AU605885B2 - Pyridylthio-, pyridylsulfinyl- and pyridylsulfonyl-phenyl-thioureas,-isothioureas and -carbodiimides, their preparation and use in the control of pests - Google Patents

Description

4 S F Ref: 62854 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Complete Specification Lodged: Accepted: Published:

Y

r Class Int Class Priority: Related Art: Name and Address of Applicant: Address for Service: Ciba-Geigy AG Klybeckstrasse 141 4002 Basle

SNITZERLAND

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydnev, New South Wales, 2000, Australia Complete Specification for the invention entitled: Pyridylthio-, oyridylsulfinyl- and p.yridylsulfonyl-phenyl-thioureas, -isothioureas and -carbodiimides, their preparation and use in the control of pests The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 5-16546/1+2 'Pyridylthio-, pyridylsulfinyl- and Fpyridylsulfonyl-phenyl-thioureas, ~isthourasand -carbodiirides, their preparation and use in the control of pests Abstract Novel pyridyithia-, pyridylsulfinyl- awid pyridylsulfonyl-phenyl-thioureas, -isothioureas and -carbodiimides of formula I

(I)

0 n in which R, represents CI-C,2alkyl, CI-C, 2 alkyl mono- or poly-substituted by halogen and/or by Ci-Csalkoxy, C 3 -Cscycloalkyl, C3-C 8 cycloalkyl monoor poly- sub Ftituted by CI-C 3 alkyl, or C 3

-C

8 cycloalkyl-CI-Ci 4 alkyl; a d R 3 eac; represents CI-C~alkyl or R4 each repre&ents hydrogen, halogen, GI-Cijalkyl, or CI-Cijrlkyl monoor poly-substituted by halogen; n represents 1, 2, 3 or 4; Y represents S, SO or S02; Z represents -Ni-'CS-NH-, -N=C(SRS)-NH- or and

R

5 represents Ci-Cloalkyl or allyl, and the salts thereof, proces -s and intermediates for their preparation, their use in the control of pests, and pesticidal compositions that contain at least one compound of formula I as active ingredient are disclosedl. The preferred field of use is the control of pests in and on animals and plants.

J1K- 5-16546/1+2 Pyridyithio-, pyridylsulfinyl- and pyridylsulfonyl-phenyl-thioureas, -isothioureas and -carbodiimiies, their preparation and use in the control of pests The present invention relates to novel substituted pyridyithio-, pyridylsulfinyl- and pyridylsulfonyl-phenyl-thioureas, -isothioureas and -carbodiimides, to their salts with organic or inorganic acids, to processes and intermediates for their preparation, to pesticidal compositions that contain these compounds, and to their use in the control of pests.

SThe compounds according to the invention correspond to formula I N~N /R II (I)

Z-RI

in which RI represents Cl-Cl 2 alkyl, C 1 -C aalkyl mono- or poly-substituted by halogen and/or by Ci-Csalkoxy, C 3

-C

8 cycloalkyl, C 3 -Ccycloalkyl mono-or poly-substituted by C 1

-C

3 alkyl, or C 3 -Cscycloalkyl-C 1 -C alkyl;

R

2 and R 3 each represents Cl-Csalkyl or C 5

-C

6 cycloalkyl; 4 R each represents hydrogen, halogen, CI-Ctalkyl, or CI-Cqalkyl monoor poly-substituted by halogen; n represents 1, 2, 3 or 4: Y represents S, SO or SOa; Z represents -NH-CS-NH-, -N=C(SRs)-NH- or and Rs represents C 1

-C

1 oalkyl or allyl.

Halogen atoms coming into consideration as substituents are fluorine and chlorine as well as bromine and iodine, fluorine and chlorine being preferred.

1 2 The alkyl radicals coming into consideration as substituents may be straight-chain or branched. Examples of such alkyl radicals that may be mentioned are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, tort-butyl or pentyl, hexyl, octyl etc. and the isomers thereof.

The Ci-Cl 2 alkyl radicals mono- or poly-substituted by halogen and/or b}

C

1 -CGalkoxy that come into consideration as substituents mP" be straightchain or branched and nay be only partially haloipnated or perhalogenated and/or substituted from one to five times by Ci-C 6 alkoxy, the above definitions applying to the halogen atoms and alkyl radicals.

Suitable examplc-, of such substituents are inter alia methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as, for example, CHF 2 or CF 3 ethyl substituted from one to five times by fluorine, chlorine and/or by bromine, such as, for example, CH 2

CF

3

CF

2

CF

3

CF

2 CCl 3 CF9CHC12, CF 2

CHF

2

CF

2 CFC12, CF 2 CHBr 2

CF

2

CHCIF,

CFaCHBrF or CClFCHC1F; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or by bromine, such as, for example,

CH

2 CHBrCH 2 Br, CF 2 CHFCn 3

CH

2

CF

2

CF

3 or CH(CF 3 2 butyl, or one of the isomers thereof, substituted from one to nine times by fluorine, chlorine and/or by bromine, such as, for example, CF(CF 3

)CHFCF

3 or CH 2

(CF

2 2 CF3; methoxymethyl, methoxyethyl, ethoxyethyl, methoxyptopyl, ethoxypropyl, propoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl or butoxybutyl, 1,2-dimethoxyethyl, 1,3-dimethoxypropyl or 2,4-dimethoxybutyl. The above statements apply accordingly to optionally mono- or poly-halogenated Ci-C 4 alkyl radicals.

S Cycloalkyl radicals coming into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. These radicals may be mono- or poly-substituted by a Ci-C 3 alkyl radical and/or bonded via a Ci-C4alkylene bridge to the rest of the molecule.

The compounds of formula I in which Z represents -N=C(SR 5 can also be in the form of acid addition salts. Both organic and inorganic acids are suitable for the formation of such salts. E>smples of such acids are inter alia hydrochloric acid, hvdrobromic acid, hydriodic acid, nitric acid, various phosphoric acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malon 4 c acid, succinic L i 3 acid, malic acid, maleic acid, fumaric acid, lactic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, cinnamic acid, phenylsulfonic acids or salicylic acid.

Compounds of formula I in which Z represents -N=C(SR 5 can be in the tautomeric forms N

R

2 N Y\R* NY

/R

2 II II I I II I S N=-NHRI n NH- =NRI Th invention includes both the individual tautomers and tautomeric mixtures.

Depending upon the value of n, the pyridyl radical may be substituted up to several times by Ri. If n is greater than 1, the various substituents a 4 a R4 may have the same or different meanings.

o a, Compounds of formula I that are of particular importance are those in which RI represents Ci-Csalkyl, Ci-Coalkyl mono- or poly-substituted by halogen and/or by Ci-Csalkoxy, or Cs-C6cycloalkyl; R 2 represents C 1 S alkyl; R 3 represents Ci-Csalkyl or cyclopentyl; each represents hydrogen or halogen; n represents 1 or 2; Y represents S, SO or SOn; Z represents -NH-CS-NH-, -N=C(SRs)-NH- or and R5 represents Ci-C 5 alkyl or allyl.

Preferred compounds of formula I are those in which a) Ri represents Ci-C 5 alkyl or cyclopentyl; R 2 and R 3 each represents Ci-C 3 alkyl; R4 represents chlorine; n represents 1 or 2; Y represents S; and Z represents -NH-CS-NH-, or b) Ri represents Ci-Csalkyl or cyclopentyl; R 2 and R 3 each represents Ci-C 3 alkyl; R4 represents chlorine; n represents 1 or 2; Y represents S; Z represents -N=C(SR 5 and R 5 represents Ci-Coalkyl, or 4 c) RI represents Ci-Csalkyl or cyclopentyl; R 2 and R 3 each represents Ci-C 3 alkyl; R4 represents chlorine; n represents 1 or 2; Y represents S; and Z represents The compounds of formula I according to the invention can be prepared according to processes that are known in principle, for example as follows: A) an isothiocyanate of formula II /N Y (RO I (II),

\N=C=:S

A3 'Loa is reacted with an amine of formula III sJ to form thiourea and optionally o B) the resulting thiourea is reacted with a compound of formula IV Ho aX-R5 (IV) o 4.

to form isothiourea, or C) the resulting thiourea is converted into the carbodiimide by removal of hydrogen sulfide. R 1

R

3 R4, R 5 Y and n have the meanings given and X represents a suitable leaving group, such as, for example, a halogen atom, especially chlorine, bromine or iodine, or alkyl sulfate.

Process A is customarily carried out under normal pressure and in the presence of an organic solvent or diluent. The temperature is from 0 to +150'C, preferably from +10 to 70 0 C. Suitable solvents and diluents are, for example, ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxan. dimethoxyethane or tetrahydrofuran; N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, such as benzene, toluene, xylenes, chloroform, I-

U

methylene chloride, carbon tetrachloride or chlorobenzene; nitriles, such as acetonitrile or propionitrile; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone or cyclohexanone.

Process B is advantageously carr:ed out in an inert organic solvent and under slightly elevated or normal pressure. The temperature is from to 250 0 C, preferably the boiling temperature of the solvent used or from to 150 0 C. Suitable solvents or diluents are, for example, ethers or ethereal compounds, such as diethyl ether, diisopropyl ether, dioxan or tetrahydrofuran; aromatic hydrocarbons, such as benzene, toluene or xylenes; ketones, such as acetone, methyl ethyl ketone or cyclohexanone, alcohols or dimethylformamide.

