HK1019447B - 1,3,4-oxadiazine derivatives and their use as pesticides - Google Patents

Description

1,3, 4-oxadiazine derivatives and their use as pesticides

The present invention relates to novel (1,3,4) -oxadiazine derivatives, to several processes and intermediates for their preparation, and to their use as pesticides, in particular as anthelmintics, insecticides, acaricides and nematicides.

To date, only the only representative compound known to date is the 2, 5-dichalcogenated (dichalcogeno) - (1,3,4) -oxadiazine, 6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione (see liebig ann. chem.1981, 1433).

The invention therefore relates to novel (1,3,4) -oxadiazine derivatives of formula (I),

wherein

R¹And R²Each independently of the others represents hydrogen, alkyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, carboxyalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, arylalkyloxycarbonylalkyl, carbamoylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxycarbonylaminoalkyl, alkylcarbonyl, cycloalkylcarbonyl, or represents cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, arylcarbonyl, heterocyclylalkyl, heteroaryl or heteroarylalkyl, each of which is optionally substituted, or

R¹,R²And the two linking nitrogen atoms represent an optionally substituted heterocyclic ring,

R³and R⁴Each independently of the others represents hydrogen, alkyl, alkenyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, each optionally substituted by halogenArylalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, arylalkyloxycarbonylalkyl, carbamoylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylcarbonyl, cycloalkylcarbonyl or represent in each case optionally substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl, or

R³And R⁴Together represent an alkylene group or a residue (a)

Wherein

R⁵And R⁶Each independently of the others represents hydrogen, alkyl, alkenyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylcarbonyl, or represents cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl, each optionally substituted,

Q¹and Q²Each independently represents oxygen or sulfur,

except for 6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione.

Depending in particular on the nature of the substituents, the compounds of the formula (I) may be present as geometric and/or optical isomers or as isomer mixtures of various compositions, which may be separated, if desired, by customary methods. The present invention provides pure isomers and isomer mixtures, processes for their preparation, their use, and compositions containing them. For the sake of simplicity, the compounds of the formula (I) are referred to below only, but include both pure isomers and, where appropriate, also mixtures of isomeric compounds in various proportions.

Furthermore, it was found that the novel compounds of the formula (I) are obtained by one of the following processes.

A) (1,3,4) -oxadiazine derivatives of formula (I-a)

Wherein

R¹To R⁴And Q¹Each as defined above, is capable of,

can be prepared by reacting carbazates of the formula (II) in the presence of reaction assistants and diluents, if appropriate in the presence of bases,

wherein

R¹To R⁴And Q¹Each as defined above.

B) (1,3,4) -oxadiazine derivatives of formula (I-b)

Wherein

R¹To R³,Q¹And Q²Each as defined above, R^4-1Representative and R⁴As well as groups other than hydrogen,

can be prepared by reacting (1,3,4) -oxadiazine derivatives of the formula (I-c) with compounds of the formula (III), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants,

wherein

R¹And R²Have a definition other than that of hydrogen,

R³,Q¹and Q²Each as defined above, is capable of,

R^4-1-E (Ⅲ)，

wherein

R^4-1As defined above, the above-mentioned,

and E represents an electron withdrawing leaving group.

C) (1,3,4) -oxadiazine derivatives of formula (I-d)

Wherein

R¹To R³,Q¹And Q²Each as defined above, R^4-2Represents residue (b)

Wherein

R⁵And R⁶Each independently represents hydrogen, optionally substituted alkyl or aryl, or,

R³and R^4-2Together represent residue (a)

Wherein

R⁵And R⁶As defined above, the above-mentioned,

can be prepared by reacting the (1,3,4) -oxadiazine derivatives of the formula (I-c), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants, with ketones or aldehydes of the formula (IV) and subsequently, if appropriate, removing water,

wherein

R¹To R³,Q¹And Q²Each as defined above, is capable of,

R⁵-CO-R⁶ (Ⅳ)，

wherein

R⁵And R⁶As defined above, the above-mentioned,

D) (1,3,4) -oxadiazine derivatives of formula (I-e)

Wherein

R^1-1Representative and R¹Same radicals other than hydrogen, R²To R⁴,Q¹And Q²Each as defined above, is capable of,

can be prepared by reacting (1,3,4) -oxadiazine derivatives of the formula (I-f), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants, with compounds of the formula (V),

wherein

R²To R⁴,Q¹And Q²Each as defined above, is capable of,

R^1-1-E (Ⅴ)，

wherein

R^1-1As defined above, and

e represents an electron withdrawing leaving group.

E) (1,3,4) -oxadiazine derivatives of formula (I-g)

Wherein

R¹,R³,R⁴,Q¹And Q²Each as defined above, R^2-1Representative and R²As well as groups other than hydrogen,

by applying, if appropriate, an adhesive to the skinIn the presence of a diluent and, if appropriate, in the presence of reaction assistants, by reacting the (1,3,4) -oxadiazine derivatives of the formula (I-h) with compounds of the formula (VI),

wherein

R¹,R³,R⁴,Q¹And Q²Each as defined above, is capable of,

R^2-1-E (Ⅵ)，

wherein

R^2-1As defined above, the above-mentioned,

and E represents an electron withdrawing leaving group.

F) (1,3,4) -oxadiazine derivatives of formula (I)

Wherein

R¹To R⁴,Q¹And Q²Each as defined above, is capable of,

can be prepared by reacting and cyclocondensing a compound of the formula (VII) with a compound of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of reaction auxiliaries,

wherein

R¹To R⁴And Q²Each as defined above, is capable of,

wherein

Y¹Represents chlorine, trichloromethoxy, C₁-C₄Alkoxy, optionally substituted phenoxy, 1-imidazolyl or 1,2, 4-triazolyl and

Y²represents chlorine, trichloromethoxy, 1-imidazolyl or 1,2, 4-triazolyl,

Q¹as defined above.

G) (1,3,4) -oxadiazine derivatives of formula (I)

Wherein

R¹To R⁴,Q¹And Q²Each as defined above, is capable of,

can be prepared by cyclocondensation of compounds of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants,

wherein

R¹To R⁴,Q¹,Q²And Y¹Each as defined above.

H) (1,3,4) -oxadiazine derivatives of formula (I-i)

Wherein

R¹To R⁴And Q¹Each as defined above, is capable of,

can be prepared by reacting a (1,3,4) -oxadiazine derivative of the formula (I-a) with a sulphuroylating agent, if appropriate in the presence of a diluent,

wherein

R¹To R⁴And Q¹Each as defined above.

It has furthermore been found that the novel compounds of the formula (I) have a very high activity as pesticides, preferably for controlling parasites in useful animals and for controlling insects, acarids and nematodes encountered in agriculture, forestry, in the protection of stores and materials and in the hygiene sector.

Formula (I) provides a general definition of the compounds of the invention. The groups and preferred substituents and ranges listed above and in the following formulae are specified below.

R¹And R²Each independently preferably represents hydrogen, C₁-C₁₅Alkyl, in particular also 3,7, 11-trimethyldodecyl, represents C in each case optionally substituted by fluorine-, chlorine-or bromine₁-C₈-alkyl radical, C₃-C₇-cycloalkyl radical, C₃-C₇-cycloalkyl-C₁-C₄-alkyl radical, C₁-C₆-hydroxyalkyl, C₁-C₄-alkanoyloxy-C₁-C₆-alkyl radical, C₁-C₄-alkoxy-C₁-C₆Alkyl, aryl-C₁-C₄-alkoxy-C₁-C₆-alkyl radical, C₁-C₆Mercaptoalkyl radicals, especially mercaptomethyl, C₁-C₄-alkylthio-C₁-C₆Alkyl, especially methylthioethyl, C₁-C₄-alkylsulfinyl-C₁-C₆Alkyl, especially methylsulfinylethyl, C₁-C₄-alkylsulfonyl-C₁-C₆Alkyl, especially methylsulfonylethyl, carboxy-C₁-C₆Alkyl, especially carboxymethyl or carboxyethyl, C₁-C₄-alkoxycarbonyl-C₁-C₆Alkyl, especially methoxycarbonylmethyl or ethoxycarbonylethyl, aryloxycarbonyl-C₁-C₆Alkyl, especially phenoxycarbonylmethyl, aryl-C₁-C₄-alkyloxycarbonyl-C₁-C₆Alkyl, especially benzyloxycarbonylmethyl, carbamoyl-C₁-C₆Alkyl, especially carbamoylmethyl or carbamoylethyl, amino-C₁-C₆Alkyl, especially aminopropyl or aminobutyl, C₁-C₄-alkylamino-C₁-C₆Alkyl, especially methylaminopropyl or methylaminobutyl, di- (C)₁-C₄) -alkylamino-C₁-C₆Alkyl, especially dimethylaminopropyl or dimethylaminobutyl, C₁-C₄-alkoxycarbonylamino-C₁-C₆-alkyl radical, C₁-C₆-alkylcarbonyl group, C₃-C₇-cycloalkylcarbonyl, or represents aryl, aryl-C₁-C₄Alkyl, arylcarbonyl, aryl-C₁-C₄-alkylcarbonyl, heteroaryl or heteroaryl-C₁-C₄-alkyl, wherein optionally one NH function of the heterocyclic ring may be derived from an amino protecting group, such as those mentioned above, and each of which may be optionally substituted with: halogen, hydroxy, nitro, cyano, amino, C₁-C₄-alkylamino, di- (C)₁-C₄-) alkylamino, benzylamino, dibenzylamino, protected amino, for example acetyl-, tert-butoxycarbonyl-, benzyloxycarbonyl-or FMOC-amino, C₁-C₆-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy, and optionally substituted with C₁-C₄-alkyl-substituted heterocycle-C₁-C₄Alkyl groups, such as dioxolane methyl.

R¹And R²With two nitrogen atoms-together preferably represent optionally halogen-, hydroxy-, nitro-, cyano-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy, or C₁-C₄-haloalkoxy-substituted 5-to 8-membered saturated or unsaturated heterocyclic ring.

R³And R⁴Each independently preferably represents hydrogen, C₁-C₁₆-alkyl, represents C, each optionally substituted by fluoro-, chloro-, or bromo-)₁-C₆-alkyl radical, C₂-C₈-alkenyl radical, C₃-C₇-cycloalkyl radical, C₃-C₇-cycloalkyl-C₁-C₄-alkyl radical, C₁-C₆-hydroxyalkyl, C₁-C₄-alkanoyloxy-C₁-C₆Alkyl, especially acetoxymethyl or 1-acetoxyethyl, C₁-C₄-alkoxy-oxy-C₁-C₆Alkyl, especially methoxymethyl or 1-methoxymethyl, aryl-C₁-C₄-alkoxy-C₁-C₆-alkyl radical, C₁-C₆Mercaptoalkyl radicals, especially mercaptomethyl, C₁-C₄-alkylthio-C₁-C₆Alkyl, especially methylthioethyl, C₁-C₄-alkylsulfinyl-C₁-C₆Alkyl, especially methylsulfinylethyl, C₁-C₄-alkylsulfonyl-C₁-C₆Alkyl, especially methylsulfonylethyl, C₁-C₄-alkoxycarbonyl-C₁-C₆Alkyl, aryloxy carbonyl-C₁-C₆Alkyl, especially phenoxycarbonylmethyl, aryl-C₁-C₄-alkyloxycarbonyl-C₁-C₆-alkyl, carbamoyl-C₁-C₆Alkyl, especially carbamoylmethyl or carbamoylethyl, amino-C₁-C₆-alkyl radical, C₁-C₄-alkylamino-C₁-C₆Alkyl, di- (C)₁-C₄) -alkylamino-C₁-C₆-alkyl radical, C₁-C₆-alkylcarbonyl group, C₃-C₇-cycloalkylcarbonyl, or represents aryl, aryl-C₁-C₄Alkyl, arylcarbonyl, heteroaryl or heteroaryl-C₁-C₄-alkyl, each of which is optionally substituted with: halogen, hydroxy, cyano, C₁-C₆-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy radical, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy radical, C₁-C₄-haloalkoxy, benzyloxy or by C₁-C₄Alkyl and/or phenylTrisubstituted silyloxy.

R³And R⁴Together preferably represent C₂-C₇Alkylene or radical (a)

Wherein

R⁵And R⁶Each independently of the others represents hydrogen, each optionally fluorine-, chlorine-or bromine-substituted C₁-C₆-alkyl radical, C₂-C₄-alkenyl or C₃-C₇Cycloalkyl or represents in each case optionally halogen-, hydroxy-, nitro-, C₁-C₆-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy radical, C₁-C₄-haloalkoxy-, phenoxy-, amino-, C₁-C₄Alkylamino or di- (C)₁-C₄) -alkylamino-substituted phenyl, phenyl-C₁-C₄-alkyl or a 5-or 6-membered heterocyclic ring.

Q¹And Q²Each independently preferably represents oxygen or sulphur.

6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione is excluded from the preferred range.

