EP0000887B1 - Cyclopropyl-substituted pyrimidine-(4)-yl-(thiono)-thiol phosphoric (phosphonic) acid esters and ester amides, process for their preparation and their use as insecticides and acaricides - Google Patents

Cyclopropyl-substituted pyrimidine-(4)-yl-(thiono)-thiol phosphoric (phosphonic) acid esters and ester amides, process for their preparation and their use as insecticides and acaricides Download PDF

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Publication number
EP0000887B1
EP0000887B1 EP78100599A EP78100599A EP0000887B1 EP 0000887 B1 EP0000887 B1 EP 0000887B1 EP 78100599 A EP78100599 A EP 78100599A EP 78100599 A EP78100599 A EP 78100599A EP 0000887 B1 EP0000887 B1 EP 0000887B1
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Prior art keywords
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cyclopropyl
iso
propyl
ethyl
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German (de)
French (fr)
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EP0000887A1 (en
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Fritz Dr. Maurer
Ingeborg Dr. Hammann
Wolfgang Dr. Behrenz
Wilhelm Dr. Stendel
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof
    • 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
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3

Definitions

  • the present invention relates to new cyclopropyl-substituted pyrimidine (4) yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or ester amides, which have insecticidal and acaricidal properties, and a process for their preparation.
  • O, O-dialkyl-O-pyrimidinylthionophosphoric acid esters e.g. O, O-dimethyl-0- [2-ethyl-4-ethoxypyrimidine (6) yl] - or O, O-diethyl-O- [2-isopropyl-4-methyl-pyrimidine (6) yl] thionophosphoric acid ester
  • O, O-dialkyl-O-pyrimidinylthionophosphoric acid esters e.g. O, O-dimethyl-0- [2-ethyl-4-ethoxypyrimidine (6) yl] - or O, O-diethyl-O- [2-isopropyl-4-methyl-pyrimidine (6) yl] thionophosphoric acid ester
  • US Pat. No. 4,012,506 discloses cyclopropyl-substituted pyrimidine- (4) -yl-thio- and dithiophosphoric acid esters with insecticidal and acaricidal activity.
  • these active compounds are inferior to the compounds according to the invention in their insecticidal and acaricidal activity.
  • the cyclopropyl-substituted pyrimidine (4) yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or ester amides have a better insecticidal and acaricidal activity than the known pyrimidine (6) yl-thionophosphoric acid esters of analogous constitution and the same direction of action.
  • the compounds of the present invention thus represent a real enrichment of technology.
  • the (thiono) (thiol) phosphorus (phosphonic) acid ester or ester amide halides (II) to be used as starting materials are known and can also be prepared industrially by processes known from the literature. Examples include: O, O-dimethyl, O, O-diethyl, 0.0-di-n-propyl, O, O-di-iso-propyl, O, O-di- n-butyl-, O, O-di-iso-butyl-, O, O-Di-sek, -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-, O-ethyl-on-propyl-, 0- Ethyl-
  • the 2-cyclopropyl-4-hydroxy-pyrimidines (III) which are also to be used as starting materials can be prepared by processes known from the literature, for example by 2-Cyclopropyl-4,6-dihydroxy-pyrimidine alkylated, e.g. with dimethyl sulfate, and optionally the products obtained are halogenated, e.g. with bromine.
  • 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
  • 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 triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.
  • the reaction temperature can be varied within a wide range. in the 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 materials are usually used in an equivalent ratio.
  • An excess of one or the other component has no significant advantages.
  • the reactants are usually combined in one of the solvents mentioned above in the presence of an acid acceptor and stirred at elevated temperature for one or more hours to complete the reaction. Then the mixture is mixed with an organic solvent, e.g. Toluene, and works up the organic phase in the usual way by washing, drying and distilling off the solvent.
  • an organic solvent e.g. Toluene
  • the new compounds are often 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.
  • Some compounds are obtained in crystalline form and are characterized by their melting point.
  • 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
  • formulations are made in a known manner, e.g. 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, e.g. organic solvents can 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.
  • water e.g. organic solvents can also be used as auxiliary 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, e.g.
  • Petroleum fractions oil 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 pressure, e.g.
  • Aerosol propellants such as halogenated hydrocarbons and 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; So 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 stems; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • 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 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.
  • the active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, diving (dipping), spraying (spraying), pouring-on and spot-on) and powdering and by parenteral use in the form of, for example, injection.
  • 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 leaves (Brassica oleracea) are sprayed to runoff point and populated with horseradish leaf beetle larvae (Phaedon cochleariae).
  • 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%.
  • the compounds of Examples 2, 3, 4 and 5 have an excellent activity which is clearly superior to that of the compounds known from the prior art.
  • the condition of the test animals is checked 3 days after starting the experiments.
  • the death rate is determined in%.
  • the active substance in question is mixed with the stated solvent in a ratio of 1: 2 and the concentrate thus obtained is diluted with water to the desired concentration.
  • the 2-cyclopropyl-4-hydroxy-pyrimidines to be used as starting materials can be prepared, for example, as follows:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (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)
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  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

Die vorliegende Erfindung betrifft neue cyclopropylsubstituierte Pyrimidin(4)yl(thiono)(thiol)-phosphor(phosphon)-säureester bzw. -esteramide, welche insektizide und akarizide Eigenschaften besitzen sowie ein Verfahren zu ihrer Herstellung.The present invention relates to new cyclopropyl-substituted pyrimidine (4) yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or ester amides, which have insecticidal and acaricidal properties, and a process for their preparation.

