O-Alkyl-O-[5-Chloro-1,2,4-Triazol(3)yl]-Thiono(thiol)-Phosphoric (Phosphonic) Acid Esters and Ester-Amides

The present invention relates to and has for its objects the provision of particular new O-alkyl-O-[5-chloro-1,2,4-triazol(3)yl]-thiono(thiol)-phosphoric (phosphonic) acid esters and ester-amides which possess arthropodicidal and nematicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. arthropods and nematodes, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification DOS 2,301,400 that O-triazolylthionophosphoric-(phosphonic) acid esters, for example O,O-diethyl-O-[1-ethyl-5-cyanomethylthio- (Compound A) or 1-ethyl-5-allylthio-1,2,4-triazol(3)yl]-thionophosphoric acid ester (Compound B), O-ethyl-O-[1-methyl-5-methoxy-1,2,4-triazol(3)yl]-thionophenylphosphonic acid ester (Compound C) and O-ethyl-N-isopropyl-O-[1-isopropyl-5-methylthio-1,2,4-triazol(3)yl]-thiono phosphoric acid esteramide (Compound D) possess insecticidal and acaricidal properties.

The present invention provides, as new compounds, the O-triazolylthiono(thiol)phosphoric(phosphonic) acid esters and ester-amides of the general formula ##STR2## in which R is alkyl with 1 to 6 carbon atoms,

R.sub.1 is alkyl, alkoxy, alkylthio or monoalkylamino each with 1 to 6 carbon atoms, and

R.sub.2 is alkylthioalkyl with 1 to 4 carbon atoms per alkyl radical, alkenyl with 2 to 5 carbon atoms, carbalkoxyalkyl with 1 to 4 carbon atoms per alkyl radical, 1-methyl-2-cyanoethyl, or phenoxyalkyl with 1 to 4 carbon atoms in the alkyl radical and optionally substituted on the phenyl radical by at least one of halogen, cyano, or alkylthio or alkyl each with 1 to 4 carbon atoms.

Preferably, R represents straight-chain or branched alkyl with 1 to 4 (especially 1 to 3) carbon atoms, R.sub.1 represents straight-chain or branched alkyl, alkoxy, alkylthio or monoalkylamino each with 1 to 4 (especially 1 to 3) carbon atoms, and R.sub.2 represents allyl, buten(2)yl, buten(3)yl, alkylthioethyl or alkylthiopropyl with 1 to 4 carbon atoms in the alkyl radical, 1-methyl-2-cyanoethyl, carbalkoxyalkyl with 1 to 3 carbon atoms per alkyl radical, phenoxyethyl, or halophenoxyethyl (especially chlorophenoxyethyl).

Surprisingly, the O-triazolylthiono(thiol)phosphoric-(phosphonic) acid esters and ester-amides according to the invention exhibit a better insecticidal, acaricidal and nematicidal action than the compounds of analogous structure and of the same type of action, previously known from the state of the art. They thus represent a genuine enrichment of the art.

Preferably, R represents straight-chain or branched alkyl with 1 to 4 (especially 1 to 3) carbon atoms, R.sub.1 represents straight-chain or branched alkyl, alkoxy, alkylthio or monoalkylamino, each with 1 to 4 (especially 1 to 3) carbon atoms, and R.sub.2 represents allyl, buten-(2)-yl, buten-(3)-yl, alkylthioethyl or alkylthiopropyl with 1 to 4 carbon atoms in the alkyl radical, 1-methyl-2-cyanoethyl, carbalkoxyalkyl with 1 to 3 carbon atoms per alkyl radical, or phenoxyethyl, the phenyl ring being optionally (but preferably) monosubstituted or polysubstituted by halogen (especially chlorine).

The present invention also provides a process for the preparation of an O-triazolylthiono(thiol)phosphoric-(phosphonic) acid ester or ester-amide of the formula (I), in which a thiono(thiol)phosphoric(phosphonic) acid ester halide or ester-amide halide of the general formula ##STR3## in which R and R.sub.1 have the above-mentioned meanings and

Hal represents halogen, especially chlorine,

is reacted, if appropriate in the presence of a solvent or diluent, with a triazole derivative of the general formula ##STR4## in which R.sub.2 has the above-mentioned meaning,

the latter being used 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.

