DE19718522A1 - New 2-phenyl-4-bi:phenyl-oxazoline derivatives - Google Patents

Abstract

Substituted 2-phenyl-4-biphenyl-oxazolines (I) are new: X<1>, X<3> = H, halo, alkyl, alkoxy or alkylthio; X<3> is especially H; X<2> = halo, alkyl, alkoxy or alkylthio; R<1> = H, halo, alkyl or CH2CR<4>=CH2; R<2> = alkyl, hydroxyalkyl or optionally substituted alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, phenylalkyl, naphthylalkyl or tetrahydronaphthylalkyl; R<3> = H, alkyl, halo or CH2CR<4>=CH2; R<4> = H or optionally substituted alkyl or aryl; compounds in which R<1> = R<3> = H are excluded.

Description

The invention relates to new biphenyloxazolines, processes for their preparation and the Use of biphenyloxazolines to control animal pests.

It is known that certain biphenyloxazolines are insecticidal and acaricidal are, for example, the compounds 2- (2,6-difluorophenyl) -4- (3'-chloro-4 '- (1,1,2,2- tetrafluoroethoxy) biphenyl-4) -2-oxazoline (EP-A-0 696 584) and 2- (2,6-difluoro phenyl) -4- (3'-chloro-4'-methylbiphenyl-4) -2-oxazoline (EP-A-0 432 661).

The level of action and / or duration of action of these known compounds is dependent however, especially against certain organisms or with low application con concentrations, not completely satisfactory in all areas of application.

New disubstituted biphenyloxazolines of the formula (I)

found,
in which
X ^{1 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio,
X ^{2 represents} halogen, alkyl, alkoxy or alkylthio,
X ^{3 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio,
R ^{1 represents} hydrogen, halogen, alkyl or -CH ₂ -CR ⁴ = CH ₂ ,
R ^{2 represents} alkyl, hydroxyalkyl, each optionally substituted alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, phenylalkyl, naphthylalkyl or tetrahydronaphthylalkyl and
R ^{3 represents} hydrogen or the radical -CH ₂ -CR ⁴ = CH ₂ , where R ¹ and R ^{3 are} not simultaneously hydrogen and
R ^{4 represents} hydrogen or in each case optionally substituted alkyl or aryl.

The compounds of the formula fall because of one or more centers of chirality (I) generally as mixtures of stereoisomers. They can be both in the form of their Diastereomer mixtures as well as pure diastereomers or enantiomers can be used be det.

It has also been found that the new compounds of the formula (I) are obtained when

• A) compounds of the formula (II)
  in which
  X ¹ , X ² , X ³ and R ^{1 have} the meanings given above,
  with compounds of the formula (III)
  ZR ² (III),
  in which
  R ^{2 has} the meaning given above and
  Z represents a leaving group,
  if appropriate in the presence of a diluent and if appropriate in the presence of a base and
• B) optionally then the compounds of the formula (IV) obtained in this way for R ² = CH ₂ -CR ⁴ = CH ₂
  in which
  R ¹ , R ⁴ , X ¹ , X ² and X ^{3 have} the meanings given above,
  undergoes a Claisen rearrangement and
• C) optionally subsequently the compounds of the formula (V) thus obtained
  in which
  X ¹ , X ² , X ³ , R ¹ and R ^{4 have} the meanings given above,
  with compounds of the formula (III)
  ZR ² (III),
  in which
  R ² and Z have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a base and
  optionally then for R ² = CH ₂ -CR ⁴ = CH ₂ and R ¹ = H, steps B) and C) are repeated, giving compounds of the formula (Va)
  in which
  X ¹ , X ² , X ³ , R ² and R ^{4 have} the meaning given above,
  and the radicals R ^{4 can be the} same or different.

It has also been found that the new compounds of the formula (I) are very good for loading control of animal pests, in particular insects, arachnids and Nematodes used in agriculture, in the forest, in the protection of stocks and materials as well as in the hygiene sector are suitable.

The compounds according to the invention are generally defined by the formula (I).

Preferred substituents or ranges of those mentioned in the above and below The radicals listed in formulas are explained below.

X ¹ preferably represents hydrogen, fluorine, chlorine, bromine, iodine, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio.

X ² preferably represents fluorine, chlorine, bromine, iodine, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio.

X ³ preferably represents hydrogen, fluorine, chlorine, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy.

R ¹ preferably represents hydrogen, fluorine, chlorine, bromine, C ₁ -C ₆ alkyl or R ² = CH ₂ -CR ⁴ = CH ₂ .