Process C is advantageously carried out in an aprotic organic solvent or 0 diluent under normal pressure. The temperature is from 0 to +150 0

C,

opreferably from +10 to 50°C. Suitable solvents or diluents are, for S example, ethers or ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxan, dimethoxyethane or tetrahydrofuran; N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, such as benzene, toluene, xylenes, chloroform, methylene chloride, carbon tetrachloride or chlorobenzene; nitriles, such as acetonitrile or propionitrile; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone or cyclohexanone. The removal of hydrogen jsulfide is effected according to procedures described in the literature Shibanuma, Chemistry Letters 1977, p. 575-576; S. Kim, Tetrahedron Letters 1985, p. 1661-1664; W. Weith, B. 6, 1873, p. 1398; G. Amiard, Bull. Soc. chim. 1956, p. 1360). As removal reagents there are used inter alia HgO, certain pyridinium salts, chloroacetic acid esters, cyanuric acid chloride, p-toluenesulfnchloride or certain phosphoric acid ester Jderivatives.

The isothiocyanates of formula II can be prepared according to methods known in principle, for example by reacting an aniline of formula V N /R2 II I(V) n

A

S^-

L 1 6 with thiophosgene, R 2

R

3 Ri,, Y and n having the meanings given for formula I.

The process for the preparation of the compounds of formula II is advantageously carried out in the presence of an organic or inorganic base, such as, for example, triethylamine or calcium carbonate, and a solvent or diluent that is inert towards the reactants, at a temperature of from 00 to +100 0 C and under normal pressure. Suitable solvents and diluents are inter alia ethers or ethereal compounds, such as, for example, diethyl ether, diisopropyl ether, dioxan or tetrahydrofuran; aromatic hydrocarbons, such as benzene, toluene or xylenes; ketones, such as acetone, methyl ethyl ketone or cyclohexanone; or chlorinated hydrocarbons, such as dichloromethane or tetrachloromethane.

q Suitable bases can be of organic or inorganic origin, such as, for 99 example, sodium hydride, sodium or calcium carbonate, tertiary amines, o o such as triethylamine, triethylenediamine or 4-dimethylaminopyridine or pyridine.

The isothiocyanates of formula II may also be prepared via the corre- S sponding thiourea that. is unsubstituted on one side. An aniline of formula V is reacted with ammonium thiocyanate in an acidic medium, S preferably a medium containing a mineral acid, to form the corresponding thiourea w ich, in turn, when heated to from +130 to 200 0 C splits off ammonia and is converted into an isothiocyanate of formula II. (see Saul Patai, "The chemistry of cyanates and their thio derivatives", John Wiley 4 and Sons, 1977; Chemistry and Industry, July 3, 1954, p. 735. J.N. Baxter et ai, "New method of preparation of aryl isothio- cyanates").

The anilines of formula V can themselves be prepared according to methods known in principle, for example by reacting a pyridine-2-thiol or pyridine-2-thione of formula VI -N -SH =S (VI) n n with a 4-haloaniline of formula VII -7- 7 /R2 Hal- 2 (VII),

R

3

R

2

R

3 R4 and n having the meanings given for formula I and Hal representing a halogen atom, especially chlorine or bromine, and optionally the amino group of tie resulting pyridylthioaniline is protected by a protecting group, the sulfur bridge is converted with an oxidising agent into a sulfinyl or sulfonyl group, and the amino group is freed again by hydrolysis.

The process for the preparatioi of the pyridylthioanilines of formula V c..o is advantageously carried out in 'e presence of an inorganic or organic base, such as, for example, an alkali metal hydroxide or carbonate, a o solvent or diluent, preferably a polar solvent or diluent, that is inert towards the reactants, and optionally a catalyst, such as, for example, B o* copper powder or copper carbonate, at a temperature of from +80 to 160'C oa and under normal pressure. Suitable solvents and diluents are inter alia ethers or ethereal compounds, such as, for example, diethyl ether, diisopropyl ether, dioxan or tetjahydrofuran; aromatic hydrocarbons, such as on benzene, toluene or xylenes; ketones, such as acetone, methyl ethyl o ketone or cyclohexanone; or alcohols, such as methanol or ethanol; dimethyl sulfoxide or dimethylformamide is also especially suitable.

Suitable oxidising agents for the conversion of the sulfur bridge into a sulfinyl or sulfonyl group are inter alia H 2 Oa/glacial acetic acid,

H

2 0 2 /acetic anhydride, per acids, such as, for example, m-chloroper- S benzoic acid, periodic acid or alkali metal periodates, chromic acid or potassium permanganate. Suitable protecting groups for the amino group of the phenylthioaniline are the customary protecting groups that can be removed again by hydrolysis or hydrogenolysis, such as, for example, acyl groups (acetyl, trifluoroacetyl), optionally substituted benzyl groups or alkoxyalkyl groups (methoxymethyl).

The compounds of formulae II and V are novel and the present invention relates also to these. The compounds of formulae III, IV, VI and VII are, however, known or can be prepared according to methods known in principle.

8 Surprisingly it has been found that the compounds of formula I according to the invention are valuable active ingrediencs in the control of pests while being well tolerated by warm-blooded animals and by plants. The compounds of formula I are therefore suitable, for example, for controlling pests in and on animals and plants. Such pests belong chiefly to the family of the arthropods, such as, especially, insects of the orders Lepidoptera, Coleoptera, Homcptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphor.aptera, Mallophaga, Thysanura, Isoptera, Psocoptera or Hymenoptera, and arachnids of the order Acarina, such as, for example, mites and ticks. It is possible to control every stage of development of the pests, that is to say the adults, pupae and nymphs as well as, especially, the larvae and eggs. Above all it is possible to control effectively the larvae and eggs of phytopathogenic insect and mite pests in ornamentals and useful plants, such as in fruit and S vegetables, and especially in cotton If the compounds of formula I are So ingested by imagines, their action can manifest itself in the immediate death of the pests or in reduced oviposition and/or hatching rates. The latter phenomenon is to be observed especially in Coleoptera. In the control of pests that parasiticise animals, especially domestic animals and productive livestock, there come into consideration especially ectoparasites, such as, for example, mites and ticks, and Diptera, such as, S for example, Lucilia sericata.

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

The action of the compounds of the invention or the compositions containing them can be considerably broadened and adapted to the prevailing circumstances by the addition of other insecticides and/or acaricides. Additives that come into consideration are, for example, representatives of the following classes of acti''p .ngredients: organic phosphorus compounds, nitropheols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

9 The compounds of formula I are used in unmodified form, or preferably together with the inert adjuvants, tolerated by plants, that are conventionally employed in the art of formulation, and can therefore be formulated in known manner, for example, to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in, for example, polymer substances. As with 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.

S The formulations, i.e. the compositions, preparations or mixtures con- S taining the active ingredient of formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, for example by homogeneously mixing and/or grinding the active ingredients with S extenders, for example 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, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane, paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers useJ, for example 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 acids or highly dispersed absorbent poly'"irs. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite 10 or sand. In addition a great number of granulated mater i norganic or organic nature can be used, for example especially dolomite or pulverised plant residues.

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

I "s Suitable anionic surfactants can be both so-called water-soluble soaps a and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids °n (Cio-C 2 2 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 tall oil. Further suitable surfactants are S also the fatty acid methyl taurin salts, and modified and unmodified phospholipids.

#a S More frequently, however, so-cailed synthetic surfEctants 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 generally contain a Gs-Calkyl radical which also includes the alkyl moiety of acyl radicals, f)r example 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 sulfated and sulfonated fatty alcohol/ethylene oxide adducts, The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing about 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzrne- L I I-u 11 sulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and f<,rmaldehyde. Also suitable are corresponding phosphates, for example salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polygiycol ether derivatives of aliphatic or cycloaliphatic alcohols, 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, ethylenediaminopolypropylene 0o o glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in a the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds oo usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of non-iunic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polpropylene/polyo ethylewe oxidt adducts, tributylphenoxypolyethoxyethanol, polyethylene o\o glycol and o tylphenoxypolyethoxyethanol. Fatty acid euters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan trioleate, are 0 a also suitable non-ionic surfactants.

Cationic surfactants are preferably q. ternary ammonium salts which oooo contain, as N-substituent, at least one Ca-C22alkyl radical and, as further substituen unsuostituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halid-s, methylsulfates or ethylsulfates, for example stearyltrimethylam'ronium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described, inter alia, in the following publications: McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1979; c -r 12 Dr. Helmut Stache, "Tensid-Taschenbuch" (Handbook of Surfactantj), Carl Hanser Verlag, Munich/Vienna 1981.

The pesticidal compositions usually contain 0.1 to 99 Z, preferably U.1 to 95 of active ingredient of formula I or combinations of these active ingredients with other insecticides or acaricides, 1 to 99.9 7 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 dilute formulations containing considerably lower concentrations of active ingredient.

The compositions may also contain further ingredients, such as stabie e lisers, antifoams, viscosity regulators, binders and tackifiers, as we]] as fertilisers o- other active ingred 'nts in order to obtain special e Seffects.

