl-pyridazin(6)on der Formel
Figure imgb0003
gegebenenfalls in Form der Alkali-, Erdalkali- oder Ammoniumsalze oder gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Lösungsmittels umsetzt.These new compounds are characterized by strong insecticidal and acaricidal properties. Furthermore, it was found that the new pyridazinone (thiono) phosphoric acid esters of the formula (I) are obtained if (thiono) phosphoric diester halides of the formula
Figure imgb0002
 in which 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
Figure imgb0003
 optionally in the form of the alkali, alkaline earth or ammonium salts or optionally in the presence of an acid acceptor tors and optionally in the presence of a solvent.

Überraschenderweise zeigen die erfindungsgemäßen Pyridazinon-(thiono)-phosphorsäureester (I) eine bessere insektizide und akarizide Wirkung als die vorbekannten Verbirduigen 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 a better insecticidal and acaricidal action 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 0-Äthyl-0-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:

Figure imgb0004
If, for example, 0-ethyl-0-sec-butyl-phosphoric acid diester chloride and 1,6-dihydro-3-hydroxy-1-isopropylpyridazine (6) one are used as starting materials, the course of the reaction can be represented by the following formula :
Figure imgb0004

Die zu verwendenden Ausgangsstoffe sind durch die Formeln (II) und (III) allgemein definiert. Vorzugsweise stehen darin jedoch

  • R und R' unabhängig voneinander für geradkettiges oder verzweigtes Alkyl mit 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen und
  • X für Schwefel.
The starting materials to be used are generally defined by the formulas (II) and (III). Preferably, however, are in it
  • R and R 'independently of one another for straight-chain or branched alkyl having 1 to 8, in particular 1 to 4, carbon atoms and
  • X for sulfur.

Die als Ausgangsstoffe zu verwendenden (Thiono)Phosphorsäure- diesterhalogenide (II) sind bekannt und nach literaturbekannten Verfahren auch technisch gut herstellbar. Als Beispiele dafür seien im einzelnen genannt:

  • 0,0-Dimethyl-, 0,0-Diäthyl-, 0,0-Di-n-propyl-, 0,0-Di-isopropyl-, 0,0-Di-n-butyl-, 0,0-Di-iso-butyl-, 0,0-Di-sek.- butyl-, 0-Methyl-0-äthyl-, 0-Methyl-O-n-propyl-, 0-Methyl-0-iso-propyl-, 0-Methyl-0-n-butyl-, 0-Methyl-O-iso-butyl-, 0-Methyl-0-sek.-butyl-, 0-Äthyl-0-n-propyl-, 0-Äthyl-0-isopropyl-, 0-äthyl-0-n-butyl-, 0-Äthyl-0-iso-butyl-, 0-Äthyl-0-sek.-butyl-,0-n-Propyl-O-iso-propyl-, 0-n-Propyl-0-n-butyl-, 0-n-Propyl-O-iso-butyl-, 0-n-Propyl-0-sek.-butyl-, 0-iso-Propyl-0-n-butyl-, 0-iso-Propyl-O-iso-butyl-, 0-iso-Propyl-O-sek.-butylphosphorsäurediesterchlorid und die entsprechenden Thionoanalogen.
The (thiono) phosphoric acid diester halides (II) to be used as starting materials are known and can also be prepared industrially by processes known from the literature. The following are examples of this:
  • 0.0-dimethyl, 0.0-diethyl, 0.0-di-n-propyl, 0.0-di-isopropyl, 0.0-di-n-butyl, 0.0-di -iso-butyl-, 0.0-di-sec-butyl-, 0-methyl-0-ethyl-, 0-methyl-on-propyl-, 0-methyl-0-iso-propyl-, 0-methyl -0-n-butyl-, 0-methyl-O-iso-butyl-, 0-methyl-0-sec-butyl-, 0-ethyl-0-n-propyl-, 0-ethyl-0-isopropyl- , 0-ethyl-0-n-butyl-, 0-ethyl-0-iso-butyl-, 0-ethyl-0-sec-butyl-, 0-n-propyl-O-iso-propyl-, 0- n-propyl-0-n-butyl-, 0-n-propyl-O-iso-butyl-, 0-n-propyl-0-sec-butyl-, 0-iso-propyl-0-n-butyl- , 0-iso-propyl-O-iso-butyl, 0-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 unter Mitverwendung geeigneter Lösungs- oder Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Solventien infrage. Hierzu gehören insbesondere aliphatische 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. Practically all inert organic solvents can be considered as such. 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 Kaliumcarbonat, -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 have proven particularly useful and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, furthermore aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

Die Reaktionstemperatur kann innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man zwischen 0 und 100 C, vorzugsweise bei 2o bis 60°C.The reaction temperature can be varied within a wide range. In general, one works between 0 and 100 ° C, preferably at 20 to 60 ° C.

