DD267904A5 - SCHAEDLINGSBEKAEMPFUNG PROCESS USING 2-PHENYLIMIDAZOL COMPOUNDS - Google Patents

Abstract

The invention relates to a method for Schaedlingsbekapfung using 2-phenylimidazole compounds of the formula I, which, for example, by converting a compound of general formula I by means of known methods, wherein R2 and R3 are both replaced by hydrogen, in a compound of general formula I in which one or both radicals R 2 and R 3 are not hydrogen, or one of their pesticidally acceptable salts. The compounds prepared according to the invention are used as shipping agents for limb follicles, plant nematodes, helminths and protozoa pests.

Description

Pest control method using 2-phenylimidazole compounds

Antvari ' boy area of the invention

The present invention relates to the use of 2-phenylimidazole compounds against arthropods, plant nematodes, helminths and protozoan pests, compositions containing them and novel 2-phenylimidazox compounds.

C harakteristik the known prior art

2- (2,4-dichlorophenyl) -4,5-dicycloenimidazole is described as having useful herbicidal activity in Japanese Patent Publication No. 52-7434 (1977).

The Japanese Patent No. Ve'röffentlichungs, 50-125031 (1975) discloses that 4 _k 5-dicyanoimidazoles and 2-alkyl-4, fl-dicyanoimidazoles are effective against acarids and have herbicidal and insecticidal effect.

British Patent No. 1,399,291 discloses i-nitroimidazoles which are found to have activity against scale insects or to produce voids; such effective compounds are usable. It is described that these compounds in the 2-position of the imidazole ring a broad upektrum of substituents. on-

finally can carry phenyl. However, no compound is described which has a 2,4-disubstituted phenyl group at the 2-position and the description contains no suggestion that these compounds may exert any activity other than the activity against scale insects

Aim of the invention

The object of the invention is to provide a pest control method using 2-phenylimidazole compounds which have valuable activity against arthropods, plant nematodes, helminths and protozoan pests.

Explanation of the essence of the invention

The object of the invention is to provide a pest control method using 2-phenylimidazole compounds.

Ee was now after intense research and experimentation

Surprisingly found that the 2-phenylimidazole Verblndungen of the general formula I shown below, in the

R ^{x represents} a hydrogen atom or a straight- or branched-chain alkyl group having 1 to 6 carbon atoms optionally substituted by a straight or branched alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl group having 1 to 6 carbon atoms or by a Cyano or carboxy group or substituted by a straight- or branched-chain alkoxycarbonyl group having 2 to 7 carbon atoms,

2 3 10 _# R and R, which may be the same or different, each represents a hydrogen atom or halogen (ie fluorine, chlorine, bromine or iodine), nitro, carboxy or cyano group, a straight- or branched-chain alkoxycarbonyl or alkanoyl group having 2 to 7 carbon atoms or a carbamoyl or sulphamoyl group which may be substituted with one or two straight or branched chain alkyl groups each having 1 to .6 carbon atoms, or an amino group selected from the nitrogen atom having one or two substituents selected from straight- or branched-chain alkyl groups having 1 to 6 carbon atoms and the straight- or branched-chain alkoxycarbonyl- * and alkanoyl groups having 2 to 7 carbon atoms may be substituted,

or a group R, RO, RS, RSO or RSO ₂ , in which R represents a straight- or branched-chain alkyl group having 1 to 6 carbon atoms, which is optionally substituted by one or more halogen atoms, and

Ar represents an optionally substituted 2,4-disubstituted phenyl group of the general formula II in which

4 R and R, which may be identical or different, each represent a halogen atom (eg fluorine, chlorine, bromine or iodine) or a group R, RO, RS, RSO or RSO ₂ , in which R is a straight- or branched-chain alkyl group with 1 to 6 carbon atoms, which is optionally substituted by one or more halogen atoms,

And R, R and R, which may be the same or different, each represent a substituent corresponding to the above definition of R and R, or a hydrogen atom, a hydroxy, carboxy, nitro, cyano or amino group, or a straight- or branched-chain alkylamino group having 1 to 6 carbon atoms which, on the nitrogen atom, have a straight- or branched-chain alkyl group having 1 to 6 carbon atoms, or one or more straight- or branched-chain Alkoxycarbonyl or alkanoyl group having 2 to 7 carbon atoms, or a straight or branched chain alkoxycarbonyl or alkanoyl group having 2 to 7 carbon atoms,

and their pesticidal salts, with the exception of

2 3

those compounds in which R and R are simultaneously hydrogen atoms have valuable activity against arthropods, plant nematodes, helminths and protozoan pests.

It will be understood by those skilled in the art that some of the compounds of general formula I, e.g. those having amino groups tend to react basicly while some of the compounds are e.g. those which have carboxyl groups show rather acidic properties.

0 7 9

The scope of the general formula I includes pesticidal compatible salts of these compounds

, Acids or bases in each case and as far as the context allows, when the compounds of general formula I is mentioned, reference is also made to these salts.

By the term "pesticide-compatible salts" as used in this specification is meant salts with acids or bases known in the art and their suitability for the preparation of salts of biologically active compounds for agricultural or horticultural use is generally accepted. When the application to vertebrates is contemplated for the control of infestation or infestation with arthropods, helminths or protozoa, the salts used are non-toxic. "Non-toxic" in this sense means that salts with acids / bases are used whose anions / cations are harmless in the doses administered to vertebrates and which do not affect the beneficial effect of the cation / anion. Suitable salts with acids include the salts with inorganic acids, e.g. Hydrochlorides, sulfates, phosphates and nitrates and the salts with organic acids such. Acetates. Suitable salts with bases include alkali metal salts, e.g. Sodium or potassium salts, alkaline earth metal salts, e.g. Calcium or magnesium salts and ammonium salts or salts with

ispielweise!

Diethanolamine or triethanolamine.

organic bases, e.g. Amines, for example

Further, it will be apparent to those skilled in the art that the compounds of general formula I in which R represents a hydrogen atom exhibit tautomerism such that the hydrogen atom may be on any of the nitrogen atoms of the imidazole ring, with the forms so circumscribed to greater or lesser extent Proportion can be present and are in a state of dynamic equilibrium with each other. In addition, in some cases, the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ cause optical and / or stereoisomerism. All of these forms are covered by the present invention.

Preferred classes of compounds of general formula I include those compounds

12 3 one or more of the radicals R, R, R and Ar corresponds to the definition below and the

12 3 '

Other radicals R, R, R and Ar of the above definition correspond to: where

(i) R represents a hydrogen atom;

2 3 (ii) R and R are each not hydrogen;

4 6 (iii) Ar is a 2-R 4-R-substituted phenyl group j

optionally having a substituent I which may be the same or different; and is selected from the halogen atoms (in particular chlorine, bromine or iodine), R, RO, RS, RSO or J RSO ₀ , in particular when Ar represents a phenyl group which carries this substituent in the 6-position, more particularly when Ar is a 2,6-dichloro-4-trifluoromethylphenyl group, a 2,6-dichloro-4-trifluoromethoxyphenyl or a 2-chloro-4-trifluoromethylphenyl group;

2 (iv) R represents a halogen atom (preferably bromine) or a nitro, cyano, trifluoromethyl or alkyl group, or a group RO, RS, RSO or RSO.sup.1, in which R is a straight- or branched-chain alkyl group having 1 to 6 Carbon atoms optionally substituted with one or more halogen atoms; (v) R represents a halogen atom (preferably bromine), or a nitro, cyano, trifluoromethyl or alkyl group;

(vi) R represents a halogen atom (preferably chlorine), and (vii) R represents a group R, RO, RS, RSO or RSO ₂ , in which R represents a straight or branched chain alkyl group having 1 to 6 carbon atoms which is substituted with a or more halogen atoms is substituted (from: group).

(preferably R 'represents a trifluoromethyl group)

Compounds of the general formula (I) in which R represents a halogen atom (preferably chlorine) are preferred.

A preferred class of compounds of general formula (I) is that in which R is a

R 2 represents hydrogen, R and R, which may each be identical or different, each represent a hydrogen atom or a halogen atom (preferably bromine) or a nitro, carboxy or cyano group or a straight- or branched-chain alkoxycarbonyl group having 2 to 7 carbon atoms, a carbamoyl or sulfamoyl group which may optionally be substituted by one or two straight- or branched-chain alkyl groups each having 1 to 6 carbon atoms, or an amino group which is substituted on the nitrogen atom by one or two sub-

substituents selected from the straight- or branched-chain alkyl groups having 1 to 6 carbon atoms and the straight- or branched-chain alkoxycarbonyl and alkanoyl groups having 2 to 7 carbon atoms,

or a straight or branched chain alkyl or alkylthio group having 1 to 6 carbon atoms, optionally with one or more

4 halogen atoms is substituted, and R is a halogen atom (preferably chlorine), R is a halogen atom (preferably chlorine) or a straight or branched chain alkyl, alkoxy or alkylthio group having 1 to 6 carbon atoms, optionally with one or more

5 7 halogen atoms is substituted, R and R are water

represent hydrogen atoms and R represents a hydrogen or a halogen atom (preferably chlorine).

A particularly preferred class of compounds of general formula I are those in which

1 2

R represents a hydrogen atom, R represents a trifluoromethyl or trifluoromethoxy group or a methylthio, methylsulphiryl or methylsulphonyl group optionally substituted with one, two or three fluorine atoms and R represents a halogen atom (preferably bromine) or a nitro or cyano group ,

Of particular importance are the following compounds of general formula I: A 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-

dicyanoimidazole B 2- (2,6-dichloro-4-trifluoromethoxyphenyl) -4,5-dicyanoimidazole

C 2- (2-chloro-4-trifluoromethylphenyl) -4,5-dicyano

imidazole D 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylimidazole E 5-bromo-2- (2,6-dichloro-4-trifluoromethylphenyl) -

4- trifluorine thy limidazole F 2- (2,6-dichloro-4-trifluoromethylphenyl) -5-nitro-4-trifluorine thyazlidazole

G 5-Cyano-2- (2,6-dichloro-4-trifluoromethylphenyl) -

imidazole-4-carboxylic acid j

H 5-Cyano-2- (2,6-dichloro-4-trifluoromethylphenyl) -!

imidazole j

4-Bromo-5-cyano-2- (2,6-dichloro-4-trifluoromethyl!

phenyl) imidazole j

J 5-Cyano-2- (2,6-dichloro-4-trifluoromethylphenyl) - j

imidazole-4-carboxyandd K 5-cyano-2- (2 _/ 6-dichloro-4-trifluoromethoxyphenyl, I) -

imidazole-4-carboxamide j

L ethyl 5-cyano-2- (2,6-dichloro-4-trifluoromethylphenyl) imidazole-4-carboxylate

M 2- (2,6-dichloro-4-trifluoromethylphenyl) imidazole

4,5-dicarboxamide ·

N 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dimethylimidazole O 2- (2, 6-dichloro-4-trifluoromethylphenyl) -4-

methylimidazole P 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methyl-5-nitroimidazole

Q 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylimidazole-5-sulphonamide

R 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methyl-

5-methylthioimidazole S 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-nitroimidazole

T 4,5-Dibromo-2- (2,6-dichloro-4-trifluoromethyl-

phenyl) imidazole U 4-bromo-2- (2,6-dichloro-4-trifluoromethylphenyl) imidazole V 4-bromo-2- (2,6-dichloro-4-trifluoromethylphenyl) -

5-nitroimidazole W 2- (2-brothl -4-trifluoromethylphenyl) -4,5-dicyanoimidazole

X, N-diethyl-2- (2,6-dichloro-4-trifluoromethyl-phenyl) -5-cyano-imidazole-4-carboxamide Y 2- (2,3,5,6-tetrachloro-4-trifluoromethylthiophenyl) -4, 5-dicyanoimidazole

Z 4-Amino-5-cyano-2- (2,4-dichlorophenyl) imidazole AA N, N-diethyl-2- (2,4-dichlorophenyl) -5-trifluoromethylimidazole-4-carboxamide BB 4- (te rt. Butoxycarbonylamino.no) -5-cyano-2

(2,4-dichlorophenyl) imidazole CC 5-Cyano-2- (2,4-dichlorophenyl) imidazole-4-carboxylic acid DD 2- (2,4-dichlorophenyl) imidazole-4,5-dicarboxylic acid

The letters A to DD are assigned to the above compounds for purposes of identification and subsequent reference.

Particularly preferred compounds of the general formula I are the compounds: A, E, E, F, T and V.

According to a further feature of the present invention there is provided a method for controlling arthropods, plant nematodes, helminths or protozoan pests in a location comprising the treatment of said location (e.g.

