DE4439335A1 - Carbonic acid and carbamic acid fluorobutenyl esters - Google Patents

Abstract

Fluorobutenyl esters have the formula (I), in which R<1> stands for hydrogen or a halogen, and R<2> stands for one of the groups (a), (b) or (c), in which V, Y, Z, R<3> and R<5> have the meanings given in the description. Also disclosed are a process and intermediate products for preparing said esters, as well as their use for controlling animal pests.

Description

The present invention relates to new carbonic acid and carbamic acid fluor Butenyl esters, processes for their preparation and their use in combating control of animal pests, in particular insects, arachnids and Nematodes used in agriculture, in the forestry, in supplies and materials protection as well as in the hygiene sector.

It has already been known that certain fluorobutenyl compounds as Nematicides are effective (cf., for example, WO 88/00183). The effectiveness and us However, the range of these connections is particularly low-cost quantities and concentrations are not always completely satisfactory.

There have now been new carbonic acid and carbamic acid fluorobutenyl esters of the formula (I) found

in which
R¹ represents hydrogen or halogen, and
R² for one of the groups

stands,
in which
Y represents oxygen or sulfur,
Z represents oxygen, sulfur or NR⁴,
R³ stands for hydrogen or for optionally substituted alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkoxycarbonyl, aryloxy carbonyl, arylsulfonyl or hetaryl and
R⁴ stands for hydrogen or for optionally substituted alkyl, alkenyl, cycloalkyl, aryl, aralkyl or hetaryl or
R³ and R⁴ together with the nitrogen atom to which they are attached form an optionally substituted ring which optionally contains oxygen, sulfur or nitrogen (which is optionally substituted by alkyl, aryl or aralkyl).

It was also found that the carbonic acid and carbamic acid fluorine butenyl ester of formula (I) is obtained when

• A) fluorobutenols of the formula (II) in which
  R¹ has the meaning given above,
  • α) with compounds of the formula (III) in which
    Y, Z and R³ have the meanings given above,
    in the presence of a diluent and optionally in the presence of a base,
    or
  • β) with an iso (thio) cyanate of the formula (IV) YCN-R³ (IV) in which
    Y and R³ have the meanings given above
    in the presence of a diluent and optionally in the presence of a catalyst
    or
• B) fluorobutene thiols of the formula (IIa) in which
  R¹ has the meaning given above,
  with a compound of formula (IIIa) in which
  Y and R³ have the meanings given above,
  in the presence of a diluent and optionally in the presence of a base,
  or
• C) compounds of the formula (V) in which
  R¹ and Y have the meanings given above,
  with a compound of formula (VI) HZ-R³ (VI) in which
  Z and R³ have the meanings given above,
  in the presence of a diluent and optionally in the presence of a base,
  or
• D) Compounds of the formula (VII) in which
  R¹ and Y have the meanings given above,
  with a compound of formula (VIII) HS-R³ (VIII) in which
  R³ has the meaning given above,
  in the presence of a diluent and optionally in the presence of a base.

Finally it was found that the new carbonic and carbamic acid fluor Butenyl esters of formula (I) have very pronounced biological properties and especially for the control of animal pests, in particular of Insects, arachnids and nematodes, which are used in agriculture, in the forest, occur in supply and material protection as well as in the hygiene sector, are suitable.

The carbonic acid and carbamic acid fluorobutenyl esters according to the invention are generally defined by formula (I).

