CA2230031A1 - 4,4-difluoro-3-butenylester derivatives or 4,4-difluoro-3-halogen-3-butenylester derivatives and the use thereof as pesticides - Google Patents

Abstract

The present invention relates to new esters of formula (I), in which R1 is hydrogen or halogen; and Q is (a), ZR9 or Z(P=W)R10R11, wherein R2, R3, R9, R10, R11, Z and W have the meaning given in the description. It also relates to a process for the production thereof, and the use thereof for the control of animal pests.

Description

,~ -!~ Le A 31 184-Forei~n countries / Ba/Kr/bo/S-P
~ - 1 -~LE, P~ Ar-.'~;;~
A~ Tl~

Esters The present invention relates to novel esters, to processes for their ~lc~udlion and to their use for controlling animal pests, in particular insects, arachnids and nematodes encountered in agriculture, in forests, in the protection of stored product and ms~teris~l~
5 and in the hygiene sector.

It is already known that the compound 3,4,4-trifluorobut-3-enyl 4-chlorobenzoate has nematicidal properties (cf. US-4 952 580). However, the efficacy and the activity spectrum of this compound, in particular at low application rates and concentrations, is not always entirely satisfactory.

10 This invention, accordingly, provides novel esters of the formula (I) CF2=C--CH2--CH2 O--CO--Q
R' (I) in which Rl represents hydrogen or halogen, and Q represents either . R
15 a) m whlch ~=~
\~ R3 R2 represents hydrogen, nitro, cyano, halogen, alkyl, alkoxy, alkylthio or - CA 02230031 1998-b2-20 ~, .. Le A 31 184-Forei~n countries optionally substituted aryl and R3 represents COOH, SO3H, NR4Rs or oR6 in which R4 represents hydrogen, alkyl or optionally substituted aryl, Rs represents hydrogen, alkyl, optionally ~ul~sliluled aryl or COR7, R6 represents hydrogen, optionally substituted aralkyl, CoNR4Rs or COR', R7 represents aL~cyl, alkenyl, optionally substituted aryl or NR4R8 and R8 represents hydrogen, alkyl or optionally substituted aryl, 10 or b) is ZR9 or Z(P=W)RI~Rll in which Z represents an aliphatic group having one to four carbon atoms with the proviso that R9 does not represent phenyl if Z represents CH2, W represents oxygen or sulphur, R9 a) represents an aromatic group or represents a heterocyclic group (such as, for example, a cyclic group from the group con~i~tin~
of pyrazolyl, imidazolyl, triazolyl, morpholinyl, piperidinyl, piperazinyl or pyrrolidinyl), each of which is optionally substituted by at least one substituent from the group consisting of cyano, trimethylsilyl, hydroxyl, alkyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-sub~LiLuled amino, thiol, alkylthio, a ~ ~ Le A 31 184-Forei~n countries radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, 13) represents hydrogen, oR'2, SRl2, halogen, NRI2RI3, cyano, trimethylsilyl, nitro, phenyl, the radical of a sulphonic acid or an ester, an amide or a thioester thereof or represents an aliphatic group which is optionally substituted by at least one radical from the group con~ ng of cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, aLkylthio, phenyl, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, in which Rl2 and Rl3 independently of one another each represent i) hydrogen, ii) an aliphatic group having one to twelve carbon atoms or an aromatic or heterocyclic group which is optionally substituted by at least one radical from the group conei.eting of alkyl having one to four carbon atoms, cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, iii) or Rl2 and Rl3 join with the linking nitrogen atom to form part of an amino acid, or Le A 31 184-Forei~n countries if Rl2 represents hydrogen or an aliphatic or aromatic group which is in each case optionally substituted by at least one substituent from the group con~ ting of alkyl having 1 to 4 carbon atoms, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted arnino, thiol, alkylthio, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, or phenyl, then ~ Rl3 may also represent ORI6, CORI6, COOR2l, NRI6Rl7, SO2RI8, P(=o)RI9R20 in which 10 Rl6 and Rl7 independently of one another each represent hydrogen, alkyl or aryl, Rl8 represents hydrogen, alkyl, halogenoalkyl or aryl, Rl9 and R20 independently of one another each represent hydrogen, alkyl, aryl, aLkyl, alkylthio, arylthio, alkylamino, dialkylamino, arylamino or OR2l and R2' represents hydrogen, alkyl or aryl, Rl~ and Rll independently of one another each leplesellt R22, OR22, SR22 or NR22R23 in which R22 and R23 independently of one another each represent hydrogen or an aliphatic or aromatic group which is in each case optionally substituted by at least one substituent from the group con~i~tin~ of cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio,phenyl, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids and salts thereof.

. CA 02230031 1998-02-20 Le A 31 184-Forei~n countries The compounds of the formula (I) may be present as salts if they contain functional groups capable of salt formation. These functional groups include, for example, the carboxyl group and the hydlv~yl group. Suitable cations are, for example, alkali metal and ~lk~line earth metal ions such as sodium, calcium, potassium and m~gnesium, 5 quaternary ammonium ions such as the ammonium ion itself, and also mono-, di- and trialkylammonium ions such as the isopropyl:~mmonium ion, and furthermore, for example, the pyridinium ion.

Including the meaning of the group Q, the following compounds of the formula (Ia), (Ib-l) or (Ib-2) are obtained:

CF2=CR1 CH2--CH2--O--Co~R3 (Ia) CF2=CRl-CH2-CH2-O-CO-ZR9 ~b-l) CF2=CRI-CH2-CH2-O-CO-Z(P=W)Rl~Rl I ~2) in which R~, R2, R3, R9, Rl~, Rll, Z and W are each as defined above.

Depending on the nature of the substit~-ent~, the compounds of the formula (I) can be 15 present as geometrical and/or optical isomers or isomer mixtures of varying composition. The present invention relates both to the pure isomers and to the isomer mixtures.