Es ist bereits bekannt, daß O,O-Dialkyl-O-pyrimidinylthionophosphorsäureester, z.B. O,O-Dimethyl-0-[2-äthyl-4-äthoxypyrimidin(6)yl]- bzw. O,O-Diäthyl-O-[2-isopropyl-4-methyl- pyrimidin(6)yl]-thionophosphorsäureester, insektizide und akarizide Eigenschaften haben (vergleiche US-Patentschriften 2 754 243 und 3 862 188).It is already known that O, O-dialkyl-O-pyrimidinylthionophosphoric acid esters, e.g. O, O-dimethyl-0- [2-ethyl-4-ethoxypyrimidine (6) yl] - or O, O-diethyl-O- [2-isopropyl-4-methyl-pyrimidine (6) yl] thionophosphoric acid ester, have insecticidal and acaricidal properties (see U.S. Patents 2,754,243 and 3,862,188).

Außerdem sind aus der US-PS 4.012.506 cyclopropylsubstituierte Pyrimidin-(4)-yl-thio- und dithiophosphorsäureester mit insektizider und akarizider Wirksamkeit bekannt. Diese Wirkstoffe sind jedoch, wie entsprechende Vergleichsversuche zeigen, den erfindungsgemäßen Verbindungen in der insektiziden und akariziden Wirksamkeit unterlegen.In addition, US Pat. No. 4,012,506 discloses cyclopropyl-substituted pyrimidine- (4) -yl-thio- and dithiophosphoric acid esters with insecticidal and acaricidal activity. However, as corresponding comparative experiments show, these active compounds are inferior to the compounds according to the invention in their insecticidal and acaricidal activity.

Es wurden nun die neuen cyclopropylsubstituierten Pyrimidin-(4)-yl(thiono)(thiol)-phosphor(phosphon)-säureester bzw. -esteramide der Formel

Figure imgb0001
synthetisiert,
in welcher

  • R für Alkyl,
  • R1 für Alkyl, Alkoxy, Alkylthio, Monoalkylamino oder Phenyl,
  • R2 für Alkyl,
  • R3 für Wasserstoff, Halogen oder Alkyl und
  • X für Sauerstoff oder Schwefel stehen.
The new cyclopropyl-substituted pyrimidine- (4) -yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or ester amides of the formula have now been found
Figure imgb0001
 synthesized,
in which
  • R for alkyl,
  • R 1 represents alkyl, alkoxy, alkylthio, monoalkylamino or phenyl,
  • R 2 for alkyl,
  • R 3 is hydrogen, halogen or alkyl and
  • X stands for oxygen or sulfur.

Diese neuen Verbindungen besitzen eine ausgezeichnete insektizide und akarizide Wirkung.These new compounds have excellent insecticidal and acaricidal activity.

Weiterhin wurde gefunden, daß man die cyclopropylsubstituierten Pyrimidin(4)yl(thiono)(thiol)-phosphor(phosphon)-säureester bzw. -esteramide der Formel (I) erhält, wenn man (Thiono)(Thiol)-Phosphor(phosphon)-säureester- bzw. -esteramidhalogenide der Formel

Figure imgb0002
in welcher

  • R, R1 und X die oben angegebene Bedeutung haben und
  • Hal für Halogen, vorzugsweise Chlor, steht, mit 2-Cyclopropyl-4-hydroxy-pyrimidinen der Formel
    Figure imgb0003
    in welcher
  • R2 und R3 die oben angegebene Bedeutung haben, gegebenenfalls in Gegenwart eines Säureakzeptors oder gegebenenfalls in Form der Alkali-, Erdalkali- oder Ammoniumsalze und gegebenenfalls in Gegenwart eines Lösungs- oder Verdünnungsmittels umsetzt.
Furthermore, it was found that the cyclopropyl-substituted pyrimidine (4) yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or esteramides of the formula (I) are obtained if (thiono) (thiol) -phosphorus (phosphonic) acid ester or ester amide halides of the formula
Figure imgb0002
 in which
  • R, R 1 and X have the meaning given above and
  • Hal represents halogen, preferably chlorine, with 2-cyclopropyl-4-hydroxy-pyrimidines of the formula
    Figure imgb0003
     in which
  • R 2 and R 3 have the meaning given above, if appropriate in the presence of an acid acceptor or if appropriate in the form of the alkali metal, alkaline earth metal or ammonium salts and if appropriate in the presence of a solvent or diluent.

Überraschenderweise zeigen die erfindungsgemäßen cyclopropylsubstituierten Pyrimidin(4)yl(thiono)(thiol)-phosphor(phosphon)-säureester bzw. -esteramide eine bessere insektizide und akarizide Wirkung als die bekannten Pyrimidin(6)yl-thionophosphorsäureester analoger Konstitution und gleicher Wirkungsrichtung. Die Verbindungen vorliegender Erfindung stellen somit eine echte Bereicherung der Technik dar.Surprisingly, the cyclopropyl-substituted pyrimidine (4) yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or ester amides have a better insecticidal and acaricidal activity than the known pyrimidine (6) yl-thionophosphoric acid esters of analogous constitution and the same direction of action. The compounds of the present invention thus represent a real enrichment of technology.