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 one of the groups

in which
Y represents oxygen or sulfur,
Z represents oxygen, sulfur or NR⁴,
R³ for hydrogen,
for optionally substituted by halogen, cyano, amino (which is optionally substituted by C₂-C₇-alkanediyl or monosubstituted or twice, identically or differently by C₁-C₈-alkyl), C₁-C₈-alkoxy, C₁-C₈-alkylthio, aminocarbonyl (which optionally by C₂-C₇-alkanediyl, single to double, identical or different by C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-cycloalkyl, C₃-C₈-halocycloalkyl, C₁-C₄-alkyl-C₃-C₈- Cycloalkyl, by phenyl optionally substituted by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio Benzyl is substituted) substituted C₁-C₁₀ alkyl,
for C₃-C₈-alkenyl optionally substituted by halogen,
for C₃-C₈-cycloalkyl optionally substituted by halogen or C₁-C₆-alkyl,
for each optionally by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio, C₁-C₈- Alkoxycarbonyl or SCN substituted phenyl, benzyl, phenyloxycarbonyl or phenylsulfonyl,
for a 5- or 6-membered heterocycle optionally substituted by halogen or C₁-C₆-alkyl having one to three nitrogen atoms or
represents optionally substituted by halogen or C₁-Cyl-alkoxy C₁-C₈-alkoxycarbonyl.
R⁴ preferably represents hydrogen,
for optionally substituted by halogen, cyano, amino (which is optionally substituted by C₂-C₇alkanediyl or optionally monosubstituted or disubstituted, identically or differently by C₁-C₈alkyl), C₁-C₈alkoxy, C₁-C₈alkylthio, aminocarbonyl ( which is optionally by C₂-C₇-alkanediyl, single to double, identical or different by C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-cycloalkyl, C₃-C₈-halocycloalkyl, C₁-C₄-alkyl-C₃-C₈ -Cycloalkyl, each optionally substituted by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-halogen alkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio Phenyl or benzyl is substituted) substituted C₁-C₁₀ alkyl,
for C₃-C₈-alkenyl optionally substituted by halogen,
for C₃-C₈-cycloalkyl optionally substituted by halogen or C₁-C₆-alkyl,
for each optionally by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkyl thio, C₁-C₈-haloalkylthio, C₁-C₈ Alkoxycarbonyl or SCN substituted phenyl or benzyl,
for a 5- or 6-membered heterocycle optionally substituted by halogen or C₁-C₆-alkyl having one to three nitrogen atoms
or
R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- to 8-membered ring, optionally substituted by C₁-C₈-alkyl, which optionally contains oxygen, sulfur or nitrogen (which cher optionally by C₁-C₈- Alkyl, phenyl or benzyl is substituted) contains.
R 1 particularly preferably represents fluorine.
R² particularly preferably represents the group

in which
Y represents oxygen or sulfur,
Z represents oxygen, sulfur or NR⁴,
R³ for hydrogen,
for optionally by fluorine, chlorine, cyano, amino (which is optionally substituted by C₂-C₆alkanediyl or monosubstituted or disubstituted, identically or differently by C₁-C₆alkyl), C₁-C₆alkoxy, C₁-C₆alkylthio, aminocarbonyl (which is optionally by C₂-C₆-alkanediyl, single to double, identical or different by C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₇-cycloalkyl, C₃-C₇-halocycloalkyl, C₁-C₃-alkyl- C₃- C₇-cycloalkyl, each optionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio Phenyl or benzyl is substituted) substituted C₁-C₆ alkyl,
for optionally substituted by fluorine, chlorine or C₁-C₄-alkyl C₄- C₈-cycloalkyl,
for each optionally by fluorine, chlorine, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkyl thio, C₁-C₆-haloalkylthio, C₁ -C₆-alkoxycarbonyl or SCN substituted phenyl, benzyl, phenoxycarbonyl or phenylsulfonyl,
represents optionally substituted by fluorine, chlorine or C₁-C₄-alkoxy C₁-C₆-alkoxycarbonyl.
R⁴ particularly preferably represents hydrogen,
for C₁-C₆-alkyl or for C₄-C₈-cycloalkyl
or
R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- to 8-membered ring, optionally substituted by C₁-C₆-alkyl, which optionally contains oxygen, sulfur or nitrogen (which may be substituted by C₁-C₆-alkyl, Phenyl or benzyl is substituted) contains.
R¹ very particularly preferably represents fluorine.
R² very particularly preferably represents the group

