DE19528778A1 - 4-alkyl-1,3-oxa (thia) zoline derivatives - Google Patents

Abstract

New 4-alkyl-1,3-oxa(thia)zoline derivatives have the formula (I), in which alk stands for C1-C2 alkyl; A stands for optionally substituted phenyl, pyridyl, thienyl or pyrazolyl; B stands for optionally substituted phenyl, pyridyl or thienyl; and Z stands for oxygen or sulphur. Also disclosed are a process for preparing these derivatives and their use for controlling animal pests.

Description

The invention relates to new 4-alkyl-1,3-oxa (thia) zoline derivatives, several processes for their manufacture and their use in combating animal Pests.

It is already known that certain 1,3-oxazoline derivatives are insecticidal and / or have acaricidal properties (see, for example, EP-A 0 345 775 or WO- A 95/04726).

The level and / or duration of action of these previously known compounds is however, especially against certain organisms or for low users not entirely satisfactory in all areas of application.

New 4-alkyl-1,3-oxa (thia) zoline derivatives of the formula (I) have been found

in which
Alk represents C₁-C₂-alkyl,
A represents in each case optionally substituted phenyl, pyridyl, thienyl or pyrazolyl,
B represents in each case optionally substituted phenyl, pyridyl or thienyl and
Z represents oxygen or sulfur.

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

It was also found that the new 4-alkyl-1,3-oxa (thia) zoline derivatives of the formula (I) is obtained if

• a) amino alcohols of the formula (II) in which
  Alk and B have the meaning given above,
  with a carboxylic acid of formula (III) A-COOH (III) in which
  A has the meaning given above,
  with a dehydrating agent, optionally in the presence of a diluent;
  or
• b) amide alcohols of the formula (IV) in which
  Alk, A and B have the meaning given above,
  with a dehydrating agent, optionally in the presence of a diluent;
  or
• c) amide derivatives of the formula (V) in which
  Alk, A and B have the meaning given above and
  X represents halogen, alkylsulfonyloxy or optionally substituted arylsulfonyloxy,
  with a base, optionally in the presence of a diluent;
  or
• d) amide alcohols of the formula (IV) in which
  Alk, A and B have the meaning given above,
  with thienylating agents, optionally in the presence of a diluent.

Furthermore, it was found that the new 4-alkyl-1,3-oxa (thia) zoline derivatives of Formula (I) are very well suited for controlling animal pests.

The compounds of the invention are generally defined by the formula (I) kidney.

Preferred substituents or ranges mentioned in the above and below Residues listed in formulas are explained below.

Alk is preferably methyl or ethyl.

A preferably represents optionally up to five times, identical or different, by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-haloalkylthio , Nitro or cyano substituted phenyl,
for pyridyl which is optionally mono- to triple, identical or different, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy or cyano,
for thienyl which is optionally monosubstituted to trisubstituted, identically or differently, by halogen or C₁-C₄alkyl,
or for pyrazolyl which is optionally monosubstituted to trisubstituted identically or differently by halogen or C₁-C₃alkyl,
B preferably represents optionally one to five times, identical or different, by halogen, C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂-alkylthio, C₁-C₄-haloalkyl, C₁-C₈-haloalkoxy, C₁-C₈- Haloalkyl thio, - (OC₂H₄) _1-3 -O-C₁-C₆-alkyl, 3,4-difluoromethylene dioxo, 3,4-tetrafluoroethylene dioxo, each optionally up to three times, identically or differently by halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-alkylthio, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy, C₁-C₃-haloalkylthio, nitro, cyano, 3,4-difluoromethylene dioxo or 3,4-tetrafluoroethylene dioxo substituted phenyl, phenoxy , phenylthio, benzyl, phenethyl, phenpropyl, benzyloxy, benzylthio, phenoxymethyl, phenylthiomethyl, benzyloxy methyl, benzylthiomethyl, phenoxyethyl, phenylthioethyl, benzyloxyethyl, benzylthioethyl, pyridyl, pyridyloxy, pyridylthio, pyridylmethyl, pyridyl ethyl, pyridylpropyl, pyridylmethoxy, pyridylmethylthio, Pyridylmeth oxymethyl, Pyri dylmethylthiomethyl, pyridyloxyethyl, pyridylthioethyl, pyridylmethoxyethyl or pyridylmethylthioethyl substituted phenyl,
for pyridyl which is optionally mono- to triple, identical or different, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or cyano,
or for thienyl which is optionally monosubstituted to trisubstituted, identically or differently, by halogen or C₁-C₄alkyl.

