KR19990044035A - 4,4-difluoro-3-butenyl ester derivatives or 4,4-difluoro-3-halogen-3-butenyl ester derivatives and their use as agrochemicals - Google Patents

Abstract

The present invention relates to novel esters of formula (I), processes for their preparation and their use for inhibiting animal pests:

(I)

In the above formula

R ¹ represents hydrogen or halogen, and Q represents the following substituents a) or b);

a) or

b) ZR ⁹ or Z (P = W) R ¹⁰ R ¹¹

In the above formula

R ² , R ³ , R ⁹ , R ¹⁰ , R ¹¹ , Z and W are each as defined in the detailed description.

Description

4,4-difluoro-3-butenyl ester derivatives or 4,4-difluoro-3-halogen-3-butenyl ester derivatives and their use as agrochemicals

It has already been known that the compound 3,4,4-trifluorobutan-3-enyl 4-chlorobenzoate has the nematode characteristic (see US-4 962 580). However, the efficacy and activity spectrum of this compound, especially at low application rates and concentrations, is entirely unsatisfactory.

The present invention relates to novel esters, to their preparation and to their use for controlling animal pests, in particular insects, arthropods and nematodes, which occur in the fields of agriculture, forestry, storage and materials protection and sanitation.

Accordingly, the present invention provides novel esters of formula < RTI ID = 0.0 > (I) <

In the above formula

R ¹ represents hydrogen or halogen, and Q represents the following substituents a) or b);

a) or

b) ZR ⁹ or Z (P = W) R ¹⁰ R ¹¹

In the above formula

R ² represents hydrogen, nitro, cyano, halogen, alkyl, alkoxy, alkylthio or optionally substituted aryl,

R ³ represents COOH, SO ₃ H, NR ⁴ R ⁵ or OR ⁶ ,

here,

R < ⁴ > represents hydrogen, alkyl or optionally substituted aryl,

R ⁵ represents hydrogen, alkyl, optionally substituted aryl or COR ⁷ ,

R ⁶ represents hydrogen, optionally substituted aralkyl, CONR ⁴ R ⁵ or COR ⁷ ,

R ⁷ represents alkyl, alkenyl, optionally substituted aryl or NR ⁴ R ⁸ ,

R < ⁸ > represents hydrogen, alkyl or optionally substituted aryl,

Z represents an aliphatic group having 1 to 4 carbon atoms, provided that when Z represents CH ₂ , R ⁹ does not represent phenyl,

W represents oxygen or sulfur,

R ⁹ represents a) aromatic group or represents a heterocyclic group (such as a pyrazolyl, imidazolyl, triazolyl, morpholinyl, piperidinyl, piperazinyl or pyrrolidinyl) Alkyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, sulfonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester of one of these acids, amide Or a radical of a thioester,

β) hydrogen, OR ^12, SR ^12, halogen, NR ¹² R ^13, cyano, trimethylsilyl, nitro, phenyl, sulfonic acid or represent an ester, amide, or the radical of a thioester of the acid, or cyano, trimethylsilyl, Or an ester, amide or thioester of one of these acids, optionally substituted with one or more substituents selected from the group consisting of hydroxy, alkoxy, halogen, nitro, optionally mono-or dialkyl-substituted amino, thiol, alkylthio, phenyl, sulfonic, phosphonic, Gt; represents an aliphatic group optionally substituted by at least one radical selected from < RTI ID = 0.0 >

R ¹⁰ and R ¹¹ independently of one another denote R ²² , OR ²² , SR ²² or NR ²² R ²³ ,

here,

R < ¹² > and R < ¹³ >

i) hydrogen,

ii) alkyl, cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, sulfonic acid, phosphonic acid, An aliphatic group or an aromatic or heterocyclic group optionally having 1 to 12 carbon atoms which is optionally substituted by at least one radical selected from the group consisting of a carboxylic acid, a carboxylic acid, a carboxylic acid or a radical of an ester, amide or thioester of one of these acids,

iii) R ¹² and R ¹³ together with the bonding nitrogen atom form part of an amino acid,

R ¹² is hydrogen or an alkyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, sulfonic acid, phosphonic acid, phosphinic acid or Or an aliphatic or aromatic group optionally substituted by at least one substituent selected from the group consisting of a radical of a carboxylic acid or an ester, amide or thioester of one of these acids, or phenyl, then R ¹³ may also be OR ¹⁶ , COR ¹⁶ , COOR ²¹ , NR ¹⁶ R ¹⁷ , SO ₂ R ¹⁸ , P (= O) R ¹⁹ R ²⁰ , wherein

R ¹⁶ and R ¹⁷ independently of one another each represent hydrogen, alkyl or aryl,

R ¹⁸ represents hydrogen, alkyl, halogenoalkyl or aryl,

R ¹⁹ and R ²⁰ independently of one another each represent hydrogen, alkyl, aryl, alkyl, alkylthio, arylthio, alkylamino, dialkylamino, arylamino or OR ²¹

R ²¹ represents hydrogen, alkyl or aryl,

R ²² and R ²³ independently from each other are each hydrogen or in each case cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, Or an aliphatic or aromatic group optionally substituted by at least one substituent selected from the group consisting of a phosphonic, phosphonic, or carboxylic acid or a radical of an ester, amide or thioester of one of these acids.

The compounds of formula I may exist as salts if they contain functional groups capable of forming salts. These functional groups include, for example, carboxyl groups and hydroxyl groups. Suitable cations include, for example, alkali metal and alkaline earth metal ions such as sodium, calcium, potassium and magnesium, quaternary ammonium ions such as the ammonium ion itself and also mono-, di- and trialkylammonium ions such as isopropylammonium, And also include, for example, pyridinium ions.

Comprising the meaning of group Q, the following compounds of formula Ia, Ib-1 or Ib-2 are obtained:

CF ₂ = CR ¹ -CH ₂ -CH ₂ -O-CO-ZR ⁹

CF ₂ = CR ¹ -CH ₂ -CH ₂ -O-CO-Z (P = W) R ¹⁰ R ¹¹

Wherein R ¹ , R ² , R ³ , R ⁹ , R ¹⁰ , R ¹¹ , Z and W are as defined above.