in which
Y stands for oxygen,
Z represents oxygen, sulfur or NR⁴,
R³ for hydrogen,
for optionally by halogen, cyano, amino (which is optionally substituted by C₂-C₆alkanediyl or monosubstituted or disubstituted, identically or differently by C₁-C₆alkyl), C₁-C₆alkoxy, C₁-C₆alkylthio or aminocarbonyl (which optionally by C₂-C₆-alkanediyl, single to double, identical or different by C₁-C₈-alkyl, or by in each case optionally by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-halogen alkyl, C₁-C₆- Alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-haloalkylthio substituted phenyl or benzyl) substituted C₁-C₆-alkyl,
for C₃-C₆ alkenyl optionally substituted by fluorine, chlorine or bromine,
for C₄-C₈-cycloalkyl optionally substituted by C₁-C₄-alkyl,
for optionally by fluorine, chlorine, cyano, C₁-C₄-alkyl, C₁-C₄-halo genalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄- haloalkylthio or C₁-C₄- Alkoxycarbonyl substituted phenyl, benzyl, phenoxy or phenylsulfonyl,
represents optionally substituted by fluorine, chlorine or C₁-C₄-alkoxy C₁-C₄-alkoxycarbonyl.
R⁴ very particularly preferably represents hydrogen,
for C₁-C₄ alkyl or
for C₄-C₆-cycloalkyl
or
R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- to 8-membered ring, optionally substituted by C₁-C₄-alkyl, which optionally contains oxygen, sulfur or nitrogen (which if necessary by C₁-C₄-alkyl or benzyl is substituted).

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 different other, that is to say combined as desired between the respective preferred areas will.

According to the invention, preference is given to the compounds of the general formula (I) in which a combination of the above as preferred (preferred) meanings.

According to the invention, particular preference is given to the compounds of the general Formula (I) in which a combination of the above is particularly preferred listed meanings is present.

According to the invention, the compounds of the general my formula (I), in which a combination of these above as a whole meanings particularly preferred are present.

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

Is used in the preparation of compounds of formula (I) according to Ver drive Aα) z. B. 3,4,4-trifluoro-but-3-enol and chloroformate as Starting materials, the course of the reaction can be by the following reaction scheme are reproduced:

Is used in the preparation of compounds of formula (I) according to Ver drive Aβ) z. B. 3,4,4-trifluoro-but-3-enol and phenyl isocyanate as starting materials, the course of the reaction can be represented by the following reaction scheme will:

Is used in the preparation of compounds of the formula (I) according to Method B) z. B. 3,4,4-trifluorobut-3-en-thiol and chlorothiol formic acid ethyl ester as starting materials, the course of the reaction by the following reaction Scheme are reproduced:

Is used in the preparation of compounds of formula (I) according to Ver drive C) z. B. chloroformic acid (3,4,4-trifluorobut-3-enyl) ester and cyclohexyl amine as starting materials, the course of the reaction by the following reaction Scheme are reproduced:

Is used in the preparation of compounds of the formula (I) according to Method D) z. B. chlorothiol formic acid (3,4,4-trifluorobut-3-enyl) ester and 2,6- Dimethylmorpholine as starting materials, the course of the reaction by fol the following reaction scheme:

The above-described methods Aα, Aβ, B, C and D for producing the Compounds of formula (I) are characterized in that the Reactions are carried out in the presence of a diluent.

All customary solvents can be used as diluents in these processes be used.

Halogenated aliphatic or aromatic hydrocarbons, ethers or nitriles such as B. cyclohexane, toluene, Chlorobenzene, chloroform, dichloromethane, dichloroethane, dioxane, tetrahydrofuran, Diethyl ether or acetonitrile.

The methods Aα, B, C and D described above for the preparation of the verbin Solutions of formula (I) are characterized in that the If appropriate, reactions are carried out in the presence of a base.

All conventional protons can be used as bases in the processes Aα, B, C and D. acceptors are used. Alkali or earth are preferably usable alkali hydroxides, alkali or alkaline earth metal carbonates or bicarbonates or nitrogen bases. Examples include sodium hydroxide and calcium hy hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine,  Diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclo nonen (DBN) and diazabicycloundecene (DBU).

The process Aβ described above for the preparation of the compounds of For mel (I) is characterized in that the reaction optionally in counter was a catalyst.

Diazabicyclooctane (DABCO), triethylamine, for example, can be used as the catalyst or pyridine or organic tin compounds such as. B. dibutyltin dilaurate ver be applied.

The reaction temperatures in the processes Aα, Aβ, B, C and D can each be varied over a wide range. In the process Aα, B, C and D are generally carried out at temperatures between -10 ° C and 150 ° C, preferably between 0 ° C and 90 ° C. The Aβ method is used generally at temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C.

