IE42674B1 - Novel substituted benzisoxazole-thionophosphoric (phosphonic) acid ester and their use as insecticides, acaricides and nematicides - Google Patents

Abstract

1501341 6-Chlore-benzisoxazole thiophosphate and thiophosphonate esters BAYER AG 9 April 1976 [11 April 1975] 14625/76 Heading C2P Novel compounds of the general formula in which R is C 1 -C 4 alkyl and R1 is C 1 -C 3 alkyl or C 1 -C 4 alkoxy are obtained by reacting in the presence of an acid acceptor, or in the form of an alkali metal, alkaline earth metal or ammonium salt with an ester halide of the formula (RO)(R1)P(S)Hal, wherein Hal is halogen, preferably Cl, optionally in the presence of a solvent or diluent. The products have insecticidal, acaricidal and nematicidal properties and may be used as active ingredients in conventional pesticidal compositions.

Description

The present invention relates to certain new 6-chlorobenzisoxazole-thionophosphoric(phosphonic) acid esters, to a process for their preparation and to their use as insecticides, acaricides and nematicides.

It is already known that 5-chloro- and 7-chloro-benzisoxazole-thionophosphoric(phosphonic) acid esters, for example O,O-dimethyl-O-[5-chloro- or -7-chloro-benzisoxazol-(3)-yl)or 0,O-diethyl-O-[5-chlorohenzisoxazol-(3)-yl]-thionophosphoric acid ester, or 0-ethyl-0-[7-chloro-benzisoxazol-(3)-yl]0 thionoethanephosphonic acid ester, have an insecticidal and acaricidal action (see German Auslegeschrift (German Published Specification) 1,253,713 and Netherlands Patent Application 7,305,731).

The present invention provides, as new compounds, the 6-chlorohenzisoxazole-thionophosphoric(phosphonic) acid esters of the general formula in which R represents alkyl with 1 to 4 carbon atoms and 20 R* represents alkyl with 1 to 3 carbon atoms or alkoxy with 1 to 4 carbon atoms.

These compounds have been found to be distinguished by powerful insecticidal, acaricidal and nematieidal properties.

Preferably, R represents straight-chain or branched 25 alkyl with 1 to 3 carbon atoms (especially methyl, ethyl, npropyl or iso-propyl), and R^ represents methyl, ethyl or straight-chain or branched alkoxy with 1 to 3 carbon atoms 4>«94 (namely methoxy, ethoxy, n-propoxy and iso-propoxy?.

The invention also provides a'process for the preparation of a 6-chlorohenzisoxazole-thionophosphoric(phosphonic) acid eater of the formula (I) in which 6-chloro-3~ hydroxy-benzisoxnzole, which has the formula Cl OH is reacted as such, in the presence of an acid acceptor, or in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt thereof, with a thionophosphoric (phosphonic) acid ester halide of the general formula RO S P-Hal (III) in which R and R^ have the above-mentioned meanings and Hal represents halogen, preferably chlorine, optionally in the presence of a solvent or diluent.

Surprisingly, the 6-chlorobenzisoxazole-thionophosphoric(phosphonic) acid esters according to the invention exhibit a better insecticidal, acaricidal and nematicidal action than corresponding 5- and 7-chloro-derivatives of analogous structure and of the same type of action. The compounds according to the present invention thus represent a genuine enrichment of the art.

If Ο,Ο-di-n-butylthionophosphoric acid diester chloride and 6-chloro-3-hydroxy-benzisoxazole are used as starting materials, the course of the reaction oan be represented by the following equation: S .(n-C4Hg0)2P-Cl Acid acceptor -> (n-e4Ii - HCl The thionophosphoric(phosphonic) acid ester halides (XI) required as starting materials are known and can be prepared in accordance with customary processes. 6-Chloro3-hydroxybenzisoxazole is also known [see Chem. Ber. 100.

Sages 954-960 (1967)].