Z preferably represents oxygen or sulfur.

Alk particularly preferably represents methyl.

A particularly preferably represents the same, if appropriate single to triple or different from F, Cl, Br, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃- Alkylthio, simple to sevenfold, identical or different through F and / or Cl substituted C₁-C₃ alkyl, simple to seven-fold, identical or ver separated by F and / or Cl substituted C₁-C₃ alkoxy, SCF₃, SCHF₂, Nitro or cyano substituted phenyl.

B particularly preferably represents optionally single to triple, identical or different by F, Cl, Br, C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂- alkylthio, simple to seven-fold, identical or different by F and / or Cl substituted C₁-C₃-alkyl, simple to seven-fold, identical or different from F and / or Cl substituted C₁-C₈-alkoxy, simple to seven-fold, identical or different substituted by F and / or Cl C₁-C₈-alkylthio, - (OC₂H₄) _1-3 -O-C₁-C₆-alkyl, 3,4-difluoromethylene dioxo, 3,4-tetrafluoroethylene dioxo,
each optionally single to triple, identical or different by F, Cl, Br, C₁-C₃-alkyl, C₁-C₃-alkoxy, simple to seven-fold, identical or different by F and / or Cl substituted C₁-C₃-alkyl, simple to sevenfold, identical or different substituted by F and / or Cl C₁-C₃-alkoxy, SCF₃, SCHF₂, nitro, cyano, 3,4-difluoromethylene dioxo or 3,4-tetrafluoroethylene dioxo,
substituted phenyl, phenoxy, phenylthio, benzyl, phenethyl, phenpropyl, benzyloxy, benzylthio, phenoxymethyl, phenylthiomethyl, benzyl oxymethyl, benzylthiomethyl, phenoxyethyl, phenylthioethyl, benzyl oxyethyl, benzylthioethyl, pyridyl, pyridyloxy, pyridylthioethyl, pyridylethyl pyridylethyl pyridylmethyl pyridylmethyl pyridylmethyl pyridylmethyl , Pyridylmethoxymethyl, pyridylmethylthiomethyl, pyridyloxyethyl, pyridylthioethyl, pyridylmethoxyethyl or pyridylmethylthioethyl substituted phenyl.

Z particularly preferably represents oxygen or sulfur.

The Koh mentioned above in the definition of the compounds according to the invention Hydrogen residues such as alkyl are - also in connection with heteroatoms such as Alkoxy - if possible, straight or branched.

The radicals listed above or listed in preferred areas Definitions or explanations can be made with each other, i.e. also between the respective areas and preferred areas can be combined as desired. they seem for 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 a combination of the meanings listed above as 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.  

Preferred compounds according to the invention are substances of the formula (IA)

in which
R1 is H, F, Cl or Br;
R² represents the general, preferred and particularly preferred phenyl substituents mentioned above under A;
m represents the numbers 0, 1 or 2;
R³ represents the general, preferred and particularly preferred phenyl substituents mentioned above under B;
R⁴ represents the general, preferred and particularly preferred phenyl substituents mentioned under A;
n stands for the numbers 0, 1 or 2 and
Z represents oxygen or sulfur.

Is used according to method (a) z. B. 2-Amino-2- (4-bromophenyl) -1-propanol and 2-chloro-4-fluorobenzoic acid as starting materials and polyphosphoric acid (PPS) as a dehydrating agent, the course of the ver can be represented by the following reaction scheme:

Is used according to method (b) z. B. N- [1-Hydroxy-2- (4-biphenylyl) propane- 2-yl] -2-chloro-6-fluorobenzamide as starting material and polyphosphoric acid (PPS) as dehydrating agent, so the course of the invention Process can be represented by the following reaction scheme:

Is used according to method (c) z. B. N- [1-chloro-2- (4-n-hexylphenyl) propane- 2-yl] -2,6-difluorobenzamide as the starting material and triethylamine as the base, so can the course of the process according to the invention by the following reaction Scheme are reproduced:

Is used according to method (d) z. B. N- {1-Hydroxy-2- [4- (4-chlorophenoxy) - phenyl] -propan-2-yl} -2,4-difluorobenzamide as starting material and phosphoric acid- (V) sulfide as thienylating agent, the course of the invention Process can be represented by the following reaction scheme:

Those used to carry out process (a) according to the invention as starting materials Amino alcohols required are generally defined by the formula (II). In the Formula (II) preferably have Alk and B or particularly preferably those Meanings already above in connection with the description of Ver Bonds of formula (I) as preferred or particularly preferred for this sub were specified.