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by application or administration) with an effective amount of a compound of general formula I or one of its pesticidally acceptable salts, wherein the different radicals correspond to the above definition. The compounds of general formula I can be used in particular in the field of veterinary medicine and livestock farming and in the maintenance of public health against arthropods, helminths or protozoa which are internal or external parasites in vertebrates, in particular warm-blooded vertebrates, eg in humans and domestic animals such as cattle, sheep, goats, horses, pigs, poultry, dogs, cats and fish, for example against Acarina , including ticks (eg Ixodes spp., Boophilus spp., Boophilus nicroplus , Amblyomma spp., Hyalomma spp., Rhipicephalu ° spp., Rhipicephalus appendiculus , Haemaphysali: spp., Dermacentor spp., Ornithodorus spp. (eg Ornithodorus moubata) and mites (eg

Damalinia spp., Dermahyssus gallinae , Sarcoptes spp. eg Sarcoptes scabiei, Psoroptes spp., Chorioptes spp., Demodex spp., Eutrombicul a spp.); Diptera (eg Aedes spp., A nopheles spp., Musca spp., Hypoderma spp., Gasterophilus spp., Simulium spp.); Kemiptera (eg Triatoma spp.); Phthiraptera (Damalinia spp., Linognathus spp.); Siphonaptera (Ctenocephalides spp,); Dictyoptera (Periplaneta spp., Blatella spp.); Hymar.cytera (Monomorium pharaonis) ; against infections of the gastrointestinal tract caused by parasitic nematode worms, eg members of the family Trichostrongylidae , Nippostrongylus brasiliensis , Trichinella spiralis , Haemonchus contortus , Trichostrongylus colubriformis, Nematodirus battus,

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Ostertagia circumcincta , 1'richostrongylus axei, Cooper ia spp. and Hymenolep i s nana, -. in the control and treatment of protozoal diseases caused by, for example, Eimeria spp, eg Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix, Trypanosoma cruzi, Leishmania spp, Plasmodium spp, Babes ia.. spp., Trichomonadidae spp., His tomonas spp., Giardia spp., Toxoplasma spp., Entam eba histolytica and Theileria spp .; for the

10. Protection of stored goods, e.g. cereals, including grain and flour, peanuts, livestock feed, timber and household goods, e.g. Carpets and textiles against infestation by arthropods, in particular beetles, including cereal beetles, mats and mites, e.g.

Fphestia spp. (Flour moth), Anthrenus spp. (Carpet beetle) Tribolium spp. (Meal beetle), Sitophilus spp. ( Corn beetle ) and Acarus spp. (Mil'oen), in the control of cockroaches, ants and similar arthropod vermin in afflicted domestic and industrial premises and in the control of mosquito larvae in waterways, taps, wells, containers or other flowing or standing waters; in the treatment of foundations, structures and floors to prevent buildings from being attacked by termites, eg Reticulitermes spp., Heterotermes spp., Coptotermes spp .; in agriculture against adult animals, larvae and eggs of Lepidoptera (butterflies and moths), eg Heliothis spp. such as Heliothis virescens (tobacco pest), Heliothis armigera and Heliothis zea , Spodop tera spp. such as Spodoptera exempta , Spodoptera littoralis (Egyptian cotton worm ), Spodoptera eridania , Mamestra configurata ; Earias spp., Eg

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Earias insulana , Pectinophora spp., Eg Pectinophora gossy game la _f Ostrinia spp. and eg Ostrinia nubilalis (European corn borer), Trichoplusia n ^, Pieris spp. (Cabbage worms), Laphygma spp. Aqrotis and Amathes spp., Wiseana spp., Chilo spp. ( Rice halyard drills), Tryporyza sp. and Diatraea spp. (Sugar cane drill and rice borer), Sparganothis pilleriana Cydia pomonella ( codling moth ), Archips spp., PIuce11a xylostella (cabbage moth) against adult animals and larvae of Coleoptera (beetle), eg Hyothenemus hampei (coffee bean borer ), Hylesinus spp. (Bark beetle), Anthonomus grandis (cotton boll beetle ), Acalymma spp. (Cucumber beetle), Lema spp., Psylliodes spp., Leptinotarsa decernlineata (Colorado potato beetle ), Diabrotica spp. (Cereal root worms ), Gonocephalum spp. (false wireworm), Agriotes spp. ( Wireworms ), Dermolepida and Heteronychus spp. (white larvae), Phaedon cochleariae (mustard beetle), Lissorhoptrus oryzophilus (rice water beetle ), Meligethes spp.

(Pollen beetle), Ceutorhynchus spp., Rltynchophorus and Cosmopolites spp- (cereal root beetle) against Hemiptera eg Psylla spp., Bemisia spp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp., AdeIges spp., Phorodon humuli , A enolamia spp., Nephotettix spp. (Rice leafhopper), Einpoasca spp., Nilaparvata spp., Perkinsiella spp., Pyrilla spp., Aonidiella spp., Coccus spp., Psuedococcus spp., Helopeltis spp. (Mosquito beetle ), Lygus spp., Dysdercus spp., Oxycarenus spp., Nezara spp .; Hymenoptera, eg Athlia spp., And Cephas spp. (Sawflies, Atta spp.); Diptera, eg Hylemyia spp. (Root flies ), Atherigona spp and Chlorops spp., (Halmflies), (Phytomyzä

247904

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spp. ( Leafminer ), Ceratifcis spp. (Fruit flies); Thysanoptera such as Thrips tabaci ; Orthoptera such as Locusta and Schistocerca spp. (Grasshoppers) and barbecues, eg Gryllus spp. and Acheta spp .; Collembola eg Sminthurus spp. and Onychiurus spp. (Springtails) Isoptera eg Odontotermes spp. (Termites), Dermaptera, eg Forficula spp. (Earwigs) and other arthropods that have agricultural significance as zF *. Acari (mites),

10 ^ eg Tetranychus spp., Panonychus »pp. and Bryobia spp. (Spider mites), Eriophyes spp. (Gall mites), Polyphagotarsonemus spp .; Blaniulus spp. (Centipedes), Scutigerella spp. (Zwergfüßer), Oniscus spp. (Drills) and Triops spp. (Crustacea); Nematodes attacking plants and trees of importance in agriculture, forestry and horticulture, such as those attacking the plants directly or spreading bacterial, viral mycoplasmas or fungal diseases in plants, root nodule nematodes such as Meloidogyne spp., Eg Meloidoqyne incognita ); Capsule nematodes such as Globodera spp. (eg Globodera rostochiensis) ; Heterodera spp. (eg 'Heterodera avenae); Radopholus spp. (eg Radopholus similis ); Lesion nematodes such as Pratylenchus spp.

(eg Pratylenchus pratensis) ; B elonolaimus spp. (eg I Belonolaimus gracilis) ; Tylenchulus spp. (eg Tylen- j chulus semipenetrans); Rotylenchulus spp. (eg Rotylenchulus reniformis) ; Rotylenchus spp. (eg, Rotylenchus robustus) ; Helicotylenchus spp. (eg

H elicotylenchus multicinctus) ; Hemicycliophora spp. (eg Hemicycliophora gracilis) ; Criconemoides spp. (eg Criconemoides similis) ; Trichodorus spp. (eg Trichodorus primitivus); Dolchnematodes such as

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Xiphinema spp. (eg Xiphinema diversicaudatum) , '

Longidorus spp. (eg Longidorus elongatus); ι

Hoplolaini spp. (eg Hoplolaimus coronatus); i

Aphelenchoides spp. (eg, Aphelenchoides ritzema-bosi , [ Aphelenchoides besseyi ); Stem and tuber thread

worms such as Ditylenchus spp. (eg Ditylenchus _; dipsaci).

The invention also provides a method for loading In the case of plants, control of arthropods or nematode pests, which requires the use of an effective amount of a compound of the general Formula I or one of their pestxzidverträglichen 'salts on the plants or on the medium in which they grow includes. j

To combat limb foot. and nematodes, the active compound is generally fought to the site j at the arthropod or nematode infestation

is applied, applied in an amount of about j 0.1 kg to about 25 kg of active ingredient per hectare of the treated of the area. Under ideal conditions, this depends on the vermin to be controlled _. lower amount for adequate protection. On the other hand, unfavorable weather conditions, resistance of the vermin and other factors may require that the active ingredient be used in higher proportions.

When the vermin lives in the soil, the mixture containing the active ingredient is evenly distributed over the area to be treated by any conventional method. The application may be

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in general, or in the immediate vicinity of the plants or the seed to be protected from infestation, to the field or area where the fruit grows. The active ingredient can be washed into the soil by spraying water

over the area, but may as well be exposed to the natural effects of rain. During or after use, if desired, the mixture may be mechanically distributed in the soil, e.g. by Pflü-10. or harrows. The application can be made before planting, during planting or after planting but before germination or even after germination.

The compounds of the general formula. may be applied to the soil in solid or liquid compositions to, in principle, control the nematodes living therein, but may also be applied to the foliage to combat, in principle, those nematodes which attack the aerial parts of the plants {eg Aphelenchoides spp. and Ditylenchus spp., named above.)

The compounds of general formula I are effective in the control of vermin living on plant parts remote from the site of application, e.g. leaf-eating insects are killed by the compounds in question that are applied to the roots. 30

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In addition, the compounds can reduce attacks on the plant by effects that repel or make the plant inedible.

The compounds of general formula I are particularly valuable for the protection of crops, forage plants, plantations, greenhouse crops, fruit crops and vineyards, ornamental plants, plantation trees and forest trees, e.g. for cereals (such as maize, wheat, rice and sorghum), cotton, tobacco, vegetables and salads (and beans, cabbages, curcurbits, lettuce, onions, tomatoes and pepper and paprika), crops (such as potatoes, sugar beet, peanuts, Soybean, ulsaat, rapeseed), sugarcane, pasture and fodder plants (such as corn, sorghum, alfalfa), plantation plants (such as tea, coffee, cocoa, bananas, ulpalmen, coconuts, rubber plants, spice plants), orchards and groves (such as drupes and pomes, citrus fruits, kiwifruit, avocados, mangoes, olives and walnuts), vineyards, ornamental plants, flowers and shrubs in hothouses and gardens and parks and forest trees (both deciduous and evergreen) in forests, plantations and nurseries.

They are also valuable for the protection of wood (standing, felled, processed, stored or timber) against the infestation of leaf wasps (eg Urocerus ), beetles (eg Borken, platypodids, lyctids, bostrychids, cerambycids, anobiids) or termites, eg Reticulitermes spp., Heterotermes spp., Coptotermes spp.

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The compounds of the invention can be used for the protection of stored goods such as e.g. Grains, fruits, nuts, spices and tobacco, be it in uncooked or ground form or incorporated into products, against the infestation with moths, beetles and mites. Also protected are stored animal products such as e.g. Hides, hair, wool and feathers in natural or worked form (for example as carpets or textiles) against moth and beetle infestation; they also protect stored fish and stored meat against beetles, mites and flies.

The compounds of general formula I are of particular value in the control of arthropods, helminths or protozoa that are harmful to, or even cause or spread to, humans or pets as pathogens, e.g. the aforementioned pathogens, and in particular the compounds of general formula I are valuable in the control of ticks, mites, lice, fleas, mosquitoes, biting flies, annoying flies and myiotic flies. The compounds of general formula I are particularly useful in the control of arthropods, helminths or protozoa which are present in domestic animals as host animals or which live in or on the skin or suck the blood of the animal, the compounds for this purpose being oral, parenteral , percutaneously or externally.

Coccidiosis, a disease caused by infections with protozoan parasites of the genus Eimeria , is an important potential cause of economic losses to domestic animals and birds, in particular

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those raised or kept under intensive conditions. For example, cattle, sheep, pigs and rabbits can be affected, but the disease is particularly significant in poultry, especially chickens.

This poultry disease is generally spread by birds picking on infectious organisms from manure or contaminated waste, or from soil, or through food or drinking water. The disease is characterized by hemorrhage, accumulation of blood in the cecum, leakage of blood with the excrement, weakness and indigestion. The disease often ends with the death of the animal, whereby the poultry surviving serious infections as a result of the infection has only a significantly reduced market value.

Administration of a small amount of a compound of general formula I or one of its pesticidally acceptable salts, preferably in combination with poultry feed, proves effective or at least greatly reduces the incidence of coccidiosis. The compounds are effective against both the cecal form (caused by E. tenella) and the forms occurring in the intestines ( principally caused by E. acervulina , E. brunetti , E. maxima and E. necatrix) .

The compounds of the general formula I also show an inhibiting effect on the oocysts by reducing their number and / or their sporulation by far.