R¹And R²Each independently of the others particularly preferably represents hydrogen, C₁-C₁₀-alkyl, represents C, each optionally substituted by fluoro-, chloro-or bromo₁-C₄-alkyl radical, C₃-C₇Cycloalkyl, especially cyclopentyl, cyclohexyl or cycloheptyl, C₃-C₇-cycloalkyl-C₁-C₄-alkyl radical, C₁-C₆Hydroxyalkyl, especially hydroxymethyl or 1-hydroxyethyl, C₁-C₄-alkanoyloxy-C₁-C₆Alkyl, especially acetoxymethyl or 1-acetoxyethyl, C₁-C₄-alkoxy-C₁-C₆Alkyl, especially methoxymethyl or 1-methoxyethyl, phenyl-C₁-C₄-alkoxy-C₁-C₆Alkyl, especially benzyloxymethyl or 1-benzyloxyethyl, C₁-C₄-alkoxycarbonylamino-C₁-C₆Alkyl, especially tert-butoxycarbonylaminopropyl or tert-butoxycarbonylaminobutyl, C₁-C₆Alkylcarbonyl, in particular acetyl, propionyl or butyryl, C₃-C₇-cycloalkylcarbonyl, in particular cyclopropylcarbonyl or cyclohexylcarbonyl, or represents phenyl, phenyl-C₁-C₄Alkyl, phenylcarbonyl, 5-or 6-membered heterocycle, in particular thienyl, thiazolyl or pyridyl, 5-or 6-membered heterocycle-C₁-C₄-alkyl or indolyl-C₁-C₄-alkyl, each of which may be optionally substituted with: fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano, amino, C₁-C₄-alkylamino, di- (C)₁-C₄-) alkylamino, benzylamino, dibenzylamino, protected amino such as acetyl-, tert-butoxycarbonyl-, benzyloxycarbonyl-or FMOC-amino, C₁-C₄-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy or C₁-C₂-haloalkoxy.

R¹And R²Together with the two attached nitrogen atoms particularly preferably represent optionally fluorine-, chlorine-, bromine-, hydroxyl-, nitro-, cyano-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-or C₁-C₂-haloalkoxy-substituted 5-to 8-membered saturated or unsaturated heterocyclic ring.

R³And R⁴Each independently of the others particularly preferably represents hydrogen, C₁-C₁₂-alkyl, represents C, each optionally substituted by fluoro-, chloro-or bromo-group₁-C₄-alkyl radical, C₂-C₆-alkenyl radical, C₃-C₇Cycloalkyl, especially cyclopentyl, cyclohexyl or cycloheptyl, C₃-C₇-cycloalkyl-C₁-C₄-alkyl radical, C₁-C₆-hydroxy radicalArylalkyl, phenyl-C₁-C₄-alkoxy-C₁-C₆Alkyl, especially benzyloxymethyl or 1-benzyloxyethyl, C₁-C₄-alkylthio-C₁-C₆Alkyl, especially methylthioethyl, C₁-C₄-alkoxycarbonyl-C₁-C₆Alkyl, especially methoxycarbonylmethyl or ethoxycarbonylethyl, phenyl-C₁-C₄-alkoxycarbonyl-C₁-C₆Alkyl, especially benzyloxycarbonylmethyl, amino-C₁-C₆Alkyl, especially aminopropyl or aminobutyl, C₁-C₄-alkylamino-C₁-C₆Alkyl, especially methylaminopropyl or methylaminobutyl, di- (C)₁-C₄) -alkylamino-C₁-C₆Alkyl, especially dimethylaminopropyl or dimethylaminobutyl, C₁-C₆Alkylcarbonyl, in particular acetyl, propionyl or butyryl, C₃-C₇-cycloalkylcarbonyl, in particular cyclopropylcarbonyl or cyclohexylcarbonyl, or represents phenyl, phenyl-C₁-C₄Alkyl, naphthylmethyl, phenylcarbonyl, 5-or 6-membered heterocycles, in particular thienyl, thiazolyl or pyridyl, indolyl, benzo-1, 3-dioxolyl, 5-or 6-membered heterocyclyl-C₁-C₄Alkyl, in particular thienylmethyl, thiazolylmethyl, imidazolylmethyl or pyridylmethyl or indolyl-C₁-C₄-alkyl, each of which is optionally substituted with: fluorine, chlorine, bromine, iodine, hydroxy, cyano, C₁-C₆-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy radical, C₁-C₄-haloalkoxy, benzyloxy or by C₁-C₄-alkyl and/or phenyl trisubstituted silyloxy.

R³And R⁴Together particularly preferably represent C₂-C₆Alkylene or radical (a)

Wherein

R⁵And R⁶Each independently of the others represents hydrogen, each optionally fluorine-, chlorine-or bromine-substituted C₁-C₄-alkyl or C₃-C₆Cycloalkyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, or represents optionally fluoro-, chloro-, bromo-, hydroxy-, nitro-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy, or C₁-C₄-haloalkoxy-, phenoxy-, amino-, C₁-C₄Alkylamino, in particular methylamino or ethylamino, or di- (C)₁-C₄) Alkylamino-, in particular dimethylamino-or diethylamino-substituted phenyl, phenyl-C₁-C₄-alkyl or a 5-or 6-membered heterocyclic ring.

Q¹Particularly preferably oxygen or sulphur.

Q²Particularly preferably oxygen.

Particularly preferred ranges exclude 6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione.

R¹And R²Each independently of the other very particularly preferably represents hydrogen, C₁-C₁₀Alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, octyl, isooctyl, sec-octyl or 3, 7-dimethyloctyl, represents C₃-C₇-cycloalkyl-C₁-C₄Alkyl, in particular cyclopentylmethyl, cyclohexylmethyl or cycloheptylmethyl, represents in each case optionally fluorine-, chlorine-, bromine-, iodine-, hydroxyl-, cyano-, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, tert-butyl-, trifluoromethyl-, trichloromethyl-, methoxy-, difluoromethoxy-, trifluoromethoxy-or benzyloxy-substituted phenyl, benzyl, phenethyl, 5-or 6-membered heteroarylMethyl, in particular thienylmethyl, thiazolylmethyl, furanylmethyl or pyridylmethyl or represents indolylmethyl.

R¹And R²Very particularly preferably together with the two linking nitrogen atoms represents a 5-or 6-membered saturated or unsaturated heterocyclic ring, in particular- (CH)₂)₃-and- (CH)₂)₄-。

R³And R⁴Each independently of the other very particularly preferably represents hydrogen, C₁-C₁₂Alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, octyl, isooctyl, sec-octyl, n-decyl or n-dodecyl, represents C in each case optionally substituted by fluorine-or chlorine-, and is preferably substituted by fluorine or chlorine₁-C₄Alkyl, in particular fluoromethyl, trifluoromethyl or trichloromethyl, represents C₂-C₆Alkenyl, in particular vinyl or allyl, represents cyclopentyl or cyclohexyl and represents C₃-C₇-cycloalkyl-C₁-C₄Alkyl, in particular cyclopropylmethyl, represents methylthioethyl or represents in each case optionally fluorine-, chlorine-, bromine-, iodine-, hydroxyl-, cyano-, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, tert-butyl-, trifluoromethyl-, trichloromethyl-, methoxy-, difluoromethoxy-, trifluoromethoxy-or benzyloxy-substituted phenyl, phenyl-C₁-C₄Alkyl, in particular benzyl, 3-naphthylmethyl, benzo-1, 3-dioxol-5-yl, thienylmethyl, imidazolylmethyl or indolylmethyl.

R³And R⁴Very particularly preferably together represent- (CH)₂)₂-,-CH(CH₃)CH₂-,-C(CH₃)₂CH₂-,-(CH₂)₃-,-(CH₂)₄-,-(CH₂)₅-, or a group (a)

Wherein

R⁵And R⁶Independently of one another, represents hydrogen, in each case optionally fluorine-or chlorine-substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or represents optionally fluorine-, ammonia-, bromine-, nitro-, amino-, methyl-, ethyl-, trifluoromethyl-, methoxy-, difluoromethoxy-or trifluoromethoxy-substituted phenyl, benzyl or pyridyl.

Very particularly preferred ranges exclude 6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione.

The definitions or explanations of the general or preferred radicals listed above can be combined with one another as desired, i.e. combinations between the given ranges and preferred ranges are possible. These radical definitions or explanations apply to the end products and in a corresponding manner to the starting materials and intermediates.

The preferred embodiments of the invention given for the compounds of formula (I) include combinations of the preferred definitions described above.

The particular preferences given for the compounds of the formula (I) according to the invention include the combinations of the above-mentioned particularly preferred definitions.

The very particularly preferred embodiments of the present invention given for the compounds of the formula (I) include the combinations of the very particularly preferred definitions mentioned above.

Saturated or unsaturated hydrocarbon radicals such as alkyl and alkenyl, including combinations with heteroatoms, for example in alkoxy, may be straight-chain or branched in each case, as far as possible.

The optionally substituted groups may be mono-or polysubstituted, and in the case of polysubstitution the substituents may be the same or different.

Using, for example, 3-methoxy-2-methyl-2- (tetrahydropyridazin-1-thiocarbonyloxy) -propionic acid as starting material, the course of the reaction of process (A) according to the invention can be carried out by the following reactionThe formula is as follows:

using, for example, 3-tert-butyl-4- (2-thienylmethyl) -2, 5-dioxo- (1,3,4) -oxadiazine and benzyl bromide as starting materials, the course of the reaction of process (B) according to the invention can be represented by the following reaction scheme:

using, for example, 3, 4-dimethyl-2, 5-dioxo- (1,3,4) -oxadiazine and acetone as starting materials, the course of the reaction of process (C) according to the invention can be represented by the following reaction scheme:

using, for example, 4, 6-dimethyl-6-vinyl-2, 5-dioxo- (1,3,4) -oxadiazine and iodomethane as starting materials, the course of the reaction of process (D) according to the invention can be represented by the following reaction scheme:

starting with, for example, 3-methyl-6- (2-methylpropyl) -2, 5-dioxo- (1,3,4) -oxadiazine and dimethyl sulfate, the course of the reaction of process (E) according to the invention can be represented by the following reaction scheme:

using, for example, 2 '- (4-chlorophenyl) -1' -methyl- (1-hydroxy-2-methyl-cyclopropane) carbohydrazide and phosgene as starting materials, the course of the reaction of process (F) according to the invention can be represented by the following reaction scheme:

using, for example, 1 '-phenyl-2' -methyl- [ 3-methyl-2- (4-nitrophenoxycarbonyloxy)]If butyrhydrazide is the starting material, the reaction sequence of the process (G) of the present invention can be represented by the following reaction formula:

starting from 4- (4-methylpentyl) -3-methyl-6-phenyl-2, 5-dioxo- (1,3,4) -oxadiazine and 2, 4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetan-2, 4-dithione (Lawesson's reagent), the course of reaction of process (H) according to the invention can be represented by the following equation:

formula (II) provides a general definition of the carbazates required to carry out process (A) according to the invention. In the formula, R¹,R²,R³,R⁴And Q¹Each preferably represents those radicals which have already been mentioned above in connection with the description of the oxadiazine derivatives of formula (i) as preferred substituents. Except that R²And R⁴Simultaneously represents hydrogen, R¹Represents C₁-C₅-alkyl and R³The carbazates of the formula (II) are novel, in addition to the compounds representing methyl or benzyl (cf. DE-OS (German laid-open Specification) 2658254).

For example by cleaving the protecting group A from a C-terminally protected hydrazinoformate of formula (X) in process (A.a) of formula²Hydrazinoformates of formula (II) can be prepared:

in the formula (X), A²Represents a C-terminal protecting group, such as tert-butyl or benzyl (see, for example, T.W.Greene, P.G.M.Wuts, protecting groups in Organic Synthesis (Protective group Organic Synthesis), second edition, John Wiley&Sons, new york 1991).

The reaction is carried out by conventional methods of C-terminal deprotection, such as acid hydrolysis, for example in the case of tert-butyl esters, or catalytic hydrogenation, for example in the case of benzyl esters.

For example by cleavage of the protecting group A from an N-terminally protected hydrazinoformate of formula (XI) in Process (A.b) of the formula³Hydrazinoformates of formula (II) can also be prepared:

in the formula (XI), A³Represents an N-terminal protecting Group, such as tert-Butoxycarbonyl (BOC), benzyloxycarbonyl (Cbz) or benzyl (BzI) (see, for example, T.W.Greene, P.G.M.Wuts, protecting groups in Organic Synthesis (Protective Group in Organic Synthesis), second edition, John Wiley&Sons, new york 1991).

The reaction is carried out by conventional methods of N-terminal deprotection, such as acid hydrolysis, for example in the case of BOC, or catalytic hydrogenation, for example in the case of benzyl esters.

The O-terminally protected carbazates of formula (X) required for carrying out process (A.a) or the N-terminally protected carbazates of formula (XI) required for carrying out process (A.b) may be prepared from N-terminally and O-terminally protected carbazates of formula (XII) by cleavage of the N-terminal protecting group by a process (A.a.b) analogous to (A.b) or by cleavage of the O-terminal protecting group by a process (A.b.a) analogous to (A.a):

depending on the nature of the protecting groups, it is also possible in a particular embodiment of the process to cleave both protecting groups in one step and to convert the compound of the formula (XII) directly into the compound of the formula (II) (process A.a/b).

For example, a compound of formula (XII) may be prepared by reacting a compound of formula (XIII) with a hydrazinoformate or hydrazine of formula (XIV), if appropriate in the presence of a diluent, according to the following reaction scheme:

in the formula (XIII), Y¹Represents chlorine, trichloromethoxy, C₁-C₄-alkoxy, optionally substituted phenoxy, 1-imidazolyl or 1,2, 4-triazolyl.

Some of the hydrazinoformates or hydrazines of formula (xiv) are known or can be prepared by known methods (see, e.g., j. chem. soc. perkin trans. i1975, 1712).

Except that R²,R⁴Each represents hydrogen, R¹Represents C₁-C₅-alkyl and R³In addition to compounds representing methyl or benzyl, the compounds of the formulae (X) and (XII) are novel.

