DE3320534A1 - Carbamates - Google Patents

Abstract

Novel substituted 2-(4-pyridyloxyphenoxy)ethyl carbamates of the formula <IMAGE> in which R1 is hydrogen, <IMAGE> R2 is C1-C6-alkyl or alkoxyalkyl having a total of 3 to 5 carbon atoms, R3 is halogen or a halogen-substituted C1-C2-alkyl and n is a number 0, 1 or 2, processes for the preparation of these compounds, and agents containing them for controlling insects and representatives of the order of the Acarina. The novel compounds are distinguished by an ovicidal and larvicidal action, in particular against insects which are harmful to plants.

Description

Carbamic acid ester

The present invention relates to new substituted 2- (S-pyridyloxyphenoxy) ethylcarbamic acid esters. Process for their production and their use in pest control.

The 2- (4-pyridyloxyphenoxy) ethylcarbamic acid esters according to the invention have the formula I. where R1 is hydrogen, or R2 is C -C -alkyl or alkoxyalkyl with a total of 3 to 5 carbon atoms, R3 is halogen or a halogen-substituted C1-C2-alkyl and n is a number 0, 1 or 2.

According to the invention, preference is given to compounds of the formula 1 in which R3 is fluorine, chlorine or bromine or a C -C -alkyl substituted by fluorine, chlorine or bromine. Because of their effect as a pest control agent, s int especially compounds of the formula I in which R is hydrogen or a radical or R2 is methyl, ethyl, n-propyl, isopropyl or 2-methoethyl; R3 is fluorine, chlorine or trifluoromethyl and n is a number 0, 1 or 2. Also of particular interest are those compounds of the formula I in which the pyridyl radical is linked to the rest of the molecular radical in the 2- or 3-position via the oxygen atom.

The compounds of the formula I can be carried out analogously to processes known per se (See e.g. European Patent Application No. 0,004,334 and British Patent Specification No. 1573620).

For example, a compound of the formula I can be obtained by a) a compound of the formula II with a compound of the formula III or b) a compound of the formula IV with a compound of the formula V X-C0-0-R or c) a compound of the formula VI with a compound of the formula VII implements. If a compound of the formula I has been obtained in which R1 is hydrogen, this compound obtained can, if desired, be prepared by reaction with a halide of the formula VIII, IX or X. convert into a compound of the formula I in which R1 is a radical means. In the above formulas, the radicals R1, R2, R3 and n have the meanings given under formula I above. X stands for halogen, preferably chlorine.

The mentioned methods a), b) and c) can preferably under normal Pressure and carried out in the presence of an organic solvent or diluent will. Suitable solvents or diluents are, for example, ethers and ethereal ones Compounds such as dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N, N-dialkylated carboxamides; aliphatic aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; Dimethyl sulfoxide as well as ketones, e.g.

Acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone. Processes a) and c) are generally carried out at a temperature of -10 to 2000C, preferably between 10 and 80 ° C, optionally in the presence of a basic substance, e.g. an alkali metal such as Na or K, alkali hydrides or amides, alkali or Alkaline earth carbonates such as potassium carbonate. The implementation of procedures b) takes place at a temperature of 0 to 150 cd, in particular at the boiling point of the inert solvent used, and preferably also in the presence of a Base indicated above.

The starting materials of the formulas II to X are known and can be carried out analogously known processes are produced.

European patent application No. 0004334 discloses 2-phenoxyphenoxy-ethylcarbamic acid esters known to have pesticidal effects. The compounds according to the invention act In contrast, it is a new type of substituted 2-pyridylphenoxy-ethylcarbamic acid ester, the surprisingly increased effectiveness as a pesticide, in particular exhibit in crop protection. A particular advantage of the compounds according to the invention of formula I results from their very low toxicity to warm blooded animals and good plant tolerance.

The compounds of the formula I are particularly suitable for combating of insects of the following orders: Lepidoptera, Coleoptera, Homoptera, Heteroptream Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, tZllophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Akarina of the families: Ixodidae, Argasidae, Tetranychidae and Dermanyssidae.