Furthermore, it has been found that the compounds of the formula (Ia) are obtained when 20 A) benzoic acid derivatives of the formula (II) Le A 31 184-Forei~n countries Ra ~ C00~ X

in which X(+) represents an aL~cali metal ion or an amrnonium ion and R2 and R3 are each as defined above S are reacted with a fluorobutenyl bromide of the formula (III) CF2=CI -CH2-CH2-Br (III) in which R1 is as defined above in the presence of a diluent 10 or B) isatoic anhydrides of the formula (IV) RZ~'~~o (IV) in which ., Le A 31 184-Forei~n countries ~_ - 7 -R2, R3 and R4 are each as defined above are reacted with a fluorobutenol of the forrnula (V) CF2= IC-CH2-CH2-OH (V) in which S R~ is as defined above, if a~.pLop.;ate in the presence of a base and if ~Lopliate in the presence of a diluent or C) acid anhydrides of the forrnula (VI) R2 ~
3 ~ ~I) in which Y represents CO or SO2 and R2 and R3 are each as defined above are reacted with a fluorobutenol of the formula (V) . Le A 31 184-Forei~n countries CF2=C;CH2-CH2-OH
R

in which R' is as defined above, if appropliate in the presence of a diluent and if a~,~fopliate in the presence of a base.

The compounds of the formulae (Tb) ((Ib-l) and (Ib-2)) can be plepaled by generally known methods. The starting materials required can be easily prepared by known methods and/or are commercially available.

Finally, it has been found that the novel esters of the formula (I) have very pronounced 10 biological properties and are suitable especialiy for controlling animal pests, in particular insects, arachnids and nematodes encountered in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector.

Formula (Ia) provides a general definition of the arylcarboxylic esters according to the invention.

15 Preferred substituents or ranges of the radicals listed in the formulae mentioned hereinabove and hereinbelow are illustrated below:

Rl preferably represents hydrogen, fluorine, chlorine or bromine.

R2 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, C,-C8-alkyl, C,-C6-alkoxy, C,-C6-aL~cylthio or optionally cyano-, fluorine-, chlorine-, bromine- or C,-C6-alkoxy-substituted phenyl.

R3 preferably represents 2-COOH, 2-SO3H, NR4R5 or oR6.

Le A 31 184-Forei~n countries g R4 preferably represents hydrogen, Cl-C8-alkyl or optionally cyano-, fluorine-,chlorine-, bromine-, Cl-C6-alkyl- or Cl-C6-alkoxy-substituted phenyl.

R5 preferably represents hydrogen, Cl-C8-alkyl, optionally cyano-, fluorine-, chlorine-, bromine-, Cl-C6-alkyl- or Cl-C6-alkoxy-substituted phenyl or ~ CS~ CoR7.

R6 preferably represents hydrogen, optionally cyano-, fluorine-, chlorine-, bromine-, Cl-C6-alkyl- or Cl-C6-alkoxy-substituted phenyl-CI-C6-alkyl or represents CONR4Rs or CoR7 R7 preferably represents Cl-C8-alkyl, C2-C6-alkenyl, optionally fluorine-, chlorine-, bromine-, Cl-C6-alkyl- or Cl-C6-aLkoxy-substituted phenyl or represents NR4R8.

R8 preferably represents hydrogen, Cl-C8-alkyl or optionally cyano-, fluorine-,chlorine-, bromine-, Cl-C6-alkyl- or Cl-C6-alkoxy-substituted phenyl.

R' particularly preferably represents hydrogen or fluorine.

R2 particularly preferably represents hydrogen, nitro, cyano, fluorine, chlorine, brornine, C~-C4-alkyl, C,-C4-alkoxy, Cl-C4-alkylthio or optionally fluorine-, chlorine-, or Cl-C4-alkoxy-substituted phenyl.

R3 particularly preferably represents 2-COOH, 2-SO3H, NR4R5 or oR6.

R4 particularly preferably represents hydrogen, Cl-C4-alkyl or optionally fluoririe-, chlorine-, Cl-C4-alkyl- or Cl-C4-alkoxy-substituted phenyl.

20 R5 particularly preferably lcpl~se~ hydrogen, Cl-C4-alkyl, optionally fluorine-, chlorine-, Cl-C4-alkyl- or Cl-C4-alkoxy-substituted phenyl or represents CoR7.

R6 particularly preferably represents hydrogen, optionally fluorine-, chlorine-, " Le A 31 184-Forei~n countries Cl-C4-alkyl- or Cl-C4-alkoxy-sllkstitllted phenyl or represents CoNR4R5 or R7 particularly preferably represents Cl-C4-alkyl, C2-C6-alkenyl, optionally fluorine-, chlorine- or Cl-C4-alkyl-substituted phenyl or represents NR4Rg.

5 R8 particularly preferably represents hydrogen, Cl-C4-alkyl or optionally fluorine-, chlorine-, Cl-C4-alkyl- or Cl-C4-alkoxy-substituted phenyl.

A most particularly preferred group of compounds of the formula (I) is the group in which Rl represents fluorine, R2 represents hydrogen and R3 represents the radical NR4Rs 10 For the radical definitions of the compounds of the formula (Ib), the following applies:

The term "halogen" alone or in combination with other radicals represents fluorine, chlorine, bromine or iodine.

The term "alkyl" represents straight-chain or branched groups of one to about seven carbon atoms.

15 The term "lower alkyl" le~lese;lll~ a group having one to about four carbon atoms.

The term "aliphatic" represents saturated or unsaluldled alkyl groups having one to about ten carbon atoms or being as defined above or represents straight-chain orbranched alkenyl groups having two to about ten carbon atoms or being as definedabove.

20 The term "alkoxy" represents a lower alkyl group which is attached via oxygen.

The term "alkylthio" represents a lower alkyl group which is attached via sulphur.

" Le A 31 184-Forei~n countries The term "alkoxyc~ubollyl" represents a lower alkyl ester of a carboxylic acid.