The compounds of formula (XIII) are prepared, for example, by reacting a protected α -hydroxycarboxylic acid of formula (XV) with a compound of formula (VIII) according to the following reaction scheme:

in formula (VIII), Y²Represents chlorine, trichloromethoxy, 1-imidazolyl or 1,2, 4-triazolyl. The compounds of the formula (VIII) are generally known (thio) phosgenating agents (see, for example, org. syntheses Coll. Vol.5,201 (1973)).

Protected α -hydroxycarboxylic acids of formula (xv) are generally prepared from the free carboxylic acid by known methods (e.g. esterification using an alkyl halide or benzyl halide in the presence of cesium carbonate, j. chem. soc. perkin trans. i1993, 11). Alpha-hydroxycarboxylic acids are commercially available or can be prepared, for example, from alpha-amino acids by deamination (see, for example, Tetrahedron letters28,1873(1987) and 26,5257 (1985); Compr. org. chem. Vol.2,739-778 (1979); Ullmanns Encyclop _ die Techn. chem. 4 th edition (1977), Vol. 13, 163).

Wherein Q¹The compounds (XII-1) of the formula (XII) which represent oxygen may also be prepared, for example, by reacting a compound of the formula (XVI) with a compound of the formula (XVII), if appropriate in the presence of a diluent, according to the following reaction scheme:

in the formula (XVI), Me¹Represents an alkali metal, preferably potassium or cesium. In formula (XVII), X represents chlorine, bromine, an alkylsulfonyl group, in particular a methylsulfonyl or trifluoromethanesulfonyl group, or an arenesulfonyl group, in particular a phenylsulfonyl or p-toluenesulfonyl group.

The compounds of formula (XVI) may be prepared by reacting a hydrazinoformate or hydrazine of formula (XIV) as hereinbefore described with an alkali metal carbonate, preferably potassium carbonate or cesium carbonate, if appropriate in the presence of carbon dioxide.

The compounds of the formula (XVII) can be prepared, for example, by generally known methods from the abovementioned alpha-hydroxycarboxylic acid derivatives. Furthermore, compounds of formula (XVII) wherein X represents bromo or chloro may be prepared, for example, by initially converting an alpha-amino acid to an alpha-chloro-or bromo-carboxylic acid (see J.Am.chem.Soc.)76,6054(1954), protein Chemistry development (Advances in protein Chemistry) Vol.IV, M.L.Anson, J.T.Edsall.1948, 33), and protecting it by generally known methods.

The oxadiazines of the formula (I-C) required for carrying out the processes (B) and (C) according to the invention form a subset of the compounds of the general formula (I) according to the invention and can be prepared, for example, by processes (A) and (D) to (H).

Formula (III) provides a general definition of the compounds which are also required for carrying out process (B). In the formula, R^4-1Preferably represents the preferred R groups, other than hydrogen, already indicated above, associated with the oxadiazine derivatives of formula (I)⁴The same groups. E preferably represents halogen, in particular chlorine or bromine, in R^4-1In the case of one of the optionally substituted alkyl radicals, also represents methylsulfonyloxy, tosyloxy or trifluoromethylsulfonyloxy, or^4-1In the case where represents a carbonyl group, E preferably represents a group-OR^4-1。

The alkylating or acylating agents of the formula (III) are generally known organic chemical reagents and/or can be prepared by known methods.

The formula (IV) provides a general definition of the aldehydes or ketones required for carrying out the process (C) according to the invention. In the formula, R⁵And R⁶Each preferably represents those radicals which have already been mentioned above in connection with the description of the oxadiazine derivatives of formula (i) as preferred substituents.

The aldehydes or ketones of the formula (IV) are generally known and/or can be prepared by known methods.

The oxadiazines of the formulae (I-E) and (I-F) required for carrying out the processes (D) and (E) according to the invention each constitute a subset of the compounds of the general formula (I) according to the invention and can be prepared, for example, by the processes (A) to (C) and (F) to (H).

The formulae (V) and (VI) provide general definitions of the compounds which are also required for carrying out the processes (D) and (E). In the formula, R^1-1And R^2-1Each preferably represents the preferred R, other than hydrogen, already indicated above in connection with the description of the oxadiazine derivatives of formula (I)¹And R²The same radicals, and E accordingly preferably represents the radicals mentioned in the description of the compounds of the formula (III). Correspondingly means that for the carboxylic anhydrides of the formulae (V) and (VI), the radical-OR^1-1and-OR^2-1Each of which may replace R^4-1。

The alkylating or acylating agents of the formulae (V) and (VI) are generally known organic chemical reagents and/or can be prepared by known methods.

The formula (VII) provides a general definition of the compounds required for carrying out the process (F) according to the invention. In the formula, R¹,R²,R³,R⁴And Q²Each preferably represents those radicals which have already been mentioned above in connection with the description of the oxadiazine derivatives of formula (i) as preferred substituents.

For example by cleaving the N-terminal protecting group A of a compound of formula (XVIII) according to the conventional method of the formula³Compounds of formula (vii) can be prepared:

α -hydroxy (thio) carbohydrazides of the formula (xviii) may be prepared, for example, by reacting an α -hydroxy (thio) carboxylic ester of the formula (xix) with a hydrazine of the formula (xxx) according to the following reaction scheme:

in the formula (XIX), R⁷Represents an optionally substituted alkyl or aryl group. The α -hydroxy (thio) carboxylic esters of the formula (XIX) are commercially available or can be prepared, for example, from α -amino acids by deamination (see, for example, Tetrahedron letters28,1873(1987) and 26,5257 (1985); Compr. org. chem. Vol.2,739-778 (1979); Ullmanns encyclopedie Techn. chem. 4 th edition (1977), Vol. 13, 163).

Some hydrazines of formula (xx) are known or they can be obtained by known methods (see, e.g., j. chem. soc. perkin trans. i1975, 1712).

The formula (IX) provides a general definition of the compounds required for carrying out the process (G) according to the invention. In the formula, R¹,R²,R³,R⁴,Q¹And Q²Each preferably represents those radicals which have already been mentioned above in connection with the description of the oxadiazine derivatives of formula (i) as preferred substituents. Y is¹Preferably represents chlorine, trichloromethoxy, 1-imidazolyl, 1,2, 4-triazolyl or Z-substituted aryloxy, in particular pentafluorophenyl, 4-nitro or 2, 4-dinitrophenyl.

For example by cleaving the N-terminal protecting group A of the compound of formula (XXI) according to the formula³A compound of formula (IX) may be prepared:

for example by reacting an alpha-hydroxy (thio) carbohydrazide of the formula (XVIII) above with a (thio) phosgenating reagent of the formula (VIII) above and, if appropriate, allowing the resulting compound Y therein to react¹The compound of formula (XXI) may be prepared by reaction of a product of formula (XXI) which does not represent a Z-substituted aryloxy group with a suitable phenol or phenoxide such as 2, 4-dinitrophenol.

The oxadiazines of the formula (I-a) required for carrying out process (H) according to the invention form a subset of the compounds of the formula (I) according to the invention and can be prepared, for example, by processes (A) to (G).

Preferred thioacylating reagents which are also required for carrying out process (H) according to the invention are phosphorus pentasulfide or 2, 4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetan-2, 4-dithione (Lawesson's reagent).

Suitable reaction auxiliaries for carrying out process (A) according to the invention are all compounds which are suitable for the formation of amide bonds (see, for example, Houben-Weyl, methods of organic chemistry (Methoden der Organischen Chemie), Vol. 15/2; Bodensky et al, peptide Synthesis (PeptideS Synthesis) 2 nd edition, Wiley & Sons, N.Y. 1976). The following methods are preferred: methods using pentafluorophenol (PfP), N-hydroxysuccinimide, activated esters of 1-hydroxybenzotriazole, coupling with carbodiimides such as dicyclohexylcarbodiimide or N' - (3-dimethylaminopropyl) -N-Ethylcarbodiimide (EBC) as in the mixed anhydride method, or coupling with phosphonium reagents such as 1-benzotriazolyloxy-tris (dimethylaminophosphonium) hexafluorophosphate (BOP), bis- (2-oxo-3-oxazolidinyl) -phosphoryl chloride (BOP-Cl), or phosphonate reagents such as diethyl cyanophosphonate (DEPC) and diphenylphosphoryl azide (DPPA). Particular preference is given to coupling with bis- (2-oxo-3-oxazolidinyl) -phosphoryl chloride (BOP-C1) and N' - (3-dimethylaminopropyl) -N-Ethylcarbodiimide (EDC) in the presence of 1-hydroxybenzotriazole (HOBt).

Suitable diluents for carrying out process (A) according to the invention are organic solvents and any mixtures thereof. Examples include aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, or diethylene glycol dimethyl ether or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n-or iso-butyronitrile or benzonitrile; amides, such as formamide, N-dimethylformamide, N-dimethylacetamide, N-methyl-N-formanilide, N-methyl-pyrrolidone, 1, 3-dimethyl-tetrahydro-2-pyrimidinone (DMPU),1, 3-dimethyl-2-imidazolidinone, tetramethylurea or hexamethylphosphoric triamide; n-oxides, such as N-methylmorpholine N-oxide; esters, such as methyl acetate, ethyl acetate or butyl acetate; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane.

The cyclization reaction is preferably carried out in the presence of a base. Suitable bases are inorganic or organic bases. Preference is given to alkaline earth metal or alkali metal hydroxides, alkoxides, acetates, carbonates or bicarbonates, for example sodium hydroxide, potassium hydroxide or amine hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium acetate, potassium acetate, calcium acetate or amine acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, and also quaternary amines, for example trimethylamine, triethylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethylaniline, N, N, -dimethyl-benzylamine, pyridine, picoline, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), Diazabicyclononene (DBN) or Diazabicycloundecene (DBU).

The reaction temperature at which process (A) according to the invention is carried out can vary within a relatively wide range. In general, the cyclization is carried out at a temperature of between-40 ℃ and +150 ℃, preferably between-20 ℃ and +100 ℃, particularly preferably between 0 ℃ and room temperature.

When carrying out the process (A) according to the invention, in general, the compound of the formula (II) and the base are used in a molar ratio of from 1: 1 to 1: 3, preferably in a molar ratio of 1: 2.

Process (B) according to the invention can be carried out in the presence of a diluent. Suitable diluents are water, organic solvents and any mixtures thereof. Examples include aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, or diglyme or anisole; amides, such as formamide, N-dimethylformamide, N-dimethylacetamide, N-methyl-N-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; n-oxides, such as N-methylmorpholine N-oxide; esters, such as methyl acetate, ethyl acetate or butyl acetate; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane; alcohols, such as methanol, ethanol, n-or isopropanol, n-, iso-, sec-or tert-butanol, ethylene glycol, 1, 2-propanediol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; and (3) water.

The process (B) according to the invention is preferably carried out in the presence of suitable reaction assistants. Suitable reaction assistants are all customary inorganic or organic bases. Preferably including alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as sodium hydride, sodium hydroxide, potassium hydroxide or amine hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium amide, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, sodium acetate, potassium acetate, calcium acetate or amine acetate, sodium carbonate, potassium carbonate, amine carbonate, sodium bicarbonate or potassium bicarbonate; alkyl lithium, such as methyl-, N-butyl-, sec-butyl-or tert-butyl-lithium, and also quaternary amines, such as trimethylamine, triethylamine, tributylamine, N, N, -dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), Diazabicyclononene (DBN) or Diazabicycloundecene (DBU).

The reaction temperature at which process (B) according to the invention is carried out can vary within a relatively wide range. In general, the reaction is carried out at a temperature of between-100 ℃ and +150 ℃, preferably between-78 ℃ and +100 ℃.

When carrying out the process (B) according to the invention, the oxadiazine derivatives of the formula (I-c), the reagent of the formula (III) and the base are generally used in approximately equimolar amounts in each case. However, it is also possible to use relatively large excesses (up to 50mol) of reagents and bases.

Process (C) according to the invention can be carried out in the presence of a diluent. Suitable diluents are preferably those listed for process (B).

Process (C) according to the invention is preferably carried out in the presence of suitable reaction assistants. Suitable reaction assistants are preferably all the bases listed for process (B).

The reaction temperature at which process (C) according to the invention is carried out can vary within a relatively wide range. In general, the reaction is carried out at a temperature of between-100 ℃ and +120 ℃ and preferably between-78 ℃ and +100 ℃.

To remove water, an acid may be used if water cannot be removed without assistance. Suitable acids are all mineral and organic protic acids and Lewis acids, and also all polymeric acids. Including, for example, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, boron trifluoride (also as ether), boron tribromide, aluminum trichloride, zinc chloride, iron (III) chloride, antimony pentachloride, acidic ion exchangers, acidic alumina and acidic silica gel.

When carrying out the process (C) according to the invention, the oxadiazine derivatives of the formula (I-C), the carbonyl compounds of the formula (IV) and the base are generally used in approximately equimolar amounts in each case. However, it is also possible to use relatively large excesses (up to 50mol) of reagents and bases.

The processes (D) and (E) according to the invention may be carried out in the presence of a diluent. Preferred diluents are those listed for process (B).

The processes (D) and (E) according to the invention are preferably carried out in the presence of suitable reaction assistants. Suitable reaction assistants are all the bases listed for process (B). They also include catalysts, such as 4- (N, N-dimethylamino) -pyridine.

