IE42181B1 - Novel pyrimidinyl(thiono)phosphoric(phosphonic)acid estersand ester-amides and their use as insecticides acaricides and nematicides - Google Patents

Abstract

1476072 Pyrimidyl esters of phosphorus acids; pyrimidines BAYER AG 17 Oct 1975 [23 Nov 1974] 42621/75 Headings C2P and C2C The invention comprises compounds of formula (wherein R is C 1-14 alkyl; R 1 is C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkylamino or phenyl; R 2 is C 1-4 alkyl, phenyl or mono- or polyhalophenyl; and X is O or S); and their preparation from the corresponding pyrimidin-2-ols (which may be in the form of hydrochloride, alkali metal, alkaline earth metal or ammonium salts) by reaction with (RO)(R 1 )P(X)-halogen, and an acid-acceptor where necessary. 2 - Hydroxy - 5 - methylthio - 4,6 - dimethylpyrimidine hydrochloride and its 5-ethylthio and 5 - (p - chlorophenylthio)analogues are prepared from 3-methylthio-2,4-pentanedione &c. by reaction with urea and HCl. Insecticidal, acaricidal and nematocidal compositions comprise a compound I and a carrier.

Description

The present invention relates to certain new substituted pyrimidinyl(thiono)phosphoric(phosphonic) acid esters and ester-amides, to a process for their preparation and to their use as insecticides, acaricides and nematicides.

It has already been disclosed that pyrimidinyl(thiono) phosphoric acid esters and ester-amides, for example 0,0dimethyl- or 0,0-diethyl-0-pyrimidin(2)ylthionophosphoric acid ester, 0,0-diethyl-0-[2,4-dimethyl-5-methylthiopyrimidin(6)yl]-phosphorio acid ester CH, >-SR,, (I), in which R is alkyl with 1 to 4 carbon atoms, R^ is alkyl, alkoxy or mono alkylamino each with 1 to 6 carbon atoms, or phenyl, Rg is alkyl with 1 to 4 carbon atoms or Optionally halogen-substituted phenyl, and X represents oxygen or sulphur. 2 43181 The compounds of this invention have been found to possess powerful insecticidal, acaricidal and nematieidal properties.

Preferably, R is straight-chain or branched alkyl with 1 to 3 (preferably 1 or 2) carbon atoms, R1 is straight-chain or branched alkyl, alkoxy or monoalkylamino with 1 to 4 (preferably 1 to 3) carbon atoms, or phenyl, Rg is straightchain or branched alkyl with 1 to 3 (preferably 1 or 2) carbon atoms or phenyl which is monosubstituted or polysubstituted by chlorine, and X is sulphur.

The present invention also provides a process for the preparation of a substitute^ pyrimidinyl(thiono)phoephoric (phosphonic) aoid ester or ester-amide of the general formula (l), in which a (thiono)phosphoric(phosphonic) aoid ester halide or ester-amide halide of the general formula RO R.

X It ‘-Hal (II) is reacted, if appropriate in the presence of an acid acceptor and if 'appropriate in the presence of an organic solvent, with a 2-hydroxy-4,6-dimethylpyrimidine derivative of the formula H»C OH N CH, SR, (III) in which formulae R, Rp Rg and X have the above-mentioned meanings, and Hal is halogen, preferably chlorine, the latter being used as the free base, or in the form of an - 3 42181 alkali metal salt, alkaline earth metal salt or ammonium salt thereof, or as the. hydrochloride.

. Surprisingly, the substituted pyrimidinyl(thiono) phosphoric(phoephonic) acid esters and ester-amides according to the invention show a better leaf-insecticidal and soilinsecticidal, acaricidal and nematicidal action than the corresponding compounds of analogous structure and of the same type of action previously known from the state of the art.

The products according to the present invention thus represent a genuine enrichment of the art.

If, for example, O^ethyl-O-isopropylthionophosphoric acid diester chloride and the hydrochloride of 2-hydroxy-4,6dimethyl-5-(2*,4'-dichlorophenylthio)-pyrimidine are used as starting materials, the course of the reaction can be represented by the following equation: c2h5oks 9 ; p-ci + ho· iso-C^O' •HC1 ,CH3 Cl Acid acceptor Cl -> -2 x HC1 iso- The (thiono)phosphorio(phosphonic) acid ester halidee and ester-amide halides (II) to be used as starting materials are known from the literature and can be prepared in accordance with generally customary methods.

