GB2098608A - Phenylurea derivative - Google Patents

Abstract

Substituted N-(p-aminophenyl)-N'-benzoylurea of the formula <IMAGE> and the salts thereof, processes for producing this compound, and also compositions containing it or a salt thereof, for use in combating insect pests. This compound exhibits an insecticidal action and in particular a high larvicidal and ovicidal activity against insects that damage plants by eating.

Description

SPECIFICATION Phenylurea derivative The present invention relates to a novel N-(p-aminophenyl)-N'-benzoylurea derivative, to processes for producing it, and to its use in combating pests. The substituted N-(p-aminophenyl)-N'-benzoylurea according to the invention has the formula I

The invention relates also to the salts of the compound of the formula I which are tolerated by plants and are suitable for use in agriculture. Examples of acids suitable for forming salts are: hydrohalic acids, such as HCI, HBr, HI, phosphoric acid, perchloric acid, thiocyanic acid, tetrafluoroboric acid, nitric acid, sulfuric acid, aliphatic and aromatic sulfonic acids, fatty acids, trichloro- and trifluoroacetic acid and also polyvalent organic acids, such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid and citric acid. The compound of the formula I can be produced by processes known per se (cf., inter alia, the German Offenlegungsschriften Nos. 2,123,236 and 2,601,780). The compound of the formula I can thus be obtained for example: a) bv reactina the compound of the formula II

with the compound of the formula III

b) by reacting the compound of the formula IV

with the compound of the formula V

The salts of the compound of the formula I are produced by procedures that are generally known. The processes a) and b) mentioned can be performed preferably under normal pressure, and in the presence of an organic solvent or diluent. Suitable solvents or diluents are for example: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles, such as acetonitrile or propionitrile; dimethyl sulfoxide, and also ketones, for example acetone, methyl ethyl ketone, methyl-isopropyl ketone and methyl-isobutyl ketone. Process a) is in general performed at a temperature of-10 to 100[deg]C, preferably between 15 and 25[deg]C, optionally in the presence of an organic base, for example triethylamine.Process b) is carried out at a temperature of 0 to 120[deg]C, preferably at the boiling point of the employed solvant, and optionally 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. The starting materials of the formulae II, III, IV and V given in the foregoing are known, or in cases where they are new they can be produced by processes analogous to known processes. Thus, for example, the p-phenylene-diamine of the formula II can be produced by N-alkylation of 3,5-dichloro-pnitroaniline, and subsequent reduction or catalytic hydrogenation of the nitro group to the amino group [cf. for example Rec. 21, 271 (1902); J. Am. Soc. 68,1604 (1946); J. Org. Chem. 11, 378 (1946); and Rec. 79, 995 (1970)]. The isocyanate of the formula IV is obtainable by reacting the N,N-substituted pphenylenediamine of the formula II with phosgene, using in general customary processes. The benzoylisocyanate of the formula III can be obtained, starting with the benzonitrile of the formula VI, as follows (cf. J. Agr. Food Chem. 21 (3),348-993):