Verwendet man beispielsweise O-Äthyl-S-n-propyl-thionothiolphosphorsäurediesterchlorid und 2-Cyclopropyl-5-methyl-6-isopropyloxy-4-hydroxy-pyrimidin als Ausgangsstoffe, so kann der Reaktionsverlauf durch das folgende Formelschema wiedergegeben werden:

Figure imgb0004
If, for example, O-ethyl-Sn-propyl-thionothiolphosphoric diester chloride and 2-cyclopropyl-5-methyl-6-isopropyloxy-4-hydroxy-pyrimidine 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 für geradkettiges oder verzweigtes Alkyl mit 1 bis 6, insbesondere 1 bis 4, Kohlenstoffatomen,
  • R1 für geradkettiges oder verzweigtes Alkyl bzw. Alkoxy, Alkylthio oder Monoalkylamino mit 1 bis 6 insbesondere 1 bis 4, Kohlenstoffatomen je Alkylrest oder Phenyl,
  • R2 für geradkettiges oder verzweigtes Alkyl mit 1 bis 6, insbesondere 1 bis 4, Kohlenstoffatomen,
  • R3 für Wasserstoff, Chlor, Brom, oder geradkettiges oder verzweigtes Alkyl mit 1 bis 5 Kohlenstoffatomen, insbesondere Methyl oder Athyl, 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 for straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms,
  • R 1 for straight-chain or branched alkyl or alkoxy, alkylthio or monoalkylamino with 1 to 6, in particular 1 to 4, carbon atoms per alkyl radical or phenyl,
  • R 2 for straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms,
  • R 3 represents hydrogen, chlorine, bromine, or straight-chain or branched alkyl having 1 to 5 carbon atoms, in particular methyl or ethyl, and
  • X for sulfur.

Die als Ausgangsstoffe zu verwendenden (Thiono)(Thiol)Phosphor(phosphon)-säureester-bzw -esteramidhalogenide (II) sind bekannt und nach literaturbekannten Verfahren auch technisch gut herstellbar. Als Beispiele dafür seien im einzelnen genannt: O,O-Dimethyl-, O,O-Diäthyl-, 0,0-Di-n-propyl-, O,O-Di-iso-propyl-, O,O-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-Methyl-O-iso-butyl-, O-Methyl-O-sek.-butyl-, O-Äthyl-O-n-propyl-, 0-Athyl-O-iso-propyl-, O-Äthyl-O-n-butyl-, O-Äthyl-O-sek.-butyl-, O-Äthyl-O-iso-butyl-, O-n-Propyl-O-butyl- bzw. O-iso-Propyl-O-butylphosphorsäurediesterchlorid und die entsprechenden Thionoanalogen, ferner O,S-Dimethyl-, O,S-Diäthyl-, O,S-Di-n-propyl-, O,S-Di-iso-propyl-, O,S-Di-n-butyl-, O,S-Di-iso-butyl-, O-Äthyl-S-n-propyl-, O-Äthyl-S-iso-propyl-, O-Äthyl-S-n-butyl-, O-Äthyl-S-sek.-butyl-, 0-n-Propyl-S-äthyl-, 0-n-Propyl-S-iso-propyl-, 0-n-Butyl-S-n-propyl- und O-sek.-Butyl-S-äthylthiolphosphorsäurediesterchlorid und die entsprechenden Thionoanalogen, ferner O-Methyl-, O-Äthyl-, O-n-Propyl-, O-iso-Propyl-, O-n-Butyl-, O-iso-Butyl- bzw. O-sek.-Butyl-methan- bzw. -äthan-, -n-propan-, -iso-propan-, -n-butan-, -iso-butan-, -sek.-butan- bzw. -phenyl-phosphonsäureesterchlorid und die entsprechenden Thionoanalogen, und O,N-Dimethyl-, 0-Methyl-N-äthyl-, 0-Methyl-N-n-propyl-, O-Methyl-N-iso-propyl-, O-Äthyl-N-methyl-, O,N-Diäthyl-, O-Äthyl-N-n-propyl-, O-Äthyl-N-iso-propyl-, O-n-Propyl-N-methyl-, 0-n-Propyl-N-äthyl-, O,N-Di-n-propyl-, O-n-Propyl-N-iso-propyl-, O-iso-Propyl-N-methyl-, 0-iso-Propyl-N-äthyl-, O-iso-Propyl-N-n-propyl, O,N-Di-iso-propyl-, O-n-Butyl-N-methyl-, 0-n-Butyl-N-äthyl-, 0-n-Butyl-N-n-propyl-, O-n-Butyl-N-iso-propyl-, O-iso-Butyl-N-methyl-, 0-iso-Butyl-N-äthyl-, O-iso-Butyl-N-n-propyl-, O-iso-Butyl-N-iso-propyl-, O-sek.-Butyl-N-methyl-, O-sek.-Butyl-N-äthyl-, O-sek.-Butyl-N-n-propyl- und 0-sek.-Butyl-N-iso-propylphosphor- säuremonoesteramidchlorid und die entsprechenden Thionoanalogen.The (thiono) (thiol) phosphorus (phosphonic) acid ester or ester amide halides (II) to be used as starting materials are known and can also be prepared industrially by processes known from the literature. Examples include: O, O-dimethyl, O, O-diethyl, 0.0-di-n-propyl, O, O-di-iso-propyl, O, O-di- n-butyl-, O, O-di-iso-butyl-, O, O-Di-sek, -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-, O-ethyl-on-propyl-, 0- Ethyl-O-iso-propyl-, O-ethyl-on-butyl-, O-ethyl-O-sec-butyl-, O-ethyl-O-iso-butyl-, on-propyl-O-butyl- or O-iso-propyl-O-butylphosphoric diester chloride and the corresponding thiono analogues, furthermore O, S-dimethyl-, O, S-diethyl-, O, S-di-n-propyl-, O, S-di-iso-propyl -, O, S-di-n-butyl-, O, S-di-iso-butyl-, O-ethyl-Sn-propyl-, O-ethyl-S-iso-propyl-, O-ethyl-Sn- butyl-, O-ethyl-S-sec-butyl-, 0-n-propyl-S-ethyl-, 0-n-propyl-S-iso-propyl-, 0-n-butyl-Sn-propyl- and O-sec.-butyl-S-ethylthiolphosphoric diester chloride and the corresponding thiono analogues, furthermore O-methyl, O-ethyl, on-propyl, O-iso-propyl, on-butyl, O-iso-butyl and O-sec.-butyl methane or - ethane, -n-propane, -iso-propane, -n-butane, -iso-butane, -sec.-butane or -phenyl-phosphonic acid ester chloride and the corresponding thiono analogues, and O, N-dimethyl -, 0-Methyl-N-ethyl, 0-methyl-Nn-propyl, O-methyl-N-iso-propyl, O-ethyl-N-methyl, O, N-diethyl, O-ethyl -Nn-propyl-, O-ethyl-N-iso-propyl-, on-propyl-N-methyl-, 0-n-propyl-N-ethyl-, O, N-di-n-propyl-, On- Propyl-N-iso-propyl, O-iso-propyl-N-methyl, 0-iso-propyl-N-ethyl, O-iso-propyl-Nn-propyl, O, N-di-iso-propyl -, On-butyl-N-methyl, 0-n-butyl-N-ethyl, 0-n-butyl-Nn-propyl, On-butyl-N-iso-propyl, O-iso-butyl N-methyl, 0-iso-butyl-N-ethyl, O-iso-butyl-Nn-propyl, O-iso-butyl-N-iso-propyl, O-sec-butyl-N-methyl -, O-sec.-butyl-N-ethyl-, O-sec.-butyl-Nn-propyl and 0-sec.-butyl-N-iso-propylphosphoric acid monoesteramide chloride and the corresponding thiono analogues.