Depending on the nature of the substituents, the compounds of formula (I) may exist as geometric and / or optical isomers or as isomeric mixtures of various compositions. The present invention relates to both pure isomers and isomer mixtures.

It has also been found that the compound of formula (Ia) is obtained by the following steps A), B) or C):

A) reacting a benzoic acid derivative of formula (II) with fluorobutene bromide of formula (III) in the presence of a diluent,

B) reacting an anhydrous isoic acid of formula (IV), if appropriate in the presence of a base, and if appropriate in the presence of a diluent, with a fluorobutanol of the formula (V)

C) reacting an acid anhydride of formula (VI) with fluorobutanol, if appropriate in the presence of a diluent and if appropriate in the presence of a base,

In the above formula

X ⁽⁺⁾ represents an alkali metal ion or ammonium ion

Y represents CO or SO ₂ ,

R ¹ , R ² , R ³ and R ⁴ are as defined above.

Compounds of formula (Ib), Ib-1 and Ib-2 may be prepared by generally known methods. The starting materials required can be easily prepared by known methods and / or can be used.

Finally, the novel esters of formula (I) have been found to be particularly suitable for inhibiting animal pests, especially insects, arthropods and nematodes, which have very pronounced biological properties and have been developed in the fields of agriculture, forestry, .

Formula Ia provides a general definition of an aryl carboxylic acid ester according to the present invention.

Preferred substituents or ranges of radicals given in the formulas mentioned above and below are as follows:

R ¹ is preferably hydrogen, fluorine, chlorine or bromine.

R ² is preferably hydrogen, nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₈ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio or optionally cyano- -, chlorine-, bromine- or C ₁ -C ₆ -alkoxy-substituted phenyl.

R ³ preferably represents 2-COOH, 2-SO ₃ H, NR ⁴ R ⁵ or OR ⁶ .

R ⁴ is preferably hydrogen, C ₁ -C ₈ -alkyl or optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy-substituted phenyl .

R ⁵ is preferably hydrogen, C ₁ -C ₈ -alkyl, optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy- Or COR ⁷ .

R ⁶ is preferably hydrogen, optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy-substituted phenyl-C ₁ -C ₆ -alkyl Or represents CONR ⁴ R ⁵ or COR ⁷ .

R ⁷ is preferably C ₁ -C ₈ -alkyl, C ₂ -C ₆ -alkenyl, optionally fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy- Substituted phenyl or NR < ⁴ > R < ^{8 &} gt ;.

R ⁸ is preferably hydrogen, C ₁ -C ₈ -alkyl or optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy-substituted phenyl .

R ¹ particularly preferably represents hydrogen or fluorine.

R ² is particularly preferably hydrogen, nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or optionally fluorine-, -, or C ₁ -C ₄ -alkoxy-substituted phenyl.

R ³ particularly preferably represents 2-COOH, 2-SO ₃ H, NR ⁴ R ⁵ or OR ⁶ . R ⁴ particularly preferably represents hydrogen, C ₁ -C ₄ -alkyl or optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl.

R ⁵ particularly preferably represents hydrogen, C ₁ -C ₄ -alkyl, optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl or represents COR ⁷ .

R ⁶ particularly preferably represents hydrogen, optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl or represents CONR ⁴ R ⁵ or COR ⁷ .

R ⁷ particularly preferably represents C ₁ -C ₄ -alkyl, C ₂ -C ₆ -alkenyl, optionally fluorine-, chlorine- or C ₁ -C ₄ -alkyl-substituted phenyl or represents NR ⁴ R ⁸ .

R ⁸ particularly preferably represents hydrogen, C ₁ -C ₄ -alkyl or optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl.

The most preferred group of compounds of formula I are those in which R ¹ represents fluorine, R ² represents hydrogen and R ³ represents radical NR ⁴ R ⁵ .

For the radical definition of a compound of formula (Ib) the following applies:

&Quot; Halogen ", alone or in combination with other radicals, denotes fluorine, chlorine, bromine or iodine.

&Quot; Alkyl " refers to a straight or branched chain group of from 1 to about 7 carbon atoms.

&Quot; Lower alkyl " refers to a group having from 1 to about 4 carbon atoms.

&Quot; Aliphatic " means from 1 to about 10 carbon atoms or a saturated or unsaturated alkyl as defined above, or from 2 to about 10 carbon atoms, or a linear or branched alkenyl group as defined above.

&Quot; Alkoxy " refers to a lower alkyl group bonded by oxygen.

&Quot; Alkylthio " refers to a lower alkyl group bound by sulfur.

&Quot; Alkoxycarbonyl " refers to lower alkyl esters of carboxylic acids.

The term " radical of amide, ester or thioester of carboxylic acid, sulfonic acid, phosphonic acid, phosphonic acid or one of these acids " means that at least one (preferably one) carbon atom is replaced by a carboxyl group (COOH) An aliphatic group substituted by a phosphoric acid group or a phosphonic acid group or by a lower alkyl ester, amide or lower alkyl thioester of one of these acids.

&Quot; Amino acid " refers to a compound having an amino group and an acid group separated by a C atom. These include natural amino acids, as well as those with other substituents on the central carbon atom.

&Quot; Alkyl- or arylsulfonamide " refers to a sulfonamido group substituted by a lower alkyl group or phenyl group, each of which may be substituted.

&Quot; Aromatic group " or " aryl " refers to phenyl optionally substituted as defined above.

&Quot; Heterocycle " refers to a cyclic compound containing at least one element other than carbon as a ring source. The rings may be saturated or unsaturated. Hetero atoms can be oxygen, nitrogen, sulfur or other elements. Heterocycles include, for example, radicals of thiadiazole, pyridine, thiazole, isothiazole, oxazole, imidazole, pyrazole, triazole, benzothiazole, morpholine, piperidine, piperazine and pyrrolidine In each case in the form of a radical of a sulfonic acid, a phosphonic acid, a phosphonic acid, an ester of one of these acids, an amide or a thioester, a cyano, a trimethylsilyl, a hydroxyl, an alkoxy, a halogen, a nitro, an amino, a thiol, , Carboxyl, alkoxycarbonyl, and phenyl. ≪ / RTI >

Among the compounds of formula (Ib) mentioned hereinbefore, a particularly highly preferred compound of formula (Ib) is 3,4,4-trifluoro-3-butenyl N- [(1,1- dimethylethoxy) carbonyl] It is Ranitate.