R ² preferably represents C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C ₁₂ alkynyl, optionally substituted by halogen or C ₁ -C ₄ alkyl tuiert C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkenyl,
is optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ - haloalkenyl, phenyl, halophenyl, styryl or Halogenstyryl sub stituiertes C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl,
for C ₄ -C ₈ cycloalkenyl-C ₁ -C ₂ alkyl optionally substituted by halogen or C ₁ -C ₄ alkyl,
or for optionally up to four times, identical or different, by nitro, halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ alkylthio, C ₁ -C ₁₂ haloalkylthio, C ₁ - C ₁₂ alkoxy or C ₁ -C ₁₂ haloalkoxy substituted phenyl-C ₁ -C ₄ alkyl, for naphthyl-C ₁ -C ₃ alkyl or tetrahydro naphthyl-C ₁ -C ₃ alkyl.

R ³ preferably represents hydrogen or -CH ₂ -CR ⁴ = CH ₂ .

R ⁴ preferably represents hydrogen, C ₁ -C ₁₂ alkyl or in each case optionally one to four times, identically or differently by halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ - Alkoxy or C ₁ -C ₁₂ haloalkoxy substituted phenyl.

X ¹ particularly preferably represents hydrogen, fluorine or chlorine.

X ² particularly preferably represents fluorine, chlorine, bromine, iodine, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy.

X ³ particularly preferably represents hydrogen, fluorine, chlorine, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy.

R ¹ particularly preferably represents hydrogen, fluorine, chlorine or C ₁ -C ₄ alkyl.

R ² particularly preferably represents C ₁ -C ₆ -alkyl, C ₁ -C ₄ -hydroxyalkyl, C ₃ -C ₁₀ -alkenyl, C ₃ -C ₅ -alkynyl, optionally by halogen or C ₁ -C ₄ -alkyl substituted C ₆ cycloalkyl or C ₃ -C ₆ cycloalkenyl,
for optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₃ haloalkenyl, phenyl, halophenyl, styryl or halostyryl C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ -alkyl,
for C ₄ -C ₆ cycloalkenylmethyl which is optionally substituted by halogen or
for optionally single or double, identical or different by nitro, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ - haloalkylthio, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy substituted benzyl, for naphthylmethyl or tetrahydronaphthylmethyl.

R ³ particularly preferably represents hydrogen or -CH ₂ -CR ⁴ = CH ₂ .

R ⁴ particularly preferably represents hydrogen, C ₁ -C ₄ -alkyl or, if appropriate, once or twice, identically or differently, by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl or C. ₁ -C ₄ haloalkoxy substituted phenyl.

X ¹ very particularly preferably represents hydrogen, fluorine or chlorine.

X ² very particularly preferably represents fluorine, chlorine, bromine, iodine, methyl or methoxy.

X ³ very particularly preferably represents hydrogen, fluorine, chlorine or methyl.

R ¹ very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl.

R ² very particularly preferably represents methyl, ethyl, n- or i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl, n-hexyl, hydroxyethyl, hydroxypropyl, hydroxy butyl, for -CH ₂ - CH = CH ₂ , -CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C∼CH or -CH (CH ₃ ) C∼CH, for one of the cycloalkylalkyl groups:

for one of the phenylalkyl groups;

Compounds of the formula (Ia) are also preferred

in which
R ¹ , R ² , X ¹ and X ^{2 have} the abovementioned general, preferred, particularly preferred or particularly preferred meanings.

A preferred group of compounds are also those of the formula (Ib)

in which
X ^{1 represents} hydrogen or fluorine,
X ^{2 represents} fluorine, chlorine, bromine or methyl,
R ^{1 represents} fluorine, chlorine, methyl, ethyl, n- or i-propyl or allyl and
R ^{2 has} the abovementioned general, preferred, particularly preferred and very particularly preferred meanings and is particularly emphasized for benzyl optionally substituted as indicated above.

It applies that R ¹ and R ^{3 are} not simultaneously hydrogen.

The carbons mentioned above in the definition of the compounds according to the invention hydrogen residues, such as alkyl or alkenyl, are - also in connection with heteroato as in alkoxy - as far as possible straight or branched.

The general or priority ranges listed above nitions or explanations can be among each other, that is, between the respective Areas and preferred areas can be combined as desired. They apply to the end products as well as for the preliminary and intermediate products accordingly.  

According to the invention, preference is given to the compounds of the formula (I) in which one Combination of the meanings listed above as preferred (preferred) is present.