The ratio of the starting materials of the formulas (II) and (III) in process Aα or the formulas (IIa) and (III) in process B is generally 1: 1 to 2: 1.

The ratio of the starting materials of the formulas (II) and (IV) in process Aβ is generally between 2: 1 and 1: 2, preference is given to equivalent amounts used.

The ratio of the starting materials of the formulas (V) and (VI) in process C or of formulas (VII) and (VIII) in process D is in general between 1: 1 and 10: 1.

The above described methods Aα, Aβ, B, C and D are general carried out under normal pressure. To work up is described in the above benen method Aα, Aβ, B, C and D the reaction mixture, for example with Diluted water, extracted with an organic solvent and the orga African phase concentrated.  

The raw materials of For. Used in the production process Aα and Aβ mel (II) are known and can be prepared by known methods (see e.g. B. WO 92/15 555).

The starting materials used in the manufacturing process Aα and B of the formula (III) or (IIIa) are known and / or can be according to known Create methods. The compounds of the formula (III) or (IIIa) are obtained. for example, if you in alcohols, thiols or amines of formula (VI) known manner and phosgene or thiophosgene (see, for example, Houben Weyl, Methods of Organic Chemistry, Volume E 4, pp. 407 ff., Georg Thieme Verlag Stuttgart, New York, 1983).

The iso (thio) cya used as starting materials in the production process Aβ Nates of the formula (IV) are generally known synthetic chemicals from orga African chemistry.

The starting materials of formula (V) used in production process C are new, but can be manufactured using known methods. You get that Compounds of formula (V), for example, when compounds of formula (II) in a manner known per se (see above) with phosgene or thiophosgene implements.

The raw materials from For mel (VI) are generally known synthetic chemicals of organic chemistry.

The starting materials of formula (VII) used in production process D are new, but can be manufactured using known methods. You get that Compounds of formula (VII), for example, if compounds of the formula mel (IIa) in a manner known per se (see above) with phosgene or thiophosgene implements.

The raw materials from For mel (VII) are generally known compounds of organic chemistry.  

With good plant tolerance and favorable warm-blood toxicity, the active ingredients are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. 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 Anoplura 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, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodaliphasum bilobatus, Nephotettix cincticeps, 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 thurberiis sppia, Fpp , Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Tumeria bellaella, Galleria tinellaella 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 chrysocephppis, Orphusus 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., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., 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., Choroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

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

The active compounds of the formula (I) according to the invention act not only against plants zen, hygiene and storage pests, but also on the veterinary nical sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, room mites, running mites, flies (stinging and licking), parasitizing Fly larvae, lice, hair lice, featherlings, fleas.

They are against normally sensitive and resistant species and strains, as well as against all Parasitic and non-parasitic stages of development of the ectoparasites effective.

The compounds of the formula (I) according to the invention are particularly noteworthy outstanding insecticidal and nematicidal activity. They show at Use against leaf and soil insects, for example against strong  Horseradish leaf beetle larvae (Phaedon cochleariae) and caterpillars caterpillars (Plutella maculipennis). When used against nematodes, they have a strong effect for example against Meloidogyne incognita.

The active compounds according to the invention show not only protective, but also leaf systemic and root systemic properties.

The active compounds of the formula (I) also have one fungicidal activity, for example against Pyricularia oryzea on rice.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient impregnated natural and synthetic materials as well as very fine encapsulation in polymeric 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 stone powder, such as highly disperse silica, aluminum oxide and Silicates, as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours and Granules made of organic material such as sawdust, coconut shells, corn cobs and tobacco stems; come in as emulsifying and / or foaming agents Question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a disper yaws are possible: B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, ver natural and synthetic polymers in powder, granular or latex form be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and na natural phospholipids such as cephalins and lecithins and synthetic phos pholipid. 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 phthalocyanine 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 substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others
Particularly cheap mixing partners are e.g. B. the following:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thlazole-5-carboxanide; 2,6-di chloro-N- (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-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, 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, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, 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,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
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, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Buto carboxin, 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, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectih, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 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, Pyrachlhrhron, Pyrachlophon, Pyrachlophon, Pyrachlophon, Pyrachlophon, Pyrachlophon, Pyrachlophon, Pyrachlophon 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.

