AU767519B2 - Derivatives of trifluoromethylpyri(mi)dine - Google Patents

Description

P:\OPER\Mal\2003\25(X)150 258.doc-24/09/03 -1- Derivatives of trifluoromethylpyri(mi)dine The present invention provides compounds of formula 0

CH

3 .nyn A D

NN

I

(0)m wherein X is CH or N; Y is halogen; n is 1, 2 or 3; m is 0 or 1; A signifies or 10 D is CH 2 or-NR 7 E is -CR 8

R

9

R

7 is hydrogen or Cl-C 6 -alkyl; and S. R 8 and R 9 independently of one another, signify hydrogen or C 1 -C6-alkyl, or together signify =0; and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form; a method of producing and the use of these compounds, pesticides whose active ingredient is selected from these compounds or from an agrochemically acceptable salt thereof, a method of producing and the use of these compositions, plant propagating material that has been treated with these compositions and a method of controlling pests.

In literature, certain pyridine derivatives have been proposed as active ingredients in pesticides. The biological properties of these known compounds, however, are not fully satisfactory in the field of pest control, which is why there is a need to produce further compounds with pesticidal properties, especially for the control of insects and members of P:\OPER\Mal200(3\25(X)150 25.do-15/09/03 -1Athe order Acarina; this problem is solved according to the invention with the development of the present compounds of formula The compounds of formula and where appropriate their tautomers can form salts, for example acid addition salts. These are formed for example with strong inorganic acids, typically mineral acids, e.g. sulphuric acid, a phosphoric acid or a hydrohalic acid, or with strong organic carboxylic acids, typically Cl-C 4 alkanecarboxylic acids substituted where appropriate for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g. oxalic, maloiic, maleic, fumaric or phthalic acid, such as 0 *0 WO 01/14373 PCT/EPOO/08082 -2hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulphonic acids, typically Cl-C 4 alkane or arylsulphonic acids substituted where appropriate for example by halogen, e.g. methane- or p-toluene-sulphonic acid. In a broader sense, compounds of formula with at least one acid group can form salts with bases.

Suitable salts with bases are for example metal salts, such as alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g.

ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine. Corresponding internal salts where appropriate may also be formed. The free form is preferred. Of the salts of compounds of formula the agrochemically beneficial salts are preferred. Hereinbefore and hereinafter, the free compounds of formula or their salts are understood where appropriate to include also the corresponding salts, or the salts are understood to include also the free compounds of formula The same applies to tautomers of compounds of formula and salts thereof.

Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings given hereinbelow.

Halogen as a group per se or as structural element of other groups and compounds such as haloalkyl, halocycloalkyl, haloalkenyl, haloalkinyl and haloalkoxy is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, mainly fluorine or chlorine, especially chlorine.

If not otherwise defined, carbon-containing groups and compounds each contain 1 to inclusively, preferably 1 to 18, in particular 1 to 10, especially 1 to 6, in particular 1 to 4, especially 1 to 3, particularly 1 or 2, carbon atoms, with methyl being preferred in particular.

Alkyl as a group per se and as structural element of other groups and compounds such as haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulphonyl and alkylsulphonyloxy is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, e.g.

methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

WO 01/14373 PCTIEP00/08082 -3- Alkenyl and alkinyl as groups per se and as structural elements of other groups and compounds, such as of haloalkenyl, haloalkinyl, alkenyloxy, haloalkenyloxy, alkinyloxy or haloalkinyloxy are straight-chained or branched and respectively contain two or preferably one unsaturated carbon-carbon bond(s). Vinyl, prop-2-en-l-yl, 2-methylprop-2-en-1-yl, but-2en-1-yl, but-3-en-1-yl, prop-2-in-l-yl, but-2-in-l-yl and but-3-in-l-yl may be mentioned by way of example.

Cycloalkyl as a group per se and as a structural element of other groups and compounds, for example of alkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred, in particular cyclopropyl.