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

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

If, for example, 2- (2,6-difluorophenyl) -4- (4'-hydroxy-3'-n-propylbiphenyl-4) -2-oxazoline and isopropyl bromide are used as starting materials, the pre-stage A) can be reproduce the process according to the invention by the following reaction scheme:

If, for example, 2- (2,6-difluorophenyl) -4- (4'-alloxy-3'-chlorobiphenyl-4) -2-oxazoline is used as the starting material, the course of stage B) of the process according to the invention can be carried out by the following Play back reaction scheme:

If, for example, 2- (2,6-difluorophenyl) -4- (3'-allyl-5'-chloro-4'-hydroxybiphenyl-4) -2-oxazoline and benzyl bromide are used as starting materials, the course of the step can be seen C) reproduce the process according to the invention by the following reaction scheme:

Those required as starting materials in stage A) of the process according to the invention ten compounds of formula (II) are new.

The compounds of the formula (II) are obtained, for example, if compounds of the formula (VI)

in which
X ¹ , X ² , X ³ and R ^{1 have} the meanings given above and
R ^{5 represents} alkyl (for example methyl), aryl (for example phenyl) or alkoxy (for example methoxy or ethoxy),
cyclized in the presence of a base, optionally in the presence of a catalyst and optionally in the presence of a diluent, and then the acyl group is split off (process D).

If, for example, 2,6-difluoro-N- [2-chloro-1- (4- (4-acetoxy-3-n-propylphenyl) phenyl) ethyl] benzamide is used as the starting material, the course of the process can be determined D) reproduce the preparation of the compounds of formula (VI) by the following reaction scheme:

All inert organic solutions are used as diluents in process D) medium in question. They can optionally be used mixed with water will. Hydrocarbons such as toluene, xylene, Tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, Chloroform, chlorobenzene, o-dichlorobenzene, alcohols such as methanol, ethanol, glycol, the isomeric propanols, butanols, pentanols, ethers such as diethyl ether, diiso propyl ether, dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as acetonitrile or Butyronitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, further Sulfolan. Alcohols or dimethylformamide are particularly preferably used.

All customary acid acceptors can be used as the base for the cyclization.

Tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBN, N, N-dimethylaniline, also alkaline earth metal oxides such as magnesium and Calcium oxide, also alkali and alkaline earth metal carbonates such as sodium carbonate, Potassium carbonate and calcium carbonate, alkali hydroxides such as sodium and potassium hy hydroxide, also alcoholates such as sodium ethanolate or potassium tert-butoxide.

If appropriate, the process is carried out in the presence of a phase transfer catalyst. As Phase transfer catalyst come for example ammonium compounds such as Tetraoctylammonium bromide or Benzyltriethylammoniumchlorid in question.  

The reaction temperature can be varied within a wide range. in the generally one works at temperatures between -20 ° C and 150 ° C, preferably between -10 ° C and 100 ° C.

The reaction is generally carried out under normal pressure.

Generally, an equimolar amount of base is used. It is also possible to work with a base excess.

Preferred diluents for the subsequent saponification are Water / alcohol mixtures used, such as water / methanol, what water / ethanol or water / propanol or water / amide mixtures such as Water / dimethylformamide (DMF) or water / dimethylacetamide.

The saponification is carried out in the presence of a base. As such come anor ganic and organic bases in question, especially alkali hydroxides such as sodium hydroxide or potassium hydroxide or ammonia.

The reaction temperature can vary within a wide range during the saponification will. Generally one works at temperatures between -10 ° C and 60 ° C, preferably between 0 ° C and 40 ° C. The implementation is generally under Normal pressure carried out.

Cyclization and cleavage of the acyl groups can be carried out both as a one-pot reaction and can also be carried out in two separate steps.

The compounds of the formula (VI) required as starting materials in process D) are new.

The compounds of the formula (VI) are obtained, for example, if compounds of the formula (VII)

in which
R ¹ and R ^{5 have} the meaning given above,
with compounds of formula (VIII)

in which
X ¹ , X ² and X ^{3 have} the meanings given above,
in the presence of an acidic catalyst, for example a Lewis acid such as iron (III) chloride, aluminum chloride or hydrogen fluoride and preferably in the presence of a diluent, for example a halogenated, in particular chlorinated hydrocarbon such as dichloromethane at temperatures between -20 ° C and 80 ° C implements (cf. the manufacturing examples and also WO 96/18619).

