EP0000198B1 - N,n-dialkyl-0-pyrimidinyl- carbamic acid estes, process for their preparation and their use as insecticides - Google Patents

N,n-dialkyl-0-pyrimidinyl- carbamic acid estes, process for their preparation and their use as insecticides Download PDF

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Publication number
EP0000198B1
EP0000198B1 EP78100251A EP78100251A EP0000198B1 EP 0000198 B1 EP0000198 B1 EP 0000198B1 EP 78100251 A EP78100251 A EP 78100251A EP 78100251 A EP78100251 A EP 78100251A EP 0000198 B1 EP0000198 B1 EP 0000198B1
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Prior art keywords
spp
dialkyl
carbamic acid
hydroxy
pyrimidinyl
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EP78100251A
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German (de)
French (fr)
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EP0000198A1 (en
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Fritz Dr. Maurer
Ingeborg Dr. Hammann
Bernhard Dr. Homeyer
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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
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
    • G05B2219/00—Program-control systems
    • G05B2219/20—Pc systems
    • G05B2219/24—Pc safety
    • G05B2219/24108—Correct fault so that microprocessor functions correctly, without reset

Definitions

  • the present invention relates to new N, N-dialkyl-O-pyrimidinyl-carbamic acid esters, processes for their preparation and their use as insecticides.
  • N, N-dimethyl-O-pyrimidinylcarbamic acid esters e.g. N, N-dimethyl-0- (2-isopropyl-6-methyl-pyrimidine (4) yl) - or -O- (2-dimethylamino-6-methyl-pyrimidine (4) yl) -carbamic acid esters have insecticidal properties (see USA - Patent 2 694 712 and British Patent 1 181 657).
  • the N, N-dialkyl-O-pyrimidinyl-carbamic acid esters according to the invention have a better insecticidal action than the compounds of analogous constitution and the same direction of action known from the literature.
  • the fabrics according to the present invention thus represent a real enrichment of technology.
  • the 2-hydroxy-4'-dialkylamino-pyrimidines (II) to be used as starting materials can be prepared by processes known from the literature; in the event that R 4 is hydrogen, alkyl or halogen, from the corresponding 2-halogen compounds by hydrolysis and in the event that R 4 is alkylthio, from the corresponding 2-hydroxy- 'pyrimidines which are unsubstituted in the 5-position , Dimethyl disulfide and sulfuryl chloride optionally in the presence of a solvent.
  • the processes for the preparation of the compounds according to the invention are 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, for example diethyl and dibutyl ether, dioxane, and also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, and also nitriles, such as aceto and propionitrile.
  • hydrocarbons such as benzene, toluene, xylene, gasoline, Methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or
  • All customary acid binders can be used as acid acceptors.
  • Alkali carbonates and alcoholates such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.
  • the reaction temperature can be varied within a wide range. Generally one works between 0 and 100 ° C, preferably at 30 to 80 ° C.
  • the reaction is generally allowed to proceed at normal pressure.
  • the carbamic acid halide component is preferably used in a 10 to 30% excess.
  • the reactants are usually combined in an organic solvent in the presence of an acid acceptor and boiled under reflux. If necessary, the undissolved is filtered off and concentrated.
  • the new compounds are obtained in crystalline form and are characterized by their melting point.
  • N, N-dialkyl-O-pyrimidinylcarbamic acid esters according to the invention are notable for excellent insecticidal activity.
  • the active ingredients can be converted into the usual 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.
  • 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; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as 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 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.
  • 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.
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • the active ingredient preparation is intimately mixed with the soil.
  • the treated soil is filled into pots and planted with cabbage (Brassica oleracea).
  • the active ingredient can be taken up from the soil by the plant roots and transported to the leaves.
  • the root systemic effect of the active ingredient is derived from the number of killings. It is 100% when all test animals have been killed and 0% - when as many test insects are still alive as in the untreated control.
  • the 2-hydroxy-4-dialkylamino-pyrimidines (II) to be used as starting materials can e.g. can be produced as follows:
  • a solution of 4.7 g (0.05 mol) of dimethyl disulfide in 150 ml of methylene chloride is mixed with 6.8 g (0.05 mol) of sulfuryl chloride at -20 ° C. within 30 minutes. After 20 minutes, this solution is added dropwise at -10 ° C. to a suspension of 17 g (0.1 mol) of 2-hydroxy-4-dimethylamino-6-methyl-pyrimidine sodium salt in 200 ml of methylene chloride. The mixture is then stirred for 18 hours at room temperature. The solution is then extracted with 200 ml of water, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. This leaves 8.8 g (45% of theory) of 2-hydroxy-4-dimethylamino-5-methylthio-6-methyl-pyrimidine in the form of colorless crystals with a melting point of 209 ° C.