The above-mentioned general or preferred radicals or examples apply to the final product, correspondingly to starting materials and intermediates. These radical definitions can be combined with one another if desired, i.e. combinations within each preferred range are possible.

Of the compounds of formula (Ia), the compounds of formula (Ia) are more preferred, including combinations of the meanings given above as being preferred (which may be preferred) according to the invention.

Among the compounds of formula (Ia), the compounds of formula (Ia) comprising a combination of the meanings given above as particularly preferred are particularly preferred according to the invention.

In the radical definitions given above and below, hydrocarbon radicals such as alkyl or alkenyl, including those linked with heteroatoms such as alkoxy or alkylthio-, are as straight or branched as possible.

For example, when sodium salicylate and 1-bromo-3,4,4-trifluorobutane-3-ene are used as starting materials for preparing the compound of formula (Ia) according to process A) Can be illustrated by the following equation:

For example, when 3,4,4-trifluorovan-3-ene is used as the starting material for the preparation of the compound of formula (Ia) according to process B), the reaction route is illustrated by the following scheme Can:

For example, when using phthalic anhydride and 3,4,4-trifluorobutan-3-en-1-ol as starting materials for preparing the compound of formula (Ia) according to process C) : ≪ / RTI >

Step A) for preparing a compound of formula (Ia) as described above is characterized by reacting the benzoic acid derivative of formula (II) with fluorobutenyl bromide of formula (III) in the presence of a diluent.

Suitable diluents include, in particular, organic solvents, such as, for example, chlorinated aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers such as dioxane or tetrahydrofuran, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, amides such as dimethylformamide Or a carboxylic acid ester such as ethyl acetate.

The reaction temperature in process A) may vary over a relatively wide range. In general, the reaction is carried out at a temperature of 0 ° C to 160 ° C, preferably 20 ° C to 120 ° C.

The molar ratio of the compound of formula (II) to the compound of formula (III) is generally from 2: 1 to 1: 2.

The reaction is generally carried out under atmospheric pressure.

For process completion, the reaction mixture is hydrolyzed, for example, and the product is extracted with an organic solvent, such as ethyl acetate, dichloromethane or toluene, and then the solvent is removed.

Step B) for the preparation of compounds of formula (Ia) as described above is characterized in that anhydrous isonic acid of formula (IV) is reacted with fluorobutanol of formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of a base.

Suitable diluents for this process are all conventional solvents.

It is preferred to use optionally halogenated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane, chloroform, dichloroethane or chlorobenzene or ethers such as tetrahydrofuran or dioxane.

The reaction may also be carried out in the absence of the above-mentioned solvents. In this case, it is useful to use an excess of fluorobutanol of formula (V).

It is useful to carry out step B) according to the invention in the presence of a base.

Amine, preferably a tertiary amine, such as triethylamine, pyridine or diazabicyclo-undecene (DBU), or an inorganic base, such as an alkali metal carbonate, bicarbonate or hydroxide such as potassium carbonate, sodium bicarbonate, It is preferable to use a lockside.

It is sufficient to use a catalytic amount of base.

The reaction temperature in process B) can be varied relatively widely. In general, the reaction is carried out at a temperature of 0 ° C to 180 ° C, preferably 20 ° C to 140 ° C.

The compounds of formulas IV and V are generally used in a molar ratio of 1: 2 to 2: 1. The reaction is generally carried out under atmospheric pressure.

For process completion, the reaction mixture is hydrolyzed, for example, and the product is extracted with an organic solvent, such as ethyl acetate, dichloromethane or toluene, and then the solvent is removed.

Process C) according to the invention for preparing a compound of formula (Ia) is characterized in that the acid anhydride of formula (VI) is reacted with fluorobutene of formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of a base.

The specifications provided for step B) apply correspondingly to the diluent, the base, the implementation of the reaction and the completion of the work.

The benzoic acid derivatives of formula II required as starting materials for step A) can be obtained by reacting the corresponding benzoic acid (easily prepared and most commonly used) with a base (e.g. alkali metal hydroxides such as lithium hydroxide, Or by reaction with sodium hydroxide or an amine such as dimethylamine, triethylamine or butylamine) in a simple known manner.

Fluorobutenyl bromide of formula III further required as starting material is known and / or can be prepared in a simple manner by known methods (cf. CA 119, 94 942).

The anhydrous isocyanic acid of formula IV required as starting material for step B) is known and is prepared by the known method (Methoden der Organ. Chemie - Houben-Weyl, Vol 4E, p. 214 ff .

Fluorobutenols of the formula V furthermore required as starting materials are known (see WO 92/15 555).

The acid anhydrides of formula VI required as starting materials for step C) are known and / or can be prepared by known methods (Methodicum Chimicum, C-O compounds, Vol. 5, p. 614 ff. (1975)).

The active compounds are suitable for controlling animal pests, in particular insects, arthropods and nematodes, occurring in the agricultural, forestry, storage product and material protection, and hygiene sectors. They can preferably be used as grain protectors. They are active against the species with common irritability and tolerance and for all stages or stages of expression. The above-mentioned pests include:

Isopoda necks, such as Oniscus asellus, Armadillidium vulgare and Porcellio scaber;

A diplopoda neck, for example Blaniulus guttulatus;

Chilopoda necks, for example Geophilus carpophagus and Scutigera spec .;

A neck of Symphyla, for example Scutigerella immaculata;

Thysanura neck, for example Lepisma saccharina;

Collembola neck, for example Onychiurus armatus;

Such as Orthoptera sp., Such as Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, But are not limited to, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, and Schistoser < RTI ID = 0.0 > Schistocerca gregaria;

Dermaptera tree, for example Forficula auricularia;

Isoptera, for example, Reticulitermes spp .;