Die weiterhin als Ausgangsstoffe zu verwendenden 2-Cyclopropyl-4-hydroxy-pyrimidine (III) können nach literaturbekannten Verfahren hergestellt werden, indem man z.B. 2-Cyclopropyl-4,6-dihydroxy-pyrimidin alkyliert, z.B. mit Dimethylsulfat, und gegebenenfalls die erhaltenen Produkte halogeniert, z.B. mit Brom.The 2-cyclopropyl-4-hydroxy-pyrimidines (III) which are also to be used as starting materials can be prepared by processes known from the literature, for example by 2-Cyclopropyl-4,6-dihydroxy-pyrimidine alkylated, e.g. with dimethyl sulfate, and optionally the products obtained are halogenated, e.g. with bromine.

Als Beispiele dafür seien im einzelnen genannt: 6-Methoxy-, 6-Äthoxy, 6-n-Propoxy-, 6-iso-Propoxy-, 6-n-Butoxy-, 6-sek.-Butoxy-, 6-iso-Butoxy- und 6-tert.-Butoxy-2-cyclopropyl-4-hydroxy- pyrimidin, ferner 5-Chlor-6-methoxy-; 5-Chlor-6-äthoxy-, 5-Chlor-6-n-propoxy-, 5-Chlor-6-iso- propoxy-, 5-Chlor-6-n-butoxy-, 5-Chlor-6-sek.-butoxy-, 5-Chlor-6-iso-butoxy- und 5-Chlor-6-tert.-butoxy-2-cyclopropyl-4-hydroxy-pyrimidin, ferner 5-Brom-6-methoxy- 5-Brom-6-äthoxy-, 5-Brom-6-n-propoxy-, 5-Brom-6-iso-propoxy-, 5-Brom-6-n-butoxy-, 5-Brom-6-sek.-butoxy-, 5-Brom-6-iso-butoxy-und 5-Brom-6-tert.-butoxy-2-cyclopropyl-4-hydroxy-pyrimidin, ferner 5-Methyl-6-methoxy-, 5-Methyl-6-äthoxy-, 5-Methyl-6-n-propoxy-, 5-Methyl-6-iso-propoxy-, 5-Methyl-6-n-butoxy-, 5-Methyl-6-sek.- butoxy-, 5-Methyl-6-iso-butoxy- und 5-Methyl-6-tert.-butoxy-2-cyclopropyl-4-hydroxy-pyrimidin, ferner 5-Äthyl-6-methoxy-, 5-Äthyl-6-äthoxy-, 5-Äthyl-6-n-propoxy-, 5-Äthyl-6-iso-propoxy-, 5-Äthyl-6-n-butoxy-, 5-Äthyl-6-sek.-butoxy-, 5-Äthyl-6-iso-butoxy- und 5-Äthyl-6-tert.-butoxy-2-cyclopropyl-4-hydroxy-pyrimidin.Examples of these are: 6-methoxy-, 6-ethoxy, 6-n-propoxy-, 6-iso-propoxy-, 6-n-butoxy-, 6-sec-butoxy-, 6-iso- Butoxy- and 6-tert-butoxy-2-cyclopropyl-4-hydroxy-pyrimidine, furthermore 5-chloro-6-methoxy- ; 5-chloro-6-ethoxy-, 5-chloro-6-n-propoxy-, 5-chloro-6-iso-propoxy-, 5-chloro-6-n-butoxy-, 5-chloro-6-sec. -butoxy-, 5-chloro-6-iso-butoxy- and 5-chloro-6-tert-butoxy-2-cyclopropyl-4-hydroxy-pyrimidine, furthermore 5-bromo-6-methoxy-5-bromo-6 -ethoxy-, 5-bromo-6-n-propoxy-, 5-bromo-6-iso-propoxy-, 5-bromo-6-n-butoxy-, 5-bromo-6-sec-butoxy-, 5th -Bromo-6-iso-butoxy and 5-bromo-6-tert-butoxy-2-cyclopropyl-4-hydroxy-pyrimidine, furthermore 5-methyl-6-methoxy-, 5-methyl-6-ethoxy-, 5-methyl-6-n-propoxy-, 5-methyl-6-iso-propoxy-, 5-methyl-6-n-butoxy-, 5-methyl-6-sec-butoxy-, 5-methyl-6 -iso-butoxy- and 5-methyl-6-tert-butoxy-2-cyclopropyl-4-hydroxy-pyrimidine, furthermore 5-ethyl-6-methoxy-, 5-ethyl-6-ethoxy-, 5-ethyl- 6-n-propoxy, 5-ethyl-6-iso-propoxy, 5-ethyl-6-n-butoxy, 5-ethyl-6-sec-butoxy, 5-ethyl-6-iso-butoxy - And 5-ethyl-6-tert-butoxy-2-cyclopropyl-4-hydroxy-pyrimidine.