Halogen-substituted carbon-containing groups and compounds, such as haloalkyl and haloalkoxy can be partially halogenated or perhalogenated, in the case of polyhalogenation it being possible for the halogen substituents to be identical or different. Examples of haloalkyl as a group perse and as structural element of other groups and compounds such as haloalkoxy, are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF 2

CF

3 or CH 2 CI; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH 2

CF

3

CF

2

CF

3

CF

2

CC

3

CF

2

CHCI

2

CF

2

CHF

2

CF

2

CFCI

2

CH

2

CH

2 CI, CF 2 CHBr 2

CF

2 CHCIF, CF 2 CHBrF oder CCIFCHCIF; propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2

CHFCF

3

CH

2

CF

2

CF

3

CF

2

CF

2

CF

3

CH(CF

3 2 or CH 2

CH

2

CH

2 CI; and butyl or one of its isomers, monoto nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF 3

)CHFCF

3

CF

2

(CF

2 2

CF

3 oder CH 2

(CF

2 2

CF

3 In di-(C 1

-C

4 -alkyl)amine, the two alkyl groups are independent of each other.

Aryl signifies especially phenyl or naphthyl, preferably phenyl.

Heterocyclyl signifies a 6- or 7-membered, saturated or unsaturated ring which is bonded to the basic structure by a carbon atom, the ring having preferably two to four hetero atoms selected from the group comprising N, O and S. Preference is given to 6-rings having a nitrogen atom as the hetero atom and two further hetero atoms, preferably nitrogen or oxygen, especially one oxygen and one nitrogen.

Depending on the substitution possibilities on the heterocyclyl radical, the heterocyclyl radicals may bear one to three, preferably one, substituent selected from the group P:\OPER\Mai\2003\.25Of)150 258.doc-15/09A)3 -4comprising Cl-C 6 -alkyl, C 2

-C

6 -alkenyl, C 3

-C

6 -alkinyl; halogen, nitro, cyano, -OH, -SH, C 3 CB-cyanoalkyl, halogen-C 3

-C

8 -cycloalkyl, Cl-C 6 -alkoxy, halogen-C 1

-C

6 -alkoxy, C 3

-C

6 alkenyloxy, Cl-C 4 -alkylthio and di-(C 1

-C

4 -alkyl)amine.

Particularly preferred in terms of the invention are the compounds of formula listed in Table 1.

The methods for producing the compounds of formula are known to the person skilled in the art from analogous processes. This relates in particular to a process for the preparation of a compound of formula (la), 0**C

S

S.

S

S S Next page is page S. 55 S S S S S. S EDITORIAL NOTE APPLICATION NUMBER 72777/00 This specification does not contain a page(s) (to WO 01/14373 PCT/EPOO/08082 wherein X, R 7 and m are defined as indicated above, A is O or S and R 3 and R 4 together are O or S. Therefore, a further object of the invention is a process for the production of the compounds of formula or a salt thereof, wherein a) a compound of formula

CF

3 0 X

NH

2 (l)

N

which is known or may be produced by processes known per se, and wherein X is defined as indicated for formula is reacted where appropriate in an inert solvent with a compound of formula R "N NR KN) (Ill)

R,

which is known or may be produced by processes known per se, to form a compound of formula CF3 0 X N N, (R I H

N

or a salt thereof, and wherein X, R 7 and m are defined as indicated for formula and b) this compound of formula (III) is reacted with phosgene or thiophosgene; c) in order to produce a compound of formula in which m is 1, a compound of formula (I) in which m is 0 is reacted with an oxidation agent, for example inorganic peroxides, such as sodium perborate, potassium permanganate or hydrogen peroxide; or with mCPBA or organic per acids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, e.g. acetic acid/hydrogen peroxide; and/or, if so desired, a compound of formula obtainable according to the method or by other means, present in free form or in the form of a salt, is converted into a different WO 01/14373 PCT/EPOO/08082 -11 compound of formula a mixture of isomers obtainable according to the method is separated and the desired isomer is isolated and/or a free compound of formula (I) obtainable according to the method or by other means is converted into a salt, or a salt of a compound of formula obtainable according to the method or by other means is converted into the free compound of formula or into a different salt.

Further compounds of formula can also be produced analogously to known processes.

For example, a compound of formula wherein Z is Ri N N R 7 can be produced by reacting a compound of formula

CF

3 NH 2 X

NH

N

or a salt thereof, and wherein X is defined as mentioned above, by reacting with formaldehyde in the presence of a compound NH 2

R

7 and the compound of formula CF3 HN N R7 X N

N

thus obtained is optionally reacted with a compound of formula Q-R 1 wherein Q is a leaving group and Ri is defined as above except for H, and the compound of formula thus obtained, wherein m is 0, is optionally oxidised in accordance with the above process c).