The amino alcohols of the formula (II) are known and / or per se known methods can be prepared by, for example, suitable Amino acids with reducing agents, such as. B. sodium borohydride in the presence a diluent, such as. B. tetrahydrofuran at temperatures between -20 ° C and + 100 ° C (see, for example, J. Org. Chem. 1993, 58, 3568-3571 and the Manufacturing examples).

The amino acids required as precursors are known and / or can NEN can be prepared by methods known per se by, for example as appropriate hydantoins in the presence of bases, optionally with Pressure splits (see also the manufacturing examples).

The hydantoins required as precursors are known and / or can prepared from the corresponding ketones by processes known per se be (see e.g. Chemical Abstract 86 29495 and the preparation examples).

The also to carry out the method (a) as off Formula (III) generalizes carbonic acids required Are defined. In formula (III), A preferably or particularly preferably has those meanings that are already above in connection with the description of the compounds of formula (I) as preferred or particularly preferred for these substituents were given.

The carboxylic acids of formula (III) are known organic synthetic chemicals.

The starting point for carrying out processes (b) and (d) according to the invention Substances required amide alcohols are generally defined by the formula (IV). In of the formula (IV) Alk, A and B preferably or particularly preferably have those meanings that are already above in connection with the description  of the compounds of formula (I) as preferred or particularly preferred for them Substituents were specified.

The amide alcohols of the formula (IV) are known and / or per se known methods can be produced. The amide alcohols of the formula are obtained (IV) for example if one derived from the carboxylic acids of the formula (III) Acid chlorides with amino alcohols of the formula (II) in the presence of an acid binding means such. B. triethylamine, pyridine, potassium carbonate, sodium hydroxide or Potassium t-butoxide, and in the presence of a diluent, such as. B. toluene, Chlorobenzene, acetone or acetonitrile, at temperatures between 0 ° C and 100 ° C implements.

Those used to carry out process (c) according to the invention as starting materials The amide derivatives required are generally defined by the formula (V). In the Formula (V) preferably or particularly preferred alk, A and B those meanings that are already related to the description above of the compounds of formula (I) preferred or particularly preferred for this Substituents were specified.

X preferably represents fluorine, chlorine, bromine, iodine, C₁-C₄-alkylsulfonyloxy, phenyl sulfonyloxy or tolylsulfonyloxy, especially for chlorine, bromine, methylsul fonyloxy or tolylsulfonyloxy.

The amide derivatives of the formula (V) are known and / or per se known methods can be produced.

The amide derivatives of the formula (V) are obtained if the corresponding amide alcohols of formula (IV) with halogenating agents, such as. B. thionyl chloride, Phosphorus tribromide, phosphorus trichloride or phosphorus (V) chloride, optionally in Presence of a diluent, or with sulfonylating agents, such as. B. Methanesulfonic acid chloride or p-toluenesulfonic acid chloride, optionally in Presence of a diluent and a base.

Aromatic, for example, come as a diluent in the halogenation Hydrocarbons such as As benzene, toluene, xylene, and halogenated carbons hydrogen such as B. methylene chloride, chloroform, carbon tetrachloride and  Dichloroethane in question. The halogenating agent can be up to five times Excess are used.

The reaction temperature in the halogenation can be in a wide range can be varied. In general, the reaction between 0 ° C and the boil point of the diluent.

In addition to the above, the diluents used in sulfonylation are those for Halogenation reaction also suitably described, for example, ethers such as B. diethyl ether or tetrahydrofuran in question.

As bases in the sulfonylation, organic bases such as, for. B. Triethylamine, N, N-dimethylaniline, pyridine and 4-N, N-dimethylaminopyridine set.

In general 0.8 to 1.5 per mole of the compound to be sulfonylated Mol used as the base.

The sulfonylating agent is generally in at least equimolar amounts gene used.

The processes (a) and (b) according to the invention are carried out using a dehydrating agent performed. It can be in the organic Chemically usual dehydrating agents are used. Preferably usable are sulfuric acid, polyphosphoric acid (PPS), phosphorus (V) oxide, di cyclohexylcarbodiimide (DCC), phosphorus (V) sulfide and the triphenylphos system phin / triethylamine / carbon tetrachloride.

