CA1185266A - Phenylurea derivative - Google Patents

Abstract

Abstract Novel substituted N-(p-aminophenyl)-N'-benzoylurea of the formula

Description

2~i~

Case 5-13396 PHENYLUREA DERIVATIVE
The present invention relates to a novel N-(p-amino-phenyl)-N'-benzoylurea derivative, to processes for producing it, and to its use in combating pests.
The substituted N-(p-aminophenyl)-N'-benzoylurea according to ~he invention has the formula I

Cl ` ~Cl -Co-~-C~- \- (I).
CH3-C~2-CH2 The invention relates also to the salts of the compound of the formula I ~hieh are tolerated by plants and are suit-able for use in agriculture. ~amples of acids suitable for forming salts are: hydrohalic acids, such as HCl, HBr, HJ, phosphoric acid, perchloric acid, thiocyanie acid, tetrafluoroborie acLd, nitric acid, sulfuric acid, aliphatic ancl aromatic sulfonic acids, fatty acids, triehloro- and trifluoroaeetie acid and also polyvalent organie acids, such as oxalic acid, malonic acid, succinic acid, tartaric aeid, adipie acid and citric acid.
The compound of the formula I can be produced by proeesses known per se (cp., inter alia, the German Offen-~8S;2~i~

legungsschriften Nos. 2,123,236 and 2,601,780).
The compound of the formula I ,-:an thus be obtained for example:
a) by reacting the compound of the formula II

Cl cll-C~l-c~ 2 (II) with the compound o; the formula III
Cl .=! (III); or -co-~=c=o b) by reacting the compound of the formula IV

c~ !_. (IV) with the compound of the formula V

Cl ~ ~- CO Nll (V) .

The salts of the compound of the Eormula 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 ~L~LB52~

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, xy~ene~ chloroform, methylene chloride, carbon tetra-chloride 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 oE -10 to 100C, preferably between 15 and 25C, optionally in the presence of an organic base, for example triethylamine. Process b) is carried out at a temperature of O to 120C, preferably at the boiling point of the employed solvent, and optionally in the presence o~ 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 kno~n, or in cases where they are new they can be produced by processes analogous to known processes. Thus, for e~ample, the p-phenylene-diamine of the formula II can be produced by N-alkylation of 3,5-dichloro-p-nitroaniline, and subsequent reduction or catalytic hydrogenation of the nitro group to the amino group [cp. for example Rec. 21, 271 (1902); J. Am. Soc. 68, 1604 (19!~6); J. Org. Chem. 11, 378 (1946); and Rec. 79, 995 tl970)~. The isocyanate of the ~ormula IV is obtainable by reacting the N,N-substituted p-phenylenediamine 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 (cp. J. Agr. Food Chem. 21(3), 348-993):

~SZ~6 Cl Cl C- N 2 ~ 2 ~ CO-~ H ? ~ ( I I I ) (VI) (V) It is already known that specific N-phenyl-N'-benzoyl-ureas have insecticidal properties (cp. German Offenleg~mgs-schriften Nos. 2,123,236, 2,504,982, 2,537,413, 2,601,7~0 and 2,726,684; the Belgian Patent Specifications Nos.
~32,304, 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 sub-stituted N-phenyl-N'-2,6-dichlorobenzoylureas, which are said to have insecticidal properties. ~here are mentioned, on page 353 of this publication, corresponding N-(4-dimethyl-amino)-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 -L3,5-halo-4-(N,N-dialkylamino)-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 ~ound that the present compound of the formuLa I is surprisingly superior, with regard to its insecticidal, particularly larvicidal and ovicidal, activity (cp. the folLowing Example 12) to the structurally simiLar compounds known Erom the said European Patent Application. This applies also to the Nl-(p-amino phenyl)-N2-(2,6-difluorobenzoyl)-ureas and Nl-(p-allylamino-phenyl)-N2-(halobenzoyl)-ureas which are emphasised in the ~1852 EuropPan 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, ~hilst having negllgible toxicity to warm-blooded 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, Coleop-tera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, ~lallophaga, 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 agairlst Spodoptera littoralis and Heliothis virescens), and also in fruit and vegetable crops (for example against Laspeyresia pomonella, Leptino-tarsa decemlineata and Pieris brassicae). To be specially emphasised is the larvicidal, ovicidal and ovolarvicidal 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 ~526~

~ormula I corresponds to a mortality rate of at least 50-60% o~ the insect pests mentioned.
The action of the compound accordin~ to the present invention, and of the compositions containing it, can b~
considerably broadened and adapted to suit prevailing conditions by the addition of other insecticides and/or acaricides. Suitable additives are for example the ~ollowing active substances: organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas~
carbamates, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
It has been sho~n that preparations containing the compound of the formula I according to the invention, together ~ith the l~no~n insecticide, "Galecron" [N -(4-chloro-2-methyl-phenyl)-Nl~Nl-dimethyl-formamidine], are distinguished by a surprisingly high insecticidal activity and by a particularly ~ide 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,S-tributylphosphorotrithioates.
The eompouncl of tle formula I is used either in an unmodiEied form or prefcrably to~cther ~ith a~xiliaries custom.lrily employcd in Eormulation practice, ancl is thus processecl, in a Icno~ln manner, For exainple into the Eorm oE emulsion concentrates, directly sprayable or clilutable solutions, dilutecl emulsions, ~ettable po~ders, solublc po~ders, clus~s or ~ranulates, and also encapsu-lations in Eor cx.l;llple polymeric substances. The applic.ltioll processes, such as spraying, atomisin~, dusting, S: ~ ~r,~ c ~

