GB2165538A - Pesticidal N-benzoylphenylureas - Google Patents

Description

SPECIFICATION N-Benzoylphenylureas The present invention relates to novel substituted N-benzoyl-N'-pyridyloxyphenylureas, to the preparation thereof and to intermediates for their synthesis, and to the use of these novel compounds in pest control.

The benzoylphenylurea derivatives of this invention have the formula I

wherein X1, X2 and X3 are each independently hydrogen, halogen or methyl, Y is hydrogen or halogen, R is hydrogen, C1-C5alkyl, C3-C5aikenyl or C3-C5alkynyl, and R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or C1-C4alkylthio.

Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent will be understood as comprising, within the scope of this invention, for example the following groups: methyl, ethyl, propyl, butyl and the isomers thereof such as isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl and the like. Alkenyl may be 1-propenyl, allyl, 1-butenyl, 2-butenyl and 3-butenyl; and alkynyl may be propargyl, 2-butynyl or 3-pentynyl. Halogen in the definition of formula (I) is preferably fluorine, chlorine and bromine, with fluorine and chlorine being most preferred.

Owing to their pesticidal activity, preferred compounds of formula I are those wherein X1, X2 and X3 are each independently hydrogen, fluorine, chlorine or methyl, Y is hydrogen, fluorine or chlorine, R is hydrogen, C1-C4alkyl, allyl or propargyl, and R1, R2, R3, R4 and B5 are each independently hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy or methylthio.

Because of their biological activity, useful compounds of formula I are also those wherein X1 is hydrogen, fluorine, chlorine or methyl, X2 and X3 are each hydrogen, Y is hydrogen or chlorine, R is hydrogen or C1-C4alkyl, R1 is fluorine, chlorine, methyl, ethyl, methoxy, ethoxy or methylthio, R2 is hydrogen, 6-fluoro, 6-chloro, 6-methyl or 6-ethyl; and R3, R4 and B5 are each hydrogen.

Particularly preferred compounds of formula I are those wherein X1 is hydrogen or chlorine, X2 and X3 are each hydrogen, Y is hydrogen or chlorine, R is hydrogen or C1-C4alkyl, R is fluorine, chlorine or methoxy, R2 is hydrogen, 6-fluoro or 6-chloro; and R3, R4 and B5 are each hydrogen.

The compounds of formula I may be prepared by methods which are known per se (q.v. European patent specification 0.056.124). For example a compound of formula I may be obtained by a) reacting a compound pf formula II

with a compound of formula Ill

or b) reacting a compound of formula IV

with a compound of formula V

or c) reacting a compound of formula II with a compound of formula VI

in which formulae II to VI above the substituents X1 to X3, Y, R and R1 to B5 have the meanings assigned to them above, and Z is a C1-C3alkyl group which is unsubstituted or substituted by halogen, preferably chlorine.

The above processes a), b) and c) may preferably be carried out under normal pressure in the presence of an organic solvent or diluent. Examples of suitable solvents or diluents are: ethers and ethereal compounds, such as diethyl, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,Ndialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g. acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone.Process a) is normally carried out in the temperature range from -10" to 200"C, preferably from 0 to 200do, if desired in the presence of an organic base, e.g. triethylamine. Process b) is carried out in the temperature range from 0 to 1 50"C, preferably at the boiling point of the solvent employed and, if desired, in the presence of an organic base such as pyridine, and/or with the addition of an alkali metal or alkaline earth metal, preferably sodium.For process c), i.e. for the reaction of the urethane of formula VI with a pyridyloxyaniline of formula II, a temperature range from about 60 to the boiling point of the reaction mixture is preferred, and the solvent employed is preferably an aromatic hydrocarbon such as toluene, xylene, chlorobenzene and the like.

The starting materials of the formulae Ill, V and VI are known and can be prepared by methods analogous to known ones. The starting materials of formula II are novel compounds which likewise constitute an object of the present invention.