As a diluent for carrying out process (a) to (d) the usual organic solvents come into consideration. Preferably aliphatic, alicyclic or aromatic, optionally halo can be used Hydrogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, Chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, Chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, Tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones like Acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide and N, N-dimethylacetamide,  N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as acetic acid methyl ester or ethyl acetate, and also sulfoxides, such as dimethyl sulfoxide, optionally also alcohols such as methanol or ethanol.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (a) can be varied over a wide range. Generally works one at temperatures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 100 ° C.

Process (a) according to the invention is generally carried out under atmospheric pressure carried out. However, it is also possible to increase or decrease it Pressure - generally between 0.1 bar and 10 bar - to work.

To carry out process (a) according to the invention, the respective be necessary starting materials are generally used in approximately equimolar amounts puts. However, it is also possible to use one of the two coms used in each case components in a larger excess. The reactions are in the generally in a suitable diluent in the presence of a water Withdrawal agent performed, and the reaction mixture is several hours the stirred at the required temperature. The processing takes place at the methods according to the invention in each case by customary methods.

In a special embodiment of method (a) according to the invention Instead of the carboxylic acids of the formula (III), corresponding nitriles are also used are then, preferably then in place of a dehydrating agent Catalyst such. B. zinc (II) chloride is used.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (b) can be varied over a wide range. Generally works one at temperatures between -20 ° C and + 150 ° C, preferably at tempera doors between 0 ° C and 100 ° C.

Process (b) according to the invention is generally carried out under normal pressure carried out. However, it is also possible to increase or decrease it Pressure - generally between 0.1 bar and 10 bar - to work.  

The process (b) according to the invention is carried out per mole Amide alcohol of the formula (IV) generally 1 to 20 mol, preferably 1 to 5 Mole of dehydrating agent.

In a preferred embodiment of process (b) according to the invention the amide alcohol of the formula (IV) is placed in a diluent and the dehydrating agent is then metered in. The reaction mixture is at the required temperature is stirred until the end of the reaction and then worked up in the usual way.

Process (c) according to the invention is carried out in the presence of a base. All common inorganic or organic bases are used here dress. Alkaline earth metal or alkali metal hydrides, hy are preferably usable droxides, amides, alcoholates, acetates, carbonates or bicarbonates, as in for example sodium hydride, sodium amide, sodium methylate, sodium ethylate, Ka lium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, Sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, Potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammo nium carbonate and tertiary amines such as trimethylamine, triethylamine, tributyl amine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylamino pyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicyc loundecen (DBU).

The reaction temperatures can be carried out when carrying out the process according to the invention Process (c) can be varied over a wide range. Generally works one at temperatures between -20 ° C and + 150 ° C, preferably at tempera doors between 0 ° C and 100 ° C.

Process (c) according to the invention is generally carried out under normal pressure carried out. However, it is also possible to increase or decrease it Pressure - generally between 0.1 bar and 10 bar - to work.

The process (c) according to the invention is carried out per mole Amide derivative of the formula (V) generally 1 to 3 mol, preferably 1.0 to 1.5 moles of a base.  

In a preferred embodiment of the method (c) according to the invention which the amide derivative of formula (V) and a base in a suitable Ver mixed fertilizer; the mixture is brought up to the required temperature stirred at the end of the reaction and then worked up in the usual way tet.

Process (d) according to the invention is carried out using a thienylating By means of. As such, the usual ones are used to transform orga African oxygen compounds in suitable sulfur compounds reagents. Phosphorus (V) sulfide, Hydrogen sulfide and its alkali metal salts as well as the so-called Lawesson Reagent [2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione].

The reaction temperatures can be carried out when carrying out the process according to the invention Process (d) can be varied over a wide range. Generally works one at temperatures between -20 ° C and + 150 ° C, preferably at tempera doors between 0 ° C and 100 ° C.

Process (d) according to the invention is generally carried out under normal pressure carried out. However, it is also possible to increase or decrease it Pressure - generally between 0.1 bar and 10 bar - to work.

The process (d) according to the invention is carried out per mole Amide alcohol of the formula (IV) generally 1 to 5 mol, preferably 1.0 to 2.5 moles of a thienylating agent.

In a preferred embodiment of process (d) according to the invention the amide alcohol of the formula (IV) is placed in a diluent and the thienylating agent is then metered in. The reaction mixture is then up to stirred at the appropriate reaction temperature at the end of the reaction and on finally worked up in the usual way.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

From the order of the Diptera z. B. Aedes spp., 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., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

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

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

They can be used with particularly good success to combat plant damage insects and mites, such as larvae of green rice cicada (Nephotettix cincticeps) or against the common spider mite (Tetranychus urticae).

