GB2144412A - Substituted phenylhydrazonopyrrolidine derivatives and their use in pesticide compositions - Google Patents

Description

1 GB 2 144 412 A 1

SPECIFICATION

Pesticidal compositions The present invention relates to novel substituted phenyl hydrazonopyrrolidine compounds, to processes for 5 producing them, to compositions containing these compounds as active ingredients, and to the use of these compounds for controlling pests, particularly phytoparasitic and zooparasitic insects, and members of the order Acarina, including especially ectoparasites, for example mites and in particular ticks.

In the German Offen legu ngssch rift No. 3,035,822, phenyl hyd razi no pyrrol ine compounds are described and their use for controlling mites suggested. These substances however can only partially satisfy the 10 demands made of them in practice.

The novel compounds correspond to the general formula 1 f \ NH-N==N 15 IR)n A 1 R C wherein R is halogen or Cl-C4-alkyl, n is zero, 1 or 2, R is the group - CH=N-Rl or OR 25 -p 2 f__R X 3 in which 30 R, is a pyridine group which is bound by way of a carbon atom, and which is unsubstituted or substituted by a methyl group, or is a 2-thiazolyl group, and R2 is methyl or ethyl, R3 is Cl-C4-alkyl, Cl-C2-alkoxy or Cl-C4-alkylthio, and X is oxygen or sulfur, and the invention relates also to the acid addition salts of these compounds. 35 Depending on the meaning of the substituent R, there are therefore embraced either amidine derivatives or (thio)phosphoryl derivates of the formula 1.

Examples of salt-forming acids are inorganic acids: hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, as well as sulfuric acid, phosphoric acid, phosphorous acid and nitric acid; and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic 40 acid, tartaric acid, formic acid, oxalic acid, succinic acid, maleic acid, lactic acid, glycolic acid, aconitic acid, citric acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid or methanesuffonic acid.

Halogen in the case of R is for example: fluorine, chlorine, bromine or iodine. Alkyl as substituent or part-substituent denoted by R3 embraces methyl and ethyl and the isomers of propyl and butyl. Cl-C2-Alkoxy as R3 is methoxy and ethoxy.

Preferred compounds of the formula 1 wherein R is the group -CH=N-Rl (compound group fa) are those in which R is chlorine andlor methyl, and n is 1 or 2, whilst R, has the meanings defined under the formula 1. Particularly advantageous among the preferred compounds are those in which R(,,) is 2,3-dichloro.

Individual compounds which are especially preferred are compounds Nos. 2a and 3a mentioned in the following (Table 1).

Of the compounds of the formula 1, the amidines of the formula la C -NH- (R)n" N==0 1 wherein R, R, and n have the meanings defined under the formula 1, are produced by reacting a compound of 60 the formula Ila with a compound of the formula Illa I \\ + R2-0-CH=N-R, -> la Rn'o (Ila) (111a) 2 GB 2 144 412 A 2 wherein R, R, and n have the aforementioned meanings, and R2 is a methyl or ethyl group.

The process is performed in a solvent or diluent inert to the reactants, and at a temperatures of -10'C to 1OWC, preferably between 10' and WC.

Of the compounds of the formula [,the compounds of the formula lb in which R is the group -P(X) 5 (ORA3 as defined above NH-N- / (ib) [R)n OR 11.11 2 10 X-P--, R3 are produced by reacting a compound of the formula lib with a compound of the formula Illb (R1n (lib) X + 1 '_OR2 Hal-P R3 (111b) --> 1 B wherein R, R2, R3, X and n have the meanings defined under the formula 1, and Hal is a halogen atom, in particular a chlorine or bromine atom.

The process is performed in the presence of a base and of a solvent or diluent inert to the reactants, at a temperature of -30'to 1 OWC, preferably between - 1 W' and 600C.