The reaction temperatures for the processes (D) and (E) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at a temperature of between-40 ℃ and +120 ℃ and preferably between-10 ℃ and +100 ℃.

When carrying out the processes (D) and (E) according to the invention, the oxadiazine derivatives of the formula (I-g) or (I-h), the compounds of the formula (V) or (VI) and the base are generally used in approximately equimolar amounts in each case. However, it is also possible to use relatively large excesses (up to 50mol) of reagents and bases. If appropriate, from 0.001 to 0.1 mol of catalyst are used per mole of oxadiazine derivative.

Process (F) according to the invention may be carried out in the presence of a diluent. Preferred diluents are those listed for process (A).

Process (F) according to the invention can be carried out in the presence of suitable reaction assistants. Suitable reaction assistants are all the bases listed for process (A).

The reaction temperature in process (F) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at a temperature between-20 ℃ and +150 ℃, preferably between +20 ℃ and +120 ℃, the cyclization reaction optionally being initiated by increasing the temperature after the reaction of the two reactants.

When carrying out process (F) according to the invention, from 1.0 to 2.0mol, preferably from 1.0 to 1.2mol, of compound (VIII) and optionally from 1.0 to 5mol of reaction auxiliary are employed per mole of compound of the formula (VII).

Process (G) according to the invention can be carried out in the presence of a diluent. Preferred diluents are those listed for process (A).

Process (G) according to the invention can be carried out in the presence of suitable reaction assistants. Suitable reaction assistants are all the bases listed for process (A).

The reaction temperature of process (G) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at a temperature between-20 ℃ and +150 ℃, preferably between +20 ℃ and +120 ℃.

When carrying out the process (G) according to the invention, the compound of the formula (II) and the base are generally used in a molar ratio of from 1: 1 to 1: 3, preferably in equimolar amounts.

Process (H) according to the invention can be carried out in the presence of a diluent. Suitable diluents are organic solvents and any mixtures thereof. Examples include aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, diethylene glycol dimethyl ether or anisole; ureas such as 1, 3-dimethyl-tetrahydro-2-pyrimidone (DMPU),1, 3-dimethyl-2-imidazolidinone, tetramethylurea; hexamethylphosphoric triamide; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane.

The reaction temperature of process (H) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at a temperature between 0 ℃ and +150 ℃, preferably between +20 ℃ and +100 ℃.

When carrying out process (H) according to the invention, in general from 1 to 20mol, preferably from 1 to 5mol, of sulfiding agent are used per mole of compound of the formula (I-a).

The reaction of the process of the invention is carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. The working-up is carried out by customary methods of organic chemistry. The purification of the end product is preferably carried out by crystallization, chromatographic purification or by removal of volatile constituents, if appropriate under reduced pressure.

These active compounds are suitable for controlling pathogenic endoparasites encountered in humans and in animal husbandry and poultry farming, in the production of poultry, domestic animals, zoo animals, laboratory animals, animals used in trials, and pets, and have low toxicity towards warm-blooded animals. It is active against resistant and generally sensitive species and all or part of the stages of pest growth. By controlling these pathogenic endoparasites, it is possible to reduce the mortality of livestock and to avoid a reduction in the yield of products (products such as meat, milk, hair, leather, eggs, honey, etc.) so that a more economical and simpler scientific management of the animals can be achieved by using the active compounds according to the invention. Pathogenic endoparasites include cestodes, trematodes, nematodes and in particular:

the order Pseudophyllales (Pseudophylloides) is, for example, the genus Brachystema (Diphyllotothriumspp.), the genus Brachystema (spiromtra spp.), the genus Brachystema (Schistocephalusspp.), the genus Tachyplegia (Ligula spp.), the genus Brachypoda (Bothridium spp.), the genus Diphyllophora spp.

The order circularly phyllales (cyclophylloides), for example the genus mesophthora (mesostemphylosis pp), the genus anoplophora (Anoplocephala spp.), the genus parapanocephalia (paraphthcephala spp.), the genus monteilia (monteizia spp.), the genus tapeworm (thysansma spp.), the genus thystoseula spp.), the genus vitellospira (thysans spp.), the genus tapeworm (thysanesis spp.), the genus tapeworm (setaria spp.), the genus anthurium (settaenia spp.), the genus anthurita (thystoseula spp.), the genus anthurium (thystophyllia spp.), the genus anthurita (merseula spp.), the genus setaria spp.), the genus tapeworm (septoria spp.), the genus septoria (septoria spp.), the genus septoria (septoria), the genus septoria, septori.

Monogenea, e.g. Cyrodactyus spp, Dactylogyrus spp, Polysiphonia spp.

The subclasses of the genera dipteroides (posthopathostom spp.), the genus schistosoma (Schistomaspp), the genus Trichophythora (Trichophytilura spp.), the genus Pithecopis of the subclasses of the family Ornithocaulus (Ornithobium spp.), the genus Australian schistosoma (Austrobia spp.), the genus Macrophyllus (Austrobilzia spp.), the genus Macrophyllus (Gigartina spp.), the genus Cicophyton. sp.), the genus Echinopsis, the genus Echophytrophus (Hypocrea sp.), the genus Echophytopneumonius, the genus Parasporidium (Hypocrea), the genus Parasporidium (Hypocrea sp.), the genus Echinus (Hypocrea (Hypopyrophyceae), the genus Echinus (Hyphocaulus), the genus Echinus (Echinus sp.), the genus Echinus (Echinus) and the genus Echinus (Echinus) the genus Echinus (, the genus Abdominal pouch (Gastrophyllus spp.), the genus Diplococcus (Notocotylus spp.), the genus Laureus inferior (Catatropis spp.), the genus Clonorchis (Plagiorchis spp.), the genus Progenital (Prosthonism spp.), the genus Diplococcus (Dicocoeliumspp.), the genus Acidospira (Collyrickum spp.), the genus Leptospira (Nanophytussp.), the genus Leptospira (Opithochos spp.), the genus Clonorchis Spp, the genus Metrophyssop (Methorchis spp.), the genus Heterophysprus, the genus Metalonis spp.

From the order of the mouth (Enaplida), for example, Trichuris (Trichuris spp.), Trichuris (Capillaria spp.), Trichurosoides spp.

Subclasses of the subclass Rhabdicatia (Rhabdditia), such as Micronema spp.

From the order of the circular nematode (stronylida), for example, Stronylus spp), tridentate nematode (trichontophous spp), oesophagostomus spp, trichinella (trichloroglenda spp), zygophyllotoides spp, angiostrongyloides spp, trichlorostomus spp, tricholepis spp, trichlorephyes spp, trichlorus spp, nephotella spp, trichlorella spp, trichlorus spp, euglene spp, trichlorus spp, euglena spp, elaphostrongylus spp., Parelaphorngylus spp., Cycloacanthous sp., Paraprenoloma spp., murine pulmonary nematode (Angiostrongylus spp.), Aeurostrongylus spp., Filaroid spp., Parasailaroid spp., Trichostrongylus spp., Haemonchus spp., Osterta sp., Marshall sp., Guoporia spp., Microptera sp., Microptera (Cooperiptera spp.), Microptera tenuis, Microptera spp., Microptera Pistacia spp., Microptera fine, Microptera Nematorius spp., porcine Spp., Hyoscyas spp., and Obelemlus spp.

From the order of the Oxyurida, for example, the genus Oxyurida (Oxyuris spp.), the genus Enterobacter (spp.), the genus Douglas (Passalurus spp.), the genus Oryza (Sypharmacispp.), the genus Nitraria (Aspicilus spp.), and the genus Nitraria (Heterakis spp.).

The order of Ascaridia (Ascaridia), for example, the genus Ascaris (Ascaris spp.), the genus toxocara (toxscaris spp.), the genus toxocara (toxocaris spp.), the genus toxocara (parascarisp.), the genus aphrodisiae (Anisakis spp.), and the genus Ascaris (Ascaridia spp.).

Cauda (spirida), such as the jaw (Gnathostoma spp.), ptera (physioptera spp.), andrussonella (Thelazia spp.), cyrtonema (Gongylonemaspp.), koxtox (Habronema spp.), juxtox (Habronema spp.), sublux (Parabronema spp.), dera (draschiza spp.), and longline (dracruculus spp.).

From the order of nematodes (Filarida), for example Stephanoferia spp., Parafilaria spp., filarial (Setaria spp.), Luomala (Loa spp.), Dirofilaria spp., LitomoSoides spp., Brugia spp., Wucheria spp., Wuchera, and Strausura (Onchoreca spp.).

Echinodermata florida (Gigantohinchida), for example, Filicolis spp, Trichosanthes spp (Moniliformes spp.), Macranthorchus spp, Echinodermata spp (Prostherchis spp.).

For example, they have excellent activity against nematodes such as Haemonchus contortus (Haemonchus contortus).

Livestock and domestic animals include mammals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, reindeer, deer, fur-bearing animals, such as minks, chinchillas or racoons, birds, such as chickens, turkeys, ducks or geese, freshwater and sea fish, such as trout, carps and eels, reptiles and insects, such as bees and silkworms.

Laboratory and experimental animals include golden hamsters, guinea pigs, rats and mice, dogs and cats.

Pets, including dogs and cats.

Administration can be prophylactic as well as therapeutic.

The active substances can be administered directly or in the form of suitable preparations, enterally, parenterally, dermally, nasally, for treating parasites or with the aid of shaped articles containing the active compound, such as strips, discs, bands, collars, ear tags, leg bands or markers.

The active compounds according to the invention can be administered enterally, for example orally in the form of powders, suppositories, tablets, capsules, pastes, potions, granules, solutions, suspensions and emulsions which can be taken orally, boluses, medicated feeds or drinking water. The skin application is carried out, for example, in the form of dipping, spraying, dipping, washing or pouring and spotting, and dusting. Parenteral administration is carried out, for example, in the form of injection solutions (intramuscular, subcutaneous, intravenous or intraperitoneal) or by means of implants.

Suitable formulations include:

solutions, such as injections, oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, Pour-on formulations, gels;

emulsions and suspensions for oral or dermal administration and for injection; a semi-solid formulation;

formulations wherein the active compound is incorporated in a cream base or an oil-in-water or water-in-oil emulsion base;

solid preparations, such as powders, premixes or concentrates, granules, pills, tablets, boluses, capsules; aerosols and inhalants, shaped articles containing active compounds.

The injections are administered intravenously, intramuscularly and subcutaneously.

Injections are prepared by dissolving the active compound in a suitable solvent and, if necessary, adding additives such as solubilizers, acids, bases, buffer salts, antioxidants, or preservatives. The solution was sterile filtered and poured into containers.

Suitable solvents include: physiologically acceptable solvents, such as water, alcohols, such as ethanol, butanol, benzyl alcohol, glycerol, hydrocarbons, propylene glycol, polyethylene glycol and N-methylpyrrolidone, and mixtures thereof.

The active compounds can, if appropriate, also be dissolved in physiologically acceptable vegetable or synthetic oils suitable for injection.

Suitable solubilizing agents include: a solvent that promotes dissolution of the active compound in the primary solvent or that prevents precipitation of the active compound. Examples of solubilizers are polyvinylpyrrolidone, polyethoxylated castor oil and polyethoxylated sorbitan esters.

The following are preservatives: benzyl alcohol, chlorobutanol, parabens or n-butanol.

The oral liquid can be administered directly. The concentrate is first diluted to the administration concentration and then administered orally. Oral solutions and concentrates were prepared as described above in the case of the injections. No sterilization process is required.

Solutions for application to the skin are applied drop by drop, spread, rubbed, splashed or sprayed, or by dipping, dipping or washing. These solutions are prepared as described above in the case of the injection solutions.

It is advantageous to add a thickener during the preparation.

The following are thickeners: inorganic thickeners, such as bentonite, colloidal silica, aluminum monostearate, or organic thickeners, such as cellulose derivatives, polyvinyl alcohol and its copolymers, acrylates and methacrylates.

The gel is applied to or flat on the skin or applied into a body cavity. The gel is prepared by adding a thickening agent to a solution prepared as described for the injection. The thickening agent is added in an amount to form a clear composition having an ointment-like consistency. The thickeners used are the thickeners indicated above.

Pour-on and spot-on formulations are those wherein the formulation is poured or splashed onto a limited area of skin. The active compound penetrates the skin to act systemically or spread over the systemic surface.

Pour-on and spot-on formulations are prepared by dissolving, suspending or emulsifying the active compound in a suitable solvent or solvent mixture which is tolerated by the skin. If appropriate, further auxiliaries, such as colorants, absorption promoters, antioxidants, light stabilizers or adhesion promoters, are added.

Suitable solvents include: water, alcohols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols, such as benzyl alcohol, phenyl ethanol or phenoxy ethanol, esters, such as ethyl acetate, butyl acetate or benzyl benzoate, ethers, such as alkylene glycol alkyl ethers, such as dipropylene glycol monomethyl ether or diethylene glycol monobutyl ether, ketones, such as acetone or methyl ethyl ketone, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, N-methylpyrrolidone, 2, 2-dimethyl-4-oxy-methylene-1, 3-dioxolane.

Colorants are all colorants that are soluble or suspendable and approved for use in animals.

Examples of absorption promoters are DMSO, spreading oils, such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils, fatty acid esters, triglycerides or fatty alcohols.

The following are antioxidants: sulfites or metabisulfites, for example potassium pyrosulfate, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole or tocopherol.

Examples of light stabilizers are benzophenones or novantisolic acid.

Tackifiers are, for example, cellulose derivatives, starch derivatives, polyacrylates or natural polymers such as alginates or gelatin.