~L~8~

scattering or pouring, and lilcewise the type of compo-sition, 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 Eormula I, or combinations of this active ingredient with other insecticicles or acaricides, and optionally a solid or liquicl 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, prefer-ably 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, kaol:in, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silicic acids or highly dispersecl absorben~ polymers. Suitable granu-lated adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. A great number of pre-granulated materials of ~3SZG~

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 ancl wetting properties. By 'tensides' are also meant mixtures of tensides.
Suitable anionic tensides are both so-called water-soluble soaps, as ~ell 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 aclds (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, or example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acicl ester or of a Fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are the salts of sulfuric acid es~ers and sulfonic acids of fatty alcohol ethylene oxide adducts. The sulfonated benæimidazole derivatives preferably con~ain 2 sulfonic acid groups and a fatty acid group having about 8-22 C
atoms. ~lkylarylsulfonates are for example the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of ~B5266 dibutylnaphthalenesulfonic acid or of a naphthalene-sulfonic acid-formaldehyde condensation product. ~lso suitable are corresponding phosp~ates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct.
Suitable nonionic tensicles are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glyco] 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 alkyl-phenols. 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 l 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: nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol. Suitable also are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylene-sorbitan-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 Eurther 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)-ethyl-~ 85266 ammonium bromide.
The tensides customarily used in Eormulation 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 ~ctive 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 oE this active substance with other insecticides or acaricides, 1 to 99.9% o~ 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) :e~e: bl~ a) b) c) active substance or active- 25% 50% 75%
substance combination sodium lignin sulfonate 5% 5%
sodium lauryl sulfate 3% - 5%
sodium diisobutylnaphthalene - 6% 10%
sulfonate octylphenolpolyethylene glycol - 2%
ether (7-8 mols of ethylene oxide) 52~i~

highly dispersed silicic acid 5~/O 10% 10%
kaolin 62~/o 27%
The active substance or active-substance combinatlon 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- 10~/o substance combination octylphenolpolyethylene glycol ether 3%
(4-5 mols of ethylene oxide) calcium dodecylbenzene sulfonate 3%
eastor oil polyglycol ether 4%
(36 mols of ethylene oxide) eyclohexanone 30%
xylene mixture 50%
Emulsions of the concentration required can be obtained from this eoneentrate by dilution with water.

3. Dusts a) b) aetive substanee or aetive- 5% 8%
substanee eombination taleum 95J/0 kaolin - 92%
Dusts ready for use are obtained by mixing the active substanee with the carriers, and grinding the mixture in a su:itable mill.
. Extruder granulat~
active substanee or active- 10%
substance combination sodium lignin sul~onate 2%
carboxymethylcellulose 1%
kaolin 8 7%

~8~2~

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.
S Coated ~ranulate n active substance or active- 3%
substance combination polyethylene glycol (MG 200) 3%
kaolin 94%
The finely ground active substance or active-substance combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. ~on-dusty coated granulates are obtained in this manner.
6. Suspension concentrate active substance or active- 40%
substance combination ethylene glycol 10%
nonylphenolpolyethylene glycol ether 6%
(15 mols of ethylene oxide) sodium lignin sulfonate 10%
carboxymethylcellulose 1%
37% aqueous formaldehyde solution0.2%
silicone oil in the form of a 0.8%
75% aqueous emulsion water 32%
The finely ground active substance or active-substance combination is intimateLy mixed with the aclditives. There is obtained a suspension concentrate from which can be produced, by dilution with water, suspensions of any concentration desired.
Example l: 5.0 g of 3,5-dichloro-(4-N-methyl-N-n-propyl-amino)-aniline are dissolved in absolute ether, and, with cooling and the exclusion of moisture, 3.9 g of 2-chloro-~8S26~i benzoylisocyanate are added. The precipitate whichhas resulted after some time is filtered off with suction, and recrystallised from ethanol to th~s obtain N -[3,5-dichloro-(4-N-methyl-N-n-propylamino)-phenyl]-N -2-chlorobenzoylurea, m.p. 134-136C.
Example 2: Action a ainst Musca domestica 50 g of freshly prepared CSM~ nutrient medium for maggots were weighed ofE into each of a series of beakers.
A specific arnount 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 Examp]e 1 exhibited a good action in the above test.
Exam~le 3: Action a~ainst Lucilia sericata 1 ml of an aqueous solution containing 0.5% of actlve substance was added to 9 ml of a culture medium at 50C.
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 ae~ypti 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 accordlng 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 24C with 60% relative humidity. At intervals in each case of 24 hours, an assessment was made of the mortality rate of the test insects, and the damage caused by eating was evaluated (cp. following Example 12, Tables I and Il).
Example 6: Action a~a:inst Spodoptera and tleliothis virescens (larvae and e~gs) 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 ~521Ei~