Ex:ample 1: Preparation 1.1. Intermediates S Pyridylthioanilines 1.1.1.1, 2,6-diethyl-4-(3' ,5'-dichloropyrid-2'-ylthio)-aniline SIn a nitrogen atmosphere, 15.0 g of 2,6-diethyl-4-mercaptoaniline are added dropwise at room temperature to 6.2 g of pulverised potassium hydroxide in 70 ml of dimethyl sulfoxide. While stirring continuously, a S solution of 15.8 g of 2,3,5-trichloropyridine in 20 ml of dimethyl sulfoxide is then added dropwise thereto, the temperature rising to 4 5 UC. The reaction mixture is then stirred for 3 hours, then concentrated under a high vacuum and the residue is taken up in 80 m 1 of dichloro- "-.thane and 80 ml of water. The organic phase is washed witii water and dried over sodium sulfate, The solvent is then removed in a rotary evaporator and the residue is recrystallised from toluene/hexane, yielding the title compound of formula N ,S

C

2

H

/CaH5 I I I I (Compound N, 1.1.1.1.) Cl Cl aH 13 in the form of light-beige crystals; m.p. 104-106'C.

The following compounds are prepared in an analogous manner: nI r HR 3t ~Comp. No. I R 2 I R 3 I In I 00 0 a a 00 1.1.1.2 1.'1.1.43 1.1. 1.51 1.1.1.20 1.1.1.21 1 1. 1. 120

CH(CH

3

Z

CR

3

C

2 H5

CH(CH

3

Z

C

2

H

5

C

2

H

5 CzH 5 CzHR.

C 2

,H

5 C 2

H

5 CzH 5

C

2 H5 CH( CR 3 z CH( CH 3 2

CH(CH

3 2 CH( CHO) 2

CH(CH

3 2

CH(CH

3 2

CH(CH

3 2 CH( CR 3 2 CH( CR 3 2

CH(CH

3 2

CR

3 CH( CH 3 )Ca H 5 CH(CHD)2 CZH5 CaR 5

C,

2

H

5 C2Hs

C

2 Rs CH3 Cyclopentyl Cyclohexyl CH( CR3) 2

CH(CH

3 2 CH( CR 3 2 CH( CR 3 2 CH( CR 3 CH( CR 3 2 CH( CR 3 2 Cycldpenty' Cycl1oh exy 1 3,5-C12 3,5-C12 3,5-012, 3-F, 5-Cl 3-Cl1, 5-CF 3 3-F, 4,6-Cl 2 5-CF 3 3,5-Cl 2 3,5-C12 3,5-C12

H

3-Cl OFCla 5-CF 3 3-01, 5-CH 3 4,6-Cl 3-01, 5-CF 3 3, 5-012I phys. data m.p. 79-81'C m.p. 138-140'C m.p. 90-92'C m.p. 83-84'C 400 00 1 .1 Pyridylthio-henyliso thiocyanates 001.1.2.1. 2,6-di ethvl-4-(3',5' -dichloropyrid-2'-vl thio) -Phenvliso thiocyaflate A) 6.3 g of thiophosgene, 9.2 g of calcium carbonate and 60 ml of dichioromethane are stir-red with 40 mli of water. To this mixture there is then added dropwise at from 0 to +10'C a solution of 14.8 g of 2,6-die thyl-4-(3' 5 1--di chloropyrid-2'-yl thio' -aniline in 30 ml, of dichloromethane. The reaction mixture is stirred at room temperature for 3 hours and then filtoed i The organic phase is separated from the filtrate nd i 14 washed twice using 30 ml of water each time, and finally r oncentrated by evaporation. The compound of formula N S CaH Cl \Cl N=C=S is obtained in the form of a yellowish-brown index of n 2 3 1.6810 and can be used as such

D

dried over sodium sulfate crude product of the title (Compound No. 1.1.2.1.) oil having a refractive for furLher processing.

B) 9.9 g of 2,6-diethyl-4-(3',5'-dichloropyra.d-2-ylthio)-aniline, 2.3 g S of ammonium thiocyanate, 4.5 ml of concentrated hydrochloric acid and 70 ml of o-xylene are mixed together and maintained at +90 0 C for 3 hours with stirring. The temperature is then rapidly increased to +130 0 C and escaping solvent, water and ammonia are collected. After 5 hours the reaction mixture is cooled to room temperature, 40 ml of toluene are added nd the mixture is filtered. The toluene phase is washed with 10 ml of water, dried over sodium sulfate and concentrated by evaporation. The S residue is a yellowish-brown oil and corresponds to compound No. 1.1.2.1 prepared according to process A.

6 4.

The following compounds are prepared in an analogous manner: (Ru) I II I 3* C=S 3 15 Comp. No.jL I R 3 I__nfI phys. data 1.1.2.2 1.1.2.3 1 .1.2.4 1.1.2.5 1.1.2.6 1.1.2.7 1.1.2.28 1.1.2.9 1.1.2.10 1.1.2.11 1.1.2.12 1. 1.2._13 1.1.2.14 1.1.2.15 1 .1.e2 .16 1.1.2.17 1.1. 2.18 1. 1. 2-19 1.1.2.20 1,1.2.21 2. 22 CH( CH 3 2

CH

3 C2H5

CH(CH

3 2

C

2

H

5

C?

2 H5

C

2 Hs

C

2

H

5

C

2 Hs C2H 5

C

2 Hs

C

2 Hs

CH(CH

3 2

CH(CH-

3 2

CH(CH

3 2

CH(CH

3 2

CH(CH

3 2

CH(CH

3 2 CH( CHa) 2

CH(CH

3 2

CH(CH

3 2

CH(CH

3

CH

3

CH(CH

3

)C

2

H

5 CH( CH3) 2

C

2

H

5

C

2 Hs

C

2 H5

C

2 H5

C

2

HS

CH

3 Cyclopentyl Cyclohexyl

CH(CH

3 2

CH(CH

3 ).2

CH(CHO)

CH(CH

3 2

CH(CH

3 2

CH(CH

3 2

CH(CH

3 2 Cyclopentyl Cyclohexyl 3, 5-Cl 2 3 ,5-Cl 2 3, 5-Cl 2 3-F, 5-Cl 3-Cl, 5-CF 3 3-F, 4, 6-Cl 2 5-CF 3 3, 5-Cl 2 3, 5-Cl 2 3, 5-Cl 2

H

3-Cl 5-CF 3 3-Cl, 5-CH 3 4,6-Cl 2 3-Cl, 5-CF 3 3,5-Cl 2 3,5-Cl 2 n23

D

Smp.

25 nD oil 1 .6590 95-98*C 1 .6571 4 444 444 '44 44* 4 1.2 End products 1 1. Pvridvlthio-phenvlthioureas.

1.2.1.1. N-[2,6-diethvl-4-(3' ,5'-dichloropvrid-2'-Ylthio)-phenvl)-N'- 443. tert-bu tylthiourea 44 44 44444 p444 44 44 15. 7 g of 2, 6-diethyl-4-(3' ,5'-dichloropyrid-2'-ylthio)-phenylisothiocyanate are diluted with 120 ml of hemane and at +50'C 3.9 g of tert.butylamine are added dropwise thereto. The reaction mixture is then stirred at +50%0 for 4 hours. The resulting precipitate is filtered off and recrystallised from toluene/hexane. The title compound of formula /N ~S /C 2

.H

L

2

H

(Compound No. 1.2.1.1.) is obtained in the form of a light-beige powder; m.p. 140%C (decomposition) .,,L0..J44g,2mjj~- Th foloin copud ar rprdi4n nlgu anr N0 Y 4 R4 Z N4 -C 4 fR 3 4 C 0440 0 0 0 4 4 0 0.0 0 .4 000 0 00 Camp. No. I iI R 2 I R 3 R4__ I_ I1 I M.P. 'C 1.2.1.2 1.2.1.3 1.2.1.4 1.2.1.5 1.2.1.6 1.2.1.7 1.2.1.8 1.2.1.9 1.2.1.10 1.2-1.11 1.2.1.12 1.2.1.13 1.2.1.14 1.2.1-15 1. 2. 1.16 1.2.1.17 1.2.1.18 1. 2. 1.19 1.2.1.20 1.2.1.21 1. 2.1.22 1.2 .1.23 1.2 24 C(CHf 3 )3 CII(C11 3 2 Cyclopentyl CII(C11 3

C

2 11 5 C(CI1 3 2

C

2 11 5 C11 3 c(C11 3

C(CH

3 )3 CHI( Cu 3 CHOC11 3 Cyclopropyl Cyclohexyl Cyclooctyl Cui(CH13)CH 2 CH(CcH 3 2

CHI(CH

3 )Cyclopropyl C(C1 3 )3

C

2 11 5 C I( C11 3 2 CI( I3 2 CHI(C1 3 2 C11( C11 3 2 CIu(C11 3 2

CHI(CH

3 2 Czu(CI1 3 2

CII(CH

3 2 CII(c11 3 2 CH(C11 3 2 CH( eli 3 2 CH(C11 3 2 CIH(cI1 3 2 C11' 3

C

2 115 CIu(Ciu 3 )2 cWIc11 3 2 CIu(C11 3 2

CII(CH

3 2 Cuu(Cu 3 2 CHI(C1 3 2 C11

CH

3

C

2 115 CH5 C11( C11 3 2 Cdi(C]1 3 2 CHI(C11 3 2 CH(C11 3 2 C11 3 CHI(C11 3

)C

2

H

5 CII( C11 3 2 Cur( CH 3 2 CII(C113 2 CIu(CI 3 2 CH(C1 3 2 CK1C11 3 2 CII(C11 3 CiI(C11 3 2 CII 3 Ca 11 5

C

2 115

C

2 115 C 21H15

C

2 11 5 C 211 3, 5-Cl 2 3,5-C1 2 3, 5-Cl 2 3,5-Clz 315-Cl 2 3, 5-Cl 2 3)5-Cl 2 3, 5-Cl 2 3 35-Clz 3, 5-Cl 2 1 3,5-Cl 2 3, 5-Cl 2 3, 5-Cl.