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  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

Die vorliegende Erfindung betrifft neue N,N-Dialkyl-O-pyrimidinyl-carbaminsäureester, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Insektizide.The present invention relates to new N, N-dialkyl-O-pyrimidinyl-carbamic acid esters, processes for their preparation and their use as insecticides.

Es ist bereits bekannt, daß N,N-Dimethyl-O-pyrimidinylcarbaminsäureester, z.B. N,N-Dimethyl-0-(2-isopropyl-6-methyl-pyrimidin(4)yl)- oder -O-(2-dimethylamino-6-methylpyrimidin(4)yl)-carbaminsäureester, insektizide Eigenschaften haben (vergleiche USA-Patentschrift 2 694 712 und Britisches Patent 1 181 657).It is already known that N, N-dimethyl-O-pyrimidinylcarbamic acid esters, e.g. N, N-dimethyl-0- (2-isopropyl-6-methyl-pyrimidine (4) yl) - or -O- (2-dimethylamino-6-methyl-pyrimidine (4) yl) -carbamic acid esters have insecticidal properties (see USA - Patent 2 694 712 and British Patent 1 181 657).

Es wurden nun die neuen N,N-Dialkyl-O-pyrimidinyl-carbaminsäureester der Formel (I)

Figure imgb0001
gefunden,
worin

  • R bis R3 für gleiches oder verschiedenes Alkyl,
  • R4 für Wasserstoff, Alkyl, Alkylthio oder Halogen und
  • R5 für Wasserstoff oder Alkyl stehen.
The new N, N-dialkyl-O-pyrimidinyl-carbamic acid esters of the formula (I)
Figure imgb0001
 found,
wherein
  • R to R 3 for the same or different alkyl,
  • R 4 represents hydrogen, alkyl, alkylthio or halogen and
  • R 5 represents hydrogen or alkyl.

Diese neuen Verbindungen zeichnen sich durch insektizide Eigenschaften aus.These new compounds are characterized by insecticidal properties.

Weiterhin wurde gefunden, daß die N,N-Dialkyl-O-pyrimidinyl-carbaminsäureester (I) erhalten werden, wenn man 2-Hydroxy-4-dialkylamino-pyrimidine der Formel (11)

Figure imgb0002
in welcher

  • R2 bis R5 die oben angegebene Bedeutung haben,
    • a) gegebenenfalls in Form der Alkali- oder Erdalkalisalze oder gegebenenfalls in Gegenwart eines Säureakzeptors mit N,N-Dialkyl-carbaminsäurehalogeniden der Formel (III)
      Figure imgb0003
      in welcher
      • R und R1 die oben angegebene Bedeutung haben und
      • Hal für Halogen, vorzugsweise Chlor, steht,

      gegebenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder
    • b) gegebenfalls in Gegenwart eines Verdünnungsmittels mit Phosgen umsetzt und anschließend mit einem Amin der allgemeinen Formel IV
      Figure imgb0004
      in welcher
      • R und R1 die oben angegebene Bedeutung haben,

      gegebenfalls in Gegenwart eines Säureakzeptors umsetzt.
Furthermore, it was found that the N, N-dialkyl-O-pyrimidinyl-carbamic acid esters (I) are obtained if 2-hydroxy-4-dialkylamino-pyrimidines of the formula (11)
Figure imgb0002
 in which
  • R 2 to R 5 have the meaning given above,
    • a) optionally in the form of the alkali metal or alkaline earth metal salts or optionally in the presence of an acid acceptor with N, N-dialkyl-carbamic acid halides of the formula (III)
      Figure imgb0003
       in which
      • R and R 1 have the meaning given above and
      • Hal represents halogen, preferably chlorine,

      if appropriate in the presence of a diluent, or
    • b) optionally reacted with phosgene in the presence of a diluent and then with an amine of the general formula IV
      Figure imgb0004
       in which
      • R and R 1 have the meaning given above,

      if appropriate in the presence of an acid acceptor.