Suitable solvents or diluents to be used in the aforementioned processes are for example: ethers and ethereal compounds, such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; also aromatic hydrocarbons, such as benzene, toluene and the xylenes, as well as ketones, such as acetone, methyl ethyl 30 ketone and cyclohexanone. There can also be used for this purpose acetonitrile, and chlorinated hydrocarbons, such as dichloromethane, methylene, carbon tetrachloride or chlorobenzene.

Bases that can be used are for example the foiicwing: alkali metal hydroxides such as sodium or potassium hydroxide, or alkylamines, such as triethylannine or diisopropylethylamine, as well as pyridine or N-methylpyrrolidone.

The compounds of the formula 1 produced in the manner described can be converted into their acid salts by methods known per se.

The compounds of the formula 1 according to the invention or the compositions containing them as active ingredients are, surprisingly, distinguished in the field of pest control by particularly good biological activity and a favourable range of action. Furthermore, they have an unexpectedly high level of stability, such as is 40 required for example with continuous use in soiled aqueous cattle dips. Compounds of the formula 1 and particularly those of the formula la have a surprisingly high tolerance to warm-blooded animals, a feature which greatly simplifies the handling of these compounds in practice.

The activity of the active substances is directed both against phytoparastic pests and against zooparasitic pests. Included amongst thu plant pests are insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.

The compounds of the formula 1 are also suitable for controlling members of the order Acarina of the families: Ixodiclae, Argasidae, Tetranychidae and Dermanyssidae. The compounds of the formula 1 can be 5() successfully used in particularfor controlling phytopathogenic mites, for example of the families:

Tetranychidae and Phytoptipalpidae (red spider mites), Tarsonemidae (thread foot mites) and Eriophydae (gall mites).

Besides their action against mosquitoes and flies, for example Addes aegypti and Musca domestica, compounds of the formula 1 also have a favourable action for use in controlling insects that damage plants by eating, in crops of ornamental Plants and productive plants, in particular in cotton crops (for example against Spodaptera littoralis and Heliothis virescens), as well as in cereal, fruit and vegetable crops (for example against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis). The compounds of the formula 1 are distinguished also by a good action against larval insect stages and nymphs, especially of eating insect pests. The compounds according to the invention are suitable moreover for controlling soil insects (for example Aulacophora femoralis, Chortophila brassicae, Diabrotica balteata, 60 Pachnoda savigni and Scotia ypsilon).

In particular, the compounds of the formula 1 can be used with great success against cicadas which damage plants, especially in rice crops, the compounds exhibiting both a systemic and a contact action, for example against Nilaparvata lugens and Laodelphax striatellus.

The compounds of the invention are particularly highly effective against ticks Oxodidae) parasitic on 65 3 GB 2 144 412 A 3 productiveanima Is, especially against the species: Rhipicephalus, Am blyomm a and Boophilus, and also against mites, for example Dermanyssus gallinae, and mange mites, for example: Psoroptes ovis, Psoroptes bovis and Chorioptes bovis.

The activity of the compounds of the formula I is directed also against further ectoparasites of the order Diptera, for instance of the families: Culicidae, Simuliiclae, Tipuliclae, Muscidae and Calliphoriclae. In this 5 respect, the active substances are particularly well suited for controlling Calliphoridae, for example Lucilia sericata (blowfly) and Lucilia cuprina.

Furthermore, members of the orders Aphaniptera (for example blood-sucking fleas) and Phthiraptera (for example blood-sucking lice) can be effectively controlled by use of the compounds of the formula 1.

In their activity, the compounds according to the invention exhibit a spectrum which embraces all stages 10 of development of the parasites, and beyond that also the oviposition of fertile eggs.

The control of the stated parasites is effected for example on the following domestic and productive animals: cattle, sheep, horese, red deer, poultry, goats, cats and dogs.

The higher stability of the compounds according to the invention ensures a cluradon of action which covers with respect to time the development cycles of several generations of parasites, so that, depending on the mode of application, for example in the case of productive animals, a single treatment per season is sufficient.