In addition to their effect on flies, such as Musca domestica, and Mosquito larvae can also use compounds of the formula I for combating plants which are harmful to plants Feeding insects in ornamental and useful plantings, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens), as well as in fruit and vegetable crops (e.g.

against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis) can be used. The compounds of the formula I are distinguished by a pronounced ovicidal and larvicidal effect against insects, especially against Eggs and larvae of eating insect pests. Are compounds of the formula I ingested with the feed of adult insect stages, so in many cases, especially in coleopteras, such as Anthonomus grandis, a reduced egg deposit and / or determine reduced slip rates.

The compounds of the formula I can also be used to combat ectoparasites, such as Lucilia sericata, are used on domestic and farm animals, e.g. by animal, Stable and pasture treatment.

The compounds of formula I are also suitable for combating the following mite species that attack fruit and vegetable crops: Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, Broybia rubrioculus, Panonychus citri, Eriophyes pyri, Eriophyes ribis, Eriophyes vitis, Tarsomemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.

The effect of the compounds according to the invention or those containing them Means can be made essential by adding other insecticides and / or acaricides broaden and adapt to given circumstances.

The following active ingredients can be considered as additives: organic Phosphorus compounds, nitrophenols and derivatives, formamides, ureas, carbamates, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compounds of the formula I can also be used with particular advantage combine with substances that have a pesticide-enhancing effect. Examples of such compounds include: piperonyl butoxide, propynyl ether, propinyloxime, Propynyl carbamates and propynyl phosphonates, 2- (3,4-methylenedioxyphenoxy) -3,6,9-trioxaundecane or S, S, S-tributyl phosphorotrithioate.

The good insecticidal action of the compounds of the invention Formula I corresponds to a death rate (mortality) of at least 50-60% of that mentioned Insect pests.

The compounds of the formula I are used in unchanged form or, preferably used together with the auxiliaries customary in formulation technology and are therefore e.g. emulsion concentrates that can be sprayed or thinned directly Solutions, diluted emulsions, wettable powders, soluble powders, dusts, Granules, encapsulations in e.g. polymeric materials are also processed in a known manner. the Application methods such as spraying, atomizing, dusting, scattering or pouring, as well as the means, the desired goals and the given circumstances chosen accordingly.

The formulations, i.e. the active ingredient of formula 1, or combinations of these active ingredients with other insecticides or acaricides, and optionally one agents, preparations or compositions containing solid or liquid additives, are produced in a known manner, e.g. by intimate mixing and / or grinding the active ingredients with extenders, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

The following solvents can be used: aromatic hydrocarbons, preferably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, Phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane, paraffins, alcohols and glycols and their ethers and esters, such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones, such as Cyclohexanone, strongly polar solvents such as ST-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized Coconut oil or soybean oil, or water.

As solid carriers, e.g. for dusts and dispersible powders, As a rule, natural rock flour is used, such as calcite, talc, kaolin, Montmorillonite or Attapulgite. To improve physical properties Highly disperse silicas or highly disperse absorbent polymers can also be added will.

As gckurLc, adsorptive granulate carriers come porous types, e.g. Pumice stone, broken bricks, sepiolite or bentonite as non-sorptive carrier materials e.g. calcite or sand in question. In addition, a variety of pre-granulated Materials of an inorganic or organic nature, such as in particular dolomite or shredded plant residues are used.

As surface-active compounds come depending on the nature of the to be formulated Active ingredient of the formula I or the combinations of these active ingredients and other insecticides or acaricides non-ionic, cationic and / or anionic surfactants with good emulsifying, Dispersing and wetting properties are taken into account. Surfactants also include mixtures of surfactants to understand.

Suitable anionic surfactants can be both so-called water-soluble Soaps can be like water-soluble synthetic surface active compounds.

Suitable soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C10-C22), such as the Na- or K salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained e.g. from coconut or day oil. Furthermore, the Mentioning fatty acid methyl taurine salts.

However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually as alkali, alkaline earth or optionally substituted ammonium salts and generally have a Alkyl radical with 8 to 22 carbon atoms, where alkyl also represents the alkyl part of acyl radicals includes, e.g. the Na or Ca salt of ligninsulphonic acid, of the dodecylsulphuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. Here also include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with about 8-22 carbon atoms. Alkyl aryl sulfonates are e.g. Na-, Ca- or triethanolamic acid of dodecyluenzenesulphonic acid, of dibutylnaphthalenesulphonic acid or of a naphthalenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product. There are also corresponding phosphates, such as salts of the phosphoric acid ester a p-nonylphenol- (4-14) -ethylene oxide adduct in question.