Some of the compounds of the formula (VII) are known (J. Amer. Chem. Soc. 61, 1447, 3037 (1939); J. Amer. Chem. Soc. 56, 202 (1934); J. Amer. Chem. Soc 64 2219 (1942); J. Amer. Chem. Soc. 89, 2711 (1967); J. Org. Chem. 27, 2671 (1962); J. Indian Chem. Soc. 12, 410 (1935); DE -1 911 520) or can be prepared by known methods, for example by reacting the corresponding hydroxybiphenyls of the formula (IX) with the acid anhydrides of the formula (X) or the acid halides (in particular acid chlorides) of the formula (in):

Some of the compounds of the formula (IX) are known (see, for example, J.Org.Chem. 29, 2640 (1964), J. Indian Chem. Soc. 12, 410 (1935), J. Amer. Chem. Soc. 80, 3271 (1958)) or can be produced by known methods (cf. examples).

For example, in the following way

the starting compound from Bull. Chem. Soc. Yep 56, 2037 (1983) is known or according to

the starting compound being known (see J. Amer. Chem. Soc. 80, 3271 (1958)).  

The compounds of the formulas (X) and (XI) are generally known and common commercially or in a simple and known manner from the corresponding carboxylic acids available.

The compounds of the formula (VIII) are known (see, for example, EP-A-0 594 179, WO 96/18619) or can be produced according to the methods described there.

The compounds of the formula (VI) can also be obtained if acid chloride of the formula (XII)

in which
X ¹ , X ² and X ^{3 have} the meanings given above,
with amino alcohols of the formula (XIII)

in which
R ^{1 has} the meaning given above,
optionally in the presence of a diluent, (all solvents which are inert to these compounds can be used as diluents, preferably hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o -Dichlorobenzene, in addition ketones, such as acetone and methyl isopropyl ketone, further ethers, such as diethyl ether, tetrahydrofuran and dioxane, in addition carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane; if the hydrolysis stability of the acid halide permits, that can Reaction can also be carried out in the presence of water) and, if appropriate, in the presence of a base (all customary acid acceptors can be used as the base, preferably tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene, can be used (DBU), diazabicyclonones (DBN), Hünig base and N, N-dimethyl-aniline, also alkaline earth metal oxides, such as magnesium and calcium oxide, in addition to the alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate and alkali - or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide) at temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 30 ° C and optionally then the compounds of formula (XIV) thus obtained

in which
X ¹ , X ² , X ³ and R ^{1 have} the meanings given above,
with a chlorinating agent such as thionyl chloride, phosgene or phosphorus oxychloride, optionally in the presence of a diluent, for example hydrocarbons such as toluene, xylene, hexane, cyclohexane, halogenated hydrocarbons such as chlorobenzene, chloroform, methylene chloride or ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran or dioxane Reacts temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C (cf. EP-A-0 696 584).

The further in stage A) of the process according to the invention as starting materials Compounds of the formula (III) required are generally known compounds of organic chemistry. Z stands for a usual leaving group, for example for Halogen (especially chlorine or bromine), alkylsulfonyloxy (especially methyl sulfonyloxy) or optionally substituted arylsulfonyloxy (especially phenyl sulfonyloxy, p-chlorophenylsulfonyloxy or tolylsulfonyloxy).

Stage A) of the process according to the invention is characterized in that a compound of formula (II) with a compound of formula (III) optionally in the presence of a diluent and optionally in the presence of a base implements.

All customary solvents are suitable as diluents. Preferably Halogenated, aromatic or aliphatic carbons can optionally be used hydrogens, ketones, nitriles and amides. Examples include toluene and Ace clay, acetonitrile, dimethylformamide and dimethylacetamide.

All common inorganic and organic bases can be used as the base. Ge Examples include tertiary amines such as triethylamine, DBN, DBU, DABCO, Alkali and alkaline earth metal hydroxides such. B. sodium hydroxide, potassium hydroxide and Cal cium hydroxide and alkali and alkaline earth carbonates such. B. sodium carbonate or Potassium carbonate.

The reaction temperature can be varied within a wide range. in the generally one works at temperatures between -20 ° C and 100 ° C, preferably between 0 ° C and 60 ° C.

The reaction is generally carried out under normal pressure.  

The compounds of formula (II) and the compounds of formula (III) are in generally used in approximately equimolar amounts. But you can also use an excess of the compounds of formula (III).

Stage B) of the process according to the invention is characterized in that Subjects compounds of formula (IV) to a Claisen rearrangement.

Here, the compounds of formula (IV) in bulk or in the presence a diluent (chlorobenzene, dichlorobenzene, diethylaniline) at tempera doors heated from 160 ° C to 290 ° C, preferably 180 ° C to 260 ° C (see also D.S. Tarbell, The Claisen Rearrangement, Org. Reactions 2, lff (1944)).

Stage C) of the process according to the invention is characterized in that Compounds of formula (V) with compounds of formula (III), optionally in Presence of a diluent and optionally in the presence of a base implements.