Anoplura, for example Pediculus humanus corporis, Haematopinus spp. And Linognathus spp.;

Mallophaga necks, such as Trichodectes spp. And Damalinea spp .;

Thysanoptera species, for example, Hercinothrips femoralis and Thrips tabaci;

Heteroptera species such as Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rodney spp. Rhodnius prolixus and Triatoma spp .;

For example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, and the like, Such as Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundi, For example, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, ), Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, and the like. , Saichetia olea (Sa Aspergillus niger, Issetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. And Psylla spp .;

Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, For example, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. , Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., And the like. For example, Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Such as Spodopter litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp. Such as Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pelionel, For example, Tinea pleeionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, and Tortrix viridana;

Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, and the like. , Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., And the like. Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthomonas spp., Pseudomonas spp., Pseudomonas spp. Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceu Thrrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp. , Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides (Gibbium psylloides), Lyctus spp., Meligethes aenaus, ), Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica;

Hymenoptera spp., For example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. Vespa spp.);

Diptera spp., For example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca subsp. Musca spp., Fannia spp., Callipora erythrocephala, Lucilia spp., Chrysomia spp., Cuterebra sp. , Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp. , Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., And Pheomia spp. Pegomyia hyoscyami, Ceratitis capitata, Dacus loeae, and Tupulapalu Four (Tipila paludosa).

Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp. And Ctenocephalides felis.

Arachnida species, for example, Scorpio maurus and Latrodectus mactans.

Acarina spp., For example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus spp., Eriophys lebis spp. Such as 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., And Tetranychus spp.).

Plant parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Hetero (Heterodera spp.), Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Key Xiphinema spp. And Trichodorus spp.

The compounds of formula I according to the invention have, for example, a remarkable carnivorous activity against Meloidogyne incognita.

They also have good leaf insecticidal activity.

The active compounds may be formulated in customary formulations, such as liquids, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspensions-emulsion concentrates, , And ultrafine capsules in polymeric materials.

These preparations are prepared in a known manner, for example by mixing the active compounds with extenders, i. E. Liquid solvents and / or solid carriers, using surfactants, i. E. Emulsifiers and / or dispersants and / or foaming agents.

When water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent. Essentially, suitable liquid solvents are: aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example mineral oil fractions , Aliphatic hydrocarbons such as mineral oil and vegetable oil, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polarities such as dimethylformamide and dimethyl sulfoxide Solvent, and water.

Suitable solid carriers are, for example, ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silicas, alumina and silicates; Suitable solid carriers for granules include, but are not limited to, ground granulated and ground natural rocks such as calcite, marble, pumice, hemastone and dolomite, as well as synthetic granules of inorganic and organic powders, and organics such as sawdust, coconut shells, cornstalks and tobacco stalks. A granule of matter; Suitable emulsifiers and / or blowing agents include, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and proteins Hydrolyzate; Suitable dispersing agents are, for example, lignin-sulfite waste solutions and methylcellulose.

Adhesives such as natural and synthetic polymers in the form of powders, granules or emulsions, such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin, and synthetic phosphatides, Can be used. As other additives, mineral oil and vegetable oil may be used.

Inorganic pigments such as iron oxide, titanium oxide and prussian blue and coloring agents such as organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc Can be used.

The preparations generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active compound.

The active compounds according to the invention can be used as commercial preparations as a mixture with other active compounds such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides, And the like. Pesticides include in particular, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms and the like.

Examples of components which are particularly advantageous for the mixtures are:

Fungicide:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxyanilide; 2,6-dichloro-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; But are not limited to, 2-phenylphenol (OPP), aldimorph, amipropos, anilazine, azaconazole, benzalacyl, benodanil, benomyl, binaparyl, biphenyl, bitterthanol, But are not limited to, bromomonasol, bupyrimate, butothiobate, calcium polysulfide, captapol, mercaptans, carbendazim, carboxyne, quinomethionate, chlornev, chloropicrin, chlorothalonil, czulolinate, But are not limited to, cymoxanil, cyprocannazole, cyprofuran, dichlorophen, diclobutrazole, diclofenanide, dichloromethane, dichlororan, diethophenecarb, diphenococonazole, dimethyimol, dimethomorph , Dinonocazole, dinocap, diphenylamine, dipyrithione, ditaliphose, dithianone, dodine, Draisonolone, ediphenose, epoxiconazole, ethidimol, etidiazole, Naphthol, naphthol, naphthol, phenol, phenanthroline, phenclodonyl, phenpropidine, But are not limited to, tetracycline, tartrate, hydroxide penitin, perhalum, perimin, fluorazin, fluoridoxonyl, fluorimide, fluquinone, flucilazole, flu sulfamide, plutyranyl, (IBPs) such as aluminum, phthalide, fueridazole, furalacox, furecylox, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imbenzonazole, iminoctadine, ), Iprodione, isoprothiolane, carzymycin, copper formulations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixtures, But are not limited to, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, - Isopropyl, Noarimol, Opulfas, Oxa But are not limited to, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, Pyrimethanil, pyroquilon, quintogen (PCNB), sulfur and sulfur preparations, tebuconazole, teclophthalam, tetracycline, Thiophene-methyl, thiam, tolclofos-methyl, tolyl fl uanide, triadimefon, triadimenol, triazide, triclamide, Triacylglycerol, triacylglycerol, triacylglycerol, triacylglycerol, triacylglycerol, triacylglycerol, triacylglycerol, triacylglycerol,

Live bacterial agent:

Hydroxypentyl, nickel dimethyldithiocarbamate, carzymycin, octylrionone, furancarboxylic acid, oxytetracycline, provenazole, streptomycin, teclophthalimide, copper sulfate and other copper formulations.