Polyglycol ether derivatives are primarily used as nonionic surfactants of aliphatic or cycloaliphatic alcohols, saturated or unsaturated Fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms may contain in the alkyl radical of the alkylphenols. Furthermore suitable non-ionic Surfactants are the water-soluble 20 to 250 ethylene glycol ether groups and 10 to 100 polyethylene oxide adducts containing propylene glycol ether groups with polypropylene glycol, Ethylenediamine polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain per propylene glycol unit 1 to 5 ethylene glycol units.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, Castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, Polyethylene glycol and Octylphenoxypolyäthoxyäthanol mentioned. Also come Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate into consideration.

The cationic surfactants are mainly quaternary Ammonium salts which contain at least one alkyl radical with 8 to 22 as N-substituent Contain carbon atoms and, as further substituents, lower ones, optionally halogenated ones Have alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyl di (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are, among others, in the following publications described: "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood, New Jersey, 1979. Sisely and Wood, "Encyclopedia of Surface Active Agents, "Chemical Publishing Codes Inc. New York.

The pesticidal preparations usually contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I or combinations of these active ingredients with other insecticides or acaricides, 1 to 99.9% of a solid or liquid Additive and 0 to 25%, in particular 0.1 to 20%, of a surfactant. While As a commodity, concentrated means are preferred, used by the end user usually dilute preparations that contain significantly lower concentrations of active ingredients exhibit.

The agents can also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients included to achieve special effects.

Formulation examples for liquid active ingredients of the formula I or combinations these active ingredients with other insecticides or acaricides (% - percent by weight) 1. Emulsion concentrates a) b) c) active ingredient resp. Active ingredient combination 25 z 40% 50 Z Ca-dodecylbenzol sulfonate 5% 8 6% castor oil polyethylene glycol ether (36 mol AeO) 5% - tributylphenol polyethylene glycol ether (3Q mol AeO) - 12% 4% cyclohexanone 15% 20% xylene mixture 65% 25% 20% From such concentrates can by diluting with water emulsions of any desired concentration can be made.

2. Solutions a) b) c) d) active ingredient resp. Active ingredient combination 80 z 10% 5% 95% ethylene glycol monomethyl ether 20% - - -Polyethylene glycol MW 400 - 70% - -N-methyl-2-pyrrolidone - 20% - -Epoxidized coconut oil - - 1% 5% gasoline (Boiling limits 160-1900C) - - 94% -The solutions are for use in the form of the smallest Suitable for drops.

3. Granules a) b) active ingredient resp. Combination of active ingredients 5% 10% kaolin 94% -Highly disperse silica 1% attapulgite - 90% The active ingredient is in methylene chloride dissolved, sprayed onto the carrier and then the solvent in vacuo evaporated.

4. Dusts a) b) Active substance resp. Active ingredient combination 2% 5% Highly disperse silica 1% 5% talc 97 X kaolin - 90% by thorough mixing the carrier materials with the active ingredient, ready-to-use dusts are obtained.

Formulation examples for solid active ingredients of the formula I, respectively. Combinations these active ingredients with other insecticides or acaricides (% = weight percent) 5. Wettable powder a) b) c) Active ingredient or combination of active ingredients 25% 50 z 75% sodium lignin sulfonate 5% 5-Na lauryl sulfate 3 - 5% Na diisobutyl naphthalene sulfonate - 6% 10% octylphenol polyethylene glycol ether (7-8 mol AeO) - 2% -Highly disperse silica 5% 10% 10% kaolin 62% 27% -Der Active ingredient or the active ingredient combination are mixed well with the additives and grind well in a suitable mill.

You get wettable powders, which can be mixed with water to form suspensions Allow to dilute the desired concentration.

6. Emulsion concentrate active ingredient or combination of active ingredients 10% octylphenol polyethylene glycol ether (4-5 mol AeO) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (36 mol AeO) 4% Cyclohexanone 30 X Xylene mixture 50% From this concentrate emulsions of any desired concentration can be prepared by dilution with water will.