For this reaction analogous to stage A), the following applies with regard to diluent, base, Reaction temperature etc. what was said there.

The active ingredients are suitable for good plant tolerance and inexpensive warmth blood toxicity to control animal pests, especially insects, Arachnids and nematodes, which are used in agriculture, in forests, in stock and Material protection and in the hygiene sector. You are against normal sen sible and resistant species as well as against all or individual stages of development sam. The pests mentioned above include:

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloido gyne spp., Aphdenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention are particularly noteworthy with excellent insecticidal and acaricidal activity.

They can be used with particularly good results in combating plant damage the insects, such as against the horseradish leaf beetle larvae (Phaedon cochleariae), the caterpillars of the owl butterfly (Spodoptera frugiperda) and the peach aphids (Myzus persicae) or for combating plant-damaging mites, such as against the common spider mite (Tetranychus urticae).

The active compounds can be converted into the customary formulations, such as solutions genes, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble Powders, granules, suspension emulsion concentrates, active ingredient-impregnated Na tur- and synthetic substances as well as very fine encapsulation in polymeric substances.  

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid carriers gerstoffe, optionally using surfactants, so Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers: e.g. B. ammonium salts and natural rock powders such as kaolins, clays, talc, Chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic Ge stone powders, such as highly disperse silica, aluminum oxide and silicates, as solid Carriers for granules are possible: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic Granules from inorganic and organic flours as well as granules from organic chemical material such as sawdust, coconut shells, corn cobs and tobacco stems; as Emulsifying and / or foam-generating agents are possible: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene Fatty alcohol ether, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. Lignin liquor and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active ingredient fabric, preferably between 0.5 and 90% and preferably in addition to extenders and / or surfactants.

The active ingredient according to the invention can be in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, Acaricides, nematicides, fungicides, growth regulators or herbi ziden available. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by Microorganisms manufactured substances u. a.

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

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloroN- (4-trifluoromethylbenzyl) benzamide; (E) 2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pynmidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, diclobutrazole, diclofluanid, didomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimancin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrhrinhrhrinhrhrinhrhrinhrinhrofhrinophhrinhrinhrinhrinhrinhrinhrinhrinhrinhrhrinhrhrinhrinhrhrinhrhrinhrhrinhrhrinhrofhrine Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidaclopnd, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomethrononium, Triaromenontronium, Triaromenhroniaz, Triaratheniazin, Triaratheniazon
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

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

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

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

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

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, tick mites, flies (stinging and licking), parasitic fly larvae, lice, Hair, feather and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp. .
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the subordinates Nematocerina and Brachycerina z. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp ., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomina spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. Pneumonyssus spp., Sternostoma spp., Varroa spp. .
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show a good development-inhibiting effect against flies larvae of Lucilia cuprina.

The active compounds of the formula (I) according to the invention are also suitable for combating of arthropods, the farm animals, such as. B. cattle, sheep, goats, Horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, Bees, other pets such as B. dogs, cats, house birds, aquarium fish as well as so-called experimental animals, such as. B. hamsters, guinea pigs, rats and Infest mice. By fighting these arthropods, deaths and Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) can be reduced so that by using the active compounds according to the invention more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in in a known manner by enteral administration in the form of, for example, tablets, Capsules, watering, drenching, granules, pastes, boluses, the feed-through process,  suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal Application, by dermal application in the form of, for example, diving or Bathing (dipping), spraying (spray), pouring (pour-on and spot-on), des Washing, powdering and with the help of shaped articles containing active ingredients, such as Collars, ear tags, tail tags, limb straps, halters, Mar marking devices etc.

When used for cattle, poultry, pets etc., you can use the active ingredients in Formula (I) as formulations (for example powders, emulsions, flowable agents), which contain the active ingredients in an amount of 1 to 80 wt .-%, directly or after Apply 100 to 10,000-fold dilution or use it as a chemical bath.

It has also been found that the compounds of the formula (I) according to the invention The technical materials show a high insecticidal effect against insects to destroy.

The following are examples and preferably - but without limitation - Called insects:

Beetle like
Hylotrupes bajulus, Chlorophorus piiosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus puboxolles, Lyctus puboxolles, Lyctus puboxolles, Lyctus pubxolles, Lyctus pubxelluses, Lyctus pubesolis, Lyctus pubis alysis Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like
Sirexjuvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwinien sis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails like
Lepisma saccarina.

In the present context, technical materials include non-living ones Understand materials, such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood and wood processing products and paints.

The one to be protected against insect attack is very particularly preferably Material around wood and wood processing products.