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The compositions for external use in humans and animals described below, as well as for the protection of stored goods, household goods, possessions and areas in the environment of humans and animals can alternatively be applied to growing; Crops and on sites where useful plants! be used as well as be used as seed dressing. I

i Suitable agents for the use of the compounds

• I

of general formula I include: j

In the case of persons or animals affected or exposed to arthropods, helminths or protozoa, by parenteral, oral or external use of the compositions in which the active substance is used. an immediate and / or lasting effect; over a period of time unfolds against atropods, helminths or protozoa, eg by incorporation into the feed or suitable orally available pharmaceutical preparations, edible baits, salt licks, dietary supplements, infusion mixes, sprays, baths, baths, showers, jets, dusts · 'powder, greases, shampoos, creams, wax-smears, as well as self-treatment systems for livestock; on

the environment in general or specific

where pests are hidden, including stored goods, wood, household goods and domestic and industrial buildings, as sprays, fog, dusts, smoke, wax grease, varnish, varnish, granules and baits, as well as by trickling supply in waterways, wells, storage tanks, and other flowing or stagnant waters; at i pets in the feed to live in their feces

2ί7904

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Combat fly larvae; growing crops as foliar sprays, dusts, granules, and fog; foams; as well as dispersions of finely divided and encapsulated compounds of formula I; as soil and root canal treatment by liquid impregnation solutions, j dusts, granules, smoke and foams; and as a seed! goodboize in the form of liquid slurries and;

Dust. j

The compounds of the general formula I can be used for combating arthropods, i

Helminths or protozoa in the form of composite;

of any type of prior art suitable for internal or external administration to vertebrates or for the application of control of arthropods to any broaching site. areas or areas within and outside | of buildings which as active ingredient least one compound of general formula I in; Compound with one or more compatible diluents or adjuvants suitable for use in the intended use. All of these compositions can be prepared in any manner known in the art.

Compositions suitable for administration \ to vertebrates or man-closing "" preparations, which for oral, parenteral, percutaneous application, for example by pouring or other externals.:

suitable for administration. j

Compositions for oral administration contain one or more of the compounds of general formula I in association with pharmaceutically acceptable carriers or wrappers and include, for example, tahletten, pills, capsules, pastes, gels, medicated drinks, medicated feeds _for fodder-added drinking water, Medicated dietary supplements, slow-release pills or other slow-release drugs

10 _# devices held up in the gastrointestinal tract. Each of these aforementioned compositions may contain the active ingredient encapsulated in microcapsules or coated with acid labile or alkali labile or other pharmaceutically acceptable enteric coatings. Premixed feeds and concentrates contain compounds according to the present invention for use in the preparation of medicament-containing food, drinking water or substances intended for consumption by animals may also be used.

Compositions for parenteral administration include solutions, emulsions or suspensions in any suitable pharmaceutically acceptable vehicle and solid or semi-solid subcutaneous implants and pellets intended to release the drug over a sustained period of time and prepared and sterilized in any manner known in the art can be.

Compositions for percutaneous and external administration include sprays, dusts, baths, baths, showers, jets, fats, shampoos, creams, wax greases or auxiliaries and devices (eg, ear clips) that are externally attached to the animals in such a way that they are localized or systemic control of arthropods is produced.

Solid or liquid baits suitable for combating arthropods contain one or more compounds of general formula I and a carrier or diluent which may contain an appropriate food substance or other substance which may be consumed by the arthropod inducer ;.

Liquid compositions include water-miscible concentrates, emulsifiable concentrates, flowable suspensions, wettable or soluble powders containing one or more compounds of general formula I which may be used to reduce them

are to be treated, with the places or substrates, buildings, storage bins inside and outside of buildings or factory grounds, containers or facilities and industrial plants and standing or flowing waters are counted.

Solid homogeneous or heterogeneous compositions containing one or more compounds of general formula I, e.g. Granules, pellets, briquettes or capsules can be used for standing or

Sites or substrates or sites and substrates that are susceptible to attack by arthropods!

- 23 -

to treat flowing waters for a certain period of time. A similar effect can be achieved

by using trickling or intermittent; supplied water-dispersible concentrates.

measured the above description. I

Compositions in the form of aerosols and aqueous j

aqueous or non-aqueous solutions or dispersions;

which are suitable for spraying, for the formation of mist j

and for spraying with low or ultra-low vowel

lumens can also be used. !

Suitable solid diluents which are used in preparations

can be used by compositions that are \

for the application of the compounds of general J

Include an aluminum silicate, diatomaceous earth, cereal husk, tricalcium phosphate, powdered cork, active compound, carbon black, magnesium silicate,

Clays such as kaolin, bentonite or attupulgite and water j

soluble polymers. Such solid compositions

can optionally one or more compatible!

Wetting agents, dispersants, emulsifiers or 'j

Contain dyes which, when they are solid, also

if they can serve as diluents. i

I

Such solid compositions which are in the form of j

Stubs, granules or wettable powders can be present, are generally prepared by

Impregnation of solid diluents with solutions of compounds of general formula I

in volatile solvents, evaporating the solu- \

and if necessary, this is necessary milling of the products so that powders are obtained and

- 24 -

optionally granulating or contacting the products so as to obtain granules, pellets or briquettes or encapsulating finely divided active ingredient in natural or synthetic polymer such as e.g. Gelatin, synthetic resins and polyamides.

Wetting agents, dispersants and emulsifiers that may be present, especially in wettable

Powders may be those of ionic or nonionic type, e.g. Sulphoricinoleates, quaternary ammonium derivatives or products based on i condensates of ethylene oxide with nonyl and octylphenol or esters of carboxylic acids with anhydrosoric

which are solubilized by etherification of the free hydroxyl groups by condensation with; Ethylene oxide, or mixtures of these types of j agents. Wettable powders may be treated with water immediately prior to use to

to obtain ready-to-use suspensions.

Liquid compositions for the application of |

Compounds of general formula I can be in i

Form of solutions, suspensions and emulsions of!

Compounds of general formula I "'lie,

optionally encapsulated in natural or synthetic polymers, and if desired also j

Wetting agents, dispersants or emulsifiers j

can contain. These emulsions, suspensions i

and solutions can be made under supply .

use of aqueous organic or aqueous j

organic diluents, e.g. Acetophenone, | Isophorone, toluene, xylene, mineral oils, animal 'ι

- 25 ~

or vegetable oils and water-soluble polymers (as well as mixtures of these diluents) which may contain wetting agents, dispersants or emulsifiers of the ionic or nonionic type or mixtures of these, e.g. those of the type described above. Optionally, the emulsions containing the compounds of general formula I may be used in the form of self-emulsifying concentrates which

10 ^ contain the active ingredient dissolved in emulsifying agents or solvents containing emulsifying agents, each of which must be compatible with the active ingredient, wherein the simple addition of water to such concentrates produces ready-to-use compositions.

Compositions containing compounds of the general formula I which can be employed for controlling arthropods, plant nematodes, helminths or protozoan vermin may also contain synergists (eg piperonyl butoxide or sesamex) as well as stabilizing substances, other insecticides, acaricides, plant nematocides , Anthelminticides or anticoccidiosis agents; Fungicides (agricultural or veterinary suitable, e.g., benomyl or iprodione), bactericides, substances which attract or repel arthropods or vertebrates, or pheromones, reodorants, flavors, dyes and other therapeutic adjuncts, e.g. Trace elements.

These may be intended to determine the effect, duration of action, reliability, capacity or, if applicable, the spectrum of

bugs have been struggling to improve or make the compositions useful to others

Functions in the same treated animal or:

Achieve area. j

Examples of other pesticidal compounds which may be included in, or used in conjunction with, the compositions of the invention are: - j

Acephate, chlorpyrifos, demeton-S-methyl, disulfonate, j

Ethoprofos, fenitrothion, malathion, monocrotophos, j

Parathion, phosalone, pirimiphos-methyl, triazophos, j

Cyfluthrin, cypermethrin, deltamethrin, _{fenpropathrin;}

Fenvalerate, permethrin, aldicarb, carbosulfan,

Methomyl, Oxamyl, Pirimicarb, Bendiocarb, Tefluben-

zumon, dicofol, endosulfan, lindane, benzoximate,: cartap, cyhexatin, tetradifon, avermectins, ivermectin, milbemycins, thiophanate, trichlorofon, dichlorvos, diaveridines and dimetridazole.

i

The fight against arthropods, plant. |

nematodes, helminths or protozoan vermin.

voted compositions usually contain j

between 0.00001 and 95 wt.%, in particular between!

0.0005 and 50% by weight of one or more compounds i

of general formula I or active ingredients in total j

(i.e., compounds of general formula I together)

with other substances that are found in arthropods j

and plant nematodes are toxic, as are anthelminti

ticides, anticoccidiosis agents, synergists, trace agents

elements or stabilizers). The actually on ^!

In order to achieve the desired effect, the use of the composition or its application amount is

- 27 -

because of the farmer, livestock owner, doctor or animal ι

doctor, weed control specialist or other specialist i

man selected. Solid and liquid compositions |

for sweeter use in animals, wood, stored;

Goods or housewares contain in the rule |

i is between 0.00005 and 90% by weight, in particular between 0.001 and 10% by weight of one or more compounds; of general formula I. In oral or parental and percutaneous administration in animals j

i 10. contain solid and liquid compositions in

usually between 0.1 and 90% by weight of one or more compounds of the general formula I. Foodstuffs containing pharmaceutical products generally contain between 0.001 and 3% by weight of one or more compounds.

Compounds of the general formula 1. Concentrates and

Additives for mixing with animal feed included _; usually between 5 and 90% by weight, preferably between 5 and 50% by weight of one or more compounds of general formula I. Mineral salt | Licking normally contains between 0.1 and 10 wt.% ^! one or more compounds of general formula I. '

Dust and liquid compounds for the supply!

delivery in livestock, people, goods, buildings or; Areas outside buildings may contain from 0.0001 to 15% by weight, in particular from 0.005 to 2% by weight, of one or more compounds of the general formula (I). Suitable concentrations in treated

Water are between 0.0001 ppm and 20 ppm, in particular between 0.001 ppm and 5.0 ppm of one or more compounds of general formula I and! may also be used therapeutically in fish production at corresponding exposure times. ;

- 28 -

Edible baits may contain between 0.01 and 5% by weight, preferably between 0.01 and 1.0% by weight of one or more compounds of general formula I. For parenteral, oral or percutaneous administration or other forms of administration in vertebrates, the particular dosage of the compounds of general formula I depends on the particular species, the age and health of the vertebrate as well as the nature and degree of current or potential infestation by arthropods , Helminths or protozoan vermin. A single dose of 0.1 to 100 mg, preferably 2.0 to 20.0 mg per kg of body weight of the animal odei dosages of 0.01 to 20.0 mg, preferably 0.1 to 5.0 ing per kg body weight of Tiei.es with ongoing treatment is usually appropriate for oral or parenteral administration. When using mixtures or devices containing a sustained release of the active ingredient, the dosages required over a period of months may be combined and administered to the animals at once.

The following mixture examples illustrate compositions for use against arthropods, plant nematodes, helminths or protozoan vermin containing as active ingredient compounds of general formula I. The compositions described in Blend Examples 1 to 6 may each be diluted with water to give sprayable compositions having suitable concentrations for field use.

- 29 -

Mixing Example 1

A water-soluble concentrate was prepared from 2- {2-6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole 7% w / v.

Ethylan BCP 10% w / v.

and N-methylpyrrolidone up to 100 vol.%

by dissolving ethylan BCP in a portion of the N-methyl-10, pyrrolidone and then adding the drug

under heating and stirring until everything was dissolved. The resulting solution was made up to the appropriate volume with the addition of the remaining solvent

 15

Mixture Example · 2

An emulsifiable concentrate was prepared from

2- (2,6-dichloro-4-trifluoromethyl)

phenyl-4 _; 5-dicyanoimidazole 7% w / v

Soprophor BSU 4% w / v.

Arylan CA 4% w / v. 'j

N-methylpyrrolidone 50% w / v.

and Solvesso 150 up to 100 Vol.%

; by dissolving Soprophor BSU, Arylan CA and the active ingredient in N-methylpyrrolidone and then filling to volume with Solvesso 150.

- 30 -

Mixture example 3

A wettable powder was prepared from

2- (2,6-dichloro-4-trifluoromethylphenyl-4,5-dicyanoimidazole 40% w / v.

Arylan S 2% w / v

Darvan No. 2 5% w / v

U1..3 Celite PF up to 100% by weight

by mixing the ingredients and grinding the mixture in a hammer mill to a particle size of less than 50 μ.

Example of Mention 4 15

An aqueous flowable mixture was prepared

2- (2,6-dichloro-4-trifluoromethylphenyl-4 _; 5-dicyanoimidazole 30% w / v 20

Ethylan BCP. 1% w / v

Sopropon T36 0.2% w / v.

Ethylene glycol 5% w / v.

Rhodigei 23 0.15% w / v

and water up to 100 vol.%

by intimately mixing the ingredients and milling in a ball mill until the mean particle size was less than 3 μ

 30

- 33 -

Mixture example 5

An emulsifiable suspension concentrate was prepared from 2- (2,6-dichloro-4-trifluoromethylphenyl-4,5-dicyanoimidazole 30% w / v.

Ethylan BCP 10% w / v.