Pesticides / acaricides / nematocides:

Azamycin, Azamycin, Azamycin, Abamectin, AC 303 630, Acetate, Acrinatrine, Allanicab, Aldicarb, Alphametriene, Amitraz, Abermectin, AZ 60541, Azadirachtin, But are not limited to, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, cyclophosphamide, Carbofenone, carbosulfan, carotene, CGA 157 419, CGA 184 699, chloetocarb, chlorethoxyphosphorus, chlorphenvinphosphorus, chlorfluramuron, chlorothiophene, But are not limited to, mesophos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, cocitorin, clofentine, cyanophores, cycloprothrin, cyfluthrin, cyhalothrin, Methylene, dicyclopentadiene, cyclopentadiene, cyclodextrin, cyclodextrin, cyclodextrin, Diethionone, dithionone, dichlopenthone, dichlorobos, dicliphorus, dichotorousus, diethion, diplubenzuron, dimethoate, dimethylbinphosphine, dioxathione, But are not limited to, but are not limited to, but are not limited to, but are not limited to, but are not limited to, camptothecin, camptothecin, camptothecin, camptothecin, camptothecin, camptothecin, camptothecin, camptothecin camptothecin, camptothecin camptothecin, camptothecin camptothecin camptothecin camptothecin camptothecin camptothecin camptothecin camptothecin camptothecin camptothecin , Phenoxycarb, fenproparin, fenpyrad, penicloximate, fention, fenvalerate, fipronil, furosine, flucyclovsulone, flucentrinate, flupenoxolone, flupenprox , Fluorovanate, phonophos, formothion, postazite, puibenpuprox, furathiocarb, HCH, heptenophores, hexaflumuron, hecityas, imidacloprid, , Isopenpose, isoprocarb, isoxathione, ibuprofen But are not limited to, tin, lambda-cyhalothrin, rufenuron, malathion, mecharbam, mebinfos, mesulfenp, methaldheid, methacryphos, methamidopos, methidathion, methiocarb, Niacin, oximetol, oxydemethine M, oxydepropos, parathion A, parathion M, permethrin, pentaerythritol, palmitic acid, Phytohemagglutinin, erythromycin, erythromycin, erythromycin, erythromycin, erythromycin, erythromycin, erythromycin, erythromycin, Pyridopropenes, pyrimidines, pyrimidifenes, pyridopropoxyphenes, quinolphos, RH 5992, salithiones, tetraphenes, silafluofenes, , Sulfapept, sulfopropyl, tebufenozide, tebufenpyrad, tebuprimipiph, tee Threonine, thionine, thionine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, Triazopos, triazuron, trichlorfon, triflumuron, trimetacarb, bromidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Other known active compounds, such as herbicides, or mixtures with fertilizers and growth-regulating agents, are also possible.

The active compounds according to the invention may also be present in the form of their commercial preparations as a mixture with a synergistic agent and in their use forms prepared from these preparations. The synergist is a compound that increases the action of the active compound without the added synergist itself being active.

The active compound content of the active form prepared from commercial preparations can vary widely. The concentration of the active compound of the type used is 0.0000001 to 95% by weight, preferably 0.0001 to 1% by weight.

The compound is used in a conventional manner suitable for the type of use.

When used in hygiene pests and stored pests, the active compounds according to the present invention exhibit excellent residual activity against wood and clay, and exhibit excellent stability against alkali on the lime surface.

The active compounds according to the invention are not only active against plant, sanitary and storage pests, but also in the field of veterinary medicine in the field of animal parasites (ex vivo parasites), such as, for example, mite mite, mite mite, Trombidium is active against culid mites, flies (saliva or blood sucking), parasitic fly larvae, ducks, hairy ducks, birds and fleas. These parasites include the following:

Anoplurida species such as Haematopinus spp., Linognathus spp., Pediculus spp., Pthirus spp. And Soleil spp. Solanopotes spp.

For example, Mallophagida neck and Amblycerina and Ischnocerina subsp., Such as Trimenopon spp., Menopon spp., Trinoton spp. ), Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., And the like. Felicola spp.

Diptera and Nematocerina and Brachycerina subsp., Such as Aedes spp., Anopheles spp., Culex spp. Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Corynebacterium spp. Crysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Filipomia subsp. Such as Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp. ), Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp. (For example, Lucilia spp., Chrysomia spp., Wohlfartia spp., Sarcophaga spp., Oestrus spp., Hypodermicus spp. Hypoderma spp., Gasterophilus spp., Hyppobosca spp., Lipoptana spp., And Melophagus spp.).

Siphonaptera spp., For example Pulex spp., Ctenocephalides spp., Xenopsylla spp. And Ceratophyllus spp.

Heteroptera spp., For example, Cimex spp., Triatoma spp., Rhodnius spp. And Panstrongylus spp.

Blattarida species, for example Blatta orientalis, Periplaneta americana, Blatta germanica and Supella spp.

Acarina, Acarida, and Meta- and Mesostigmata, for example Argas spp., Ornithodorus spp., Otabius spp. ), Ixodes spp., Amblyomma spp., Boophilus spp., Dermancentor spp., Haemaphysalis spp., And the like. ), Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Pseudomonas spp. ), Sternostoma spp. And Varroa spp.

Actinidia (Prostigmata) neck and Acaridida (Astigmata) neck, for example Acarapis spp., Cheyletiella spp. , Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Pseudomonas spp. ), Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., And the like. ), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Pseudomonas spp. ), Notoedres spp., Knemidocoptes spp., Cytodi spp. tes spp.) and Laminosioptes spp.

For example, these compounds show excellent activity against Boophilus microplus and Lucilia cuprina.

The active compounds of the formula I according to the invention can also be used in the production of agricultural livestock such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, Such as animals, such as dogs, cats, birds in cages and fish tanks, and also arthropods that infect so-called laboratory animals such as hamsters, guinea pigs, rats and mice. By inhibiting these arthropods, the use of the active compounds according to the invention results in reduced mortality and reduced yields (for example in the production of meat, milk, wool, leather, eggs, honey) Breeding is possible.

The active compound according to the present invention can be administered orally in the form of tablets, capsules, drinks, powders, granules, pastes, lozenges, mixes with feeds in the field of water, intramuscular administration in the form of suppositories, parenteral administration, For example, by intramuscular, subcutaneous, intravenous and intraperitoneal injection, by means of injection, by injection (by intramuscular, subcutaneous, intravenous and intraperitoneal), by means of implant, by intranasal administration, for example by dipping or dipping, spraying, Is used in a manner known percutaneously in the form of a molded article containing the compound, for example in the form of a necklace, an ear tag, a tail tag, a leg band, a sling or a display device.