The emulsion can be administered orally, transdermally or as an injection.

Emulsions may be of the water-in-oil or oil-in-water type.

Emulsions are prepared by dissolving the active compound in a hydrophobic or hydrophilic phase and homogenizing this phase with the aid of suitable emulsifiers and, if appropriate, further auxiliaries, such as colorants, absorption promoters, preservatives, antioxidants, light stabilizers and viscosity-increasing substances, with the solvent of the other phase.

Suitable hydrophobic phases (oils) include: paraffin oil, silicone oil, natural vegetable oil, such as sesame oil, almond oil or castor oil, synthetic triglycerides, such as n-caprylic/n-capric diglyceride, and C_8-12A triglyceride mixture of vegetable fatty acids of chain length or other specifically selected natural fatty acids, a mixture of partial glycerides of saturated or unsaturated fatty acids which may also contain hydroxyl groups, and C₈/C₁₀Fatty acid mono-and diglycerides.

Fatty acid esters are, for example, ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol pelargonate, branched fatty acids with medium chain length and C₁₆-C₁₈Esters of saturated fatty alcohols of chain length, isopropyl myristate, isopropyl palmitate,C₁₂-C₁₈esters of n-octanoic/n-decanoic acids with saturated fatty alcohols of chain length, isopropyl stearate, oleyl oleate, decyl oleate, ethyl lactate, wax fatty acid esters, such as artificial light canvas uropygial fat, dibutyl phthalate, diisopropyl adipate, ester mixtures related to the latter, etc.

Fatty alcohols are, for example, isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol or oleyl alcohol.

Fatty acids are for example oleic acid and mixtures thereof.

Suitable hydrophilic phases include: water, alcohols, such as propylene glycol, glycerol, sorbitol and mixtures thereof.

Suitable emulsifiers include: nonionic surfactants, such as polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate or alkylphenol polyglycol ethers; amphoteric surfactants, such as disodium N-lauryl- β -iminodipropionate or lecithin; anionic surfactants such as sodium lauryl sulfate, fatty alcohol ether sulfates, and monoethanol amine salts of mono/dialkyl polyglycol ether orthophosphate; cationic surfactants, such as cetyltrimethylammonium chloride.

Suitable other adjuvants include: substances which increase the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, methyl vinyl ether/maleic anhydride copolymers, polyethylene glycols, waxes, colloidal silica or mixtures of the substances listed.

The suspension can be administered orally, transdermally or as an injection. They are prepared by suspending the active compounds in a liquid vehicle, if desired with the addition of further auxiliaries, such as wetting agents, colorants, absorption promoters, preservatives, antioxidants and photostabilizers.

Suitable liquid excipients include all homogeneous solvents and solvent mixtures.

Suitable wetting agents (dispersants) include the surfactants further indicated above.

Suitable other adjuvants include those further indicated above.

The semisolid formulations can be administered orally or transdermally. It is distinguished from the above-mentioned suspensions and emulsifiers only by its higher viscosity.

To prepare solid preparations, the active compounds are mixed with suitable excipients, if appropriate with the addition of auxiliaries, and the mixtures are formulated as desired.

Suitable excipients include all physiologically acceptable solid inert substances. Suitable for this purpose are inorganic and organic substances. Inorganic substances are, for example, common salts, carbonates, such as calcium carbonate, bicarbonates, aluminas, silicas, clays, precipitated or colloidal silicas, and phosphates.

Organic substances are, for example, sugars, cellulose, foodstuffs and animal feeds, such as milk powder, animal meals, cereal meals, coarse cereal meals and starches.

Auxiliaries are preservatives, antioxidants and colorants which have already been mentioned above.

Other suitable auxiliaries are lubricants and glidants, for example magnesium stearate, stearic acid, talc, bentonite, disintegrants, for example starch or crosslinked polyvinylpyrrolidone, binders, for example starch, gelatin or linear polyvinylpyrrolidone, and dry binders, for example microcrystalline cellulose.

In the formulations, the active compounds may also be present in a mixture with synergists or other active compounds active against pathogenic endoparasites. Examples of such active compounds are L-2,3,5, 6-tetrahydro-6-phenyl-imidazolyl thiazole, benzimidazole carbamates, praziquantel, pyrantel or phenylthionocarbamate.

Ready-to-use preparations contain the active compound in a concentration of from 10ppm to 20% by weight, preferably from 0.1 to 10% by weight.

The preparations to be diluted before use contain the active compounds in concentrations of from 0.5 to 90% by weight, preferably from 5 to 50% by weight.

In general, it has proven advantageous to administer an amount of active compound of approximately 1 to 100mg per kg of body weight per day to achieve effective results.

Furthermore, these active compounds are suitable for controlling animal pests, in particular insects, mites and nematodes, encountered in agriculture, forestry, in the protection of stores and in the protection of materials, and in the hygiene sector, and have good plant tolerance and low toxicity to warm-blooded animals. It is effective against generally sensitive and resistant varieties and at all or some stages of pest development. The pests include:

isopoda (Isopoda), such as Oniscus aselluse, Armadillidium and Porcellioscaber.

Polypod (Diplopoda), for example, Blaniulus guttulatus.

From the order of the subphyla labialis (Chilopoda), for example Geophilus carpophagus and Scutigera spec (Scutigera spec.).

A comprehensive outline (symphylla), such as Scutigerella immeculata.

From the order of the Thysanura, for example, Lepisma saccharina (Lepisma saccharana).

From the order of the Collelmola (Collelmbola), for example Onyhiurus armatus.

Orthoptera (Orthoptera), for example, Fibrata orientalis (Blatta orientalis), Periplaneta americana (Periplaneta americana), Matricaria maderana (Leucophaeamaderma), Blattella germanica (Blattella germanica), Trojan (Acheta stomatica), Gryllotalpa spp.), locustaria tropica (Loustamigra tororidioides), locusta longiligularis (Melanoplus differalis) and Schistocerca gregaria.

From the Dermaptera (Dermaptera), for example, Forficula auricularia (Forficula auricularia).

From the order of the Isoptera (Isoptera), for example, the genus termitum (Reticulitermes spp.).

From the order of the Anoplura, for example head lice (Pediculus humanus murroris), Leptophthirus (Haematopinus spp.) and Carpesium longissimum (Linogaphus spp.).

From the order of the Mallophaga (Mallophaga), for example the genus lupulus (trichoectes spp.) and damalina spp.

From the order of the Thysanoptera (Thysanoptera), for example, Thrips femoralis (Hercinothrips femoralis) and Thrips gossypii (Thrips tabaci).

From the order of the Heteroptera (Heteroptera), for example, the genus Prinsepia fusca (Eurygaster spp.), Dysdercus intermedia, Phlebopus betanus (Piesma quadrata), bed bugs (Cimexlecteralis), Rhodnius prolixus and Nephophora sutra (Triatoma spp.).

Homoptera (Homoptera), such as Aleurodes brassicae, Sophora gossypii (Bemisia tabaci), Trialeurodes vaporariorum, Aphis gossypii (Aphis gossypii), Aphis brassicae (Brevicornus), Aphis virescens (Cryptomyzus rius), Aphis fabae (Aphis fabae), Aphis piricola (Aphis aphisporus), Aphis woolla (Eriosoma lanugium), Aphis persicae (Hyalopterus grandis), Phyllostachys nigra (Phyllostachys pratensis), Phyllostachys nigra (Phyllostachys nigra), Aphis pomorum (Pemphigus spp.), Macrosiphilus avenae (Physiophilus avenae), Aphis nodorum (Phyllostachys spp.), Aphis virginosa (Pholonella persica), Phyllophora persica spp.), Phyllophora (Phyllostachydis persica), Phyllophora indica (Phyllophora), Phyllophora spp., Phyllophora (Phosphaera), Phyllophora viridae (Phyllophora, Phyllophora (Phosphaera), Phyllophora niphacidula (Phyllophora), Phyllophora (Phyllophora), Phyllophora (Physaloides), and Lepotus (Phyllophora), Phyllophora viride), Phyllophora (Phyllophora), Phyllophora (Phyllophora, Phyllo.

Lepidoptera (Lepidoptera), for example, Heliothis rubra (Pectinophorpogypiella), looper (Bupalus piniarius), Cheimatobia brumata, Lithocolletis blancardella, cherry moth (Hypomeuta padelila), diamondback moth (Plutella maculipennis), Trichophyton (Malacosa Neurospora), Euproctis chrysoides, Chryseoea, Pothida (Lymantria trispora), Periploca gossypii (Bucctrix thurbieriella), Phylocistina citrella, Geotrichum (Agrotis sp.), Euonymus sp., Euonymus pratensis Spp, Spodoptera (Spodoptera), Spodoptera fusca (Spodoptera), Spodoptera Trichoplusia (Spodoptera), Spodoptera litura), Spodoptera (Spodoptera ), Spodoptera (Spodopteria (Spodoptera), Spodoptera (Spodopteria), Spodoptera (Spodoptera), Spodoptera (Spodoptera), Spodoptera (Spodoptera), Sp, brown leaf moth (hofmanophila pseudostella), Cacoecia podana, carpueraria, spruce leaf roller moth (chlamydobiguella), grape fruit moth (Clysia ambiguella), yellow leaf roller moth (Homona magnania) and oak green leaf roller moth (torrix viridana).

Coleoptera, e.g., bark beetles (Anobium punctatus), Rhizophora dominica, Bruchidia obtectus, elephant (Acanthoscelides obtectus), Carnius domestica (Hypertrupes bajuus), Agrastica annuus, Rhizomyia beetle (Leptinocara decemlineata), Phanochloride, Diabrotica (Diabrotica spp.), Phlebia brassicae (Psyllideschrysospora), Phlebia variola (Epilachthyophia varivestis), Atomaria sawara, Thoralpus, Oryza serogroups, Anodon sp, Trigonopsis nigra (Thiophyte), Trigonococcus spp. sp., Thiela sp., Thielavia, Trigonococcus sp. The genera of Flammulina (Conoderus spp.), Melothalameoylontha, Serissa sericea (Amphimalon solstialis), and Costelytrazendica.

Membrana ptera (Hymenoptera), such as serrata (Diprion spp.), serrata (hoplocpa app), ant (Lasius spp.), cheira (monogama pharaonis), and vespid (Vespa spp.).

Diptera (Diptera), for example, babble mosquitoes (Aedes spp.), anopheles (anopheles spp.), Culex (Culex spp.), Drosophila peltata (Drosophila melanogaster), housefly (Musca spp.), stable fly (Fannia spp.), red fly (calliphora erythrepha), Lucilia sericata (Lucilia spp.), Chrysomyia chrysomyziae (Chrysomyia spp.), melitus spp, Chrysomyia spp, gangrene (cutebra p), gammophilus spp, hypopouca spp, hippopora spp, stinging fly (Stomoxys spp), nasus spp (orula spp.), dermaphasia spp, Tanus spp, cattle bug (tarus spp.), callitrichia spp), and trypanosoma spp (callitrichia spp), callimastix spp, callitrichia spp, and euglena (callitrichia spp).

Siphonaptera (Siphonaptera), for example, Achillea species (Xenopsylla cheopis), and Ceratophyllus spp.

Arachnida, for example Scorpio maurus, Black widow ball spider (Latridectus macrantans).

Acarina (Acarina), for example, Dermatophagoides pteronyssinus (Acarinus srio), Taraxacum cryptorhizum (Argasspp.), Rhynchophorus rhynchophyllus (Ornithodoros spp.), Dermanyssus gallinarum (Dermanyssusgallinae), Eriophyses ribis, Triphytes citri (Phylloptruta oleivora), Tyrophus (Boophilus spp.), Dermatophagus spp.), Orthophys spp., Orthophycus sp., Orthophys spp., Orthophyes sp., Tyrophagus sp., Orthophytes sp., Sarcophagus sp., and Red Spyprophagus.

Parasitic plant nematodes include Pratylenchus (Pratylenchus spp.), Radophyllussimilis, Heterodera (Heterodera spp.), Meloidogyne (Meloidogyne spp.), Apelenchoides (Apelenchoides spp.), Longidotus (Longidorus spp.), Candidatus (Xipehenema spp.), and Trichostrongylus (Tricoderus spp.).

The active compounds according to the invention have a very strong action in particular against the caterpillars of the Plutella xylostella (Plutella maculipennis).

The active compounds can be formulated in the customary formulations, for example as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspended emulsifiable concentrates, and natural and synthetic materials impregnated with active compound and microencapsulations in polymeric substances.

These formulations can be produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, if appropriate with the use of surfactants, that is, emulsifiers and/or dispersants and/or foam formers.

If water is used as extender, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are mainly: aromatic compounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or ethylene glycol and ethers and esters thereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and also water.

Suitable solid carriers are, for example: ammonium salts, ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and crushed natural minerals such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of organic and inorganic powders, and granules of organic substances such as: such as sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifiers and/or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and albumin hydrolysates; suitable dispersants are: such as lignin sulfite waste liquor and methyl cellulose.

In the formulation, viscosity-increasing agents such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used. Other possible additives are mineral and vegetable oils.

It is also possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

In general, the formulations contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90%.

The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations as a mixture with other active compounds, for example insecticides, attractants, fungicides, acaricides, nematicides, fungicides, growth regulators or herbicides. Pesticides include, for example, phosphates, carbamates, carboxylates, chlorohydrocarbons, phenylureas and substances which pass, inter alia, microorganisms.