Überraschenderweise besitzen die erfindungsgemäßen N,N-Dialkyl-O-pyrimidinyl-carbaminsäureester eine bessere insektizide Wirkung als die aus der Literatur vorbekannten Verbindungen analoger Konstitution und gleicher Wirkungsrichtung. Die Stoffe gemäß vorliegender Erfindung stellen somit eine echte Bereicherung der Technik dar.Surprisingly, the N, N-dialkyl-O-pyrimidinyl-carbamic acid esters according to the invention have a better insecticidal action than the compounds of analogous constitution and the same direction of action known from the literature. The fabrics according to the present invention thus represent a real enrichment of technology.

Verwendet man beispielsweise bei Verfahrensvariante a) 2-Hydroxy-4-dimethylamino-5-chlor- pyrimidin und N,N-Diäthylcarbaminsäurechlorid als Ausgangsmaterialien, so kann der Reaktionsverlauf durch das folgende Formelschema wiedergegeben werden:

Figure imgb0005
For example, if process variant a) uses 2-hydroxy-4-dimethylamino-5-chloro pyrimidine and N, N-diethylcarbamic acid chloride as starting materials, the course of the reaction can be represented by the following formula:
Figure imgb0005

Verwendet man beispielsweise bei Verfahrensvariante b) 2-Hydroxy-4-dimethylamino-pyrimidin Phosgen und Dimethylamin als Ausgangsmaterialien, kann der Reaktionsverlauf durch das folgende Formelschema wiedergegeben werden

Figure imgb0006
Figure imgb0007
 If, for example in process variant b), 2-hydroxy-4-dimethylamino-pyrimidine is used as phosgene and dimethylamine as starting materials, the course of the reaction can be represented by the following formula
Figure imgb0006
Figure imgb0007

Die zu verwendenden Ausgangsstoffe sind durch die Formeln (11), (III) und (IV) allgemein definiert. Vorzugsweise stehen darin jedoch

  • R bis R3 für gleiches, geradkettiges oder verzweigtes Alkyl mit 1 bis 6 Kohlenstoffatomen, insbesondere Methyl oder Äthyl,
  • R4 für Wasserstoff, Chlor, geradkettiges oder verzweigtes Alkyl bzw. Alkylthio mit 1 bis 4 Kohlenstoffatomen je Alkyl- bzw. Alkylthiorest, insbesondere 1 oder 2 Kohlenstoffatome und
  • R5 für Wasserstoff oder geradkettiges oder verzweigtes Alkyl mit 1 bis 4, insbesondere 1 oder 2, Kohlenstoffatome.
The starting materials to be used are generally defined by the formulas (11), (III) and (IV). Preferably, however, are in it
  • R to R 3 are identical, straight-chain or branched alkyl having 1 to 6 carbon atoms, in particular methyl or ethyl,
  • R 4 represents hydrogen, chlorine, straight-chain or branched alkyl or alkylthio having 1 to 4 carbon atoms per alkyl or alkylthio radical, in particular 1 or 2 carbon atoms and
  • R 5 represents hydrogen or straight-chain or branched alkyl having 1 to 4, in particular 1 or 2, carbon atoms.

Die als Ausgangsstoffe zu verwendenden 2-Hydroxy-4'-dialkylamino-pyrimidine(II) können nach literaturbekannten Verfahren hergestellt werden; für den Fall, daß, R4 für Wasserstoff, Alkyl oder Halogen steht, aus den entsprechenden 2-Halogenverbindungen durch Verseifung und für den Fall, daß R4 für Alkylthio steht, aus den entsprechenden in 5-Stellung unsubstituierten 2-Hydroxy-' pyrimidinen, Dimethyldisulfid und Sulfurylchlorid gegebenenfalls in Gegenwart eines Lösungsmittels.The 2-hydroxy-4'-dialkylamino-pyrimidines (II) to be used as starting materials can be prepared by processes known from the literature; in the event that R 4 is hydrogen, alkyl or halogen, from the corresponding 2-halogen compounds by hydrolysis and in the event that R 4 is alkylthio, from the corresponding 2-hydroxy- 'pyrimidines which are unsubstituted in the 5-position , Dimethyl disulfide and sulfuryl chloride optionally in the presence of a solvent.