It is already known that specific N-phenyl-N'-benzoylureas have insecticidal properties (cf. German Offenlegungsschriften Nos. 2,123,236, 2,504,982, 2,537,413, 2,601,708 and 2,726,684; the Belgian Patent Specification Nos. 832,304, 843,906, 844,066 and 867,046; as well as the U.S. Patent Specification No. 4,089,975). From J. Agr. Food Chem. 21, No. 3, 348 ff. (1973), are also known substituted N-phenyl-N'-2,6-dichlorobenzoylureas, which are said to have insecticidal properties. There are mentioned, on page 353 of this publication, corresponding N-(4-dimethylamino)-phenyl derivatives and N-(3-chloro-4-dimethylamino)phenyl derivatives; these exhibit however- as can be seen from the Table III given therein - inadequate insecticidal activity. Furthermore, in the published European Patent Application No. 0,016,729, N -[3,5-halo-4-(N,Ndialkylamino)-phenyl]-N -halobenzoylureas are described; the compound of the formula I according to the present invention is embraced by the general scope stated therein, but is not specifically disclosed as such. It has now been found that the present compound of the formula I is surprisingly superior, with regard to its insecticidal, particularly larvicidal and ovicidal, activity (cf. the following Example 12) to the structurally similar compounds known from the said European Patent Application. This applies also to the N -(p-aminophenyl)-N -(2,6-difluorobenzoyl)-ureas and N -(p-allylaminophenyl)-N -(halobenzoyl)ureas which are emphasised in the European Patent Application as being especially effective.It was not to be expected that the compound of the formula I according to the present invention, which can be produced from relatively easily obtainable starting materials, would be suitable for the complete extermination of populations of harmful eating insects, whilst having negligible toxicity to warmblooded animals and a high degree of tolerance to plants. The compound of the formula I is particularly suitable for combating insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera. Besides having a favourable action against flies, for example Musca domestica, and against mosquito larvae, the compound of the formula I is suitable in particular for combating insects that damage plants by eating, in crops of ornamental plants and productive plants, especially in cotton crops (for example against Spodoptera littoralis and Heliothis virescens), and also in fruit and vegetable crops (for example against Laspeyresia pomonella, Leptinotarsa decemlineata and Pieris brassicae). To be specially emphasised is the larvicidal, ovicidal and ovalarvicidal action of the compound of the formula I. When the compound of the formula I is taken up with the feed by adult insects, there is observed in many cases, especially with Coleoptera, for example Anthonomus grandis, a reduced oviposition and/or a lessened rate of hatching. The compound of the formula I is suitable also for combating ectoparasitic insects in both domestic and productive animals, for example by treatment of animals, livestock housing and pasture land. The good insecticidal action of the compound of the formula I corresponds to a mortality rate of at least 50-60% of the insect pests mentioned. The action of the compound according to the present invention, and of the compositions containing it, can be considerably broadened and adapted to suit prevailing conditions by the addition of other insecticides and/or acaricides. Suitable additives are for example the following active substances: organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, chlorinated hydrocarbons and Bacillus thuringiensis preparations. It has been shown that preparations containing the compound of the formula I according to the invention, together with the known insecticide, "Galecron" [N -(4-chloro-2-methyl-phenyl)-N ,N dimethyl-formamidine], are distinguished by a surprisingly high insecticidal activity and by a particularly wide spectrum of application. The compound of the formula I can be combined with particular advantage also with substances which have the effect of intensifying pesticidal activity. Examples of compounds of this type are, inter alia: piperonylbutoxide, propynyl ethers, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane or S,S,Stributylphosphorotrithioates. The compound of the formula I is used either in an unmodified form or preferably together with auxiliaries customarily employed in formulation practice, and is thus processed, in a known manner, for example into the form of emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example polymeric substances. The application processes, such as spraying, atomising, dusting, scattering or pouring, and likewise the type of composition, are selected to suit the objectives to be achieved and the given conditions. The formulations, that is to say, the compositions or preparations containing the active ingredient of the formula I, or combinations of this active ingredient with other insecticides or acaricides, and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active substances with extenders, such as with solvents, solid carriers and optionally surface-active compounds (tensides). Suitable solvents are: aromatic hydrocarbons, preferably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl- or dioctylphthalates, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water. The solid carriers used, for example for dusts and dispersible powders, are as a rule 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 acids or highly dispersed absorbent polymers. Suitable granulated absorptive carriers are porous types, for example pumic, ground brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. A great number of pre-granulated materials of inorganic or organic nature, such as in particular dolomite or ground plant residues, can also be used. Suitable surface-active compounds are nonionic, cationic and/or anionic tensides having good emulsifying, dispersing and wetting properties. By 'tensides' are also meant mixtures of tensides. Suitable anionic tensides are both so-called water-soluble soaps, as well as water-soluble, synthetic surface-active compounds. Soaps which may be mentioned are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higher fatty acids (C10 C22), for example the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained for example from coconut oil or tallow oil. Also to be mentioned are the fatty acid-methyl-taurine salts. So-called synthetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline-earth metal or optionally substituted ammonium salts, and they generally contain an alkyl group having 8 to 22 C atoms, 'alkyl' including also the alkyl moiety of acyl groups, for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are 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 group having about 8-22 C atoms.Alkylarylsulfonates are for example the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acidformaldehyde condensation product. Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct. Suitable nonionic tensides are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable nonionic tensides are the water-soluble polyethylene oxide adducts, which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, with polypropylene glycol, ethylene-diaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.Examples of nonionic tensides which may be mentioned are: nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable also are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan-trioleate. In the case of the cationic tensides, they are in particular quaternary ammonium salts which contain as N-substituents at least one alkyl group having 8 to 22 C atoms and, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethyl ammonium chloride or benzyldi-(2-chloroethyl)-ethylammonium bromide. The tensides customarily used in formulation practice are described, inter alia, in the following publications: "My Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, 1979, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York. The pesticidal preparations contain as a rule 0.1 to 99%, particularly 0.1 to 95%, of active substance of the formula I, or of combinations of this active substance with other insecticides or acaricides, 1 to 99.9% of a solid or liquid additive, and 0 to 25%, especially 0.1 to 20%, of a tenside. Whereas commercial products are preferably in the form of concentrated compositions, the products employed by the end-user are as a rule preparations having considerably lower concentrations of active substance. The compositions can also contain additives such as stabilisers, antifoaming agents, viscosity regulators, binders and adhesives, as well as fertilisers or other active substances for obtaining special effects. Formulation examples for liquid active substances of the formula I or combinations of these active substances with other insecticides or acaricides (% = per cent by weight)