7. Dusts a) b) Active ingredient or combination of active ingredients 5% 8% Talc 95% -Kaolin - 92% Ready-to-use dusts are obtained by adding the Active ingredient is mixed with the carrier and ground on a suitable mill.

8. Extruder granulate active ingredient or combination of active ingredients 10% sodium lignin sulfonate 2% carboxymethyl cellulose 1% kaolin 87% The active ingredient is with the additives mixed, ground and moistened with water. This mixture is extruded, granulated and then dried in a stream of air.

9. Enveloping granules, active ingredient or combination of active ingredients, 3% polyethylene glycol (MG 200) 3% Kaolin 94% The finely ground active ingredient or the active ingredient combination is mixed evenly on the kaolin moistened with polyethylene glycol applied. In this way, dust-free coated granules are obtained.

10. Suspension concentrate active ingredient or combination of active ingredients 40 % Ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol AeO) 6% sodium lignin sulfonate 10% carboxymethyl cellulose 1 Z 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32% The finely ground active ingredient or the active ingredient combination is intimately mixed with the additives. One obtains such a suspension concentrate, from which suspensions by diluting with water any desired concentration can be produced.

Example 1: Preparation of 2- [4- (pyridyl-2-oxy) phenoxy] ethyl carbamic acid ethyl ester: There are 8.2 g of 4- (pyridyl-2-oxy) -phenol, 13.2 g of 2- (chloroethyl) -carbamic acid ethyl ester and 23.2 g of potassium carbonate in 150 ml of dimethylformamide for 5 hours at 100C.

The reaction mixture is taken up in 300 ml of ice water and 150 ml of toluene. The organic phase is twice with 100 ml of 2N sodium hydroxide solution and twice with washed 100 ml of saturated sodium chloride solution, dried over sodium sulfate and evaporated in vacuo.

The residue is recrystallized from toluene with the addition of a little hexane. The title compound of the formula is obtained in this way as a white powder; m.p. 64 to 66 ° C (compound no. 1).

Example 2: Preparation of 2- [4- (5-trifluoromethyl-2-pyridyloxyphenoxy] -ethyl-N- (4-chlorophenylthio) -carbamic acid ethyl ester: 5.5 g of 2- [4- (5-trifluoromethyl-2-pyridyloxy) -phenoxy] -äthylcarbaminsäureäthylester, are placed in 20 ml of pyridine and 2.7 g of 4-chlorophenylsulfenyl chloride are slowly added dropwise with stirring and cooling at 5 to 10 ° C. The reaction mixture is stirred for 3 hours at room temperature and then to a mixture of 200 ml Ice water and 100 ml of toluene are poured in. The organic phase is washed several times with water, then dried over sodium sulfate and evaporated. The yellow oil obtained is chromatographed over silica gel with a dichloromethane-hexane mixture (volume ratio 3: 2) and finally with dichloromethane alone. After evaporation, the title compound of the formula is obtained 20 as a yellowish oil with the refractive index nD = 1.5632; (Compound No. 2).

The following compounds of formula 1 were prepared analogously to the procedures described above: Conn. R1 R2 binding of the | R3 | n Iphys. data No. L pyridyl residue , ~ ~ ~ 1 H -C2H5 2-position - O m.p. 64-660C . ~. 2-position -C1 2 5 1 2-position 5-CF3 1 nD = 1, 563220 2 = 0 C, H, 2-position 5-CF3 1 nD = 1> 5632 3 H 2 5 2-position 3-C1, 5-C1 2 m.p. 95-960C 4 H | -G2H5 2-position 5-CF3 1 m.p. 80-81 ° C 5 H -CH3 2-position 5-CF3 1 Sup, 79-81 ° C 6 H j-C2H5 3-position 2-C1 5-C1 2 m.p. 7-74 "C 7 H -C2H5 3-position 5-C1 6-C1 2 and = 1.5748 8 H -CH3 1 2-position - O m.p. 69-71 ° C 9 9 H -n-C3H7 2-position - | O m.p. 39-41 ° C 10 H (Cll?)?. OCll3 2-position - O m.p. 57-590C 11 S- -C1 -C2H5 2-position - O nD = 1.5971 1 =. 1 12 H 3 2-position I 5-CF3 1 semi-solid 1 1 20 mass 13 -cl- (CH) -S- 2-position 5-CF3 1 "D = 1.5555 I 2 2 3 14 H -n-C6H13 2-position - O m.p. 48-50 15 H -s-C4H9 2-position ~ O m.p. 59-61 ° C 16 -S-ev <. -C2R5 2-position - O nD 1.5946 17 H -C2H5 2-position - 3-C1 1 m.p. 80-820C 18 -S-.P -c 2 5 2-position 3-C1 1 20 1-5983 ~ 25 fl1) = The following compounds of the formula I can be obtained in a corresponding manner: Example 3: Action against Musca domestica: 50 freshly prepared CSMA nutrient substrate for maggots is weighed into beakers. A certain amount of a 1% strength by weight acetone solution of the active ingredient in question is pipetted onto the nutrient substrate in the cups. After mixing the substrate, the acetone is allowed to evaporate for at least 20 hours.