The following may be mentioned as examples of the thionophosphorie(phosphonic) acid ester halides (III) which can be used as starting materials: 0,0-dimethyl-, Ο,Ο-diethyl-, Ο,Ο-di-n-propyl-, 0,0-di-iso-propyl-, Ο,Ο-di-n-butyl-, 0,0-diiso-butyl-, Ο,Ο-di-sec.-butyl-, 0,0-dl-tert.-butyl-, 0-methylΟ-ethyl-, Ο-methyl-O-n-propyl-, O-ethyl-O-iso-propyl-, 0-ethyl-0-seo.-butyl- and O-n-propyl-O-n-butyl-thionophos15 phorie aoid diester chlorides and Ο-methyl-, 0-ethyl-, Ο-n-propyl-, O-ieo-propyl-, Ο-η-butyl-, O-iso-butyl-, 0-sec.butyl- and O-tert.-butyl-methane-, -ethane-, n-propane- and -iso-propane-thionophosphonio acid ester chlorides.

The process for the preparation of the compounds according to the invention is preferably carried ouf in the presence of a suitable solvent or diluent. As such it is • possible to use practically all inert organic solvents, especially aliphatic and aromatic, optionally chlorinated, - 4 d#«t4 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 as acetonitrile and propionitrile.

All customary acid-binding agents can be used a3 acid acceptors. Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate, sodium methylate and ethylate and potassium methylate and ethylate, 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 between 0° and 120°C, preferably at from 40° to 60°C.

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

To carry out the process, the 6-chloro-3-hydroxybenzisoxazole is preferably employed in 10 - 20% excess.

The reaction is preferably carried out in a solvent in the presence of an acid acceptor, in most cases at an elevated temperature. At the end of the reaction time, the reaction mixture is poured into water and is extracted by shaking with an organic solvent, for example toluene. The organic phase is washed and dried and the solvent is distilled off.

The new compounds are frequently obtained in the form of oils which in most cases cannot be distilled without decomposition but are freed from the last volatile con• 4074 stituents by so-called slight distillation, that is to say by prolonged heating under reduced pressure to moderately elevated temperatures, and are purified ih this way. They may be characterised by the refractive index. Some com5 pounds are obtained in a crystalline form and may be characterised by their melting point.

The 6-chlorobenzisoxazole-thionophosphoric(phosphonic) acid esters according to the invention are distinguished by a low phytotoxicity and by an excellent action against sucking and biting insects and against spider mites.

To the sucking insects there belong, in the main, aphids (Aphididae) such as the green peach aphid (Myzus jjersicae), the bean aphid (Doralis fabae), the bird cherry aphid (Bhonalosiphum padi). the pea aphid (Macrosiphum pis!) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korsohelti). the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (M,vzub cerasi): in addition, scales and mealybugs (Cocoina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Iiecanium hesperidum) as Well as the grape mealybug (Pseudococcus marltimus); thrips (Thysanoptera). such as HercinothrjpB femoralis. and bugs, for example the beet bug (Piesma quadrata). the red cotton bug (Dysdercus intermedins), the bed bug (Cimex lectu25 larius), the assassin bug (Bhodnlus prolixus) and Chagas' bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilohatus and Nephotettix bipunctatus.

In the case of the biting insects, above all there should be mentioned butterfly and moth caterpillars (liepidoptera) such as the diamond-back moth (Plutella - 6 maculipennis), the gipsy moth (lymantria dispar), the browntail moth (Euproctis chryaorrhoea) and tent caterpillar(Malacosoma neustria); further, the cabbage moth (Mamestra hrassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris hrassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana). the fall armyworm (laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera). for example the granary weevil (Sitophilus granarius = Calandra granaria), the Colorado beetle (leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochlearlae). the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturns tonentosus), the bean weevil (Bruchidhs = Acanthosoelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium). the flour beetle (Tribolium castaneum). the northern com billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), but also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha): cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana). Madeira cockroach (Beucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus gjganteus) and the black giant cockroach (Blaberus fuacus) as well as Henschoutedenia flexi- 7 4»β74 vitta; further, Orthoptera. for example the house cricket (Srvllus domesticus); termites such as the eastern subterranean termite (Reticulitennes flavines) and Hymenoptera such as ants, for example the garden ant (lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Oeratitis oapitata). the house fly (Musca domestica), the little house fly (Pannia canicularis). the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythroce10 phala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow II fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acarina) there are classed, in particular, the spider mites (Tetranvchidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranvchus pllosus = Panonychus ulmi). gall mites, for example the black currant gall mite (Eriophyes rlbis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Omithodorus moubata).