By virtue of their properties, the compounds of the formula I are very suitable for controlling ectoparasitic acarids and insects, for example by the direct treatment of animals, livestock housing and pastureland.

The action of the compounds according to the invention or of the compositions contaning them can be 20 considerably broadened and adapted to suit given conditions by the addition of other insecticides and/or acaricides. Suitable additives are for example representatives of the following classes of active substances:

organic phosphorus compounds,nitrophenols and derivatives thereof, ureas, carbamates or chlorinated hydrocarbons.

For the control of pests, the compounds for the formula I according to the invention are used either alone 25 or in the form of compositions, which additionally contain suitable carriers and/or additives, or mixtures of such substances. Suitable carriers and formulation auxiliaries can be solid or liquid and they correspond to the substances customarily used in formulation practice, for example natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners or binders.

The formulations, that is to say, the compositions or preparations containing the active ingredient of the 30 formula 1, or combinations of these active ingredients 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 ingredients 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 35 or substituted naphthalenes, phthalic esters, such as clibutyl- or clioctylphalate, aliphatic hydrocarbons, such as cyclohexane, paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene gy1col, ethylene glycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide 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, surh as calcite, talcum, kaolin, montmoreillonite 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, ground brick, sepiolite or bentonite, and suitable nonsorbent carriers are materials such as calcite or sand. There can also be used a great number of pre-granulated materials of inorganic or organic nature, such as in particular dolomite or ground plant residues.

Suitable surface-active compounds are, depending on the nature of the active ingredients of the formula 1, or of the combinations of these active ingredients with other insecticides or acaricides, to be formulated:

nonionic, cationic and/or anionic tensides having good emulsifying, dispersing and wetting properties. By 50 tensides'are also meant mixture of tensides.

Suitable anionic tensides are both so-called water-soluble soaps as well as water-soluble, synthetic, surface-active compounds.

Soaps which are applicable are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higherfatty acids (Clo-C22), for example the Na or K 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, as well as modified and unmodified phospholipides.

So-called synthetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimiclazole 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 contain in 60 general an alkyl group having 8 to 22 C atoms.

Examples of nonionic tensides which may be mentioned are: nonyl phenol polyethoxyethano Is, castor oil-polyglycol ether, polypropylenepolyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyox yethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

4 GB 2 144 412 A 4 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, benzyi or lower hydroxyalkyl groups. These salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethyl-ammonium chloride or benzyi-di-(25 chloroethyi)- ethyi-ammonium bromide.

The tensides customarily used in formulation practice are described, inter alia, in the following publication:

---Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1982.

The pesticidal perparations contain as a rule 0.1 to 99%, particularly 0. 1 to 95%, of active ingredient of the 10 formula 1, or of combinations of these active ingredients 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 end- user employs as a rule diluted preparations containing 0.001 - 1% of active ingredient.

The compositions according to the invention are produced, in a manner known per se, by the intimate mixing andlor grinding of active ingredients of the formula 1 with suitable carriers, optionally with the addition of dispersing agents and solvents which are inert to the active ingredients.

The compositions can contain further additives, such as stabilisers, antifoaming agents, viscosity regulators, binders, adhesives and phospholipides, or other active ingredients for obtaining special effects.

Depending on the purpose and aim of the application, the compounds of the formula 1 or the compositions 20 containing them are applied for exampe by spraying, for example in spray races, by dipping, for example in cattle dips, by the pour-on method, bywashing, for example by the animal dressing procedure, and also by atomising, dusting, scattering or pouring.

Example 1:

Production of N-(2-[N'-(2,3'-dichlorophenylhydrazono)-pyrrolidin-lyljmethylidene)-N-(6-m ethylpyridin-2- yll-amine [compound No. lal A solution of 65.6 g (0.4 moll of N-(6-methylpyridin-2-yi)-formiminoethyI ether in 100 mi of toluene is slowly added dropwise at about 25'C with vigorous stirring, to 98 g (0.4 mol) of 2-[N'-(2',3' dich lo ro phenyl hyd razi n o)l-pyrro line dissolved in 900 mi of toluene. The reaction mixture is subsequently 30 stirred for 48 hours at about 45C until the reaction is completed; the mixture is then filtered and the filtrate is concentrated by evaporation. After the addition of about 300 mi of diethyl ether, a yellow final product crystallises out; yield: 100 g (= 68% of theory); melting point 150-1520C.