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 ensurlng that no condensation ~ater was formed. Direct light falling onto the plants was avoided. The three plants were then inested in all as follows:
a) 50 larvae of Spodoptera littoralis and lleliothis virescens, respectively, of the ~irst larval stage;
b) 20 larvae of Spodoptera l;ttoralis and lleliothis virescens, respectively, of the third larval stage; and c) two coatings of eggs of Spodoptera littoralis 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, ~) inhibition of larval development and sheclding, c) damage caused by eating (scraping and hole damage), d) hatching rate (n~lmber o~ larvae which have emergecl from the eggs).
The compound o~ the invention according to E~ample 1 e~hibitccl a good overall eEEectiveness in the above test.
E~am~lc 7: Ovicid.ll action ~ainst Spodo~era llttor.~lis Eggs oE SpodopLcra littoralis deposited on Eil~er paper were cut out of the papcr and imlllersed in a 0.05~u (by weigllt) .,.,, ~ 'I`r:l~lc ~ r~

~L: L8~2~6 solution of the active substance in an acetone/watermixture (l:L). The deposited eggs treated in this manner were then removed from this mixtu~e, and placed at 21C
with 60% relative humidity into plastics dishes. An assessment was made aEter 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 but untreated control eggs had hatched. An evaluation was made under a binocular microscope with regard to the percentage mortality rate achieved.
'L'he compound oE the invention according to Example 1 exhibited a good action in the above test.
Example 9: Ovicidal action against ~leliothis and Leptinotarsa decemlineate ~ppropriate 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 oE
increasillg ccncentration of active substance. ~le-day-old clusters of eggs of l-leliothis cleposited on cellophane* ancl of Leptinotarsa cleyosited on potato leaves were immersed for three minutes in tlle above respective emulsions contain-ing the active substance to be testecl> and were then Eiltered by suction on ro~lcl filters. The egg cl~lsters treatecl in -this manller were subsequently laid out in Pctri clishcs ancl kept in clarkness. ~\fter 6 to 8 clays, the hatching rate comparecl with that of untreated control clusters was de-termined. The criterion for the evaluation was the minimum concentration of active substance required to effect a 100% destruction of the eggs.
The compowld 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 ~ept at a temperature of 28C. After 6 days, the percentage hatching rate from the treated eggs and the % ,nortality rate, respectively, were determined with the aid of a binocular microscope (cp. Example 12, Table I in the following).
Examele 11: E~EEect on reproduction of ~nthonomus granclis -Aclult Anthollolnus granclis, which llacl been hatchecl no longer than 24 hours, were transferrecl, in groups each of 5 beetles, to cages having lat-tice walls. The cages conta:illing tlle beetles were then immersecl for 5 -to 10 seconds in an acetonic solution containing 1.0 per cent by weight oE the active sub-stance to be testecl. After tlle beetles were again dry, they were placed, for * Tracle ~lark ~sz~

copulation and oviposition, into covered dishes containing feed. Deposited eggs were flushed out with r~mning water 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* I00"), md then deposited into dishes containing a suitable larval diet. The eggs were examined after 7 days to determine whether larvae had cleveloped from the deposited eggs.
In order to ascertain the duration of the reproduction-influencing effect of the active substances to be tested, the oviposi-tion 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 un-treated control specimens.
The compound of the invention according to Example 1 exhibited a good action in the above test.
Example 12: Biolo~ical results c.
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 effec-tiveness 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 percen-tage mortality figures have been summarised in Tables I and II. The assessment of the ovicidal tests with Laspeyresia pomonella according to E.~ample 10 W1S made by taking the resulting % mortality rate as the cri-terion ancl using the following inde~ of ratings:

* Trade Mark ~135~6~

A: 80-100 % mortality at a concentration of 12.5 ppm of the test compound, B: 80-100 % mortality at a concencration of 50 ppm of the test compound, C: 80-100 % mortality at a concentration o~ 100 ppm oE
the test compound, and D: 80-lO0 % mortality at a concentration oE 200 ppm of the test compound.
The results given in the Tables I and II clearly show the superiority oE 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.

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Claims (6)

WHAT IS CLAIMED IS:

1. A compound of the formula I

(I) and the salts thereof.

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

(II) with the compound of the formula III

(III), or b) reacting the compound of the formula IV
(IV) with the compound of the formula V

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

3. A method for combating insects, which method comprises applying thereto or to the locus thereof a pesticidally effective amount of the compound of tile formula I

(I) or of one of its salts.

4. A method according to Claim 3, which method comprises the use of the compound of formula I or of a salt thereof as a larvicide and/or ovicide for combating insects which damage plants.

5. A method according to Claim 4 for combating insects which damage plants by eating.

6. A method according to Claim 5 for combating Heliothis virescens and Lapeyresia pomonella.