The term "radical of a carboxylic acid, sulphonic acid, phosphinic acid, phosphonic acid or an amide, ester or a thioester of one of the mentioned acids" represents an aliphatic group in which at least one (preferably one) carbon atom is replaced by a S carboxyl group (COOH), a sulphonic acid group, a phosphinic acid group or a phosphonic acid group or by a lower alkyl ester, an amide or a lower alkyl thioester of one of the mentioned acids.

The term "amino acid" represents any compound having an amino group and an acid group which are separated by a C atom. These include natural amino acids, and also 10 those having other substituents at the central carbon atom.

The term "alkyl- or arylsulphonamide" represents a sulphonamide group which is substituted by a lower alkyl group or a phenyl group, each of which may in turn be substituted.

The terms "aromatic group" or "aryl" represent phenyl which is optionally substituted 15 as defined above.

The term "heterocyclic" represents any cyclic compound co.~ ;..;..g as ring member at least one element other than carbon. The ring may be saturated or uns~uldt~d. The hetero atom may be oxygen, nitrogen, sulphur or another element. The heterocycles include, for example, radicals of thi~ 7cle, pyridine, thiazole, isothiazole, oxazole, 20 imida_ole, pyrazole, triazole, benzothiazole, morpholine, piperidine, piperazine and pyrrolidine and may in each case be substituted by at least one substituent from the group con~i~ting of radical of a sulphonic acid, phosphonic acid, phosphinic acid, an ester, amide or thioester of one of these acids, cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl and phenyl.

25 Amongst the compounds of the formula (Ib) mentioned here, a very particularly~ ;r~ d compound of the formula (Ib) is 3,4,4-trifluoro-3-butenyl N-[(l,l-Le A 31 184-Forei~n countries dimethylethoxy)c~l,ollyl]-L-~l~nin~te.

The abovementioned general or preferred definitions of radicals or illustrations apply to the end products and, correspondingly, to the starting materials and intermediates.
These radical definitions can be combined with each other as desired, i.e. combinations S between the respective ~l~f~lled ranges are also possible.

Among the compounds of the formula (Ta), preference according to the invention is given to those compounds of the formula (Ia) which contain a combination of the meanings given above as being preferred (preferable).

Among the compounds of the formula (Ia), particular preference according to the 10 invention is given to those compounds of the formula (Ia) which contain a combination of the meanings given above as being particularly preferred.

In the radical definitions listed hereinabove and hereinbelow, hydrocarbon radicals such as alkyl or alkenyl - including in conjunction with hetero atoms such as an alkoxy or alkylthio - are straight-chain or branched as far as this is possible.

15 Using, for example, sodium salicylate and l-bromo-3,4,4-trifluorobut-3-ene as starting m~teri~ls for ~le~aling compounds of the formula (Ia) according to process A), the course of the reaction can be illustrated by the following scheme:

~COONa ~J OH + CF2=CF-CH2-CH2-Br ~CO-OCH2-CH2-CF=CF2 ~OH
Using, for example, isatoic anhydride and 3 ,4,4-trifluorobut-3-en- 1 -ol as starting 20 materials for ~ alhlg compounds of the formula (Ia) according to process B), the Le A 31 184-Forei~n countries course of the reaction can be illustrated by the following scheme:

~,~ + CF2=cF-cH2-cH2-oH
N O
H

~CO-OCH2-CH2-CF=CF2 Using, for example, phthalic anhydride and 3,4,4-trifluorobut-3-en-1-ol as starting materials for ~lepalmg compounds of the formula (Ia) according to process C), the 5 course of the reaction can be illustrated by the following scheme:

~0 + CF2=CF-CH2-CH2 OH
o [~co-ocH2-cH2-cF=cF2 COOH

The process A) for ~ g compounds of the formula (Ia) described above is characterized in that benzoic acid derivatives of the formula (II) are reacted with fluorobutenyl bromides of the formula (III) in the presence of a diluent.

10 Suitable diluents are in particular organic solvents, for example optionally chlorinated aromatic hydrocarbons such as toluene, xylene or chlorobenzene, ethers such as dioxan or tetrahydrofuran, nitriles such as acetonitrile, sulphoxides such as dimethyl sulphoxide, amides such as dimethylformamide or carboxylic esters such as ethyl acetate.

Le A 31 184-Forei~n countries The reaction ten~e.dLule in the process A) can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0~C and 160~C, preferably between 20~C and 120~C.

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

The reaction is generally carried out under atmospheric pressure.

For work-up, the reaction mixture is for example hydrolysed, the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene and the solvent is subsequently removed.

10 The process B) for ~l~a hlg compounds of the formula aa) described above is characterized in that isotoic anhydrides of the formula aV) are reacted with fluorobutenols of the formula (V), if a~plo~iate in the presence of a diluent and if apl)Lopliate in the presence of a base.

Diluents suitable for this process are all conventional solvents.

15 Preference is given to using optionally halogenated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane, chloroform, dichloroethane or chlorobenzene or ethers such as tetrahydrofuran or dioxan.

The reaction can also be carried out in the absence of one of the mentioned solvents.
In this case, it may be advantageous to employ an excess of the fluorobutenol of the 20 formula (V).

It may be advantageous to carry out the process B) according to the invention in the presence of a base.

Preference is given to using ~mine~, preferably tertiary amines such as triethylamine, Le A 31 184-Forei~n countries pyridine or diazabicycloundecene (DBU) or inorganic bases, for example alkali metal carbonates, bicarbonates or hydroxides such as potassium carbonate, sodium bicarbonate or sodium hydroxide.

It is sufficient to employ catalytic amounts of base.

5 The reaction temperature in the process B) can be varied within a relatively wide range. In general, the reaction is carried out at telllpeldlules in the range from 0~C to 180~C, preferably from 20~C to 140~C.

The compounds of the formulae (TV) and (V) are generally employed in a molar ratio of 1:2 to 2:1. The reaction is generally carried out under atmospheric pressure.
10 For work-up, the reaction mixture is for example hydrolysed, the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene and the solvent is subsequently removed.