Herbicides:

for example anilides, such as. B. Diflufenican and Propanil; Aryl carboxylic acids, such as e.g. B. dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, Haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates: such as B. chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as e.g. B. alachlor, acetochlor, butachlor, Metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines such as e.g. B.  Oryzalin, pendimethalin and trifluralin; Diphenyl ether, such as. B. Acifluorfen, Bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and Methabenzthiazuron; Hydroxylamines, such as. B. Alloxydim, Clethodim, Cyclo xydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazamethabenz, imazapyr and imazaquin; Nitriles such as B. bromoxynil, Dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as B. amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, such as B. butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, Thiobencarb and triallates; Triazines, e.g. B. atrazine, cyanazine, simazine, Simetryne, Terbutryne and Terbutylazin; Triazinones such as e.g. B. hexazinone, Metamitron and metribuzin; Others, such as B. aminotriazole, benfuresate, Bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, Ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.

The active ingredient according to the invention can also be in its 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 active compounds or pesticides according to the invention are suitable also for controlling insects, mites, ticks, etc. in the field of Animal husbandry and animal husbandry, being better by combating pests Results, e.g. B. higher milk yields, higher weight, more beautiful animal fur, longer life, etc. can be achieved.

Good control successes are achieved, for example, against flying (Lucilia cuprina and Musca domestica), against cockroaches (Blatella germanica) and against Ticks (Boophilus microplus).

The use of the active compounds or pest control according to the invention medium happens in this area in a known manner, as by external means Application in the form of, for example, diving (dipping), spraying (spraying), Pour-on and spot-on and powdering.

The preparation of the compounds of the formula (I) according to the invention will be explained using the following examples:
Unless otherwise stated, percentages relate to percentages by weight.

Manufacturing examples Example I-1

CF₂ = CF-CH₂-CH₂-O-CO-OC₂H₅ (I-1)

5.4 g (50 mmol) of ethyl chloroformate are added dropwise to the solution of 6.3 g (50 mmol) of 3,4,4-trifluorobut-3-enol in 50 ml of methylene chloride, followed by 5.4 g (53 mmol) with ice cooling. Triethylamine. The mixture is allowed to warm to 20 ° C. and stirring is continued overnight. After dilution with water, the product is extracted with methylene chloride and concentrated in vacuo. The residue is distilled at 30 mm, the ethyl (3,4,4-trifluorobut-3-enyl) carbonate passing over at 80 ° C.
Yield 2.9 g (30% of theory).

Example I-2

3.5 g (22.5 mmol) of 2,6-difluorophenyl isocyanate are added to the solution of 2.8 g (20 mmol) of 3,4,4-trifluorobut-3-enol in 20 ml of methylene chloride. After stirring overnight at 40 ° C, washed with water, the org. Phase and dries this over magnesium sulfate. The solvent is removed in vacuo and the residue is stirred with cyclohexane.
Yield 5.4 g (96% of theory).
Mp 56-60 ° C

Example I-3

To a solution of 5.0 g (32 mmol) of hydroxyacetic acid-N, N-hexamethylene amide and 3.1 g (30 mmol) of triethylamine in 50 ml of dichloromethane are added dropwise Stir at 10.degree. C. 5.65 g (30 mmol) of 3,4,4-trifluorobut-3-enyl chloroformate to. After stirring overnight, dilute with dichloromethane and wash the Solution with water. The org. Phase is separated, i. Vac. evaporated and the oily residue on silica gel in the chloroform / ethyl acetate (4: 1) chromato system graphed. 4.2 g (yield 45.6% of theory) of the desired carbonic acid are obtained esters as oil from log p = 2.47.

In a corresponding manner and according to the general information on the production keep the following compounds of formula (I):  

Table 1

Production of raw materials Example V-1

With ice cooling and stirring, 28 g (0.28 mol) of phosgene are passed into 30 g (0.24 Mol) 3,4,4-trifluorobut-3-enol and then allowed to stir at 20 ° C. for 5 h. After blowing out the excess phosgene with nitrogen, the oily back stood distilled. 21.2 g of colorless chloride with a boiling point of 72-74 ° C./100 are obtained mm. (Educ. 46.8 th.)  