The following may be mentioned as examples thereof: Ο,Ο-dimethyl-, 0,0-diethyl-, Ο,Ο-di-n-propyl-, 0,0-di-isopropyl-, O-ethyl-O-n-propyl-, Ο-ethyl-O-isopropyl-, O-n-butylΟ-ethyl-, O-ethyl-O-sec.-butyl- and O-ethyl-O-methyl-phosphoric - 4 42181 acid dieater chloride and the corresponding thiono analogues; O-methyl-, Ο-ethyl-, 0-n-propyl- and O-lsopropyl-methane-, -ethane-, -η-propane-, -isopropane-, -η-butane-, -isobutane-, -sec.-butane-, -tert.-butane- and -phenyl-phoephonic acid ester chloride and the corresponding thiono analogues; and O-methyl-N-methyl-, Ο-ethyl-N-methyl-, O-n-propyl-N-methyl-, O-isopropyl-N-methyl-, Ο-methyl-N-ethyl-, O-ethyl-N-ethyl-, O-n-propyl-N-ethyl-, Ο-isopropyl-N-ethyl-, O-ethyl-N-isopropyl-, O-ethyl-N-tert.-butyl-, Ο-methyl-N-n-propyl-, O-ethyl-N-npropyl-, Ο-n-propyl-N-n-propyl-, O-n-propyl-N-n-butyl-, Ο-isopropyl-N-ethyl-, O-isopropyl-N-n-butyl- and O-tert.butyl-N-ethyl-phosphoric acid ester-amide chloride and the corresponding thiono analogues.

The hydrochlorides of the 2-hydroxy-4,6-dimethylpyrimidine derivatives (XII), some of which are new, can be obtained according to generally customary methods known from the literature,' for example by reacting 3-substituted pentane2, 4-diones with urea in alcoholic eolutlon in the presence of hydrochloric acid, in accordance with the following equation; sr2 HjC-CO-CH-CO-OHj + HgN-CO-NHg concentrated hydrochloric aeid/ethanol jj OH · HC1 wherein Rg has the above-mentioned meaning.

The following may be mentioned as examples of 2-hydroxy4,6-dimethylpyrimidine derivatives (III) to be reacted in accordance with the process: 5-methylthio-, 5-ethylthio-, 5-n-propylthio-j, 5-isopropylthio-, 5-(2*-chlorophenylthio)-, 5-(4'-chlorophenylthio)- or 5-(21,3’»4’»5’,6’-pentachlorophenylthio)-4,6-dimethyl-2-hydroxypyrimidine.

The process forVthe preparation of the compounds according to the invention is preferably carried out in the presence of suitable solvents or diluents. Practically all inert organic solvents can be used for this purpose, especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxan; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such aB acetonitrile and propionitrile.

All customary acid-binding agents can be used as acid acceptors. Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate and potassium tert.-butylate have proved particularly suitable, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly wide range. In general, the reaction is carried out at from 0° -bo 120°C, preferably at from 40° to 65°C.

The reaction, is in general allowed to take place under normal pressure.

To carry out the process, the starting materials are in general employed in the equimolar ratio. An excess of one or other reactant produces no significant advantages. In most - 6 42181 cases, the hydrochloride of the 2-hydroxy-4,6-dimethylpyrimJdine derivatives, in one of the stated solvents or diluents, is first mixed with the acid aooeptor and the phosphorus-containing reagent is added dropwise. After stirring for one or more hours at the stated temperatures, the reaction mixture is poured into an organic solvent, for example toluene, and worked up in the usual manner, for example by separating off the organic phase, washing and drying it, and distilling off the solvent.

The new compounds are obtained in the form of oils which cannot be distilled without decomposition but are freed from the last volatile constituents by so-called slight distillation, that is to say by prolonged heating under reduced pressure to moderately elevated temperatures, and are purified in this way. They are characterised by the refractive index.