Als Beispiele für die 2-Hydroxy-4-dialkylamino-pyrimidine (II) seien im einzelnen genannt;

  • 2-Hydroxy-4-dimethylamino-pyrimidin,
  • 2-Hydroxy-5-diäthylamino-pyrimidin,
  • 2-Hydroxy-4-dimethylamino-5-chlor-pyrimidin,
  • 2-Hydroxy-4-dimethylamino-5-methyl-pyrimidin,
  • 2-Hydroxy-4-dimethylamino-5-methylthio-pyrimidin,
  • 2-Hydroxy-4-dimethylamino-5-äthyithio-pyrimidin,
  • 2-Hydroxy-4-dimethylamino-5,6-dimethyl-pyrimidin,
  • 2-Hydroxy-4-dimethylamino-5-methylthio-6-methyl-pyrimidin,
  • 2-Hydroxy-4-dimethyiamino-5-chlor-6-methyl-pyrimidin,
  • 2-Hydroxy-4-diäthylamino-5-chlor-pyrimidin,
  • 2-Hydroxy-4-diäthylamino-5-methyl-pyrimidin,
  • 2-Hydroxy-4-diäthylamino-5-methylthio-pyrimidin,
  • 2-Hydroxy-4-diäthylamino-5-äthylthio-pyrimidin,
  • 2-Hydroxy-4-diäthylamino-5,6-dimethyl-pyrimidin,
  • 2-Hydroxy-4-diäthylamino-5-methylthio-6-methyl-pyrimidin,
  • 2-Hydroxy-4.-diäthylamino-5-chlor-6-methyl-pyrimidin.
Specific examples of the 2-hydroxy-4-dialkylamino-pyrimidines (II) are;
  • 2-hydroxy-4-dimethylamino-pyrimidine,
  • 2-hydroxy-5-diethylamino-pyrimidine,
  • 2-hydroxy-4-dimethylamino-5-chloropyrimidine,
  • 2-hydroxy-4-dimethylamino-5-methyl-pyrimidine,
  • 2-hydroxy-4-dimethylamino-5-methylthio-pyrimidine,
  • 2-hydroxy-4-dimethylamino-5-ethyithio-pyrimidine,
  • 2-hydroxy-4-dimethylamino-5,6-dimethyl-pyrimidine,
  • 2-hydroxy-4-dimethylamino-5-methylthio-6-methyl-pyrimidine,
  • 2-hydroxy-4-dimethyiamino-5-chloro-6-methyl-pyrimidine,
  • 2-hydroxy-4-diethylamino-5-chloropyrimidine,
  • 2-hydroxy-4-diethylamino-5-methyl-pyrimidine,
  • 2-hydroxy-4-diethylamino-5-methylthio-pyrimidine,
  • 2-hydroxy-4-diethylamino-5-ethylthio-pyrimidine,
  • 2-hydroxy-4-diethylamino-5,6-dimethyl-pyrimidine,
  • 2-hydroxy-4-diethylamino-5-methylthio-6-methyl-pyrimidine,
  • 2-hydroxy-4.-diethylamino-5-chloro-6-methyl-pyrimidine.

Die weiterhin als Ausgangsstoffe zu verwendenden N,N-Dialkylcarbaminsäurehalogenide (III) sowie die Amine (IV) sind literaturbekannt und nach üblichen Methoden gut herstellbar. Als Beispiele dafür seien im einzelnen genannt:

  • N,N-Dimethyl- und N,N-Diäthyl-carbaminsäurechlorid sowie Dimethylamin und Diäthylamin.
The N, N-dialkylcarbamic acid halides (III) and the amines (IV) which are also to be used as starting materials are known from the literature and can be readily prepared by customary methods. The following are examples of this:
  • N, N-dimethyl and N, N-diethyl-carbamic acid chloride as well as dimethylamine and diethylamine.

Die Verfahren zur Herstellung der erfindungsgemäßen Verbindungen werden bevorzugt unter Mitverwendung geeigneter Lösungsmittel oder Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Solventien in Frage. Hierzu gehören insbesondere aliphatische und aromatische, gegebenenfalls chlorierte, Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Benzin, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, oder Ather, z.B. Diäthyl- und Dibutyläther, Dioxan, ferner Ketone, beispielsweise Aceton, Methyl-äthyl-, Methyl-isopropyl- und Methyl-isobutylketon, außerdem Nitrile, wie Aceto- und Propionitril.The processes for the preparation of the compounds according to the invention are 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, for example diethyl and dibutyl ether, dioxane, and also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, and also nitriles, such as aceto and propionitrile.

Als SäureakzepLoren 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 and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.

Die Reaktionstemperatur kann innerhalb eines größeren Bereichs variiert werden. Im allgemeinen arbeitet man zwischen 0 und 100°C, vorzugsweise bei 30 bis 80°C.The reaction temperature can be varied within a wide range. Generally one works between 0 and 100 ° C, preferably at 30 to 80 ° C.