The process C) according to the invention for plep~illg compounds of the formula (Ia) is characterized in that acid anhydrides of the formula (VI) are reacted with a 15 flurobutenol of the formula (V), if a~propl;ate in the presence of a diluent and if a~plopl;ate in the presence of a base.

With regard to the diluent, base, practice of the reaction and work-up, the specifications given for the process B) apply correspondingly.

The benzoic acid d~l;vdliv~s of the formula (II) required as starting materials for the 20 process A) can be plepal~d in a simple, known manner by reacting the corresponding benzoic acids (which are easily preparable and the greater part of which are commercially available) with bases (for example alkali metal hydroxides such as lithium hydroxide, potassium hydroxide or sodium hydroxide or amines such as dimethylamine, triethylamine or butylamine).

Le A 31 184-Forei~n countries The fluorobutenyl bromides of the formula aII) further required as starting m~t~ lc are known and/or can be prepared in a simple manner by known processes (cf. C.A.119. 94 942).

The isotoic anhydrides of the formula aV) required as starting m~ten~l~ for the process 5 B) are known and/or can be prepared by known methods (Methoden der Organ.
Chemie - Houben-Weyl, Vol. 4E, p. 214 ff (1983)).

The fluorobutenols of the formula (V) further required as starting m~teri~l~ are known (see for example WO 92/15 555).

The acid anhydrides of the formula (VI) required as starting materials for the process 10 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, arachnids and nematodes, encountered in agriculture, in forests, in the protection of stored products and of materials, and in the hygiene sector. They are preferably used 15 as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus, ~rmzl-lillidium vulgare and Porcellio scaber.

20 From the order of the Diplopoda, for example, Blaniulus glltt~ tllc~

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

Le A 31 184-Forei~n countries From the order of the Thy~a~ , for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus ~rm~tne From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta S migratoria migratorioides, Melanoplus diLrelc;lllialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.
.
From the order of the Anoplura, for example, Pediculus hllm~nlle corporis, Haematopinus spp. and Linogn~hlle spp.

10 From the order of the Mallophaga, for example, Trichodectes spp. and D~m~line~ spp.

From the order of the Thysanoptera, for exarnple, Hercinothrips femoralis and Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lect~ riue, Rhodnius prolixus and Triatoma spp.

15 From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arlln-linie7 Phylloxeravastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, 20 Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus Le A 31 1 84-Forei~n countries piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella,Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias in~nl~n~ Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis 5 fl~mme~, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona m~gn~nim~
and Tortrix viridana.

10 From the order of the Coleoptera, for example, Anobium punctatum, Rhizoperthadominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinarnensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,15 Ceuthorrhynchus ~imili~, 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 and Costelytra 7~ n(1ica.

20 From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys 25 spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortnl~nlls7 Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus Le A 31 1 84-Forei~n countries spp. and Ctenocephalides felis.

From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., S Dermanyssus gslllin~, Eriophyes ribis, Phylloco~ 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.

The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus10 similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. andTrichodorus spp.

The compounds of the formula (I) according to the invention in particular have o~ltet~nc1ing nematicidal activity, for example against Meloidogyne incognita.

15 They also have good foliar insecticidal activity.

The active compounds can be converted to the customary formulations, such as-solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic mz~teri~l~
impregnated with active compound and very fine capsules in polymeric substances.
20 These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if a~ o~.;ate with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.

In the case of the use of water as an exf~n-ler, organic solvents can, for example, also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such Le A 3 l l 84-Forei~n countries as xylene, toluene or alky1n~phth~1enes, chlorinated aromatics and chlorinated ~lirh~tic hydrocarbons, such as chloroben7~ones, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or ~aldLrlns, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and 5 esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide and water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, l0 chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs 15 and tobacco staLks, suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable di~allL~ are: for example lignin-sulphite waste liquors and methylcellulose.

20 Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl ?,ce~te, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

25 It is possible to use colorants such as inorganic pigment~, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as ~1i7~rin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, m~ngzlnese, boron, copper, cobalt, molybdenum and zinc.

Le A 31 184-Forei~n countries The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in its commercially available formulations and in the use forms, prepared from these formulations, as a S mixlu~; with other active compounds, such as insecticides, attractants, stçrili7in~
agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insectic;des include, for example, phnsph~tçs, carb~m~tes, carboxylates, chlorinated hydrocarbons, ph~nylu~eas and substances produced by microorg~ni~m~, inter alia.

10 Examples of particularly advantageous mixing components are the following:

Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimi~line; 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl- 1 ,3-thia_ole-5-carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)-ben7~mi-le; (E)-2-methoxyi~ o-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; 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, al.lplo~ylfos, ~nil~7ine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, 20 bromuconazole, bu~; .; ., .~tç, buthiobate, calcium polysulphide, captafol, captan, carben~l~7im, carboxin, quinomethionate,chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cypro-conazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran, diethofencarb,25 difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, di~yl;tl~ione, ditalimfos, ~lithi~non, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, felill.~one, fl~.;.,;l.~....