If, for example, O-ethyl-N-methylthionophosphoric acid ester-amide chloride and 1-(1-methyl-2-cyanoethyl)-3-hydroxy-5-chlorotriazole are used as starting materials, the course of the reaction can be represented by the following equation: ##STR5##

The thiono(thiol)phosphoric(phosphonic) acid ester halides 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 processes.

The following may be mentioned as individual examples thereof: O,O-dimethyl-, O,O-diethyl-, O,O-di-n-propyl-, O,O-di-isopropyl-, O,O-di-n-butyl-, O,O-di-sec.-butyl-, O,O-di-isobutyl-, O,O-di-tert.-butyl-, O-methyl-O-ethyl-, O-ethyl-O-n-propyl-, O-ethyl-O-isopropyl-, O-ethyl-O-tert.-butyl- or O-ethyl-O-sec.-butyl-thionophosphoric acid diester chloride; O,S-dimethyl-, O,S-diethyl-, O,S-di-n-propyl-, O,S-di-iso-propyl-, O,S-di-n-butyl-, O,S-di-isobutyl-, O,S-di-sec.-butyl-, O,S-di-tert.-butyl-, O-methyl-S-ethyl-, O-ethyl-S-n-propyl-, O-ethyl-S-isopropyl-, O-ethyl-S-n-butyl-, O-n-propyl-S-ethyl-, O-n-propyl-S-n-butyl- or O-isopropyl-S-ethyl-thionothiolphosphoric acid diester chloride; O-methyl-N-methyl-, O-ethyl-N-ethyl-, O-n-propyl-N-n-propyl-, O-iso-propyl-N-isopropyl-, O-n-butyl-N-n-butyl-, O-isobutyl-N-isobutyl-, O-sec.-butyl-N-sec.-butyl-, O-tert.-butyl-N-tert.-butyl-, O-ethyl-N-isopropyl-, O-isopropyl-N-ethyl-, O-tert.-butyl-N-ethyl- or O-sec.-butyl-N-ethyl-thionophosphoric acid ester-amide chloride; and O-methyl-, O-ethyl-, O-n-propyl-, O-isopropyl-, O-n-butyl-, O-isobutyl-, O-sec.-butyl- or O-tert.-butyl-methane-, -ethane-, -n-propane-, -isopropane-, -n-butane-, -isobutane-, -sec.-butane- or -tert.-butane-thionophosphonic acid ester chloride.

The triazole derivatives of the formula (III) can be prepared in accordance with generally customary processes, in particular by reacting correspondingly substituted hydrazines or their hydrochlorides with N-chlorocarbonylisocyanide-dichloride in accordance with the following equation: ##STR6## wherein R.sub.2 has the above-mentioned meaning.

The following may be mentioned as individual examples of triazole derivatives (III) to be reacted in accordance with the process: 1-(1-methyl-2-cyanoethyl)-, 1-allyl-, 1-[2-methylpropen(2)yl]-, 1-buten-(3)-yl-, 1-(2-methylthioethyl)-, 1-(2-ethylthioethyl)-, 1-(2-n-propylthioethyl)-, 1-(2-iso-propylthioethyl)-, 1-(2-n-butylthioethyl)-, 1-(2-sec.-butyl-thioethyl)-, 1-(2-iso-butylthioethyl)-, 1-(2-tert.-butylthio-ethyl)-, 1-(3-methylthio-n-propyl)-, 1-(3-ethylthio-n-propyl)-, 1-(3-n-propylthio-n-propyl)-, 1-(3-iso-propylthio-n-propyl)-, 1-(3-n-butylthio-n-propyl)-, 1-(3-tert.-butylthio-n-propyl)-, 1-(1-methylthioethyl)-, 1-(1-ethylthioethyl)-, 1-(iso-propylthiomethyl)-, 1-(ethylthiomethyl)-, 1-(2-phenoxyethyl)-, 1-[2-(2,4-dichlorophenoxy)-ethyl]-, 1-[2-(4-chlorophenoxy)-ethyl]-, 1-[2-(2,4,6-trichlorophenoxy)-ethyl]-, 1-[2-(3,4-dichlorophenoxy)-ethyl]-, 1- 8 2-(pentachlorophenoxy)-ethyl]-, 1-carbomethoxymethyl-, 1-carbethoxymethyl-, 1-carbo-n-propoxy-methyl-, 1-carbo-iso-propoxymethyl-, 1-(1-carbomethoxyethyl)-, 1-(1carbethoxyethyl)-, 1-(1-carbo-n-propoxyethyl)-, 1-(1-carbo-iso-propoxyethyl)-, 1-(1-carbomethoxy-n-propyl)-, 1-(1-carbethoxy-n-propyl)-, 1-(1-carbo-n-propoxy-n-propyl)- and 1-(1-carbo-iso-propoxy-n-propyl)-5-chloro-3-hydroxy-1,2,4-triazole.