When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the present compounds are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the invention couple a low toxicity to warm-blooded animals with powerful - 8 4**f< nematicidal properties and can therefore he used to combat nematodes, especially phytopathogenic nematodes. These essentially include leaf nematodes (Arphelenchoides), such as the chrysanthemum eelworm (A. ritzemabosi). the leaf5 blotch eelworm (A. fragarjae) and the rice eelworm (A.oryzae); stem nematodes (Ditylenchus), such as the stem eelworm (D. Dipsaci): root-knot nematodes (Meloidogyne). such as M. arenaria and M. incognita; cyst-forming nematodes (Heterodera). such as the potato cyst eelworm (H. rosto10 chiensis) and the beet cyst eelworm (H. schachtii); and also free-living root nematodes, for example of the genera Pratylenchus. Faratylenchus. Rotylenchus. Xiphinema and Radopholus.

The compounds according to the invention are not only active against plant pests, pests harmful to health and pests of stored products but also, in the veterinary medicine field, against animal parasites (ectoparasites), such as parasitic fly larvae. Some of them are also fungicidally active.

For these reasons, the compounds according to the invention can be employed successfully as pesticides in plant protection and in the hygiene field, the field of protection of stored products and the veterinary field.

The active compounds according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or - 9 dX74 foam-forming agents. In the oase 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, suoh as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, suoh as halogenated hydrocarbons, for example Fteon (Trade Mark.).

As 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 albumin hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste - 10 4»·Τ< 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 ean be used as such, in the form of their formulations or as the use forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, powders, pastes, soluble powders, dusting agents and granules. 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 (ULV) method, where it is possible to apply formulations of up to 95% active compound or even to use the active compound by itself.

The present invention also provides an insecticidal, acaricidal or nematocidal 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 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, 41*74 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 action of the compounds according to the invention can be seen from the biotest Examples which follow.

Example A Ceratltis test Solvent: 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 and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration. ml of the preparation of the active compound was ’5 pipetted onto a filter paper disc of about 7 cm diameter.

This was placed wet over the orifice of a glass vessel in which there were about 30 fruit flies (Ceratltis capitata). and was covered with a glass plate.

After the specified periods of time, the destruction 0 was determined as a percentage. 100% means that all the - 12 10 iWt flies were killed. 0% means that none of the flies were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the degree of destruction can be seen from the following table.

Table A (Insects which harm plants) Active compound Oeratitis Test Active compound Degree of concentration destructin fi> ion in % after 1 day Cl 0.02 100 0.004 85 0.0008 0 (known) 0.02 0.004 0.0008 100 100 Example B Phaedon larvae test 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 - 13 «βΝ stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) were sprayed with the preparation of the active compound until dripping wet and were then infested with mustard beetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction was determined in %: 100% means that all the beetle larvae had been killed whereas 0% means that none of the beetle larve had been killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen flom the following table; Table B (Insects which harm plants) Phaedon larvae test Active compound Active com- Degree of pound con- destructcentration ion in % in % after 3 . days (known) (known) Table B (continued) (Insects which, harm plants) Phaedon larvae test Active compound Active com- Degree of pound con- destructcentration ion in in after 3 days 0.1 0.01 0.001 0.1 0.01 0.001 100 100 100 100 100 100 OC^Hy-iso (4) 0.1 0.01 0.001 100 100 '^oc2h5 0.1 0.01 0.001 100 100 (3) ltS74 Example C Buscelis test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglyeol ether ί To produce a suitable preparation of active compound, part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate was diluted with water to the desired concentration.

Bean plants (Vioia faba) were sprayed With the preparation of the active compound until dew-moist and were then infested with cicadas (Buscelis bilobatus).

After the specified period of time, the degree of destruction was determined in %. 100% means that all the cicadas had been killed; 0% means that none of the cicadas had been killed.