The compounds of formula II can be prepared in a manner known per se by reacting suitable 5-aminosalicylic acid derivatives of formula VII with a pyridine derivative of formula VIII

In the formulae VII and Vlil above, the substituents X1, X2r X3, R and Y have the meanings assigned to them in formula I, and Xis fluorine or chlorine.

Substituted N-benzoyl-N'-phenylureas with insecticidal properties and carrying an alkoxycarbonyl substituent at the phenyl ring are already known from European patent specification 0.056.124.

N-Benzoyl-N '-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)phenylureas with insecticidal properties are also known from German Offenlegungsschrift 3033 512. Corresponding insecticidal N-benzoyl-N'-phenylureas carrying a carboxyl or alkoxycarbonyl substituent in 3-position at the phenyl ring are disclosed in Japanese published patent specifications 5-7099.569,5-7109.768, 5-7144.258, 5-7144.259,5-7145.861 and 5-8039.657.

Compared with these prior art compounds, the compounds of the present invention differ essentially in the presence of a -CF2-CFCI2 side-chain instead of a -CF3 radical in the 5-position of the pyridine ring.

Surprisingly, it has been found that the compounds of Formula I of this invention have excellent properties as pesticides while being well tolerated by plants and having very low toxicity to warm-blooded animals.

They are particularly suitable for controlling pests that attack plants and animals. The compounds of the present invention are also readily biodegradable, especially in the field.

In particular, the compounds of the formula I are suitable for controlling insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Acarina.

The good pesticidal acivity of the compounds of the formula I according to the invention corresponds to a mortality of at least 50-60% of the above pests.

In addition to their very good action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are also suitable for controlling plant-destructive feeding insects in ornamentals and crops of useful plants, especially in cotton (e.g. against Spodoptera littoralis and Heliothis virescens) and in fruit and vegetables (e.g. against Leptinotarsa decemlineata and Pieris brassicae). The larvicidal and ovicidal action of the compounds of formula I merits particular mention. If compounds of formula I are ingested by adult insect stages with the feed, then a diminished oviposition and/or reduced hatching rate is observed in many insects, especially in Coleopterae, e.g. Anthonomus grandis.

The compounds of formula I are also suitable for controlling ecto- parasites, e.g. Lucilia sericata, as well as ticks in domestic animals and productive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and pastures.

The activity of the compounds of the formula I and of the compositions containing them can be substantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorous compounds, nitrophenols and derivatives thereof, formamidines, ureas, pyrethroids, carbamates, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

The compounds of the formula I are used in unmodified form or preferably together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/cr grinding the active ingredients with extenders, e.g. solvents, solid carriers and, in some cases, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of the formula I to be formulated, or of combinations thereof with other insecticides or acaricides, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, akaline earth metal salts of unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts or oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, e.g. from coconut oil or tallow oil. Further suitable surfactants are also the fatty acid methyltaurin salts as well as modified and unmodified phospholipids.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise 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 one fatty acid radical containing 8 to 22 carbon atoms.Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminepolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan triolate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi-(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ridgewood, New Jersey, 1979; Dr. Helmut Stache, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hauser Verlag, Munich/Vienna, 1981.

The pesticidal compositions usually contain 0.1 to 99%, preferably 0.1 to 95% of a compound of the formula I or combination thereof with other insecticides or acaricides, 1 to 99.9% of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 20 %, of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ diluted formulations of substantially lower concentration.

The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples further illustrate the persent invention.

Example I a) Preparation of 4-[5'-(2,2-dichloro-1 ,1,2-trifluoroethyl ,1 ,2-trifluoroethyl)-3'-chloropyridyl-2'-oxy]-3-carbomethoxyaniline: 16.7 g of methyl 5-aminosalicylate are dissolved in 160 ml of dimethylsulfoxide. To this solution are added 25 g of K2CO3 and the mixture is heated, with stirring, to 90"C. Then 28.2 g of 2-fluoro-3-chloro-5-(2,2 dichloro-1,1,2-trifluoroethyl)pyridine are added dropwise and the mixture is stirred for 5 hours at 90"C. The dimethylsulfoxide is distilled off from the reaction mixture and the residue is stirred in water. The crude filter product is dissolved in ether, and the ethereal solution is washed with water, dried over Na2SO4 and the ether is removed by distillation.The residual crude product is purified by chromatography (100 cm column, diameter 7 cm; packing: 1 kg of silica gel; solvent: hexane 45%, ether 45%, isopropanol 10%; fractions of 150 ml). Fractions 11-17 contain the purified product. The title compound ofthe formula

is obtained in the form of beige crystals with a melting point of 130 -132 C.

