DE3438919A1 - Substituted phenylcarbamic acid esters - Google Patents

Abstract

Novel phenylcarbamic acid esters of the formula <IMAGE> are provided, in which R represents hydrogen or optionally substituted radicals of the alkyl or cycloalkyl series and Az represents an azolyl radical bonded via nitrogen. The novel phenylcarbamic acid esters of the formula (I) are distinguished by a particularly high and long activity as pesticides, in particular as insecticides.

Description

Substituted phenyl carbamic acid esters

The invention relates to new phenylcarbamic acid esters, a process for their production and their use in pesticides, in particular as insecticides.

It is known that certain carbamates such as 2- (1-methylethoxy) phenyl methyl carbamate are insecticidal (cf. DE-AS 1 108 202).

The action and duration of action of these compounds are, however, in particular with certain insects, not always satisfactory.

New substituted phenylcarbamic acid esters of the formula (I) have now been found in which R stands for hydrogen or optionally substituted radicals from the series alkyl or cycloalkyl and Az stands for an azolyl radical bonded via nitrogen.

It has also been found that the new substituted phenyl-carbamic acid esters of the formula (I) are obtained if phenol ethers of the formula (II) with methyl isocyanate of the formula (III) H3C-N =C =O (III), if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent.

The new substituted phenyl carbamic acid esters of the formula (I) are characterized by a particularly high and long-term effectiveness as a pesticide, especially as insecticides.

As substituents of the optionally substituted alkyl or cycloalkyl radicals The following are preferred: halogen, OH, alkoxy (C1-C4).

The alkyl or cycloalkyl radicals are preferably unsubstituted.

The invention preferably relates to compounds of the formula (1) in which R stands for hydrogen, alkyl with 1 to 4 carbon atoms or for cycloalkyl with 3 to 8 carbon atoms and Az stands for one bonded via nitrogen 1,2,4-triazolyl, pyrazolyl or imidazolyl radical.

The compounds of the formula (I) in which R represents hydrogen, methyl or ethyl, cyclopropyl, cyclopentyl or cyclohexyl and Az stands for a 1,2,4-triazolyl, pyrazolyl or imidazolyl radical bonded via nitrogen stands.

If, for example, methyl isocyanate and 2- (pyrazol-1-yl-methylenoxy) -phenol are used as starting materials for the process according to the invention, the corresponding reaction can be represented by the following equation: The phenol ethers to be used as starting materials for the preparation of the new compounds of the formula (I) in the process according to the invention are generally defined by the formula (II). In this formula, R and Az stand for those radicals which are given above in the definition in formula (I) as preferred or as particularly preferred.

Examples of the phenol ethers of the formula (II) include: Table 1 R Az R Az H ~ C -sa -cj EtJ H -NINI / = N / rN H -N 2 N ~ -N CH3 -N CH3 -N NÖC 3 4 -N rJ CH3 -Nx J 4 -N C 2H5 -N C -N j 25 - H NJ C2H5 Ns 2 | e NJ NNJ The compounds of the formula (II) are new.

Production takes place by reaction according to processes known per se of halides of the formula (IV) Az-CHR-Hal (IV) in which R and Az are those given above Have meanings and Hal represents halogen, such as, in particular, chlorine or bromine, with an alkali or alkaline earth salt of 2-hydroxyphenol, such as sodium 2-hydroxphenolate, in the presence of inert diluents such as acetonitrile in general at temperatures between 0OC and 1200C, preferably between 200C and 800C.

The halides of the formula (IV) are known and / or can be found on Manufacture easily using known methods and processes (see e.g. EP-OS 60 222, EP-OS 8056 and EP-OS 8057).

The halides of formula (IV) are in a preferred embodiment in the usual manner from the corresponding acid addition salts of the compounds of the formula (IV) with, for example, hydrochloric acid (see preparation examples).

The inventive method for producing the new substituted Phenyl carbamic acid ester of the formula (I) is preferred using diluents carried out. Practically all inert organic solvents can be used as diluents in question.

These include in particular aliphatic and aromatic, if appropriate halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, Gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, Carbon tetrachloride, chlorobenzene, o-dichlorobenzene, ethers such as diethyl and dibutyl ethers, Glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl esters, nitriles such as acetonitrile and propionitrile, amides such as e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone as well as dimethyl sulfoxide, Tetramethylene sulfone and hexamethylphosphoric acid triamide.

The process is preferably carried out in the presence of catalysts.