The process for the preparation of the compounds according to the invention is preferably carried out in the presence of a suitable solvent or diluent. 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 or chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; 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 as 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.degree. and 120.degree. C, preferably at from 30.degree. to 75.degree. C.

In general, the reaction is allowed to take place under normal pressure.

To carry out the process, the starting components are in general employed in equimolar amounts. An excess of one or other reactant produces no significant advantages. The reaction is preferably carried out in one of the above-mentioned solvents or diluents, in the presence of an acid acceptor, at the stated temperatures, while stirring. After a reaction time of from one to several hours, in most cases at an elevated temperature, the reaction mixture is worked up in accordance with generally customary methods.

The new compounds are obtained in the form of oils, which can frequently not 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 characterized by the refractive index.

As already mentioned, the O-triazolylthiono(thiol)-phosphoric(phosphonic) acid esters and ester-amides according to the invention are distinguished by an excellent insecticidal, acaricidal and nematicidal activity. They are not only active against plant pests but also against pests harmful to health and pests of stored products. They have a low phytotoxicity and 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 as well as in the hygiene field and the field of protection of stored products.

The active compounds are well tolerated by plants, have a favorable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects and arachnids, and nematode pests which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development.

The above-mentioned pests include from the class of the Isopoda, for example, Oniscus ascellus, Armadillidium vulgare and Porcellio scaber; from the class of the Diplopoda, for example Blaniulus guttulatus; from the class of the Chilopoda, for example Geophilus carpophagus and Scutigera spec.; from the class of the Symphyla, for example Scutigerella immaculata; from the class of the Thysanura, for example Lepisma saccharina; from the class of the Collembola, for example Onychiurus armatus; from the class of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria; from the class of the Dermaptera, for example Forficula auricularia; from the class of the Isoptera, for example Reticulitermes spp.; from the class of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.; from the class of the Mallophaga, for example Trichodectes spp. and Damalinea spp. from the class of the Thysanoptera, for example Hercinothrips femoralis and Thrips tabaci; from the class of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.; from the class 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, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.; from the class of the Lepidoptera, for example 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 kuebniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana; from the class of the Coleoptera, for example 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 and Costelytra zealandica; from the class of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharanois and Vespa spp.; from the class 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, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.; from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans; from the class of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The plant-parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semi-penetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., and Trichodorus spp.

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

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, 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, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.

These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as solid carriers, ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for granules; crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Adhesives such as carboxymethylcellulose 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.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other arthropodicides and nematicides, or fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferably 0.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0000001-100, preferably 0.01-10%, by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95%, by weight of the mixture.

When used against nematodes, the preparations are generally applied to an area of agriculture in amounts of 1 to 100 kg of active compound per hectare, and are then incorporated into the soil.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 100 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. arthropods such as insects and acarids, or nematodes, which comprises applying to at least one of correspondingly (a) such arthropods, (b) such nematodes, and (c) the corresponding habitat thereof, i.e. the locus to be protected, e.g. to a growing crop, to an area where a crop is to be grown or to a domestic animal, a correspondingly combative or toxic amount, i.e. an arthropodicidally or nematicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

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 containing the stated amount of emulsifier, and the concentrate was diluted with water to the desired concentration.