Examples of use Example A Limit concentration test

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

To produce a suitable preparation of active compound, 1% by weight is mixed. Part of active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

The active ingredient preparation is intimately mixed with the soil, which with the Test nematodes is heavily contaminated. The concentration of the active ingredient plays a role practically no role in the preparation, only the active ingredient is decisive amount per unit volume of soil, which is given in ppm (= mg / l). Man fills the treated soil into pots, sows lettuce and holds the pots at one Greenhouse temperature of 25 ° C.

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

In this test, e.g. B. the compounds according to the preparation examples I-4 and I-5 at an exemplary drug 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 produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired 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, the kill is determined 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 compound according to Preparation Example I-6 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 amount of emulsifier and dilute the concentrate with water to the desired 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, the kill is determined 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 I-2, I-4, I-5, I-6, I-7 and I-8 at an exemplary drug concentration of 0.1% kills 100% after 7 days.  

Example D Spodoptera test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the owl butterfly (Spodoptera frugiperda) occupied while the leaves are still moist.

After the desired time, the kill is determined 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 I-5 and I-7 at an exemplary drug concentration of 0.1% 100% kill after 7 days.  

Example E Nephotettix test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

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

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

In this test, e.g. B. the compounds according to the preparation examples I-2, I-4, I-5, I-6, I-7 and I-8 at an exemplary drug concentration of 0.1% kills 100% after 6 days.  

Example F Test with Boophilus microplus resistant / SP-resistant Parkhurst strain Test animals: adult sucked females

Solvent: 35 parts by weight of ethylene glycol monomethyl ether
Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

3 parts by weight are mixed to prepare a suitable formulation Active ingredient with seven parts of the solvent emulsifier Ge specified above mix and dilute the emulsion concentrate thus obtained with water to the desired concentration.

10 adult Boophilus microplus res. are in the drug preparation to be tested Immersed for 1 minute. After transfer into plastic cups and storage in The degree of killing is determined in an air-conditioned room.

100% means that all ticks have been killed; 0% means that none Ticks were killed.

In this test, e.g. B. the compounds according to the preparation examples I-5, I-6 and I-7 at an exemplary drug concentration of 1000 ppm a 100% kill.  

Example G Blowfly larva test / anti-development effect Test animals: Lucilia cuprina larvae

Solvent: 35 parts by weight of ethylene glycol monomethyl ether
Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

3 parts by weight are mixed to prepare a suitable formulation Active ingredient with seven parts of the solvent emulsifier specified above Mix and dilute the emulsion concentrate thus obtained with water to desired concentration.

About 20 Lucilia cuprina larvae are placed in a test tube, which contains approx. Contains 1 cm³ horse meat and 0.5 ml of the active ingredient preparation to be tested. The effectiveness of the active substance preparation is determined after 24 and 48 hours. The test tubes are transferred to beakers with a sand-covered bottom. To The test tubes are removed for a further 2 days and the dolls are counted.

The effect of the drug preparation is based on the number of hatched Flies after 1.5 times the development time of an untreated control judged. 100% means that no flies have hatched; 0% means that all flies hatched normally.

In this test, e.g. B. the compounds according to the preparation examples I-1, I-4 and I-8 at an exemplary active ingredient concentration of 1000 ppm a 100% kill.

Claims (13)

