DE19756115A1 - Substituted phenylpyrazolones, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests - Google Patents

Abstract

The invention relates to substituted phenylpyrazolones of formula (I) in which the substituents have the following meanings: Y represents halogen, alkyl, halogen alkyl or alkoxyl; n represents 0, 1 or 2, whereby the radical Y can be different when n = 2; E represents a group A (A), whereby # characterizes the bond with the phenyl ring; R<A> represents halogen, cyano, alkyl or halogen alkyl; R<B> represents hydrogen or alkyl; R<C> represents alkyl or halogen alkyl; T represents a direct bond, oxygen or CH2O; Z represents a) when T represents oxygen or oxymethylene, a group X, N=CWR<1> or N=C(R<1>)-C(R<2>)=NOR<3>, whereby X represents optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylmethylene or optionally substituted heteroarylmethylene; W represents optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkinyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl; R<1> represents hydrogen, cyano, alkyl, halognealkyl, alkoxyl, alkoxyl alkyl, cycloalkyl; R<2> represents hydrogen, cyano, halogen, C(R<d>)=NOR<3> or W, OW, SW or NR<c>W, whereby R<c> represents hydrogen, alkyl, alkenyl or alkinyl; R<d> represents hydrogen or alkyl; R<3> represents hydrogen, optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkinyl, and b) when T represents a direct bond, Z represents a group W, CH2-CH2-W, CH=CH-W, CC-W, S-W, CH2-S-W, CH=N-O-CH2-W, CH2-O-C(=O)-W or CH2-O-C(CH3)=N-N=C(CH3)-W. The invention also relates to a method and intermediate products for the production of said phenylpyrazolones used for combating parasitic fungi and animal parasites.

Description

The present invention relates to substituted phenylpyrazolones of the formula I,

in which the substituents have the following meaning:
Y halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxy;
n is 0, 1 or 2, where the radicals Y can be different if n = 2;
E a group A,

where # indicates the bond with the phenyl ring;
R ^{A is} halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;
R ^{B is} hydrogen or C ₁ -C ₄ alkyl;
R ^C C ₁ -C ₆ alkyl or C ₁ -C ₄ haloalkyl;
T is a direct bond, oxygen or oxymethylene;
Z a) when T is oxygen or oxymethylene, a group X, N = CWR ¹ or N = C (R ¹ ) -C (R ² ) = NOR ³ , where
X if necessary subst. Heterocyclyl, optionally subst. Aryl, if necessary subst. Hetaryl, possibly subst. Arylmethylene or optionally subst. Het arylmethylene;
W if necessary subst. Alkyl, optionally subst. Alkenyl, if necessary subst. Alki nyl, if necessary subst. Cycloalkyl, optionally subst. Cycloalkenyl, optionally subst. Heterocyclyl, optionally subst. Aryl or optionally subst. Hetaryl;
R ^{1 is} hydrogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C _6- cycloalkyl;
R ^{2 is} hydrogen, cyano, halogen, C (R ^d ) = NOR ³ or W, OW, SW or NR ^c W, where
R ^{c is} hydrogen, alkyl, alkenyl or alkynyl;
R ^{d is} hydrogen or alkyl;
R ³ hydrogen, optionally subst. Alkyl, optionally subst. Alkenyl or subst. Mean alkynyl and
b) if T stands for a direct bond,
a group W, CH ₂ -CH ₂ -W, CH = CH-W, C∼CW, SW, CH ₂ -SW, CH = NO-CH ₂ -W, CH ₂ -OC (= O) -W or CH ₂ -OC (CH ₃ ) = NN = C (CH ₃ ) -W means.

In addition, the invention relates to processes and intermediates for the preparation of the compounds I and the use of the verbin I to combat harmful fungi and animal pests gene.

Cyclic amides ortho to the amide carbonyl group carry an ortho substituted phenyl ring are off WO-A 95 / 14,009, WO-A 96 / 26,191, WO-A 96 / 36,229, WO-A 96 / 36,615, WO-A 96 / 36,616, WO-A 96 / 38,425, WO-A 97 / 00,612 and WO-A 97 / 05,120 known. Cyclic amides ortho to the amide car bonyl group carry a substituted heterocycle are in WO-A 96 / 36,633.

The verb described in the above scriptures are plant protection products against harmful fungi and z. T. suitable against animal pests.

However, their effect is unsatisfactory in many cases. Therefore, the task was based on connections with improved Find effectiveness.

Accordingly, the substituted phenylpyrazolones of the formula I found. Intermediates and processes for Preparation of the compounds I and the use of the verb  I and this contained means to combat harmful Pil zen and animal pests. The fungicidal effect is preferred.