As has already been mentioned, the substituted pyrimldinyl(thiono)phosphoric(phosphonie) acid esters and ester-amides acoording to the invention are distinguished by an excellent insecticidal, acaricidal and nematioidal activity. They are active againBt plant pests, pests harmful to health and pests of stored products and couple a low phytotoxielty with a good action against both sucking and biting insects and against mites.

For this reason, the compounds according to the invention can be employed successfully as pesticides in plant protection and in the hygiene field and the field of protection of Btored products.

The active compounds according to the invention are well-tolerated by plants, have a favourable level of toxicity to larm-blooded animals and can be used for combating all or individual stages of development, including the pre-embryonie, - 7 42181 normally sensitive and resistant stages of development, of . insects, arthropods and nematodes where these are known as pests in agriculture, in forestry, in the protection of stored products and of materials, and in hygiene.

The economically important pests in agriculture and forestry, as well as pests of stored products, pests destructive of materials and pests harmful to health, include: from the order of the Isopoda. for example, Oniscus asellus. Armadillidium vulgare and Porcellio scaber; from the order of the Piplopoda. 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.immaoulata; from the order of the Arachnida. for example, Scorpio maurus end Latrodectus mactans; from the order of the Acarina. for example, Acarus siro, Argas reflexus..Omithodoros moubata. Permanyseus gallinae. Eriophyes ribls, Phyllocoptruta oleivora. Boophilus microplus. Rhipicephalus evertsi, Sarcoptes scabiei, Tarsonemus spec. Bryobia praetiosa. Panonychus citri. Panonychus ulmi. Tetranychus tumidus and Tetranychus urticae; from the order of the Thysanura. for example, lepisma Baccharina: from the order of the Collembola, for example, Onychiurus armatus: from the order of the Orthoptera. for example, Blatta orientalls. Perlplaneta americana. leucophaea maderae, Blattella germanica. Acheta domesticus. Gryllotalpa spec., locusta mlgrotoria migratorioides. Melanoplus differentialis and Schistocerca gregaria; from the order of the Permantera. for example, Porfloula auricularia; from the order of the Isoptera. for example, Reticulltermes epee.; from the order of the Anoplura. for example, Phylloxera vagtatrix. Pemphigus - 8 42181 epeo. and Pediculus humanus corporis; from the order of the Thvsanoptera. for example, Hercinothrips femoralis and Thrlpa tabaci; from the order of the Heteroptera. for example, Eurygaster spec., Pysdercus intermedius. Piesma quadrata. Olmex lectularius. Rhodnius prolixus and Triatoma spec.; from the order of the Homoptera. for example, Aleurodes brassicae. Bemisia tabaci. Trialeurodes vaporariorum. Aphis gossypii. Brevicoryne brassicae. Cryptomyzus ribis. Poralis fabae. Poralis poml. Eriosoma lanigerum, Hyalopterus arundinis. Macroslphum avenae. Myzus cerasi. Myzus persicae. Phorodon humuli, Rhopalosiphum padi. EmpoaBca spec., Euscelis bilobatus, Hephotettix cincticeps. Lecanium corn!, Saissetia oleae. laodelphax striatellus. Milaparvata lugens. Aonidiella aurantii. Aspidiotus hederae, Pseudococcus spec, and Psylla spec.; from the order of the lepidoptera. for example, footipaptipga &gggjjMsXte> BttPalqg piniarius. Oheimat.obla brumata. llthooolletlB blancardella. Hyponomeuta padella. Plutella maculipennis. Malacosoma neustria. Euproctis chrysorrhoea. lymantria spec., Bucculatrix thurberlella. PhyllooniBtls citrella. Agrotis spec., Euxoa spec., Peltia spec., Earias insulana. Heliothis spec., laphygma exigua. Mamestra brassicae. Panolis flammea. Prodenia litura. Spodoptera spec., Trichoplusia nl. Oarpocapsa pomonella. Pieris spec., Chilo spec., Pyrausta nubHalls. Ephestia kuhniella. Galleria mellonella. Oacoecia podana. Capua reticulana. Chorlstoneura fumiferana, Clysia ambjguella. Homona magnanima and Tortrix viridana; from the order of the Coleoptera. for example, Anobiua punotatum. Rhizopertha dominioa. Bruchidius obtectus. Acanthoseelldes obteotus, Hylptrupes ba .lulus. Agelastica alni. leptinotarsa decemlineata. Phaedon cochleariae, Piabrotlca epee., PB.vlliodes ohrysocephala. Epil- 9 42181 achna variveatis. Atomaria spec.. Oryzaephllus surinamensis, Anthonomus spec., Sitophilus spec., Otiorrhynchus suloatus, Cosmopolites sordidus, Ceu.thorrhya.chus assimilis. Hypera postica. Permestes spec., Trogoderma spec..Anthrenus spec., Attagenus spec., lyctus spec,, Meligethes aeneus. -Ptinus spec. Niptus hololeucus, Gibbium pyslloides. Irlbolium spec., Tenebrlo molitor. Agriotes spec., Oonoderus spec., Melolontha melolontha. Amphimallus solstitialis and Costelytra zealandica; from the order of the Hymenoptera. for example, Piprion spec., Hoplooampa spec., Laslus spec., Monomorium pharaonia and Vespa spec.; from the order of the Piptera. for example, tl Aedes spec,, Anopheles spec., Oulex spec., Prosophila melanogaster. Musoa domeatica. Fannia Bpec., 8tomoxys calcitrane. Hypoderma.spec.. Blbio hortulanus. Oscjnella frit. Fhorbia spec., Fegomyla hyoaoyaml. Calllphora erythr&cephala. Lucllia spec., Chrysomyia spec., Ceratltis capitata. Pacus oleae and Tjpula paludoBa; and from the order of the Siphonaptera. for example, Xenopsylla oheopls.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules In polymeric substances and in coating compositions, for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils as well as ULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, - 10 42181 optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also he used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, Buch as butanol or glycol as well as their etherB and esters, ketonee, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide, dimethyl sulphoxide or acetonitrile, as well as water.