Tertiary amines, for example triethylamine, have proven particularly useful Trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The process according to the invention is generally carried out at temperatures performed between OOC and 1400C. The range between 200C and 200C is preferred 1200C. The reactions are generally carried out under normal pressure.

To carry out the process according to the invention, 1 mol Phenol ethers of the formula (II) 1 to 3 mol, preferably 1 to 2 mol, of methyl isocyanate of formula (III) are used.

The reaction is generally carried out in a suitable diluent carried out in the presence of a catalyst and the reaction mixture is several Stirred for hours at the required temperature.

The subsequent work-up and isolation takes place in accordance with the usual methods Methods.

The active ingredients are suitable and cheaper if they are well tolerated by plants Warm-blooded toxicity for the control of animal pests, especially insects, those in agriculture, in forests, in store and material protection as well as on occur in the hygiene sector. They are against normally sensitive and resistant species as well as effective against all or individual stages of development. To the above mentioned Pests include: From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, e.g. Blaniulus guttulatus.

From the order of the Chilopoda, e.g. Geophilus carpophagus and Scutigera spec.

From the order of the Symphyla, e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola, e.g. Onychiurus armatus.

From the order of the Orthoptera, e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, e.g. Forficula auricularia.

From the order of the Isoptera, e.g. Reticulitermes spp ..

From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera, e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera, e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus ,. Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, e.g. Xenopsylla cheopis, Ceratophyllus spp ..

From the order of the Arachnida, e.g. Scorpio maurus, Latrodectus mactans.

The active compounds of the formula (I) according to the invention are distinguished by very good insecticidal effectiveness. They particularly show when in use as soil insecticides an excellent effect and a long-term effectiveness against Beetle larvae such as Phaedon chochleariae and aphids such as Myzus persicae. The compounds of the formula (I) also show a fungicidal action against Oomycetes and against Pyricularia oryzae on rice.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Active ingredient-impregnated natural and synthetic materials, fine encapsulation in polymers Substances and in coating compounds for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, coils and the like, as well as ULV cold and warm smoke formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalk; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes substances and micro-nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used in their commercially available formulations and in the use forms prepared from these formulations as a mixture with other active ingredients such as insecticides, attractants, sterilants, acaricides, nematicides, Fungicides, growth regulators or herbicides are present. To the insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated ones Hydrocarbons, phenylureas, substances produced by microorganisms i.a.

The active ingredients according to the invention can also be used in their commercially available form Formulations and in the use forms prepared from these formulations present in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist itself must be actively effective.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges. The active ingredient concentration the use forms can contain from 0.0000001 to 95% by weight of active ingredient, preferably are between 0.0001 and 1% by weight.

They are used in a customary manner adapted to the use forms Way.

When used against hygiene and storage pests stand out the active ingredients through an excellent residual effect on wood and clay as well as through good alkali stability on cold substrates.

Preparation examples Example 1 20.5 g (0.1 mol) of 2- [1- (1,2,4-triazol-1-yl) -ethylene-1-oxy] -phenol are dissolved in 150 ml of tetrahydrofuran, and a few drops of triethylamine are added. 11.4 g (0.2 mol) of methyl isocyanate in 50 ml of tetrahydrofuran are then added. The reaction mixture is refluxed for 3 hours and then evaporated in vacuo. The remaining residue is recrystallized from ether.

18.9 g (72% of theory) of N-methyl-2-z1- (1,2,4-triazol-1-yl) -ethylene-1-oxy7-phenyl-carbamic acid ester are obtained in the form of white crystals with a melting point of 970C.

Analogously to Example 1, the following compounds of the formula (I) can be obtained from Table 2: Table 2 Sample no. R Az Fp (OC) 2 H - ç ll0 3 CH3 77 77 4 CH3 -N 1 120 5 H. 6 H. Starting compounds of the formula (III) Example (III-1) 11.5 g (0.5 mol) of sodium are dissolved in 500 ml of methanol, 55 g (0.5 mol) of 2-hydroxyphenol are added and the mixture is then evaporated to dryness in vacuo.

The solid residue is mixed with 100 ml of toluene and again im Evaporated to dryness in vacuo. The remaining sodium salt of 2-hydroxyphenol is suspended in 500 ml of acetonitrile and added dropwise with stirring with a solution of 65.8 g (0.5 mol) of 1-chloro-1- (1,2,4-triazol-1-yl) ethane in 150 ml of acetonitrile added and heated under reflux for 3 hours.