4-[5'-(2,2-Dichloro-1 ,1 ,2-trifluoroethyl )-3'-chloropyrid-2-yloxyj-3-carbethoxy-5-cloroani line (white crystals, m.p. 169"-170"C) is obtained in analogous manner.

b) Preparation of N-(2,6-difluorobenzoyl)-N '-[445'-(2,2-dichloro-1 1 ,2-trifluoroethyl)-3'-chloropyridyl]-2'- oxy:-3-carbomethyoxyphenyl]urea : 5.62 g of the 4-[5'-)2,2-dichloro-1,1,2-trifluoroethyl)-3'-chloropyridyl-2'-oxy]-3-carbomethoxyaniline prepared in a) are dissolved in a mixture of 50 ml oftoluene and 20 ml of chloroform. To this solution are added 0.02 g of triethylamine and then 2.39 g of 2,6-difluorobenzoylisocyanate. The reaction mixture is then stirred for 10 hours at room temperature. The precipitated product is filtered with suction, washed on the filter with hexane and dried, affording colourless crystals of the title compound of the formula

with a melting pointof215 -217 C (compound 1).

The following compounds of formula I are prepared in accordance with the procedure described above: Com- XZ X2 X3 Y R R1 R2 R3 R4 R5 mp.

pound PC] 2 H H H Cl -CH3 Cl H H H H 170-171 3 H H H Cl -CH3 -OCH3 H H H H 161-164 4 Cl H H Cl -CH3 F 6-F H H H 219-220 5 Cl H H Cl -CH3 Cl H H H H 184-185 6 Cl H H Cl -CH3 Cl 6-CI H H H 133-136 7 Cl H H Cl -CH3 F H H H H 179-180 8 H H H Cl H F 6-F H H H 202-203 The following compounds of formula I can also be prepared in corresponding manner:: Com- XZ X2 X3 Y R R7 R2 R3 R4 R5 pound 9 H H H Cl -C2H5 F 6-F H H H 10 H H H Cl -C3H7(i) F 6-F H H H 11 H H H Cl -C4Hg(n) F 6-F H H H 12 Cl H H H -CH3 F 6-F H H H 13 H H H Cl -C4H9(t) F 6-F H H H Example 2 Formulations for active ingredients of the formula I orofExample 1 or combinations thereof with other insecticides or acaricides (throughout, percentages are by weight) 1. Wettablepowders a) b) c) compound of formula I or combination 25% 50% 75% sodium lignosufonate 5% 5% sodium laurylsulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% The active ingredient or combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

2. Emulsifiable concentrate compound of formula I or combination 10% octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% calcium dodecylbenzensulfonate 3% castor oil polyglycol ether (36 moles of ethylene oxide) 4% cyclohexanone 30% xylene mixture 50% Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

3. Dusts a) b) compound offormula I or combination 5% 8% talcum 95% kaolin - 92% Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.

4. Extruder granulate compound of formula I or combination 10% sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 87% The active ingredient or combination is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

5. Coated granulate compound offormula I or combination 3% polyethylene glycol 200 3% kaolin 94% The finely ground active ingredient or combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

6. Suspension concentrate compound of formula I or combination 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% sodium lignosulfonate 10% carboxymethylcellulose 1% 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 combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration may be obtained by dilution with water.

Example 3 Action against Musca domestica 50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers. A specific amount of a 1 % acetonic solution of the respective test compound is pipetted onto the nutrient substrate present in the beakers to give an active ingredient concentration of 800 ppm. The substrate is then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.