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels, Wooden windows and doors, plywood, chipboard, carpentry or wood products, which are generally used in house construction or in carpentry.

The active ingredients can be used as such, in the form of concentrates or in a conventional manner Formulations such as powders, granules, solutions, suspensions, emulsions or Pastes can be applied.

The formulations mentioned can be prepared in a manner known per se, e.g. B. by mixing the active ingredients with at least one solution or Diluents, emulsifiers, dispersants and / or binders or fixatives, Water repellants, optionally desiccants and UV stabilizers and if necessary Dyes and pigments as well as other processing aids.  

The insecticidal agents or used to protect wood and wood-based materials Concentrates contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. In general however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active ingredient, based on the material to be protected.

An organic chemical solution serves as the solvent and / or diluent medium or solvent mixture and / or an oily or oily low volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, used. As such volatile, Water-insoluble, oily and oily solvents become corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures preferably white spirit, petroleum and / or alkylbenzene used.

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, test petrol with a boiling range of 170 to 220 ° C, spindle oil with a boiling range from 250 to 350 ° C, petroleum or aromatics with a boiling range from 160 to 280 ° C, Turpentine oil and the like are used.

In a preferred embodiment, liquid aliphatic hydrocarbons substances with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180  up to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably α-mono chloronaphthalene used.

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above half 45 ° C, can be partly due to slightly or medium volatile organic chemical Solvents are replaced, with the proviso that the solvent mixture also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture in this solvent mixture is soluble or emulsifiable.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture through an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come aliphatic containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, ester or the like. to use.

As organic-chemical binders in the context of the present invention the known water-dilutable and / or in the organic used chemical solvents soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, polyester resin, Polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modes fused alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, Silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin used.

The synthetic resin used as a binder can be in the form of an emulsion, dispersion or solution. Bitumen or bitumi can also be used as binders nous substances up to 10 wt .-% can be used. In addition, in itself  known dyes, pigments, water repellants, odor correctors and Inhibitors or anti-corrosion agents and the like are used.

According to the invention, preference is given to at least one organic chemical binder an alkyd resin or modified alkyd resin and / or a drying vegetable oil contained in the medium or in the concentrate. Are preferred according to the invention Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions are meant to volatilization of the active ingredients and crystallization or precipitation prevent. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

Water is also particularly suitable as a solvent or diluent, optionally mixed with one or more of the above organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, e.g. B. vacuum, double vacuum or printing process.  

The ready-to-use agents can, if appropriate, still further insecticides and optionally contain one or more fungicides.

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides such as chlorpyriphos are particularly preferred mixing partners. Phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, Permethrin, imidacloprid, M-25, flufenoxuron, hexaflumuron and triflumuron, as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, Tebuconazole, cyproconazole, metconazole, imazalil, dichlofluanid, tolylfluanid, 3- Iodine-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octyliso called thiazolin-3-one.

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

Manufacturing examples

Example (I-1)

2- (2,6-difluorophenyl) -4- (4- (4-propyl-2-oxy) -3-n-propylphenyl) phenyl-2-oxazoline: 1.5 g (3.8 mmol) 2- ( 2,6-difluorophenyl) -4- (4- (4-hydroxy-3-n-propylphenyl) phenyl) -2-oxazoline are dissolved in 30 ml acetonitrile with 0.6 g (4.5 mmol) potassium carbonate and 6.0 g (48 mmol) of 2-bromopropane boiled under reflux for 10 hours. It is then poured into water and the product extracted with ethyl acetate. The organic phase is dried, concentrated in vacuo and the residue is purified on silica gel in the cyclohexane / ethyl acetate (2: 1) system.
Yield: 0.45 g; Mp 60-62 ° C.

The compounds of the formula (I) listed in the following tables are obtained analogously or in accordance with the general instructions for the preparation:

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Preparation of starting compounds

Example (VI-1)

2-6-difluoro-N- [2-chloro-1- (4- (4-acetoxy-3-n-propylphenyl) phenyl) ethyl] benzamide

To the solution of 14.9 g (59 mmol) of 4-acetoxy-3-n-propylbiphenyl and 16.2 g (65 mmol) 2,6-difluoro-N- [2-chloro-1-methoxyethyl] benzamide in 100 ml of dichlorme 28.5 g (0.215 mol) of aluminum are added in portions at 0 ° C. with stirring chloride too. After 30 minutes of stirring, another 4 g (30 mmol) of aluminum chloride added and stirring continued at 0 ° C for 2 hours. You pour the reaction mix on ice, extract the product with dichloromethane and narrow the organic Phase in a vacuum. 27 g of resinous crude product are obtained (log p = 3.92, pH = 2.3), which is implemented without further purification (∼100% raw yield).  