When administered to livestock, poultry, rabbits and the like, the active compounds of formula (I) may be administered directly, or in the form of powders, emulsions, flowables, containing from 1 to 80% It can be used by dilution or as a chemical bath.

The preparation and use of the active compounds according to the invention are illustrated as the following examples.

<Production Example>

&Lt; Example 1 >

50.5 g (0.31 mol) of anhydrous isantoic acid in 300 ml of toluene were mixed with 1 g of 4-dimethylaminopyridine, 0.1 g of potassium carbonate and 44.1 g (0.35 mol) of 3,4,4-trifluorobutan- &Lt; / RTI &gt; under reflux for 15 hours. After cooling, the reaction mixture is washed with water and the toluene is removed under reduced pressure. Trifluoromethyl-3,4,4-trifluorobutan-3-en-1-yl 2-aminobenzoate (67.7 g) was obtained as a clear oil.

Yield: 89.1% of theory

log p ^* (pH 2) = 3.05; n ²⁰ _D = 1.5160

&Lt; Example 2 >

32 g (0.2 mol) of sodium salicylate in 100 ml of dimethylsulfoxide was heated at 50 DEG C for 15 hours with 28.4 g (0.15 mol) of 1-bromo-3,4,4-trifluorobutane- do. After cooling, the reaction mixture is diluted with water, the product is extracted with methylene chloride and the organic phase is concentrated under reduced pressure. The residue is then distilled under reduced pressure. 24.3 g (yield: 65.8% of theory) of colorless 3,4,4-trifluorobutan-3-en-1-yl 2-hydroxy-benzoate having a boiling point of 102-108 DEG C / 1.5 mm is obtained.

According to the general preparation process analogous to examples 1 and 2 and / or the following compounds of formula Ia are obtained:

(Ia)

Logs for criterion 10 of n-octanol / water partition coefficient, as determined by reverse phase HPLC analysis using ^* log p: H ₂ O / CH ₃ CN

Examples for compounds of formula (Ib):

&Lt; Example 23 >

(C ₂ H ₅ O) 2P (= O) CH ₂ COOH + CF ₂ = CF-CH ₂ -CH ₂ -Br

→ (C ₂ H ₅ O) ₂ P (═O) CH ₂ COO-CH ₂ -CH ₂ -CF═CF ₂

2 g (0.01 mol) of O, O-diethylphosphonoacetic acid and 1.52 g of DBU (diazabicyclooctane) in 35 ml of acetonitrile were added to a solution of 4-bromo-1,1,2-trifluoro-butane- - ene (2.5 g, 0.12 mol) and the mixture is stirred at 60 &lt; 0 &gt; C for 7 hours. The reaction mixture is then poured into water and extracted twice with ether. The combined ether phases are washed twice with 5% strength aqueous NaOH solution, then twice with water and dried over magnesium sulfate. Evaporation of the ether afforded 0.93 g of 3,4,4-trifluorobutan-3-enol O, O-diethylphosphonoacetate as a clear solution.

Elemental analysis: calculated value; C 39.48; H 5.30

Found; C 38.97; H 5.24

&Lt; Example 24 >

(C ₂ H ₅ O) ₂ P (═O) CH ₂ -COO-CH ₂ -CH ₂ -CF═CF ₂

→ (HO) ₂ P (= O) -CH ₂ -COO-CH ₂ -CH ₂ -CF═CF ₂

While cooling with ice, 4.9 ml (0.037 mol) of trimethylsilyl bromide in 6 ml of acetonitrile is added dropwise to 0.93 g (0.0031 mol) of the compound of Example 23 in 8 ml of acetonitrile, and the mixture is stirred overnight at room temperature. The mixture is then concentrated under reduced pressure and the residue is mixed with methanol. The mixture is stirred at room temperature for 30 minutes and then the methanol is removed under reduced pressure. The residue is dissolved in ether. The ether was removed under reduced pressure to give 0.71 g of 3,4,4-trifluorobutan-3-ylphosphonoacetate as a viscous, pale yellow oil.

Elemental analysis: calculated value; C 27.64; H 3.63

Found; C 27.54; H 3.50

&Lt; Example 25 >

98 g (0.52 mol) of 4-bromo-1,1,2-trifluorobutan-1-ene was added to 50 g (0.37 mol) of phenylacetic acid in 400 ml of acetonitrile and 55.9 g (0.37 mol) . The mixture is stirred at room temperature for several hours under reflux overnight, and then for another 2 days at room temperature. The solvent is removed under reduced pressure, the residue is mixed with water and extracted with ether. The ether phase is washed twice with a 5% aqueous NaOH solution, washed twice with water and then evaporated to dryness on magnesium sulphate. To obtain 42.05 g of 3,4,4-trifluorobutan-3-enylphenylacetate as an amber transparent liquid.

Elemental analysis: calculated value; C 59.02; H 4.54

Found; C 59.29; H 4.60

&Lt; Example 26 >

1.22 g (0.01 mol) of carbonyldiimidazole (from Aldrich) was added to 1.89 g (0.01 mol) of (L) -N-Boc-alanine in 20 ml of anhydrous tetrahydrofuran (THF) Stir for 30 minutes. 1.5 g (0.012 mol) of 4-hydroxy-1,1,2-trifluorobutane-1-ene (see Synthesis Example 16 in US 5 389 680) are then added and the mixture is stirred overnight at room temperature. The solvent is removed under reduced pressure and the residue is mixed with water and extracted with ether. The ether phase is washed with water (3 times) and dried over magnesium sulfate. The ether is evaporated under reduced pressure. To obtain 2.25 g of 3,4,4-trifluorobutan-3-enyl N-tert-butyloxycarbonyl-L-alaninate as a clear liquid.