Then 25 one-day maggots of Musca domestica in which contain the nutrient substrate treated in this way - put the cup. After the maggots have pupated, the pupae that have formed are flushed out separated from the substrate with water and placed in vessels closed with sieve lids deposited.

The pupae flushed out per batch are counted (toxic influence of the active ingredient on the maggot development). Then after 10 days the number of the flies hatched from the pupae are determined.

Show compounds of formula I according to the above examples good effect in the above test.

Example 4: Action against Lucilia sericata: To 9 ml of a culture medium are given at 50 "C 1 ml of an aqueous solution containing 0.5 z active substance. Now about 30 freshly hatched Lucilia sericata larvae are added to the culture medium, and after 48 and 96 hours the insecticidal effect is determined by measuring the kill rate established.

Show compounds of formula I according to the above examples good activity against Lucilia sericata in this test.

Example 5: Action against ASdes aegypti: On the surface of 150 ml of water in a container becomes 0.1% acetone Solution of the active ingredient are pipetted into concentrations of 800 and 400 ppm each will. After the acetone has evaporated, the container is filled with 30 to 40 2-day Ades larvae loaded. Mortality is checked after 1, 2 and 5 days.

Example 6: Insecticidal feed poison effect: potted around 25 cm high Cotton plants are sprayed with aqueous active ingredient emulsions that contain the active ingredient contained in concentrations of 400, 50, 12.5, 3.0 and 0.75 ppm.

After the spray coating has dried, the cotton plants are with Spodoptera littoralis or Heliothis virescens larvae in the third larval stage populated. The experiment is carried out at 24 ° C. and 60% relative humidity. After 120 hours, the% blortality of the test insects is determined.

Show compounds of formula I according to the above examples good action in this test. Example 7: Action against Epilachna varivestis: Approx 15-20 cm high Phaseolus vulgaris plants (French beans) are mixed with watery, den containing active substance to be tested in concentrations of 400 ppm or 800 ppm Sprayed emulsion preparations. After the spray coating has dried on, pro Plant 5 larvae of Epilachna varivestis (Mexican bean beetle) in the 4th larval Stage set. A plastic cylinder is placed over the infected plants, which is covered with a copper gauze lid. The experiment is carried out at 280C and 60% relative humidity carried out.

The acute effect (% mortality) is determined after 2 and 3 days.

For evaluation of any damage caused by feeding (antifeeding effect), The test animals suffered from developmental and molting disorders for a further 3 days observed.

Show compounds of formula I according to the above examples good effect in the above test.

Example 8: Ovicidal effect on Heliothis virescens: Corresponding Quantities of a wettable powdery formulation containing 25% by weight of the active ingredient to be tested are mixed with enough water that result in aqueous emulsions of increasing concentration of active ingredient.

One-day egg clutches of Heliothis immersed on cellophane for three minutes and then on circular filters sucked off. The clutches treated in this way are laid out in Petri dishes and placed in the Preserved darkness. After 6 to 8 days, the hatching rate is compared to untreated Controls detected.

The evaluation required to kill the eggs 100% minimum active ingredient concentration determined.