2 3, 5-Cl 2 3-F, 5-Cl 3,5-Cl 2 3, 5-Cl 2 3, 5-Cl 2 3, 5-Cl 2 3,5-Cl 2 3,5-Cl 2 4,6-C1 2 154 /decomp.

16 7-1 69 172-1 74 134-1 36 142-143 127-129 147/decomp.

127-129 125-1 26 147-150 174-17 7 154-156 131-133 138-1 115-116 4.

N

Comp.No. Ri ,R RI, In y L.2 2 C11(C11 3 2 C2IIS c 2 11 5 5-CF 3 1 S L.2. 1. 2( CI(CHi 3 2

C

2

H

5 CI( C11 3

C

2 11 5 3,5-cl:! 2 S

CHI(C[

3 2 Ci( CH 3 2 CHI(C11 3 3,5-Cl 2 2 SO .2.1.2E CHI(C11 3 2 Cl(C11 3 2 CI(C11 3 2 3,5-Cl 2 2 SO 2 .2.1.2S CII(C11 3 2 CHI(C11 3 2 ClH(c1 3 2 3-Cl, 5-CF 3 2 S

CII(CH

3 2 CII(C11 3 2 CII(C11 3 2 3-F, 5-cl 2 S 31 CII(cH 3 2 1(C11 3 2 Clli(C113) 2 4,6-Cl 2 2 S .213 C( C11 3 3 213 c 2 11 5 3,5-Cl 2 2 S .213- C(C1 3 3 c 2 11 5

C

2 115 3,5-Cl 2 2 SO .213 C( C11 3 3 c 2 1 5

C

2 11 5 3,5-Cl 2 2 S0 2 .2 C( C11 3 3

C

2 11 5

C,

2 11 5 5-Cl 1 S C( C1 3 3 C215 C 2 11 5 3-Cl,5-CF 3 2 S .2 3- C( C11 3 3

C

2 H1 5 C911 5 3-F,5-Cl 2 S 1, 3E c( C1 3 3

C

2 11 5

C

2 1 5 4,6-Cl 2 2 S .2.1.3S C(C11 3 3 C 2 11 5 Cyclopentyl 3,5-Cl 2 2 S 2.1. 4 CC1Cl1 3 3 c 2 l1 5 Cyclohiexyl 3,5-Cl 2 2 S .2.1.41 C(Cl 3 3 C1( C11 3 )z C II( Cli 3 2 3,5-Cl 2 2 SO 4 C(C 1 3 3 ClII CH 3 2 C I I( C11 3 2 3,5-Cl 2 2 SOL, .2C. CCH 3 3 C II(C11 3 2 C11( C11 3 2 11 1 S .2.1.44 C(C11 3 3 CII( C11 3 2 ClI( C11 3 2 5-CF 3 1 S .2.1.4c C( C11 3 3 CI( C11 3 2 CH( C11 3 2 3-Cl, 5-CuI 3 2 S C(C11 3 3 CuI(C1 3 2 CHI(C11 3 2 4,6-Cl 2 2 S 2.1. 4Y C(C11 3 3 CII(C1 3 2 CII(C11 3 2 3-Cl,5-CF 3 2 S .2.1.4E C(C11 3 3

CII(CJ

3 2 Cx!(C11 3 3-Cl, 5-CFZCFC12 2 .2.1.4S C(C11 3 )3 CII(C11 3 2 CII(C11 3 2 5-Cl I S .2 .1.5C C(C11 3 3 CII(C11 3 2 Cyclopentyl 3,5-Cl 2 2 S .215 C(C11 3 3 CII(C11 3 2 Cyclohexyl 3,5-Cl 2 2 S .215 C(CH 3 3 Cyclopent. Cyclopentyl 3,5-Cl 2 2 S .215 CH(CI 3 )C115 112115 C,91 5 3,5-Cl 2 2 S Comp.No. RR2R 3 Rn Y 1 51 cI( C1 3

)C

2 11 5 C 2 11 5 C2Ib 3,5-Cl 2 2 SO L. 2.1. 5- CHI(C1 3

)CH

5

C

2 11 5

C

2 11 5 3,5-Cl 2 2 so 2 L.2.1.5( Ci1(C11 3 )C 2 11 5 CII (CH 3 )2 Cl C11 3 2 3, 5-Cl 2 2 SO L. 2.1.57 C11(C11 3 )C 2 5 CII(C11 3 2 C1Cif c 3 2 3,5-Cl 2 2 So 2 L. 2.1 51 1 c( C 2 11 5 2 cII( c11 3 2 CII(C11 3 2 3, 5-cl 2 2 S 5 C1I[CI!( CHI cll H f 3 2 cf( C11 3 2 3, 5-c1 2 2 S L. 2.1.6( C 1 2 11 2 5 CI!( C11 3 )2 CII(CIH 3 2 3, 5-Cl 2 2 S 1.2.1. 6 C1H 2

CF

3 CHf(cH) cC11 3 l C 3) 2 3, 5-cl 2 2 S 1.2.1. 6 CH 2 3

OCI,

1 19 CI( C11 3 2 CII( C1 3 2 3, 5-Cl 2 2 S L.2 6' Cl( CH 3 CYCo- L. 2.1. 6 hexyl C~I(C!1 3 2 Ci!( C11 3 2 3, 5-cl 2 2 S L.2. 1. 6 -C(CH1 3 )zCyclo- L.2 hexyl CI!( C11 3 2 CiI( C11 3 2 3,5-Cl 2 2 S 2 Cyclopentyl C 2 I1k C 2 Hs 3,5-Cl 2 2 S 1.2.1. 6 Cyclopentyl C 2 11 5

C

2 5 3,5-Cl 2 2 SO 1.2 1. 6! Cyclopentyl C21l5 C 2 11 5 3,5-cl 2 2 So 2 1.2.1.7 cyclopentyl CI( C11 3 2 CII( C11 3 2 3,5-Cl 2 2 S L.2. 1.7 Cyclopentyl C11( C11 3 2 CII( C11 3 2 3,5-Cl 2 2 S02 L.2. 1.7 2,6-Diethyl- L.2 7 Cyclohexyl Cll(CII3) 2 CII( C11 3 2 3,5-Cl 2 2 S 19 1.2.2. Pyridylthio-phenylisothioureas 1.2.2.1. N-[2,6-diethyl-4-(3',5'-dichloropyrid-2'-ylthio)-phenyl]-N' tert-butyl-S-me thylisothio-urea 2.2 g of methyl iodide are added at room temperature to 5.0 g of N-[2,6diethyl-4-(3' ,5'-dichloropyrid-2'-ylthio)-phenyl]-N'-tert.-butylthiourea in 50 ml of ethanol and the mixture is stirred for 3 hours under gentle reflux. The reaction solution is then concentrated by evaporation and the residue is taken up in 100 ml of dichloromethane and 50 ml of 10 sodium carbonate solution. The organic phase is separated off, washed with water, dried over sodium sulfate and concentrated to dryness by evaporation. The residue is recrystallised from hexane, yielding the title compound of formula 00 /N C 2 o II II (Compound No.1.2.2.1.) CH3 o Cl N= -NH-C(CH 3 3 ft o in the form of yellowish-beige crystals; mn.p. 122-124 0

C.

o o: The following compounds are prepared in an analogous manner: So o o 0 0 1N k

(R

4 11 11 Comp. No. R 2 phys. data I I- 1 I 1.2.2.5 1.2. 6 1.2.2.7 1.2.8 1. 2 .2 94 1. 2. 2. 1 .2.2.1- 1. 2.2.1: 1.2. 2 .1 1.2. 2. 1 1. 2. 2. 1 L2.2.1f L1. 2. .1 1.2.2. 2( L.2 2]2

C(CH

3 )3 CHI(C11 3

')C

2

H

5 0(0113 )2C2115 Cyclopentyl

C(CH

3 3

CII(CH

3 2 011(C11 3 2 dI(CII 3 2 CHI(C11 3 2 CHI(C0 3 2 011(0113) 2 C(C11 3 3 C(c11A 3 C(0113)3 0(0113)3 0(0113) 3 0(C113) 3 0(0113)3 C(C11 3 3 C(011 3 )3 C(C1I 3 )3 C11(C11 3 2

COH(CH

3 2 C11(0113)2 011(0113)2 S2115 02115

C

2 115 0c 115 C2ll 5 clI( C11 3 2 C11( C113)2 O 2115~ 011(0C11 3)2 011(0C113)2 c11( C11 3 2 011(0113) 2 011( C11 3) 2 011(C113) 2 C11( C11 3 2 011(0113) 2 011(0113) 2 011(0113) 2 011(0113) 2 011(0113)0C2115 02115 C2Hs C-,H5 011(0113) 2 011(01132 02115 011(0113) 2 011(0113)2 011(0113)2 011(0113) 2 011(0113) 2 011(0113) 2 011(0113)2 011(0113)2 011(0113) 2 3, 5-C12 3, 5-C12 3, 5-012 3,5-012 3, 5-01 2 3, 5-012 3, 5-012 3, 5-C12 3, 5-012 3, 5-C12 3, 5-012 3,5-Cl 2 3, 5-C1 2 3, 5-C12 3,1 5-C12 31 5-C12 3, 5-012 3, 5-C12 3, 5-C12 0113 0113 C113 0113 0113 O 3117 C14119

C

2 Ils 011(0113) 0 2115 02115 0 2115 0 3117 C iI 19 0 6111 3 0331117 Ci 331121 All yl M. P.

M.P.