The active compounds, the concentrations of the active compounds, the evaluation times and. the results can he seen from the table which follows: Table 0 (insects which harm plants) Buscelis test Active compound Cl Active com- Degree of pound con- destructcentration ion in % in % after 3 days 0.1 0.02 0.004 (known) 100 - 16 Table Ο (continued) (Insects which harm plants) Buscelis test 4*β?4 Active compound Active com- Degree of pound con- destructcentration ion in % in % after 3 flass ΎΊη S ι H 0—P(OC2H5)2 (2) Cl ~ Π p 0.1 0.02 0.004 100 100 100 Ύ; h0ch3 0.1 0.02 0.004 100 100 0.1 0.02 0.004 100 100 100 (5) 4«βϊ4 Example D Tetranychus test (resistant) Solvent: 3 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.

Bean plants (Ehaseolus 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 twospOtted spider mite (Tetranychus urticae) in all stages of development.

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

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: - 18 Table D (Mites which harm plants) Tetranychus test Active compound Active compound concentration in % Degree of destruction in % after 2 days Cl 6—p(och3)2 0.1 «*·?< (known) XJ fx0CH3 0— P. ΟΟ^Ηγ-η 0.1 (7) -s y ,vch3 0—P C3V iso 0.1 100 (4) (2) 0.1 —p(oc2h5)2 oc2h5 0.1 100 (5) -iso Example Ε Critical concentration test/soil insects Test insect: Hiorbia 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 emulsifer 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 herein 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 insects 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, amounts used and results can be seen from the table which follows: - 20 (Soil insecticides) Phorbla antiqua grubs in the soil Active compound Active com- Degree of pound con- destructcentration ion in fi = 20 ppm Cl (known) (5) 100 OC^Hy-n (6) 100 (9) 100 »«Τ4 Example ff Critical concentration test/soil insects Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight of acetone i Emulsifier: 1 part by weight of alkylaryl polyglyool ether To produce a suitable preparation of active oompound, 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 IO 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 herein 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 insects were introduced into the treated.soil and after a further 2 to 7 days the degree Ϊ0 of effectiveness of the active compound was determined in 5½ 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?έ 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 the table which follows: - 22 <»·Τ4 (Soil insecticides) Tenebrlo molitor larvae in the soil Active compound Active Degree of compound destructconoentra- ion in % tion =i.J? KF S (known) 100 XoC^-iso 100 100 - 23 43074 Table R (continued) (Soil insecticides) Tenebrio molitor larvae in the soil Active compound Active com- Degree of pound con- destructcentration ion in fi - 5 PPffl ......

Example S Critical concentration test Test nematode: Meloidogyne incognita Solvent: 3 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 active compound was mixed with the stated amount of solvent, the stated amount of emuisifer 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 herein 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, and the degree of effectiveness of the active compound was determined as a - 24 4*β74 percentage. The degree of effectiveness was 100% when infestation wae completely avoided; it was 0% when the infestation waB 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 the following table: Table G (Nematicides) Meloidogyne incognita Active compound Active com- Degree of pound con- destructcentration ion in % = 10 ppm Cl 4»β74 Table G (continued.) (Nematicides) Meloidogyne incognita Active compound Active com- Degree of pound con- destructcentration ion in % = 10 ppm - P ^OCH^-iso (5) 100 Example H 1D1OO test Test insects: Sitophilus granarius ) Solvent: Acetone parts hy weight of the active compound were taken up in 1,000 parts by volume of the solvent. The solution so obtained was diluted with further solvent to the desired concentrations. 2.5 ml of the solution of the active compound were pipetted into a Petri dish. On the bottom of the Petri dish there was a filter paper with a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per 2 m of filter paper varied with the concentration of the solution of active compound. About 25 test insects were then placed in the Petri dish and it was covered with a - 26 <*·τ< glass lid.

The condition of the test insects was observed 3 days after the commencement of the expei’iments. The destruction, in %, was determined. 100% denotes that all test animals had been killed; 0% denotes that no test animals had been killed.