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-, Methylisopropyl- und Methylisobutylketon, 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 Triäthylamin, Trimethylamin, 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 triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.

Die Reaktionstemperatur kann innerhalb eines größeren Bereichs 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. in the generally 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 Ausgangsmaterialien meist in äquivalentem Verhältnis ein. Ein Überschuß der einen oder anderen Komponente bringt keine wesentlichen Vorteile. Die Reaktionspartner werden meist in einem der oben angegebenen Lösungsmittel in Gegenwart eines Säureakzeptors vereinigt und bei erhöhter Temperatur zur Vervollständigung der Reaktion eine oder mehrere Stunden gerührt. Danach versetzt man die Mischung mit einem organischen Lösungsmittel, z.B. Toluol, und arbeitet die organische Phase in üblicher Weise durch Waschen, Trocknen und Abdestillieren des Lösungsmittels auf.To carry out the process, the starting materials are usually used in an equivalent ratio. An excess of one or the other component has no significant advantages. The reactants are usually combined in one of the solvents mentioned above in the presence of an acid acceptor and stirred at elevated temperature for one or more hours to complete the reaction. Then the mixture is mixed with an organic solvent, e.g. Toluene, and works up the organic phase in the usual way by washing, drying and distilling off the solvent.

Die neuen Verbindungen fallen oft 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. Einige Verbindungen fallen in kristalliner Form an und werden durch ihren Schmelzpunkt charakterisiert.The new compounds are often 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. Some compounds are obtained in crystalline form and are characterized by their melting point.

Wie bereits mehrfach erwähnt, zeichnen sich die erfindungsgemäßen cyclopropylsubstituierten Pyrimidin(4)yl(thiono)(thiol)-phosphor(phosphon)-säureester bzw. -esteramide durch eine hervorragende insektizide und akarizide Wirkung aus. Sie wirken gegen Pflanzen-, Hygiene- und Vorratsschädlinge und auf dem veterinär-medizinischen Sektor. Sie besitzen bei geringer Phytotoxizität sowohl eine gute Wirkung gegen saugende als auch fressende Insekten und Milben.As already mentioned several times, the cyclopropyl-substituted pyrimidine (4) yl (thiono) (thiol) -phosphorus (phosphonic) acid esters or ester amides are distinguished by an excellent insecticidal and acaricidal action. They act against plant, hygiene and storage pests and in the veterinary medical sector. With low phytotoxicity, they have a good effect against sucking as well as feeding 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 Spinntieren, die in der Landwirtschaft, in Forsten, im Vorrats- und Material-schutz 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 Isopoda z.B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Aus der Ordnung der Diplopoda 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 femoraiis.'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, Panolis flammea, 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., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., 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. Scorpio 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., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
With good plant tolerance and favorable warm-blood toxicity, the active ingredients are suitable for controlling animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods 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 Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • From the order of the Diplopoda, 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 femoraiis.'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, Phusopalosum, Myzus sonppi. Empoasca 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., Agristella sppber, Bucculisellappl ., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kauelliaellaellaiaellaella eu , Capua 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 chrysoisisamamysppas, Atomic spp. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus holole, Ptinus holpp. Tribolium spp., 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 Scorpio 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, Chorioptes 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 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 Streckmitteln 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 Kohlenwasserstoffe, 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; also 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 made in a known manner, e.g. 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, e.g. organic solvents can 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, e.g. 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 pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and 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; So 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 stems; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. 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.