Example 2:

Production of N-(2-[N'-(2',3'-dichlorophenylhydrazono)-pyrrolidin-lyl)llmethylidene-N-(3-m ethylpyridin-2- yl)-amine [compound No. 2a] To 9.8 9 (0.04 mol of 2-[N'-(2',3'-dichlorophenyi-hydrazino)l-pyrroline, dissolved in 90 mi of toluene, is slowly added dropwise at 20-26'C, with vigorous stirring, a solution of 6. 6g (0.04 mol) of N-(3 methyl pyridi n-2-yl)-formim i noethyl ether in 60 mi of toluene. The reaction mixture is subsequently stirred 40 for 12 hours at about 45'C until the reaction has finished; the mixture is then filtered and the filtrate is concentrated by evaporation. Afterthe addition of about 50 mi of diethyl ether, a yellow final product crystallises out; yield: 7.3 g (= 50.3% of theory); melting point: 155- 158'C.

Example 3:

Production of 1-(0-ethyl-S-n-propyl-thiophosphinyl)-2-[N'-(2',3'dichlorophenylhydrazono)l -pyrrolidine /compoundNo. 1b] To 14.6 9 (0.06 mol) of 2-[N'-(2',3'-dich 1 oro phenyl -hyd razi no)]- pyrroli ne, dissolved in 50 m] of tetrahydro furan, are added 7.6 g (0.075 mol) of triethylamine in 80 mi of toluene. There is then slowly added dropwise at 0-5'C, with continuous stirring, a solution of 13.1 g (0.06 mol) of 0ethy]-S-n-propyithioch 1 orophosph ate 50 in 80 m] of toluene. Stirring is subsequently maintained for 24 hours at about 50'C until the reaction has finished; the reaction mixture is filtered, the filtrate is concentracted by evaporation and afterwards chromatographed through aluminium oxide with a diethyl etherlhexane mixture (M vlv). There is thus obtained a colourless final product; yield 11.5 g (= 45% of theory); melting point: 91 -,93cC.

GB 2 144 412 A 5 The following compounds of the formula 1 are produced in a manner analogous to that described in the Examples given in the foregoing:

TABLE 1

R, Nfl-N- j 10 1 C-Rl 15 No. R' W' R' R, .p. [OCI la H cl cl n,.. 150-152 -- "IN'-C13 20 1 2a H cl cl 1 155-158 25 11 1J 3a H cl cl F7 137-139 30 S N Y F7 35 4a H H cl S N 122-124 Y 40 5a cl cl H nl--CH3 - 167-169 6a cl cl H CH3 179-180 "N 7a H cl cl 1 164167 '-N 55 8a H cl cl Njl 60 9a H cl cl (Nl 65 6 GB 2 144 412 A is 6 TABLE 11 cl NH-N-<I 1 __---OR2 XP"-R3 No. R2 R3 X M.P. ['C] 1b C2H5 SC31-17(n) S 91-93 2b C21-1s C2H5 S 79-81 3b C2R5 SC4Hg(i) 0 20 4b C2H5 0C2H5 0 5b CH:3 OCH3 0 25 6b C2H5 SC31-17(n) 0 Example 4

Action against ticks: killing action in various stages of development The test objects used are larvae (in each case about 50) and nymphs (in each case about 25) of the tick 30 species Amblyomi-na hebraeurn and Boophilus microplus, respectively. The test organisms are immersed for a short time in aqueous emulsions or solutions of the salts of the substances to be tested at a specific concentration. The emulsions or solutions in the sma!l +es, tubes are absorbed with cotton wool and the wetted test insects are then left in the contaminated test tubes. An evaluation with respect to larvae is made after 3 days and with respect to nymphs and imagines after 14 days. There is determined the minimum substance concentration which results in a 100% mortality rate, expressed in ppm of active substance, relative to the total amount of emulsion or solution.