The aotive compounds, the concentrations of the active compounds, the test animals and the results can be seen from the following table: Table H LD^OO 'k®3'*' Active compound Active com- Destruction pound con- in % centratxons % strength solution (known) 0.2 0.02 0.002 100 100 0.2 0.02 0.002 0.2 0.02 0.002 100 100 100 100 100 100 43β74 'Table Η (continued) ED 100 test Active compound Active com- Destruction pound con- in % centrations % strength solution 0.2 0.02 0.002 0.2 0.02 0.002 0.2 0.02 0.002 0.2 0.02 0,.002 100 100 100 100 100 100 100 100 100 100 100 100 Example J Mosquito larvae test 11 Test insects: Aedes aegypti larvae Solvent: 99 parts by weight of acetone Emulsifier: 1 part by weight of benzylhydroxydiphenyl polyglycol ether To produce a suitable preparation of active compound, parts by weight of the active compound were dissolved in 1,000 parts by volume of the solvent containing the amount of emulsifier stated above. The solution thus obtained was diluted with water to the desired lower concentrations. - 28 10 The aqueous preparations of the active compounds were placed in glass vessels and about 25 mosquito larvae were then placed in each glass vessel.

After 24 hours, the degree of deetruotion was determined as a percentage. 100% means that all the larvae were killed. 0|4 means that no larvae at all were killed.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following table: Table J Mosquito larvae test Active compound Active compound concentrations of the solution in EB Degree of destruction in 0.1 0.01 100 0.1 0.01 0.001 0.1 0.01 0.001 0.0001 0.1 0.01 0.001 100 100 100 100 100 100 100 4074 Table J (continued) Mosquito larvae test Active compound Active com- Degree of pound con- destructcentrations ion in % of the solution in - . . -EE®— 0.1 100 0.01 100 0.001 80 0.1 100 0.01 90 0.1 100 0.01 90 ethylene polyglyeol monoExample K Test with parasitic fly larvae Solvent: 35 parts by weight of methyl ether Emulsifier:35 parts by weight of nonylphenol polyglyeol ether To produce a suitable preparation of active oompound, parts by weight of the active substance in question were mixed with the stated amount of solvent which contained the above-mentioned proportion of emulsifier and the concentrate thus obtained was diluted with water to the desired concentration.

About 20 fly larvae (Ducilia ouprina) were introduced into a test tube which contained approx. 2 ern^ of horse muscle. 0.5 ml of the preparation of active compound was - 30 applied to this horse meat. After 24 hours, the degree of destruction in % was determined. 100% means that all the larvae had been killed and 0% means that no larvae had been killed.

The active compounds investigated, the concentrations of the active compounds used and the results obtained can be seen from the table whioh follows: Table K (Test with parasitic fly larvae (lucilia cuprina/resistant)) Active compound Active com- Degree of pound con- destructcentration ion in % in ppm 100 Cl 100 100 100 100 100 100 100 10 <50 100 100 <50 <50 (5) - 51 4ie?4 Table K (continued) (Test with parasitic fly larvae (lucilia cuprina/resistaiit)) Active compound Active com- Degree of pound con- destructcentration Ion in fi in ppm , . 100 100 100 C OC„Hr 2 5 oc3h?iso 100 100 100 OC^Hy-iso '^DCjHy-iso 100 100 100 100 100 100 100 (7) ^OCjHy-n 100 100 100 The process of the present invention is illustrated by the following preparative Examples.

Example 1: Cl (1) 0-P(0CH3)2 A mixture of 61 g (0.36 mole) of 6-ohloro-3-hydroxybenzisoxazole in 500 ml of acetonitrile and 54 g (0.39 mole) of potassium carbonate was stirred for 30 minutes at 50°C. g (0.3 mole) of Ο,Ο-dimethylthionophosphoric acid diester chloride were added dropwise at 50°C and stirring was continued for a further hour at this temperature and overnight at room temperature. Water was then added and the oil which separated out was taken up in toluene. The organic phase was extracted by shaking with water and then twice with 2 N sodium hydroxide solution and was washed neutral with water. After drying over sodium sulphate, the solvent was distilled off. 63 g (72.5% of theory) of 0,0-dimethyl-0-6-chloro15 benzisoxazol-(3)-yl-thionophosphoric acid ester were obtained as an oil which on trituration with a petroleum ether/ether mixture (5:1) gave pale yellow, coarse crystals of melting point 37°C.