Examples of particularly useful compounding ingredients are as follows:

fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6 ' -dibromo-2-methyl-trifluoromethoxy-4 ' -trifluoromethyl-1, 3-thiazole-5-carboxanilide; 2, 6-dichloro-N- (4-trifluoromethylbenzyl) formanilide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) -acetamide; 8-hydroxyquinoline sulfate; (E) -methyl 2- {2- [6- (2-cyanophenoxy) -pyrimidin-4-yloxy ] -phenyl } -3-methoxyacrylate; (E) -ethyl methoxyimino [ α - (o-tolyloxy) -o-tolyl ] acetate; 2-phenylphenol (OPP), aldimorph, aminopropanophosphoric acid, trichlofop, penconazole,

benalaxyl, o-iodoanilide, benomyl, binapacryl, biphenyl, bitertanol, blasticidin, bromuconazole, bupirimate, buticacid,

lime sulphur, captafol, captan, carbendazim, carboxin, chlorfenapyr, chloroneb, chlorothalonil, ethiprole, maneb, cymoxanil, cyproconazole, estericam,

bisaminophen, benzyl chlorotriazole alcohol, diclofluanid, diclofenamate, niclosamide, diethofencarb, difenoconazole, dimethenamid, morpholine enoate, diniconazole, dinitrocrotonate, diphenylamine, pyrithion, sterile phosphorus, dithianon, dodine, aminooxazolone,

kewensan, epoxyconazole, ethirimol and terramycin

Fenarimol, fenbuconazole, mefuranilide, peritate, fenpiclonil, fenpropidin, fenpropimorph, triphenyltin acetate, triphenyltin hydroxide, ferbamate, ferimzone, fluazinam, fludioxonil, dichlorfluquinconazole, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, tetrachlorophthalide, fuberidazole, furalaxyl, fenpyrad,

the seed of the millet is fixed,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, amidazole, bivalvular acetate, Iprobenfos (IBP), iprodione, isoprothiolane,

kasugamycin, copper formulations, for example: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, copper 8-hydroxyquinoline, and bordeaux mixture,

mancopper, maneb, mancozeb, mepanipyrim, mefenoxam, metalaxyl, metconazol, sulfydryl, furametocam, metiram, tiadinil, myclobutanil,

nickel dimethyldithiocarbamate, nitrothalopropyl, fluoropyrimidinol,

methylfuroamide, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, isoprothiolane, 2-benzo [ c ] furanone, polymalein, mazopyr, polyurethane, polyoxin, entenosis isothiazole, gushan, procymidone, propionamide, cyproconazole, propineb, pyrimiphos, pyribenzoxim, pyrimethanil, pyroquilon,

a Pentachloronitrobenzene (PCNB),

sulphur and sulphur preparations, tebuconazole, bismerthiazol, tetrachloronitrobenzene, fluacril, thiabendazole, thiophanate-methyl, thiram, tolclofos-methyl, methyl fluorosulfonamide, triadimefon, triadimenol, pyrazoxazine, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazol,

the rice grain powder, the ethephon sclerotium,

zineb, ziram.

A bactericide:

bronopol, dichlorophen, chloromethylpyridine, nickel dimethyldithiocarbamate, kasugamycin, isothiazolone, furancarboxylic acid, oxytetracycline, enesulfonazole, streptomycin, biscumylphthalein, copper sulfate and other copper preparations.

Insecticide/acaricide/nematicide:

abamectin, AC303630, acephate, fluthrin, boll-bell-carbofuran, aldicarb, alpha-cypermethrin, acetamiprid, avermectin, AZ60541, azadirachtin, azinphos-A, baotide, azocyclotin,

bacillus thuringiensis, bendiocarb, benfuracarb, bensulam, cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos, carboxim, buprofezin, butoxycarb, butylpyridaben,

cadusafos, carbaryl, carbofuran, trithion, carbosulfan, cartap, GA157419, CGA184699, chlorethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos-methyl, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyhalothrin, cypermethrin, cyromazine,

deltamethrin, systemic phosphorus-M, systemic phosphorus-S, systemic phosphorus-methyl, diafenthiuron, diazinon, dichlorvos, dichlorphos, chlorothalonil, ethion, diflubenzuron, dimethoate, chlorfenvinphos, dioxaphos, phorate,

kewensan, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimfos,

fenpyrad, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenoxycarb, fenpropyr, fenpyroximate, fenthion, fenvalerate, fipronil, flufenoxaprop, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fenthion, difenoconazole, thiacloprid, thiazoline, fubfenprox, furdiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

pyracloprid, iprobenfos, chlorzophos, isopropylamine, cicada powder, oxazoline, mectin, cyhalothrin, lufenuon,

malathion, aphis, fenamiphos, dimethosphol, mesulfenphos, metaldehyde, chlorfenvinphos, methamidophos, methidathion, methiocarb, methomyl, milbemectin, monocrotophos, moxidectin,

dibromophosphate, NC184, NI25, nitenpyram,

omethoate, oxamyl, phosphorus sulfoxides, phosphorus isosulfones,

parathion-A, parathion-M, permethrin, phenthoate, phorate, flufenthion, phosmet, phosphamidon, phoxim, pirimiphos-A, profenofos, mecarb, propaphos, propoxur, prothiofos, pomathifos, pymetrozin, pyrachlophos, pyradaphenthiton, pyremethrin, pyrethrin, pyridaben, pyrimidifen, pyriproxyfen,

the quinalphos is a compound of quinalphos,

RH5992，

vegetable and fruit phosphorus, sebufos, silafluofen, sesamothion, meprobamate,

tebufenozid, tebufenpyrad, tebufirimiphos, fluometuron, tefluthrin, temephos, terbufos, chlorfenvinphos, thiafenox, thiodicarb, monocrotophos, disulfoton, ethoprophos, thiringiensin, tralomethrin, thiabendazole, triazophos, triazuron, trichlorfon, chlorfluazuron, hymexazol, methomyl, XMC, methiocarb, YI5301/5302, zetamethrin.

Mixtures with other known active compounds, for example herbicides, or with fertilizers and plant growth regulators are also possible.

The active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations as a mixture with synergists. A synergist is a compound that enhances the action of an active compound without itself being active.

The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration in the use forms is from 0.0000001 to 95% by weight of active compound, preferably from 0.0001 to 1% by weight.

These compounds are applied in a conventional manner suitable for these forms of use.

When used against hygiene pests and pests of stored products, these active compounds are characterized by an excellent residual action on wood and clay, and a good stability to alkali on limed materials.

Furthermore, it has been found that the active compounds of the formula (I) according to the invention have a strong insecticidal action against insects which destroy industrial materials.

Preferred but non-limiting examples may be mentioned the following insects.

Beetles, e.g.

Domestic cattle (Hypertaurus bajulus), Chlorophorus pelosisi, furniture beetle (Anobium punctium), Xestobium ruvalsum, Ptilinupocetinis, Dendrobium pertinense, Ernobius mollis, Priniumcarpini, European bamboo bark beetle (Lyctus brunneus), Lyctus africanus, bark beetle (Lyctus platicolus), Lyctus lineris, Lyctus pubesens, Troxyloxylophyceae, Minthesaurus species (Xylebroussusespec), Trotodon sporus, Apate monascus, Bostrophyceae Dibotrys, Heterobotrys and Simulos.

From the order of the hymenoptera (Dermapterans), e.g.

Mecanus horneri (Sinex juvenus), Cyrtotrachelus buergeri (Urocerus gigas), Urocerus gigas taignus and Urocerus augur.

Termite (Termites), e.g. Termites

Kalottermes flaviolis, Cryptotermes brevis, Heterotermes sindicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Australian Termite (Mastotermes darwiniensis), Zootermopsis nevadensis and Taiwan Termite (Coptotermes formosanus).

Bristle-tail, for example, Chlamydomonas occidentalis (Lepisma saccharana).

Industrial materials in the sense of the present invention are understood to be non-living materials, such as preferably synthetic materials, adhesives, sizes, paper, cardboard, leather, wood and wood processing products and coatings.

Very particularly preferred materials to be protected against insect attack are wood and wood processing products.

Wood and wood working products which can be protected with the composition according to the invention and the mixtures containing such a composition are understood to be, for example, building wood working products, wood beams, rail sleepers, bridge timbers, wharfs, wooden vehicles, boxes, pallets, containers, utility poles, wooden barrels, wooden windows, wooden doors, plywood, particle board, joinery products, or wood products which are very commonly used in the building or joinery industry.

The active compounds according to the invention can be used as such, in the form of emulsifiable concentrates or in the customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned may be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate desiccant and UV stabilizer and, if appropriate, colorants and pigments and other processing aids.

The insecticide compositions or emulsifiable concentrates for the protection of wood and wood products contain the active compounds according to the invention in concentrations of from 0.0001 to 95% by weight, preferably from 0.001 to 60% by weight.

The amount of the composition or emulsifiable concentrate used depends on the kind and presence of the pest and on the substrate. The optimum ratio of application can be determined by the test series according to the use in each case. In general, however, it is sufficient to use from 0.0001 to 20% by weight, preferably from 0.001 to 10% by weight, of active compound, based on the material to be protected.

The solvents and/or diluents used are organic chemical solvents or solvent mixtures and/or oil-type organic chemical solvents or solvent mixtures of low volatility and/or polar organic chemical solvents or solvent mixtures and/or water and, if appropriate, emulsifiers and/or wetting agents.

The organic chemical solvents preferably used are oil or oil-like solvents having a volatility greater than 35 and a flash point greater than 30 ℃, preferably greater than 45 ℃. Suitable substances for use as such oil or oil-like solvents having low volatility and being insoluble in water are mineral oils or aromatic fractions thereof, or solvent mixtures containing mineral oils, preferably white spirit, petroleum and/or alkylbenzenes.

Preferably used substances are mineral oil with a boiling point range of 170-220 ℃, petroleum solvent with a boiling point range of 170-220 ℃, spindle oil with a boiling point range of 250-350 ℃, petroleum or aromatic hydrocarbons with a boiling point range of 160-280 ℃, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling point range of 180-2l0 ℃ or high boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling point range of 180-220 ℃ and/or spindle oil and/or monochloronaphthalene, preferably α -monochloronaphthalene, are used.

Low volatility organic or oil-like solvents having a volatility greater than 35 and a flash point greater than 30 ℃, preferably greater than 45 ℃, may be partially replaced with high or medium volatility organic chemical solvents, provided that the solvent mixture also has a volatility greater than 35 and a flash point greater than 30 ℃, preferably greater than 45 ℃, and the pesticide/fungicide mixture is soluble or emulsifiable in the solvent mixture.

In a preferred embodiment, part of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture. Substances which are preferably used are aliphatic organic chemical solvents having hydroxyl and/or ester and/or ether groups, such as glycol ethers, esters, etc.

The organic chemical binders used within the scope of the present invention are synthetic resins and/or binding drying oils known per se and can be diluted with water and/or are soluble or dispersible or emulsifiable in the organic chemical solvents used, in particular binders consisting of or containing: acrylic resins, vinyl resins, such as polyvinyl acetate, polyester resins, polycondensation or polyaddition resins, polyurethane resins, alkyd resins or modified alkyd resins, phenol resins, hydrocarbon resins, such as indene/benzofuran resins, silicone resins, drying vegetable oils and/or drying oils and/or physical drying binders based on natural and/or synthetic resins.

The synthetic resin used as the binder may be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances may also be used as binders in amounts of up to 10% by weight. In addition, colorants, pigments, water repellents, odor masking substances and inhibitors or corrosion inhibitors and the like known per se can also be used.

According to the invention, the compositions or emulsifiable concentrates preferably contain at least one alkyd resin or modified alkyd resin, and/or a drying vegetable oil as organic chemical binder. According to the invention, preference is given to using alkyd resins having an oil content of greater than 45% by weight, preferably from 50 to 68% by weight.

All or part of the above-mentioned binders may be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization and crystallization or precipitation of the active compound. Preferably 0.01-30% of the binder (based on 100% binder used) is replaced.

Plasticizers are from the group of phthalic acid esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, phosphoric acid esters, such as tributyl phosphate, adipic acid esters, such as di- (2-ethylhexyl) adipate, stearic acid esters, such as butyl stearate or amyl stearate, oleic acid esters, such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.

The chemical basis of the fixing agent is a polyvinyl alkyl ether, for example polyvinyl methyl ether, or a ketone, for example benzophenone or ethylenebenzophenone.

Particularly suitable as solvent or diluent is water, if appropriate as a mixture with one or more of the abovementioned organic chemical solvents or diluents, emulsifiers and dispersants.

Particularly effective wood protection is achieved by a large number of industrial impregnation processes, for example vacuum, double vacuum or pressure processes.

The ready-to-use compositions may, if appropriate, also contain other insecticides and, if appropriate, one or more further fungicides.

Suitable additional ingredients which may be admixed are preferably insecticides and fungicides as mentioned in WO 94/29268. The compounds mentioned in this document are expressly incorporated into the present application by reference.