Then 25 one-day-old maggots of Musca domestica are put into each of the beakers containing the treated nutrient substrate for testing with each active ingredient at one of its given concentrations. After the maggots have pupated, the pupae are separated from the substrate by flushing them out with water and then deposited in containers closed with a perforated top.

Each batch of flushed out pupae is counted to determine the toxic effect of the test compound on the maggot development. A count is then made after 10 days of the number of flies which have hatched out of the pupae.

The compounds of formula I obtained according to Example 1 have good activity in this test.

Example 4 Action against Lucilia sericata 1 ml ofan aqueous solution containing 0.5 % of test compound is added at500Cto9 ml of a culture medium. Then about 30 freshly hatched Lucilia sericata larvae are added to the culture medium, and the insecticidal action is determined after 48 and 96 hours by evaluating the mortality rate.

In this test, compounds of the formula I according to Example 1 exhibit good activity against Lucilia sericata.

Example 5 Action againstAedes aegypti A concentation of 800 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound in acetone onto the surface of 150 ml of water on a beaker. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aedes aegypti are put into the beaker containing the test compound. Mortality counts are made after 1,2 and 5 days.

In this test, compounds of Example 1 exhibit good activity against Aedes aegypti.

Example 6 Insecticidal action against feeding insects Cotton plants about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the respective test compound in increasing concentrations. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothis virescens larvae in the L3-stage. The test is carried out at 24"C and 60 % relative humidity. The percentage mortality of the test insects is determined after 120 hours.

The results of biological tests carried out with the compounds of the invention in accordance with this Example are reported in the following table. Evaluation of the tests in terms of percentage mortality is made using the following rating: A: 80-100 % mortality at a concentration of 0.75 ppm of the tested compound.

B: 80-100 % mortality at a concentration of 3.0 ppm of the tested compound.

C: 80-100 % mortality at a concentration of 12.5 ppm of the tested compound.

D: 80-100 % mortality at a concentration of 50 ppm of the tested compound.

E: 80-100% mortality at a concentration of 100 ppm of the tested compound.

F: 80-100 % mortality at a concentration of 200 ppm of the tested compound.

-: not tested.

Com- Pesticidal activity pound Spodoptera larvae Heliothis larvae 1 A C 2 B B 3 E E 4 B C 5 D C 6 F 7 A C Example 7 Ovicidalaction against Heliothis virescens Corresponding amounts of a wettable powder formulation containing 25 % by weight of the test compound are mixed with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 800 ppm. One day-old egg desposits of Heliothis on cellophane are immersed on these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark. The hatching rate in comparison with untreated controls is determined after 6 to 8 days.

Compounds of formula I according to Example 1 are very effective in this test.

Example 8 Action against laspeyresia pomonella (eggs): Egg deposits of Laspeyrasia pomonella not more than 24 hours old are immersed on filter paper for 1 minute in an aqueous acetonic solution containing 800 ppm of the test compound.

After the solution has dried, the eggs are placed in petri dishes and kept at a temperature of 28"C. The percentage of larvae hatched from the treated eggs ad the percentage mortality is evaluated after 6 days.

The compounds of formula I according to Example 1 exhibit good activity in this test.

Example 9 Influence on the reprodution ofAnthonomous grandis Anthonomous grandis adults which are not more than 24 hours old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 seconds in an acetonic solution containing 0.1 % by weight of the test compound. After the beetles have dried, they are placed in covered dishes containing feed and leftforcopulation and oviposition. Egg deposits are flushed out with running water twice to three times weekly, counted, disinfected by putting them for 2 to 3 hours into an aqueous disinfectant, and then placed in dishes containing a suitable larval feed. A count is made after 7 days to determine whether larvae have developed from the eggs.

The duration of the reproduction inhibiting effect of the test compounds is determined by monitoring the egg deposits over a period of about 4 weeks. Evaluation is made by assessing the reproduction in the number of deposited eggs and hatched lavae in comparison with untreated controls.