The active substance or active-substance combination is well mixed with the additives and ground in a suitable mill. There are obtained wettable powders which can be diluted with water to give suspensions of the concentration desired. 2. Emulsion concentrate active substance or active-substance

Emulsions of the concentration required can be obtained from this concentrate by dilution with water.

Dusts ready for use are obtained by mixing the active substance with the carriers, and grinding the mixture in a suitable mill. 4. Extruder granulate

The active substance is mixed and ground with the additives, and the mixture is subsequently moistened with water. This mixture is afterwards extruded, granulated, and then dried in a stream of air. 5. Coated granulate

The finely ground active substance or active-substance 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

The finely ground active substance or active-substance combination is intimately mixed with the additives. There is obtained a suspension concentrate from which can be produced, by dilution with water, suspensions of any concentration desired. The invention is illustrated by the following Examples. EXAMPLE 1 5.0 g of 3,5-dichloro-(4-N-methyl-N-n-propylamino)-aniline are dissolved in absolute ether, and, with cooling and the exclusion of moisture, 3.9 g of 2-chlorobenzoylisocyanate are added. The precipitate which has resulted after some time is filtered off with suction, and recrystallised from ethanol to thus obtain N -[3,5-dichloro-(4-N-methyl-N-n-propylamino)-phenyl]-N -2chlorobenzoylurea, m.p. 134-136[deg]C. EXAMPLE 2 Action against Musca domestica 50 g of freshly prepared CSMA nutrient medium for maggots were weighed off into each of a series of beakers. A specific amount of a 1 % (by weight) acetonic solution of the respective active substance was transferred by pipette to the nutrient medium in each beaker. After a thorough mixing of the nutrient medium, the acetone was allowed to evaporate off for at least 20 hours. There were then deposited per active substance and concentration in each case 25 one-day-old Musca domestica maggots into each beaker containing the treated nutrient medium. After completion of pupation, the formed pupae were separated from the nutrient medium by flushing with water, and were placed into vessels closed with perforated lids.The pupae flushed out per batch were counted (toxic effect of the active substance on the development of the maggots), and after 10 days the number of flies which had emerged from the pupae was determined. The compound of the invention according to Example 1 exhibited a good action in the above test. EXAMPLE 3 Action against Lucilia sericata 1 ml of an aqueous solution containing 0.5% of active substance was added to 9 ml of a culture medium at 50[deg]C. About 30 freshly hatched Lucilia sericata maggots were then placed onto the culture medium, and after 48 and 96 hours, respectively, the insecticidal action was determined by ascertaining the mortality rate. The compound of the invention according to Example 1 exhibited in this test a good action against Lucilia sericata. EXAMPLE 4 Action against Aedes aegypti Sufficient of a 0.1 % acetonic solution of the respective active substance was transferred by pipette to the surface of 150 ml of water in a container to obtain concentrations of 10, 5 and 1 ppm in each case. After the acetone had evaporated off, 30-40 three-day-old Aedes larvae were placed into each container. The mortality rate was ascertained after 1, 2 and 5 days. The compound of the invention according to Example 1 exhibited in this test a good action against Aedes aegypti. EXAMPLE 5 Action against Heliothis virescens (larvae) Cotton plants about 25 cm in height in pots were sprayed with aqueous active-substance emulsions containing the respective active substance at concentrations of 100, 50, 12.5, 3.0 and 0.75 ppm. After the drying of the applied coating, larvae of Heliothis virescens in the third larval stage were settled onto the cotton plants. The test was carried out at 24[deg]C with 60% relative humidity. At intervals in each of 24 hours, an assessment was made of the mortality rate of the test insects, and the damage caused by eating was evaluated (cf. following Example 12, Tables I and II). EXAMPLE 6 Action against Spodoptera