The following compounds of the formula could be prepared analogously to Example 1: 43374 Ex- ^Physical data Yield ample . (melting point, of No. Ε E1 °C; theory) refractive index) 2 -C2H5 -oc2H5 njj1: 1.5365 73 3 -C2H5 -c2h5 n21: 1.5565 85 4 -C^Hy-iSO -och3 4β - 47 62 5 -C-Hy-iso -oc2h5 n21: 1.5158 65.5 6 -CjHy-iso -OC^Hy-iso Πρ1: 1.4792 57 7 -CH3 -OCjHy-n n21: 1.5383 72 8 -CjHy-n -OCjHy-n nj*1: 1.5225 55 9 -c2h5 -OCjHy-n n21: 1.5334 75.5 - 34 4X94

Claims (27)

1. CLAIMS:1. 6-Chlorotenzisoxazole-thionophosphoric(phosphonic) acid esters of the general formula in which R represents alkyl with 1 to 4 carbon atoms and βΐ represents alkyl with 1 to 3 carbon atoms or alkoxy with 1 to 4 carbon atoms.

2. Compounds according to claim 1, in which R represents straight-chain or branched alkyl with 1 to 3 carbon atoms and Rl represents methyl, ethyl or straight-chain or branched alkoxy with 1 to 3 carbon atoms.

3. The compound of the formula

4. The compound of the formula

5. The compound of the formula (5) - 35 «··*♦

6. The compound of the formula Cl L· 0CH 3 'Όσ^Ηγ-ίθο (4),

7. The compound of the formula Cl .-/°¾¾ ^OCUL-ieo

8. The compound of the fornula (5), (6) ti iso P Όσ-Β,-iso

9. The compound of the formula Cl r//- 0 A 1-1- 001 ¾ u ^ΟΟ^Ηγ-η

10. The compound of the formula 14/°¾¾ u ΌΟ^Ήγ-η

11. The compound of the formula (7) (9) il 0 —Ρ(οσ 3 Η γ -η) 2 (8)

12. A process for the preparation of a 6-chlorobenzisoxazolethionophosphoric(phosphonic) acid ester according to claim 1 in which 6-chloro-3-hydroxybenzisoxazole of the formula Cl is reacted as such, in the presence of an acid acceptor, or in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt thereof, with a thionophosphoric (phosphonic) acid ester halide of the general formula RO.^ S II 'P-Hal (III) 10 in which R and R 1 have the meanings stated in claim 1 and Hal represents halogen, optionally in the presence of a solvent or diluent.

13. A process according to claim 12, in which Hal is 15 chlorine.

14. A process according to claim 12 or 13 in which the reaction is effected in the presence of an inert organic solvent.

15. A process according to claim 12, 13 or 14, in which 20 the reaction is effected at between 0° and 120°C.

16. A process according to claim 15» in which the reaction is effected at from 40° to 60°0.

17. A process according to any of claims 12 to 16, in which the reaction is effected in the presence, as an acid 25 acceptor, of an alkali metal carbonate, an n1knιi metal - 37 4**74 alcoholate or an aliphatic, aromatic or heterocyclic amine.

18. A process according to any of claims 12 to 17, in which the ester halide (III) is one that is hereinbefore specifically mentioned.

19. A process for the preparation of a compound according to claim 1, substantially as described in Example 1.

20. Compounds according to claim 1, whenever prepared by a process according to any of claims 12 to 19.

21. An insecticidal, acaricidal or nematocidal composition containing as active ingredient a compound according to any of claims 1 to 11 and 20 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

22. A composition according to claim 21 containing from 0.1 to 95% of the active compound, by weight.

23. A composition according to olaim 22 containing from 0.5 to 90% of the active compound, by weight.

24. · A method of combating insects, acarids or nematodes which comprises applying to the insects, acarids or nematodes, or to a habitat thereof,a compound according to any of claims 1 to 11 and 20 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 to 11 and 20 in admixture with a diluent or carrier.

25. A method according to olaim 23 in whioh a composition is used containing from 0.0001 to 10% of the active compound, by weight.

26. A method according to olaim 25 in which a composition is used containing from 0.01 to 1% of the active oompound, by weight. - 38 4X94

27. ^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 according to any of claims 1 to 11 and 20 was applied alone or in 5 admixture with a diluent or carrier.