1. carbonic acid and carbamic acid fluorobutenyl esters of the formula (I), in which
R¹ represents hydrogen or halogen, and
R² for one of the groups stands,
in which
Y represents oxygen or sulfur,
Z represents oxygen, sulfur or NR⁴,
R³ stands for hydrogen or for optionally substituted alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkoxycarbonyl, aryloxycarbonyl, arylsulfonyl or hetaryl and
R⁴ stands for hydrogen or for optionally substituted alkyl, alkenyl, cycloalkyl, aryl, aralkyl or hetaryl or
R³ and R⁴ together with the nitrogen atom to which they are attached form an optionally substituted ring which optionally contains oxygen, sulfur or nitrogen (which is optionally substituted by alkyl, aryl or aralkyl). 2. Compounds of formula (I) according to claim 1, in which
R¹ represents hydrogen, fluorine or chlorine,
R² for one of the groups stands,
in which
Y represents oxygen or sulfur,
Z represents oxygen, sulfur or NR⁴,
R³ for hydrogen,
for optionally by halogen, cyano, amino (which is optionally substituted by C₂-C₇alkanediyl or monosubstituted or disubstituted, identically or differently by C₁-C₈alkyl), C₁-C₈alkoxy, C₁-C₈alkylthio, aminocarbonyl (which optionally by C₂-C₇-alkanediyl, one to two times, the same or different by C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-cycloalkyl, C₃- C₈-halocycloalkyl, C₁-C₄-alkyl-C₃-C₈ -Cycloalkyl, each optionally substituted by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkyl thio, C₁-C₈-haloalkylthio Phenyl or benzyl is substituted) substituted C₁-C₁₀ alkyl,
for C₃-C₈-alkenyl optionally substituted by halogen,
for C₃-C₈-cycloalkyl optionally substituted by halogen or C₁-C₆-alkyl,
for each optionally by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio, C₁-C₈ Alkoxycarbonyl or SCN substituted phenyl, benzyl, phenyloxycarbonyl or phenylsulfonyl,
for a 5- or 6-membered heterocycle optionally substituted by halogen or C₁-C₆-alkyl having one to three nitrogen atoms or
represents C₁-C₈-alkoxycarbonyl optionally substituted by halogen or C₁-C₆-alkoxy,
R⁴ for hydrogen,
for optionally by halogen, cyano, amino (which is optionally substituted by C₂-C₇-alkanediyl or optionally mono- or disubstituted, identically or differently by C₁-C₈-alkyl), C₁-C₈-alkoxy, C₁-C₈-alkylthio, aminocarbonyl (which is optionally by C₂-C₇-alkanediyl, single to double, identical or different by C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈- cycloalkyl, C₃-C₈-halocycloalkyl, C₁-C₄-alkyl-C₃- C₈-Cyclo alkyl, each optionally by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-halogen alkoxy, C₁-C₈-alkylthio, C₁-C₈- Haloalkylthio substituted phenyl or benzyl is substituted) substituted C₁-C₁₀ alkyl,
for C₃-C₈-alkenyl optionally substituted by halogen,
for C₃-C₈-cycloalkyl optionally substituted by halogen or C₁-C₆-alkyl,
for each optionally by halogen, cyano, nitro, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio, C₁-C₈- Alkoxycarbonyl or SCN substituted phenyl or benzyl,
represents a 5- or 6-membered heterocycle optionally substituted by halogen or C₁-C₆-alkyl having one to three nitrogen atoms,
or
R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- to 8-membered ring which is optionally substituted by C₁-C₈-alkyl and which optionally contains oxygen, sulfur or nitrogen (which may be substituted by C₁-C₈-alkyl, Phenyl or benzyl is substituted) contains. 3. Compounds of formula (I) according to claim 1, in which
R¹ represents fluorine,
R² for the group stands,
in which
Y represents oxygen or sulfur,
Z represents oxygen, sulfur or NR⁴,
R³ for hydrogen,
for optionally by fluorine, chlorine, cyano, amino (which is optionally substituted by C₂-C₆-alkanediyl or monosubstituted or disubstituted, identically or differently by C₁-C₆-alkyl), C₁-C₆-alkoxy, C₁-C₆-alkylthio, aminocarbonyl (Which is optionally by C₂-C₆-alkanediyl, single to double, identical or different by C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₇-cycloalkyl, C₃-C₇-halocycloalkyl, C₁-C₃-alkyl-C₃ -C₇-cycloalkyl, each because optionally halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆- alkylthio, C₁-C₆- Haloalkylthio substituted phenyl or benzyl) substituted C₁-C₆ alkyl,
for C₄-C₈-cycloalkyl optionally substituted by fluorine, chlorine or C₁-C₄-alkyl,
for each optionally by fluorine, chlorine, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁- C₆-alkoxycarbonyl or SCN substituted phenyl, benzyl, phenoxycarbonyl or phenylsulfonyl,