Die Umsetzung läßt man im 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 Lösungsmittel zusammengegeben und meist bei erhöhter Temperatur zur Vervollständigung der Reaktion ein oder mehrere Stunden gerührt.Danach gibt man ein organisches Lösungsmittel, z.B. Toluol, 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. An organic solvent, e.g. Toluene, and work 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 unzersetzt destillieren 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 can usually not 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 Phytotoxizität 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 not only work against plant, hygiene and storage pests, but also in the veterinary medical sector against animal parasites (ectoparasites), such as parasitic fly larvae. With low phytotoxicity, 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 Vorräts- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:

  • Aus der Ordnung der Iaopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
With good plant tolerance and favorable warm-blood toxicity, the active ingredients are suitable for combating animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of supplies and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
  • From the order of the Iaopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

Aus der Ordnung der Diplopoda z. B. Blaniulus guttulatus.From the order of the Diplopoda z. B. Blaniulus guttulatus.

Aus der Ordnung der Chilopoda z. B. Geophilus carpophagus, Scutigera spec.From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

Aus der Ordnung der Symphyla z. B. Scutigerella immaculata.From the order of the Symphyla z. B. Scutigerella immaculata.

Aus der Ordnung der Thysanura z. B. Leplsma saocharina.From the order of the Thysanura z. B. Leplsma saocharina.

Aus der Ordnung der Collembola z. B. Onychiurus armtus.From the order of the Collembola z. B. O nychiurus armtus.

Aus der Ordnung der Orthoptera z. B. Blatta orientalis,From the order of the Orthoptera z. B. Blatta orientalis,

Periplaneta americana, Leucophaea maderae, Blattella germanica,Periplaneta americana, Leucophaea maderae, Blattella germanica,

Acheta domeaticus, Gryllotalpa spp., Locuata migratoriaAcheta domeaticus, Gryllotalpa spp., Locuata migratoria

miaratorioides, Melanoplus differentialis, Schtatocerca gregarla.miaratorioides, Melanoplus differentialis, Schtatocerca gregarla.

Aus der Ordnung er Dermaptera z. B. Forficula auricularia.From the order he Dermaptera z. B. Auricular Forficula.

Aus der Ordnung der Isoptera z. B. Reticulitermea spp..From the order of the Isoptera z. B. Reticulitermea spp ..

Aus der Ordnung der Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.From the order of the 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.From the order of the Mallophaga e.g. Trichodectes spp., Damalinea sPP.

Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.

Aus der Ordnung der Heteroptera z.B. Eurygaster spp.,From the order of the Heteroptera e.g. Eurygaster spp.,

Dysdercus intermedius, Piesma auadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.Dysdercus intermedius, Piesma auadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

Aus der Ordnung der Homoptera z.B. Aleurodes brassicae,From the order of the Homoptera e.g. 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., Euscells bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp..Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalobpouscillusphypsophile spp. Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp ..

Aus der Ordnung der Lepidoptera z. B. Pectinophora gosrypiella, 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 inaulana, Heliothis spp., Laphygma exigua, Mameatra brasaicae, Panolis flammea,From the order of the Lepidoptera z. B. Pectinophora gosrypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberistiisellappellappiapplppellappiappella, Phyll , Heliothis spp., Laphygma exigua, Mameatra brasaicae, Panolis flammea,

Prodsnia litura, Spodoptera spp., Trichoplusia ni,Prodsnia litura, Spodoptera spp., Trichoplusia ni,

Carpocapaa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella,Carpocapaa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella,

Cacoecia podana, Capua reticulana, Choristonewra fumiferana, Clysia ambiguella, Homona magnanimn, Tortrix viridana.Cacoecia podana, Capua reticulana, Choristonewra fumiferana, Clysia ambiguella, Homona magnanimn, Tortrix viridana.

Aus der Ordnung der Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidiua obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidiua obtectus, Acanthoscelides obtectus, Hylotrupes ba j ulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,

Psylliodes chryaocephala, Epilachna varivestis, Atomaria spp., Oryzttphilus surinamensis, Anthonomua spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assiailis, Hypera postica, Dermsates spp., Trogoderma spp., Anthrenus spp., Attaasnus spp., Lyctus spp., Meligethes aeneus, Ptinua spp., Niptus hololeucus, Gibbiun psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderua spp., Melolontha melolontha, Aaphimallon solatitialis,Psylliodes chryaocephala, Epilachna varivestis, Atomaria spp., Oryzttphilus surinamensis, Anthonomua spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assiailis, Hypera postica, Spp., Spp., Spp spp., Meligethes aeneus, Ptinua spp., Niptus hololeucus, Gibbiun psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderua spp., Melolontha melolontha, Aaphimallon solatitialis,

Costslytra zealandica.Costslytra zealandica.