and Heliothis virescens (larvae and eggs) Three cotton plants about 15-20 cm in height and grown in pots were treated with a sprayable liquid preparation of the respective active substance to be tested. After the drying of the applied coating, the potted plants were placed into a tin container of about 20 litres capacity, which was covered with a glass plate. The humidity inside the covered container was controlled in a manner ensuring that no condensation water was formed. Direct light falling onto the plants was avoided.The three plants were then infested in all as follows: a) 50 larvae of Spodoptera littoralis and Heliothis virescens, respectively, of the first larval stage; b) 20 larvae of Spodoptera littoralis and Heliothis virescens, respectively, of the third larval stage; and c) two coatings of eggs of Spodoptera littoalis and Heliothis virescens, respectively: for this purpose, 2 leaves of a plant were in each case enclosed in a plexiglass cylinder sealed at each end with gauze; two coatings of eggs of Spodoptera, or a portion of a cotton-plant leaf on which were deposited eggs of Heliothis, were added to the enclosed leaves. An evaluation, using untreated control plants as a comparison, was made after 4 to 5 days on the basis of the following criteria: a) number of living larvae, b) inhibition of larval development and shedding, c) damage caused by eating (scraping and hole damage), d) hatching rate (number of larvae which have emerged from the eggs). The compound of the invention according to Example 1 exhibited a good overall effectiveness in the above test. EXAMPLE 7 Ovicidal action against Spodoptera littoralis Eggs of Spodoptera littoralis deposited on filter paper were cut out of the paper and immersed in a 0.05% (by weight) solution of the active substance in an acetone/water mixture (1:1). The deposited eggs treated in this manner were then removed from this mixture, and placed at 21 [deg]C with 60% relative humidity into plastics dishes. An assessment was made after 3 to 4 days of the hatching rate, that is, of the number of larvae which had developed from the treated eggs. The compound of the invention according to Example 1 exhibited a good action in the above test. EXAMPLE 8 Ovicidal action against Epilachna varivestis 20 per cent by weight of active substance, 70 per cent by weight of xylene and 10 per cent by weight of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate were mixed together, and from this concentrate were produced aqueous emulsions containing 800 ppm and 1600 ppm, respectively, of active substance. In each case, about 100 eggs of Epilachna varivestis (Mexican bean beetle), freshly deposited on Phaseolus vulgaris leaves, were moistened with the aqueous emulsions described above (concentrations 800 ppm and 1600 ppm, respectively, of active substance), and slightly dried. The treated clusters of eggs were kept in a ventilated vessel until the simultaneously deposited by untreated control eggs had hatched. An evaluation was made under a binocular microscope with regard to the percentage mortality rate achieved. The compound of the invention according to Example 1 exhibited a good action in the above test. EXAMPLE 9 Ovicidal action against Heliothis and Leptinotarsa decemlineate Appropriate proportions of a wettable pulverulent formulation containing 25 per cent by weight of . the active substance to be tested were mixed with specific amounts of water to give aqueous emulsions of increasing concentration of active substance. One-day-old clusters of eggs of Heliothis deposited on cellophane and of Leptinotarsa deposited on potato leaves were immersed for three minutes in the above respective emulsions containing the active substance to be tested, and were the filtered by suction on round filters. The egg clusters treated in this manner were subsequently laid out in Petri dishes and kept in darkness. After 6 to 8 days, the hatching rate compared with that of untreated control clusters was determined.The criterion for the evaluation was the minimum concentration of active substance required to effect a 100% destruction of the eggs. The compound of the invention according to Example 1 exhibited in this test a good ovicidal action against the insect pests tested. EXAMPLE 10 Ovicidal action against Laspeyresia pomonella Deposited