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

These formulations are prepared in a known manner, e.g. B. by Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, that is emulsifiers and / or dispersants and / or foam generators resources.

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

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

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

The formulations generally contain between 0.1 and 95% by weight of active ingredient fabric, 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 in a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms and others
Particularly cheap mixing partners are e.g. B. the following:
Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazole, dicloflomolanidol, dicloflomolanidolol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, diclofolomidol, dicloflolonidol, dicloflomolonidol, dicloflolomolonidol , Dinocap, Diphenyl amine, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fen propimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flu dioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, fulfolidolide, flu triafolet , Furalaxyl, Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

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

Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazi non, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipro nil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenproxophof, Fufionphonophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufone , Heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver mectin, 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, Pro mecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyradaphrhumophin , Pyridaben, pyrimidifen, pyriproxifen, quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomichonon, Triaromenontron, Triaromenontron, Triarathenlarbon, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triaromenontrin, Triarathenltronium, Triaromenontrin, Triarathenltron, Triaromenontron
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

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

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

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

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

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

The active compounds according to the invention act not only against plant and hygiene and storage pests, but also against in the veterinary sector animal parasites (ectoparasites) such as tortoise ticks, leather ticks, mite mites, Running mites, flies (stinging and licking), parasitic fly larvae, lice, Hair lice, featherlings and fleas.

The active compounds of the formula (I) according to the invention are also suitable for combating treatment 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 and so-called experimental animals, such as. B. hamster, sea pigs, rats and mice. By fighting this arthro deaths and reduced performance (for meat, milk, wool, Hides, eggs, honey, etc.) can be reduced, so that by using the Active ingredients according to the invention a more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, Tab Latvian, capsules, watering, drenching, granules, pastes, boluses, feed-through Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implants, by nasal application, by dermal application in the form for example diving or bathing (dipping), spraying (spray), pouring on (Pour-on and spot-on), washing, powdering and with the help of  molded articles containing active ingredients, such as collars, ear tags, tail tags, Limb straps, holsters, marking devices etc.

When used for cattle, poultry, pets etc. you can use the active ingredients of the 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 100 to 10,000-fold dilution, or as a chemical Use bath.

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

Manufacturing examples example 1 (Method c)

14.37 g (0.0288 mol) of N- [1-methylsulfonyloxy-2- (4-tert-butylphenyl) propan-2-yl] - 2,6-difluorobenzamide in 130 ml of absolute tetrahydrofuran with 4.16 g (0.0372 mol) potassium tert-butoxide added and overnight at room temperature touched. It is then concentrated by distilling off the solvent and the residue was partitioned between water and methylene chloride. The organic Phase is separated off, dried over sodium sulfate, concentrated and over silica gel chromatographed using methylene chloride.

2.3 g (24.3% of theory) of 4- (4-tert-butylphenyl) -2- (2,6-difluorophene) are obtained nyl) -4-methyl-1,3-oxazoline with a refractive index = 1.5392.  

Manufacture of the starting product

9.99 g (0.0288 mol) of N- [1-hydroxy-2- (4-tert-butylphenyl) propan-2-yl] -2,6-difluoro benzamide, 3.63 g (0.0317 mol) of methanesulfonyl chloride and 3.5 g (0.0346 mol) Triethylamine are in 100 ml of absolute tetrahydrofuran overnight at room temperature stirred. Then by distilling off the solvent concentrated and the residue partitioned between ether and water. The organic Phase is separated, dried over sodium sulfate and concentrated.

14.8 g of crude N- [1-methylsulfonyloxy-2- (4-tert-butylphenyl) propane-2- are obtained. yl] -2,6-difluorobenzamide as a yellow-orange oil, which can be directly reacted further can.

A solution of 6.83 g (0.033 mol) of 2-amino-2- (4-tert-butylphenyl) -1-propanol and 6.68 g (0.066 mol) of triethylamine in 40 ml of absolute acetonitrile is combined in one Cooled ice bath, mixed with 5.82 g (0.033 mol) of 2,6-difluorobenzoyl chloride and stirred overnight at room temperature. The reaction mixture is then added to water and extracted with ethyl acetate.

10.1 g (88.2% of theory) of N- [1-hydroxy-2- (4-tert-butylphenyl) - are obtained. propan-2-yl] -2,6-difluorobenzamide as a slowly crystallizing solid with a Content of 96% (GC / MS).