Example (II-1)

2- (2,6-difluorophenyl) -4- (4- (4-hydroxy-3-n-propylphenyl) phenyl) -2-oxazoline

To dissolve 27 g (57 mmol) of 2,6-difluoro-N- [2-chloro-1- (4- (4-acetoxy-3-n-propylphenyl) phenyl) ethyl] benzamide in 150 ml of dimethylformamide a solution of 3.7 g (92 mmol) of sodium hydroxide in 10 ml of water is stirred at -10 ° C. After stirring overnight, 43 ml of 25% ammonia solution are added and the mixture is stirred overnight. Then the reaction mixture is poured onto ice water and extracted several times with ethyl acetate. The combined ethyl acetate extracts are dried over MgSO ₄ and concentrated in vacuo.

21 g of crude product (lg p = 3.77, pH = 7.5) are obtained (crude yield 93.7%). A a small sample of the crude product was mixed with petroleum ether / chloroform product of mp 210-215 ° C.  

The following compounds of the formula (II) are obtained analogously or according to the general information on the preparation

Preparation of 4-acetoxy-3-ethyl-biphenyl

To dissolve 7.3 g (37 mmol) of 4-hydroxy-3-ethyl-biphenyl and 3.2 g (40 mmol) Pyridine in 60 ml of chloroform is added dropwise 4.6 g (45 mmol) of acetic anhydride and boiled 3 Hours at reflux. The cooled solution is then diluted with water and Washed hydrochloric acid, the organic phase evaporated after drying. Man receives 8.0 g (90% yield of theory) of 4-acetoxy-3-ethyl-biphenyl as a water-clear oil from log p = 3.92 (pH = 2.3).

Preparation of 4-acetoxy-3-propyl-biphenyl

To dissolve 10.6 g (50 mmol) of 4-hydroxy-3-propyl-biphenyl, 4.3 g (55 mmol) Pyridine and 0.1 g of 4- (N, N-dimethylamino) pyridine are added dropwise to 6.1 g (60 mmol) acetic anhydride and heated at 50 to 60 ° C for 2 hours. After standing overnight at 20 ° C the reaction solution with water and dilute hydrochloric acid washed and the organic phase concentrated after drying. You get 11.4 g (yield: 89.8% of theory) of 4-acetoxy-3-propyl-biphenyl as a light oil from log p = 4.32 (pH = 2.3).  

Preparation of (4-phenyl-2-propyl-phenyl) ethyl carbonate

For the solution of 36.3 g (0.17 mol) of 4-hydroxy-3-propyl-biphenyl in 160 ml of ethyl acetate and 17.2 g (0.17 mol) of triethylamine are added dropwise with cooling at 5 to 10 ° C. 18.4 g (0.17 mol) of carbonic acid chloride. After standing overnight at 20 ° C the solution is washed with water and dilute hydrochloric acid and the organic is concentrated Phase after drying. 45 g (yield 93.2% of theory) (4-phenyl- 2-propylphenyl) ethyl carbonate as a light oil with a log p = 4.76 (pH = 2.3).

In an analogous manner, one obtains e.g. B .:
(2-methyl-4-phenylphenyl) ethyl carbonate: log p = 4.04 (pH = 2.3)

(2-chloro-4-phenylphenyl) ethyl carbonate: log p = 4.16 (pH = 2.3)

Examples of use Example A Myzus test

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

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

Cabbage leaves (Brassica oleracea), heavily from the peach aphid (Myzus persicae) are infested, by dipping into the active ingredient preparation of the desired Concentration treated.

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

In this test, e.g. B. the compounds according to the preparation examples I-19, I-24, I-30 and I-31 at an exemplary active ingredient concentration of 0.01% a kill of at least 90% after 6 days.  

Example B Phaedon larval test

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

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

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

After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae are killed were.

In this test, e.g. B. the compounds according to the preparation examples I-2, I-19, 1-20, I-30 and I-31 at an exemplary drug concentration of 0.01% each a 100% kill after 7 days.  

Example C Spodoptera test

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

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

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

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

In this test, e.g. B. the compounds according to the preparation examples I-2, I-19, I-21, I-23, I-25 and I-30 at an exemplary drug concentration of 0.0001% a kill of at least 90% after 7 days.  

Example D Tetranychus test (OP-resistant / immersion treatment)

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water containing emulsifier desired concentration.