Bentone 38 0.5% w / v.

and Solvesso 150 up to 100 Vol.%

by intimately mixing the ingredients and milling in a ball mill until the mean particle size was less than 3 μ

 15

Exemplary embodiment 6

A water-dispersible granule was prepared from

2- (2,6-dichloro-4-trifluoromethylphenyl-4,5-dicyanoimidazole 30% w / v Darvan No. 2 15% w / v ·

Arylan S 8% w / v

and Celite PF up to 100% by weight

by mixing the ingredients, micronizing in a jet mill, and then granulating in a rotary grinder with spraying a sufficient amount of water (up to 10% w / w). The resulting granules were then placed in a F. dutch dryer to remove excess water dried.

- 32 -

Description of the commercial ingredients used in the previous mixtures: -

Ethylan BCP A nonylphenol-ethylene oxide condensate Soprophor BSU A condensate of tristyrylphenol and

Ethylene oxide Arylan CA 70% weight / volume solution of

Calcium dodecylbenzenesulfonate Solvesso 150 Light aromatic C,, .- Solvent Arylan S Sodium dodecylbenzenesulphonate Darvan Sodium lignosulphonate Celite PF Synthetic magnesium silicate carrier Sopropon T36 Sodium salt of a polycarboxylic acid Rhodigel 22 Polysaccharide xanthan gum

Bentone 38 Organic derivative of magnesium montmorillonite

Mixing Example 7 20

A dusty powder can be prepared by intimately mixing

2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole 1 to 10% w / w. Superfine talc up to 100% by weight

This powder may be applied to an arthropod-infested site, e.g. on a dump or debris pile, stored goods or housewares or animals infested by arthropods or where there is a risk of such infestation, the arthropods being

- 33 -

Fighting food. Suitable means for dispersing the powdered powder at the arthropod-infested site are e.g. mechanical blowers, hand-operated vibrators and devices for the self-treatment of livestock.

Mixture example 8

An edible bait can be made by inni-10. mixing of:

2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole 0.1 to 1.0% w / w. Wheat flour 80 l.wt./g.

Molasses up to ICO% w / w

This edible bait can be laid out in one place, e.g. in a house or industrial building, e.g. a kitchen, a hospital, a warehouse or even an area outside a building infested with arthropods, e.g. with ants, grasshoppers, cockroaches or flies, whereby the arthropods are each combated by oral intake of the agent through the diet.

Mixing Example 9 25

A solution containing:

2- (2,6-dichloro-4-trifluoromethyl-j

phenyl) -4,5-dicyanoimidazole 15% w / v. j dimethyl sulfoxide up to 100 vol.% j

can be obtained by dissolving the imidazole compound in a part of dimethylsulfoxide and then

addition of further dimethylsulfoxide and up-

fill to the desired volume, ί

- 34 -

This solution may be administered to arthropod infested animals either percutaneously or by overmolding or after sterilization by filtration through a 0.22 micron polytetrafluoroethylene membrane by parenteral injection at a dosage of between 1.2 and 12 ml solution per 100 kg body weight of the animal.

Mixing Example 10 10

A wettable powder can be prepared from:

2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole 50% w / w. Ethylene BCP (a nonylphenol / ethylene oxide condensate containing 3 moles of ethylene oxide per mole of phenol) 5% w / w.

Aerosil (a microfine particle size silica) 5% w / w. Celite PF (a synthetic magnesium silicate carrier), 40 * w / w.

by adsorbing the ethylan BCP to Aeirosil, blending with the other ingredients and milling the mixture in a hammer mill to give a wettable powder, as with water, to a concentration of the imidazole compound of 0.001%. can be diluted to 2% w / v, and then applied to an arthropod-infested site, for example, by infestation with larvae of two-winged or plant nematodes by spraying, as well as in domestic animals infected with arthropods, helminths or Protozoa are infested or at risk

- 35 -

infestation, by spraying or dipping 'or by oral administration in drinking water, which fights the arthropods, helminths or protozoa.

^!

Mixing Example 11

A slow release pill (bolus) j may be prepared from granules containing a sealant, binder, a slow release agent and 2- (2,6-dichloro-4-trifluoromethyl-phenyl) 4, 5-dicyanoimidazole in varying percentage->

contains alen compositions. By compacting the!

Mix is a bolus with a specific weight i

made of 2 or more, the ruminant house:

animals can be administered orally to within the;

Netzmagens - Vansens to be detained and a ι

continuous slow release of imidazole compounds

bond over a longer period of time, where j

by the infestation of the ruminant by arthropods, |

Helminths or protozoa is combated.

M ischungsbeispiel 12 '

A slow release drug release composition!

can be made from: - j

2- (2,6-dichloro-4-trifluoromethyl-j

phenyl) -4,5-dicyanoimidazole 0.5 to 25% w / w.

iOlyvinylchloride base up to 100% w / w. j

by mixing the polyvinyl chloride base with the imidazole j

ι compound and a suitable plasticizer, e.g. Diocytylphtalate, and melt extruding or hot casting

- 36 -

the homogeneous composition into a suitable form, e.g. Grains, pellets, briquettes or strips, e.g. suitable for addition to stagnant water, or in the case of strips for incorporation in rings or ear tags for attachment to domestic animals, to control insect pests by slow release of the imidazole compound.

Similar compositions can be prepared by replacing the 2- (2 _/ 6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole in the mixing examples with an appropriate amount of another compound of the general formula I.

The compounds of general formula I can be prepared by use or adaptation of known methods, i. Methods used before the filing date or known from the literature.

Compounds of the general formula I, wherein R represents a hydrogen atom, may be reacted with a suitable alkyl halide, e.g. Chloride, bromide or iodide are reacted in the presence of a base to give the corresponding N-alkylated compounds of general formula T in which R represents an optionally substituted alkyl group as described above.

According to a feature of the present invention, compounds of the general formula I in which R is a

2 represents hydrogen, R represents a cyano or optionally substituted carbamoyl group as described above, R represents a cyano group and Ar

- 37 -

corresponds to the above definition, i. links

of general formula III in which R represents a cyano or optionally substituted carbamoyl group as defined above and Ar is as defined above, are prepared within the scope of general formula I by oxidative cyclization of a compound of the general formula

Formula IV wherein R and Ar are as defined above, e.g. in the presence of a quinone, e.g. 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in an inert organic solvent, e.g. Acetonitrile at elevated temperature, e.g. at the reflux temperature of the reaction mixture; or in the presence of chlorine, bromine or iodine, if appropriate in the presence of a buffer reagent, for example sodium acetate, in an inert organic solvent, e.g. Dichloromethane, N-methyl-2-pyrrolidone or dimethylformamide at a temperature between room temperature and the reflux temperature of the reaction mixture or in the presence of N-chlorosuccinimide in the presence of a base, e.g. Triethylamine in an inert organic soive.

Other representative methods for forming the substituted heterocycle include the reaction of the corresponding benzaldehydes with tartaric acid nitrate in the presence of ammonium hydroxide (to produce compounds of general formula I)

1 2 3 are supplied in the R = H, R and R ^β carboxy), with cyanogen in the presence of hydrogen chloride (whereby compounds ά r supplied general formula I ι chloro),

1 2 3 are provided in which R = H, R and R

- 38 -

with a <X-ketoaldehyde (which is optionally prepared in situ from a dibromomethyl alkyl ketone and sodium acetate) in the presence of ammonia (whereby compounds of the general formula T.

1 2

those in which R = H, R = optionally substituted alkyl and R = H) or with dialkylglyoxal in the presence of ammonium acetate (whereby compounds

the general formula I are supplied in which

1 2 3

R = H, R and R = optionally substituted alkyl); or reaction of a compound of general formula V with bromomethyl alkyl ketone in the presence of sodium carbonate and dimethylformamide or alkali metal alkoxide and alkali metal hydroxide (to provide compounds of general formula I)

2 3 ·

in which R = alkanoyl and R = amino) or by reaction of a compound of general formula VI with (optionally substituted amino) acetonitrile hydrochloride in the presence of triethylamine or alkali metal alkoxide in alkanol (whereby compounds of general formula I are obtained in which

2 3

R = cyano and R = amino) or by reaction of a compound of general formula VII with 1- (optionally substituted alkyl) -2-trimethylsilyloxyethylene: in the presence of pyridine in chloroform (yielding compounds of general formula I in which R "= optionally substituted alkyl and R = H) or by reaction of a compound of general formula VIII with ammonium acetate and acetic acid (to provide compounds of general formula I in which R = H,

2 3 R and R = optionally substituted alkyl).

- 39 -

Conversions of General For-> connections

mel I are possible by application or customization! known methods, e.g.

(i) compounds of general formula I in which j

2

each R is either a carbamoyl group

and R represents a cyano group (or I

2 3 ' R represents a cyano group and R represents a car-

2 3

bamoyl group) or R and R both;

each represent carbamoyl groups, R a ι

Represents hydrogen atom and Ar is the above |

can be produced. j

from compounds of general formula III, |

9 I

in which R represents a cyano group and j

Ar of the above description corresponds to j

Hydrolysis, e.g. in the presence of an alkali metal |

hydroxide, e.g. Sodium hydroxide at temperatures ί

between 15 ° C and 100 ⁰ C or in the presence of a!

Alkali metal hydroxide, e.g. Potassium hydroxide in '

Ethanol at reflux,!

(ii) compounds containing amino groups can be prepared by reduction of compounds containing a nitro group, for example by kata.ly- • technical hydrogenation in the presence of 5% palladium on carbon; ^!

(iii) Compounds containing amino groups can be prepared by reaction of unsubstituted th compounds with hydroxylamine; | (iv) Compounds containing carboxy groups can be prepared by hydrolysis of compound

fertilize containing alkoxycarbony! groups, e.g.

 using aqueous solutions of an alkali metal hydroxide; |

(v) Compounds containing alkoxycarbonyl groups can be prepared by esterification of compounds containing carboxy groups or by transesterification of compounds containing other alkoxycarbonyl groups, e.g. through He

overheat with the appropriate alcohol at the reflux temperature of the reaction mixture in the presence of an acid catalyst such as concentrated sulfuric acid, currently;

(vi) compounds containing nitro groups can be prepared by nitration of unsubstituted compounds by heating with a mixture of nitric acid and sulfuric acid at a temperature between 7O ⁰ C and 12O ⁰ C; (vii) compounds containing alkoxycarbonyl groups

can be prepared by solvolysis, eg hydrolysis of compounds containing cyano groups in the presence of an acid catalyst such as concentrated hydrochloric acid; (viii) compounds containing carboxy groups can be decarboxylated, for example, by heating at a temperature between 15O ⁰ C and 25O ⁰ C in an inert organic solvent, such as diethylene glycol;

(ix) Compounds containing halogen atoms can

are prepared by halogenating unsubstituted compounds in an organic solvent such as e.g. Chloroform or acetic acid optionally in the presence of a buffering agent, e.g. Sodium acetate at a temperature

zv / ischen the room temperature and the Rückf Lußtemperatur the reaction mixture;

- 41 -

(χ) Compounds containing chlorine, bromine or iodine atoms can be prepared by diazotization of compounds containing amino groups followed by, e.g. Reaction with aqueous hydrochloric or hydrobromic acid in the presence of copper chloride or copper bromide or with sodium iodide in sulfuric acid; (xi) Compounds containing alkylthio groups can be prepared by reaction of

compounds containing halogen atoms with thiol derivatives in an inert organic solvent such as e.g. Dimethylformamide or by alkylation of thiols (prepared from halogen-containing compounds by, e.g., reaction with

Hydrogen sulfide in the presence of a base such as e.g. Pyrodine or sodium hypochlorite sulfide in an organic solvent); (xii) compounds containing alkylthio groups can be prepared by the reaction of

unsubstituted compounds with (optionally halogen-substituted) Alkylaulphenylhalogeniden optionally in the presence of an organic base or a Lewis acid catalyst at a temperature between ^{0 0} C.

and 8O ⁰ C under increased pressure if necessary;

(xiii) Compounds containing alkylthio groups can be prepared by chlorosulphonation of the unsubstituted compounds

Use of chlorosulfonic acid at elevated temperatures followed by reduction of the corresponding sulfonyl chlorides using zinc chloride in hydrochloric acid

- 42 -

followed by alkylation using

an alkyl halide in the presence of a \

Base, such as e.g. alkali metal hydroxide; j

(xiv) Compounds containing alkylsulphinyl or j

Alkylsulphonyl groups can be produced!

contained by the oxidation of compounds

tend alkylthio groups using a;

oxidizing agent, e.g. Hydrogen per j

oxide or an organic peracid, such as j

e.g. metachloroperbenzoic;

(xv) Compounds containing carbamoyl groups can be rearranged from carbamates, e.g.

using halogen, e.g. Chio-j

chloride or bromide in the presence of an aqueous

Alkali metal hydroxide solution at Tempe- j

between 5O ⁰ C and 100 ⁰ C; I

(xvi) Compounds containing sulphamoyl groups {

can be prepared by chlorosulphon

nierung the unsubstituted compounds j

using Chlorsu! "onic acid at j

elevated temperature and subsequent reaction. |

tion of the corresponding Sulphonylchlorids ι

with ammonia or an amiη in aqueous!

or aqueous alcoholic medium!