Die Umsetzung läßt man im allgemeinen bei Normaldruck ablaufen.The reaction is generally allowed to proceed at normal pressure.

Zur Durchführung der Verfahrensvariante a) setzt man die Carbaminsäurehalogenidkomponente vorzugsweise in 10 bis 30%igem Überschuß ein. Die Reaktionspartner werden meist in einem organischen Lösungsmittel in Gegenwart eines Säureakzeptors zusammengegeben und am Rückfluß gekocht. Gegebenenfalls wird vom Ungelöstem abfiltriert und eingeengt.To carry out process variant a), the carbamic acid halide component is preferably used in a 10 to 30% excess. The reactants are usually combined in an organic solvent in the presence of an acid acceptor and boiled under reflux. If necessary, the undissolved is filtered off and concentrated.

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

Wie bereits mehrfach erwähnt, zeichnen sich die erfindungsgemäßen N,N-Dialkyl-O-pyrimidinyl- carbaminsäureester durch eine hervorragende insektizide Wirksamkeit aus.As already mentioned several times, the N, N-dialkyl-O-pyrimidinylcarbamic acid esters according to the invention are notable for excellent insecticidal activity.

Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, die in der Landwirtschaft, in Forsten, im Vorrats- 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 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. Geophiliis carpophagus, Scutigera spec.
  • Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.
  • Aus der Ordnung der Thysanura z.B. Lepisma saccharina.
  • Aus der Ordnung der Collembola z.B. Onychiurus armatus.
  • Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Aus der Ordnung der Dermaptera z.B. Forficula auricularia.
  • Aus der Ordnung der Isoptera z.B. Reticulitermes spp.
  • Aus der Ordnung der Anoplura z.B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.
  • Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.
  • Aus der Ordnung der Heteroptera z.B. Eurygaster spp.,
  • Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalsiphum padi; Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, 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.
With good plant tolerance and favorable warm-blood toxicity, the active ingredients are suitable for combating animal pests, in particular insects, 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, Geophiliis carpophagus and Scutigera spec.
  • From the order of the Symphyla, for example, Scutigerella immaculata.
  • From the order of the Thysanura, for example Lepisma saccharina.
  • From the order of the Collembola, for example Onychiurus armatus.
  • From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • From the order of the Dermaptera, for example, Forficula auricularia.
  • From the order of the Isoptera, for example Reticulitermes spp.
  • From the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.
  • From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci.
  • From the order of the Heteroptera, for example 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, Phusopalsonum, Myzusalsonpp. Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, 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 spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Ph o rbi a s pp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae , Tipula paludosa.
  • From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp.

Die Wirkstoffe können in die überlichen 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 usual 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 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; 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-polyglykoJ-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; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl-polyglykoJ 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 anorganishe 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.

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

  • Lösungsmittel: 3 GewichtsteileSolvent: 3 parts by weight
  • Emulgator : 1 Gewichtsteil AlkylarylpolyglykolätherEmulsifier: 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 imgb0008
Active substances, active substance concentrations, evaluation times and results are shown in Table A below:
Figure imgb0008

Beispiel BExample B Grenzkonzentrations-Test/Wurzelsystemische WirkungLimit concentration test / root systemic effect

  • Testinsekt: Myzus persicaeTest insect: Myzus persicae
  • Lösungsmittel: 3 Gewichtsteile AcetonSolvent: 3 parts by weight of acetone
  • Emulgator: 1 Gewichtsteil AlkylarylpolyglykolätherEmulsifier: 1 part by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt, die angegebene Menge Emulgator zu 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, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Die Wirkstoffzubereitung wird innig mit dem Boden vermischt. Dabei spielt die Konzentration des Wirkstoffs in der Zubereitung praktisch keine Rolle, entscheidend ist allein die Wirkstoffgewichtsmenge pro Volumeneinheit Boden, welche in ppm (= mg/I) angegeben wird. Man füllt den behandelten Boden in Töpfe und bepflanzt diese mit Kohl (Brassica oleracea). Der Wirkstoff kann so von den Pflanzenwurzeln aus dem Boden aufgenommen und in die Blätter transportiert werden.The active ingredient preparation is intimately mixed with the soil. The concentration of the Active ingredient is practically irrelevant in the preparation, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (= mg / I). The treated soil is filled into pots and planted with cabbage (Brassica oleracea). The active ingredient can be taken up from the soil by the plant roots and transported to the leaves.