Die Anwendung der erfindungsgemäßen Wirkstoffe geschieht im Veterinärsektor in bekannter Weise, wie durch orale Anwendung in Form von beispielsweise Tabletten, Kapseln, Tränken, Granulaten, durch dermale Anwendung in Form beispielsweise des Tauchens (Dippen), Sprühens (Sprayen), Aufgießens (pour-on and spot-on) und des Einpuderns sowie durch parenterale Anwendung in Form beispielsweise der Injektion.The active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, diving (dipping), spraying (spraying), pouring-on and spot-on) and powdering and by parenteral use in the form of, for example, injection.

BEISPIEL AEXAMPLE A Phaedon-Larven--TestPhaedon larvae test

Figure imgb0005
Figure imgb0005

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 besprüht man Kohlblätter (Brassica oleracea) tropfnaß und besetzt sie mit Meerrettichblattkäfer-Larven (Phaedon cochleariae).With the preparation of active substance, cabbage leaves (Brassica oleracea) are sprayed to runoff point and populated with horseradish leaf beetle larvae (Phaedon cochleariae).

Nach bestimmten Zeiten wird die Abtötung in % bestimmt. In diesem Test zeigten z.B. die Verbindungen der Beispiele 1, 3, 6, 9 und 14 eine ausgezeichnete Wirkung, die der Wirkung der aus dem Stand der Technik bekannten Verbindungen deutlich überlegen ist.After certain times, the kill is determined in%. In this test e.g. the compounds of Examples 1, 3, 6, 9 and 14 have an excellent action which is clearly superior to the action of the compounds known from the prior art.

BEISPIEL BEXAMPLE B Tetranychus-Test (resistent)Tetranychus test (resistant)

Figure imgb0006
Figure imgb0006

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 bestimmten Zeiten wird die Abtötung in % bestimmt. In diesem Test zeigen z.B. die Verbindungen der Beispiele 2, 3, 4 und 5 eine ausgezeichnete Wirkung, die derjenigen der aus dem Stand der Technik bekannten Verbindungen deutlich überlegen ist.After certain times, the kill is determined in%. In this test e.g. the compounds of Examples 2, 3, 4 and 5 have an excellent activity which is clearly superior to that of the compounds known from the prior art.

BEISPIEL CEXAMPLE C LD100-TestLD100 test

Figure imgb0007
2 Gewichtsteile Wirkstoff werden in 1000 Volumenteilen Lösungsmittel aufgenommen. Die so erhaltene Lösung wird mit weiterem Lösungsmittel auf die gewünschten Konzentrationen verdünnt.
Figure imgb0007
 2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution thus obtained is diluted to the desired concentrations with further solvent.

2,5 ml Wirkstofflösung werden in eine Petrischale pipettiert. Auf dem Boden der Petrischale befindet sich ein Filterpapier mit einem Durchmesser von etwa 9,5 cm. Die Petrischale bleibt so lange offen stehen, bis das Lösungsmittel vollständig verdunstet ist. Je nach Konzentration der Wirkstofflösung ist die Menge Wirkstoff pro m2 Filterpapier verschieden boch. Anschließend gibt man etwa 25 Testtiere in die Petrischale und bedeckt sie mit einem Glasdeckel.2.5 ml of the active ingredient solution are pipetted into a petri dish. On the bottom of the Petri dish is a filter paper with a diameter of approximately 9.5 cm. The petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m 2 of filter paper is different. Then add about 25 test animals to the Petri dish and cover them with a glass lid.

Der Zustand der Testtiere wird 3 Tage nach Ansetzen der Versuche kontrolliert. Bestimmt wird die Abtötung in %.The condition of the test animals is checked 3 days after starting the experiments. The death rate is determined in%.

In diesem Test zeigen z.B. die Verbindungen der Beispiele 1, 2, 3 und 4 eine ausgezeichnete Wirkung, die derjenigen der aus dem Stand der Technik bekannten Verbindungen deutlich überlegen ist.In this test e.g. the compounds of Examples 1, 2, 3 and 4 have an excellent activity which is clearly superior to that of the compounds known from the prior art.

BEISPIEL DEXAMPLE D Test mit parasitierenden FliegenlarvenTest with parasitic fly larvae

Figure imgb0008
1 Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 20 Gewichtsteile der betreffenden aktiven Substanz mit der angegebenen Menge des Emulgators und verdünnt das so erhaltene Gemisch mit Wasser auf die gewünschte Konzentration.
Figure imgb0008
 1 To produce a suitable preparation of active compound, 20 parts by weight of the active substance in question are mixed with the stated amount of the emulsifier and the mixture thus obtained is diluted with water to the desired concentration.

Etwa 20 Fliegenlarven (Lucilia cuprina) werden in ein mit Wattestopfen entsprechender Größe beschicktes Teströhrchen gebracht, welches ca. 3 ml einer 20%igen Eigelbpulver-Suspension in Wasser enthält. Auf diese Eigelbpulver-Suspension werden 0,5 ml der Wirkstoffzubereitung gebracht. Nach 24 Stunden wird der Abtötungsgrad in % bestimmt.About 20 fly larvae (Lucilia cuprina) are placed in a test tube filled with cotton plugs of the appropriate size, which contains approx. 3 ml of a 20% egg yolk powder suspension in water. 0.5 ml of the active ingredient preparation is added to this egg yolk powder suspension. After 24 hours, the degree of destruction is determined in%.