The compounds from TaMes 1 and 11 result in a complete killing (100% mortality rate) at an application concentration of 25 ppm, the compounds Nos. 1 a, 2a, 3a and 6a as well as the compounds Nos. 1 b and 2b producing this result at a concentration as low as 12.5 ppm. This activity is retained by solutions of the 40 compounds Nos. 2a and 3a, respectively, even after a period of several weeks.

Example 5: Action against ticks: inhibition of oviposition The test insects used are engorged females of the cattle tick Boophilus microplus. There are treated per concentration 10 ticks of an OP- resistant strain (for example Biarra strain) and 10 ticks of a normally sensitive strain (for example Yeerogpilly strain). The ticks are fixed on plates covered with double adhesive tape, and are then either wetted with aqueous emulsions or with solutions of the salts of the compounds to be tested, or brought into contact with a cotton-wool pad soaked with these liquids, and are subsequently kept in an air-conditioned chamber under constant conditions. An evaluation is made after three weeks, and the overall 50 inhibition of the oviposition of fertile eggs is determined.

The inhibitory effect of the substances is expressed in terms of the minimum substance concentration in ppm to produce a 100% effect against normally sensitive adult female ticks and resistant adult female ticks, respectively. The compounds from Tables 1 and 11 effect a complete killing in the above test at a concentration of 25 ppm.

Example 6: Action againstphytoparasitic insects Cotton plants are sprayed with test solutions containing 25, 50 and 100 ppm, respectively, of the compound to be tested.

After the drying of the moist coating, Spodoptera littoralis larvae (L3) are settled onto the cotton plants. The test is carried out at 24'C with 60% relative humidity.

The compounds from the Tables 1 and 11 exhibit a good stomach-poison action against Spodoptera larvae, the compounds Nos. 1 a - 3a effecting complete killing at an applied concentration of 50 ppm, and the compounds of Table 11 a killing rate of over 90% at a concentration of 25 ppm.

7 GB 2 144 412 A 7 Example 7:

Action against Lucifia sericata (L 1) The test organisms used are freshly emerged larvae IL,. 1 mi of an aqueous suspension of solution of the active ingredient, the active-ingredient content being 1000 ppm, is mixed with a special larval culture medium at WC in such a manner that a homogeneous mixture of 250 ppm of active ingredient is obtained. 5 About 30 Lucilia larvae are used per test. The mortality rate is determined after four days.

The compounds in Table 1 effect a mortality rate of over 90%, and the compounds in Table 11 a mortality rate of over 80%. The compounds Nos. 1, 2 and 3 of Table 1 result in a complete killing of the larvae.

Example 8: Action against Nilaparvata lugens (nymphs) The test is carried out on growing plants. There are used in each case 4 rice plants (thickness of stem 8 mm) about 20 cm in height in pots (diameter 8 cm). The plants are sprayed, on a rotary plate, with in each case 100 mi of an acetonic solution containing 100, 200,300 and 400 ppm, respectively, of active ingredient.

Afterthe drying of the applied coating, each plant is infested with 20 nymphs of the test insects in the third 15 stage. in order to prevent the cicadas from escaping, a glass cylinder is placed over each of the infested plants and is covered with a gauze lid. The nymphs-are kept on the treated plants over a period of 10 days until the following development stage is reached. An evaluation of the % mortality rate is made 1, 4 and 8 days after the treatment.

Compounds of Tables 1 and 11 exhibit a good action in the above test. A mortality rate of 80% is effected by 20 the compound No. 1 a at an applied concentration of 100 ppm and by the compound No. 2a at an applied concentration of 400 ppm.