Le A 31 1 84-Forei~n countries fludioxonil, fluoromide, fluquinconazole, flusilazole, flus- lf~mide, flutolanil, flutriafol, folpet, fosetyl-alu,.liniul.., fthalide, fuberidazole, furalaxyl, furmecyclox, gu~ ine, hexachlorobenzene, hexaconazole, hym~ 7 )1, 5 im~7~1il, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper ~le~a alions such as: copper hydroxide, copper n~phthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, m~l,~i~y-;---, mepronil, metalaxyl, metconazole, methasulfocarb, mell~ o~al--, metiram, metsulfovax, myclobutanil, 10 nickel dimethyldithiocarbamate, nitrothal-isopropyl, nll~rim ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidone, ~,lo~all,ocarb, propiconazole, propineb, ~yld~ophos, pyrifenox, pyrimethanil, pyroquilon, 15 quintozene (PCNB), sulphur and sulphur ~ dldtions, tebuconazole, tecloftalam, tecn~7ene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tlichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, 20 validamycin A, vinclozolin, zineb, ziram Bactericides:
bronopol, dichlorophen, niLId~ylill, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, 25 tecloftalam, copper sulphate and other copper ple~a dlions Insecticides/AcaricidestNematicides:
abamectin, AC 303 630, acephate, acrin~thrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, a_ocyclotin, Bacillus 1hnringiensis, bendiocarb, benfuracarb, ben~111t~p, beta-cyfluthrin, bifenthrin, 30 BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, Le A 31 184-Forei~n countries buLyl~ylidaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157419, CGA 184699, chloethocarb, chlorethoxyfos, . chlorfenvinphos, chlolnuaGulon, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofente7:ine, 5 cyanophos, cycloprothrin, cylllllhl ;~, cyhalothrin, cyhexatin, cypermethrin, cyroma_ine, deltamethrin, demeton M, demeton S, demeton-S-met~yl, diafenthiuron, dia7~inon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflube~ ull, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, 10 etrimfos, fenamiphos, fena_aquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, ren~yloximate, fenthion, fenvalerate, fipronil, flnsl7.in~m, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonofos, formothion, fosthi~7~te, fubfenprox, furathiocarb, 15 HCH, heptenophos, hexanumulol1, hexythia_ox, imidacloprid, iprobenfos, isa_ofos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, m~l~thion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, 20 monocrotophos, moxidectin, naled, NC 184, NI 25, nilt;ll~yldlll, omethoate, oxamyl, oxydemeton M, oxydeprofos, parathion A, parathion M, permethrin, phentho~te, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, 25 promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, pyrachlofos, pyridaphenthion, pyresmethrin, p~ lll, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, RH 5992, salithion, sebufos, silafluofen, sulfotep, sulprofos, 30 tebufenozide, tebufenpyrad, tebu~uilllifos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathene, triazophos, tria_uron, trichlorfon, triflumuron, Le A 31 184-Forei~n countries trimethacarb, vamidothion, XMC, xylylcarb, Y~ 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides, or with fertilizers and growth-regulators is also possible.

5 The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.

10 The active compound content of the use forms pieparcd from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 9$% by weight of active compound, preferably between 0.0001 and 1% by weight.

The compounds are employed in a customary manner applopliate for the use forms.

15 When used against hygiene stored-products pest, the active compound has an excellent residual action on wood and clay and a good stability to alkali on limed substrates.

The active compounds according to the invention are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, 20 trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp., Linogn~thll~ spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, Le A 31 184-Forei~n countries for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., D~m~lin~ spp., Trichodectes spp. and Felicola spp.

From the order of the Diptera and the sub-orders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., F~ m~ um spp., S Phlebotomus spp., LuL:~oll~yia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., E~m~topota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., C~llirh<)ra spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., 10 Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Ht;l~ ro~ ida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.

15 From the order of the Bl~ ri(l~ for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesosti~n~t~, for example, Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma 20 spp., Rhipicephalus spp., Dcll-lally~u~ spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigm~t~) and Acaridida (A~tigm~t~), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp.,25 Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Le A 31 184-Forei~n countries Cytodites spp. and T ~min~sioptes spp.

For example, they have an ol~t~t~n~ling activity against all Boophilus microplus and .
Lucllla cuprma.

The active compounds of the formula a) according to the invention are also suitable S for controlling ~hlopods which attack agricultural livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic ~nim~l~, such as, for example, dogs, cats, caged birds, a~lu~;um fish, and so-called t;~.t;.hllent ~nim~l~, such as, for example, hamsters, guinea-pigs, rats and mice. By controlling these ~l~llopods, it is intended to reduce mortality and decreased performances (in meat, milk, wool, hides, eggs, honey and the like), so that more economical and' simpler animal keeping is made possible by using the active compounds according to the invention.

In the veterinary sector, the active compounds according to the invention are used in a known marmer by enteral ~lministration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral ~lmini~ration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, hlL.d~l;Loneal and the like), implants, by nasal ~lmini~tration~ by dermal ~1mini~tration~ for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, cln~ting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, limb bands, halters, mslrking devices and the like.

When ~lmini~tered to livestock, poultry, domestic ~nim~l~ and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to 80%
by weight, either directly or after dilution by a factor of 100 to 10 000, or they may be used in the form of a chemical bath.

The preparation and the use of the active compounds according to the invention is illustrated by the examples which follow.

Le A 31 184-Forei~n countries Preparation ExamPles Example 1 ~CO-O-CH2-CH2-CF=CF2 50.5 g (0.31 mol) of isatoic anhydride in 300 ml of toluene are heated under reflux with 1 g of 4-dimethylaminopyridine, 0.1 g of potassium carbonate and 44.1 g (0.35 mol) of 3,4,4-trifluorobut-3-en-1-ole for 15 hours. After cooling, the reaction mixture is washed with water and the toluene is removed under reduced pressure. 67.7 g of 3,4,4-trifluorobut-3-en-1-yl 2-aminobenzoate are obtained as a clear oil.
Yield: 89.1 % of theory.
10 log p~ (pH 2) = 3.05; n20D= 1.5160 Example 2 ~CO-O-CH2-CH2-CF=CF2 OH
32 g (0.2 mol) of sodium salicylate in 100 ml of dimethyl sulphoxide with 28.4 g(0.15 mol) of 1-bromo-3,4,4-trifluorobut-3-ene are heated to 50~C for 15 hours. After 15 cooling, the reaction llliX~ iS diluted with water, the product is extracted with methylene chloride and the organic phase is concentrated under reduced pressure. The residue is subsequently distilled under reduced pressure. 24.3 g (yield: 65.8 % of theory) of colourless 3,4,4-trifluorobut-3-en-1-yl 2-hydroxy-benzoate of boiling point 102-108~C/ 1.5 mm are obtained.