Elemental analysis: calculated value; C 48.48; H 6.10; N 4.71

Found; C 48.54; H 6.08; N 4.69

&Lt; Example 27 >

Excess HCl gas is introduced into a solution of 1.54 g (0.0052 mol) of the compound of Example 26 in 50 ml of ether. The reaction tube is then closed and the mixture is stirred at ambient temperature for another 6 hours. The resulting colorless precipitate is filtered, washed with ether and dried under reduced pressure. 3, 4-trifluorobutan-3-enyl L-alaninate 0.8 g as a colorless solid.

Elemental analysis: calculated value; C 35.99; H 4.75; N 6.00; Cl 15.18

Found; C 36.00; H 4.71; N 5.96; Cl 15.12

<Usage example>

<Example A>

Critical concentration test / nematode

Test nematode: Meloidogine incognita

Solvent: 4 parts by weight of acetone

Emulsifier: alkylaryl polyglycol ether 1 part by weight

To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active compound preparation is thoroughly mixed with the soil that is severely infested with test nematode. The concentration of the active compound in the formulation is not critical and the amount of active compound per unit soil volume, expressed in ppm (= mg / l), is important. The treated soil is transferred to a pot, lettuce seeds are sown, and the pot is maintained at a greenhouse temperature of 25 ° C.

After 4 weeks, lettuce roots are examined for nematode infestation (roothead) and the efficacy of the active compound is determined in%. When the infection is completely prevented, the efficacy is 0% when the efficacy is 100% and the infection level is untreated but equally infected, the same size as the control plant in the soil.

In this test, 100% efficacy was shown for the compounds of Preparations 1 and 5 at a typical active compound concentration of 20 ppm.

<Example B>

Test / development-inhibition effect using fly larvae

Test animals: Lucilia cuprina (OP resistance) of all larva stages [pupa and adult (not in contact with active compound)]

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable preparation, 3 parts by weight of the active compound are mixed with 7 parts of the above-mentioned solvent-emulsifier mixture and the resulting emulsion concentrate is diluted with water to the respective desired concentration.

For each concentration, 30 to 50 larvae are placed in a test tube containing about 1 cm ³ of horse meat. Pipette 500 μl of test dilution into this horse meat. The test tube is placed in a plastic beaker with the bottom of the sea sand and kept in the air chamber (26 ° C ± 1.5 ° C, relative humidity 70% ± 10%). After 24 hours and 48 hours, the activity (live larva) is tested. After emergence of the larvae (approximately 72 hours), the test tube was removed and a perforated plastic lid was placed on the beaker. After a lapse of 1.5-fold (hatching of control flies), the hatching flies and pupae / cocoon are calculated.

The activity criterion is the mortality rate (larval effect) of the larvae treated after 48 hours, or the inhibition of embryogenesis or pupa formation in the pupa. The in vitro activity criterion of a substance is the inhibition of the development of flies, or the arrest before the adult stage. 100% live larvae means that all larvae died after 48 hours. 100% of the development-inhibiting activity means that the adult flies were not hatched at all.

In this test, for example, the compounds of Preparation Examples 1 and 5 exhibited 100% activity in each case at a typical active compound concentration of 1000 ppm.

&Lt; Example C >

Tests with Bupillus microsplasia / SP-resistant Parkhurst species

Test animals: fully female sucked females

Solvent: Dimethylsulfoxide

20 mg of the active substance is dissolved in 1 ml of dimethylsulfoxide and diluted with the same solvent to give a low concentration.

Repeat the test five times. 1 μl of solution is injected into the abdomen, the animal is transferred to a dish and kept in the anchoring chamber. Activity is measured by scattering inhibition. 100% means that one tick did not spawn.

In this test, for example, the compounds of Preparation Examples 1 and 5 each exhibited 100% activity at a typical concentration of 20 μl / individual.

<Example D>

This test is performed as described in US-5 389 680, which is expressly incorporated herein by reference.

In the nematode test (tomato and soybeans), the compound of Preparation 26 had 95% activity of Method 1 at 500 ppm and had a Stage 2 activity of Method 2 at a concentration of 1 mg / port and 0.5 mg / &Lt; / RTI &gt; The active phase is described in US 5 389 680, where 0 means an activity of 50% or less, Step 1 means an activity of 50 to 75%, Step 2 means an activity of 75 to 90% 3 means 91 to 100% activity.

Claims (10)