After cooling to 20 ° C., the precipitated sodium chloride is filtered off and the filtrate evaporated in vacuo. The remaining residue is in 500 ml Water and 500 ml of ethyl acetate were added, and the aqueous phase was mixed with hydrochloric acid neutralized and extracted several times with ethyl acetate. The United organic phases are dried over sodium sulfate, filtered off and in vacuo evaporated.

75 g of an oily residue which is added to the mixture of chloroform are obtained (3 parts) and ethyl acetate (1 part) is chromatographed as the eluent.

This gives 48.5 g (47% of theory) of 2-L1- (1,2,4-triazol-1-yl) -ethylene-1-oxy7-phenol in the form of colorless crystals with a melting point of 1350C.

The following compounds of the formula (III) from Table 3 can be prepared analogously to Example (III-1): Table 3 Sample no. R Az Fp. (OC) (111-2) H -N <137 N 1 137 (III-3) CH3 / N-7 NJ 77 (III-4) CH3 -N a 138 (III-5) H -N s (111-6) H. Starting compounds of the formula (IV) Example (IV-1) 168 g (1 mol) of 1-chloro-1- (1,2,4-triazol-1-yl) ethane hydrochloride are suspended in 300 ml of acetonitrile, and 101 g (1 mol) of triethylamine are added dropwise while stirring. The mixture is kept at a maximum of 200C by cooling. The mixture is stirred for a further 1 hour and then cooled to about -50C. The precipitate of triethylamino hydrochloride which separates out is filtered off. The filtrate from 1-chloro-1- (1,2,4-triazol-1-yl) ethane and acetonitrile can be used for the reaction to prepare compounds of the formula (III) without further purification. However, 1-chloro-1- (1,2,4-triazol-1-yl) ethane can be isolated in pure form if the filtrate obtained above is evaporated to dryness.

114 g (87% of theory) of 1-chloro-1- (1,2,4-triazol-1-yl) ethane are obtained in this way in the form of a colorless oil.

The following compounds from Table 4 can be prepared analogously to Example (IV-1): Az-CHR-Hal (IV) Table 4 Sample no. R Az Hal boiling point (0C / mbar) (IV-2) H -N Cl viscous oil (1V-3) H -N cl viscous oil (IV-4) H -N g cl 62-65 / 0.3 (IV-5) CH3 - -Nx to cl 52-54 / 0.9 (IV-6) CH3 -NQ cl viscous oil Precursors for the preparation of the compounds of the formula (IV) 113.3 g of 1-hydroxy-1- (1,2,4-triazol-1-yl) ethane are dissolved in 200 ml of methylene chloride at 200C, added dropwise to 142.7 g (1.2 mol) of boiling thionyl chloride and 1 Heated under reflux for an hour. After cooling to room temperature, the precipitated crystals are filtered off with suction, washed with ether and dried in vacuo.

124.8 g (74% of theory) 1-chloro-1- (1,2,4-triazol-1-yl) ethane hydrochloride are obtained in the form of white, hygroscopic crystals with a melting point of 870C. The product can used without further purification for the preparation of the compounds of the formula (IV) will.

The following compounds from Table 5, for example, can be produced analogously to the above example: Table 5 t S-CH, C1 x HC1 880C üN-CH2Cl x HCl mp: 88 ° C L N-CH2Cl x HCl. Mp:. 1130C t N-CH2Cl x HCl m.p .: 1220C CH3 N-CHCl x HCl Xp: 700C / 22 mbar CH3 J X N-CHCl x HCl viscous oil Precursors for the preparation of the hydrochlorides of the compounds of the formula (IV) 69 g (1 mol) of triazole are stirred with 150 ml of methylene chloride, cooled to OOC, and 50 g (1.13 mol) of acetaldehyde are added dropwise with stirring. The mixture is stirred for 2 hours at 0.degree. C. and then evaporated in vacuo at a maximum bath temperature of 150.degree.

In this way, 107 g (94% of theory) 1-hydroxy-1- (1,2 , 4-triazol-1-yl) ethane in the form of a yellow viscous oil.

The following compounds from Table 6, for example, can be produced analogously to the above example: Table 6 = \ N-CH2OH Fp: 880C - L N-CH2OH Afp: 600C p LgN-CH2OH Mp: 71 ° C CH L N-CH - OH viscous oil CH3 L, N-CH-OH viscous oil Use example In the biological tests described below, the following compound was used as a reference substance: 2- (1-methylethoxy) -phenyl-methylcarbamate (DE-AS 1 108 202) Example A Limit Concentration Test / Root Systemic Action Test insect: Myzus persicae Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight is mixed Active ingredient with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / l). The treated soil is filled in Pots and plant them with cabbage (Bras sica oleracea). The active ingredient can so from the plant roots are taken up from the soil and transported into the leaves.