Example 9:

Action against soil insects (Diabrotica balteata) 25 350 mi of soil (consisting of 95 % by volume of sand and 5% by volume of peat) are mixed in each case with m 1 of the respective aqueous emulsion preparation, the preparations contai ning the active ing redient to be tested in increasing concentration levels from 3 ppm to 400 ppm. Plastic beakers having an upper diameter of 10 cm are then partially filled with the treated soil. Into each beaker are placed ten Diabrotica balteata larvae in the third larval stage; four maize seedlings are then planted in each beaker and the beakers 30 are topped up with soil. The filled beakers are covered over with plastic foil and kept at a temperature of about 22'C. Ten days after commencement of the test, the soil contained in the beakers is sieved, and the larvae remaining are examined with respect to the mortality rate.

Compounds from Tables 1 and 11 exhibit in this test a good action in that a mortality rate exceeding 80% is effected by the compound No. 1 a at an applied concentration of 12.5p ppm, and by compound No. 2a at a 35 concentration of 400 ppm.

Results similar to those given in the above Examples 3 to 9 can be obtained with active ingredients from the Tables 1 and 11 also with application over a longer period of time under practical conditions, without additional measures being carried out to stabilise the pH value of the preparations being applied.

Example 10: Emulsion concentrate 20 parts by weight of active ingredient are dissolved in 70 parts by weight of xylene, and to the solution are added 45 10 parts by weight of an emulsifier consisting of a mixture of tributylphenylpolyethylene glycol ether and 45 the calcium salt of dodecylbenzenesulfonic acid. A milky emulsion can be prepared by adding water in any desired proportion to the above emulsion concentrate.

Example 11:

Wettablepowder to 30 parts by weight of active ingredient are vigourously mixed, in a mixing apparatus, with parts by weight of an absorbent carrier (for example highly dispersed silicic acid) and to 80 parts by weight of a carrier [bolus alba or kaolin] and a dispersing agent mixture consisting of 5 parts by weight of sodium lauryl sulfonate and 5 parts by weight of actylphenolpolyethylene glycol.

This mixture is ground in a dowelled disk mill or air jet mill to a particle size of 5-15 pm. The wettable powder thus obtained gives a good suspension in water.

Example 12:

Dust parts byweight of finely ground active ingredient arethoroughly mixedwith 2 parts byweight of a precipitated silicicacid, and 93 parts byweightof talcum.

8 GB 2 144 412 A 8 Example 13:

Pour-on solution active substance sodium dioctyisuifosuccinate benzy] alcohol peanutoil 30.0 g 3.0 g 48.0 g 19.8 g 100.8 9 = 100 m] The active ingredient is dissolved with stirring in the benzy] alcohol, if necessary with gentle heating. To 10 the solution are then added the sodium dioctyisulfosuccinate and the peanut oil, and these are dissolved with heating and thorough stirring.

Example 14.. 15 Dressing solution wherein R is halogen or Cl-C4-alkyi.. n is zero, 1 or 2, R is the group -CH=N -R, or active ingredient sodium dioctyisuifosuccinate benzyl alcohol ethylene glycol monomethyl ether 30.00 g 3,00 g 35-46 g 35.46 g 103-92 9 = 100 mi The active ingredient is dissolved in the major portion of the mixture of the two solvents with vigorous stirring. The sodium dioetyisuifosuccinate is subsequently dissolved, if necessary with heating, and is finally added to the other constituents forming the mixture.

CLAWS 1. Asubstituted phenylhydrazonopyrrolidine compound of the general formula 1 C\\1-NH-N==n IRIn N 1, R _p,_-OR2 11 '--, R X 3 R1 is a pyridine group which is bound byway of a carbon atom, and which is unsubstituted or substituted by a methyl group, or is a 2-thiazolyl group, and R2 is methyl or ethyl, R3 is Cl-C4-alkyl, Cl-C2-aikoxy or Cl-C4-alkylthio, and X is oxygen or sulfur, including the acid addition salts of a compound of the formula 1.