Byliquefied gaseous diluents or carriersare meant liquide which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example .Freon (Trade Mark) Ab solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as - 11 albumin hydrolyzation products; and preferred examples of , dispersing agents include lignin sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other active compounds.

The formulations in general contain from 0.1 to 95 per cent by weight, of active compound, preferably from 0.5 to 90 per cent.

The active compounds can be employed as such, in the form of their formulations or as the use forms prepared therefrom. They may be used in.the customary manner, for example by squirting, spraying, atomising, dusting, Scattering, fumigating, gassing, watering, dressing or encrusting.

The active-compound concentrations in the ready-to-use preparations can be varied within fairly wide ranges. In general they are from 0.0001 to 10%, preferably from 0.01 to 1%, by weight.

The active compounds can also be used with good success in the ultra-low-volume (U1V) method where it is possible to apply formulations of up to 95% active compound or even to use the active compound by itself.

When used against pests harmful to health and pests of stored products, the active compounds are distinguished by an excellent residual action on wood and clay, as well as a good stability to alkali on limed substrates.

The present invention also provides an insecticidal, acaricidal or nematioidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a - 12 42181 surface-active agent.

The present invention also provides a method of combating Insects, acarids or nematodes which comprises applying to the insects, acarids or nematodes, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by insects, acarids or nematodes by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

The pesticidal activity of the present compounds is illustrated in and by the following bioteet Examples.

Example A Critical concentration test/soil insects I Test insect: Phorbia antiqua grubs in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight of active compound per unit - 13 42181 volume of eoil, which is quoted in ppm (= mg/l). The soil was filled into pots and the pots were left to stand at room temperature.

After 24 hours the test animals were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was determined in % hy counting the dead and live insects. The degree of effectiveness is 100% if all the test insects had been killed and is 0% if exactly as many test insects were still alive as in the case of the untreated control.

The active compounds, amounts used and results can be Seen from Table A: Table A Phorbla antiqua grubs in the soil Active compound Degree of destruction in % at an'active compound concentration of ppm OC„H, '2 5 N^-O-P' 0C2h5 (known) Σ.

