DE19542935A1 - Fluorobutenoyloxyacetic acid amides - Google Patents

Abstract

The invention concerns fluorobutenoyloxyacetamides of formula (I), in which R<1>, R<2>, R<3> and R<4> are as defined in the description, methods of preparing them and their use in the control of animal pests.

Description

The present invention relates to new fluorobutenoyloxyacetic acid amides, Ver drive to their manufacture and their use to control animal Pests, especially insects, arachnids and nematodes, which in the Agriculture, in the forests, in the protection of stocks and materials as well as on the Hygiene sector occur.

It has already been known that certain fluoroalkenyl compounds as Insecticides, acaricides and nematicides are effective (see, for example, WO 92/15 555, U.S. 4,952,590, U.S. 4,950,666, U.S. 3,914,251). The effectiveness and effectiveness However, the width of these compounds is particularly low at low application rates and concentrations are not always completely satisfactory.

New compounds of the formula (I) have now been found

in which
R¹ represents hydrogen or halogen,
R² represents hydrogen, alkyl or optionally substituted aryl,
R³ and R⁴ independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, alkoxy or in each case optionally substituted aryl or hetaryl,

or

R³ and R⁴ together represent alkanediyl or -CH₂-CH₂-X-CH₂-CH₂-,
wherein
X represents oxygen, sulfur or NR⁵ and
R⁵ represents hydrogen, alkyl or optionally substituted aryl.

The compounds of formula (I) can, depending on the nature of the Substi tuenten as geometric and / or optical isomers or isomer mixtures under different composition. The invention relates to both the pure Isomers as well as the isomer mixtures.

It has also been found that the compounds of the formula (I) are obtained when
Hydroxyacetic acid amides of the formula (II)

HO-CHR²-CO-NR³R⁴ (II)

in which
R², R³ and R⁴ have the meaning given above,
with acid chlorides of the formula (III)

in which
R¹ has the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of a base.

Finally, it was found that the new compounds of formula (I) are strong possess pronounced biological properties and above all for combating of animal pests, especially insects, arachnids and Nematodes used in agriculture, in forests, in the protection of stocks and materials as well as in the hygiene sector are suitable.  

The compounds of the invention are general by the formula (I) Are defined.

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
R1 is preferably hydrogen, fluorine or chlorine.
R² preferably represents hydrogen, C₁-C₆-alkyl or phenyl which is optionally monosubstituted to triple, identically or differently, substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy.
R³ and R⁴ independently of one another preferably represent hydrogen, C₁-C₆-alkyl, C₂-C₁₀-alkenyl, C₄-C₅-cycloalkyl, C₁-C₆-alkoxy, if appropriate through
Fluorine, chlorine, bromine, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-halo alkylthio substituted phenyl, optionally Hetaryl with 5 or 6 ring atoms and one or two heteroatoms from the series nitrogen, oxygen and sulfur substituted by fluorine, chlorine or C₁-C₄-alkyl,

or

R³ and R⁴ together represent C₄-C₈-alkanediyl.
R 1 particularly preferably represents hydrogen or fluorine.
R² particularly preferably represents hydrogen or C₁-C₄-alkyl.
R³ and R⁴ independently of one another particularly preferably represent hydrogen, C₁-C₄-alkyl, C₃-C₈-alkenyl, C₅-C₆-cycloalkyl, C₁-C₂-alkoxy if appropriate by fluorine, chlorine, C₁-C₄-alkyl or C₁-C₄ Alkoxy substituted phenyl or for pyridyl, furanyl or thienyl,

or

R³ and R⁴ together represent C₅-C₇-alkanediyl or -CH₂-CH₂-X-CH₂- CH₂- stand,

wherein

X represents oxygen, sulfur or NR⁵.
R⁵ preferably represents hydrogen, C₁-C₄-alkyl or phenyl optionally substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl.
R¹ is particularly highlighted for hydrogen or fluorine.
R² is particularly highlighted for hydrogen or methyl.
R³ and R⁴ are independently highlighted for hydrogen, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, allyl, optionally substituted by fluorine or chlorine or phenyl
R³ and R⁴ together represent C₅- or C₆-alkanediyl.

The radicals listed above or listed in preferred areas definitions and explanations apply to the end products and to the initial and intermediates accordingly. These residual definitions can be thus also be combined as desired between the respective preferred areas.

According to the invention, preference is given to the compounds of the formula (I) in which a combination of the Be listed as preferred (preferred) interpretations are available.

According to the invention, particular preference is given to the compounds of the formula (I), in which are a combination of those listed as particularly preferred above Meanings exist.

According to the invention, particular emphasis is given to the compounds of the formula (I), in which a combination of the above is highlighted as special listed meanings is present.