The starting materials of formulae (II) and (III), listed hereinbefore and hereinafter, which are used to produce the compounds of formula in free form or in salt form, are known or may be produced by methods known per se. The starting materials of formula (IV) are novel and therefore similarly form an object of the invention.

WO 01/14373 PCT/EP00/08082 -12- The reactions described hereinbefore and hereinafter are carried out in a known manner, e.g. in the absence or, where appropriate, in the presence of a suitable solvent or diluent or a mixture thereof, proceeding as required under conditions of cooling, of ambient temperature, or of heating, e.g. in a temperature range of about -80 0 C to the boiling temperature of the reaction medium, preferably about -20°C to about +150 0 C, and where appropriate in a closed vessel, under pressure, in an inert gas atmosphere, and/or under non-aqueous conditions. Especially advantageous reaction conditions are described in the Examples.

The reaction of process a) is effected in the presence of an acid, for example HCI, sulphuric acid or phosphoric acid.

The reaction is generally carried out at temperatures of -30°C to +70"C, preferably from to +50 0 C. The process is conveniently carried out in the presence of an inert solvent or solvent mixture. Suitable solvents for this purpose are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene tetrachloride; ethers and ether-like compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert.-butylmethyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; ketones such as acetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone; and mixtures of such solvents with one another.

The reaction is carried out at atmospheric pressure, although it may also be carried out at elevated or reduced pressure.

In process variant the reaction is advantageously carried out in the presence of an inert solvent or solvent mixture at temperatures of -30 0 C to +70°C, preferably -10°C to +50*C. It is preferably carried out in the presence of a base, for example in the presence of an organic amine such as a trialkylamine (trimethylamine, triethylamine, triisopropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), a morpholine (N-methylmorpholine) or a N,N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents for this purpose are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene tetrachloride; ethers such as dialkyl ether (diethyl WO 01/14373 PCTIEP00/08082 -13ether, diisopropyl ether, tert.-butylmethyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; and mixtures of such solvents with one another.

In process variant the reactions are expediently carried out in the presence of an inert solvent or solvent mixture at temperatures of -40*C to +120°C, preferably -20°C to +80 0

C.

The solvents in question may be the same as those mentioned for variant The process is optionally carried out in the presence of a base, for example alkali or alkaline earth metal hydroxides or for example alkali or alkaline earth metal carbonates or hydrogen carbonates, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,Ndialkylaniline, or a bicyclic, non-nucleophilic base such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene

(DBU).

Compounds of formula obtainable according to the method or by other means may be converted in a manner known per se into other compounds of formula by replacing one or more substituents of the starting compound of formula in conventional manner with (an)other substituent(s) according to the invention.

Depending on the choice of appropriate reaction conditions and starting materials, it is possible to replace only one substituent with another substituent according to the invention in one reaction step, or several substituents may be replaced with other substituents according to the invention in the same reaction step.

Salts of compounds of formula may be prepared in a known manner. For example, it is possible to obtain salts of compounds of formula with bases, by treating the free compounds with an appropriate base or with an appropriate ion exchanger reagent.

Salts of compounds of formula may be converted in conventional manner into the free compounds of formula e.g. by treatment with a suitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula may be transformed in known manner into other salts of a compound of formula The compounds of formula in free form or in salt form may exist in the form of one of the possible isomers or as a mixture thereof, e.g. depending on the number, the absolute and WO 01/14373 PCT/EP00/08082 -14relative configuration of asymmetric carbon atoms appearing in the molecule and/or depending on the configuration of non-aromatic double bonds appearing in the molecule, as pure isomers such as antipodes and/or diastereoisomers, or as isomer mixtures such as enantiomer mixtures, e.g. racemates, diastereoisomer mixtures or racemate mixtures. The invention relates both to the pure isomers and to all the possible mixtures of isomers, and hereinbefore and hereinafter is to be understood as such accordingly, even if the stereochemical details are not specifically mentioned in each case.

Depending on the choice of starting materials and methods, diastereoisomer mixtures, racemate mixtures and mixtures of double bond isomers of compounds of formula in free form or in salt form, which are obtainable by the process or in another way, may be separated in known manner, on the basis of the physical-chemical differences in their components, into the pure diastereoisomers or racemates, for example by fractiional crystallisation, distillation and/or chromatography.