D

n40 ln5-1070C 100-103%C 106-1080C 80- 8300 1.5890 1.6014

I_

21 1.2.3. Pyridylthio-phenylcarbodiimides 1.2.3.1. N-[2,6-diethyl-4-(3',5'-dichloropyrid-2'-ylthio)-phenyl]-N'tert-butylcarbodiimide 2.7 g of triethylamine in 10 ml of acetonitrile are added dropwise at room temperature, with stirring, to 5.0 g of N-[2,6-diethyl-4-(3',5'dichloropyrid-2'-ylthio)-phenyl]N'-tert-butylthiourea and 3.5 g of 2 -chloro-l-methylpyridinium iodide in 25 ml of acetonitrile and the mixture is stirred at a bath temperature of +700C for 2 hours. The reaction mixture is then concentrated by evaporation in a rotary evaporator at +5000C and the residue is taken up in 50 ml of hexane and 30 ml of water. The hexane phase is separated off, washed with water, dried over sodium sulfate and finally concentrated by evaporation. The title S compound of formula

/CHS

I II II I (Compound No. 1.2.3.1.) Cl Cl N=C=N-C(CH 3 3 is obtained in the form of a yellowish oil; refractive index: n D2 1.6129.

The following compounds are prepared in an analogous manner: r il 22 I i n \=C=N-Ri 1 3 Comnp.No.

1.2.3.2.

1.2.3.3.

1.2.3.4.

1.2.3.5.

1.2.3.6.

1.2.3.7.

1.2.3.8.

1.2.3.9.

1.2. 3. 10.

1. 2.3. 11.

1.2.3.12.

1.2 .3.13.

C(CIf 3 )3 CH(CHj)2

CH(CH

3

)C

2 H5

C(CH

3 aC2H5 Cyclopentyl CHl 3 CH( CH 3 2

C(CH

3 3

C(CH

3 )3

C(CH

3 3 CH( CH 3

CH

2 0CI 3 Cyclopropyl

CH(CH>O

CH(CH

3 2

CH(CH

3 2

CH(CH

3 )2

CH(CH

3 2 CH( CH3) 2 C 2115

CH-

3 Ca-H5 CH( CH 3 2 CH( CH 3 2

CH(CH

3 2

CH(CH

3 2 CH(CH3) 2

CH(CH

3 2

CH(CH.

3

)Z

CH CH i) 2

CH(CH

3 2

CH(CH

3

)C

2

H

5 CHs

CH(CH

3 )C2H5

CH(CH

3 2 CH(( 13)2

CH(CH-

3 2 3, 5-Cl 2 3,5-Cl 2 3,75-C1 2 3,5-Cl 2 3,5-Cl 2 3,5-Cl 2 3,5-Cl 2 3, 5-cl 2 3, 5-Cl: 3-F, 5-Cl 3,5-Cl 2 3,5-Cl 2 phys. data m-p. 58-60 0

C

n 25 1.6070

D

n 25 1.6011

D

n 5:1.5959 n 5:1.6081

D

n25:1.2 n 5:1.6045

D

n25 :165 ns .5961

D

n 25: 1.6806

D

n24:1.622

D

ii a- Comp.___ R2 R3 Ri nI YL 2, 6-D~thy1 1.2. 3. 14 1.2.3.15 1. 2.3. 16 1. 2.3. 17 1.2. 3. 12 1.2.3.19 1.2.3.20 1.2. 3.21 1.2.3.22 1.2. 3.23 1.2. 3.24 1.2.3.25 1. 26 11.2.3.27 1.2.3.29 1.2.3.30 1.2.3.31 1.2.3.32 1.2. 3.33 1.2. 3. 34 1.2 35 1. 2. 3.36 1.2 .3 .37 1.2.3.3 cyclohexyl cyclooctyl Cf( Cl! 3 0112 C11( 113) 2 CH( CI 3 Cyclopropyl 0 2115 011(0113) 2 CH(C11 3

Z

CI1(C113)2 011(0113) 2 CIl(C11 3 2 CH(C11 3 2 011(0113)2 C11(C11 3 CI1(CI 3 2 011(0113) 2 011(0113)2? 011(0113)2 011(0113) Z 0(0113)3 0(0113)3 0(0113)3 C(C113) 3 0(0113)3 0(0113) 3 0(0113) 3 011(0113 )2 011(013)'2 011(0113) 2 011(0113)2 011(0113) 2 0113 0113 02115 02115 Q2115 S2 115 02115 02115 011(0113) 2 011(0113)2 011(0113)2 011(011 3) 2 011(0113)2 0113 C 2115 02115j 02115 0 2115 02115 0 2115 CHI(011 3 )2 011(0113) C If(C If3 .2 011(011 la 011(0113 )2 011 3 02115 02115 0 2115 02115 02115 02115 02115 011(013 2 011(0113) 2 CH1(C113) 2 011(0113)2 011(0113)2 0 2115 02115 02115 02115 02115 02115 02115 3 ,5-C12 3, 5 -0c1 3,5-012 3, 5-012 3,5-C12 3, 5-012 3,5-C12 3, 5-C12 3,5-C12 315-C12 5-01 4, 6-C12 5-CF 3 3, 5-C12 3, 5-012 3-01,5-CF 3 3-F, 4, 6-C12 3, 5-012 3 ,5-C12 3, 5-C12 3-01, 5-CF 3 3-F 5-01 4, 6-Cla

SI

SI

SI

SI

S

so s so S0 2

S

S3 2

S

phys. Daten 1610 41.607 n?51.5891 n251.6072

I

0 0 0 Comp. No. RiP.,R 4n Y 1.2.3. 31 C(Cii 3 3

C

2 11 5 Cyclopentyl 3,5-Cl 2 2 S 1.2.3.40 C(C11 3 3 Cz1i 5 Cyclohexyl 3,5-Cl 2 2 S 1. 2. 3. 4 C(Cii 3 3 CII(d11 3 2 cHI(cI 3 3,5-cl 2 2 SO 2. 3.4' C( C11 3 3 CH I(CHb~ -2 Cll(c11 3 2 3,5-Cl 2 2 302

C(CH

3 3 cfH( 11 3 2

CHI(CH

3 2 if I S L.2.3.4 C(CI1 3 3 CH( C11 3 2 Cll(c11 3 5-CF 3 1 S L.2. 3 .4 C( C11 3 3 CH'(CH 3 2 CII C11 3 2 3-Cl,5-CH1 3 2 S L. 2-.3.4 C(C!1 3 3 Cfl(C11 3 2 CHI(C1 3 2 4,6-Cl 2 2 S L. 2.3.4- C(CI1 3 3 C11(CH 3 )2 CII(CH3)2 3-Cl,5-CF 3 2 S L.2.3 .4 c(CH 3 3 CHI(CH1 3 2 CII(CH1 3 )a 3-Cl, 2 CFCl 2 2 S L.2. 3.4! C(ci 3 3 C11( C11 3 Z CII( C1 3 2 5-Cl I S L.2.3.5( C( C11 3 3 Cl( C11 3 )2 Cyclopentyl 3,5-Cl 2 2 S L. 2.3 .5 C( C11 3 3 CII(CH13) 2 Cyclohexyl 3,5-Cia 2 S .2.3.5 C(CIIA) 3 Cyclopent. Cyclopentyl 3,5-0l 2 2 S 3. 5- Clf( C11 3

)C

2 11 5

C

2 1 5 C 2 11 5 3,5-Cl.