Very particularly preferred ingredients which may be mixed are insecticides, for example chlorpyrifos, phoxim, silafluofin, alphacypermethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and chlorbenzuron, and fungicides, for example epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazol, imazalil, benfluanid, tolylfluanid, 3-iodo-2-propynylbutyl carbamate, N-octyl-isothiazolin-3-one and 4, 5-dichloro-N-octyl-isothiazolin-3-one.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Preparation examples

Examples I-1

(method A)

0℃Next, to a solution of 3.0g (2-methyl-1-propyl hydrazyl) -carbonyloxy-acetic acid (e.g. from example II-1) in 750ml dry dichloromethane was added 5.49g ethyl dipropylamine followed after a while by 5.19g bis- (2-oxo-3-oxazolidinyl) -phosphoryl chloride. The mixture was stirred at 0 ℃ for 2 hours and then allowed to warm to room temperature overnight. The solution was concentrated and the residue was dissolved in 300ml of ethyl acetate. The solution was washed with half-saturated ammonium chloride solution and saturated sodium chloride solution and dried over sodium sulfate. The drying agent was filtered, the solution was concentrated and the product was purified by column chromatography (stationary phase: silica gel; mobile phase cyclohexane: ethyl acetate = 2: 1). 1.70g (71% of theory) of 3-propyl-4-methyl-1, 3, 4-oxadiazine-2, 5-dione are obtained as a yellowish-brown oil.¹H NMR(500MHz,CDCl₃)δ[ppm]:0.97(t,3H,CH₂CH₃)；1.62(sx,2H,CH₂CH₃)；3.23(s,3H,NCH₃)；3.68(t,2H,NH₂)；4.59(s,2H,OCH₂)

Examples I-2 to I-15

In analogy to example I-1, the compounds of formula (I-j) listed in Table 1 below were obtained.

TABLE 1(Ⅰ-j) R²=CH₃ R⁴=H

Examples I to 16

In analogy to example I-1, 5.0g of [2- (2-chloro-5-pyridyl) -methyl-1-ethylhydrazyl) -carbonyloxy-acetic acid ] (e.g. from example II-16) 3.33g (79% of theory) of 4- (2-chloro-5-pyridylmethyl) -3-ethyl-1, 3, 4-oxadiazine-2, 5-dione are obtained, m.p. 125-128 ℃.

Example II-1

(method A.a)

4.36g of (2-methyl-1-propyl hydrazyl) -carbonyloxy-acetic acid benzyl ester (e.g. from example III-1) are dissolved in 100ml of ethyl acetate. The catalyst 100mg Pd/C (10%) was added and the reaction solution was hydrogenated under 1 bar hydrogen pressure. After the reaction was completed, nitrogen gas was introduced into the solution, followed by passing through diatomaceous earth (Celite)^_) The catalyst was removed from the solution by filtration. Concentration under reduced pressure gave 3.0g (100% of theory) of (2-methyl-1-propylhydrazyl) -carbonyloxy-acetic acid as a brown viscous oil. The crude product was further reacted according to example I-1 without any purification.

¹H NMR(500MHz,CDCl₃)δ[ppm]:0.90(t,3H,CH₂CH₃)；1.65(m,2H CH₂CH₃)；

2.65(brs,3H；NCH₃)；3.37(t,2H,NCH₂)；4.68(brs,2H,OCH₂)；6.65(brs,2H,NH,

CO₂H)

Examples II-2 to II-12

In analogy to example II-1, the compounds of formula (II) listed in Table 2 below were obtained.

TABLE 2(Ⅱ) R²=CH₃ R⁴=H Q¹=O

Examples II to 13

(method A.a/b)

To a solution of 10g (2-tert-butoxycarbonyl-2-methyl-1- (3-thienylmethyl) -hydrazyl) -carbonyloxy-acetic acid tert-butyl ester (e.g. from example IV-13) in 100ml of anhydrous dichloromethane at 0 ℃ 50.5g trifluoroacetic acid are added dropwise. After 2 hours, the mixture was allowed to warm to room temperature and the reaction was checked for completion by TLC (silica gel, cyclohexane: ethyl acetate = 2: 1). Under reduced pressure, the solution was added dichloromethane and concentrated repeatedly to remove the acid (finally under high vacuum). 12.56g 2-methyl-1- (3-thienylmethyl) -hydrazyl-carbonyloxy-acetic acid were obtained as a brown viscous oil. The crude product was reacted further without purification according to example I-13.

¹H NMR(500MHz,CDCl₃)δ[ppm]:2.83(brs,3H NCH₃)；4.80and4.90(2s,2×2H,

NCH₂,OCH₂)；7.10(m,1H,arom)；7.35(m,1H,arom)；7.40(m,1H,arom.)；7.63(br

s,2H,NH,CO₂H)

Examples II to 14

(method A.a/b)

2.5g (2-benzyloxycarbonyl-2-methyl-1- (3-indolylmethyl) -hydrazyl) -carbonyloxy-acetic acid benzyl ester (e.g. from example IV-14) are dissolved in 30ml ethanol. The catalyst was added in the amount of 50mg Pd/C (10%), and the reaction solution was hydrogenated under a hydrogen pressure of 1 bar. After the reaction was completed, nitrogen gas was introduced into the solution, followed by passing through diatomaceous earth (Celite)^_) The catalyst was removed from the solution by filtration. The mixture is concentrated under reduced pressure to give 1.3g (95% of theory) of [1- (3-indolyl) -2-methyl-hydrazyl ] hydrazine]Carbonyloxy-acetic acid, mp 50-53 ℃. The crude product was reacted further according to example I-14 without purification.¹H NMR(500MHz,CDCl₃)δ[ppm]:2.65(brs,3H,NCH₃)；4.80(2s,4H,OCH₂,NCH₂)；7.0-8.2(m,6H,NH,arom)

Examples II to 15

By the method of example II-14, (2-benzyloxycarbonyl-2-methyl-1- (2, 2-dimethyl-1, 3-dioxo-4-yl) -methyl-2-methyl-hydrazyl) -carbonyloxy-acetic acid benzyl ester (e.g. from example IV-15) gives [1- (2, 2-dimethyl-1, 3-dioxo-4-yl) -methyl-2-methyl-hydrazyl ] -carbonyloxy-acetic acid.

¹H NMR(500MHz,CDCl₃)δ[ppm]:1.35u.1.43(2s,2×3H,C(CH₃)₂)；2.63(brs,

3H,NCH₃)；3.60(brm,2H,NCH₂)；3.84(brm,1H,OCHCH₂)；4.08u.4.37(2brm,

2×1H,OCH₂CH)；4.68(brm,2H,CO-CH₂O)；6.0(brs,2H,NH,CO₂H).

Examples II to 16

By the method of example II-13, 7.52g of tert-butyl [ 2-tert-butoxycarbonyl-2- (2-chloro-5-pyridyl) -methyl-1-ethyl-hydrazyl ] -carbonyloxy-acetic acid (e.g. from example IV-16) gave 4.9g (100% of theory) of [2- (2-chloro-5-pyridyl) -methyl-1-ethyl-hydrazyl ] -carbonyloxy-acetic acid.

¹H NMR(500MHz,CDCl₃)δ[ppm]:1.10(brt,3H,CH₂CH₃)；3.30(brs,2H,NCH₂)；

4.10(brs,2H,NCH₂)；4.72(s,2H,OCH₂)；7.43/7.89/8.38(3m,3×1H,arom).

Example III-1

(method A.a.b)

To a solution of 6.65g (2-tert-butoxycarbonyl-2-methyl-1-propylhydrazyl) -carbonyloxy-acetic acid benzyl ester (e.g. from example IV-1) in 50m1 anhydrous dichloromethane at 0 deg.C was added dropwise 16.9g trifluoroacetic acid. The solution was stirred at 0 ℃ for 2-3 hours and then allowed to warm to room temperature overnight. The reaction solution was concentrated under reduced pressure, and the residue was dissolved in 300ml of ethyl acetate. The solution was washed with saturated sodium bicarbonate solution and saturated sodium chloride solution and the organic phase was dried over sodium sulfate. The drying agent was filtered and the filtrate was concentrated under reduced pressure. 4.76g (100% of theory) of benzyl (2-methyl-1-propylhydrazyl) -carbonyloxy-acetate are obtained as a brown viscous oil. The crude product was reacted further according to example II-1 without purification.

¹H NMR(500MHz,CDCl₃)δ[ppm]:0.88(t,3H,CH₂CH₃)；1.64(sx,2H,CH₂CH₃)；

2.60(brs,3H,NCH₃)；3.35(t,2H,CH₂CH₃)；4.69(brs,2H,CH₂Ph)；5.20(s,2H,

OCH₂),7.37(m,5H,arom.)

Examples III-2 to III-12

By the method of example III-1, the compound of the formula (X) shown in Table 3 below was obtained.

TABLE 3A²= benzyl group R²=CH₃ R⁴=H Q¹=O

Example IV-1

Carbon dioxide gas was bubbled through a suspension of 22.80g cesium carbonate and 6.55g 1-tert-butoxycarbonyl-1-methyl-2-propyl-hydrazine in 140ml anhydrous dimethylformamide over about 1 hour. Then, 8.02g of benzyl bromoacetate was slowly added dropwise, and carbon dioxide was introduced for 30 to 45 minutes. The reaction mixture was stirred overnight, poured into 300ml of half-saturated sodium chloride solution and extracted with 3X 150ml of ethyl acetate. The organic phase is dried over sodium sulfate, the drying agent is filtered off and the filtrate is concentrated under reduced pressure at a temperature of not more than 50 ℃. The product was purified by column chromatography (silica gel; cyclohexane: ethyl acetate = 5: 1). 8.9g (67% of theory) of benzyl (2-tert-butoxycarbonyl-2-methyl-1-propyl-hydrazyl) -carbonyloxy-acetate are obtained as a pale yellow viscous oil.

¹H NMR(500MHz,CDCl₃)δ[ppm]:0.93(t,3H,CH₂CH₂)；1.47(ms,9H,C(CH₃)₃；

1.63(m,2H,CH₂CH₃)；2.90-3.55(ms,5H,NCH₂,NCH₃)；4.40-5.25(ms,4H,CH₂Ph,

OCH₂)；7.36(m,5H,C₅H₅)

Example IV-2

A solution of 25.63g 25.63g D-benzyl phenyllactate and 11.13g triethylamine in 130ml anhydrous tetrahydrofuran was added dropwise to a solution of 19.8g phosgene in 100ml toluene at 0-5 ℃ over 1 hour. Stirring was carried out at 0 ℃ for about 30 minutes and at room temperature for 1 hour, the precipitated solid was filtered, and the filtrate was concentrated under reduced pressure. The resulting crude chloroformate was dissolved in 50ml of anhydrous tetrahydrofuran and added dropwise over 1 to 2 hours to a solution of 20.24g of 1-tert-butoxycarbonyl-1-methyl-2-sec-butyl-hydrazine and 10.12g of triethylamine in 70ml of anhydrous tetrahydrofuran, which had been cooled to 0 ℃. The mixture was then warmed to room temperature and stirred overnight. The reaction mixture was added to 200ml of half-saturated sodium chloride solution and extracted with 3X 150ml of ethyl acetate. The organic phase is dried over sodium sulfate, the drying agent is filtered off and the filtrate is concentrated under reduced pressure. The product was purified by column chromatography (silica gel; cyclohexane: ethyl acetate = 10: 1). 36.83g (76% of theory) of benzyl 1- (2-tert-butoxycarbonyl-2-methyl-1-sec-butylhydrazyl) -carbonyloxy-2-phenylpropionate were obtained as a pale yellow viscous oil.

¹H NMR(500MHz,CDCl₃)δ[ppm]:0.90(ms,6H,CH(CH₃)₂)；1.30-1.75(ms,10H,

CH(CH₃)₂,C(CH₃)₃)；2.60-3.40(ms,6H,OCH,NCH₂,NCH₃)；5.0-5.40(ms,4H,

2CH₂Ph)；7.25(m,10H,2C₆H₅)

Examples IV-3 to IV-12

By the methods of examples IV-1 and IV-2, the compounds of the formula (XII) shown in Table 4 below were obtained.

TABLE 4A²= benzyl A³=BOC R²=CH₃ R⁴=H Q¹=O

Examples IV to 13

Carbon dioxide gas was bubbled through a suspension of 22.80g cesium carbonate in 140ml anhydrous dimethylformamide for about 20 minutes. Then 8.47g 1-tert-butoxycarbonyl-1-methyl-2- (3-thienylmethyl) -hydrazine was slowly added dropwise, and carbon dioxide was introduced for 60 minutes, and then 6.83g tert-butyl bromoacetate was slowly added dropwise, and carbon dioxide was introduced for 30 to 45 minutes. The reaction mixture is stirred overnight, poured into 200ml of half-saturated sodium chloride solution and extracted with 3X 150ml of ethyl acetate. The organic phase is dried over sodium sulfate, the drying agent is filtered and the filtrate is concentrated under reduced pressure at a temperature not higher than 50 ℃. The product was purified by column chromatography (silica gel; cyclohexane: ethyl acetate = 5: 1). 14.1g (100% of theory) of tert-butyl [ 2-tert-butoxycarbonyl-2-methyl-1- (3-thienylmethyl) -hydrazyl) -carbonyloxy-acetate are obtained.

¹H NMR(500MHz,CDCl₃)δ[ppm]:1.35-1.55(m,18H,2×C(CH₃)₃)；2.87(m,3H,

NCH₃)；4.25-5.05(ms,4H,OCH₂,NCH₂)；7.20(m,3H,arom.)

Examples IV to 14

By the method of example IV-1, 10.8g 1-benzyloxycarbonyl-1-methyl-2- (3-indolylmethyl) -hydrazine and 8.02g benzyl bromoacetate were trisected to give 6.41g of benzyl [ 2-benzyloxycarbonyl-2-methyl-1- (3-indolylmethyl) -hydrazyl ] -carbonyloxy-acetate which was pure and 7.04g (76% of theory) with a small amount of impurities.