Enantiomer mixtures that are obtainable correspondingly, such as racemates, may be broken down by known methods into the optical antipodes, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, e.g. high pressure liquid chromatography on acetyl cellulose, with the assistance of suitable microorganisms, by cleavage with specific, immobilised enzymes, through the formation of inclusion compounds, e.g. using chiral crown ethers, whereby only one enantiomer is complexed, or by converting into diastereoisomeric salts and separating the diastereoisomer mixture obtained in this way, e.g. on the basis of their different solubilities, by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be released upon the action of suitable agents.

According to the invention, apart from isolation of corresponding isomer mixtures, generally known methods of diastereoselective or enantioselective synthesis can also be applied to obtain pure diastereoisomers or enantiomers, e.g. by carrying out the method of the invention using educts with correspondingly suitable stereochemistry.

It is advantageous to isolate or synthesise the biologically more active isomer, e.g.

enantiomer or diastereoisomer, or isomer mixture, e.g. enantiomer mixture or diastereoisomer mixture, provided that the individual components have differing biological efficacy.

WO 01/14373 PCT/EP00/08082 Compounds of formula in free form or in salt form can also be obtained in the form of their hydrates and/or also can include other solvents, used for example where necessary for the crystallisation of compounds present in solid form.

The invention relates to all those forms of the method, according to which one starts from a compound obtainable as a primary material or an intermediate at any stage of the method and carries out all or some of the missing steps, or uses, or especially under the reaction conditions produces a starting material in the form of a derivative or a salt and/or its racemate or antipodes.

In the method of the present invention, the starting materials and intermediates used, each in free form or in salt form, are preferably those that lead to the compounds of formula or salts thereof described at the beginning as being especially useful.

The invention relates especially to the method of preparation described in Example P1.

The compounds of formula according to the invention are active ingredients of preventive and/or curative merit for use in pest control and offer a very favourable spectrum of biocidal activity with favourable tolerability in warm-blooded animals, fish, and plants even at low concentrations. The active ingredients according to the invention are active against all or individual development stages of animal pests showing normal sensitivity, as well as those showing resistance, such as insects or members of the order Acarina. The insecticidal or acaricidal effect of the active substances of the invention can manifest itself directly, i.e.

killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a pesticidal rate (mortality) of at least 50 to The said animal pests include, for example, those which are mentioned in the European Patent application EP-A-736'252, page 2, line 55 to page 6, line 55. The pests mentioned therein are thus included by reference in the object of the present invention. The compounds according to the invention are also active against pests from the class of the nematodes, for example, of the families Filariidae and Setariidae and the genera Haemonchus, Trichostrongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostumum, Oesophagostonum, Chabertia, Trichuris, especially Trichuris vulpis, Strongylus, Trichonema, Dictyocaulus, Capillaria, Strongyloides, Heterakis, Toxocara, especially Toxocara canis, Ascaridia, Oxyuris, Ancylostoma, especially Ancylostoma caninum, Uncinaria, Toxascaris and WO 01/14373 PCT/EPOO/08082 -16- Parascaris; Dirofilaria, especially Dirofilaria immitis (heartworm); also especially against representatives of the genera Heterodora spp., for example Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., for example Globodera rostochiensis; Meloidogyne spp., for example Meloidogyne incoginita and Meloidogyne javanica; Radopholus spp., for example Radopholus similis; Pratylenchus, for example Pratylenchus neglectans and Pratylenchus penetrans; Tylenchulus, for example Tylenchulus semipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus, Aphelenchoides and Anguina.

The active ingredients according to the invention are especially suitable for controlling sucking insects, especially of the order Homoptera, preferably for controlling these pests in vegetable, fruit, rice and cotton crops. One particular advantage of the compounds according to the invention is their systemic action.

Pests of said type which occur on plants, especially on crops and omamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredients of the invention, this protection remaining for parts of some plants whose growth does not occur until later.

Target crops include especially cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder beet; fruit, e.g. pomes, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g. strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybean; oleaginous fruits, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as squashes, cucumbers or melons; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; lauraceae, such as avocado, cinnamon or camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.

Other indication areas for the active ingredients of the invention are the protection of stored products and stores and of material and, in the hygiene sector, especially the protection of domestic animals and livestock against pests of said type.

WO 01114373 PCT/EPOO/08082 -17- The invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances, chosen in accordance with the intended objectives and prevailing circumstances, and comprising at least one active ingredient of the invention.