In the residue definitions listed above and below are hydrocarbons material residues, such as alkyl or alkenyl, - also in combination with heteroatoms such as Alkoxy or alkylthio - as far as possible, straight-chain or branched.  

Is used in the preparation of compounds of formula (I), e.g. B. 3,4,4- Trifluorobut-3-ene acid chloride and hydroxyacetic acid-N, N-dibutylamide as Aus materials, the course of the reaction can be determined by the following reaction scheme are reproduced:

CF₂ = CF-CH₂-COCl + HO-CH₂-CO-N (C₄H₉) ₂
→ CF₂ = CF-CH₂-CO-O-CH₂-CO-N (C₄H₉) ₂.

The method described above for the preparation of compounds of the formula (I) is characterized in that hydroxyacetic acid amides of the formula (II) with acid chlorides of the formula (III), if appropriate in the presence of a ver diluent and optionally in the presence of a base.

The process according to the invention is preferably carried out in the presence of a diluent medium carried out.

Organic solvents are particularly suitable as diluents, for example optionally chlorinated aliphatic or aromatic coal water substances such as cyclohexane, toluene, xylene, dichloromethane, dichloroethane, chloroform or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran or Nitriles such as acetonitrile.

In principle, all or suitable for such acylation reactions can be used as the base ganic or inorganic bases can be used.

Amines are preferably used, in particular tertiary amines such as tri ethylamine, diazabicycloundecene (DBU), diazabicyclonones (DBN), diazabicyclo octane (DABCO) or pyridine or alkali or alkaline earth carbonates, hydrogen carbonates or hydroxides. Examples include sodium carbonate, potassium carbonate, Sodium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hy called hydroxide.

The reaction temperature can be varied within a wide range. in the generally one works at temperatures between -20 ° C and 180 ° C, preferably between 0 ° C and 120 ° C.  

The molar ratio of the compound of formula (II) to the compound of formula (III) is generally 3: 1 to 1: 3, preferably 1.5: 1 to 1: 1.5.

The reaction is generally carried out under normal pressure.

For working up, for example, the reaction mixture is hydrolyzed and that Product with an organic solvent such as ethyl acetate, dichloromethane or Toluene extracted.

The hydroxyacetic acid amides of the formula (II) required as starting materials are known and / or can be prepared in a simple manner by known methods put.

The acid chlorides of the formula (III) required as starting materials are known (see. e.g. B. 5,389,680 and EP-432,861).

The active ingredients are particularly suitable for controlling animal pests insects, arachnids and nematodes, which are used in agriculture, in forests, in storage and material protection as well as in the hygiene sector. she can preferably be used as pesticides. You are against normally sensitive and resistant species as well as against all or individual developments Stages effective. The pests mentioned above include:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Por cellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiurus armatus.  

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp.

From the order of the Ahoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cinctice′ps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.  

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. Aedes spp., Ahopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The plant parasitic nematodes include z. B. Pratylenchus spp., Radopho- Ius similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.  

The compounds of the formula (I) according to the invention are particularly noteworthy with an excellent nematicidal effect, for example against Meloido gyne incognita.

They show systemic effects and can also be applied over the leaf will.

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, active ingredient impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surfaces active agents, ie emulsifiers and / or dispersants and / or foam generating means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons substances such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic Koh hydrogen, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo hexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersing agent come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90%.

The active ingredient according to the invention can be in its commercially available formulations as well as in the use forms prepared from these formulations in Mix with other active ingredients, such as insecticides, attractants, sterilants, Bactericides, acaricides, nematicides, fungicides, growth-regulating substances fen or herbicides. The insecticides include, for example, Phos phosphoric esters, carbamates, carboxylic esters, chlorinated hydrocarbons, Phe nylureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. B. the following:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cydopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanil-id; 2,6-di chloroN- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tdyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, B enodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fen propimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flu dioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, fulfolidolide, flu triafolet , Furalaxyl, Furmecyclox, Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamate, Nitrothal-Isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Phthalid, Pimaricin, Piperalin, Polycarbamate, Polyoxin, Prob enazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon, Quroquilon, PCro
Sulfur and sulfur preparations,
Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadi menol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triforazol, Tri,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Di azinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxatophion, Fufionophon, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufox
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver mectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarb m, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, M 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomichonon, Triaromenontron, Triaromenontron, Triarathenlarbon, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triaromenontrin, Triarathenltronium, Triaromenontrin, Triarathenltron, Triaromenontron
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.
A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

The active compounds according to the invention can also be used in their commercially available form formulations and in the application forms prepared from these formulations in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist must be actively active itself.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration the use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the stands out Active ingredient through an excellent residual effect on wood and clay as well due to good stability to alkali on limed substrates.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1 CF₂ = CF-CH₂-CO-O-CH₂-CO-N (n-C₄H₉) ₂