¹H NMR(500MHz,CDCl₃)δ[ppm]:2.83(m,3H,NCH₃)；4.10-5.35(ms6H,NH₂,

OCH₂,CH₂Ph)；7.35(m,15H,arom)；8.05(brs,1H,NH)

Examples IV to 15

By the method of example IV-1, 1-benzyloxycarbonyl-1-methyl-2- (2, 2-dimethyl-1, 3-dioxo-4-yl) -methyl-hydrazine and benzyl bromoacetate gave [ 2-benzyloxycarbonyl-2-methyl-1- (2, 2-dimethyl-1, 3-dioxo-4-yl) -methyl-2-methyl-hydrazyl hydrazine]-carbonyloxy-acetic acid benzyl ester.¹H NMR(500MHz,CDCl₃)δ[ppm]:1.23to1.43(m,6H,C(CH₃)₂；3.12-3.20(m3H,NCH₃)；3.25-4.97(m,7H,OCH₂,NCH₂,NCH₂CH,OCHCH₂O):5.17(m.4H,2×CH₂Ph)；7.35(m,1H,arom).

Examples IV to 16

By the method of example IV-13, 7.13g 1-tert-butoxycarbonyl-1- (2-chloro-5-pyridyl) -methyl-2-ethyl-hydrazine and 4.87g tert-butyl bromoacetate gave 955g (86% of theory) of [ 2-tert-butoxycarbonyl-2- (2-chloro-5-pyridyl) -methyl-1-ethyl hydrazyl ] -carbonyloxy-acetic acid tert-butyl ester.

¹H NMR(500Hz,CDCl₃):1.0(m,3H,CH₃CH₂)；1.47(ms,18H,2×C(CH₃)₃)；

3.15-3.45(ms,2H,NCH₂)；4.05-5.0(ms,4H,NCH₂,OCH₂)；7.30/7.75/8.40(3m,

3×1H,arom).

Application examples

Example A

Haemonchus contortus/sheep

Haemonchus contortus infected sheep were treated after the parasite latency expired.

The active compounds are administered orally as pure active compounds in gelatin capsules.

Efficacy was determined by quantitatively counting the number of nematode eggs excreted in feces before and after treatment.

Complete cessation of egg production after treatment means that the nematodes have been eliminated or killed and are no longer able to lay eggs (effective dose)

The following results were obtained:

active Compound examples No	Effective dose mg/kg
		Ⅰ-2	5
Ⅰ-3	5
		Ⅰ-11	5

Example B

Cabbage moth (Plutella) assay

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 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by immersion in a preparation of the active compound to the desired concentration and infested with caterpillars of the diamondback moth (Plutella aculeatus) while the leaves are still moist.

After a certain time, the percent kill was determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars were killed.

In this test, the compounds of preparation example I-2, for example at an active compound concentration of 0.1% give a kill of 100% after 7 days.

Claims (8)

1. Oxadiazine derivatives of formula (I)Wherein

R¹And R²Each independently of the others represents hydrogen, alkyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, carboxyalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, arylalkyloxycarbonylalkyl, carbamoylalkyl, aminoalkyl, each optionally substituted by halogenArylalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxycarbonylaminoalkyl, alkylcarbonyl, cycloalkylcarbonyl or in each case optionally substituted by halogen, hydroxy, nitro, cyano, amino, C₁-C₄-alkylamino, di- (C)₁-C₄-) alkylamino, benzylamino, dibenzylamino, protected amino, C₁-C₆-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy-substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, arylcarbonyl, heterocyclylalkyl, heteroaryl or heteroarylalkyl, or

R¹,R²And the two connecting ammonia atoms represent optionally substituted halogen-, hydroxy-, nitro-, cyano-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-or C₁-C₄-a haloalkoxy-substituted heterocycle,

R³and R⁴Each independently of the others represents hydrogen, alkyl, alkenyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, arylalkyloxycarbonylalkyl, carbamoylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylcarbonyl, cycloalkylcarbonyl, each optionally substituted by halogen, hydroxy, cyano, C₁-C₆-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy radical, C₁-C₄-haloalkoxy, benzyloxy or by C₁-C₄Alkyl-and/or phenyl-trisubstituted silyloxy-substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl, or R³And R⁴Together represent an alkylene group or a residue (a)Wherein

R⁵And R⁶Each independently of the others represents hydrogen, alkyl, alkenyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylcarbonyl, each optionally substituted by halogen-, hydroxy-, nitro-, C₁-C₆-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, phenoxy-, amino-, C₁-C₄Alkylamino or di- (C)₁-C₄) -alkylamino-substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl,

Q¹and Q²Each independently represents oxygen or sulfur,

except for 6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione.

2. A process for preparing the oxadiazine derivatives of formula (I) according to claim 1,wherein

R¹And R²Each independently of the others represents hydrogen, alkyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, carboxyalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, arylalkyloxycarbonylalkyl, carbamoylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxycarbonylaminoalkyl, alkylcarbonyl, cycloalkylcarbonyl, each optionally substituted by halogen, hydroxy, nitro, cyano, amino, C₁-C₄-alkylamino, di- (C)₁-C₄-) alkylamino, benzylamino, dibenzylamino, protected amino, C₁-C₆-alkyl radical，C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy-substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, arylcarbonyl, heterocyclylalkyl, heteroaryl or heteroarylalkyl, or

R¹,R²And the two connecting nitrogen atoms represent optionally substituted halogen-, hydroxy-, nitro-, cyano-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-or C₁-C₄-a haloalkoxy-substituted heterocycle,

R³and R⁴Each independently of the others represents hydrogen, alkyl, alkenyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, arylalkyloxycarbonylalkyl, carbamoylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylcarbonyl, cycloalkylcarbonyl, each optionally substituted by halogen, hydroxy, cyano, C₁-C₆-alkyl radical, C₁-C₄-haloalkyl radical, C₁-C₄-alkoxy radical, C₁-C₄-haloalkoxy, benzyloxy or by C₁-C₄Alkyl-and/or phenyl-trisubstituted silyloxy-substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl, or

R³And R⁴Together represent an alkylene group or a residue (a)Wherein

R⁵And R⁶Each independently of the others represents hydrogen, alkyl, alkenyl, hydroxyalkyl, alkanoyloxyalkyl, alkoxyalkyl, arylalkoxyalkyl, mercaptoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, aryloxycarbonylalkyl, aminoalkylalkylAlkylaminoalkyl, dialkylaminoalkyl, alkylcarbonyl or represents in each case optionally halogen-, hydroxy-, nitro-, C₁-C₆-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, phenoxy-, amino-, C₁-C₄Alkylamino or di- (C)₁-C₄) -alkylamino-substituted cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl,

Q¹and Q²Each independently of the others, oxygen or sulphur, except for 6, 6-diphenyl- (1,3,4) -oxadiazine-2, 5-dione,

is characterized in that

A) (1,3,4) -oxadiazine derivatives of formula (I-a)Wherein

R¹To R⁴And Q¹Each as defined above, is capable of,

prepared by reacting carbazates of the formula (II) in the presence of reaction assistants and diluents, if appropriate in the presence of bases,wherein

R¹To R⁴And Q¹Each as defined above, is capable of,

B) (1,3,4) -oxadiazine derivatives of formula (I-b)Wherein

R¹To R³,Q¹And Q²Each as defined above, R^4-1Representative and R⁴As well as groups other than hydrogen,

by reacting (1,3,4) -oxadiazine derivatives of the formula (I-c) with compounds of the formula (III), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants,wherein

R¹And R²Have a definition other than that of hydrogen,

R³,Q¹and Q²Each as defined above, is capable of,

R^4-1-E (III), wherein

R^4-1As defined above, the above-mentioned,

and E represents an electron-withdrawing leaving group,

C) (1,3,4) -oxadiazine derivatives of formula (I-d)Wherein

R¹To R³,Q¹And Q²Each as defined above, R^4-2Represents residue (b)Wherein

R⁵And R⁶Each independently represents hydrogen, alkyl optionally substituted by halogen or optionally substituted by halogen, hydroxy, nitro, C₁-C₆-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, phenoxy-, amino-, C₁-C₄Alkylamino or di- (C)₁-C₄) -alkylamino-substituted aryl, or,

R³and R^4-2Together represent residue (a)Wherein

R⁵And R⁶As defined above, the above-mentioned,

by reacting (1,3,4) -oxadiazine derivatives of the formula (I-c), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants, with ketones or aldehydes of the formula (IV) and subsequently, if appropriate, removing water,wherein

R¹To R³,Q¹And Q²Each as defined above, is capable of,

R⁵-CO-R⁶(IV) in which

R⁵And R⁶As defined above, the above-mentioned,

D) (1,3,4) -oxadiazine derivatives of formula (I-e)Wherein

R^1-1Representative and R¹Same radicals other than hydrogen, R²To R⁴,Q¹And Q²Each as defined above, is capable of,

by reacting (1,3,4) -oxadiazine derivatives of the formula (I-f) with compounds of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,wherein

R²To R⁴,Q¹And Q²Each as defined above, is capable of,

R^1-1-E (V), wherein

R^1-1As defined above, and

e represents an electron-withdrawing leaving group,

E) (1,3,4) -oxadiazine derivatives of formula (I-g)Wherein

R¹,R³,R⁴,Q¹And Q²Each as defined above, R^2-1Representative and R²As well as groups other than hydrogen,

by reacting (1,3,4) -oxadiazine derivatives of the formula (I-h) with compounds of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants,wherein

R¹,R³,R⁴,Q¹And Q²Each as defined above, is capable of,

R^2-1-E (VI), wherein

R^2-1As defined above, the above-mentioned,

and E represents an electron-withdrawing leaving group,

F) of formula (I)(1,3,4) -oxadiazine derivativesWherein

R¹To R⁴,Q¹And Q²Each as defined above, is capable of,

by reacting and cyclocondensing a compound of the formula (VII) with a compound of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of a reaction promoter,wherein

R¹To R⁴And Q²Each as defined above, is capable of,wherein

Y¹Represents chlorine, trichloromethoxy, C₁-C₄Alkoxy, phenoxy, 1-imidazolyl or 1,2, 4-triazolyl and

Y²represents chlorine, trichloromethoxy, 1-imidazolyl or 1,2, 4-triazolyl,

Q¹as defined above, the above-mentioned,

G) (1,3,4) -oxadiazine derivatives of formula (I)Wherein

R¹To R⁴,Q¹And Q²Each as defined above, is capable of,

by cyclocondensation of a compound of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of reaction assistants,wherein

R¹To R⁴,Q¹,Q²And Y¹Each as defined above, is capable of,

H) (1,3,4) -oxadiazine derivatives of formula (I-i)Wherein

R¹To R⁴And Q¹Each as defined above, is capable of,

by reacting, if appropriate in the presence of a diluent(1,3,4) -oxadiazine derivatives of formula (I-a) are prepared by reaction with a sulphinylation agent,wherein

R¹To R⁴And Q¹Each as defined above.

3. The process according to claim 2, characterized in that the starting hydrazinoformic acid ester of the formula (II) in process A) is prepared by the following process:

a) cleavage of the protective group A from the C-terminally protected hydrazinoformate of the formula (X) by methods known per se²Wherein

R¹,R²,R³,R⁴And Q¹Each as defined in claim 2, respectively,

A²represents a C-terminal protecting group,

in addition to the following compounds of formula (X), wherein, simultaneously, R²And R⁴Represents hydrogen, R¹Represents C₁-C₅-alkyl, and R³Methyl or benzyl; and

in addition to the following compounds of formula (X), wherein R¹Represents methyl, R²Represents hydrogen, Q¹Represents oxygen, R³Represents phenyl, R⁴Represents hydrogen, and A²Represents a tert-butyl group; and

also in addition to the following compounds of the formula (X), in which R¹Represents methyl, R²Represents phenylcarbonyl, R³Represents methyl or phenyl, R⁴Represents hydrogen, Q¹Represents oxygen, and A²Represents a benzyl group;

or

b) Cleavage of the protecting group A from the N-terminally protected hydrazinoformate of formula (XI) by methods known per se³Wherein

R¹,R²,R³,R⁴And Q¹Are each as defined in claim 2，

A³Represents an N-terminal protecting group.

4. Hydrazinoformic acid esters of formula (II)Wherein

R¹,R²,R³,R⁴And Q¹Each as defined in claim 2, respectively,

in addition to the following compounds of formula (II) wherein, simultaneously, R²And R⁴Each represents hydrogen, R¹Represents hydrogen or C₁-C₅-alkyl, and R³Methyl or benzyl; and

in addition to the following compounds, wherein, simultaneously, R¹Represents methyl, R²Represents phenylcarbonyl, R³Represents phenyl, R⁴Represents hydrogen, and Q¹Represents sulfur; and

also in addition to the following compounds, wherein R¹Represents methyl, R²Represents phenylcarbonyl, R³Represents methyl or phenyl, R⁴Represents hydrogen, and Q¹Represents oxygen.

5. Pesticidal compositions, characterized in that they contain at least one 1,3, 4-oxadiazine derivative of formula (i) according to claim 1.

6. Use of 1,3, 4-oxadiazine derivatives of formula (i) according to claim 1 for controlling pests.

7. A method for controlling pests, characterized in that a1, 3, 4-oxadiazine derivative of formula (i) according to claim 1 is allowed to act on the pests and/or their habitat.

8. Use of 1, 3-oxadiazine derivatives of formula (i) according to claim 1 for preparing insecticides and endoparasiticides.