20 Similar to Examples 1 and 2 and/or according to the general ~ ion procedures, the following compounds of the formula (Ia) are obtained:

Le A 31 184-Forei~n countries CF2=C--CH2--CH2--O--CO~R3 (Ia) Ex. Rl R2 R3 Physic. constant No.
3 F H H Bp.180~C/100mm 4 F H 2-COOH log p(pH2)=2.14 F H 2-NHCH3 log p(pH2)=3.86 6 F 6-Cl 2-NH2 log p(pH2)=3.04 7 F H /~ log p(pH2)=4.94 2 -NH~

8 F 4-C1 2-NH2 log p(pH2)=3.68 9 F 5-C1 2-NH2 log p(pH2)=3.58 F H 2-SO3H log p(pH2)=1.29 11 F 5-NO2 2-NH2 Mp.102-104~C
12 F H 3-N(CH3)2 log p(pH2)=3.29 13 F H 4-N(CH3)2 log p(pH2)=3.49 14 F H Mp.: 294~C
~0--CO--NH~CI

F H 2-NHCOCH3 Mp.: 76~C
16 F H Mp.: 158~C
2--NH--CO~CI

Le A 31 184-Forei~n countries Ex. R~ R2 R3 Physic. constant No.
17 F H F Mp.: 128~C
~NH--CO~

18 F H Mp.: 186~C
~NH--CO--NH~;~CI

19 F H 2-NH-CO-NHCH3 Mp.: 136~C
F H Cl Mp.: 168-170~C
~NH--CO--NH ~CI

21 H H 2-NH2 log p(pH2)=3.06 22 F H 2-NH-CO-C(CH3)=CH2 Mp.: 106~C

log p: logarithm to base ten of the n-octanol/water partition coefficient, determined by reversed phase HPLC analysis using H2O/CH3CN.

Le A 31 184-Forei~n countries Examples of compounds of the forrnula (Ib):

Example 23 (C2H50)2P(=O)CH2COOH + CF2=CF-CH2-CH2-Br ~ (C2H50)zP(=O)CH2COO-CH2-CH2-CF=CF2 2 g (0.01 mol) of O,O-diethylphosphonoacetic acid and 1.52 g of DBU
(diazabicycloundecane) in 35 ml of acetonitrile are admixed with 2.5 g (0.12 mol) of 4-bromo-1,1,2-trifluoro-but-1-ene, and the mixture is stirred at 60~C for 7 hours. The reaction mixture is then poured into water and extracted with ether twice. The combined ether phases are washed with water, twice with 5 % strength aqueous NaOH

10 and then another 2 times with water and dried over m~gnesium sulphate. Evaporation of the ether gives 0.93 g of 3,4,4-trifluorobut-3-enyl O,O-diethylphosphonoacetate as a clear liquid.

Elemental analysis: calculated: C 39.48; H 5.30 found: C 38.97; H 5.24 15 Example 24 (C2H50)2P(=O)CH2-COO-CH2-CH2-CF=CF2 ~ (HO)!P(=O)-CH2-COO-CH2-CH2-CF=CF2 With ice-cooling, 4.9 ml (0.037 mol) of trimethylsilyl bromide in 6 ml of acetonitrile are added dropwise to 0.93 g (0.0031 mol) of the compound of Example 23 in 8 ml of 20 acetonitrile, and the mixture is then stirred at room temperature overnight. The mixture is subsequently concentrated under reduced pressure and the residue is admixed with methanol. The mixture is stirred at room te~ c;ldlulc; for 30 minutes and the methanol is removed under reduced ples~ . The residue is dissolved in ether. The ether is removed under reduced pressure, affording 0.71 g of 3,4,4-trifluorobut-3-enyl 25 phosphonoacetate as a viscous, slightly yellow oil.

Le A 31 184-Forei~n countries Elemental analysis: calculated: C 27.64; H 3.63 found: C 27.54; H 3.50 Example 25 <~ 3CH2 COOH + CF2=CF-CH2-CH2Br ~ ~CH2--COO--CH2 CH2--CF=CF2 S At room temperature, 98 g (0.52 mol) of 4-bromo-1,1,2-trifluorobut-1-ene are added dropwise to 50 g (0.37 mol) of phenylacetic acid and SS.9 g (0.37 mol) of DBU in 400 ml of acetonitrile. The mixture is stirred for several hours at room temperature, overnight under reflux and then for another 2 days at room te~ )eldLule. The solvent is removed under reduced pressure and the residue is admixed with water and extracted with ether. The ether phase is washed twice with S % strength aqueous NaOH and twice with water, dried over magnesium sulphate and evaporated. 42.05 g of 3,4,4-trifluorobut-3-enyl phenyl acetate are obtained as a clear amber liquid.

Elemental analysis: calculated: C 59.02; H 4.54 found: C 59.29; H 4.60 Le A 31 184-Forei~n countries Example 26 CH3--fH--NH--CO--O--C(CH3)3 + HO--CH2--CH2--CF=CF2 COOH

CH3--f H--NH--CO--O--C(CH3)3 COO--CH2--CH2--CF = CF2 1.62 g (0.01 mol) of carbonyl-liimicl~7Qle (obtainable from Aldrich) are added to 1.89 g (0.01 mol) of (L)-N-Boc-alanine (obtainable from Sigma) in 20 ml of anhydrous 5 tetrahydrofuran (THF), and the mixture is stirred at room temperature for 30 minlltes 1.5 g (0.012 mol) of 4-hydroxy-1,1,2-trifluorobut-1-ene (c~ synthesis example 16 from US 5 389 680) are then added and the mixture is stirred at room temperature overnight.
The solvent is removed under reduced pressure and the residue is admixed with water and extracted with ether. The ether phases are washed with water (3 times) and dried 10 over m~gnecium sulphate. The ether is evaporated under reduced pressure. 2.25 g of 3,4,4-trifluorobut-3-enyl N-tert-butyloxycarbonyl-L-~l~nin~te are obtained as a clear liquid.