To a solution of 9.35 g (50 mmol) of hydroxyacetic acid-N, N-dibutylamide in 30 ml of acetonitrile and 7.3 g (53 mmol) of potassium carbonate are added dropwise at 20 ° C. Stir 7.9 g (50 mmol) 3,4,4-trifluorobut-3-enoic acid chloride. After 1 hour after stirring time is poured onto water and the product extracted with methylene chloride. The organic phase is separated off, evaporated in vacuo and the residue was cleaned on the silica gel in the chloroform / ethyl acetate (9: 1) system. You get 5.6 g (36% of theory) 3,4,4-trifluoro-but-3-enoic acid-N, N-dibutylaminocarbonyl methyl ester of bp 130 ° / 0.3 mm and a log p = 3.43 (log p = decimal logarithm of the n-ocanol / water distribution coefficient ten, determined by HPLC analysis on reversed phase with H₂O / CH₃CN.).

Analogously or according to the general information on the preparation, the the following compounds of formula (I):

Examples of use Example A Limit concentration test / nematodes

Test nematode: Meloidogyne incognita
Solvent: 4 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the information the same amount of emulsifier and dilute the concentrate with water to the wanted concentration.

The active ingredient preparation is intimately mixed with soil, the one with the test nematodes is heavily contaminated. The concentration of the active ingredient plays in the Preparation practically does not matter, the decisive factor is the amount of active ingredient per Volume unit of soil, which is given in ppm (= mg / l). You fill it treated soil in pots, seeds lettuce and keeps the pots in a crop house temperature of 25 ° C.

After four weeks, the lettuce roots are attacked by nematodes (root galls) examined and the effectiveness of the active ingredient determined in%. The effect degree is 100% if the infestation is completely avoided, it is 0% if the Is just as high as in the control plants in untreated, but in same way contaminated soil.

In this test z. B. the compounds according to the preparation examples 2 and 8 at an exemplary active ingredient concentration of 20 ppm 100% efficiency.  

Example B Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified ne quantity of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist.

After the desired time, which determines the kill in%. Here means 100% that all beetle larvae have been killed; 0% means that no beetles Larvae were killed.

In this test, e.g. B. the connection according to preparation example 5 an exemplary active ingredient concentration of 0.1% a kill of 100% after 7 days.  

Example C Plutella test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified ne quantity of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plutella maculipennis) occupied while the leaves are still moist.

After the desired time, which determines the kill in%. Here means 100% that all caterpillars have been killed; 0% means that no caterpillars were killed.

In this test, e.g. B. the compounds according to the preparation examples 2, 3, 4, 5, 6 and 7 with an exemplary active ingredient concentration of 0.1% 100% kill after 7 days.  

Example D Nephotettix test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified ne quantity of emulsifier and dilute the concentrate with water to the desired one Concentration.

Rice seedlings (Oryzae sativa) are dipped into the active ingredient preparation the desired concentration and treated with larvae of green rice leafhopper (Nephotettix cincticeps) occupied while the seedlings are still moist.

After the desired time, which determines the kill in%. Here means 100% that all cicadas have been killed; 0% means no cicadas ab were killed.

In this test, e.g. B. the connection according to Production Example 6 in a exemplary drug concentration of 0.1% after 6 days of killing degree of 100%.

Claims (7)

1. Compounds of formula (I) in which
R¹ represents hydrogen or halogen,
R² represents hydrogen, alkyl or optionally substituted aryl,
R³ and R⁴ independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, alkoxy or in each case optionally substituted aryl or hetaryl, orR³ and R⁴ together represent alkanediyl or for -CH₂-CH₂-X-CH₂-CH₂-,
wherein
X represents oxygen, sulfur or NR⁵ and
R⁵ represents hydrogen, alkyl or optionally substituted aryl. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that
Hydroxyacetic acid amides of the formula (II) HO-CHR²-CO-NR³R⁴ (II) in which
R², R³ and R⁴ have the meaning given in claim 1,
with acid chlorides of the formula (III) in which
R¹ has the meaning given in claim 1,
if appropriate in the presence of a diluent and if appropriate in the presence of a base. 3. pesticide, characterized by a content of at least one compound of formula (I) according to claim 1. 4. Use of compounds of formula (I) according to claim 1 for Pest control. 5. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or let their living space take effect. 6. Process for the preparation of pesticides, thereby characterized in that compounds of the formula (I) according to Claim 1 mixed with extenders and / or surfactants. 7. Use of compounds of formula (I) according to claim 1 for Manufacture of pesticides.