IL· 0C?Hc ch,s-z \-o-p' ά 5 (1) 100 > ν_ϊΓ 0C2H5 CH, =rN K C2H5 (2) 10O lie A 16 076 table A (continued) Phorbia antique grubs in the soil Active compound Degree of destruction in % at an active compound concentration of ppm 0C,H~-n Z 3 7 oc2h5 (15) 100 c2H5SCiY \ oc2h5 (4) 100 CH, .» 5/¾¾ (5) 100 OC2H5 (6) 100 C2H5S_\\ OCjft^-n OCH, |/0CH5 Z°-\o „ (,°> c2h5 100 (15) 100 Example Β Critical concentration test/aoil insects IX Test insect: Tenebrio molitor larvae in the soil Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight of active compound per unit volume of soil, which is quoted in ppm (= mg/l). The soil was filled into pots and the pots were left to stand at room temperature.

After 24 hours the test animals were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was determined in % by counting the dead and live test insects. The degree of effectiveness was 100% if all the test insects had been killed and was 0% if exactly as many test insects were still alive as in the case of the untreated control.

The active compounds, amountB used and results can be seen from Table B: - 16 42181 Table Β Tenebrio molitor larvae in the soil Active compound Degree of destruction in % at an active compound concentration of 2.5 mam _ °°η3 -o-p' 0 XOCH3 (known) (2) 100 (4) 100 (5) 100 OC^Hy-n (6) 100 Example C Critical concentration test/nematodes Test nematodes Meloidogyne incognita Solvent: 3 parts by weight of acetone Emulsifier: t part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of active compound.was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given in ppm, was decisive. The soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse temperature of 27°C.

After 4 weeks, the lettuce roots were examined for infestation with nematodes (root knots), and the degree of effectiveness of the active compound was determined as a percentage. The degree of effectiveness was 100% when infestation was completely avoided; it was 0% when the infestation was exactly the same as in the case of the control plants in untreated soil which had been infested in the same manner.

The active compounds, the amounts applied and the results can be seen from Table C: - 18 42181 Table Ο Meloldoavne incognita Active compound Degree of destruction in # at an active compound concentration of .20 ppm v fl ,°CH, fV°-p/ N \ OCH, (known) (1) (2) 100 100 (15) 100 (4) 100 (5) 100 - 19 42181 Table 0 (continued) Meloidogyne incognita Active coppound Degree of destruction in # at an active compound concentration of ppm (6) (10) 100 100 Example D Plutella test t Solvents 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulBifier and the concentrate was diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the caterpillars were killed whereas 0% means that none of the caterpillars were killed. - 20 42181 The active compounds, the concentrations of the active compounds, the evaluation time: and the results can be seen from Table D: Table D Plutella test Active compound Active com- Degree of pound con- destruction centration in % after in % 5 days CH·, . O-PiOCgHij^ (known) 0.1 0.01 100 0.1 0.01 100 (known) 0-P. >oo2h5 (1) oc2h5 0.1 0.01 100 100 - 21 42181 Table D (continued) Plutella test Active compound Active oom- Degree of pound con- destruction 0.1 0.1 0.01 0.1 100 100 100 100 100 100 S-V3 :· oc2h5 0.01 100 100 (11) - 22 42181 Table D (continued) Plutella teat Active oompound Active com- Degree of Example E Drosophila test Solvent: 5 parts hy weight of acetone Emulsifier: 1 part hy weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate was diluted with water to the desired concentration. 1 cm3 of the preparation of the active compound was applied with a pipette to a filter paper disc of 7 cm diameter. The wet disc was placed over the orifice of a glass vessel containing 50 vinegar flies (Drosophila melanogaster) and covered with a glass plate.

After the specified periods of time, the destruction was determined in %. 100% means that all the flies were killed; 0% means that no flies were killed.

The active compounds, the concentrations of the active compounds, the evaluation time- and the results Can be seen from Table E: Table S Drosophila test Active compound Active com- Degree of pound eon- destruction centration in % after in % 1 day 100 - 24 42181 Table B (continued) Droaophila test Active compound Active com- Degree of pound con- destruction eentration in % after ...... in % 1 day CH.