In diesem Test zeigten z.B. die Verbindungen die Beispiele 1 bis 7, 9 und 11 eine ausgezeichnete Wirkung.In this test e.g. the compounds Examples 1 to 7, 9 and 11 have an excellent effect.

BEISPIEL EEXAMPLE E Test mit parasitierenden adulten Rinderzecken (Böophilus microplus res.)Parasitic adult tick test (Böophilus microplus res.)

Figure imgb0009
Figure imgb0009

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man die betreffende aktive Substanz mit dem angegebenen Lösungsmittel im Verhältnis 1:2 und verdünnt das so erhaltene Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, the active substance in question is mixed with the stated solvent in a ratio of 1: 2 and the concentrate thus obtained is diluted with water to the desired concentration.

10 adulte Rinderzecken (B. microplus res.) werden in der zu testenden Wirkstoffzubereitung 1 Min. getaucht. Nach Überführung in Plastikbecher und Aufbewahrung in einem klimatisierten Raum wird der Abtötungsgrad in Prozent bestimmt.10 adult beef ticks (B. microplus res.) Are immersed in the active ingredient preparation to be tested for 1 min. After being transferred to a plastic cup and stored in an air-conditioned room, the degree of destruction is determined in percent.

In diesem Test zeigt z.B. die Verbindung des Beispiels 4 eine ausgezeichnete Wirkung.In this test e.g. the compound of Example 4 has an excellent effect.

Herstellungsbeispiele

Figure imgb0010
Manufacturing examples
Figure imgb0010

BEISPIEL 1EXAMPLE 1

Eine Mischung aus 16,6 g (0,1 Mol) 2-Cyclopropyl-4-hydroxy-6-methoxy-pyrimidin, 20,7 g (0,15 Mol) Kaliumcarbonat, 16 g (0,1 Mol) 0,0-Dimethylthionophosphorsäurediesterchlorid und 300 ml Acetonitril wird 4 Stunden bei 50°C gerührt. Dann kühlt man den Ansatz auf Raumtemperatur ab und schüttelt ihn nach Zugabe von 400 ml Toluol zweimal mit je 300 ml Wasser aus. Die organische Phase wird abgetrennt, über Natriumsulfat getrocknet, im Vakuum vom Lösungsmittel befreit und der Rückstand andestilliert. Man erhält so 22,6 g (78% der Theorie) 0,0-Dimethyl-0-[2-cyclopropyl-6-methoxy- pyrimidin(4)yl]-thionophosphorsäureester in Form eines gelben Öles mit dem Brechungsindex nß3: 1,5441.A mixture of 16.6 g (0.1 mol) of 2-cyclopropyl-4-hydroxy-6-methoxy-pyrimidine, 20.7 g (0.15 mol) of potassium carbonate, 16 g (0.1 mol) of 0.0 -Dimethylthionophosphoric diester chloride and 300 ml of acetonitrile is stirred at 50 ° C for 4 hours. Then the mixture is cooled to room temperature and, after adding 400 ml of toluene, it is shaken twice with 300 ml of water each time. The organic phase is separated off, dried over sodium sulfate, freed from solvent in vacuo and the residue is distilled. 22.6 g (78% of theory) of 0.0-dimethyl-0- [2-cyclopropyl-6-methoxypyrimidine (4) yl] thionophosphoric acid ester are thus obtained in the form of a yellow oil with a refractive index of 3: 1 5441.

Analog Beispiel 1 können die folgenden Verbindungen der Formel

Figure imgb0011
hergestellt werden:
Figure imgb0012
 Analogously to Example 1, the following compounds of the formula
Figure imgb0011
 getting produced:
Figure imgb0012

Die als Ausgangsmaterialien zu verwendenden 2-Cyclopropyl-4-hydroxy-pyrimidine können z.B. wie folgt hergestellt werden:

Figure imgb0013
The 2-cyclopropyl-4-hydroxy-pyrimidines to be used as starting materials can be prepared, for example, as follows:
Figure imgb0013

BEISPIEL aEXAMPLE a

Zu einer Lösung von 76 g (0,5 Mol) 2-Cyclopropyl-4,6-dihydroxypyrimidin in 250 ml 2 n Natronlauge tropft man bei 50°C 76 g (0,6 Mol) Dimethylsulfat. Durch gleichzeitige Zugabe von 2 n Natronlauge wird der pH-Wert der Reaktionslösung auf 8 bis 8,2 gehalten. Dann wird 2 Stunden unter weiterer pH-Kontrolle bei 50°C nachgerührt. Anschließend kühlt man das Gemisch auf 0°C ab und saugt das ausgefallene Produkt ab. Man erhält auf diese Weise 33 g (40% der Theorie) 2-Cyclopropyl-4-hydroxy-6-methoxypyrimidin in Form farbloser Kristalle mit dem Schmelzpunkt 186°C.76 g (0.6 mol) of dimethyl sulfate are added dropwise at 50 ° C. to a solution of 76 g (0.5 mol) of 2-cyclopropyl-4,6-dihydroxypyrimidine in 250 ml of 2N sodium hydroxide solution. The pH of the reaction solution is kept at 8 to 8.2 by simultaneous addition of 2N sodium hydroxide solution. The mixture is then stirred at 50 ° C. for a further 2 hours under further pH control. The mixture is then cooled to 0 ° C. and the precipitated product is suctioned off. In this way, 33 g (40% of theory) of 2-cyclopropyl-4-hydroxy-6-methoxypyrimidine are obtained in the form of colorless crystals with a melting point of 186 ° C.