(xvii) Compounds containing carbamoyl groups j

can be made from compounds;

containing carboxy groups by conversion to the corresponding acid halides, e.g.

by reaction with thinoyl chloride or di-,

Ethylaminosulphur trifluoride at e / .ner Tem-.

temperature between O ⁰ C and the Rückflußtempe-; with the reaction mixture and then reacting the acid halide with

67904

- 43 -

Ammonia or an amine in an inert organic solvent such as e.g. dichloromethane;

(xviii) Compounds containing amino groups can be prepared from compounds

tend carboxyl groups, e.g. by reaction with diphenylphosphoryl azide in the presence of an alcohol, e.g. 2-methylpropan-2-ol and a base, e.g. Triethylamine in the

10. return the temperature of the reaction mixture and then decompose the carbamate of formula I which has been obtained, e.g. with iodotrimethylsilane in an inert organic solvent, e.g. acetonitrile; (xix) Compounds containing 1,1-difluoroalkyl or Trifluoruiethylgruppen can be prepared from compounds containing alkanoyl. or carboxy groups by reaction with a fluorinating agent, e.g. Sulfur tetrafluoride or a modified reagent,

such as diethylaminosulfur trifluoride and potassium fluoride at a temperature between ⁰ ° C and 100 ^° C in an inert organic solvent such as 2-methoxyethyl ether; (xx) Compounds containing cyano groups can be prepared by dibromination of methyl groups. Use of, for example, N-bromosuccinimide, if appropriate in the presence of a free-radical initiator such as, for example, dibenzoyl peroxide, followed by hydrolysis of the

corresponding dibromomethyl compound to a. Formyl group, subsequent reaction with hydroxylamine, optionally as

_ 67904

- 44 -

Chloride in aqueous alcoholic medium and subsequent dehydration of the corresponding oxime using e.g. phosphorus oxychloride;

(xxi) agriculturally acceptable salts as described above can be prepared by reacting an acidic or basic compound of general formula I with a suitable base or acid. 10

It is useful in the preparation of compounds of the general formula I to apply the abovementioned processes or corresponding treatises in a suitable combination in order to obtain the desired compound, e.g. (viM + (iv) + (viii) + (ix) (whereby compounds of general formula I are

2 3

in which R = cyano and R = halogen).

Compounds of a ^1! Common formula I as defined above, which have not yet been described in the chemical literature with the exception

2 3

Taking the compounds in which R end R is simultaneously a hydrogen atom, form together with their preparation process and compositions containing them, another Mernmal the present invention. Medicated feed containing known compounds of general formula I or their pesticidally acceptable salts and an edible carrier or diluent are also provided by the present invention.

- 45 -

Compounds of the general formula I in which R and R are simultaneously hydrogen atoms form intermediates for the preparation of compounds intended for use in the process according to the invention. These and their production processes are also part of the present invention. Intermediates of the general

2 3

NEN formula I in which R and R are simultaneously hydrogen atoms can be prepared 10. by reaction of the corresponding benzaldehydes with glyoxal in the presence of ammonia or ammonium acetate and optionally subsequent N-alkylation as described above.

Compounds of the general formula IV can be prepared by application or adaptation of known methods, for example by reaction of the corresponding benzaldehyde with a V -> b of the general formula R ⁹ (NH ₂ ) C = C (CN) NH ₂ . The connections

the general formula IV and their preparation are a further part of the present invention.

Compounds of the general formula R (NH ₂ ) CC (CN) NH ₂ are known or can be prepared by application or adaptation of known methods. The following examples illustrate the preparation of compounds of general formula I as shown in FIG. 1 and the reference examples illustrate the preparation of intermediates.

embodiments example 1 Connection A

A solution of 1-araino-2- (2,6-dichloro-4-trifluoromethylbonzylideneamino) -l, 2-dicyanoethylene (3.3 g, 0.01 mol) and 2,3-dichloro-5,6-dicyano-1,4-dione benzoquinone (3.3 g, 0.01 mol) in acetonitrile (75 ml) was stirred at reflux for 48 hours.

Evaporation of the solvent leads to a brown pesticide, which was extracted continuously with boiling toluene «. The solution was evaporated under reduced pressure and the red-brown residue was dissolved in a mixture of ethyl acetate and dichloromethane (1:10) and filtered through silica. Evaporation of the filtrate yielded a brown solid which was triturated with Hoxan, after which the solid was separated by filtration and 2- (2,6-dichloro-4-trifluoropropyl) -4,5-dicyanoimidazole (1.4 g) was obtained as a light brown solid, m.p. 194-195 ⁰ C.

Reference example 1

Diaminomalonitrile (4.4 ^ 0.04 mol) was dissolved in methanol (100 ml) and 2,6-dioichloro-4-trifluoroethyl-1-aldehyde (9.6 g, 0.04 mol) was added with stirring room temperature. The reaction mixture was stirred for 30 minutes and heated at reflux for 1 hour. To

- 46a -

After cooling to 10 ⁶ C, a solid which had formed was filtered off to give 1-amino-2- (2,6-dichloro-4-trifluorothiiethylbenzylideneamino) -l, 2-dicyanoethylene (10.3 g) as a crystalline yellow solids were obtained, F. 218-219 ⁰ C.

- 47 -

Reference example 2

1-Bromo-2,6-dichloro-4-trifluoromethylbenzene (80 g, i

0 _r 27 mol) were dissolved in anhydrous diethyl ether (480 ml) j and the solution was cooled to -78 ⁰ C. It was j butyllithium (2.5 molar solution in hexane, 100 ml) was added dropwise with stirring a nitrogen atmosphere ivi I, while the temperature was kept below -7O ⁰ C j. After another hour at -78 ° C!

was stirred, N-formylpiperidine (30.8 ^g,? 0.27 mol) was added dropwise. The mixture was stirred at -78 j ⁰ C overnight and was then allowed to di.ese j slowly to ⁰ ° C warm up. Hydrochloric acid (2 molar, 290 ml) was added dropwise to the solution

added with ice cooling. The two phases were

and the organic phase was washed with water, dried over anhydrous sodium sulphate and evaporated to dryness. The oily residue!

'Was dissolved in a mixture of ethyl acetate and petroleum spirit ι (boiling point 60-8C ¹ C) (1: 10) and |

the solution was filtered through a silica gel column. Evaporation of the filtrate and distillation of the resulting oil gave 2,6-dichloro-4-trifluoromethylbenzaldehyde (43.7 g) as a colorless liquid,

Boiling point 115 ^° C. at 4 mm Hg.

Reference Example 3

Nitrosylsulfuric acid prepared from sodium nitrite (69 g, 1 mol) and concentrated sulfuric acid

(600 ml) was added dropwise with stirring to a cooled solution of 2,6-dichloro-4-trifluoromethylaniline (230 g, 1 mol) in glacial acetic acid (1250 ml)

- 48 -

15-20 ⁰ C added. The mixture was stirred for 1 hour at room temperature. The diazonium mixture was

slowly into a solution of copper bromide (143.4 g, j

1 mole), hydrobromic acid (49%, 1 1) and ice!

(approximately 1000 g) poured with such a j

schwinaigkeit that the temperature of 35 ⁰ C is not exceeded:

step. After one hour, the mixture with ι

Steam distilled, with 1 liter of distillate j

which was diluted with water (3 l) |

_t and with diethyl ether (2 × 500 ml) was extracted. The organic fractions were combined and

with aqueous sodium hydroxide solution (2 M, 2 × 250 ml) j

and water (250 ml), over anhydrous'

Dried sodium sulfate and added to dryness ί

evaporated. The oily residue was distilled and!

thereby l-bromo-2,6-dichloro-4-trifluoromethylbenzene \

(256.8 g) as a colorless liquid, boiling point · ι

74-78 ° C at 6 mm Hg. ;

example 2

Compounds B and C '

The procedure was the same as described above under Example 1, except that 1-amino-2- (2,6-dichloro-4-trifluoromethylbenzylideneamino) -1,2-dicyano-ethylene was replaced by the following starting materials. it produced: - j

2- (2,6-dichloro-4-trifluoromethoxyphenyl) -4,5-dicyano

imidazole, which was recrystallized from toluene as an off white solid, mp 119.5 to 122.5 ⁰ C, from 1-amino ~ 2- (2,6-dichloro-4-trif luorinethoxybenzylidenamino) -l, 2-dicyanoethylene; and

- 49 -

2- (2-chloro-4-trifluoromethylphenyl) -4,5-dicyano-;

imidazole / which was recrystallized from toluene as a j

cream-colored solid, mp. i63-164 ° C, of l-Asuno- | 2- (2-chloro-4-trifiuormethylbenzylidenamino) -1,2-di-

eyanoethylen. j

Reference Example 4 ;

The procedure was repeated as described above under Example 1, but 2,6-dichloro-4-trifluoromethylbenzaldehyde was replaced by the starting materials mentioned below, to prepare: -j 1-amino-2- (2,6-) 'iichloro-4-trifluoromethoxybenzylidene \ amino) -1,2-dicyanoethylene as a yellow crystalline _: solid, mp 108-112 ⁰ C, from! 2,6-dichloro-4-trifluoromethoxybenzaldehyde; and l-amino-2- (2-chloro-4-trifluormethoxybenzyliden- j amino) -1,2-dicyanoethylene as a yellow crystalline solid, m.p. 197-199 ⁰ C, 4-trifluoromethoxybenzaldehyde of 2-chloro ~.

Reference Example 5

The procedure was the same as described above under reference example 2, except that 1-bromo; 2,6-dichloro-4-trifluoromethylbenzene was replaced by the following starting materials, I

i were produced: - ι

2,6-dichloro-4-trifluoromethoxybenzaldehyde as pale; yellow liquid, boiling point 113 ⁰ C at 20 mm Hg from 1-bromo-2,6-dichloro-4-trifluoromethoxybenzene; and i 2-chloro-4-trifluoromethylbenzaldehyde as a colorless liquid, bp 67-71 ⁰ C at 8 mm Hg from; l-bromo-2-chloro-4-trifluoromethylbenzene. i

- 50 -

Re f erenzbeispie l 6

The procedure was the same as described above under Reference Example 3 except that 2,6-dichloro-4-trifluoromethylaniline was replaced by the following starting materials, wherein:

l-3rom-2,6-dichloro-4-trifluoromethoxybenzene as a colorless liquid, bp 54-58 ⁰ C at 3 mm Hg from 2,6-dichloro-4-trifluoromethoxyaniline; and 1-bromo-2-chloro-4-trifluoromethylbenzene as a colorless liquid, bp 55-58 ⁰ C at 8 mm Hg from 2-chloro-4-trifluoromethylaniline.

Example 3 Connection D

(59.4 g, 0.22 mol) was added to a solution of sodium acetate trihydrate (59.8 g, 0.44 mol) in water (200 ml) and the resulting solution was heated on a steam bath for 30 minutes. After cooling to room temperature, the turbid solution was added with stirring to a solution of 2,6-dichloro-4-trifluoromethylbenzaldehyde (48.6 g, 0.2 mol) in methanol (500 ml) and aqueous ammonia (33%, 250 ml ) and the red suspension was stirred at room temperature overnight. The supernatant liquid was decanted from the insoluble resin and concentrated by evaporation to one quarter of the volume. Water (200 ml) was added and the solid was filtered off and from a mixture of

- 51 -

Methanol and water, recrystallized, to give 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylimidazole (14.0 g) was obtained as a light brown solid, m.p. 213-215 ⁰ C.

 5

Example 4 Connection E

A solution of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylimidazole (0.7 g, 0.002 mol) and bromine (0.32 g, 0.1 mL, 0.002 mol) in glacial acetic acid (5 mL was stirred and heated at reflux for 2 hours. The cooled suspension was poured into ice-water (50 ml) and the resulting solid was filtered off and washed with water. The solid was dissolved in glacial acetic acid (5 ml) and bromine was added (0.32 g, 0.1 ml, 0.002 mol). The mixture was stirred and heated at reflux for 2 hours, cooled and poured into cold water (50 ml). The solid was filtered off and washed well with water to give 5-bromo-2- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylimidazole (0.6 g) as a white solid, mp 295 ° C with decomposition.