Affl-C^-iso (known) 0.1 0.01 °8 CH3 (15) 100 100 100 100 CH, ch3s· ocb, χ:-Η- 0.1 100 0.01 100 C. 2 do) 0.001 90 CH3 - 25 42181 table E (continued) . Drosophila test Active compound V S Cl£ (4) ,oc2h5 oc2h5 02Η53Λχ Active com- Degree of pound con- destruction centration in % after in % 1 day 0.1 100 0e01 100 0.1 0.01 100 100 100 100 100 100 100 too 100 Example ? Tetranvchua test (resistant) Solvent! 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the Btated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which had a height of approximately 10-30 cm, were sprayed with the preparation of the active compound until dripping wet. These bean plants were heavily infested with the two-spotted spider mite (Tetranychus urtioae) in all stages of development.

* After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the spider mites were killed whereas 0% means that none of the spider mites were killed.

The aotive compounds, the concentrations of the active compounds, the evaluation time and the results can be seen from Table F: Table g Tetranvchua test Active compound Active oom- Degree of depound oon- struction in centration % after 2 -:iaJ5 daxs - 27 42181 I a b X g '? (continued) Tetranychus test Active qompound ft 0-P(0C2H5)2 (known) Active com- Degree of pound con- destruction oentration in % after in % 2 days 0.1 ?CH3 S OCHj NH-CjH^-iso (known) 0.1 (15) - 28 42181 Table g (continued) Tetranyohue test Active compound Active oom- Degree of pound con- destruction centration in # after in # 2 days (13) 100 -0-P L0C2H5 0.1 C2H5 100 (5) The process of this invention is illustrated in the following preparative Example.

Example 1 oo2h5 oc2h5 (1) 18.8 g (0.1 mole) of Ο,Ο-diethylthionophosphoric acid diester chloride were added dropWise to a suspension of 20.6 g (0.1 mole) of 2-hydroxy-5-methylthio-4,6-dimethylpyrimidine hydrochloride and 29 g (0.21 mole) of potassium carbonate in 200 ml of acetonitrile. The reaction mixture was warmed to 5O-6O°C for 5 hours and was then poured into 300 ml of toluene. The mixture was extracted by shaking with twice 300 ml of water and the organic phase was separated off and dried over sodium sulphate. The solvent was then stripped off ip vacuo and the residue was subject to slight distillation at 100°C. 27 g (84% of theory) of 0,0-diethyl0-[4,6-dimethyl-5-methylthiopyrimidin(2)yl]-thionophosphoric acid ester were obtained in the form of a yellow oil having a refractive index of 1 *5379.

The compounds of the general formula could be prepared analogously to Example 1: ω *rl •Ρ ο .« Ήβ 3-9 So? ώ*·8 Η'—·»» CM CH Μ Φ 00 Ο σ\ VO m 00 CM ιη <ρ s Ο s IS σ\ -4 ο CM < CM 4· 4 ΙΛ m in in in in in • • ♦ « ♦ • Η Η Η Η r4 H ΚΊ m Ν\ m m m in CM Ρ CMP CM Ρ CMP CM P CMP CMP β β β β β β β M3 M3 ΙΑ ία κ\ ΙΑ ο M3 ια •4 Ο ΙΑ βΓ ο βΓ CM Ο ^(Α ΙΑ ΙΑ « CM ϋ βΓ ow ΰΓ cm ο I I χ* CM a* (Μ ϋ β ι C ΚΊ χ° CM βΓ CM Ο in IA m in in in X 35 x X X X X CM CM CM CM CM CM CM u U U O ϋ O U co O ω CO co CO CO CM ΙΑ -4 ΙΑ Ό Α- 00 ID l> o ·· S3 M w H o CO o in in rd cn id «it m m in co id m in CM . m in in in in in in • • * • • • • rd rd H rd H jd id ·· > VO ~ to Ό lO Ό in CMP CMP CM Q CMP CMP CMP cmq G G β G G G β Η O 0 ID ® •ΗΊ&Λ CM bctl in Φ in to w CO ef af* u o w •H I S3~ tn ϋ . I m o aT CM O σ» in in X CM O w •d I a5^ m o I .in °fc «CM ST £ ΙΛ e m £ .1°1 8 in as, cd o CO jn in x, aT m m X CM CM X X o o ϋ o o co co CO to co in a co Of H * CM m H H rd rd rd in rt The pyrimidine derivatives of the formula (XII) required as starting materials could be prepared, for example, as follows: . HCl A solution of 146 g (1 mole) of 3-methylthio-2,4-pentanedione [see German OffenlegungeBchrift (German Published H Specification) 2,155>493 and S. Hunig and 0« Bocs, Liebigs Annalen der Chemie, volume 579, page 23 (1953)] and 75 g (1,25 moles) of urea in 800 ml of ethanol and 100 ml of con10 oentrated hydrochloric aoid was heated for 8 hours under reflux. The solution was then cooled to -10°C and 1 litre of ether was added. A precipitate formed, which was filtered off and dried, 127 g (62# of theory) of 2-hydroxyg5-methylthio-4,6-dimethylpyrimidine hydrochloride were obtained in the form of odourless crystals of melting point /> 210°0.