Compounds of formula I according to Example 1 have a good reproduction inhibiting effect in this test.

Example 10 Action againstAnthonomus grandis (adults) Two cotton plants in the 6-leaf stage, in pots, are each sprayed with a wettabie aqueous emulsion formulation containing the test compound in a concentration of 400 ppm. After the spray coating has dried (about 1 1/2 hours), each plant is populated with 10 adult beetles (Anthonomus grandis). Plastic cylinders, covered at the top with gauze, are then slipped over the treated plants populated with the test insects to prevent the beetles from migrating from the plants. The treated plants are then kept at 25"C and about 60% relative humidity. Evaluation is made after 2,3,4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.

Compounds of the formula I according to Example 1 exhibit good activity in the above test.

Claims (19)

1. Acompound oftheformula

wherein X1, X2 and X3 are each independently hydrogen, halogen or methyl, Y is hydrogen or halogen, R is hydrogen, C1-C5alkyl, C3-C5alkenyl or C3-C5alkynyl, and R,, R2, B3, R4 and B5 are each independently hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or C1-C4alkylthio.

2. A compound of the formula I according to claim 1, wherein X1, X2 and X3 are each independently hydrogen, fluorine, chlorine or methyl, Yis hydrogen, fluorine or chlorine, R is hydrogen, C1-C4alkyl, allyl or propargyl, and R1, R2, R3, R4 and B5 are each independently hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy or methylthio.

3. A compound of the formula I according to claim 1,wherein X1 is hydrogen, fluorine, chlorine or methyl, X2 and X3 are each hydrogen, Y is hydrogen or chlorine, R is hydrogen or C1-C4alkyl, R1 is fluorine, chlorine, methyl, ethyl, methoxy, ethoxy or methylthio, R2 is hydrogen, 6-fluoro, 6-chioro, 6-methyl or 6-ethyl; and R3, R4 and B5 are each hydrogen.

4. A compound of the formula I according to claim 3, wherein X1 is hydrogen or chlorine, X2 and X3 are each hydrogen, Y is hydrogen or chlorine, R is hydrogen or C,-C4alkyl, R1 is fluorine, chlorine or methoxy, B2 is hydrogen, 6-fluoro or 6-chloro; and R3, R4 and B5 are each hydrogen.

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 process for the preparation of a compound of the formula I according to any of claims 1 to 8, which comprises a) reacting a compound of formula II

with a compound of formula Ill

or b).reacting a compound of formula IV

with a compound of formula V

or c) reacting a compound of formula II with a compound of formula iV

in which formulae 11 to VI above the substituents X1 to X3, Y, R and R1 to B5 are as defined in claims 1 to 4, and Z is a C1-C8alkyl group which is unsubstituted or substituted by halogen.

10. A compound of formula II

wherein X1, X2 and X3 are each independently hydrogen, halogen or methyl, Y is hydrogen or halogen, and R is hydrogen, C1-C5alkyl, C3-C5alkenyl or C3-C5alkynyl.

11. A pesticidal composition which contains a compound as claimed in any one of claims 1 to 8, together with suitable carriers andlor other adjuvants.

12. Use of a compound according to any one of claims 1 to 8 or controlling insects and representatives of the order Acarina.

13. Use according to claim 12 for controlling larval insect stages of plant-destructive feeding insects.

14. A method of controlling insects and representatives of the order Acarina, which comprises treating or contacting said pests, their various development stages or the locus thereof, with a pesticidally effective amount of a compound of the formula I according to any one of claims 1 to 8, or with a composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers suitable therefor.

15. A compound of formula I according to claim 1 substantially as described with reference to Example 1.

16. Process for producing a compound of formula I, according to claim 9, substantially as described with reference to Example 1.

17. A compound of formula I when reproduced by a process claimed in claim 9 or 16.

18. Pesticidal composition according to claim 11 substantially as described with reference to Example 2.

19. Method of controlling insects according to claim 14 substantially as described with reference to any of Examples 3 to 10.