For the proof of the root systemic effect after 7 days only the leaves are occupied with the above-mentioned test animals. After further The evaluation is carried out for 2 days by counting or estimating the dead animals.

The root-systemic effect of the active substance is derived from the number of deaths derived. She is 100% when all Test animals are killed and 0% if just as many test insects are still alive as in the untreated control.

In this test, for example, the following compounds of the preparation examples show (1) and (2) at an active ingredient concentration of 10 ppm, a kill of 100%.

Example B Limit Concentration Test / Root Systemic Effect Test Insect: Phaedon cochleariae Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight Alkylaryl polyglycol ethers For the production of an expedient active ingredient preparation mixing 1 part by weight of active ingredient with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water the desired concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / l). The treated soil is filled in Pots and plant them with cabbage (Brassica oleracea). The active ingredient can so from the plant roots are taken up from the soil and transported into the leaves.

For the proof of the root systemic effect after 7 days only the leaves are occupied with the above-mentioned test animals. After further The evaluation is carried out for 2 days by counting or estimating the dead animals.

The root-systemic effect of the active substance is derived from the number of deaths derived. She is 100% when all Test animals are killed and 0% if just as many test insects are still alive as in the untreated control.

In this test, for example, the following compounds of the preparation examples show (1) and (2) at an active substance concentration of 10 ppm a kill of 100%, example C Phaedon larvae test solvent: 3 parts by weight emulsifier: 1 part by weight alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight is mixed Active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the active ingredient preparation of the desired concentration and treated with mustard beetle larvae (Phaedon cochleariae) occupied as long as the leaves are still moist.

After the desired time, the destruction is determined in%. Thereby means 100% that all beetle larvae have been killed; 0% means that there are no beetle larvae were killed.

In this test, for example, the following compounds of the preparation examples show (1) and (4) with an active ingredient concentration of 0.01%, a kill after 3 days from 80 and 100%.

Claims (10)

Claims 1. Phenylcarbamic acid ester of the formula (I) in which R stands for hydrogen or optionally substituted radicals from the series alkyl or cycloalkyl and Az stands for an azolyl radical bonded via nitrogen. 2. Phenylcarbamic acid ester of the formula (I) according to claim 1, characterized characterized in that R represents hydrogen, alkyl having 1 to 4 carbon atoms or represents cycloalkyl of 3 to 8 carbon atoms and Az represents one above nitrogen bonded 1,2,4-triazolyl, pyrazolyl or imidazolyl radical. 3. Phenylcarbamic acid ester of the formula (I) according to claim 1, characterized characterized in that R represents hydrogen, methyl or ethyl, cyclopropyl, cyclopentyl or cyclohexyl and Az is a nitrogen-bonded 1,2,4-triazolyl, Pyrazolyl or imidazolyl radical. 4. Process for the preparation of compounds of the formula (1) in which R stands for hydrogen or optionally substituted radicals from the series alkyl or cycloalkyl and Az stands for an azolyl radical bonded via nitrogen, characterized in that phenol ethers of the formula (II) with methyl isocyanate of the formula (III) H3C-N =C =O (III), if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent. 5. Pesticides, characterized by a content of at least one phenylcarbamic acid ester of the formula (I) 6. insecticidal agent, characterized by a content of at least one phenylcarbamic acid ester Formula (I). 7. A method of combating insects, characterized in that that one phenylcarbamic acid esters of the formula (I) on insects or their habitat can act. 8. Process for the manufacture of pesticides, thereby characterized in that one phenylcarbamic acid esters of the formula (I) with extenders and / or surfactants mixed together. 9. Phenol ethers of the formula (II) in which R stands for hydrogen or optionally substituted radicals from the series alkyl or cycloalkyl and Az stands for an azolyl radical bonded via nitrogen. 10. Process for the preparation of phenyl ethers of the formula II in which R stands for hydrogen or optionally substituted radicals from the series alkyl or cycloalkyl and Az stands for an azolyl radical bonded via nitrogen, characterized in that halides of the formula (IV) Az-CHR-Hal (IV) in which R and Az have the meaning given above and Hal is halogen, reacted with an alkali or alkaline earth metal salt of 2-hydroxyphenol in the presence of inert diluents at temperatures between OOC and 1200C.