1 cm.sup.3 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 times and the results can be seen from the following table:

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 containing the stated amount of emulsifier 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 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 larvae had been killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:

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 containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active compound until dripping wet.

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

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:

Solvent: 3 parts by weight Aceton

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.

Bean plants (Phaseolus vulgaris) which were heavily infested with the two-spotted spider mite (Tetranychus urticae) in all stages of development were sprayed with the preparation of the active compound until dripping wet.

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 active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:

Test insect: Tenebrio molitor larvae 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, 1 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 hereinafter in ppm (= mg/1). 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 is 100% if all 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 the table which follows:

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, 1 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 hereinafter in ppm (= mg/1). 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 is 100% if all 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 the table which follows:

Test nematode: Meloidogyne incognita

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkyl polyglycol ether

To produce a suitable preparation of active compound, 1 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 hereinafter in ppm (= mg/l), was decisive. The treated soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse temperature of 27.degree. C.

After 4 weeks, the lettuce roots were examined for infestation with nematodes (root galls), and the degree of effectiveness of the active compound was determined as a percentage. The degree of effectiveness was 100% when infestation had been 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 the following table:

Lt.sub.100 test for Diptera

Test insects: Musca domestica

Solvent: Acetone

2 parts by weight of active compound were taken up in 1000 parts by volume of solvent. The solution so obtained was diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of 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 square meter of filter paper varied with the concentration of the solution of active compound used. About 25 test insects were then placed in the Petri dish and it was covered with a glass lid.

The condition of the test insects was continuously observed. The time which was necessary for a 100% knock down effect was determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there was a 100% knock down effect can be seen from the following table:

Test insects: Sitophilus granarius

Solvent: Acetone

2 parts by 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 m.sup.2 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 glass lid.

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

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following table:

The process of the present invention is illustrated by the following preparative examples:

The starting materials of the formula (III) were prepared, for example, as follows: ##STR99##

30.4 g (0.2 mole) of 2-phenoxyethylhydrazine were dissolved in 200 ml of anhydrous acetonitrile and 7.3 g of hydrogen chloride gas were passed in at 0.degree. C. 32 g (0.2 mole) of N-chlorocarbonyl-isocyanide-dichloride were then added dropwise to the mixture at 15.degree.-20.degree. C, while cooling and stirring vigorously, and after completion of the addition, 30 g of potassium carbonate were also added. The batch was next stirred for 4 hours at room temperature, in the course of which the temperature in the reaction vessel at times rose to as much as 45.degree. C, and was then heated under reflux until no further evolution of hydrogen chloride was detectable (4-6 hours). After cooling, the residue was filtered off and washed with acetonitrile, and the total filtrate was evaporated under reduced pressure. The crystalline residue was recrystallized from a little ethanol. 21 g (43.8% of theory) of 1-(2-phenoxyethyl)-5-chloro-3-hydroxy-1,2,4-triazole of melting point 166.degree. C were obtained. ##STR100##

33.7 g (0.2 mole) of 1-hydrazinopropionic acid ethyl ester hydrochloride were dissolved in 150 ml of anhydrous acetonitrile and 32 g (0.2 mole) of N-chlorocarbonyl-isocyanide-dichloride were added dropwise to the mixture at 20.degree. C. After completion of the addition, 30 g of potassium carbonate were added to the reaction mixture, and the latter was stirred for 3 hours at room temperature. The batch was then heated under reflux until no further evolution of hydrogen chloride was detectable (4-6 hours). After cooling, the residue was filtered off and washed with acetonitrile and the entire filtrate was evaporated under reduced pressure.

The crystalline residue was recrystallized from a little ethanol. 16.3 g (37% of theory) of 1-(1-carbethoxyethyl)-5-chloro-3-hydroxy-1,2,4-thiazole of melting point 141.degree.-142.degree. C were obtained.

The following compounds were prepared analogously to the procedure described in (a) and (b):

The following compounds of the formula ##STR111## could be prepared analogously:

Other compounds which can be similarly prepared include:

and the like.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.