Example 5

Connection F 30

A mixture of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylimidazole (1.0 g, 0.0027 mol) in fuming nitric acid (95%, 1 ml) and fuming sulfuric acid (30% strength by weight) , SO ₃ ~ free, 1 ml)

0 7 9

- 52 -

stirred and heated at 12O ⁰ C for 3.5 hours. The mixture was poured into cold water (50 ml) and the solid was filtered off and washed with water. The resulting solid was purified by chromatography on silica gel, eluting with a mixture of ethyl acetate and n-hexane (1: 5) to give 2- (2,6-dichloro-4-trifluoromethylphenyl) -5-nitro-4-trifluoromethylimidazole ( 0.7 g) as an off-white solid was obtained, mp 244-252 ⁰ C.

Example 6 Compound G

A solution of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole (25.3 g, 0.08 mol) in absolute ethanol (80 ml) and concentrated hydrochloric acid (30 ml) was refluxed Heated for 69 hours. The mixture was poured into cold water (200 ml) and extracted with dichloromethane (2 × 150 ml). The combined organic phases were extracted with saturated sodium bicarbonate solution (2 × 200 ml), which was acidified carefully to pH 3 and extracted with dichloromethane (100 ml). The aqueous phase was acidified to pH 1 and extracted with ethyl acetate (2 × 100 ml), washed with water (100 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The resulting resin was treated with dichloromethane (50 ml) and evaporated to dryness to give 5-cyano-2- (2,5-dichloro-4-trifluoromethylphenyl) -imidazole-4-carboxylic acid (6.31 g) as a was broken white solid which decomposed at 80 to 13O ⁰ C.

- 53 -

Example 7 Compound H

A solution of 5-cyano-2- (2,6-dixchloro-4-trifluoromethylphenyl) -imidazole-4-carboxylic acid (7.09 g, 0.02 mol) in diethylene glycol (70 ml) was stirred and brought to 17O ⁰ C under heated in an atmosphere of nitrogen for 36 hours. The reaction mixture was cooled to room temperature and 150 ml of water was added. The reaction mixture was extracted with ethyl acetate (2 × 100 ml), washed with water (50 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The resulting solid was purified by chromatography on silica gel (60-80 ⁰ C boiling point) with a mixture of ethyl acetate and petroleum ether (1: 1) and eluted from a mixture of ethyl acetate and petroleum ether (b.p. 60-80 ⁰ C) recrystallized, so that 5-cyano-2- (2,6-dichloro-4-trifluoromethylphenyl) imidazole (2.15 g) was obtained as a white solid of mp 210-212 ° ^C.

Example 8 Compound I

A mixture of 5-cyano-2- (2,6-dichloro-4-trifluoromethylphenyl) imidazole (1.0 g, 0.0033 mol) and bromine (1.9 g, 0.64 ml, 0.13 mol) in 1,1,2,2-tetrachloroethane (20 ml) was stirred and heated at 9O ⁰ C for 7 hours. Ethyl acetate (50 ml) was added and the solution was washed with water (50 ml) and with aqueous sodium metabisulphite solution (50 ml) and

6 7 9

- 54 -

again with water (50 ml) and then dried over anhydrous sodium sulfate and evaporated to dryness. The solid residue was purified by chromatography on silica gel eluting with a mixture of ethyl acetate and petroleum ether (b.p. 60-80 ⁰ C): was eluted using 4-bromo-5-cyano-2- (2,6- (3 10) dichlor4-trifluornethylphenyl) imidazole (2.15 g) was obtained as a white solid with F. 270.5 to 272 ⁰ C.

Example 9 Compounds J and K

A mixture of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole (3.31 g, 0.01 mol) and sodium hydroxide (1.0 g, 0.025 mol) in water (10 ml). was stirred at 40 ⁰ C overnight. Concentrated _% hydrochloric acid was added to the mixture and the precipitated solid was filtered off and purified by medium pressure liquid chromatography (mplc) on silica gel, eluting with a mixture of ethyl acetate and dichloromethane (1: 1). Umkristallisacion of the white solid with a mixture of ethyl acetate and petroleum (b.p. 60-80 ⁰ C) (1: 1) gave 5-cyano-2- (2,6-dichloro-4-trifluormethy phenyl!) Imidazole-4-carlo acid (0.61 g), mp 254-255 ⁰ C as a white solid.

The procedure was the same, except that 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole was replaced by 2- (2,6-dichloro-4-trifluorourethoxyphenyl) 4,5- dicyanoimidazole replaced:

5-Cyano-2- (2,6-dichloro-4-trifluoromethoxyphenyl) -imidazole-4-carboxylic acid was obtained as a white solid with mp 220-222.5 ° C.

- 55 -

Example 10 Compound L

A mixture of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole (3.3g, 0.01mol), ethanol (10ml) and concentrated hydrochloric acid, 10ml) stirred and heated at reflux for 24 hours. After cooling the mixture, it was poured into water (50 ml) and extracted with dichloromethane (2 × 50 ml). The combined extracts were washed with water (50 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by MPLC on silica, wobai with a mixture of ethyl acetate and petroleum (b.p. 60-80 ⁰ C) (1: 1), to afford ethyl 5-cyano-2- (2,6-dichloro-4 -trifluoromethylphenyl) -imidazo1-4-carboxylate (0.35 g) was obtained with mp 180-181 ⁰ C, which after recrystallization from a mixture of toluene and petroleum (boiling point 60-80 ⁰ C). (1: 2) gave a white solid.

Example 11 25

Connection M

A mixture of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole (3.3 g, 0.01 mol) and potassium hydroxide (85%, 1.64 g, 0.025 mol) in ethanol (20 ml) and water (2 ml) was heated at reflux for 3.5 hours. After cooling the mixture, it was poured into water (100 ml) and acidified to pH 1 by adding conc.

- 56 -

trated hydrochloric acid. The solid obtained was abfiltr.iert and dried at 80 ⁰ C and 10 mm Hg, to give 2- (2,6-Oichlor-4-trifluoromethylphenyl) -imidazole-4,5-dicarboxamide (0.6 g), m.p. 306-308 ° C when an off-white solid was obtained.

Example 12 Connection N

A mixture of 2,6-dichloro-4-trifluoromethylbenzaldehyde (5 g, 0.02 mol), butane-2,3-dione (1.7 g, 0.02 mol), ammonium acetate (16.0 g, 0, 2 moles) and acetic acid (40 ml) was heated at reflux for 6 hours. The mixture was evaporated to a small volume and poured into water (100 ml). The mixture was then neutralized to pH 7 and the solid precipitated was filtered off to give 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dimethylimidazole (0.5 g), m.p. 282 ⁰ C, after recrystallization from a mixture of toluene and petroleum ether (boiling point 60-80 ⁰ C) (1: 1) as a white solid

was obtained. '!

Example 13 !

!

Compound O

Pyruvic aldehyde (40% aqueous solution, 50 ml) was added dropwise to a solution of 2,6-dichloro-4-trifluoromethylbenzaldehyde (12.15 g, 0.05 mol) in methanol (150 ml) and aqueous ammonia (30 % strength,

207904

100 ml) with stirring and heating to the reflux temperature. The mixture was stirred and heated at reflux temperature for 2 more hours, cooled, and the supernatant solution was separated from the rubbery glass. The solution was evaporated and extracted with dichloromethane (3 × 100 ml). The combined extracts were washed with water (c, 75 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by mplc on silica / eluting with a mixture of ethyl acetate and dichloromethane (1: 4) to give 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylimidazole (1.7 g), F. 211-212 ⁰ C, UNR after recrystallization from a mixture of toluene? Petroleum ether (60-80 ⁰ C) (1: 2) as a broken white solid was obtained.

Example 14 Connection P

A mixture of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylimidazole (1.0 g, 0.003 mol), nitric acid (70% w / w, 1 ml) and sulfuric acid (98% w / w). weight, 1 ml) was stirred and heated to 75 ⁰ C for 4 hours and then heated to .100 ⁰ C for 2 hours. After cooling, the reaction mixture was added to a mixture of ice and water (20 ml) and the precipitated solid was filtered off.

Recrystallization from toluene gave 2- (2,6-dichloro-4-trifluormethylpheny]) - 4-methyl-5-nitroimidazole (0.66 g), Fv 316.5 to 317.5 ⁰ C as a white solid.

- 58 -

Example 15 Compound Q

An aqueous ammonia solution (approximately 33% w / w 1.2 ml) was added dropwise with stirring to a solution of 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methyl-imidazole-5-sulphonyl chloride (2, 0 g, 0.005 mol) in dioxane (15 ml) and the mixture was stirred for 3 hours. The mixture was poured into water (50 ml) and extracted with diethyl ether (3 × 25 ml). The combined extracts were washed with water (2 × 50 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by MPLC on silica, eluting with a mixture of ethyl acetate and petroleum ether (60-80 ⁰ C) (1: 2) was eluted. Umkr ^ stallisation from a mixture of ethyl acetate and petroleum ether (60-80 ⁰ C) (1: 3) gave 2- (2,6-dichloro-4-triflucrmethylphenyl) -4-methylimidazole-5-sulphonamide (0.45 g) , F. 266-267 ⁰ C, as an off-white solid.

Example 16 Connection R

A solution of stannous chloride dihydrate (18.62 g, 0.08 mol) in hydrochloric acid (36% w / w, 16 ml) was added dropwise with stirring to a dispenser of 2- (2,6-dichloro-4-trifluoromethylphenyl) - stirred for 4-methyl-imidazol-5-sulphonyl chloride (6.65 g, 0.017 mol) in acetic acid (100 ml) in a nitrogen atmosphere, was heated to 7O ⁰ C. Stirring and heating

- 59 -

to 70 ⁰ C was continued for 22 hours. After cooling, the mixture was poured into a mixture of water (350 ml) and hydrochloric acid (36% w / w, 5.3 ml) and extracted with ethyl acetate (3 × 100 ml). The combined extracts were washed with water (2 x 10 & * ml) and dried over anhydrous sodium sulfate and evaporated to dryness. The residue was dissolved in an aqueous sodium hydroxide solution (20% w / w, 20 ml) and filtered off to remove the insoluble material. The solution was diluted with water (70 ml) and warmed with iodomethane (9.3 g, 0.065 ml) with stirring in a nitrogen atmosphere. After 22 hours, the mixture was extracted with ethyl acetate (4 × 50 ml). The combined extracts were washed with water (2 × 50 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by MPLC on silica, eluting with a mixture of ethyl acetate and petroleum ether (boiling point 60-80 C ⁰⁾ (1: 5) was eluted to give, after recrystallization from toluene 2- (2,6-dichloro-4-tr -fluoromethylphenyl) -4-methyl-5-methylthioiir, idazole (0.18g), m.p. 243-244 ⁰ C as a white solid.

Reference Example 7

2- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylimidazole (1.0 g, 0.0034 mol) was added portionwise to chlorosulfonic acid (3 ml) and the mixture was stirred at 100 ^° C. for 2 hours and heated. After cooling, thionyl chloride (0.2 ml) was added and the mixture was again heated at 100 ^° C. for 2 hours. The mixture was vorsizntig on ice (20 g) "

247904

- 60 -

and extracted with ethyl acetate (2 × 20 ml). The combined extracts were washed with water (20 ml), dried over anhydrous sodium sulfate and evaporated to dryness. Recrystallization from a mixture of ethyl acetate and petroleum ether (b.p. 60-80 ⁰ C) (I: 3) gave 2- (2,6-dichloro-4-trifluormethylphe iyl) ^ - methyl-imidazol-S-sulphonyl chloride (0.21 g) , F. 227-23O ⁰ C as a broken white. solid fuel

 10th

Example 17 Compound S

A mixture of 2- (2,6-dichloro-4-trifluoromethylphenyl) -imidazole (5.62 g, 0.02 mol), nitric acid (70% w / w, 5.6 ml) and sulfuric acid (98% w / w). Weight, 5.6 ml) was stirred and heated to 70 ^° C. for a total of 51 hours. After cooling, the reaction mixture was poured into a mixture of ice and water (approximately 75 ml) and the precipitated solid was filtered off. It was purified by mplc on silica eluting with a mixture of ethyl acetate and dichloromethane (1:20) to give 2- (2,6-dichloro-4-trifluoromethylphenyl) -4-nitroimidazole (4.21 g). F. was obtained from 254 to 255 ⁰ C as a cream crystalline solid.

Example 18 30

Connection T

N-bromosuccinimide (5.07 g, 0.028 mol) was added portionwise to a solution of 2- (2,6-dichloro-4-trifluoro-

I - 61 -!

methylphenyl) imidazole (4.0 g, 0.014 mol) in chloroform (300 ml) with stirring. Stirring was continued for 6 hours and the precipitated solid was filtered, so that 4,5-dibromo-2- (2,6-dichloro-4-trifluoromethylphenyl) imidazole (4.46 g), mp 328-329 ⁰ C, when an off-white solid was obtained.