The following compounds were prepared analogously: OH HCl 31# yield; melting point 220°C 62# yield; melting point 220°C (decomposition)

Claims (17)

1. , Substituted acid esters and pyrimidinyl(thiono)phosphoric(phosphonic) pfl*pr. q nHdan o f the general formula X CH* KO. ί N_X 5 CHj (I) in which R. is alkyl with 1 to 4 carbon atoms, Rj is alkyl, alkoxy or mono alkylamino each with 1 to 6 carbon atoms, or phenyl, . Rg is alkyl with 1 to 4 carbon atoms or optionally halogen-substituted phenyl, and X is oxygen or sulphur.

2. Compounds according to claim 1, ia which a is straightchain or branched alkyl with 1 to 5 carbon atoms, Rj is straight-chain or branched alkyl, alkoxy or monoalkylamino with 1 to 4 carbon atoms, or phenyl, Eg is straight-chain or branched alkyl with 1 to 5 carbon atoms or phenyl which is monosubstituted or polysubstituted by chlorine, and X is sulphur.

3. The compound of the formula “ OC»H,0-^ 2 5 ' °c 2 h 5 (1)

4. The ootnpound of the formula (3) - 34 43181

5. The compound of the formula CH00 Λ (4)

6. The compound of the formula CHj °A (5)

7. » The compound of the formula (7)

8. The compound of the formula CH, 4/ 0 ¾ '°2 H 5 (10)

9. The compounds that are identified in Examples 2, 6, 8, 9 10. And 11 to 15.

10. A process for the preparation of a substituted pyrimidinyl(thiono)phosphorio(phoBphonic) acid ester or esteramide according to any of claiflB 1 to 9 in which a (thiono) phosphoric(phosphonic) acid ester halide or ester-amide 15 halide of the general formula P-Hal (ID, in which R, and X have the meanings stated in claim 1 and - 35 4318 1 Hal is halogen, is reacted with a 2-hydroxy-4,6-dimethylpyrimidine derivative of the general formula (in), in which fig has the meaning stated in claim 1, the latter being used in the form of the free base, an alkali metal salt, alkaline earth metal salt or ammonium Salt thereof, or its hydrochloride.

11. A process according to claim 10, in which Hal is chlorine.

12. A process according to claim 10 or 11, ih which the reaction is effected in the presence of an organic solvent or diluent.

13. A process according to claim 10, 11 or 12, in which the 2-hyaroxy-4,6-dimethylpyrimidine derivative (III) is employed as the free base or as its hydrochloride, the reaction being effected in the presence of an acid acceptor.

14. A process according to claim 13, in which the acid acceptor is an alkali metal alcoholate, an alkali metal carbonate or an aliphatic, aromatic or heterocyclio amine.

15. A process according to any of claims 10 to 14, in which the reaction is effected at from 0° to 120°0.

16. A process according to claim 15 in which the reaction is effected at from 40° to 65°C,

17. A process according to any of claims 10 to 16, in which the reactants (II) and (III) are employed in an equimolar ratio.