The compounds of formula I differ from those of the above-mentioned writings known compounds by the Ausge Design of the cycle 'E: In the compounds of formula I is Group E is a pyrazolone.

The compounds of formula I have one compared to the known Compounds increased effectiveness against harmful fungi and animal Pests on.

The compounds I can be obtained in various ways, it being irrelevant for the synthesis whether the pyrazolone or the TZ group is built up first. For better clarity, the description is therefore in the following reaction descriptions
E ^# for group A or a suitable preliminary stage for it and
Z ^# for the grouping TZ, or a suitable preliminary stage for it
used.

The introduction of the TZ grouping is preferred at the level where E ^# stands for nitro.

The grouping T-Z in the compounds of formula I per se analogous to that in WO-A 93 / 15,046, WO-A 96 / 07,633, and WO-A 97 / 24,317 described methods can be obtained.

Compounds I in which R ^{A is} halogen or C ₁ -C ₄ alkyl are advantageously accessible from the corresponding hydroxypyrazoles of the formula II ^# .

The hydroxypyrazoles of the formula II ^{# are} obtained in a particularly advantageous manner by first converting a nitrobenzene derivative III ^# , for example by hydrogenation, into the corresponding aniline IV ^# , then IV ^# diazotizing and reducing the resulting diazo compound into the hydrazine V ^# and V ^# with an alkoxymethylene malonic acid alkyl ester of the formula VIa, in which R ″ is C ₁ -C ₄ -alkyl, to give the dicarboxylic acid ester VI ^# , which under basic conditions via the ester VIII ^# and the acid VIIIb ^# to II ^# is cyclized.

1) The reduction of the nitro group of III ^# can be carried out under generally customary conditions, preferably by catalytic hydrogenation, by reduction with iron, tin or zinc in the presence of an acid, by reduction with alkali metals in the presence of a base or by enzyme-catalyzed reduction [cf. . Houben-Weyl, Vol. IV / 1c, 4th ed., Pp. 506ff., Thieme Verlag Stuttgart and New York (1980); ibid. Vol. IV / 1d, 4th ed., p. 473ff. (1981); Heterocycles, vol. 31, p. 2201 (1990)].

Suitable solvents are water, in the case of enzyme-catalyzed ones Reduction also aqueous buffer solutions, aliphatic hydrocarbons substances such as pentane, hexane, cyclohexane and petroleum ether, aromatic Hydrocarbons such as toluene, o-, m- and p-xylene, halogenated Hydrocarbons such as methylene chloride, chloroform and chlorobes  zole, ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide, dimethylacetamide or Esters such as ethyl acetate, particularly preferably methanol, Ethanol, ethyl acetate and water. Mixtures can also be used of the solvents mentioned can be used.

As catalysts in the catalytic hydrogenation han conventional catalysts, for example platinum, platinum oxide or contain palladium on a support, or Raney nickel or Raney cobalt.

The use of platinum or palladium catalysts is preferred. The platinum or palladium content of the catalyst is not critical and can be varied within wide limits. A content of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on the carrier material, is expedient. The amount of platinum or palladium used is between 0.001 and 10% by weight, preferably between 0.01 and 0.1% by weight, based on the nitro compound. In the preferred embodiment, coal is used as the carrier material. Other non-amphoteric supports such as graphite, BaSO ₄ or SiC are also suitable.

The temperature range for the hydrogenation is between -20 ° C and + 180 ° C, preferably between -5 and + 40 ° C. The minimum temperature is only by the freezing point of the solvent used certainly. Usually hydrogenation is carried out at a hydrogen pressure, which is between normal pressure and 30 bar overpressure. More normal the hydrogen becomes normal pressure or slightly increased Pressure gassed.

Inorganic acids such as hydrofluoric acid, Hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, as well as organic acids such as formic acid, acetic acid, propion Acid, oxalic acid, citric acid and trifluoroacetic acid dung.

The acids are generally used in catalytic amounts sets, but they can also equimolar, in excess or given can also be used as a solvent.

The reduction with alkali metals, for example with sodium, generally takes place in the presence of a base. Come as bases generally alkali metal amides such as lithium amide, sodium amide and Potassium amide, and alkali metal and alkaline earth metal alcoholates, such as sodium methoxide, sodium ethoxide, potassium ethoxide and  Potassium tert-butoxide, also organic bases, e.g. B. tertiary Amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, Lutidine and 4-dimethylaminopyridine and bicyclic amines in Consideration. Ammonia and primary amines are particularly preferred. The bases are generally equimolar, in excess or optionally used as a solvent.