In analoger Weise können die folgenden Verbindungen der Formel

Figure imgb0014
hergestellt werden:
Figure imgb0015
 The following compounds of the formula
Figure imgb0014
 getting produced:
Figure imgb0015

BEISPIEL iEXAMPLE i

Figure imgb0016
Figure imgb0016

Eine Lösung von 12,4 g (0,075 Mol) 2-Cyclopropyl-4-hydroxy-6-methoxypyrimidin in 100 ml Methylenchlorid wird bei Raumtemperatur mit 12 g (0,075 Mol) Brom versetzt. Man rührt das Gemisch 1 Stunde bei Raumtemperatur nach, wäscht es dann mit 100 ml 2,5%iger Natriumhydrogencarbonatlösung und mit 100 ml Wasser und trocknet die organische Phase über Natriumsulfat. Nach Abdestillieren des Lösungsmittels bleiben 6,7 g (36% der Theorie) 2-Cyclopropyl-4-hydroxy-5-brom-6-methoxy-pyrimidin als farbloses Pulver mit dem Schmelzpunkt 174°C (Z) zurück.A solution of 12.4 g (0.075 mol) of 2-cyclopropyl-4-hydroxy-6-methoxypyrimidine in 100 ml of methylene chloride is mixed with 12 g (0.075 mol) of bromine at room temperature. The mixture is stirred for 1 hour at room temperature, then washed with 100 ml of 2.5% sodium hydrogen carbonate solution and with 100 ml of water and the organic phase is dried over sodium sulfate. After the solvent has been distilled off, 6.7 g (36% of theory) of 2-cyclopropyl-4-hydroxy-5-bromo-6-methoxy-pyrimidine remain as a colorless powder with a melting point of 174 ° C. (Z).

Claims (5)

1. Compounds of the formula
Figure imgb0023
in which
R represents alkyl,
R1 represents alkyl, alkoxy, alkylthio, monoalkylamino or phenyl,
R2 represents alkyl,
R3 represents hydrogen, halogen or alkyl and
X represents oxygen or sulphur.
2. A process for the preparation of compounds of formula (I) characterised in that (thiono)(thiol)-phosphoric(phosphonic) acid ester halides or ester-amide halides of the formula
Figure imgb0024
in which
R, R1 and X have the meaning stated in claim 1 and
Hal represents halogen, preferably chlorine,

are reacted with 2-cyclopropyl-4-hydroxy-pyrimidines of the formula
Figure imgb0025
in which
R2 and R3 have the meaning stated in claim 1, optionally in the presence of an acid acceptor or optionally in the form of the alkali metal salts, alkaline earth metal salts of ammonium salts and optionally in the presence of a solvent or a diluent.
3. Insecticides and acaricides, characterised in that they contain compounds according to claim 1.
4. The use of compounds according to claim 1 for combating insects and Arachnida.
5. A process for the preparation of insecticides and acaricides, characterised in that compounds according to claim 1 are mixed with extenders and/or surface-active agents.
EP78100599A 1977-08-19 1978-08-07 Cyclopropyl-substituted pyrimidine-(4)-yl-(thiono)-thiol phosphoric (phosphonic) acid esters and ester amides, process for their preparation and their use as insecticides and acaricides Expired EP0000887B1 (en)

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DE19772737401 DE2737401A1 (en) 1977-08-19 1977-08-19 CYCLOPROPYL-SUBSTITUTED PYRIMIDINE (4) YL (THIONO) - (THIOL) -PHOSPHOR (PHOSPHON) -ACIDESTERS OR. -ESTERAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES
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AU531545B2 (en) * 1979-08-06 1983-08-25 Dow Chemical Company, The Phosphorus esters of alkylcycloalkyl- 5-pyrimidinols
US4426379A (en) 1982-01-27 1984-01-17 Chevron Research Company Insecticidal 2-oxo-3-dialkoxyphosphoro-5-cyclopropyl-1,3,4-oxadiazoline
US4486421A (en) * 1982-11-22 1984-12-04 The Dow Chemical Company Insecticidal phosphorus derivatives of 4-pyrimidinols
US4588711A (en) * 1982-11-22 1986-05-13 The Dow Chemical Company Insecticidal phosphorus derivatives of 6-cycloalkyl-4-pyrimidinols
US4486422A (en) * 1982-11-22 1984-12-04 The Dow Chemical Company Insecticidal phosphorus derivatives of 5-pyrimidinols
US4489068A (en) * 1983-04-28 1984-12-18 The Dow Chemical Company Method and composition for enhancing the insecticidal activity of certain organophosphorus compounds
DE3445465A1 (en) * 1984-12-13 1986-06-19 Bayer Ag, 5090 Leverkusen PYRIMIDINYL THIONOPHOSPHORIC ACID ESTER
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CA1091671A (en) 1980-12-16
PL209120A1 (en) 1979-05-21
ES472672A1 (en) 1979-02-16
DE2737401A1 (en) 1979-02-22
TR19984A (en) 1980-05-09
US4202889A (en) 1980-05-13
CS199216B2 (en) 1980-07-31
AU3905878A (en) 1980-02-21

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