2 2 S L2.3. 5 C1(ClI3)' 2 li5 C 2 11 5

C

2 5 3,5-Cl 2 2 SO 1.2.3. 5 CII(CEJA)C2lic 2 11 5

C

2 H C 2 1 5 3,5-Cl 2 2 so 2 5( C I( CHI 3

C

2 11 5 CHI(CH1 3 2 CII(CH1 3 2 3,5-Cl 2 2 SO 235 c(C)c1 5 CJ( C11 3 2 CHI(Cr 3 2 3,5-Cl 2 2 S02

CHI(C

2 11s) z CII( Cl! 3 2 CHI(CW:- Y2 3,5-Cl 2 2 S 5( CiIECII(C11 3 2] CHI(Cf 3 2 CHI(C11 3 )2 3,5-Cl 2 2 6 C 1 2112 5 2Cif(C 3 2 CII(CI1 3 2 3,5-Clz 2 S bii CII 2

CF

3 CHI(C11 3 2

CII(CI

3 2 3,5-Clz 2 S .23 61(Cl1 2 3 OC!l 9 CIH(C11 3 2 CHI(CHU) 2 3,5-Cl 2 Ch"(C11)CyclO- G hexyl CII(C1 3 2 CII(C11 3 3,5-Cl 2 2 S 3.6C(CH1 3 2 CYC1o-I 2.3 6 hexyi CI!(C11 3 2 CI!(C11 3 3,5-Cl 2 2 S 2 3 6 Cyclopentyl C 2 Hs C 2 11 5 3,5-C12 2 S 23 C yclopentyl Calls Calls 3,5-Cl 2 2 S0 q~ 77 CopN. R R 3 Ri 1-236 Cycloreantyl C 2 11 5 C 2 11 5 3,5-ClI 2 1.237 Cyclopentyl CHI(C11 3 2 CJI(C11 3 2 3,5-CII. 2 1...-Cyclopentyl CHI(C1 3 2 CII(C11 3 2 3,5-Cl. o .2.3 Cyclohexyl CH(C1 3 2 CII(C11 3 2 3,5-C1 2 2 S 1 L 7 i. 26 Example 2: Formulations for active ingredients of formula I according to Preparation Examples 1.2.

(throughout percentages are by weight) 2.1. Emulsifiable concentrates active ingredient according to Preparation Examples 1.2.

calcium dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 moles of ethylene oxide) cyclohexanone butanol xylene mixture ethyl mcetate Emulsions of any desired concentration trates by dilution vith water.

a) b) 10 #4' *o S 4 .4 4 I *e *4(A1 25 5 40 15 25 50 can be produced from such concen- 2.2. Solutions active ingredient according to Preparation Examples 1.2.

polyethylene glycol (mol. wt. 400) N-iimethyl-2-pyrrolidone epoxidised coconut oil petroleum fraction (boiling range 160-1900C) a) b) 10 5 70 20 20 1% S 74 These solutions are suitable for application in the form of microdrops.

2.3. Granulates a) b) active ingredient according to Preparation Examples 1.2. 5 10 kaolin 94 highly dispersed silicic acid 1 attapulgite 90 ii -27 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.

2.4. Extruder granulate active ingredient according to Preparation Examples 1.2. 10 sodium lignosulfonate 2 carboxymethylcellulose 1 kaolin 87 The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

9 S 2.5. Coated granulate active ingredient according to Preparation Examples 1.2. 3 polyethylene glycol (mol. wt. 200) 3 kaolin 94 The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obta-. I in this manner.

2.6. Dusts a) b) c) d) active ingredient according to Preparation Examples 1.2. 2 5 5 8 highly dispersed silicic acid 1 5 talcum 97 95 kaolin 90 92 Ready for use dusts are obtained by intimately mixing the active ingredient with the carriers and optionally grinding the mixture in a suitable mill.

1 28 2.7. Wettable powders active ingredient according to Preparation Examples 1.2.

sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) b) c) 20 5% 3% 50 75 6 10 5% 67 2% 10 27 10 44 4 44 4 4 44* The active ingredient is thoroughly mixed with the adjuvants and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

S2.8. Suspension concentrate active ingredient according to Preparation Examples 1.2.

4 ethylene glycol S nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) sodium lignosulfonate carboxymethylcellulose 37 aqueous formaldehyde solution silicone oil in the form of a aqueous emulsion water 6 1 0.2 0.8 32 The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

L~_

29 Example 3: Biological tests 3.1. Action against Musca domestica A sugar cube is so moistened with a solution of the test compound that the concentration of active ingredieni: in the cube after drying is 500 ppm. The treated cube is placed on a dish together with a wet cotton wool swab and covered with a beaker. 10 adult one week-old, OP-resistant flies are placed under the beaker and kept at 25 0 C and humidity. The insecticidal action is determined after 24 hours by evaluating the mortality rate.

Compounds according to Examples 1.2.2. and 1.2.3. exhibit good S' activity in this test.

S* I 3.2. Action against Lucilia sericata 1 ml of an aqueous formulation containing 0.5 test compound is added at S 500C to 9 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, Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity against Lucilia sericata in this test.

3.3. Action against ticks in various stages of development fresh Boophilus microplus females fully replete with blood are affixed in a row in the dorsal position to a PVC plate and covered with a cotton Swool swab, 10 ml of the aqueous test solution are then poured over the test organis's. One hour later the cotton wool swab is removed and the ticks are dried overnight at 24 0 C. After drying, the ticks are kept at 28°C and 80 humidity for 4 weeks until oviposition has taken place and the larvae have started to hatch.

Each test compound is tested in a concentration of 500 ppm. The acaricidal action manifests itself either in the females as mortality or sterility or in the egg deposits as the blocking of embryogenesis or 1the act of hatching. All the compounds are tested against two different tick strains, the OP-resistant BIARRA strain and the amidine-resistant ULAM strain.

Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in the above test.

3.4. Insecticidal stomach poison action against Spodoptera littoralis larvae (L 1 Cotton plants in the cotyledon stage are sprayed with an aqueous emulsion (obtained from a 10 emulsifiable concentrate) containing 400 ppm of the test compound.

After the coating has dried, each cotton plant is populated with o Spodoptera littoralis larvae in the first larval stage. The test is S carried out at 26 0 C and about 50 relative humidity. Mortality is assessed after 2 and 3 days, and defects in the development and sloughing S of the developed larvae are assessed after 5 days.

o Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

0 3.5. Insecticidal stomach poison action against Spodoptera littoralis and Heliothis virescens larvae (L 3 Potted soybean plants (pot size: 10 cm diameter) in the 4-leaf stage are sprayed with aqueous emulsions containing the test compound in a concen- S tration of 400 ppm.

After 2 days the treated soybean plants are populated with 10 larvae of Spodoptera littoralis or 10 larvae of Heliothis virescens in the third larval stage. The test is carried out at 26 0 C and about 60 relative humidity in dim light. After 2 and 5 days evaluation is made to determine the percentage mortality of the larvae.

Compounds according to Examples 1.2.2. and 1.2.3. are 80-10u effective (mortality).

L L- 31 3.6. Insecticidal stomach poison action against Plutella xylostella larvae (L 2 Potted Chinese cabbage plants (pot size: 10 cm diameter) in the 4-leaf stage are sprayed with aqueous emulsions containing the test compound in a concentration of 400 ppm.

After 2 days, the treated Chinese cabbage plants are populated with Plutella xylostella larvae in the L 2 stage. The test is carried out at 26°C and about 60 relative humidity in dim light. After 2 and days evaluation is made to determine the percentage mortality of the larvae.

Compounds according to Examples 1.2.2. and 1.2.3. are 80-100 effective (mortality).

a a 3.7. Contact action against Nilaparvata lugens (nymphs) The test is carried out with growing plants. For this purpose rice plants about 20 days old and about 15 cm in height are planted into pots (diameter 5.5 cm).

a 44 S The plants are each sprayed on a rotary table with 40 ml of an acetonic solution containing 400 ppm of the test compound. After the spray-coating has dried, each plant is populated with 20 nymphs of the test organisms in the second or third stage. In order to prevent the cicadas from escaping, a plexiglass cylinder is slipped over each of the populated plants and sealed with a gauze top. The nymphs are kept for 6 days on the treated plants which have to be watered at least once. The test is carried out at a temperature of about 23 0 C and at 55 relative humidity and the plants are exposed to light for a period of 16 hours per day.

Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

3.8. Systemic action against Nilaparvata lugens Rice plants about 10 days old (about 10 cm in height) are placed in a plastic beaker which contains 20 ml of an aqueous emulsion formulation of the test compound in a concentration of 100 ppm and which is closed by a 32 perforated plastic lid. The roots of each rice plant are pushed through a hole in the plastic lid into the aqueous test formulation. The hole is sealed with cotton wool to fix the plant and to exclude the effect of the gas phase from the test formulation. Each rice plant is then populated with 20 nymphs of Nilaparvata lugens in the N 2 to N 3 stage and is covered with a plastic cylinder. The test is carried out at 26 0 C and about 60 relative humidity and the plants are exposed to light for a period of 16 hours per day. After 2 and 5 days a count is made of the number of test organisms killed in comparison with untreated controls, thereby establishing whether the test compound absorbed via the roots kills the test organisms on the upper parts of the plants.

r Compounds according to Examples 1.2.2. and 1.2.3. are 80-100 effective (mortality) against Nilaparvata lugens in this test.

3.9. Action against soil insects (Diabrotica balteata) 350 ml of soil (consisting of 95 by volume sand and 5 by volume peat) Sare mixed with 150 ml of each of a number of aqueous emulsion formulations containing the test compound in a concentration of 400 ppm. Then plastic beakers having an upper diameter of about 10 cm are partly filled with the treated soil. In each beaker, ten larvae of Diabrotica balteata in the third larval stage are used and four maize seedlings are planted and the beakers are filled up with soil. The filled beakers are covered with plastic film and kept at a temperature of about 24°C and a relative humidity of about 50 Six days after the start of the test, the soil contained in the beakers is sieved and the mortality of the larvae that remain is assessed.

Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

3.10. Contact a, 'on against Aphis craccivora Before the start of the test, 4-5 day-old pea seedlings (Pisum sativum) raised in pots are each populated with about 200 insects of the species Aphis craccivora. The treated plants are sprayed direct to drip point 24 hours later with an aqueous formulation containing 400 ppm of the 33 test compound. Two plants are used for each test compound. A mortality count is made after 3 and 5 days. The test is carried out at about 21°C and a relative humidity of about 55 Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

3.11. Contact action against Myzus persicae Before the start of the test, pea seedlings (Pisum sativum) about days old and raised in water are each populated with about 200 insects of the species Myzus persicae. The treated plants are sprayed direct to drip point 24 hours later with an aqueous suspension S containing 100 ppm of the test compound. Two plants are used for each S* test compound. A mortality count is made 3 and 5 days after appli- S cation. The test is carried out at about 21 0 C and about 60 relative a o humidity.

S Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

S3.12. Action against Tetranychus urticae (OP-sensitive) 24 hours before the test for acaricidal action, the primary leaves of Phaseolus vulgaris plants are infected with an infested piece of leaf from a mass culture of Tetranychus urticae (OP-sensitive) (mixed population). The tolerance refers to diazinone.

The treated infested plants are sprayed to drip point with a test solution in emulsion form containing 400 ppm of the test compound. During the test run the plants are kept in greenhouse compartments at about and about 50 relative humidity.

After 6 days, a count of the number of living and dead imagines and larvae (all mobile stages) and egg deposits is made under a stereoscopic microscope.

Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

r' 4. 34 3.13. Action against Panonychus ulmi (OP- and carbamate-resistant Apple seedlings having about 20-30 leaves, in pots, are each populated with 60 adult Panonychus ulmi females. After 7 days the infested plants are sprayed to drip point with an aqueous emulsion containing 100 ppm of the test compound. The treated plants are then kept in a greenhouse for 14 days at about 25°C and about 50 relative humidity.

After this time, the test is evaluated by detaching 20 leaves from each plant, removing the mite population from the detached leaves using a brushing-off device and counting the eggs, post-embryonic stages and adults under a stereoscopic microscope. The percentage reduction in the po S mite population is evaluated in comparison with untreated controls.

4 S Compounds according to Examples 1.2.2. and 1.2.3. exhibit good activity in this test.

S* 3.14. Action against Dermanyssus gallinae 2 to 3 ml of a solution containing 100 ppm of the test compound and about 4 200 mites in various development stages are placed in a glass container open at the top. The container is then closed with a cotton wool plug, S shaken for 10 minutes until the mites are completely wet and then briefly S inverted in order that the remaining test solution can be absorbed by the cotton wool. After 3 days the percentage mortality of the mites is determined by counting' the dead insects.

Compounds according to Examples 1.2.2. and 1.2.3. are 80-100 effective (mortality).

Claims (9)

1. Compounds of formula I (R )i 11 11 (1) in which RI represents Cl-Ci 2 alkyl, CI-Claalkyl mono- or poly-substituted by halogen and/or by CI-C 6 alkoxy, C 3 -Cscycloalkyl, C 3 -Cacycloalkyl iono- or poly-substituted by Cj-C 3 alkyl, or C 3 -Cscycloalkyl-Cl-Cialkyl; RZ arnd R 3 each represents CI-Cbalkyl Or C 5 -C~cycloalkyl; R4 each represents hydrogen, halo".en, C 1 -Cijalkyl, or C 1 -Cifalkyl mono- or poly-substituted by-halogen; n represents 1, 2, 3 or 4; Y represents S, SO Or SO 2 Z represents -NH-CS-NH-, -N=C(SRs)-NH- or and represents CI-Cloalkyl or allyl, and -alts thereof with organic or inorganic acids.

2. Compounds of formula I according, to claim 1 in which R 1 represents CI-C 8 alkyl, C 1 -Csalkyl mono- or poly-substituted by halogen and/or by CI-C 5 alkoxy, or C 5 -C~cycloalkyl; R 2 represents CI-Csalkyl; R3 repre- sent& Cl-Csalkyl or cyclopentyl; R 4 each represents hydrogen or halogen; n represents 1 or 2; Y represents 5, SO or SO 2 Z represents -NH-CS-NH-, -N=C(SR 5 or and R5 represents C 1 -C 5 alkyl or allyl.

3. Compounds of formula I according to claim 2 iTV which R, represents C 1 -C 5 alkyl or cyclopentyl; R 2 and R 3 each represents Cl-C 3 alkyl; R4 represents chlorine; n represents 1 or 2; Y represents S; and Z repre- sents -NH-CS-N11-. 43

13. A pesticidal composition according to claim 11 in which R 1 represents C 1 -C 5 alkyl or cyclopentyl; R 2 and R 3 each represents C 1 -C 3 alkyl; R 4 represents chlorine; n represents 1 or 2; Y represents S; Z represents -N=C(SR 5 and R 5 represents CI-C 4 alkyl.

14. A pesticidal composition according to claim 11 in which R 1 represents C -C 5 alkyl or cyclopentyl; R 2 and R 3 each represents C 1 -C 3 alkyl; R 4 represents chlorine; n represents 1 or 2; Y represents S; and Z represents A method of controlling pests in and on animals and plants, characterised in that the pests in their various stages of development are brought into contact with a compound of formula I If I (I) Z-RI in which R 1 represents C 1 -C 12 alkyl, C 1 -C 12 alkyl mono- or poly-substituted by halogen and/or by C -C 6 alkoxy, C 3 -CgCycloalkyl, C 3 -C 8 cyclo- alkyl mono- or poly-substituted by C 1 -C 3 alkyl, or C 3 -C 8 cycloalkyl- C -C 4 alkyl; R2 and R 3 each represents C -C 5 alkyl or C 5 -C cycloalkyl; R 4 each represents hydrogen, halogen, C -C 4 alkyl, or C 1 -C 4 alkyl mono- or poly-substituted by halogen; n represents 1, 2, 3 or 4; Y represents S, SO or SO;0 Z represents -NH-CS-NH-, -N=C(SR 5 or and R 5 represents C 1 -C 10 alkyl or allyl, or with one of the salts thereof with an organic or inorganic acid.