Für den Nachweis des wurzelsystemischen Effektes werden nach 7 Tagen ausschließlich die Blätter mit den obengenannten Testtieren besetzt. Nach weiteren 2 Tagen erfolgt die Auswertung durch Zählen oder Schätzen der toten Tiere. Aus den Abtötungszahlen wird die wurzelsystemische Wirkung des Wirkstoffs abgeleitet. Sie ist 100%, wenn alle Testtiere abgetötet sind und 0%-, wenn noch genau so viele Testinsekten leben wie bei der unbehandelten Kontrolle.To prove the root systemic effect, only the leaves are populated with the test animals mentioned above after 7 days. After a further 2 days, the evaluation is carried out by counting or estimating the dead animals. The root systemic effect of the active ingredient is derived from the number of killings. It is 100% when all test animals have been killed and 0% - when as many test insects are still alive as in the untreated control.

Wirkstoffe, Aufwandmengen und Resultate gehen aus der nachfolgenden Tabelle B hervor:

Figure imgb0009
Figure imgb0010
 Active ingredients, application rates and results are shown in Table B below:
Figure imgb0009
Figure imgb0010

HerstellungsbeispieleManufacturing examples Beispiel 1example 1

Figure imgb0011
Figure imgb0011

Eine Mischung aus 14g (0,1 Mol) 2-Hydroxy-4-dimethylaminopyrimidin, 16,6g (0,12 Mol) Kaliumcarbonat, 200 ml Chloroform und 12,8 g (0,12 Mol) N,N-Dimethylcarbaminsäurechlorid wird 20 Stunden unter Rückfluß gekocht. Dann filtriert man vom Ungelöstem ab und dampft das Filtrat im Vakuum ein. Zurück bleiben 17,6 g (84% der Theorie) N,N-Dimethyl-0-(4-dimethylamino- pyrimidin(2)yl)carbaminsäureester in Form hellbrauner Kristalle mit dem Schmelzpunkt 92°C.A mixture of 14 g (0.1 mol) of 2-hydroxy-4-dimethylaminopyrimidine, 16.6 g (0.12 mol) of potassium carbonate, 200 ml of chloroform and 12.8 g (0.12 mol) of N, N-dimethylcarbamic acid chloride became 20 Cooked under reflux for hours. The undissolved matter is then filtered off and the filtrate is evaporated in vacuo. This leaves 17.6 g (84% of theory) of N, N-dimethyl-0- (4-dimethylamino-pyrimidin (2) yl) carbamic acid ester in the form of light brown crystals with a melting point of 92 ° C.

Analog dem Beispiel 1 können die folgenden Verbindungen der Formel

Figure imgb0012
hergestellt werden:
Figure imgb0013
 Analogously to Example 1, the following compounds of the formula
Figure imgb0012
 getting produced:
Figure imgb0013

Die als Ausgangsmaterialien zu verwendenden 2-Hydroxy-4-dialkylamino-pyrimidine (II) können z.B. wie folgt hergestellt werden:The 2-hydroxy-4-dialkylamino-pyrimidines (II) to be used as starting materials can e.g. can be produced as follows:

Beispiel a:Example a:

Figure imgb0014
Figure imgb0014

15,8g (0,1 Mol) 2-Chor-4-dimethylamino-pyrimidin (Herstellung siehe J. Chem. Soc. Perkin Trans. 11, 1972, Seite 457) werden zusammen mit 16,4g (0,2 Mol) Natriumacetat in 100 ml Eisessig 4 Stunden unter Rückfluß gekocht. Dann destilliert man das Lösungsmittel im Vakuum ab, versetztden Rückstand mit 150 ml Wasser und dampft wieder ein. Der Rückstand wird in 150 ml Wasser gelöst und 3x mit je 100 ml Chloroform extrahiert. Die organischen Phasen werden über Natriumsulfat getrocknet, dann destilliert man das Lösungsmittel im Vakuum ab. Zurück bleiben 9,3g (68% der Theorie) 2-Hydroxy-4-dimethylamino-pyrimidin in Form farbloser Kristalle mit dem Schmelzpunkt 242°C.15.8 g (0.1 mol) of 2-chloro-4-dimethylamino-pyrimidine (for preparation see J. Chem. Soc. Perkin Trans. 11, 1972, page 457) together with 16.4 g (0.2 mol) of sodium acetate boiled in 100 ml of glacial acetic acid under reflux for 4 hours. The solvent is then distilled off in vacuo, 150 ml of water are added to the residue and the mixture is evaporated again. The residue is dissolved in 150 ml of water and extracted 3 times with 100 ml of chloroform. The organic phases are dried over sodium sulfate, then the solvent is distilled off in vacuo. This leaves 9.3 g (68% of theory) of 2-hydroxy-4-dimethylamino-pyrimidine in the form of colorless crystals with a melting point of 242 ° C.