Aus der Ordnung der Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the 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 sop., Tannia spp.,From the order of the Diptera e.g. 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 Oestrus spp., Hypoderma spp., Tabanus sop., Tannia spp.,

Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.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..From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp ..

Aus der Ordnung der Arachnida z.B. Scorpio maurus,From the order of the Arachnida e.g. Scorpio maurus,

Latrodectus mactans.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., Assblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp..From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Assblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spptes, ., 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 fog formulations.

Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden 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, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kuhlenwasseratoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig 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; als feste Trägerstoffe für Granulate:

  • gebrochene und fraktionierte 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, optionally 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 cooling water substances, 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 their 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 liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated carbon substances such as butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, 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 and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; 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 handelsüblichen 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 angepaßten üblichen 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.

Beispiel AExample A Myzus-Test (Kontakt-Wirkung)Myzus test (contact effect)

Lösungsmittel: 3 Gewichtsteile Aceton Emulgator : 1 Gewichtsteil AlkylarylpolyglykolätherSolvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

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 Kohlpflanzen (Brassica oleracea), welche stark von der Pfirsichblattlaus (Myzus persicae) befallen sind, tropfnaß besprüht.Cabbage plants (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), 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 Blattläuse abgetötet 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:

Figure imgb0005
Figure imgb0006
 Active substances, active substance concentrations, evaluation times and results are shown in Table A below:
Figure imgb0005
Figure imgb0006

Beispiel B Example B Tetranychus-Test (resistent)Tetranychus test (resistant)

Lösungsmittel: 3 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil AlkylarylpolyglykolätherSolvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

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, tropfnaß besprüht.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:

Figure imgb0007
Active substances, active substance concentrations, evaluation times and results are shown in Table B below:
Figure imgb0007

HerstellungsbeispieleManufacturing examples Beispiel 1:Example 1:

Figure imgb0008
Ein Gemisch aus 15,4 g (o,l Mol) 1-Isopropyl-1,6-dihydro-3-hydroxy-6-oxo-pyridazin, 20,7 g (o,15 Mol) Kaliumcarbonat, 3oo ml Acetonitril und 18,9 g (o,l Mol) 0,0-Diäthylthionophosphorsäurediesterchlorid wird 5 Stunden bei 45°C gerührt. Dann gibt man 4oo ml Toluol zu und schüttelt das Reaktionsgemisch 2 mal mit je 3oo 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) 0,0-Diäthyl-0-[1-iso-propyl-1,6-dihydro-6-oxo- pyridazin(3)yl]-thionophosphorsäureester in Form eines hellbraunen Öles mit dem Brechungsindex
Figure imgb0009
 : 1,5078.
Figure imgb0008
 A mixture of 15.4 g (o, l mol) of 1-isopropyl-1,6-dihydro-3-hydroxy-6-oxo-pyridazine, 2 0, 7 g (o.15 mole) of potassium carbonate, 3oo ml of acetonitrile and 18.9 g (0.1 mol) of 0.0-diethylthionophosphoric diester chloride is stirred at 45 ° C. for 5 hours. Then add 4oo ml of toluene and shake the reaction mixture twice with 3oo ml of water. 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 0.0-diethyl-0- [1-iso-propyl-1,6-dihydro-6-oxopyridazin (3) yl] thionophosphoric acid ester are obtained in the form of a light brown oil with the refractive index
Figure imgb0009
 : 1.5 0 78.

Analog Beispiel 1 können die folgenden Verbindungen der Formel

Figure imgb0010
hergestellt werden:
Figure imgb0011
 Analogously to Example 1, the following compounds of the formula
Figure imgb0010
 getting produced:
Figure imgb0011

Das als Ausgangsmaterial zu verwendende 1-Isopropyl-1,6-dihydro-3-hydroxy-6-oxo-pyridazin kann zum Beispiel wie folgt hergestellt werden:

Figure imgb0012
The 1-isopropyl-1,6-dihydro-3-hydroxy-6-oxopyridazine to be used as the starting material can be prepared, for example, as follows:
Figure imgb0012

Zu einer Lösung von 73,8 g (0,6 Mol) Isopropylhydrazinsulfat in 18o ml Wasser und lo ml konzentrierter Salzsäure gibt man bei 6o°C 58,8 g (0,6 Mol) Maleinsäureanhydrid. Dann 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-Isopropyl-1,6-dihydro-3-hydroxy-6-oxo-pyridazia in Form farbloser Kristalle mit dem Schmelzpunkt 148°C.To a solution of 73.8 g (0 6 mol) Isopropylhydrazinsulfat in 18o ml of water and lo ml of concentrated hydrochloric acid are added 58.8 g (0.6 mol) of maleic anhydride at 6o ° C. The mixture is then refluxed for 3 hours and then cooled to 0 ° C. After half an hour, the precipitated product is suctioned off. This gives 59 g (64% of theory) of 1-isopropyl-1,6-dihydro-3-hydroxy-6-oxopyridazia in the form of colorless crystals with a melting point of 148 ° C.