Show compounds of formula I according to the above examples good effect in the above test Example 9: Effect on Laspeyresia pomonella (eggs): Laspeyresia pomonella laid eggs that are not older than 24 hours on filter paper for 1 minute in an acetone-aqueous solution containing 0.2, 12.5, 100 and 400 ppm of the active ingredient to be tested, immersed. After drying the solution, the eggs are laid out in Petri dishes and stored at a temperature of Leave 280C. After 6 days the percentage hatched from the treated eggs rated.

Compound no. 1 according to example 1 shows 100% effect (mortality) in the above test already at an active ingredient concentration of 0.2 ppm.

Example 10: Influence on reproduction of Anthonomus grandis: Adult Anthonomus grandis, which were not older than 24 hours after hatching, are caged in groups of 25 beetles each Lattice walls convicted. The cages occupied with the beetles are then for 5 to 10 seconds immersed in an acetone solution containing 1.0% by weight of the active ingredient to be tested.

After the beetles are dry again, they become a population and Laying eggs in covered bowls containing food.

Eggs are laid two to three times a week with flowing Water flushed out, counted, by soaking in a watery one for two to three hours Disinfectants (such as "Actamer B 100 red) and then disinfected in bowls, which contained a suitable larval diet, deposited. After 7 days it is examined whether larvae have developed from the deposited eggs.

To determine the duration of the effect influencing reproduction The active ingredients to be tested are the beetles' oviposition for a period of time checked by about 4 weeks. The rating is based on the reduction in Number of eggs laid and the larvae hatched from them compared to untreated ones Controls.

Show compounds of formula I according to the above examples a good reproduction-reducing effect in the above test.

Example 11: Acaricidal action: Phaseolus vulgaris plants become 12 hours before the test for acaricidal activity with an infected piece of leaf from a mass breed of Tetranychus urticae. The defected movable Stages are made from a chromatography nebulizer with the emulsified test preparations sprayed in such a way that the spray liquid does not run off. After two and seven days larvae, adults and eggs are examined under the dissecting microscope for living and dead individuals evaluated; the result is expressed as a percentage.

During the "holding time", the treated plants stand in greenhouse cabins at 25 ° C.

Show compounds of formula I according to the above examples good effect in the above test.

Claims (17)

Claims 1. Compound of formula I where R1 is hydrogen, or R2 is C1-C6-alkyl or alkoxyalkyl with a total of 3 to 5 carbon atoms, R3 is halogen or a halogen-substituted C1-C2-alkyl and n is a number 0, 1 or 2. 2. Compound of formula I according to claim 1, characterized in that that R3 is fluorine, chlorine or bromine or one substituted by fluorine, chlorine or bromine C 1 -C 2 alkyl means. 3. A compound of the formula I according to claim 1, characterized in that R1 is hydrogen, or R2 methyl, ethyl, n-propyl, isopropyl or 2-methoxyethyl; R3 is fluorine, chlorine or trifluoromethyl and n is a number O, 1 or 2. 4. A compound of the formula I according to claims 1 to 3, characterized in that that the pyridyl radical is linked to the oxygen atom in the 2- or 3-position. 5. A compound according to claim 4 of the formula 6. A compound according to claim 4 of the formula 7. A compound according to claim 4 of the formula 8. A compound according to claim 4 of the formula 9. A compound according to claim 4 of the formula 10.Compound according to claim 4 of the formula 11. Compound according to claim 4 of the formula 12. A compound according to claim 4 of the formula 13. Process for the preparation of a compound of the formula I according to claims 1 to 12, characterized in that a) a compound of the formula with a compound of the formula III or b) a compound of the formula IV with a compound of the formula V X-CO-O-R2 (V) or c) a compound of the formula VI with a compound of the formula VII and that, if appropriate, a compound of the formula I obtained in which R1 is hydrogen, with one of the compounds or reacted, where in the formulas II to X the radicals R1, R2, R3 and n have the meanings given in claims 1 to 4 and X is halogen, preferably chlorine. 14. Pesticides, which as an active component a Compound according to claims 1 to 12 together with suitable carriers and / or contains other aggregates. 15. Use of a compound according to claims 1 to 12 for Control of insects and representatives of the order Akarina. 16. Use according to claim 15 for combating plants which are harmful to plants Insects. 17. Use according to claim 16 as an ovicide or larvicide.