Example 19 Connection U

A solution of N-bromosuccinimide (0.63 g, 0.0036 mol) in dimethylformamide (dried over 4A molecular sieve, 18 ml) was added dropwise with stirring to a solution of 2- (2,6-dichloro-4-trifluoromethylphenyl) -. imidazole (1.0 g, 0.0036 mol) in dimethylformamide (dried over

4A molecular sieve, 18 ml) was added and heated for 7 hours. The mixture was (180 ml) was poured into water and extracted with dichloromethane (5 30 ml χ) extre ^v iiert. The combined extracts were washed with water (3 × 50 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by MPLC on i silica, eluting with a mixture of ethyl acetate and petroleum ether (b.p. 60-80 ⁰ C) (3: 5) j

eluisrt, so that 4-bromo-2- (2,6-dichloro-4-trifluoromethylphenyl) -imidazole (0.17 g), mp 224-225 ° C as! broken white solid was obtained.

Reference Example 8

Glyoxal (40% w / w aqueous solution, j 160 ml 1.1 mol) was added dropwise with stirring to a mixture of 2,6-dichloro-4-trifluoromethyl-

2 (57904

- 62 -

Benzaldehyde (48.6 g, 0.2 mol), methanol (600 ml) j and ammonia (33% w / w aqueous solution, 400 ml) over a period of 4 hours! added, the mixture was heated to reflux temperature. The mixture was stirred and heated to reflux for 2 more hours, cooled and the methanol was removed by evaporation. removed. The aqueous residue was washed with dichloromethane ^! than (5 χ 250 ml) extracted and the combined; Extracts were washed with water (3 × 250 ml),

• ι

dried over anhydrous sodium sulfate and added to the j

Dry evaporated. The residue was replaced by j

mplc cleaned on silica, with one!

Mixture of ethyl acetate and dichloromethane (1:10) I eluted, wherein after recrystallization from

Ethyl acetate 2- (2,6-dichloro-4-trifluoromethylphenyl) -j

imidazole (6.24 g), mp 193-194 ° C as a light brown |

Solid was obtained. ;

Example 20 j

Connection V

A mixture of 4-bromo-2- (2,6-dichloro-4-trifluoro-j

methylphenyl) imidazole (0.9 g, 0.025 mol), nitric j

acid (70% w / w, 1 ml) and sulfuric acid!

(98% w / w, 1 ml) was stirred and i

7O ⁰ C heated for 7.5 hours. After cooling, the mixture was added to a mixture of ice and water (50 ml). The precipitated solid was filtered off and purified by mplc on silica, where! with a mixture of ethyl acetate and petroleum ether

26790t

- 63 -

(Boiling point 60-8O ⁰ C) (1: 5) was eluted, so that 4-bromo-2- (2,6-dichloro-4-trifluoromethylphenyl) -5-nitroimidazole (0.2 g), F. 292- 293 ⁰ C, when an off-white solid was obtained. 5

Example 21 Compounds W and Y

The procedure was the same as described above in Example 1, except that 1-amino-2- (2,6-dichloro-4-trifluoromethylbenzylideneamino) -1,2-dicyanoethylene was replaced by the following starting materials to produce: - 2- (2-bromo-4-trifluoromethylphenyl) -4,5-dicyano-imidazol ei.i as a white solid after trituration with hexane-ethyl acetate, mp 139-14O ⁰ C, of I-amino-2- (2 -Bromo-4-trifluoromethylbenzylideneamiro) -1,2-dicyanoethylene; and 2- (2,3,5,6-tetrachloro-4-trifluoromethylthiophenyl) -4,5-dicyanoimidazole prepared from toluene was recrystallized and as a white solid, |

ι F. 245-246.5 ° C, was obtained from l-amino-2- |

(2,3,5,6-tetrachloro-4-trifluoromethyl.'thiobenzylideneamino) -1,2-dicyanoethylene

 25

Reference Example 9

The same procedure was followed as described above in Reference Example 1, but 2,6-dichloro-4-trifluoromethylbenzaldehyde was replaced by the following starting materials to produce:

- 64 -

1-amino-2- (2-bromo-4-trifluoromethylbenzylideneamino) -1,2-dicyanoethylene as a sticky yellow solid from 2-bromo-4-trifluorine of benzaldehyde; 1-amino-1,2-dicyano-2- (2,3,5,6-tetrachloro-4-trifluoromethylthiobenzylideneamino) ethylene as a yellow one

crystalline solid, recrystallized from toluene.

F. 191-191.5 ⁰ C off

2,3,5,6-tetrachloro-4-trifluormethjlthiobenzaldehyd.

Reference Example 10

2,3,5,6-tetrachloro-4-trifluormethylthiobenzylbromid

(6.48 g, 0.016 mol) was added to a mixture

of 2-nitropropane (1.95g, 0.021mol) and sodium ethoxide in ethanol (from sodium 0.36g, 0.016mol, in ethanol, 95ml). The mixture was stirred at room temperature for 66 hours and evaporated to dryness. The residue was washed with water (50 ml)! and extracted with diethyl ether (2 × 50 ml). ; The combined extracts were washed with aqueous sodium hydroxide solution (5%, 50 ml), water (2 × 75 ml), dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was purified by mplc on silica, using

η-hexane was eluted and 2,3,5,6-tetrachloro-4-trifluoromethylthiobenzaldehyde (2.79 g), mp 98.5-100 ⁰ C was obtained as a white solid. I

Reference Example 11 i

It was carried out in the same manner as described above in Reference Example 10, but I was 2,3,5,6-tetrachloro-4-trifluoromethylthiobenzyl bromide ί

- 65 -

replaced by the following starting materials, wherein:

2-bromo-4-trifluoromethylbenzaldehyde as a low viscosity oil ZnmR (CDCl-) chemical shift 7.5-8.2 ppm (multiplet, 3H); 10.3 ppm (s, 1H) 7 from 2-bromo-4-trifluoromethylbenzyl bromide.

Reference Example 12

A mixture of 2, 3,5,6-tetrachloro-4-trifluoromethylthiotoluene (13.46 g, 0.041 mol) and N-bromosuccinimide (7.26 g, 0.041 mol) in carbon tetrachloride (34 ml) was stirred and refluxed 21 Heated for hours. After cooling, the mixture was filtered and the filtrate was washed with an aqueous solution of sodium! hydroxide (5%, 2 × 100 ml), water (100 ml) and dried over anhydrous magnesium sulfate and evaporated to dryness. Umkristallierung of the residue gave 2,3,5,6-tetrachloro-4-trifluoromethyl-j thiobenzylbromid (8.17 g), mp 117-118 ⁰ C as a white crystalline solid .. j Eh was in the same | However, 2,5,5,6-tetra-chloro-4-trifluoromethyl-toluene was replaced by the following starting material to give: 2-bromo-4-trifluoromethylbenzyl bromide as a slightly yellow liquid yellow oil from 2-bromo-4-trifluoromethyltoluene.

2-methyl-5-trifluoromethylaniline (10.1 g) was (iq 50%, 50 ml) in 3romwasserstoffsäure and treated with sodium nitrite (2.8 g) at 0-5 ⁰ C treated. The diazonium solution was treated with copper bromide (8.6 g) and dissolved in hydrobromic acid (50 ml), and man

- 66 -

allowed the solution to warm to room temperature, i

in order subsequently to subject them to steam distillation.

toss. The distillate was extracted with ether (3 × 100 ml) and the resulting combined extracts

were filtered over sodium sulfate and evaporated to give an oil which was distilled

wherein 2-bromo-4-trifluoromethyltoluene (9.5 g),.

K. 98-101 ° C / 45 mm Hg. j

2-Methyl-5-trifluoromethylnitrobenzene (14.8 g) was dissolved in ί

Dissolved ethanol (100 ml) and hydrogenated at room temperature and under pressure in the presence of palladium on carbon (10%, 0.5 g). The solution was filtered and

evaporated to dryness, so cat-2-methyl-5-tri- j

fluoromethylaniline (10.1 g) as a pale yellow oil!

was obtained. '

4-trifluoromethyl toluene (12.8 g) was added at 60-70 ⁰ C m.it a mixture of concentrated nitric acid

(25 ml) and concentrated sulfuric acid (25 ml)

Treated for 5 hours. The solution was poured onto ice (0.5 liter) and extracted with ether (3 × 100 ml). The combined ether extracts were washed with water, dried over sodium sulfate,

filtered and evaporated to dryness, so that

2-methyl-5-trifluoromethylnitrobenzene (14.8 g) was obtained as a pale yellow oil.

4-Trifluoromethyl benzaldehyde (20.0 g) was dissolved in acetic acid (100 ml) and treated with hydrogen in the presence of platinum (0.5 g) at room temperature and under pressure for 10 hours. The solution was filtered, poured into water (400 ml) by addition of a

- 67 -

aqueous sodium hydroxide solution (2 M) and extracted with ether (3 × 100 ml). The combined extracts were washed with water (2 × 100 ml), dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was distilled to give 4-trifluoromethyl toluene (14.3 g), boiling point 131-132 ⁰ C as a colorless mobile liquid was obtained.

Reference Example 13

Chlorine gas was passed through a mixture of 4-trifluoromethylthiotoluene (10 g, 0.052 mol) and anhydrous iron chloride (2.3 g, 0.014 mol) in dry dichloromethane (300 ml) over a period of 1.7 hours, during which time the Temperature to 3O ⁰ C increase. Nitrogen was passed through the mixture to remove the excess chlorine and then the mixture was washed with water (4 × 200 ml), dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was recrystallized from aqueous ethanol (1: 1) to give 2,3,5,6-tetrachloro-4-trifluoromethylthiotoluene (16.25 g), mp 49.5-50.5 ⁰ C as colorless prisms ,

At game 22

Connection Z 30

A solution of iodotrimethylsilane (2.83 g, 0.014 mol) in acetonitrile (5 ml) was added dropwise with stirring to a suspension of 4- (tert-butoxycarbonylamino) -

- 68 -

5-cyano-2- (2,4-dichlorophenyl) imidazole (5.0 g, 0.014 mol) in acetonitrile (250 mL) was added, keeping the temperature at about ⁰ ° C. The mixture was stirred at room temperature for 48 hours and the precipitated beige solid was filtered off. The solid was purified by mplc on silica eluting with a mixture of ethyl acetate and hexane (1: 2) and, after recrystallization from ethanol, an off-white solid 4-amino-5-cyano-2- (2,4- dichlorophenyl) imidazole (1.35 g), mp 223-225 ⁰ C obtained.

Example 23 Connection BB

A mixture of 5-cyano-2- (2,4-dichlorophenyl) imidazole-4-carboxylic acid (40.0 g, 0.142 mol), diphenylphosphoryl azide (37.0 g, 0.142 mol) and triethylamine (14.4 g, 19.8 ml, 0.142 mol) in 2-methyl-2-propanol (dried by distillation over calcium hydride, 1400 ml) was heated at reflux for 24 hours. · After cooling, the mixture was filtered and | Filtrate was zn: evaporated to dryness. The residue j was dissolved in ethyl acetate (2250 ml) and washed with hydrochloric acid (IM, 250 ml) and with saturated aqueous sodium bicarbonate solution (2 × 250 ml), dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was recrystallized from ethanol, and 4- (tert-butoxycarbonylamino) -5-cyano-2- (2,4-dichlorophenyl) imidazole (22.2 g), mp covered 185 ⁰ C (with decomposition) as an obtained white solid.

- 69 -

Example 24 Compound CC

The procedure was repeated as described above under Example 6 except that 2- (2,6-dichloro-4-trifluoromethylphenyl) -4,5-dicyanoimidazole was replaced by the following starting materials to produce:

5-cyano-2- (2,4-dichlorophenyl) imidazole-4-carboxylic acid, mp 206-209 ⁰ C (with decomposition) from 2- (2,4-dichlorophenyl) -4,5-dicyanoimidazole.

Example 25 j

'j

Connection AA j

NfN-diethylaminosulfur trifluoride (11.4 mL, 0.08 g mol) was added dropwise to a stirred solution of 2- (2,4-dichlorophenyl) -indnazole-4,5-dicarboxylic acid (5.05 g, 0.017 mol) in 2-methoxyethyl ether (18 ml), keeping the temperature below ⁰ ° C. Sodium fluoride (1.82 g, 0.040 mol)

: Added and the mixture was stirred and heated to 80-85 ⁰ C for 41 hours. The mixture was added to water (100 ml) and extracted with dichloromethane (2 × 100 ml). The combined extracts were washed with water (1 μg ml), dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was purified by mplc on silica eluting with a mixture of ethyl acetate and n-hexane (1: 2) to give Ν, Ν-diethyl 2- (2,4-dichlorophenyl) -5-trifluoro: ethyl-

- 70 -

imidazole-4-carboxamide (0.27 g), m.p. 186.5-19O ⁰ C, as a covered white solid.