Analog Beispiel a) können die folgenden Verbindungen hergestellt werden:The following compounds can be prepared analogously to example a):

Beispiel b:Example b:

Figure imgb0015
Figure imgb0015

in 88%iger Ausbeute mit dem Schmelzpunkt von 265°C.in 88% yield with a melting point of 265 ° C.

Beispiel c:Example c:

Figure imgb0016
Figure imgb0016

in 51%iger Ausbeute mit dem Schmelzpunkt von 234°C.in 51% yield with a melting point of 234 ° C.

Beispiel d:Example d:

Figure imgb0017
Figure imgb0017

Beispiel e:Example e:

Figure imgb0018
Figure imgb0018

in 89%iger Ausbeute mit einem Schmelzpunkt von 208°C.in 89% yield with a melting point of 208 ° C.

Beispiel f:Example f:

Figure imgb0019
Figure imgb0019

Beispiel g:Example g:

Figure imgb0020
Figure imgb0020

Eine Lösung von 4,7g (0,05 Mol) Dimethyldisulfid in 150 ml Methylenchlorid wird bei -20°C innerhalb von 30 Minuten mit 6,8 g (0,05 Mol) Sulfurylchlorid versetzt. Nach 20 Minuten tropft man diese Lösung bei -10°C zu einer Suspension von 17g (0,1 Mol) 2-Hydroxy-4-dimethylamino-6-methyl-pyrimidin-Natriumsalz in 200 ml Methylenchlorid. Das Gemisch wird dann 18 Stunden bei Raumtemperatur nachgerüht. Anschließend extrahiert man die Lösung mit 200 ml Wasser, trocknet die organische Phase über Natriumsulfat und destilliert das Lösungsmittel im Vakuum ab. Zurück bleibe 8,8 g (45% der Theorie) 2-Hydroxy-4-dimethyl-amino-5-methylthio-6-methyl-pyrimidin in Form farbloser Kristalle mit dem Schmelzpunkt 209°C.A solution of 4.7 g (0.05 mol) of dimethyl disulfide in 150 ml of methylene chloride is mixed with 6.8 g (0.05 mol) of sulfuryl chloride at -20 ° C. within 30 minutes. After 20 minutes, this solution is added dropwise at -10 ° C. to a suspension of 17 g (0.1 mol) of 2-hydroxy-4-dimethylamino-6-methyl-pyrimidine sodium salt in 200 ml of methylene chloride. The mixture is then stirred for 18 hours at room temperature. The solution is then extracted with 200 ml of water, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. This leaves 8.8 g (45% of theory) of 2-hydroxy-4-dimethylamino-5-methylthio-6-methyl-pyrimidine in the form of colorless crystals with a melting point of 209 ° C.

Analog Beispiel g kann hergestellt werden:The following can be produced analogously to example g:

Beispiel h:Example h:

Figure imgb0021
Figure imgb0021

Claims (5)

1. N,N-Dialkyl-O-pyrimidinyl-carbamic acid esters of the formula (I)
Figure imgb0026
wherein
R to R3 represent identical or different alkyl,
R4 represents hydrogen, alkyl, alkylthio or halogen and
R5 represents hydrogen or alkyl.
2. Process for the preparation of the N,N-dialkyl-O-pyrimidinyl carbamic acid esters (I), characterised in that 2-hydroxy-4-dialkylamino-pyrimidines of the formula (II)
Figure imgb0027
in which -
R2 to R5 have the meaning mentioned in Claim 1
a) are reacted, if appropriate in the form of the alkali metal salts or alkaline earth metal salts or, if appropriate, in the presence of an acid acceptor, with N,N-dialkyl-carbamic acid halides of the formula (III)
Figure imgb0028
in which
R and R1 have the meaning mentioned in Claim 1 and Hal represents halogen, preferably chlorine, if appropriate in the presence of a diluent, or
b) are reacted, if appropriate in the presence of a diluent, with phosgene, and subsequently with an amine of the general formula (IV)
Figure imgb0029
in which
R and R1 have the meaning mentioned in Claim 1 and
if appropriate in the presence of an acid acceptor.
3. Insecticidal agents, characterised in that they contain N,N-dialkyl-0-pyrimidinyl-carbamic acid esters according to Claim 1.
4. Use of N,N-dialkyl-0-pyrimidinyl-carbamic acid esters according to Claim 1 for combating insects.
5. Process for the preparation of insecticidal agents, characterised in that N,N-dialkyl-0-pyrimidinyl-carbamic acid esters according to Claim 1 are mixed with extenders and/or surface-active compounds.
EP78100251A 1977-07-05 1978-06-28 N,n-dialkyl-0-pyrimidinyl- carbamic acid estes, process for their preparation and their use as insecticides Expired EP0000198B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772730273 DE2730273A1 (en) 1977-07-05 1977-07-05 N, N-DIALKYL-O-PYRIMIDINYL-CARBAMINIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES
DE2730273 1977-07-05