The following compounds of formula (I) and salts thereof: (I) In the above formula R ¹ represents hydrogen or halogen, and Q represents the following substituents a) or b); a) or b) ZR ⁹ or Z (P = W) R ¹⁰ R ¹¹ In the above formula R ² represents hydrogen, nitro, cyano, halogen, alkyl, alkoxy, alkylthio or optionally substituted aryl, R ³ represents COOH, SO ₃ H, NR ⁴ R ⁵ or OR ⁶ , wherein R &lt; ⁴ &gt; represents hydrogen, alkyl or optionally substituted aryl, R ⁵ represents hydrogen, alkyl, optionally substituted aryl or COR ⁷ , R ⁶ represents hydrogen, optionally substituted aralkyl, CONR ⁴ R ⁵ or COR ⁷ , R ⁷ represents alkyl, alkenyl, optionally substituted aryl or NR ⁴ R ⁸ , R &lt; ⁸ &gt; represents hydrogen, alkyl or optionally substituted aryl, Z represents an aliphatic group having 1 to 4 carbon atoms, provided that when Z represents CH ₂ , R ⁹ does not represent phenyl, W represents oxygen or sulfur, R ⁹ represents a) aromatic group or represents a heterocyclic group (such as a pyrazolyl, imidazolyl, triazolyl, morpholinyl, piperidinyl, piperazinyl or pyrrolidinyl) Alkyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, sulfonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester of one of these acids, amide Or a radical of a thioester, β) hydrogen, OR ^12, SR ^12, halogen, NR ¹² R ^13, cyano, trimethylsilyl, nitro, phenyl, sulfonic acid or represent an ester, amide, or the radical of a thioester of the acid, or cyano, trimethylsilyl, Or an ester, amide or thioester of one of these acids, optionally substituted with one or more substituents selected from the group consisting of hydroxy, alkoxy, halogen, nitro, optionally mono-or dialkyl-substituted amino, thiol, alkylthio, phenyl, sulfonic, phosphonic, Gt; represents an aliphatic group optionally substituted by at least one radical selected from &lt; RTI ID = 0.0 &gt; R ¹⁰ and R ¹¹ independently of one another denote R ²² , OR ²² , SR ²² or NR ²² R ²³ , here, R &lt; ¹² &gt; and R &lt; ¹³ &gt; i) hydrogen, ii) alkyl, cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, sulfonic acid, phosphonic acid, An aliphatic group or an aromatic or heterocyclic group optionally having 1 to 12 carbon atoms which is optionally substituted by at least one radical selected from the group consisting of a carboxylic acid, a carboxylic acid, a carboxylic acid or a radical of an ester, amide or thioester of one of these acids, iii) R ¹² and R ¹³ together with the bonding nitrogen atom form part of an amino acid, R ¹² is hydrogen or an alkyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, sulfonic acid, phosphonic acid, phosphinic acid or Or an aliphatic or aromatic group optionally substituted by at least one substituent selected from the group consisting of a radical of a carboxylic acid or an ester, amide or thioester of one of these acids, or phenyl, then R ¹³ may also be OR ¹⁶ , COR ¹⁶ , COOR ²¹ , NR ¹⁶ R ¹⁷ , SO ₂ R ¹⁸ , P (= O) R ¹⁹ R ²⁰ , wherein R ¹⁶ and R ¹⁷ independently of one another each represent hydrogen, alkyl or aryl, R ¹⁸ represents hydrogen, alkyl, halogenoalkyl or aryl, R ¹⁹ and R ²⁰ independently of one another each represent hydrogen, alkyl, aryl, alkyl, alkylthio, arylthio, alkylamino, dialkylamino, arylamino or OR ²¹ R ²¹ represents hydrogen, alkyl or aryl, R ²² and R ²³ independently from each other are each hydrogen or in each case cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, Or an aliphatic or aromatic group optionally substituted by at least one substituent selected from the group consisting of a phosphonic, phosphonic, or carboxylic acid or a radical of an ester, amide or thioester of one of these acids. 2. A compound of formula (I) according to claim 1, which is of formula (Ia), Ib-1 or Ib-2: (Ia) (Ib-1) CF ₂ = CR ¹ -CH ₂ -CH ₂ -O-CO-ZR ⁹ (Ib-2) CF ₂ = CR ¹ -CH ₂ -CH ₂ -O-CO-Z (P = W) R ¹⁰ R ¹ 1 Wherein R ¹ , R ² , R ³ , R ⁹ , R ¹⁰ , R ¹¹ , Z and W are as defined in claim 1, respectively. A process for the preparation of a compound of formula (Ia) according to claim 2, characterized by the following step A), B) or C): A) reacting a benzoic acid derivative of formula (II) with fluorobutene bromide of formula (III) in the presence of a diluent, B) reacting an anhydrous isoic acid of formula (IV), if appropriate in the presence of a base, and if appropriate in the presence of a diluent, with a fluorobutanol of the formula (V) C) reacting an acid anhydride of formula (VI) with fluorobutanol, if appropriate in the presence of a diluent and if appropriate in the presence of a base, &Lt; RTI ID = 0.0 & (III) (IV) (V) (VI) In the above formula X ⁽⁺⁾ represents an alkali metal ion or ammonium ion Y represents CO or SO ₂ , R ¹ , R ² , R ³ and R ⁴ are as defined in claim 1, respectively. 3. The method of claim 2, R ¹ represents hydrogen, fluorine, chlorine or bromine, R ² is hydrogen, nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₈ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio or optionally cyano-, -, bromine- or C ₁ -C ₆ -alkoxy-substituted phenyl, R ³ represents 2-COOH, 2-SO ₃ H, NR ⁴ R ⁵ or OR ⁶ , R ⁴ represents hydrogen, C ₁ -C ₈ -alkyl or optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy-substituted phenyl, R ⁵ represents hydrogen, C ₁ -C ₈ -alkyl, optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy-substituted phenyl COR ⁷ , R ⁶ represents hydrogen, optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy-substituted phenyl-C ₁ -C ₆ -alkyl CONR ⁴ R ⁵ or COR ⁷ , R ⁷ is selected from the group consisting of C ₁ -C ₈ -alkyl, C ₂ -C ₆ -alkenyl, optionally fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy- Or represents NR &lt; ⁴ &gt; R &lt; ⁸ & Wherein R ⁸ represents hydrogen, C ₁ -C ₈ -alkyl or optionally cyano-, fluorine-, chlorine-, bromine-, C ₁ -C ₆ -alkyl- or C ₁ -C ₆ -alkoxy- Lt; / RTI &gt; 3. The method of claim 2, R ¹ represents hydrogen or fluorine, R ² is hydrogen, nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or optionally fluorine-, Or C ₁ -C ₄ -alkoxy-substituted phenyl, R ³ represents 2-COOH, 2-SO ₃ H, NR ⁴ R ⁵ or OR ⁶ , R ⁴ represents hydrogen, C ₁ -C ₄ -alkyl or optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl, R ⁵ represents hydrogen, C ₁ -C ₄ -alkyl, optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl or represents COR ⁷ , R ⁶ represents hydrogen, optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl or represents CONR ⁴ R ⁵ or COR ⁷ , R ⁷ represents C ₁ -C ₄ -alkyl, C ₂ -C ₆ -alkenyl, optionally fluorine-, chlorine- or C ₁ -C ₄ -alkyl-substituted phenyl or represents NR ⁴ R ⁸ , Compounds of formula la in which R ⁸ represents hydrogen, C ₁ -C ₄ -alkyl or optionally fluorine-, chlorine-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl. A pesticide characterized in that it comprises at least one compound of formula (I) according to claim 1. Use of a compound of formula I according to claim 1 for inhibiting insects. A method of inhibiting insect pests, characterized in that the compound of formula (I) according to claim 1 is allowed to act on pests and / or their habitats. A process for producing an agrochemical, which comprises mixing a compound of formula (I) according to claim 1 with an extender and / or a surfactant. Use of a compound of formula I according to claim 1 for the preparation of pesticides.