The active ingredient is used in these compositions in pure form, a solid active ingredient e.g. in a specific particle size, or preferably together with at least one of the adjuvants conventionally employed in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).

The adjuvants which can be used for formulation are, for example, solid carriers, solvents, stabilisers, "slow-release" agents, dyes, and where appropriate surfactants. Carriers and adjuvants can be any substance conventionally used in crop protection agents, especially agents for slug and snail control. Adjuvants such as solvents, solid carriers, surface-active agents, non-ionic surfactants, cationic surfactants, anionic surfactants, and other adjuvants in the compositions of the invention can, for example, be the same as those described in EP- A-736'252, and are included by reference in the object of the present invention.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as follows percent by weight): Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 5 to surfactant: 1 to 30%, preferably 10 to 20 solvent: 5 to 98%, preferably 70 to Dusts: active ingredient 0.1 to 10%, preferably 0.1 to 1% solid carrier 99.9 to 90%, preferably 99.9 to 99% WO 01/14373 PCTEP00/08082 -18- Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to water: 94 to 24%, preferably 88 to surfactant: 1 to 40%, preferably 2 to Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to surfactant: 0.5 to 20%, preferably 1 to solid carrier: 5 to 99%, preferably 15 to 98% Granulates: active ingredient: 0.5 to 30%, preferably 3 to solid carrier: 99.5 to 70%, preferably 97 to The activity of the compositions of the invention can be substantially broadened and adapted to prevailing circumstances by adding other insecticidal substances. Additional active ingredients are, for example, substances from the following classes: organic phosphorus compounds, nitrophenols and their derivatives, formamidines, acylureas, carbamates, pyrethroids, neonicotinoides and their derivatives, pyrroles, thioureas and their derivatives, chlorinated hydrocarbons and Bacillus thuringiensis preparations. Especially suitable components in the mixture are azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin highcis; cyromazin; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cy-halothrin; alpha-cypermethrin; zetacypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb; fenvalerate; formothion; methiocarb; heptenophos; imidacloprid; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; abamectin; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; NI-25, acetamiprid; avermectin B, (Abamectin); an insect-active extract from a plant; a preparation containing insect-active nematodes; a preparation obtainable from WO 01/14373 PCTIEP00/08082 19- Bacillus subtilis; a preparation containing insect-active fungi; a preparation containing insectactive viruses; AC 303 630; acephat; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; betacyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben; cadusafos; carbaryl; carbopheno-thion; chloethocarb; chlorethoxyfos; chlormephos; cis-res-methrin; clocythrin; clofentezin; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-Smethyl; dichlofenthion; dicliphos; diethion; dimethoat; dimethylvinphos; dioxathion; edifenphos; emamectin; esfenvalerat; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatinoxid; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinat; flufenoxuron; flufenprox; fonophos; fosthiazat; fubfenprox; HCH; hexaflumuron; hexythiazox; iprobenfos; isofenphos; isoxathion; ivermectin; lambda-cyhalothrin; malathion; mecarbam; mesulfenphos; metaldehyd; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoat; oxamyl; oxydemethon m; oxydeprofos; permethrin; phenthoat; phorat; phosmet; phoxim; pirimiphos M; pirimiphos A; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyrada-phenthion; pyresmethrin; pyrethrum; RH 5992; salithion; sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlor- vinphos; thiacloprid; thiamethoxam; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarthen; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; YI 5301/5302; zetamethrin; DPX-MP062; RH-2485; D 2341 and XMC (3,5,-xylyl methyl carbamate).

The compositions of the invention can also contain further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils, epoxidized where appropriate epoxidized coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, as well as fertilisers or other active ingredients to achieve specific effects, e.g. acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides.

The compositions of the invention are prepared in a known manner, in the absence of adjuvants, for example, by grinding, sieving, and/or compressing a solid active ingredient or active ingredient mixture, e.g. to a specific particle size, and in the presence of at least one adjuvant, for example, by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s). These methods for preparing compositions of the invention and the use of compounds I for preparing these compositions likewise form an object of the invention.

WO 01/14373 PCT/EP00/08082 The methods of application for the compositions, i.e. the methods of controlling pests of said type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are chosen in accordance with the intended objectives and prevailing circumstances, and the use of the compositions for controlling pests of said type are further objects of the invention.

Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The rates of application are generally 1 to 2000 g of active ingredient per hectare, especially 10 to 1000 giha, and preferably 20 to 600 glha.

A preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question. However, the active ingredients can also penetrate the plant through the roots (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the active ingredient in solid form to the locus of the plants, e.g. the soil, for example in granular form (soil application).

With paddy rice cultures, granules may be metered into the flooded paddy field.

The compositions of the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from animal pests. The propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown. The active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition.

The composition can also be applied when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow. The treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention.

The invention is illustrated by the following examples. They do not impose any limitation on the invention. The temperatures are given in degrees Celsius, and the proportions of solvents in the mixture are given as parts by volume.

WO 01/14373 PCTEP00/08082 -21- Preparation examples Example P1: Preparation of the compound of formula 0

CF

3 O N 3(A)

N

Pla): Preparation of the compound of formula

CF

3

O

N HCI (B) H H

N

ml of acetonitrile are placed in a flask and 1.06 g of hydrogen chloride gas passed in.

Cooling is then effected to -40 0 C and 0.58 g of 1,3,5-trimethylhexahydro-1,3,5-triazine are added dropwise. Stirring is continued for 10 minutes at -40oC and then 2.5 g of 4-trifluoromethyl-nicotinic acid amide are added in portions. The temperature is allowed to rise to room temperature and stirring continues over night. 40 ml of tert.butylmethyl ether are added, the mixture is stirred for a further 15 minutes and filtered. The residue of filtration is washed twice with 20 ml of tert.-butylmethyl ether. Compound is obtained as a solid.

P1 Preparation of the title compound (A) 3.4 g of the compound of the above formula and 40 ml of ethyl acetate are prepared.

They are cooled to 0 to 5°C and 5 ml of 30% sodium hydroxide solution is added dropwise.

The reaction mixture is extracted twice with 20 ml of ethyl acetate, and the combined organic phases are dried over sodium sulphate and concentrated on a rotary evaporator. The residue is admixed with 20 ml of dimethoxyethane and added dropwise over the course of one hour at 0°C to a mixture of 6.5 g of phosgene in 20 ml of dimethoxyethane. The temperature of the mixture is allowed to rise to room temperature and then 2.61 g of pyridine, dissolved in 20 ml of dimethoxyethane, are added dropwise. The reaction mass is stirred over night with slight refluxing.

The mixture is then concentrated on a rotary evaporator, the residue is taken up in 20 ml of ethyl acetate, washed twice with 10 ml of water, the organic phase is dried over sodium WO 01/14373 PCT/EPOO/08082 -22sulphate and the residue purified on silica gel with hexane/ethyl acetate (volume ratio 3/7).

Compound is obtained as a viscous oil (compound 1.2).

Example P32: The remaining compounds of Table 1 may be produced analogously to the manner described above.

Table 1: Compounds of formula 0

CF

3 A 'K NR7 x N- (la) Ex. No. R 7 X A m phys. data 1.1 H CH 0 0 1.2 methyl CH 0 0 oil 1.3 ethyl CH 0 0 1.4 n-propyl CH 0 0 i-propyl CH 0 0 oil 1.6 n-butyl CH 0 0 1.7 phenyl OH 0 0 1.8 4-CI-phenyl OH 0 0 1.9 4-CF 3 -0-phenyl OH 0 0 1.10 4-CF 3 -phenyl OH 0 0 1.11 4-F-phenyl OH 0 0 1.12 benzyl OH 0 0 1.13 cyclopropyll OH 0 0 1.14 cyclohexyl OH 0 0 1.15 methyl OH 0 1 .1.16 ethyl OH 0 1 1.17 n-propyll CH 0 1 1.18 i-propyll CH 0 1 WO 01/14373 WO 0114373PCTIEPOO/08082 -23- Ex. No. R 7 X A m phys. data 1.19 n-butyl CH 0 1 1.20 phenyl CH- 0 1 1.21 4-CI-phenyl CH 0 1 1.22 4-CF 3 -O-phenyl CH 0 1 1.23 4-CF 3 -phenyl CH 0 1 1.24 4-F-phenyl CH 0 1 1.25 benzyl CH 0 1 1.26 cyclopropyl CH 0 1 1.27 cyclohexyl CH 0 1 1.28 methyl N 0 0 1.29 ethyl N 0 0 1.30 n-propyl N 0 0 1.31 -propyl N 0 0 1.32 n-butyl N 0 0 1.33 phenyl N 0 0 1.34 4-CI-phenyl N 0 0 1.35 4-CF 3 -0-phenyl N 0 0 1.36 4-CF 3 -phenyl N 0 0 1.37 4-F-phenyl N 0 0 1.38 benzyl N 0 0 1.39 cyclopropyl N 0 0 1.40 cyclohexyl N 0 0 1.41 methyl CH S 0 1.42 ethyl CH S 0 WO 01/14373 PCT/EP00/08082 -24- Formulation examples percent by weight) Example Fl: Emulsion concentrates a) b) c) active ingredient 25% 40% calcium dodecylbenzenesulphonate 5% 8% 6% castor oil polyethylene glycol ether(36 mols EO) tributyl phenol polyethylene glycol ether (30 mols EO) 12% 4% cyclohexanone 15% xylene mixture 65% 25% Mixing of finely ground active ingredient and adjuvants results in an emulsion concentrate which is diluted with water to yield emulsions of the desired concentration.