Bean plants (Phaseolus vulgaris) which are strong from all stages of common spinning mite Tetranychus urticae are infested in an active ingredient preparation of the ge wished concentration immersed.

After the desired time, the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites are killed were tested.

In this test, e.g. B. the compounds according to Preparation Examples I-2, I-19, I-21, I-24, I-25, I-27, I-30 and I-31 at an exemplary drug concentration tration of 0.0001% an effect of at least 98% after 13 days.  

Example E Test with fly larvae / development-inhibiting effect

Test animals: All larval stages of Lucilia cuprina (OP-resistant)
[Dolls and adults (without contact to the active ingredient)]
Solvent: 35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight of nonylphenol polyglycol ether.

Three parts by weight are mixed to produce a suitable formulation Active ingredient with seven parts of the solvent-emulsifier mixture mentioned above and dilute the emulsion concentrate thus obtained with water to each desired concentration.

30-50 larvae per concentration are placed on horse meat (1 cm ³ ) in glass tubes, onto which 500 µl of the dilution to be tested are pipetted. The glass tubes are placed in plastic beakers, the bottom of which is covered with sea sand, and stored in an air-conditioned room (26 ° C ± 15 ° C, 70% relative humidity ± 10%). The effects are checked after 24 hours and 48 hours (larvizi de effect). After the larvae have emigrated (approx. 72 h), the glass tubes are removed and perforated plastic lids are placed on the beakers. After a development period of 1½ times (hatching of the control flies), the hatched flies and the dolls / doll covers are counted.

The criterion for the effect is the occurrence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of adult hatching from the dolls or the inhibition of pupa formation. As a criterion for the in vitro effect of a Substance applies to the inhibition of flea development or a development standstill the adult stage. 100% larvicidal activity means that after 48 hours all the larvae have died. 100% development inhibitory effect meaning that no adult flies hatched.  

In this test, e.g. B. the compounds according to Preparation Examples I-19, I-20, I-22 and I-23 at an exemplary concentration of 100 ppm development inhibitory effect of 100% each.

Claims (8)

1. Compounds of formula (I)
in which
X ^{1 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio,
X ^{2 represents} halogen, alkyl, alkoxy or alkylthio,
X ^{3 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio,
R ^{1 represents} hydrogen, halogen, alkyl or -CH ₂ -CR ⁴ = CH ₂ ,
R ^{2 represents} alkyl, hydroxyalkyl, in each case optionally substituted alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, phenylalkyl, naphthylalkyl or tetrahydronaphthylalkyl and
R ^{3 represents} hydrogen or the radical -CH ₂ -CR ⁴ = CH ₂ , where R ¹ and R ^{3 are} not simultaneously hydrogen and
R ^{4 represents} hydrogen or in each case optionally substituted alkyl or aryl. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• A) compounds of the formula (II)
  in which
  X ¹ , X ² , X ³ and R ^{1 have} the meanings given in Claim 1,
  with compounds of the formula (III)
  ZR ² (III),
  in which
  R ^{2 has} the meaning given in claim 1 and
  Z represents a leaving group,
  optionally in the presence of a diluent and if appropriate in the presence of a base and
• B) optionally subsequently the compounds of the formula (IV) thus obtained for R ² = CH ₂ -CR ⁴ = CH ₂
  in which
  R ¹ , R ⁴ , X ¹ , X ² and X ^{3 have} the meanings given in Claim 1,
  undergoes a Claisen rearrangement and
• C) optionally subsequently the compounds of the formula (V) thus obtained
  in which
  X ¹ , X ² , X ³ , R ¹ and R ^{4 have} the meanings given above,
  with compounds of the formula (III)
  ZR ² (III),
  in which
  R ² and Z have the meanings given above,
  optionally in the presence of a diluent and if appropriate in the presence of a base and
  optionally then for R ² = CH ₂ -CR ⁴ = CH ₂ and R ¹ = H, steps B) and C) are repeated, giving compounds of the formula (Va)
  in which
  X ¹ , X ² , X ³ , R ² and R ^{4 have} the meaning given above,
  and the radicals R ^{4 can be the} same or different.

3. Compounds of formula (II)
in which
X ¹ , X ² , X ³ and R ^{1 have} the meanings given in claim 1. 4. pesticides, characterized by a content of minde at least one compound of formula (I) according to claim 1. 5. Use of compounds of formula (I) according to claim 1 for loading pest control. 6. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 for pests and / or lets their living space take effect. 7. Process for the manufacture of pesticides, thereby ge indicates that compounds of formula (I) according to claim 1 with Extenders and / or surfactants mixed. 8. Use of compounds of formula (I) according to claim 1 for the Her provision of pesticides.