Example 26 5

Connection DD

A mixture of 2- (2,4-dichlorophenyl) -4,5-dicyanoimidazole (10.05g, 0.038mol), glacial acetic acid (41ml), concentrated sulfuric acid (19ml) and water (9.4ml) became 120 -125 ⁰ C heated for 1.5 hours. After cooling, the mixture was poured into water (300 ml) and the precipitated solid was filtered off and dried in vacuo (100 ^° C. at 50 mm Hg)

.15 2- (2,4-dichlorophenyl) imidazole-4,5-dicarboxylic acid (10.24 g), m.p. 237.5-238.5 ⁰ C was obtained as a white solid.

Example 27 20

Connection X

Diethylamine-sulfuric trifluoride (1.5 ml) was added dropwise to a stirred suspension of 5-cyano-2- (2,6-dichloro-4-trifluoromethyl-phenyl) -imidazole-4-carboxylic acid (1.4 g, 0.014 mol) in 2 -Methoxyethylether (11 ml) was added, the temperature was maintained at about 0 ⁰ C. Potassium fluoride (0.67 g, 0.0115 mol) was added and the mixture was stirred at ⁰ ° C for 0.5 h and then added slowly to a solution of diethylamine (8.8 g, 12.5 mL, 0.12 mol) of 75 ml) in dichloromethane (wherein the temperature is in the range of 0-5 ⁰ C was maintained. The mixture was added

_ 6 7 9 O

- 71 -

0-5 ⁰ C stirred for 1 hour and then at room temperature for another half an hour. The mixture was washed with saturated aqueous sodium bicarbonate solution (50 ml), dried over anhydrous sodium sulfate and evaporated to dryness. The residue i was purified by mplc on silica, with; A mixture of ethyl acetate and dichloromethane (1: 2) was eluted, with Ν, Ν-diethyl 5-cyano-2- <(2,6-dichloro-4-trifluoromethylphenyl) imidazole-4-carj boxamid (0 , 26 g), F. 195-197 ⁰ C as a covered white; Solid was obtained. ;

In experiments on the activity represent! tative compounds of general formula I against |

Arthropods, the following results were

hold (where ppm is the concentration of the compound!

in parts per million. · € the test solution

indicates): -

One or more dilute solutions of the test compounds in 50% aqueous acetone were prepared.

Test Species: Plutella xylostella (Diamondback moth) Pieces of turnip leaves were placed in petri dishes in agar and with 10 2nd instar Plutella larvae

infected. Four replicate dishes were determined for each treatment and were sprayed under a potter tower (Potter Towv.r) with the appropriate test solution. Four or five days after treatment, the bowls from the room became more constant

Temperature (25 ⁰ C) in which they were stored until then removed and the mean percentage mortality of the larvae was determined. These daters were against the mortality in shells that came to control

- 72 -

counteracted with 50% aqueous acetone alone.

The compounds listed below all resulted in greater than 90% mortality of Plutella xylostella larvae when treated at a dilution of 100 ppm. Compounds A, B, C, E, F and T.

- 73 -

Ar

II

NC

R-

'' Γ ™

Ar

III

R ⁹ (NH ₂ ) CaC (CN) N »CHAr

IV

NC-N = C (Ar) NHR ^{1 v} NC-N = C (Ar) OCH j VI Cl-N = C (Ar) NHR ¹ VII AxCOOCH (alkyl) C (= 0) alkyl VIII

Claims (12)

- 74 - CLAIM THE INVENTION A method for controlling arthropods, plant nematodes, helminths or protozoan pests in situ, comprising treating said site with an effective amount of a 2-phenylimidazole compound of the general formula: h'- » ² H _% , HR wherein R represents a hydrogen atom or a straight- or branched-chain alkyl group having 1 to 6 carbon atoms optionally with a straight or branched chain alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl group having 1 to 6 carbon atoms or a cyano or carboxy group or a straight or branched chain alkoxycarbonyl group having 2 to 7 carbon atoms 2 3
each R and R, which are the same or different, each represents a hydrogen atom or a halogen atom, a nitro, carboxy or cyano group, a straight- or branched-chain alkoxycarbonyl or alkanoyl group having 2 to 7 carbon atoms, a carbamoyl Or Sulphamyl group which may be substituted by one or two straight or branched chain alkyl groups each having 1 to 6 carbon atoms, or an amino group which may be substituted on the nitrogen atom with sin or two substituents selected from the straight or branched chain ones Alkyl groups having 1 to 6 carbon atoms and - 75 - straight or branched chain alkoxycarbonyl and alkanoyl groups having 2 to 7 carbon atoms, or a group R, RO, RS, RSO or RSO, in which R represents a straight or verzvelgtkettige alkyl group having 1 to 6 carbon atoms, optionally with one or is substituted by several halogen atoms and Ar represents an optionally substituted 2,4-disubstituted phenyl group of the general formula II: II 4 6
in which R and R, which may be the same or different, each represents a halogen atom or a group R, RO, RS, RSO or RSO ₂ , in which R represents a straight or branched chain alkyl group having 1 to 6 carbon atoms, optionally with a or more than one halogen atom is substituted, 5 7 8 and R, R and R, which may be the same or different, each represent a substituent as defined above for R and R, or represent a hydrogen atom, a hydroxy, carboxy, nitro, cyano or amino group, or a straight or branched chain one Alkylamino group represent with 1 to 6 carbon atoms, on the nitrogen atom with a straight or branched chain alkyl group having 1 to 6 carbon atoms or a straight or branched chain alkoxycarbonyl or a Alkanoyl group having 2 to 7 carbon atoms may be substituted or »represent a straight or branched chain alkoxycarbonyl or alkanoyl group having 2 to 7 carbon atoms or their pesticidally acceptable salts, with the exception of those compounds in which R and R simultaneously represent a hydrogen atom. A method according to claim 1 for controlling arthropods or nematode pests in plants. A process for the preparation of a 2-phenyllimidazole compound of general formula I as defined in claim 1 or one of its pesticidally acceptable salts except 2- (2 ', 4-dichlorophenyl) -4,5-dicyanoimidazole, characterized in that Ar is of the definition of claim 1, comprising: 1 2 (A) when R represents a hydrogen atom " { " represents a cyano or optionally substituted carbamoyl group as defined in claim 1 and R represents a cyano group, "the oxidative cyclization of a compound of the general formula R ⁹ (NH ₂ ) CC (CN JN-CHAr wherein R represents a cyano group or optionally substituted carbamoyl group as defined in claim 1 and Ar is as defined in claim 1; (B) when R ^{1 is} hydrogen and R ² and R ^{3 are} both carboxy groups, the reaction of the corresponding benzaldehydes with tartaric acid nitrate in the presence of ammonium hydroxide; 1 2 3 (C) when R represents hydrogen and R and R both represent chlorine, the reaction of the corresponding benzaldehydes with cyanogen in the presence of Hydrochloric; 1 2 (O) when R represents hydrogen, R represents an optionally substituted alkyl group according to the definition of claim 1 and R represents hydrogen, the reaction of the corresponding benzaldehyde with an alpha-ketoaldehyde in the presence of ammonia; 1 2 3 (E) when R is hydrogen and R and R are both optionally substituted alkyl groups as defined in claim 1, the reaction of the debouncing benzaldehyde with a dialkylglyoxal in the presence of 10 _# ammonium acetate; (F) when R represents an alkanoyl group and R represents an amino group, the reaction of a compound of the general formula: NC-N = C (Ar) NIIR " in the Ar and R of the definition of claim 1 correspond to a Bromomethylalkylketon in the presence of potassium carbonate and dimethylformamide or an alkali metal alkoxide and an alkanol; 2 3 (G) when R is cyano and R is an amino group, the reaction of a compound of the general formula: NC-N = C (Ar) OCH ₃ in the Ar of the definition of claim 1 corresponds to an (optionally substituted amino) -acetonitrile hydrochloride in the presence of triethylamine or an alkali metal alkoxide in an alkanol; 2
(H) when R represents an optionally substituted alkyl group and R represents hydrogen, the reaction of a compound of the general formula: Cl-NC (Ar) NHR ¹ in the Ar and R of the definition of item 1 correspond to a! - (optionally substituted alkyl) -2-trimethylsilyloxyethylene in the presence of pyridine in chloroform; 1 2 3 (I) when R represents hydrogen and R and R both each represent an optionally substituted alkyl group, the reaction of a compound of the general formula: ArCOOCH (alkyl) C (-O) alkyl in the Ar the definition of claim 1 corresponds with Ammonium acetate and acetic acid; or (O) the conversion of a compound of the general Formula I using methods known per se « 2 3
R and R are both replaced by hydrogen, in one A compound of general formula I in which one or 2 3 both radicals R and R are not hydrogen "optionally followed by a conversion by means of methods known per se of a compound of general formula I which has been obtained in this way" in another compound of general formula I; and / or by converting a compound of the general formula I into one of its pesticidally acceptable salts. 4. Method n .- ^ h claim 3, characterized in that «hergest
Represents a substance atom. Compounds are made in which R is a water 5. The method according to claim 3 or 4, characterized in that compounds are prepared in which Each R and R are not hydrogen. 6. A process as claimed in claim 3, 4 or 5, characterized in that compounds are prepared in which Ar represents a 2-R4-R substituted phenyl group which optionally carries a substituent which may be the same or different selected from the group consisting of Halogen atoms «R« RO, RS, RSO or RSOp. 7. The method according to claim 6, characterized in that «compounds are prepared in which Ar represents a phenyl group which carries a substituent in the 6-position. 8. The method according to any one of claims 3 to 7, characterized in that compounds are prepared in which Ar is a 2,6-dichloro-4-trifluoromethylphenyl, a 2,6-Dlchlor-4-trifluoromethoxyphenyl or a 2-chloro-4 trifluoromethylphenyl group. 9. The method according to any one of claims 3 to 8, characterized characterized in that compounds are prepared in which R represents a halogen atom or a nitro, cyano-trifluoromethyl or alkyl group or a Group R, RO, RS "represents RSO or RSO ₂ " in which R represents a straight or branched chain alkyl group having 1 to 6 carbon atoms "which is optionally substituted with one or more halogen atoms. 10. The method according to any one of claims 3 to 9, characterized in "DAC compounds are hergestallt" in which R represents a halogen atom or a nitro _f cyano, trifluoromethyl or alkyl group. 11. The method according to any one of claims 3 to 10, characterized in that compounds are prepared in which R represents a halogen atom. 12. The method according to any one of claims 3 to 11 «characterized« that compounds are prepared * in which R represents a group R «RO« RS «RSO or RSO ₂ « in which R is a straight or branched chain alkyl group having 1 to 6 carbon atoms represents substituted with one or more halogen atoms. 13. Method according to claim 12, characterized in that connections are made w
Trifluornethylgruppe represents that connections are made "in which R is a 14. Method according to one of claims 3 to 13, characterized in that connections are made, 8th
in which R represents a halogen atom. Process according to any one of Claims 3 to 14, characterized in that compounds are prepared in which R represents a hydrogen atom R _{2 represents} a trifluoromethyl, trifluoromethoxy, methylthio, methyleulphtnyl or methylsulphonyl group containing one or two carbon atoms or three fluorine atoms is substituted and R _{1 represents} a Halocqnatom or a nitro or cyano group. 16. The method according to claim 3, characterized in that compounds are prepared in which R ₁ represents a hydrogen atom, R ₂ and R ₃ , which may be the same or different, each represents a hydrogen atom or a halogen atom, a nitro, carboxy or a cyano group, a straight-chain or branched-chain alkoxycarbonyl group having 2 to 7 carbon atoms, a carbamoyl-odor sulphamoyl group which may be substituted by one or two straight-chain or branched-chain alkyl groups each having 1 to 6 carbon atoms, an amino group attached to the nitrogen atom one or two substituents may be substituted by the straight-chain or branched-chain alkyl groups having 1 to 6 carbon atoms and the straight-chain or branched-chain alkoxycarbonyl and alkanoyl groups having 2 to 7 carbon atoms, or a straight or branched chain alkyl or alkylthio group represented by 1 to 6 carbon atoms, optionally with one or more erene halogen atoms is substituted, and R _{4 represents} a Halogenatoni "R _{6 represents} a halogen atom or a straight or branched chain alkyl, alkoxy or alkylthio group having 1 to 6 carbon atoms substituted with one or more halogen atoms, R ₅ . υ.id R _{7 represent} hydrogen atoms and R _{8 represents} a hydrogen atom or a halogen atom. 17. The method according to claim 3, characterized in that compounds of formula I are prepared. In which R * "and R are replaced by hydrogen atoms and R and Ar are as defined in claim 1. 18, pesticidal composition containing as active ingredient a compound of general formula I, as defined in claim 1 or one of its pesticidal salts in association with one or more compatible diluents or carriers, characterized in that, when the composition is a single compound of the contains general formula I which is 4,5-dicyanoimidazole 2- (2,4-DichlorphenyJ), this composition comprises a pharmaceutically acceptable adjuvant or a feedstuff or is substantially sterile and pyrogenfrsi or i ^c orm a unit dose is present.