Laspeyresia pomonella eggs, not more than 24 hours old, were immersed on filter paper for 1 minute in acetonic/aqueous solutions containing 12.5, 50, 100 and 200 ppm of the active substance to be tested. After drying of the solution, the eggs were laid out in Petri dishes, and kept at a 4 temperature of 28[deg]C. After 6 days, the percentage hatching rate from the treated eggs and the % mortality rate, respectively, were determined with the aid of a binocular microscope (cf. Example 12, Table I in the following). EXAMPLE 11 Effect on reproduction of Anthonomus grandis 5 Adult Anthonomus grandis, which had been hatched no longer than 24 hours, were transferred, in groups each of 25 beetles, to cages having lattice walls. The cages containing the beetles were then immersed for 5 to 10 seconds in an acetonic solution containing 1.0 per cent by weight of the active substance to be tested. After the beetles were again dry, they were placed, for copulation and oviposition, into covered dishes containing feed. Deposited eggs were flushed out with running water 5 two to three times weekly; they were counted, disinfected by being placed for two to three hours in an aqueous disinfectant (such as "Actamer B 100"), and then deposited into dishes containing a suitable larval diet. The eggs were examined after 7 days to determine whether the larvae had developed from the deposited eggs. In order to ascertain the duration of the reproduction-influencing effect of the active substances to be tested, the oviposition of the beetles was observed during a period of about four weeks. The evaluation was on the basis of the reduction of eggs laid and hatched larvae in comparison with that of untreated control specimens. The compound of the invention according to Example 1 exhibited a good action in the above test. EXAMPLE 12 Biological results The following Tables I and II show results of insecticidal comparative tests on the basis of the above biological Examples 5 and 10, wherein the effectiveness of the compound according to the invention is compared with that of structurally similar compounds known from the European Patent Application No. 0,016,729. For evaluation of the tests on Heliothis virescens larvae according to Example 5, the attained percentage mortality figures have been summarised in Tables I and II. The assessment of the ovicidal tests with Laspeyresia pomonella according to Example 10 was made by taking the resulting % mortality rate as the criterion and using the following index of ratings: A: 80-100% mortality at a concentration of 12.5 ppm of the test compound, B: 80-100% mortality at a concentration of 50 ppm of the test compound, C: 80-100% mortality at a concentration of 100 ppm of the test compound, and D: 80-100% mortality at a concentration of 200 ppm of the test compound. The results given in the Tables I and II clearly show the superiority of the compound according to the invention, as a larvicide and ovicide, compared with the compounds according to the European Patent Application No. 0,016,729.

1. A compound of the formula I

and the salts thereof.

Claims (1)

1. 2. A process for producing the compound according to Claim 1, which process comprises: a) reacting the compound of the formula II

   with the compound of the formula III

   b) reacting the compound of the formula IV

   with the compound of the formula V

   and optionally converting the resulting compound of the formula I with an acid into a salt.

   3. A pesticidal composition which contains as active ingredient the compound according to Claim 1 or a salt thereof, together with suitable carriers and/or other additives.

   4. A method for combating insects, which method comprises applying thereto or to the locus thereof a pesticidally effective amount of the compound according to Claim 1 or of one of its salts. 5. A method according to Claim 4, which method comprises the use of the compound according to Claim 1 or of a salt thereof as a larvicide and/or ovicide for combating insects which damage plants.

   6. A method according to Claim 5 for combating insects which damage plants by eating.

   7. A method according to Claim 6 for combating Heliothis virescens and Lapeyresia pomonella. Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1982. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained