EP1474418A1

EP1474418A1 - Substituted 4-hetaryl-pyrazolines as pest control agents

Info

Publication number: EP1474418A1
Application number: EP03737279A
Authority: EP
Inventors: Fritz Maurer; Rainer Fuchs; Christoph Erdelen; Jörg KONZE; Peter Lösel; Andreas Turberg
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2002-02-07
Filing date: 2003-01-28
Publication date: 2004-11-10
Also published as: AU2003244438A1; BR0307527A; US7345009B2; US20080064732A1; JP2005523274A; WO2003066625A1; DE10205057A1; CN1646521A; US20050119128A1; KR20040075111A

Abstract

The invention relates to novel substituted pyrazolines of formula (I) wherein R1, R2, R3 and R4 have the designations cited in the description, a plurality of methods for producing said substances, and the use of the same for controlling pests. The invention also relates to novel intermediate products and to methods for producing the same.

Description

SUBSTITUTED 4-HETARYL-PYRAZOLINE AS A PEST CONTROL

The present invention relates to new substituted 4-hetaryl-pyrazolines, processes for their preparation and their use as pesticides.

It is known that certain substituted pyrazolines have insecticidal and acaricidal properties (cf. e.g. DE-A 44 16 112, EP-A 0 679 644 or EP-A 0 438 690). However, the action of these compounds is not always entirely satisfactory, especially at low active compound concentrations and application rates.

New substituted 4-hetaryl-pyrazolines of the formula (I) have been found

in which

R ^{1 represents} optionally substituted oxadiazolyl, thiadiazolyl or tetrazolyl,

R represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl or cyano,

R ^{3 represents} halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl or cyano and

R, 4 represents hydrogen, cyanomethyl or alkoxycarbonyl.

Depending on the type and number of the substituents, the compounds of the formula (I) can, if appropriate, be used as geometric and / or optical isomers, regions Isomers or configuration isomers or their isomer mixtures are present in different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention.

It was also found that the substituted 4-hetaryl-pyrazolines of

Formula (I) is obtained by

a) pyrazolines of the formula (II)

in which

1 9

R and R have the meanings given above,

with isocyanates of the formula (III)

in which

R has the meanings given above,

optionally in the presence of a diluent and optionally in

Reacting the presence of a catalyst; and

b) optionally the pyrazoline derivatives of the formula (Ia) according to the invention thus obtained

R, ι, R and R have the meanings given above,

with halides of the formula (IV). Shark ¹ - R ⁴ (IV) in which

R has the meanings given above and

Shark ^{1 represents} halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of a base; or

c) anilines of the formula (V)

in which

R and R have the meanings given above,

first reacted with phosgene, in the presence of a diluent and optionally in the presence of a base, and the carbamoyl chlorides of the formula (VI) thus obtained in which

R ³ and R ^{4 have} the meanings given above,

directly or after intermediate isolation with pyrazolines of the formula (II)

in which

R and R have the meanings given above,

in the presence of a diluent and optionally in the presence of a base.

Finally it was found that the new substituted 4-hetaryl-pyrazolines of

Formula (I) has highly pronounced biological properties and is particularly suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector.

The 4-hetaryl-pyrazolines according to the invention are generally defined by the formula (I).

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below: R ¹ preferably stands for optionally substituted oxadiazolyl or thiadiazolyl, examples of which may be mentioned as substituents: optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl or optionally substituted arylalkyl; and for optionally substituted tetrazolyl, examples of which may be mentioned as substituents: optionally substituted alkyl, optionally substituted alkylthio or alkylsulfonyl, in each case optionally substituted aryl or arylalkyl or optionally substituted cycloalkyl.

R ² preferably represents fluorine, chlorine, bromine, iodine; C ₁ -C ₄ haloalkyl, Cι-C - alkoxy, -C ₄ -haloalkoxy, C ₁ -C ₄ alkylthio, _Cι-C4 haloalkylthio, Q-C - alkylsulfonyl, C ₁ -C haloalkylsulfinyl, C ₁ - C -haloalkylsulfonyl or cyano.

R ³ preferably represents fluorine, chlorine, bromine, iodine; C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, Cι _. -C ₄ -alkylthio ₅ C ₁ -C -haloalkylthio, C _\ - C -haloalkylsulfinyl, C ₁ -C -haloalkylsulfonyl or cyano.

R preferably represents hydrogen, cyanomethyl or Ci- -alkoxy-carbonyl.

R ¹ particularly preferably represents in each case optionally substituted oxadiazolyl, or thiadiazolyl, which are exemplified as substituents: C - C alkyl, C ₁ -C ₄ haloalkyl, Cι-C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, - Gr alkylthio, CrC ₄ -haloalkylthio, and in each case optionally mono- to triple, identical or different, substituted by halogen, C ₁ -C ₄ -haloalkyl or C ₁ -C ₄ -haloalkoxy-substituted phenyl or benzyl; or optionally substituted tetrazolyl, wherein mentioned as substituents: C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkylthio, Cι-C - alkylsulfonyl, furthermore in each case optionally mono- to trisubstituted by identical or phenyl or benzyl substituted by halogen, CrG _t -haloalkyl or dC ₄ -haloalkoxy, furthermore optionally Multiple to triple, identical or different, cyclopentyl or cyclohexyl substituted by CrC ₄ alkyl.

R ² particularly preferably represents fluorine, chlorine, bromine, iodine, cyano; C ₁ -C ₂ -alkylthio, CrC ₂ - alkylsulfonyl and C ₁ -C ₂ haloalkyl, Cι-C ₂ haloalkoxy;

C ₁ -C ₂ haloalkylthio or C _! -C ₂ -Halogenalkylsulfonyl each having 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and

Bromine.

R ³ particularly preferably represents chlorine, bromine, iodine, cyano; as well as for -C ₂ -

Haloalkyl, Cι-C ₂ haloalkoxy, C ₁ -C ₂ haloalkylthio, C ₁ -C ₂ -Halo- genalkylsulfinyl or C ₁ -C ₂ haloalkylsulfonyl having in each case. 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine.

R particularly preferably represents hydrogen, cyanomethyl or C ₁ -C ₄ -alkoxycarbonyl.

R ¹ very particularly preferably represents the following thiadiazolyls and oxadiazolyls:

in which

X ¹ and X ² independently of one another are hydrogen, C - alkyl, C ₁ -C ₄ -Ha- logenalkyl, C CJ alkylthio, C ₁ -C ₄ -haloalkylthio, and in each case optionally mono- to trisubstituted by identical or different substituents Halogen, C ₁ -C ₂ haloalkyl or C ₁ -C ₂ haloalkoxy each having 1 to 3 identical or different halogen atoms from the Are fluorine, chlorine and bromine substituted phenyl or benzyl; as well as for the following tetrazolyls:

in which

X ³ and X ⁴ independently of one another for hydrogen, C ₁ -C alkyl, C ₁ -C ₂ haloalkyl with 1 to 3 identical or different halogen atoms from the series fluorine, chlorine and bromine; -C ₄ - alkylthio, -C ₄ alkyl sulfonyl, represents in each case optionally mono- to trisubstituted by identical or different substituents from halogen, Cι-C ₂ haloalkyl, or C ₁ -C ₂ alkoxy-halo same with in each case 1 to 3 identical or different halogen atoms from the series fluorine, chlorine and bromine substituted phenyl or benzyl, as well as cyclopentyl or cyclohexyl which are optionally monosubstituted to trisubstituted by C 1 -C ₄ -alkyl.

R ² very particularly preferably represents fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

R ³ very particularly preferably represents chlorine, bromine, iodine, cyano; trifluoromethyl,

Trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,

R ⁴ very particularly preferably represents hydrogen, cyanomethyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl and n-, i-, s- and t-

Butoxycarbonyl.

R ¹ particularly preferably represents the following thiadiazolyls and oxadiazolyls: in which

X ¹ and X ^{2 are} independently hydrogen; Methyl, ethyl, n- or i-

Propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoromethoxy or trifluoromethylthio as well as phenyl or benzyl optionally substituted once or twice, identically or differently by fluorine, chlorine, bromine, trifluoromethyl or trifluoromethoxy;

as well as for the following tetrazolyls:

in which

X ³ to X ⁴ independently of one another for hydrogen; Methyl, ethyl, n- or i-

Propyl, n-, i-, s- or t-butyl; Fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl; for each optionally single to double, identical or different by fluorine, chlorine, bromine, methyl,

Methoxy, trifluoromethyl or trifluoromethoxy substituted phenyl or benzyl, and also represent cyclohexyl which is monosubstituted or disubstituted by methyl. • R ² particularly preferably represents fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

R ³ particularly preferably represents chlorine, bromine, iodine, cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

R ⁴ particularly preferably represents hydrogen or cyanomethyl.

Furthermore, very particular preference is given to compounds of the formula (I) in which

R ^{1 represents} optionally substituted tetrazolyl, where the following may be mentioned as substituents: C ₁ -C alkyl, C ₁ -C haloalkyl, C ₁ -C alkylthio, C ₁ -C alkyl sulfonyl, furthermore in each case optionally once to three times, the same or differently substituted by halogen, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ -haloalkoxy-substituted phenyl or benzyl, each further optionally monosubstituted to trisubstituted by identical or different substituents from Cι-C ₄ alkyl, cyclopentyl or cyclohexyl.

R ^{2 represents} chlorine.

Furthermore, very particular preference is given to compounds of the formula (I) in which R ^{4 represents} hydrogen.

Furthermore, very particular preference is given to compounds of the formula (I) in which R ^{4 represents} cyanomethyl.

Furthermore, very particular preference is given to compounds of the formula (I) in which R ^{3 represents} trifluoromethoxy or trifluoromethylthio.

The radical definitions or explanations listed above or listed in preferred areas apply to the end products and to the initial and intermediate products accordingly. These residual definitions can be combined with one another, i.e. also between the respective preferred areas.

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

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

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

In the radical definitions listed above and below, hydrocarbon radicals, such as alkyl - are also straight-chain or branched as far as possible, even in compounds with heteroatoms such as alkoxy.

If, for example, 3- (4-chlorophenyl) -4- (5-methyl-l, 3,4-thiadiazol-2-yl) - 4,5-dihydro-1H-pyrazole and 4-trifluoromethoxyphenyrisocyanate are used as starting materials, then the The course of the reaction of process (a) according to the invention can be represented by the following formula:

If, for example, 3- (4-chlorohenyl) -4- (5-methyl-l, 3,4-thiadiazol-2-yl) - 4,5-dihydro-l-pyrazolecarboxylic acid-4-trifluoromethoxyanilide and bromoacetonitrile are used as starting materials, the reaction sequence of process (b) according to the invention can be represented by the following formula:

If, for example, N-cyanomethyl-4-trifluoromethoxyaniline, phosgene and 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) -4,5-dihydro-1H-pyrazole are used as starting materials, the course of the reaction can Process (c) according to the invention can be represented by the following formula:

+ Phosgene

Formula (II) provides a general definition of the pyrazolines to be used as starting materials for carrying out processes (a) and (c) according to the invention. In this formula, R ¹ and R ^{2 are} preferably, particularly preferably, very particularly preferably and particularly preferably for those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred, very particularly for these radicals were preferred or particularly preferred.

The pyrazolines of formula (II) are new and also the subject of this application. They are obtained by using substituted acetophenones of the formula (VII)

in which

R, 1 "and J Ώ R2 have the meanings given above,

in a first stage with known bis-dialkylaminomethanes of the formula (VIÜ) (Alk) ₂ N-CH ₂ -N (Alk) ₂ (VIII) in which

Alk represents C ₁ -C alkyl, preferably methyl, in the presence of an inert, organic solvent (preferably halogenated hydrocarbons, such as methylene chloride or ethylene chloride) at temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 80 ° C (see, for example, EP-A 0 546 420) and the resulting dialkylammoalkyl ketones of the formula (IX)

in which

R ¹ , R ² and Alk have the meanings given above,

optionally isolated and reacted in a second stage with hydrazine (hydrate) in the presence of an inert organic solvent (preferably alcohols, such as methanol or ethanol) at temperatures between 0 ° C. and 80 ° C., preferably between 20 ° C. and 50 ° C. (see also the manufacturing examples).

Some of the substituted acetophenones of the formula (VII) are known (see, for example, Chemiker-Zeitung 1989, 113, 217-219; Synthesis 1988, 453-55; J. Chem. Soc, Perkin Trans. 1 1986, 1157-63; chemist -Newspaper 1985, 109, 432-433 and WO 99/08678) or they can be obtained in a generally known manner.

For example, the acetophenones of the formula (VII a)

in which

R and X have the meanings given above, can be obtained by using haloacetophenones of the formula (X)

in which

R ^{2 has} the meanings given above and

Hai ^{2 represents} halogen, preferably chlorine or bromine,

with tetrazoles of the formula (XI)

in which

X has the meanings given above,

in the presence of an organic or inorganic base (eg potassium carbonate) and optionally in the presence of an inert organic solvent (eg acetonitrile), at temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 80 ° C (cf. also the manufacturing examples).

The haloacetophenones of the formula (X) and the tetrazoles of the formula (XI) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

Acetophenones of the formula (VII b)

in which,

R and X have the meanings given above,

can be obtained by using 2-cyanoacetophenones of the formula (XII)

in which

R ^{2 has} the meanings given above,

with sodium azide and amine hydrochloride (for example triethylamine-nyαrocnioriü) in the presence of an inert solvent (for example acetonitrile, dimethylformamide, toluene), preferably under reflux (cf. also the preparation examples) and, if appropriate, the acetophenones of the formula (VII c)

in which,

R ^{2 has} the meanings given above,

with compounds of the formula (XIII)

EX ^{3 "1} (Xiπ) in which

X ^{3 "1} for C ₁ -C alkyl, C ₁ -C ₂ haloalkyl with 1 to 3 identical or different

Halogen atoms from the series fluorine, chlorine and bromine; -Q- alkylthio, C _\ - C - alkylsulfonyl, each optionally mono- to triple, the same or different by halogen, C ₁ -C ₂ haloalkyl or C ₁ -C ₂ haloalkoxy with 1 to 3 identical or different halogen atoms from the series fluorine, chlorine and bromine substituted phenyl or benzyl, and for each optionally monosubstituted to trisubstituted by C ₁ -C ₄ alkyl substituted cyclopentyl or cyclohexyl and

E for an anionic leaving group, preferably chlorine, bromine, iodine,

Acetoxy, tosyl or mesyl,

in the presence of an organic or inorganic base (eg potassium carbonate) and optionally in the presence of an inert organic solvent (eg acetonitrile), at temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 50 ° C (cf. also the manufacturing examples).

In the preparation of acetophenone of the formula (VIIIb), in which X represents a tertiary alkyl radical, it proves to be advantageous in some cases to mix the acetophenones of the formula (VIIc) with tertiary alcohols in the presence of strong acids, e.g. Implement trifluoroacetic acid and / or sulfuric acid.

The 2-cyanoacetophenones of the formula (XII) and the compounds of the formula (Xffl) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

The acetophenones of the formula (VII d)

in which

9 1

R and X have the meanings given above,

can be obtained by using ethyl benzoate of formula (XIV) in which

R ^{2 has} the meanings given above,

with methylthiadiazoles of the formula (XV)

in which

X ^{1 has} the meanings given above,

in the presence of a strong base (e.g. sodium hydride or tert-butyllithium) in the presence of an inert organic solvent (e.g. toluene), preferably under reflux (see also Chemiker-Zeitung 1989, 113, 217-219).

The acetophenones with other thiadiazolyl radicals can be obtained in a corresponding manner.

The ethyl benzoates of the formula (XIV) and the methylthiadiazoles of the formula (XV) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

The acetophenones of the formula (VII e)

in which

R and X have the meanings given above, can be obtained by using amidoximes of the formula (XVI)

in which

R> 2 has the meanings given above,

heated under reflux in a conventional manner with corresponding acetic acid derivatives substituted by X, such as preferably alkyl esters or anhydride.

The amidoximes of the formula (XVI) can be obtained in a generally known manner by reacting 2-cyanoacetophenones of the formula (XII) or their ketals with hydroxylamine hydrochloride in the presence of a base (e.g. potassium carbonate).

The acetophenones of the formula (VII f)

in which

R and X have the meanings given above,

can be obtained by using hydrazides of formula (XVII)

in which R has the meanings given above,

heated under reflux in a conventional manner with corresponding acetic acid derivatives substituted by X ² , such as preferably alkyl esters, also in the form of corresponding orthoesters.

The hydrazides of the formula (XVII) can be obtained in a generally known manner by reacting corresponding ester derivatives with hydrazine.

The acetophenones of the formula (Vn g)

in which

9 9

R and X have the meanings given above,

can be obtained by using esters of formula (XVIII)

(XVIII) in which

R and All have the meanings given above,

in the usual way with amidoximes of the formula (XIX)

in which X ^{2 has} the meanings given above,

heated under reflux.

The esters of the formula (XVIH) and the amidoximes of the formula (XIX) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

Formula (III) provides a general definition of the ϊsocyanates to be used as starting materials in process (a) according to the invention. In this

Formula R ^{3 is} preferably, particularly preferably, very particularly preferably or particularly preferably for those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred, very particularly preferred or in particular for this radical were preferred.

The isocyanates of the formula (III) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

Formula (IV) provides a general definition of the halides to be used as starting materials for carrying out process (b) according to the invention. In this formula, R ^{4 is} preferably, particularly preferably, very particularly preferably or particularly preferably for those meanings which have already been given in connection with the description of the compounds of the formula (I) according to the invention

^■ rest have been mentioned as preferred, particularly preferred, very particularly preferred or particularly preferred. Shark ¹ preferably represents chlorine or bromine.

The halides of the formula (IV) are generally known compounds of organic chemistry. Formula (V) provides a general definition of the anilines to be used as starting materials for carrying out process (c) according to the invention. In this formula, R and R ^{4 are} preferably, particularly preferably, very particularly preferably and particularly preferably for those meanings which have already been given in connection with the description of the compounds of the formula (I) according to the invention

Residues were mentioned as preferred, particularly preferred, very particularly preferred or particularly preferred.

The anilines of the formula (V) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

Process (a) according to the invention is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane,

Hexane, heptane, cyclohexane, petroleum ether, petrol, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, methyl tert-butyl ether, methyl ether tert-amyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl or

Methyl isobutyl ketone, esters such as methyl or ethyl acetate, nitriles such as e.g. Acetonitrile or propionitrile, amides such as e.g. Dimethylformamide, dimethyl acetamide and N-methylpyrrolidone as well as dimethyl sulfoxide, tetramethylene sulfone or hexamethylene phosphoric acid triamide

Process (a) according to the invention is preferably also carried out using a catalyst. In particular, tertiary organic amines such as triethylamine are suitable as catalysts.

The reaction temperatures in process (a) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 120 ° C, preferably at temperatures between 20 ° C and 80 ° C. Process (a) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (a) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in a smaller excess. The processing is carried out according to customary methods (cf. the manufacturing examples).

Processes (b) and (c) according to the invention are preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as

Pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycoledimethyl ether and tetrahydrofuran dimethyl ether, tetrahydrofuran and tetrahydrofuran , Ketones such as acetone, methyl ethyl, methyl isopropyl or methyl isobutyl ketone, esters such as methyl acetate or ethyl acetate, nitriles such as Acetonitrile or propionitrile, amides such as e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone as well as dimethyl sulfoxide, tetramethylene sulfone or hexamethylene phosphoric acid triamide.

Bases which can be used in carrying out processes (b) and

(c) all acid binders which can usually be used for such reactions are used. Alkali metal and alkaline earth metal hydrides, such as lithium, sodium, potassium or calcium hydride; Alkali metal and alkaline earth metal hydroxides, such as lithium, sodium, potassium or calcium hydroxide; Alkali metal and alkaline earth metal carbonates or bicarbonates, such as sodium or potassium carbonate or bicarbonate or calcium carbonate; Alkali metal acetate, such as sodium or potassium acetate, alkali metal alcoholates, such as sodium or Potassium tert-butoxide; also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl , 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methylpyridine, l, 5-diazabicyclo [4.3.0] -non-

5-ene (DBN), 1,8-diaza-bicyclo [5.4.0] -undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO).

The reaction temperatures in process (b) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 120 ° C, preferably at temperatures between 20 ° C and 80 ° C.

Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (b) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use the halide and the base in excess. The processing is carried out according to customary methods (cf. the manufacturing examples).

The reaction temperatures in process (c) according to the invention can be varied within a substantial range. In general, temperatures between -10 ° C and 120 ° C, preferably at temperatures between 0 ° C and 100 ° C.

Process (c) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (c) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use the chloride and the base in excess. Working up is carried out using customary methods (cf. the production examples).

With good plant tolerance and favorable warm-blooded toxicity, the active substances are suitable for controlling animal pests, especially insects,

Arachnids and nematodes found in agriculture, in forests, in the protection of stocks and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus. From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spp.

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus.

From the order of the Orthoptera e.g. Acheta domesticus, Gryllotälpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp. From the order of the Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci,

Thrips palmi, Frankliniella accidentalis.

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

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci,

Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobixiaieaeaeisphis, Saobis corniophobia, Neobis Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppppi, Fitrella, Phyllocnist spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionellaanaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaella pellaella , Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephuspp sulcatus, Cosmopolites sordidus,

Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Agribiole spp., Tenebrio molitor. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,

Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp. From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp. From the class of the Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., ., Psoroptes ^' spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.

The substances according to the invention can be used with particularly good success for combating plant-damaging insects, such as e.g. against caterpillars of the cotton capsule worm (Heliothis virescens and Heliothis armigera), the larvae of the horseradish leaf beetle (Phaedon cochliariae), the eggs or larvae and caterpillars of the cabbage cockroach (Plutella xylostella) as well as caterpillars of the host worm (Spodoptera exigugio) and Spodoptera exigua.

If appropriate, the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungal agents and bactericides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants that can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, impregnated with active ingredients

Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say

Emulsifiers and / or dispersants and / or foaming agents.

If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methylsobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers: for example ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; Possible emulsifiers and / or foam-generating agents are: ^' for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid

Esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Ligmn sulfite liquor and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%. The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

Aldirnorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole,

azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, butbiobate,

Calcium polysulphide, carpropamid, capsimycin, captafol, captan, carbendazim, carbonyl xin, carvone, chinomethionat (Quinomethionat) Chlobenthiazon, chlorfenazole, chlorides roneb, chloropicrin, chlorothalonil, chlozolinate, Clozylacon, Cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb , dichlorophen, diclobutrazol, dichlofluanid, diclomezine, dicloran, Dietho- fencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, Dipyrithione, Ditalimfos, dithianon, dodemorph, dodine, Drazoxolon, Ediphenphos, epoxiconazole, etaconazole, ethirimol , Etridiazol, Famoxadon, Fenapanil, Fenarimol, Fenbuconazol, Fenfuram, Fenhexamid, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromidololidololidololidololidololidololidololidololidololidol, fluoridololidol, fluoridololidol, fluoridololidol, fluoridololidol , Flutriafol, folpet, fosetyl-aluminum, fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole , Furconazole-cis, Furmecyclox,

Guazatin, hexachlorobenzene, hexaconazole, hymexazole, Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Iprovalicarb, Irumamycin, Isopropothiolan, Isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations such as: copper hydride, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and

B ordeaux mix,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin, Nickel-dimethyldithiochalamopropyl, Nitrile

OFIRRACE , Pyrazo- phos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

Quinconazole, quintozen (PCNB), quinoxyfen sulfur and sulfur preparations, spiroxamines,

Tebuconazole, cyofen tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, thionyl, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, zol Tricycla-, tridemorph, trifloxystrobin, Triflumizol, Triforin, Triticonazol, Uniconazol, Validamycin A, Vinclozolin, Viniconazol, Zarilamid, Zineb, Ziram as well as Dagger G, OK-8705, OK-8801, α- (1, 1 -Dimethy lethy l) -ß- (2-phenoxy ethyl) - 1 H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-fluoro-ß-propyl-1H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-methoxy-α-methyl-1H-1, 2,4-triazol-1-ethanol, α- (5-methyl-l, 3-diox.an-5-yl ) -ß - [[4- (trifluoromethyl) phenyl] methylene] -IH-l, 2,4-triazole-1-ethanol, (5RS, 6RS) -6-hydroxy-2,2,7,7- tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone,

(E) -α- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide, l- (2,4-dichlorophenyl) -2- (lH-l, 2,4-triazol-l-yl) -ethanone- O- (phenyhnethyl) oxime 1 - (2-methyl-1-naphthalenyl) - lH-ρyrrol-2,5-dione, l- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione, l - [( Diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2,4-dichlorophenyl) -l, 3-dioxolan-2-yl] methyl] -lH-imidazole, l - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -lH-l, 2,4-triazole, l- [l- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] - 1H-imidazole, 1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

2 ^ 6'-Dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide, 2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate .

2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,

2,6-dichloro-N- [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole, 2 - [[6-deoxy-4-O- (4-O-methyl-β-D-glycopyranosylj -α-D-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) -pentandinitril,

2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1 H-inden-4-yl) -3-pyridinecarboxamide, 2-chloro-N- (2,6-dimethylphenyl) -N - (isothiocyanatomethyl) acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1 - [4- (difluoromethoxy) phenyl] -1 H-pyrrole-2,5-dione,

3,5-dichloro-N- [cyano [(l-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3 - (1,1-dimethylpropyl-1-oxo-lH-indene-2-carbonitrile, 3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,

4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) - IH-imidazole-1 -sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,

8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-chlorophenyl) -2- (1H-1, 2,4-triazol-1-yl) -cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethylmorpholine hydrochloride,

Ethyl - [(4-chlorophenyl) azo] cyanoacetate,

Potassium hydrogen carbonate, methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-IH-inden-1-yl) - 1H-imidazole-5-carboxylate,

Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazo ^{'lylcarbonyl)} -DL-alaninate,

Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2 -oxo-3-thienyl) acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,

N- (4-cyclohexylphenyl) - 1,4,5,6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine,

N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide, N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,

N- [2,2,2-trichloro-l - [(chloroacetyl) -amino] -ethyl] -benzamide,

N- [3-chloro-4,5-bis- (2-propynyloxy) phenyl] -N'-memoxy-methanimidamid,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-diethyl- [2- (dipropylamino) -2-oxoethyl3-ethylphosphoramidothioate, O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -1-benzopyran-2, 1 '(3Η) -isobenzofuran] -3'-one,

4- [3,4-dimethoxyphenyl) -3- (4-fluorophenyl) acryloyl] morpholine

bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides: Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb,

Alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin,

Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb,

Bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin,

Biopermethrin, bistrifluron, BPMC, bromophos A, bufencarb, buprofezin,

Butathiofos, butocarboxime, butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos,

Chlo yrifos, Chlorpyrifos M, Chlovaporthrin, Chromafenozide, Cis-Resmethrin,

Cispermethrin, clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos,

Cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,

Cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon,

Dichlorvos, dicofol, diflubenzuron, dimethoate, dimethylvinphos, diofenolan,

Disulfoton, Docusat-sodium, Dofenapyn,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothimocarb, Fenacrim

Fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate,

Fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,

Flumethrin, Flutenzine, Fluvalinate, Fonophos, Fosmethilan, Fosthiazate, Fubfen- prox, Furathiocarb, Granuloseviruses

Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,

Imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,

Nuclear polyhedron viruses, lambda cyhalothrin, lufenuron

Malathion, mecarbam, metaldehyde, methamidophos, metharhilic anisopliae, metharhilic flavoviride, methidathione, methiocarb, methoprene, methomyl,

Methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin,

Milbemycin, monocrotophos, Naled, Nitenpyram, Nithiazine, Novaluron

Omethoate, Oxamyl, Oxydemethon M

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat,

Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothoat,

Pymetrozine, Pyraclofos,. Pyresmethrin, pyrethrum, pyridaben, pyridathione,

Pyrimidifen, pyriproxyfen,

Quinalphos, ribavirin,

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos, Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron,

Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Tetradifon Thetacypermethrin ,. Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thuringiensin, Tralocythrin, Tralomethrin,

Triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,

Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302

Zeta-cypermethrin, zolaprofos

(IR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate

(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine -2 (lH) - imine

2- (2-Chloro-6-fluorophenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazole 2- (acetyloxy) -3 -dodecyl-1, 4-naphthalenedione

2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] -benzamide

2-Chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] benzamide

3-methylphenyl propylcarbamate

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -l-fluoro-2-phenoxy-benzene 4-chloro-2- (l, l-dimethylethyl) -5 - [[2- (2,6- dimethyl-4-ρhenoxyphenoxy) ethyl] thio] -

3 (2H) pyridazinone 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone

Bacillus thuringiensis strain EG-2348 benzoic acid [2-benzoyl-1 - (1, 1-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloro phhenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] cyanamide

Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde ethyl- [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy ] ethyl] carbamate

N- (3, 4,4-trifluoro-1-oxo-3 -butenyι) -g ycin

N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-lH-pyrazol-

1-carboxamide

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-riitro-guanidine N-methyl-N '- (1-methyl-2-propenyl) -1, 2-hydrazinedicarbothioamide

N-methyl-N'-2-propenyl-1, 2-hydrazinedicarbothioamide

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat

N-cyanomethyl-4-trifluoromethyl-nicotinamide

3,5-dichloro-l- (3,3-dichloro-2-propenyloxy) -4- [3- (5-trifluoromethylpyridin-2-yloxy) propoxy] benzene

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

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.

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

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

When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.

As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, wild or treated by conventional biological breeding, such as crossing or ^'protoplast fusion plant species and plant cultivars obtained and parts thereof. In a further preferred embodiment, transgenes are

Plants and plant varieties that have been obtained by genetic engineering methods, possibly in combination with conventional methods (Genetic Modified Organisms) and their parts treated. The term "parts" or "parts of plants" or "plant parts" was explained above.

Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or widening of the spectrum of action and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth and increased tolerance against high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible that go beyond the expected effects.

The preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous, valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated ripening, higher crop yields, higher quality and / or higher nutritional value Local products, higher shelf life and / or workability of the harvested products. Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes and cotton and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryIA (b), CryΙA (c), CryllA, CrylllA, CrylTfB2, Cry9c, Cry2Ab, Cry3Bb and CryTF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). As

Properties ("traits") are also particularly emphasized the increased defense of plants against fungi, bacteria and viruses by systemic acquirers Resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins. The properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene). The genes imparting the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are corn varieties, cotton varieties, soy varieties and potato varieties which are sold under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard®

(Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soybeans), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to Imidazolinone) and STS® (tolerance to sulfonylureas such as corn). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (e.g. maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

The active compounds according to the invention act not only against plants, hygiene and

Storage pests, but also in the veterinary sector against animal parasites (ectoparasites) such as shield ticks, leather ticks, and mite mites, Running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas. These parasites include:

From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina as well

Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp.,

Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

From the order Diptera and the subordinates Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,

Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.,

Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp.,

Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp ., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida e.g. Pulex spp., Ctenocephalides spp.,

Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of Acaria (Acarida) and the orders of the Meta and

Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,

Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,

Pneumonyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) e.g.

Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypppectoles spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats,

Horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice. By fighting these arthropods, deaths and reduced performance (in meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets,

Capsules, watering, drenching, granules, pastes, boluses, the feed-through method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal Application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), des

Washing, the powder and with the help of shaped articles containing active ingredients, such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.

When used for cattle, poultry, pets etc., you can use the active ingredients in

Use formula (I) as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10,000 times dilution, or use them as a chemical bath.

It has also been found that the compounds according to the invention have a high insecticidal action against insects which destroy industrial materials. The following insects may be mentioned by way of example and preferably, but without limitation:

Beetle like

Hylotrapes bajulus, Chlorophoras pilosis, Anobium punctatum, Xestobium rafovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubescis, Lyctus pubis linearis, Lyctus pubis linearis, Lyctus pubescis, Lyctus pubescis Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like

Sirex juvencus, Urocerus gigas, Uroceras gigas taignus, Uroceras augur.

Termites like

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails such as Lepisma saccharina.

In the present context, technical materials are to be understood as non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.

The material to be protected against insect infestation is very particularly preferably wood and wood processing products.

Among wood and wood processing products, which by the invention

Agents or mixtures containing them can be protected is to be understood as an example: Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles,

Boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wood products that are used in general in house construction or joinery.

The active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellant, optionally siccatives and UV stabilizers and, where appropriate, dyes and pigments and other processing aids.

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

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

An organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatility organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents. The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.

Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous.

Turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of

180 to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably α-monochlomaphthalene used.

The organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 35 and has a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced. Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used. In the context of the present invention, the known organic-chemical binders are the water-thinnable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders on the Base of a natural and / or synthetic resin used.

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellent agents, odor correctors and additives, or anticorrosive agents and the like can be used.

According to the invention, preference is given to at least one alkyd resin or modified alkyd resin and / or a drying plant-based organic-chemical binder

Contain oil in the medium or in the concentrate. Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.

All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

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

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

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

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

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

The insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners. The compounds mentioned in this document are an integral part of the present application.

Insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, trifluoropuron,

and also fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro - octylisothiazolin-3-one. At the same time, the compounds according to the invention can be used to protect objects, in particular ship hulls, sieves, nets, structures, quay systems and signaling systems which come into contact with sea or brackish water.

Overgrowth by sessile oligochaetes, such as lime tube worms, and by mussels and species of Grappe Ledamorpha (barnacles), such as various types of Lepas and Scalpellum, or by species of Grappe Balanomorpha (barnacles), such as Baianus or Pollicipes species, increases the frictional resistance of Ships and subsequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.

In addition to the growth by algae, for example Ectocarpus sp. and Ceramium sp., vegetation by sessile Entomostraken grapples, which are grouped under the name Cirripedia (barnacles), is of particular importance.

It has now surprisingly been found that the compounds according to the invention, alone or in combination with other active ingredients, have an excellent antifouling effect.

By using compounds according to the invention alone or in combination with other active ingredients, the use of heavy metals such as e.g. in bis (trialkyltin) sulfides, tri-π-butyltin laurate, tri-π-butylzirchloride, copper (I) oxide, triethyltin chloride, tri-π-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenum disulfide , Antimony oxide, polymeric butyl titanate, phenyl- (bispyridine) bismuth chloride, tri-rc-butylzirine fluoride, manganese ethylene bisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridinethiol-1-oxydi-oxamimidibarbamidylbimidimide, bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium bisdimidium diboylimidoyldimidoybimidoyldi-bisdimidoyldi-bisdimidoyldi-bisdimide,

Zinc oxide, copper (I) ethylene bisdithiocarbamate, copper thiocyanate, copper phthalate and tributyltin halides are omitted or the concentration of these

Connections are significantly reduced. The ready-to-use antifouling paints may also contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.

Suitable combination partners for the antifouling agents according to the invention are preferably:

Algicides like

2-tert.-butylamino-4-cyclopropylamino-6-methylthio-l, 3,5-triazine, dichlorophen, diuron, endothal, fentin acetate, isopro turon, methabenzthiazuron, oxyfluorfen,

Quinoclamine and Terbutryn;

Fungicides like

Benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluorofolpet, 3-iodo-2-propynyl butyl carbamate, tolyl fluanide and azoles such as

Azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;

Molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb;

or conventional antifouling agents such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol -l-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-

Tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5, 6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleimide.

The antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight. The antifouling agents according to the invention furthermore contain the usual constituents such as, for example, in Ungerer, Chern. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

In addition to the algicidal, fimgicidal, moUuscicidal and insecticidal active compounds according to the invention, antifouling paints contain in particular binders.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile Rubbers, drying oils, such as linseed oil,. Resin esters or modified hard resins in combination with tar or birumina, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, modifiers that affect the theological properties, and other conventional ingredients. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.

The active ingredients are also suitable for combating animal pests, in particular insects, arachnids and mites, which live in closed spaces such as apartments, factory halls, offices, vehicle cabins, etc. occurrence. To control these pests, they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products.

They are effective against sensitive and resistant species and against all stages of development. These pests include: From the order of the Scorpionidea, for example Buthus occitanus.

From the order of the Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp.,

Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula aurumnalis,

Dermatophagoides pteronissimus, Dermatophagoides forinae.

From the order of the Araneae e.g. Aviculariidae, Araneidae.

From the order of the Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. From the order of the Isopoda e.g. Oniscus asellus, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.

From the order of the Chilopoda e.g. Geophilus spp.

From the order of the Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina,

Lepismodes inquilinus. From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa,

Supella longipalpa.

From the order of the Saltatoria e.g. Acheta domesticus. From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Kalotermes spp., Reticulitermes spp.

From the order of the Psocoptera e.g. Lepinatus spp., Liposcelis spp.

From the order of the Coleptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp.,

Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis,

Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example Achroia grisella, Galleria mellonella, Plodia mterpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella. From the order of the Siphonaptera, for example Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of the Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius ger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

From the order of the anoplura e.g. Pediculus humanus capitis, Pediculus humanus corporis, Phthiras pubis.

From the order of the Heteroptera e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

The application in the field of household insecticides is carried out alone or in combination with other suitable active ingredients such as phosphoric acid esters, carbamates, pyrethroids, growth regulators or active ingredients from other known classes of insecticides. They are used in aerosols, non-pressurized sprays, e.g. Pump and

Atomizer sprays, automatic fog machines, foggels, foams, gels, vaporizer products with vaporizer platelets made of cellulose or plastic, liquid vaporizers, gel and membrane vaporizers, propeller-driven vaporizers, energy-free or passive evaporation systems, moth papers, moth sachets and moth gels, as granules or dusts, in scattered edema or bait stations.

Preparation Examples

example 1

(Method a)

To a mixture of 1.3 g (5 mmol) of 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) - 4,5-dihydro-1H-pyrazole, 0.1 ml of triethylamine and 50 ml of methyl tert-butyl ether is added at 70 ° C. to 1 g (5 mmol) of 4-trifluoromethylphenyl isocyanate. You stir that

Mix for 15 minutes at 70 ° C and then slowly cool to room temperature. Then the solvent is distilled off in vacuo, the residue is purified by silica gel chromatography (methylene chloride / diethyl ether 5: 1).

1.2 g (52% of theory) of 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) -4,5-dihydro-1-pyrazolecarboxylic acid-4-trifluoromethoxyanilide are thus obtained with the logP (pH2.3) = 4.00.

Manufacturing dj! S_AusgangSDr duktes

2.16 g (0.021 mol) of bis-dimethylaminomethane and. Are added to a solution of 5 g (0.02 mol) of 2- (5-methyltetrazol-2-yl) -4'-chloroacetophenone in 50 ml of methylene chloride at room temperature the mixture is refluxed for 18 hours. Then the solvent is distilled off in vacuo and the residue is dissolved in 50 ml of ethanol. After adding 1.13 g (0.0226 mol) of hydrazine hydrate, the reaction mixture is stirred at 30 ° C. for 3 hours. The precipitated product is filtered off, washed with a little cold ethanol and with water.

3.3 g (61% of theory) of 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) -4,5-dihydro-1H-pyrazole with the logP (pH2, 3) = 2.11.

Manufacture of the product

A mixture of 17.5 g (0.075 mol) of 2-bromo-4'-chloroacetophenone, 6.3 g (0.075 mol) of 5-methyltetrazole, 12.4 g (0.09 mol) of potassium carbonate and 200 ml of aceto-nit il is stirred for 16 hours at room temperature. Then the solvent is distilled off in vacuo, about 200 ml of water are added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo.

This gives 17.5 g of a mixture of the two isomers 2- (5-methyltetrazol-2-yl) -4'-chloroacetophenone with the logP (pH2.3) = 2.14 and 2- (5-methyltetrazole-l - yl) -4'-chloroacetophenone with the logP (pH2.3) = 1.81. The target product is separated off by silica gel chromatography (methylene chloride / ethyl acetate 10: 1). 6.3 g (35% of theory) of colorless crystals are obtained. 3Example 2

(Method c)

To a solution of 1.3 g (5 mmol) of 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) - 4,5-dihydro-lH-pyrazole and 0.84 ml (6 mmol) of triethylamine in 30 ml of methylene chloride are added dropwise at 0 ° C. 1.5 g (5.6 mmol) of N-cyanomethyl-N- (4-trifluoromethoxy) - ^' phenyl-carbamoyl chloride and the mixture is boiled under reflux for 3.5 hours. The mixture is then stirred for 18 hours at room temperature and then washed twice with 100 ml of water. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is purified by silica gel chromatography (methylene chloride / diethyl ether 7: 1).

1.7 g (68% of theory) of 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) -4,5-dihydro-l-pyrazolecarboxylic acid (N-cyanomethyl) are thus obtained. -trifluoromethoxyanilide with the logP (pH2.3) = 3.68.

Manufacturing Aes_AusgangS r duktes

A solution of 20.7 g (0.0958 mol) of N-cyanomethyl-4-trifluoromethoxyaniline is added dropwise to a solution of 10.4 g (0.105 mol) of phosgene in 100 ml of toluene at 0.degree and 11.6 g (0.115 mol) of triethylamine in 150 ml of toluene, the mixture is stirred for 18 hours at room temperature. Then the excess phosgene is blown out. The reaction mixture is washed twice with cold water, the organic phase is dried with sodium sulfate and the solvent is then distilled off in vacuo.

This gives 26.3 g (94% of theory) of N-cyanomethyl-N- (4-trifluoromethoxy) phenylcarbamoyl chloride with the refractive index n 2 _D 0 = 1.4816.

Example 3

(Method a) To a mixture of 0.8 g (3 mmol) of 3- (4-chlorophenyl) -4- (2-methyltetrazol-5-yl) -

4,5-dihydro-1H-pyrazole, 0.1 ml of triethylamine and 50 ml of methyl tert-amyl ether are added at 70 ° C to 0.7 g (3 mmol) of 4-trifluoromethylphenyl isocyanate. The mixture is stirred for 15 minutes at 70 ° C and then allowed to cool slowly to room temperature. The precipitated product is suctioned off.

This gives 1.2 g (52% of theory) of 3- (4-chlorophenyl) -4- (5-methyltetrazol-2-yl) -4,5-dihydro-l-pyrazolocarboxylic acid 4-trifluoromethoxyanilide with the logP (pH2.3) = 4.25.

1.6 g (0.016 mol) of bis-dimethyl- are added at room temperature to a solution of 3.5 g (0.015 mol) of 2- (2-methyltetrazol-5-yl) -4'-chloroacetophenone in 50 ml of methylene chloride. aminomethane and boil the mixture under reflux for 18 hours. Then the solvent is distilled off in vacuo and the residue is dissolved in 50 ml of ethanol. After adding 0.85 g (0.017 mol) of hydrazine hydrate, the reaction mixture is stirred at 30 ° C. for 3 hours. Then the solvent is distilled at max. 30 ° C bath temperature in a vacuum, the residue is triturated with a little ethanol, the product is suctioned off after crystallization. And wash it off with ethanol and water.

1.7 g (44% of theory) of 3- (4-chlorophenyl) -4- (2-methyltetrazol-5-yl) -4,5-dihydro-1H-pyrazole with the logP (pH2, 3) = 1.67.

Production of the JYρrDrojluktes

A mixture of 13 g (0.058 mol) of 2-tetrazol-5-yl-4'-chloroacetophenone, 9.7 g (0.07 mol) of potassium carbonate, 10 g (0.07 mol) of methyl iodide and 100 ml of acetonitrile is used for 16 Stirred for hours at room temperature. Then you distill the solution medium in a vacuum, add about 200 ml of water to the residue and extract with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo.

This gives 12.2 g of a mixture of the two isomers 2- (2-methyltetrazol-5-yl) -4'-chloroacetophenone with the logP (ρH2.3) = 2.03 and 2- (l-methyltetτazol-5 - yl) -4'-chloroacetophenone with the logP (pH2.3) = 1.78. The target product is separated off by silica gel chromatography (methylene chloride / diethyl ether 3: 1). 3.5 g (21% of theory) of colorless crystals are obtained.

10th

A mixture of 15 g (0.084 mol) of 2-cyano-4'-chloroacetophenone, 14.4 g (0.105 15 mol) of triethylamine hydrochloride, 6.9 g (0.105 mol) of sodium azide and 100 ml of toluene is boiled under reflux for 72 hours , Then the solvent is distilled off in vacuo, the residue is dissolved in 200 ml of about 5% sodium hydroxide solution and the undissolved solution is filtered. The filtrate is adjusted to about pH 2 with dilute hydrochloric acid, then the precipitated product is suctioned off and washed with water. The crude product 20 is dissolved in excess sodium bicarbonate solution, the solution is filtered and that

Filtrate again adjusted to approx. PH 2 with dilute hydrochloric acid. The precipitated product is suctioned off and washed with water.

This gives 16.2 g (87% of theory) of 2-tetrazol-5-yl-4'-chloroacetophenone with the 25 logP (pH2.3) = 1.44. Example 4

(Method a)

To a mixture of 1.4 g (5 mmol) of 3- (4-chlorophenyl) -4- (5-methyl-l, 3,4-thiadiazol-2-yl) -4,5-dihydro-lH-pyrazole , 0.1 ml of triethylamine and 50 ml of methyl tert-amyl ether are added at 70 ° C. to 1 g (5 mmol) of 4-trifluoromethoxyphenyl isocyanate. The mixture is stirred for a further 15 minutes at 70 ° C. and then allowed to cool slowly to room temperature. Then the solvent is distilled off in vacuo

The residue is purified by silica gel chromatography (methylene chloride / diethyl ether 7: 1).

This gives 0.15 g (6% of theory) of 3- (4-chlorophenyl) -4- (5-methyl-l, 3,4-thiadiazol-2-yl) -4,5-dihydro-l -pyrazolecarboxylic acid-4-trifluoromethoxyanilide with the logP (ρH2,3)

= 3.77.

Production of the output product

To a solution of 4.5 g (0.018 mol) of 2- (2-methyl-l, 3,4-thiadiazol-5-yl) -4'-chloroacetophenone (preparation see Chemiker-Zeitung 1989, 113, 217 -219) in 50 ml of methylene chloride, 1.9 g (0.0187 mol) of bis-dimethylaminoethane are added at room temperature and the mixture is boiled under reflux for 18 hours. Then the solvent is distilled off in vacuo and the residue is dissolved in 50 ml of ethanol. After adding 1 g (0.02 mol) of hydrazine hydrate, the reaction mixture is stirred at 30 ° C. for 3 hours. Then the solvent is distilled at max. 30 ° C bath temperature in a vacuum, adds about 200 ml of water to the residue and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo.

4.9 g (98% of theory) of 3- (4-chlorophenyl) -4- (2-methyl-l, 3,4-thiadiazol-5-yl) -4,5-dihydro-1H are thus obtained -pyrazole with the logP (pH2.3) = 1.77.

The compounds of the formula (I) given in Table 1 below can be obtained analogously to Examples 1 to 4 or according to the general information on the preparation:

Table 1:

The compounds of the formula (II) given in Table 2 below can be obtained analogously to Examples 1, 3 and 4 or according to the general information on the preparation:

Table 2:

The compounds of the formula (VII) given in Table 3 below can be obtained analogously to Examples 1 and 3 or according to the general information on the preparation: Table 3:

The logP values given in the tables and manufacturing examples above are determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.

The determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.

The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the

Retention times by linear interpolation between two consecutive alkanones).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. Application examples:

Example A

Heliothis armigera test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.

Soybean shoots (Glycine max) are treated by being dipped into the preparation of active ingredient of the desired concentration and populated with caterpillars of the cotton capsule worm (Heliothis armigera) while the leaves are still moist.

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

In this test, at an exemplary active ingredient concentration of 500 ppm, for example, the compounds 2, 4 and 10 of the preparation examples show a kill of 100% after 7 days. Example B

Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with Heliothis virescens caterpillars while the leaves are still moist.

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

In this test, at an exemplary active ingredient concentration of 500 ppm, compound 1 of the preparation examples, for example, shows a kill of 100% after 7 days.

Example C

Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish leaf beetle (Phaedon cochleariae) while the leaves are still moist.

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

In this test, at an exemplary active ingredient concentration of 500 ppm, for example the compounds 1, 2, 3, 4, 5, 8, 10 and 11 of the preparation examples show a kill of 100% after 7 days.

Example D

Plutella Test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound is ^{mixed, "1} part by weight of active compound with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella xylostella) while the leaves are still moist.

In this test, with an exemplary active ingredient concentration of 500 ppm, for example, the compounds 1, 2, 4 and 10 of the preparation examples show a kill of 100% after 7 days.

Example E

Spodoptera exigua test

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera exigua) while the leaves are still moist.

Example F

Spodoptera frugiperda test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera fragiperda) while the leaves are still moist.

In this test, at an exemplary active ingredient concentration of 500 ppm, for example, the compounds 1, 2, 3, 4, 5, 8, 10 and 11 of the preparation examples show a kill of 100% after 7 days).

Example G

Plutella Test

Solvent: 100 parts by weight of acetone 1900 parts by weight of methanol

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with methanol to the desired concentrations.

A specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of synthetic feed. After the methanol has evaporated, approx. 200-300 eggs of the cockroach (Plutella xylostella) are added to the feed.

After the desired time, the death of the eggs or larvae is determined in%. 100% means that all animals have been killed; 0%> means that no animals have been killed.

In this test, at an exemplary active ingredient concentration of 1000 ppm, for example, compound 6 of the production examples shows a kill of 100% and compound 7 of the production examples shows a kill of 95%, in each case after 7 days. Example H

Diabrotica balteata test (larvae in the soil)

Limit concentration test / soil insects - treatment of transgenic plants

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

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the specified amount is given

Amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). The bottom is filled in 0.25 l pots and these are left to stand at 20 ° C.

Immediately after the preparation, 5 pre-germinated maize kernels of the YIELD variety are added to each pot

GUARD (trademark of Monsanto Comp., USA). After 2 days, the appropriate test insects are placed in the treated soil. After a further 7 days, the effectiveness of the active ingredient is determined by counting the maize plants that have accumulated (1 plant = 20%> activity). Example I

Heliothis virescens - test (treatment of transgenic plants)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce 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.

Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and are populated with the tobacco bud caterpillar Heliothis virescens while the leaves are still moist.

The killing of the insects is determined after the desired time. 100% means that all caterpillars have been killed, 0% means that no caterpillars have been killed.

Claims

Patentansprttche

1. Substituted 4-hetaryl-pyrazolines of the formula (I)

R represents optionally substituted oxadiazolyl, thiadiazolyl or tetrazolyl,

R represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl or cyano and

R represents hydrogen, cyanomethyl or alkoxycarbonyl.

Substituted 4-hetaryl-pyrazolines of the formula (I) according to approach 1, in which

R ^{1 stands} for optionally substituted oxadiazolyl or thiadiazolyl, examples of which may be mentioned as examples: optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl or optionally substituted arylalkyl; as well as optionally substituted tetrazolyl, examples of which may be mentioned as substituents: optionally substituted alkyl, optionally substituted alkylthio or alkylsulfonyl, in each case optionally substituted aryl or arylalkyl or optionally substituted cycloalkyl,

R ² for fluorine, chlorine, bromine, iodine; Q- -haloalkyl, CC ₄ -alkoxy, - C -haloalkoxy, CrC ₄ - alkylthio, C ₁ -C ₄ -haloalkylthio, C ₁ -C - alkylsulfonyl, C i -C ₄ -haloalkylsulfinyl, C i -C ₄ -haloalkylsul - fonyl or cyano,

R ³ for fluorine, chlorine, bromine, iodine; C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, Ci- _{C4-haloalkoxy,} -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C - haloalkylsulfinyl, CrC is ₄ haloalkylsulfonyl or cyano .

R ^{4 represents} hydrogen, cyanomethyl or C ₁ -C ₄ alkoxy-carbonyl.

3. Substituted 4-hetaryl-pyrazolines of the formula (I) according to spoke 1, in which

R ¹ represents in each case optionally substituted oxadiazolyl, or thiadiazolyl, which are exemplified as substituents: -C ₄ - alkyl, C ₁ -C ₄ haloalkyl, dC ₄ - alkoxy, C ₁ -C ₄ -haloalkoxy, C _\ - C - alkylthio , C ₁ -C ₄ -Halogenalkylthio, and each optionally one to three times, identical or different by halogen, -C-C -

Haloalkyl or C 1 -C ₄ -haloalkoxy substituted phenyl or benzyl; as well as optionally substituted tetrazolyl, where the following may be mentioned as substituents: C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C _\ - C ₄ -alkylthio, CrC - alkylsulfonyl, furthermore in each case optionally in one to three times, identical or differently substituted by halogen, CrC - haloalkyl or C ₁ -C ₄ haloalkoxy or Benzyl, moreover in each case optionally to triple, identical or different, cyclopentyl or cyclohexyl substituted by Cχ-C - alkyl,

R ² for fluorine, chlorine, bromine, iodine, cyano; dC ₂ - alkylthio, dC ₂ - alkylsulfonyl and Cι-C ₂ haloalkyl, C ₁ -C ₂ Ηalogenalkoxy; d- C ₂ alkylalogenalkylthio or C ₁ -C ₂ -halogenalkylsulfonyl each having 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine,

R ^{3 represents} chlorine, bromine, iodine, cyano; and for C ₁ -C ₂ haloalkyl, dC ₂ - haloalkoxy, C ₁ -C ₂ haloalkylthio, C ₁ -C ₂ -HalogenalJkylsulfinyl. or C ₁ -C ₂ haloalkylsulfonyl each having 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine,

R ^{4 represents} hydrogen, cyanomethyl or C ₁ -C ₄ alkoxy-carbonyl.

4. Substituted 4-hetaryl-pyrazolines of the formula (I) according to spoke 1, in which

R ^{1 represents the} following thiadiazolyls and oxadiazolyls:

in which

1

X and X independently of one another for hydrogen, CrC-alkyl, d- C ₄ -haloalkyl, C ₁ -C - alkylthio, C ₁ -C ₄ -haloalkylthio as well as phenyl or benzyl which are optionally monosubstituted to trisubstituted, identically or differently, by halogen, C ₁ -C ₂ -haloalkyl or d-d-haloalkoxy each having 1 to 3 identical or different halogen atoms from the series fluorine, chlorine and bromine;

as well as for the following tetrazolyls:

in which

X and X independently of one another for hydrogen, C ₁ -C ₄ -alkyl, d- C ₂ -haloalkyl having 1 to 3 identical or different halogen atoms from the series fluorine, chlorine and bromine; dC ₄ - alkylthio, C ₁ -C ₄ - alkylsulfonyl, for each optionally one to three times, identical or different by halogen, d-

C ₂ haloalkyl or dC ₂ haloalkoxy, each having 1 to 3 identical or different halogen atoms from the series fluorine, chlorine and bromine substituted phenyl or benzyl, and for each cyclopentyl or cyclohexyl which is monosubstituted to trisubstituted by d C ₄ alkyl stand,

R ^{2 represents} fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio,

R ^{3 represents} chlorine, bromine, iodine, cyano; Trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, R ^{4 represents} hydrogen, cyanomethyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl and n-, i-, s- and t-butoxycarbonyl.

5. Substituted 4-hetaryl-pyrazolines of the formula (I) according to spoke 1, in which

R ^{1 represents the} following thiadiazolyls and oxadiazolyls:

in which

1

X and X are independently hydrogen; Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoromethoxy or trifluoromethylthio as well as for each optionally single or double, identical or different

Fluorine, chlorine, bromine, trifluoromethyl or trifluoromethoxy substituted phenyl or benzyl;

as well as for the following tetrazolyls:

in which

X ³ to X ⁴ independently of one another for hydrogen; Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; Fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, meth- thylthio, ethylthio, methylsulfonyl, ethylsulfonyl; are each phenyl or benzyl which is monosubstituted or disubstituted, identically or differently, by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy, and cyclohexyl which is monosubstituted or disubstituted by methyl,

R represents fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio,

R represents chlorine, bromine, iodine, cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

R ^{4 represents} hydrogen or cyanomethyl.

6. Compounds of formula (I) according to spoke 1, in which R ^{1 represents} optionally substituted tetrazolyl, where the following may be mentioned as substituents: -C ₄ -alkyl, dC ₄ -haloalkyl, dC ₄ - alkylthio, C _r C ₄ - Alkylsulfonyl, furthermore in each case optionally monosubstituted to trisubstituted, identically or differently by halogen, -CC -haloalkyl or dC -halogenalkoxy, phenyl or benzyl, furthermore in each case optionally monosubstituted to trisubstituted, identically or differently, by C ₁ -C ₄ -alkyl or cyclopentyl cyclohexyl.

7. Compounds of formula (I) according to spoke 1, in which R ^{2 represents} chlorine.

8. Compounds of formula (I) according to spoke 1, in which R ^{4 represents} hydrogen.

9. Compounds of formula (I) according to claim 1, in which R ^{4 is} cyanomethyl.

10. Compounds of formula (I) according to spoke 1, in which R represents trifluoromethoxy or trifluoromethylthio.

11. A process for the preparation of substituted 4-hetaryl-pyrazolines of the formula (I) according to claim 1, characterized in that

a) pyrazolines of the formula (II)

in which

R ¹ and R ^{2 have} the meanings given in spoke 1,

with isocyanates of the formula (III)

in which

R, 3 has the meanings given in spoke 1,

if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst; and

R, R and R have the meanings given in spoke 1,

with halides of the formula (IV) Hai ¹ - R ⁴ (IV) in which

R has the meanings given in spoke 1 and

Shark ^{1 represents} halogen,

c) anilines of the formula (V)

in which

R ³ and R ^{4 have} the meanings given in claim 1,

first reacted with phosgene, in the presence of a diluent and optionally in the presence of a base, and the carbamic acid chlorides of the formula (VI) thus obtained in which

R ³ and R ^{4 have} the meanings given in spoke 1,

directly or after intermediate isolation with pyrazolines of the formula (II)

in which

R ¹ and R ^{2 have} the meanings given in spoke 1,

in the presence of a diluent and optionally in the presence of a base.

12. pesticides, characterized by a content of at least one compound of the formula (I) according to spoke 1 in addition to extenders and / or surface-active substances.

13. Use of compounds of the formula (I) according to spoke 1 for controlling pests.

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

15. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to spoke 1 are mixed with extenders and / or surface-active substances.

16. pyrazolines of the formula (II)

in which

R and R have the meanings given in speech 1.