Elemental analysis: calculated: C 48.48; H 6.10, N 4.71 found: C 48.54; H 6.08; N 4.69 15 Example 27 CH3--fH--NH--CO--O--C(CH3)3 CH3--fH--COO--CH2--CH2--CF=CF2 COO--CH2--CH2--CF=CF2 NH2 x HCI

An excess of HCl gas is troduced into the solution of 1.54 g (0.0052 mol) of thecompound of Example 26 in 50 ml of ether. The reaction vessel is then closed and the mixture is stirred at room telllpeldl-ue for another 6 h. The resulting colourless 20 precipitate is filtered off, washed with ether and dried under reduced ~les~ . 0.8 g of 3,4,4-difluorobut-3-enyl L-~l~nin~t~ are obtained as a colourless solid.

Le A 31 184-Forei~n countries Elemental analysis: calc~ te(1 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 Le A 31 184-Forei~n countries Use Example , --Example A

Critical concentration test / nematodes Test nematode: Meloidogyne incognita 5 Solvent: 4 parts by weight of acetone Fm~ ifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable p,~dldlion of active compound, 1 part by weight of active compound is mixed with a stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

10 The active compound pr~a dlion is intim~tely mixed with soil which is heavilyinfested with the test nematodes. The concentration of the active compound in the pl~paldlion is imm~terial~ only the amount of active compound per unit volume of soil, which is given in ppm (= mgA), matters. The treated soil is transferred into pots, lettuce is sown in, and the pots are kept at a greenhouse tt;lllp~ldlule of 25~C.

15 After four weeks, the lettuce roots are checked for infestation with nematodes (root galls) and the efficacy of the active compound in % is determined. The efficacy is 100 % when infestation is avoided completely and 0 % when the infestation level is just as high as in the control plants in untreated, but equally infested, soil.

In this test, an efficacy of 100 % is shown, for example, by the compounds of 20 Preparation Examples 1 and 5 at an exemplary active compound concentration of20 ppm.

Le A 31 184-Forei~n countries Example B

Test with fly larvae / development-inhibitory action .

Test ~nim~l~ All larval stages of Lucilia cuprina (OP resistant) [pupae and adults (without contact wit_ the active compound)]

Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, 3 parts by weight of active compound are mixed with 7 parts of t_e abovementioned solvent-em~ ifier mixture, and the resulting emulsion concentrate is diluted with water to the respective desired concentration.

For each individual concentration, 30 to 50 larvae are introduced into a test tube which contains 1 cm3 of horse meat. 500 ~Ll of the dilution to be tested are pipetted onto this horse meat. The test tubes are placed in plastic beakers whose bottoms are covered with sea sand, and kept in an air-conditioned room (26~C ~t 1.5~C, 70 % ~ 10 %
relative humidity). The activity (larvicidal action) is examined after 24 hours and again after 48 hours. After emergence of larvae (about 72 h), the test tubes are removed and perforated plastic lids are fitted onto the beakers. After 1.5 times the development time (hsltching of control flies), the hatched flies and the pupae/cocoons are counted.

The activity criterion is the incidence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of the hatching of the adults from pupae or the ~u m ml~lllOn OI pupa rormallon. lne crllerlon Ior tne m vltro acuvlty or a su~stance lS
the inhibition of the development of the flies, or a development st~nfl~till before the adult stage. lOû % larvicidal action means that all the larvae have been killed after 48 hours. 1 Oû % development-inhibitory action means that no adult flies have hatched.

In this test, an activity of 100 % was shown, for example, by the compounds of Plepaldlion Examples 1 and 5 at an exemplary active compound concentration of 1000 ppm.

Le A 31 184-Forei~2n countries E~ample C

Test with Boophilus microplus reSi~t~nt / SP-resistant Parkhurst strain Test ~nim~l~ Adult females which have sucked themselves full Solvent: Dimethyl sulphoxide 5 20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide, and lower concentrations are prepared by dilution with the same solvent.

The test is carried out in S replications. 1 ~11 of the solution is injected into the abdomen, and the ~nim~l~ are transferred into dishes and kept in an air-conditioned room. The activity is determined via the inhibition of oviposition. 100 % means that no 10 tick has deposited eggs.

In this test, an activity of 100 % was shown, for example, by the compounds of Pl~;pal~tion Examples 1 and 5 at an exemplary active compound concentration of 20 ~Lg/animal.

Le A 31 184-Forei~n countries Example D

This test is carried out as described in US-S 389 680 which is expressly inco~porated herein by reference.

In the nematode test (tomato and soybean), the compound of P~ dlion Example 26 S had an activity of 95 % in method 1 at 500 ppm, a stage 2 activity in method 2 at a concentration of 1 mg/pot and no activity at concentrations of 0.5 mg/pot and 0.25 mg/
pot, the activity stages being defined as described in US 5 389 680 where stage 0 means an activity of up to 50 %, stage 1 means an activity of 50 to 75 %, stage 2 means an activity of 75 to 90 % and stage 3 means an activity of 91 to 100 %.