A solution of 30.9 g (0.14 mol) of 2-amino-2- (4-tert-butylphenyl) -1-propane carboxylic acid in 400 ml of absolute tetrahydrofuran is used under argon protective gas 12.7 g (0.336 mol) of sodium borohydride are added, the mixture is cooled to 0 ° C. and inside of 30 minutes with a solution of 35.5 g (0.14 mol) of iodine in 100 ml of absolute Tetrahydrofuran added. The reaction mixture is left under overnight Stir reflux, then cool and 100 ml of methanol are added dropwise. The mixture is then stirred for 30 minutes and by distilling off the solution medium concentrated. The residue is taken up in 280 ml of 20% potassium hydroxide solution, Stirred for 4 hours at room temperature and three times with extra methylene chloride here. The combined organic phases are washed with water, over Dried sodium sulfate and concentrated. The residue is dissolved in toluene with concentrated hydrochloric acid acidified and stirred vigorously. The solid is removed sucks, suspended in water / methylene chloride and with dilute sodium hydroxide solution ba posed. The organic phase is separated off and dried over sodium sulfate and constricted.

18 g (62.3% of theory) of 2-amino-2- (4-tert-butylphenyl) -1-propanol are obtained melting point 107-108 ° C.

34.4 g (0.14 mol) of 5- (4-tert-butylphenyl) -5-methyl-hydantoin are mixed with a Solution of 20.8 g (0.52 mol) of sodium hydroxide in 115 ml of water and in Autoclave heated at 170 ° C for 6 hours. The product mass is then in 300 ml of water suspended and neutralized to pH 7 with concentrated hydrochloric acid. The resulting solid is filtered off, washed with water and dried.

30.9 g (100% of theory) of 2-amino-2- (4-tert-butylphenyl) propane are obtained carboxylic acid as a crystalline solid.

A mixture of 4-tert-butylacetophenone, 70 g (0.73 mol) ammonium carbonate and 20 g (0.31 mol) of potassium cyanide in 200 ml of n-propanol and 150 ml of water Heated in an autoclave at 80 ° C for 16 hours, then cooled and with 1.5 l Water stirred. The resulting solid is suctioned off with 1.5 l warm Washed water and dried.

34.9 g (94.6% of theory) of 5- (4-tert-butylphenyl) -5-methyl are obtained hydantoin.

Analogously to Example 1 and according to the general information on the preparation the following compounds of formula (I):

Table I

Examples of use Example A Nephotettix test

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

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

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

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

In this test, e.g. B. the compound according to Production Example 1 in a exemplary drug concentration of 0.1% after 6 days a killing of 100%.  

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

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 what contains the emulsifier water to the desired concentrations.

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development common spider mite Tetranychus urticae are infested in a Drug preparation of the desired concentration dipped.

After the desired time, the effect is determined in%. Here means 100% that all spider mites have been killed; 0% means that no spinning mites were killed.

In this test, e.g. B. the compound according to Production Example 1 in a exemplary drug concentration of 0.01% after 13 days a kill of 98%.

Claims (7)

1. Compounds of formula (I) in which
Alk represents C₁-C₂-alkyl,
A represents in each case optionally substituted phenyl, pyridyl, thienyl or pyrazolyl,
B represents in each case optionally substituted phenyl, pyridyl or thienyl and
Z represents oxygen or sulfur. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• a) amino alcohols of the formula (II) in which
  Alk and B have the meaning given in claim 1,
  with a carboxylic acid of formula (III) A-COOH (III) in which
  A has the meaning given in claim 1,
  with a dehydrating agent, optionally in the presence of a diluent;
  or
• b) amide alcohols of the formula (IV) in which
  Alk, A and B have the meaning given above,
  with a dehydrating agent, optionally in the presence of a diluent;
  or
• c) amide derivatives of the formula (V) in which
  Alk, A and B have the meaning given above and
  X represents halogen, alkylsulfonyloxy or optionally substituted arylsulfonyloxy,
  with a base, optionally in the presence of a diluent;
  or
• d) amide alcohols of the formula (IV) in which
  Alk, A and B have the meaning given above,
  with thienylating agents, optionally in the presence of a diluent.

3. pesticide, characterized by a content of min at least one compound of formula (I) according to claim 1. 4. Use of compounds of formula (I) according to claim 1 for loading pest control. 5. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or let their living space take effect. 6. Process for the preparation of pesticides, thereby characterized in that compounds of the formula (I) according to Claim 1 mixed with extenders and / or surfactants. 7. Use of compounds of formula (I) according to claim 1 for Manufacture of pesticides.