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EP0000198A1 EP0000198A1 (en) 1979-01-10
EP0000198B1 true EP0000198B1 (en) 1980-07-23

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EP78100251A Expired EP0000198B1 (en) 1977-07-05 1978-06-28 N,n-dialkyl-0-pyrimidinyl- carbamic acid estes, process for their preparation and their use as insecticides

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US (1) US4162320A (en)
EP (1) EP0000198B1 (en)
JP (1) JPS5414984A (en)
AR (1) AR220717A1 (en)
AT (1) AT359333B (en)
AU (1) AU515147B2 (en)
BR (1) BR7804295A (en)
CS (1) CS197325B2 (en)
DE (2) DE2730273A1 (en)
DK (1) DK302678A (en)
EG (1) EG13466A (en)
ES (1) ES471418A1 (en)
IL (1) IL55060A0 (en)
IT (1) IT1098344B (en)
NZ (1) NZ187759A (en)
PT (1) PT68215A (en)
TR (1) TR19760A (en)
ZA (1) ZA783822B (en)

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US4391810A (en) * 1981-01-06 1983-07-05 Ciba-Geigy Corporation 2-Methyl-4-N,N-dimethylcarbamoyloxy-6-amino-pyrimidines and salts thereof, processes for producing them, and their use for combating pests
US4490375A (en) * 1981-11-25 1984-12-25 Ciba-Geigy Corporation 4-N,N-Dimethylcarbamoyloxy-6-aminopyrimidines and salts thereof, and their use for combating pests
GB8606262D0 (en) * 1986-03-13 1986-04-16 Ici Plc Insecticidal compositions
SE468410B (en) * 1991-05-08 1993-01-11 Asea Brown Boveri EXPLANATORY LED
JP7376245B2 (en) 2019-03-29 2023-11-08 シスメックス株式会社 Fluorescence image analysis device and fluorescence image analysis method

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IT476454A (en) * 1949-08-22
GB1181657A (en) * 1966-03-31 1970-02-18 Ici Ltd Pyrimidine Derivatives and Compositions Containing them
US3627891A (en) * 1969-10-17 1971-12-14 Mobil Oil Corp Use of pyrimidylthiuronium salts as fungicides
SU551329A1 (en) * 1975-01-20 1977-03-25 Киевский научно-исследовательский институт фармакологии и токсикологии Method for preparing 2-hydroxy-4-amino-substituted pyrimidine

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BR7804295A (en) 1979-03-20
TR19760A (en) 1979-11-30
NZ187759A (en) 1979-10-25
JPS5414984A (en) 1979-02-03
ATA486678A (en) 1980-03-15
AT359333B (en) 1980-11-10
DE2860049D1 (en) 1980-11-13
JPS6231709B2 (en) 1987-07-09
US4162320A (en) 1979-07-24
ZA783822B (en) 1979-07-25
IL55060A0 (en) 1978-09-29
CS197325B2 (en) 1980-04-30
AR220717A1 (en) 1980-11-28
EP0000198A1 (en) 1979-01-10
ES471418A1 (en) 1979-09-01
AU3775778A (en) 1980-01-10
DK302678A (en) 1979-01-06
EG13466A (en) 1982-03-31
AU515147B2 (en) 1981-03-19
PT68215A (en) 1978-07-01
IT1098344B (en) 1985-09-07
IT7825287A0 (en) 1978-07-03
DE2730273A1 (en) 1979-01-25

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