represents C₁-C₆-alkoxycarbonyl optionally substituted by fluorine, chlorine or C₁-C₄-alkoxy,
R⁴ for hydrogen,
represents C₁-C₆-alkyl or C₄-C₈-cycloalkyl,
or
R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- to 8-membered ring, optionally substituted by C₁-C₆-alkyl, which optionally contains oxygen, sulfur or nitrogen (which may be substituted by C₁-C₆-alkyl, Phenyl or benzyl is substituted) contains. 4. Compounds of formula (I) according to claim 1, in which
R¹ represents fluorine,
R² for the group stands,
in which
Y stands for oxygen,
Z represents oxygen, sulfur or NR⁴,
R³ for hydrogen,
for optionally by halogen, cyano, amino (which is optionally substituted by C₂-C₆alkanediyl or monosubstituted or disubstituted, identically or differently by C₁-C₆alkyl), C₁-C₆alkoxy, C₁-C₆alkylthio or aminocarbonyl ( which is optionally by C₂-C₆-alkanediyl, single to double, identical or different by C₁-C₈-alkyl, or by in each case optionally by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆- Alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-halo genalkylthio substituted phenyl or benzyl is substituted) substituted C₁-C₆-alkyl,
for C₃- C₆ alkenyl optionally substituted by fluorine, chlorine or bromine,
for C₄-C₈-cycloalkyl optionally substituted by C₁-C₄-alkyl,
for optionally by fluorine, chlorine, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkyl thio, C₁-C₄-haloalkylthio or C₁-C₄- Alkoxycarbonyl substituted phenyl, benzyl, phenoxy or phenylsulfonyl,
represents C₁-C₄-alkoxycarbonyl optionally substituted by fluorine, chlorine or C₁-C₄-alkoxy,
R⁴ for hydrogen,
for C₁-C₄ alkyl or
represents C₄-C₆-cycloalkyl,
or
R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- to 8-membered ring, optionally substituted by C₁-C₄-alkyl, which optionally contains oxygen, sulfur or nitrogen (which may be substituted by C₁-C₄-alkyl or Benzyl is substituted) contains. 5. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• A) fluorobutenols of the formula (II) in which
  R¹ has the meaning given above,
  • α) with compounds of the formula (III) in which
    Y, Z and R³ have the meanings given above,
    in the presence of a diluent and optionally in the presence of a base,
    or
  • β) with an iso (thio) cyanate of the formula (IV) YCN-R³ (IV) in which
    Y and R³ have the meanings given above,
    in the presence of a diluent and, if appropriate, in the presence of a catalyst,
    or
• B) fluorobutene thiols of the formula (IIa) in which
  R¹ has the meaning given above,
  with a compound of formula (IIIa) in which
  Y and R³ have the meanings given above,
  in the presence of a diluent and optionally in the presence of a base,
  or
• C) compounds of the formula (V) in which
  R¹ and Y have the meanings given above,
  with a compound of formula (VI) HZ-R³ (VI) in which
  Z and R³ have the meanings given above,
  in the presence of a diluent and optionally in the presence of a base,
  or
• D) Compounds of the formula (VII) in which
  R¹ and Y have the meanings given above,
  with a compound of formula (VIII) HS-R³ (VIII) in which
  R³ has the meaning given above,
  in the presence of a diluent and optionally in the presence of a base.

6. Compounds of formula (V) in which
R¹ and Y have the meanings mentioned in claim 1. 7. A process for the preparation of compounds of formula (II) according to claim 6, characterized in that fluorobutenols of formula (II) in which
R¹ has the meaning given in claim 1,
reacted with phosgene or thiophosgene. 8. Compounds of formula (VII) in which
R¹ and Y have the meanings mentioned in claim 1. 9. A process for the preparation of compounds of the formula (VII) according to claim 8, characterized in that fluorobutene thiols of the formula (IIa) in which
R¹ has the meaning given in claim 1,
reacted with phosgene or thiophosgene. 10. pesticide, characterized by a content of min at least one compound of formula (I) according to claim 1.   11. Use of compounds of formula (I) according to claim 1 for loading control of animal pests. 12. A method for controlling animal pests, characterized is characterized in that compounds of formula (I) according to claim 1 on the Pests and / or their habitat. 13. Process for the preparation of agents for controlling animal Pests, characterized in that compounds of the formula (I) according to claim 1 with extenders and / or surface-active substances mixed.