16. The method according to claim 15 for controlling insects and arachnids.

17. Compounds of the formula V R2 I i I V) n Y \NHI K13 KXW:1047yo, -36- 4. Compounds of formula I according to claim 2 in which R, ri;presents CI-C 5 alkyl or cyclopentyl; R 2 and R 3 each !r'-presen CI~-C, 3 alkyl; RI, represents chlorine; L reprQents 1 or 2; Y rr-,presenLsF Z represents and R 5 repr~ecens C 1 -Ci~alkvl. Compounds of formula I according to claim 2 in which R, represents Cj-C 5 alkyl or cyclopentyl; R 2 -f~d R.-i each represents CI-C 3 alkyl; R4 represents chlorine; n represents 1 2; Y represents S; and Z represents 6. A compound according to claim% of the formulae N S CH I I II, I I- S N H N S CH(C1 3 2 c6HCH 3 2 Cl Cl NH-CS-NH-Cfl( clI 3 2 3 2 N S\ ,CH(CH 3 2 Cl ~Cl NU-CS-NH-- H N S (CH(C) ~N S\ CH(CFH 3 2 Cl Cl NH-CS-NH-C(CH 3 )aCH Cl N\/\/~CHCH 3 -37 N S CH(CH 3 2 ci" c~ 1 NH-CS-NH-CH 3 C"H(CH 3 2 N S H ci" c7 "'i"'\NH-CS-NH-C(CH 3 3 N S H 6HCH 3 )C 2 H s H(dH 3 2 I NH-CS-NH-CH(CH 3 )CH 2 oCH 3 N H(CH 3 )2 Ci Ci I 3 2 N S cH(CH 3 2 ci"l ""ci CS -Nf- /I (6H(CH 3 ,N S CH(CH[ 3 2 I ,I I ci" cl NH-CS -NH-CHC3- 1 anH 6HCH 3 2 -38- N S *,CHWCH 3 2 F" 1 NH-CS-NH-.C(CH 3 3 &(H~c 3 2 7. Compounds according to claim 41 of the formulae: N S C C 2 [I Cl" C1 N=-NH-C(CH 3 3 N S\ CH(CH 3 2 Cl~* ~cl ~7N=-NH-C(CH 3 3 6HCH 3 2 N S CH(CH 3 2 Cl" cl \=-NH--CH(CH 3 )C 2 H (hHCH 3 2 N (CH 3 2 N H(CH 3 2 H(C 3 Cl Cl N C-NH-(C H n 6HCH 3 )C 2 H Cl" Cl* '7 N= -N11-C(CH 3 )3 n &H(CH 3 )CzH -39 8. Compounds according to claim /of the formulae: Lq4 C 2 Cl /Cl \(N=C=N-C(CH 3 3 N S\ /CH(CH 3 2 N H(CH 3 2 H(CH 3 2 S\ /CH(H) cji NC=N-C(CH 3 )2CaH N s (H(C 3 2 N\ B CH(CH 3 2 :0 Ci" "LC-NC(H 3 2 CH Cl CI* '\NH(C=N-H 2) IN\ /S\.I*C\.CC 3 Cl C, N=HCH 3 2 H3) L3v 2 40 N S CH LH(CH 3 )C 2 H N S C(H \F /C (CH 3 3 N 6 CH 3 2 IM\ IS\ I /C I H WiCHO) 3 2 *C ci" j \(/H(CH3 2 2.- N S CH(CH 3 2 Ci" I. "Ci H I1 6~H(CH,) 2 7 Cjl Ci \N=C=N-CH(CH 3 )CH 2 CH(CH 3 2 and (WHCH 3 2 \,IS \/CH(CH 3 2 CI II -CIC3I 6HCH0)2 9. A process for the preparation of a compound of formula I n "Z-R 1 13 41 in which RI represents C 1 -C 1 ialkyl, Ci-C 2 ialkyl mono- or poly-substituted by halogen and/or by C 1 -C 6 alkoxy, C 3 -Cscycloalkyl, C 3 -Cscycloalkyl mono- or poly-substituted by C 1 -C 3 alkyl, or C 3 -Cscycloalkyl-Ci-Calkyl; R 2 and R 3 each represents Ci-Csalkyl or Cs-C 6 cycloalkyl; R4 each represents hydrogen, halogen, Ci-C 4 alkyl, or Ci-CiLalkyl mono- or poly-substituted by halogen; n represents 1, 2, 3 or 4; Y represents S, SO or SO 2 Z represents -NH-CS-NH-, -N=C(SR 5 or and R 5 represents Ci-C 1 oalkyl or allyl, S characterised in that A) an isothiocyanate of formula II (R II II I (II) \N-C=S *n is reacted with an amine of formula III SH 2 N--R (III) in an organic solvent or diluent at normal pressure and at a temperature of from 0 to +150uC to form thiourea and optionally B) the resulting thiourea is reacted with a compound of formula IV X-Rs (IV) in an inert solvent under slightly elevated or normal pressure and at a temperature of from +10 to 250°C to form isothiourea, or C) the resulting thiourea is converted into the carbodiimide by removal of hydrogen sulfide, in an aprotic organic solvent or diluent under normal pressure and at a temperature of from 0 to +150 0 C, wherein Ri, R z R 3 R4, Rs, Y and n have the meanings given and X represents a leaving group. 42 A pesticidal composition which contains as active ingredient at least one compound of formula I i I (I) n Z-R 1 3 in which R 1 represents Cl-CI 2 alkyl, Ci-Claalkyl mono- or poly-substituted by S halogen and/or by Cl-Csalkoxy, C 3 -Cscycloalkyl, C3-Cscycloalkyl mono- or poly-substituted by C 1 -C 3 alkyl, or C 3 -Cscycloalkyl-Ci-Cialkyl; R 2 and R 3 each represents Ci-Csalkyl or Cs-C 6 cycloalkyl; R4 each represents hydrogen, halogen, Ci-C 4 alkyl, or Ci-C4alkyl mono- or poly-substituted by halogen; n represents 1, 2, 3 or 4; Y represents S, SO or SOz; Z represents -NH-CS-NH-, -N=C(SRs)-NH- or and ,"oa Rs represents Ci-Cioalkyl or allyl, or one of the salts thereof with an organic or inorganic acid, together with suitable carriers and/or adjuvants. 00 11. A pesticidal composition according to claim 10 which contains as active ingredient at least one compound of formula I in which RI represents Ci-Caalkyl, Ci-Csalkyl mono- or poly-substituted by halogen and/or by Ci-Csalkoxy, or Cs-C 6 cycloalkyl; R 2 represents Ci-Csalkyl; R 3 represents C 1 -Csalkyl or cyclopentyl; R4 each represents hydrogen or halogen; n represents 1 or 2; Y represents S, SO or SO 2 Z represents -NH-CS-NH-, -N=C(SR 5 or and Rs represents Ci-Csalkyl or allyl. 12. A pesticidal composition according to claim 11 in which Ri re- presents Ci-Csalkyl or cyclopentyl; R 2 and R 3 each represents C 1 -C 3 alkyl; R 4 represents chlorine; n represents 1 cr 2; Y represents S; and Z represents -NH-CS-NH-. A 43 13. A pesticidal composition according to claim 11 in which R 1 represents C 1 -C 5 alkyl or cyclopentyl; R 2 and R 3 each represents C 1 -C 3 alkyl; R 4 represents chlorine; n represents 1 or 2; Y represents S; Z represents -N=C(SR 5 and R 5 represents C 1 -C 4 alkyl. 14. A pesticidal composition according to claim 11 in which R represents C 1 -C 5 alkyl or cyclopentyl; R 2 and R 3 each represents CI-C 3 alkyl; R 4 represents chlorine; n represents 1 or 2; Y represents S; and Z represents A method of controlling pests in and on animals and plants, characterised in that the pests in their various stages of development are brought into contact with a compound of formula I (Ru I i (I) Z-R in which R 1 represents C 1 -C 12 alkyl, C 1 -C 12 alkyl mono- or poly-substituted by halogen ana/or by C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 3 -C 8 cyclo- alkyl mono- or poly-substituted by C 1 -C 3 alkyl, or C 3 -C 8 cycloalkyl- C1-C 4 alkyl; R 2 and R 3 each represents C--C 5 alkyl or C 5 -C 6 cycloalkyl; R 4 each represents hydrogen, halogen, C -C 4 alkyl, or C -C 4 alkyl mono- or poly-substituted by halogen; n represents 1, 2, 3 or 4; Y represents S, SO or S02; Z represents -NH-CS-NH-, -N=C(SR 5 or and R 5 represents C -C 10 alkyl or allyl, or with one of the salts thereof with an organic or inorganic acid. 16. The method according to claim 15 for controlling insects and arachnids. 17. Compounds of the formula V N a (R4)-4 IJ 1 I (V) \KXW 1H 2 KXW:1047\M I- 44 in which R 2 and R 3 each represents C 1 -C 5 alkyl or C 5 -C 6 cycloalkyl; R 4 each represents hydrogen, halogen, C 1 -C 4 alkyl, or C 1 -C 4 alkyl mono- or poly-substituted by halogen; n represents 1, 2, 3 or 4; and Y represents S, SO or S02.

18. Compounds according to claim 17 in which R 2 represents C1-C 5 alkyl; R 3 represents C 1 -C 5 alkyl or cyclopentyl; R 4 each represents hydrogen or halogen; n represents 1 or 2; and Y represents S, SO or SO2.

19. Compounds according to claim 18 in which R 2 and R 3 each represents C 1 -C 3 alkyl; R 4 represents chlorine; n represents 1 or 2; and Y represents S. 444 00* 4404 0 44 0*4r Ir~ KXW:1047y L 2 The compounds according to claim 2 .Erof the formulae: N S /C 2 N S /CH( CH 3 2 4, ~JHCH 3 2 a CH 3 aCl C, NH2 H 3 N S CH aCl C1 NH 2 c6HCH 3 )C 2 H 5 and F1 Cl 'NH 2 (6HCH 3 2 ytI Compounds of formula II N\ /R 2 i i I (T \-NC-S k 3 in which R 2 and R 3 each represents C 1 -Csalkyi or R4 each represents hydrogen, halogen, Cl-Ci~alkyl, or CI-Ct 4 alkyl mono- or poly-substituted by halogen; n represents 1, 2, 3 or 4; and Y represents S, SO or S0 2 46 2-2-1 2 Compounds according to claim -2-29 in which R 2 represents C 1 -C 5 alkyl; R 3 represents CI-Csalkyl or cyclopentyl; Rij each represents hydrogen or halogen; n represents 1 or 2; and Y represents S, SO or S0 2 4.Compounds according to claim[2 in which R 2 and R 3 each represents CI-C 3 alkyl; R4 represents chlorine; n represents 1 or 2; and Y re- presents S. *Ot 2. The compounds according to claim 2-<of the formulae: 1 5l 65 NC= Cl Cl N=C=-S /6/CH 3 N H(CH 3 L H 3 N S CH Cl" ~K Cl \jN=C=S (CH 3 )C 2 H- 5 and N H(CH(3)2 FO -"q 4 47 ,6 Substituted pyridylthio-, pyridylsulfinyl- and pyridylsulfonyl- phenyl-thioureas, -isothioureas and -carbodiimides, substantially as hereinbefore described with reference to any one of compounds 1.2.1.1 to 1.2.1.73, 1.2.2.1 to 1.2.2.22 or 1.2.3.1 to 1.2.3.72. 2 A process for preparing substituted pyrldylthio-, pyridylsulfinyl- and pyridylsulfonyl-phenyl-thioureas, -isothioureas and carbodiimides, substantially as hereinbefore described with reference to Example 1.2.1.1, Example 1.2.2.1 or Example 1.2.3.1. 27 .28. Substituted pyridylthio-, pyridylsulfinyl- and pyridylsulfonyl- phenyl-thioureas, -isothioureas and -carbodiimides whenever produced by the process of claim 9 or claim T 2-3 Substituted pyridylthioanilines, substantially as hereinbefore described with reference to any one of compounds 1.1.1.1 to 1.1.1.22. 2 3er Substituted pyridylthiophenylisothiocyanates, substantially as hereinbefore described with reference to any one of compounds 1.1.2.1 to 1.1.2.22. A pesticidal composition, substantially as hereinbefore described with reference to Example 2.1 to 2.8. 3 A method of controlling pests in and on animais and plants characterized in that the pests in their various stages of development are brought into contact with a compound according to claim 26 or a composition according to claim 3- 3 0 DATED this SEVENTEENTH day of OCTOBER 1990 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON KX:O47y i 7 KXW:1047y 4_ i