Claims (6)

1. Verbindungen der Formel
Figure imgb0013
worin R und R' für gleiches oder verschiedenes Alkyl und X für Sauerstoff oder Schwefel stehen. 1. Compounds of the formula
Figure imgb0013
 wherein R and R 'for the same or different alkyl and X stands for oxygen or sulfur. 2. Verfahren zur Herstellung von Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, daß man (Thiono)Phosphorsäure- diesterhalogenide der Formel
Figure imgb0014
in welcher R, R' und X die in Anspruch 1 angegebene Bedeutung haben und Hal für Halogen, vorzugsweise Chlor, steht, mit 1,6-Dihydro-3-hydroxy-1-isopropyl-pyridazin(6)on der Formel
Figure imgb0015
gegebenenfalls in Form der Alkali-, Erdalkali- oder Ammoniumsalze oder gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Lösungsmittels umsetzt. 2. A process for the preparation of compounds according to claim 1, characterized in that (thiono) phosphoric acid diester halides of the formula
Figure imgb0014
 in which R, R 'and X have the meaning given in claim 1 and Hal represents halogen, preferably chlorine, with 1,6-dihydro-3-hydroxy-1-isopropyl-pyridazine (6) one of the formula
Figure imgb0015
 if appropriate in the form of the alkali metal, alkaline earth metal or ammonium salts or if appropriate in the presence of an acid acceptor and if appropriate in the presence of a solvent. 3. Insektizides und akarizides Mittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung gemäß Anspruch 1.3. Insecticidal and acaricidal agent, characterized by a content of at least one compound according to claim 1. 4. Verfahren zur Bekämpfung von Insekten und Spinnentieren, dadurch gekennzeichnet, daß man Verbindungen gemäß Anspruch 1 auf Insekten und Spinnentiere oder ihren Lebensraum einwirken läßt.4. A method for controlling insects and arachnids, characterized in that compounds according to claim 1 are allowed to act on insects and arachnids or their habitat. 5. Verwendung von Verbindungen gemäß Anspruch 1 zur Bekämpfung von Insekten und Spinnentieren.5. Use of compounds according to claim 1 for controlling insects and arachnids. 6. Verfahren zur Herstellung von insektiziden und akariziden Mitteln, dadurch gekennzeichnet, daß man Verbindungen gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt.6. A process for the preparation of insecticidal and acaricidal agents, characterized in that compounds according to claim 1 are mixed with extenders and / or surface-active agents.
EP78100345A 1977-07-15 1978-07-11 Pyridazinon(thiono)-phosphoric acid esters, process for their preparation and their use as insecticides and acaricides Expired EP0000388B1 (en)

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DE2732101 1977-07-15

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ZA (1) ZA784027B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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

Citations (3)

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US3100206A (en) * 1961-05-05 1963-08-06 Dow Chemical Co O-(1,6-dihydro-6-oxo - 3 - pyridazinyl) o - alkyl phosphoramidate and phosphoramidothioate
JPS4912702B1 (en) * 1970-09-11 1974-03-26
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

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NL93954C (en) * 1955-03-21 1900-01-01
CH507304A (en) * 1968-03-27 1971-05-15 Bayer Ag Process for the preparation of thionophosphonic acid esters
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3100206A (en) * 1961-05-05 1963-08-06 Dow Chemical Co O-(1,6-dihydro-6-oxo - 3 - pyridazinyl) o - alkyl phosphoramidate and phosphoramidothioate
JPS4912702B1 (en) * 1970-09-11 1974-03-26
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

Also Published As

Publication number Publication date
JPS5419988A (en) 1979-02-15
US4219546A (en) 1980-08-26
BR7804540A (en) 1979-03-06
IT7825663A0 (en) 1978-07-13
CS207631B2 (en) 1981-08-31
ES471749A1 (en) 1979-02-01
IL55123A (en) 1982-05-31
ZA784027B (en) 1979-07-25
DE2860340D1 (en) 1981-02-12
AU3795978A (en) 1980-01-17
IL55123A0 (en) 1978-09-29
AU514922B2 (en) 1981-03-05
PT68271A (en) 1978-08-01
ATA510578A (en) 1979-06-15
AT354812B (en) 1979-01-25
TR19756A (en) 1979-11-30
AR218924A1 (en) 1980-07-15
NZ187841A (en) 1980-04-28
EG13407A (en) 1982-03-31
DE2732101A1 (en) 1979-01-25
DK318478A (en) 1979-01-16
EP0000388B1 (en) 1980-11-26
CA1099270A (en) 1981-04-14

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