Example F2: Solutions a) b) c) d) active ingredient 80% 10% 5% ethylene glycol monomethyl ether 20% polyethylene glycol (MW 400) 70% N-methylpyrrolid-2-one 20% epoxidised coconut oil 1% petrol (boiling limits: 160-190") 94% Mixing of finely ground active ingredient and adjuvants results in a solution which is suitable for application in the form of fine droplets.

Example F3: Granulates a) b) c) d) active ingredient 5% 10% 8% 21% kaolin 94% 79% 54% highly dispersed silicic acid 1% 13% 7% attapulgite 90% 18% The active ingredient is dissolved in dichloromethane, the solution sprayed onto the carrier mixture, and the solvent evaporated off under vacuum.

Biological Examples Example BI: Effect on Diabrotica balteata larvae Corn seedlings are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After drying of the spray deposit, the corn seedlings are colonised with P:\OPER\M.1i\2OO)3\SOOISO 258.doc-1509/03 second instar larvae of Diabrotica balteata and placed in a plastic container. Six days later they are evaluated. The percentage reduction of the population response) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.

The compounds of table 1 show good efficacy against Diabrotica balteata in this test.

Especially compound 1.2 has an effect of over Example B2: Systemic effect against Mzus persicae Pea seedlings are infected with Myzus persicae, then the roots are placed in a spray mixture containing 400 ppm of active ingredient, and incubated at 20 0 C. 3 and 6 days later, they are evaluated. The percentage reduction of the population response) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.

The compounds of the tables show good efficacy against Myzus persicae in this test.

Especially compound 1.2 has an effect of over The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

*S

Claims (10)

1. A compound of formula 0 CH3.nYn A D X N LN 0 I (0)m wherein X is CH or N; Y is halogen; n is 1, 2 or 3; m is 0 or 1; A signifies or SD is CH 2 or -NR 7 E is -CR 8 R 9 R 7 is hydrogen or C 1 -C 6 -alkyl; and R 8 and R 9 independently of one another, signify hydrogen or C 1 -C 6 -alkyl, or together signify =0; and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form.

2. A compound of formula according to claim 1, in free form.

3. A compound of formula according to claim 1 or 2, wherein A is

4. A compound of formula according to any one of claims 1 to 3, wherein Re and R 9 are hydrogen.

P:\OPER\M1\2(UX)3U2X)150 BU.do-15A39103 -27- A pesticidal composition comprising at least one compound of formula according to claim 1 as active ingredient, eithr in free form or in the form of an agrochemically acceptable salt, and at least one adjuvant.

6. Method of producing a composition as described in claim 5, in which the active ingredient is intimately mixed with the adjuvant(s).

7. A method for the control of pests in which a compound of formula according to any one of claims 1 to 4 as the active ingredient is applied, in free form or optionally in the form of an agrochemically acceptable salt, to pests or their habitat.

8. Use of a compound of formula according to any one of claims 1 to 4, in free form or optionally in the form of an agrochemically acceptable salt, in the preparation of a composition as described in claim 6.

9. A compound of formula according to claim 1 substantially as hereinbefore described with reference to table 1.

10. A pesticidal composition according to claim 5 substantially as hereinbefore described 20 with reference to the formulation examples. 0 015t *DATED this 15 th day of September, 2003 o* Syngenta Participations AG By DAVIES COLLISON CAVE Patent Attorneys for the Applicants *o 0 0 *0 0 00*