Claims (10)

claims

1. Compounds of the formula (I) in which R1 represents hydrogen or halogen, and Q represents either a) in which R2 represents hydrogen, nitro, cyano, halogen, alkyl, alkoxy, alkylthio or optionally substituted aryl and R3 represents COOH, SO3H, NR4R5 or OR6 in which R4 represents hydrogen, alkyl or optionally substituted aryl, R5 represents hydrogen, alkyl, optionally substituted aryl or COR7, R6 represents hydrogen, optionally substituted aralkyl, CONR4R5 or COR7, R7 represents alkyl, alkenyl, optionally substituted aryl or NR4R8 and R8 represents hydrogen, alkyl or optionally substituted aryl, or b) is ZR9 or Z(P=W)R10R11 in which Z represents an aliphatic group having one to four carbon atoms with the proviso that R9 does not represent phenyl if Z represents CH2, W represents oxygen or sulphur, R9 .alpha.) represents an aromatic group or represents a heterocyclic group (such as, for example, a cyclic group from the group consisting of pyrazolyl, imidazolyl, triazolyl, morpholinyl, piperidinyl, piperazinyl or pyrrolidinyl), each of which is optionally substituted by at least one substituent from the group consisting of cyano, trimethylsilyl, hydroxyl, alkyl, alkoxy, halogen, niko, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, .beta.) represents hydrogen, OR12, SR12, halogen, NR12R13, cyano, trimethylsilyl, nitro, phenyl, the radical of a sulphonic acid or an ester, an amide or a thioester thereof or represents an aliphatic group which is optionally substituted by at least one radical from the group consisting of cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, in which R12 and R13 independently of one another each represent i) hydrogen, ii) an aliphatic group having one to twelve carbon atoms or an aromatic or heterocyclic group which is optionally substituted by at least one radical from the group consisting of alkyl having one to four carbon atoms, cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, iii) or R12 and R13 join with the linking nitrogen atom to form part of an amino acid, or if R12 represents hydrogen or an aliphatic or aromatic group which is in each case optionally substituted by at least one substituent from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids, or phenyl, then R13 may also represent OR16, COR16, COOR21, NR16R17, SO2R18, P(=O)R19R20 in which R16 and R19 independently of one another each represent hydrogen, alkyl or aryl, R18 represents hydrogen, alkyl, halogenoalkyl or aryl, R19 and R20 independently of one another each represent hydrogen, alkyl, aryl,alkyl, alkylthio, arylthio, alkylamino, dialkylarnino, arylamino or OR21 and R21 represents hydrogen, alkyl or aryl, R10 and R11 independently of one another each represent R22, OR22, SR22 or NR22R23 in which R22 and R23 independently of one another each represent hydrogen or an aliphatic or aromatic group which is in each case optionally substituted by at least one substituent from the group consisting of cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, optionally mono- or dialkyl-substituted amino, thiol, alkylthio, phenyl, a radical of a sulphonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the mentioned acids and salts thereof.

Compounds of the formula (I) according to Claim 1 having the structures (Ia), (Ib-1) or (Ib-2):

CF2=CR1-CH2-CH2-O-CO-ZR9 (Ib-1) CF2=CR1-CH2-CH2-O-CO-Z(P=W)R10R11 (Ib-2) in which R1, R2, R3, R9, R10, R11, Z and W are each as defined in Claim 1.

Process for preparing compounds of the formula (Ia) according to Claim 2, characterized in that A) benzoic acid derivatives of the forrnula (II) in which X(+) represents an alkali metal ion,or an ammonium ion and R2 and R3 are each as defined in Claim 1 are reacted with a fluorobutenyl bromide of the formula (III) in which R1 is as defined in Claim 1 in the presence of a diluent or B) isatoic anhydrides of the formula (IV) in which R2, R3 and R4 are each as defined in Claim 1 are reacted with a fluorobutenol of the formula (V) in which R1 is as defined above, if appropriate in the presence of a base and if appropriate in the presence of a diluent or C) acid anhydrides of the formula (VI) in which Y represents CO or SO2 and R2 and R3 are each as defined in Claim 1 are reacted with a fluorobutenol of the formula (V) in which R1 is as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a base.

4. Compounds of the formula (Ia) according to Claim 2 in which R1 represents hydrogen, fluorine, chlorine or bromine, R2 represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, C1-C8-alkyl, C1-C6-alkoxy, C1-C6-alkylthio or optionally cyano-, fluorine-, chlorine-, bromine- or C1-C6-alkoxy-substituted phenyl, R3 represents 2-COOH, 2-SO3H, NR4R5 or OR6, R4 represents hydrogen, C1-C8-alkyl or optionally cyano-, fluorine-, chlorine-, bromine-, C1-C6-alkyl- or C1-C6-alkoxy-substituted phenyl, R5 represents hydrogen, C1-C8-alkyl, optionally cyano-, fluorine-, chlorine-, bromine-, C1-C6-alkyl- or C1-C6-alkoxy-substituted phenyl or represents COR7, R6 represents hydrogen, optionally cyano-, fluorine-, chlorine-, bromine-, C1-C6-alkyl- or C1-C6-alkoxy-substituted phenyl-C1-C6-alkyl or represents CONR4R5 or COR7, R7 represents C1-C8-alkyl, C2-C6-alkenyl, optionally fluorine-, chlorine-;
bromine-, C1-C6-alkyl- or C1-C6-alkoxy-substituted phenyl or represents NR4R8 and R8 represents hydrogen, C1-C8-alkyl or optionally cyano-, fluorine-, chlorine-, bromine-, C1-C6-alkyl- or C1-C6-alkoxy-substituted phenyl.

5. Compounds of the formula (Ia) according to Claim 2 in which R1 represents hydrogen or fluorine, R2 represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or optionally fluorine-, chlorine-, or C1-C4-alkoxy-substituted phenyl, R3 represents 2-COOH, 2-SO3H, NR4R5 or OR6, R4 represents hydrogen, C1-C4-alkyl or optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted phenyl, R5 represents hydrogen, C1-C4-alkyl, optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted phenyl or represents COR7, R6 represents hydrogen, optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted phenyl or, represents CONR4R5 or COR7, R7 represents C1-C4-alkyl, C2-C6-alkenyl, optionally fluorine-, chlorine- or C1-C4-alkyl-substituted phenyl or represents NR4R3 and R8 represents hydrogen, C1-C4-alkyl or optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted phenyl.

6. Pesticides, characterized in that they comprise at least one compound of the formula (I) according to Claim 1.

7. Use of compounds of the formula (I) according to Claim 1 for controlling pests.

8. Method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and/or their habitat.

9. Process for preparing pesticides, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.

10. Use of compounds of the formula (I) according to Claim 1 for preparing pesticides.