2. A compound of the formula[ according to claim 1, in which R is the group -CG=N-Rj, and R, R, and n have the meanings defined in claim 1.

3. A compound of the formula 1 according to claim 1, in which R is the group _p,..AR2 11 X R3 and R, R2, R3r X and n have the meanings defined in claim 1.

4. A compound of the formula 1 according to claim 2, in which R is chlorine andlor methyl, and n is 1 or 2, 65 and R, hasthe meaning defined undertheformula 1.

(1) 30 so 9 GB 2 144 412 A 9 5. A compound of the formula 1 accord,Ing to claim 4, in which (R)n is 2, 3-dichloro.

6. W(2-[ W-(T,X-Dich lo roph enyi hyd razono)-pyrrol id in-1 -yi]-methyl idene)-N-(6-methyl pyridi n-2-yi)amine.

7. W(2-[W-(T,X-Dich lo rop henyl hyd razo no)-pyrro licii n- 1 -yi]-m ethyl idene)-N-(3-methyl pyrid in-2-yi)5 amine.

8. W(2- [N'-(2',3'-Dich lorophenyl hyd razo no)-pyrro lidi n- 1 -yl]-methyl idene)-N-(th iazol-2-yi)-am i ne.

9. A process for producing a compound of the formula la -- -1 10 (R)n,O-NH-N- < 1 (1a) t,Htv-tfj wherein R is halogen or Cl-C4-alkyl, and R, is a pyridine group which is bound by way of a carbon atom, and which is unsubstituted or substituted by a methyl group, or is a 2-thiazolyl group, and n is zero, 1 or 2, which process comprises reacting a compound of the formula lla (11 a) r-<N I<- 1 [R)n 'A/ 25 H with a compound of the formula Ilia R2-0-CH=N-Rl (Ilia) 30 wherein R,131 and n have the meansings defined under the formula la, and R2 is methyl or ethyl, in the presence of a 35 solvent or diluent at a temperature of -10'tolOO'C.

10. A process according to claim 9, wherein the reaction temperature is between 10' and 600C.

11. A process for producing a compound of the formula lb (Ib) CY-NH-N-C 40 (R)n N OR 2 R3 wherein R is halogen or Cl-C4-alkyl, n is zero or 1, 50 R2 is methyl or ethyl, R3 is Cl-C4malkyl, Cl-C2-alkoxy or Cl-C4-alkylthio, and X is oxygen or sulfur which process comprises reacting a compound of the formula lib (lib) 1 \-NH-NH--rl 55 [R)n GB 2 144 412 A with a compound of the formula [lib X 1 Hal-P 11.1 R3 wherein R, n, R2, R3 and X are as defined under the formula lb, in the presence of a base and a solvent or 10 diluent inertto the reactants at a temperature of -3Tto 100T. 12. A process according to claim 11 wherein the reaction temperature is between -100 and 600C. 13. A pesticidal composition which contains as active ingredient at least one compound of the formula 1 according to claim 1, together with inert carriers and formulation auxiliaries. 14. A pesticidal composition according to claim 13, which contains as active ingredient at least one 15 compound according to claims 2 to 8. 15. A process for controlling pests, which process comprises the use of a compound of the formula 1 according to claim 1. 16. A process according to claim 15, wherein the pests are ectoparasites. 17. A process according to claim 15, wherein the pests are insects, or members of the order Acarina. 20 18. A method of controlling pests, which method comprises the use of a compound according to claim 1 20 to 8. 19. A method according to claim 18 for controlling ectoparasites. 20. A method according to claim 18 for controlling insects, and members of the order Acarina. 21. A compound of the formula 1 according to claim 1 substantially as hereinbefore described with 25 reference to any one of the foregoing Examples. 22. A pesticidal composition according to claim 13 substantially as hereinbefore described with reference to anyone of Examples 10 to 14.

Printed in the UK for HMSO, D8818935, V85, 7102.

Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY. from which copies may be obtained.