Nitrobenzene derivatives of the formula III ^# are z. T. known from the literature [cf. EP-A 498 396; WO-A 93 / 15,046; WO-A 95 / 14,009] or can be prepared according to the literature cited.

2a) The reaction of IV ^# with nitrite takes place at temperatures from -10 ° C. to 25 ° C., preferably -5 ° C. to 10 ° C., in water or an inert organic solvent in the presence of an acid [cf. Organikum, 15th edition 1976, pp. 654ff., VEB Publishing House of Sciences, Berlin].

Suitable solvents are water, aliphatic hydrocarbons substances such as pentane, hexane, cyclohexane and petroleum ether, aromatic Hydrocarbons such as toluene, o-, m- and p-xylene, halogenated Hydrocarbons such as methylene chloride, chloroform and chlorobes zole, ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetone tril and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably water and acetic acid. Gemi cal of the solvents mentioned are used.

As acids and acidic catalysts find inorganic acids such as Hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfur acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum umtrichloride, ferric chloride, tin IV chloride, titanium IV chloro rid and zinc-II-chloride, as well as organic acids such as ants acid, acetic acid, propionic acid, oxalic acid, citric acid and Trifluoroacetic acid use.

The acids are generally used in catalytic amounts sets, but they can also equimolar, in excess or given can also be used as a solvent.

Alkali or earth are usually used as nitrosating agents Alkaline nitrites are used, especially sodium or potassium nitrite.  

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the nitrifying agent in an excess based on IV ^# .

2b) The reduction of the diazo compound can be done under generally normal Chen conditions are carried out, preferably by Reduk tion with iron, tin or zinc or their salts in the presence an acid or by reduction with alkali metals in counter were a base [cf. Houben-Weyl, Vol. IV / 1c, 4th ed., P. 506ff., Thieme Verlag Stuttgart and New York (1980); ibid. vol. IV / 1d, 4th ed., P. 473ff. (1981); Heterocycles, vol. 31, p. 2201 (1990)]. The reduction of the is also preferred Diazonium salts with sulfite or disulfite [see: Organikum, 15. Ed., VEB, p. 662, 1976; J. Chem. Soc, 1927, pp. 1325ff .; Chem. Ber., Vol. 55, pp. 1827, 1922; Houben-Weyl, Vol. 10/2, P. 182, Thieme Verlag, Stuttgart].

Suitable solvents are water or aliphatic coal water substances such as pentane, hexane, cyclohexane and petroleum ether, aromatics hydrocarbons such as toluene, o-, m- and p-xylene, halogen hydrocarbons such as methylene chloride, chloroform and Chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-Bu tylmethyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as Acetonitrile and propionitrile, ketones such as acetone, methylethylke clay, diethyl ketone and tert-butyl methyl ketone, alcohols such as metha nol, ethanol, n-propanol, isopropanol, n-butanol and tert-buta nol and dimethyl sulfoxide, dimethylformamide and dimethylaceta mid, particularly preferably water. Mixtures of mentioned solvents are used.

As acids and acidic catalysts find inorganic acids such as Hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfur acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum umtrichloride, ferric chloride, tin IV chloride, titanium IV chloro rid and zinc-II-chloride, as well as organic acids such as ants acid, acetic acid, propionic acid, oxalic acid, citric acid and Trifluoroacetic acid use.

The acids are generally used in catalytic amounts sets, but they can also equimolar, in excess or given can also be used as a solvent.

In general, inorganic compounds such as alkali come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as  Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate as well as alkali metal hydrogen car Bonate such as sodium bicarbonate, organometallic compounds gene, especially alkali metal alkyls such as methyl lithium, butylli thium and phenyllithium, alkyl magnesium halides such as methylma magnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, also organic Bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri isopropylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well bicyclic amines. Potassium and sodium hydroxide, potassium and sodium carbonate.

The bases are generally added in catalytic amounts sets, but they can also equimolar, in excess or given can also be used as a solvent.

Particularly suitable reducing agents are NaHSO ₃ , Na ₂ S ₂ O ₅ or SnCl ₂ .

The starting materials are generally together in equimolar amounts the implemented. It can be advantageous for the yield that Reducing agents in an excess based on the nitrosovers use binding.

3) The reaction of the hydrazine V ^# with the alkoxymethylene malon acid alkyl ester VIa usually takes place at temperatures from -10 ° C. to 80 ° C., preferably 0 ° C. to 30 ° C., in an inert organic solvent.

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and Propionitrile, as well as dimethyl sulfoxide, dimethylformamide and dime thylacetamide, particularly preferably petroleum ether, toluene, tert. Butyl methyl ether, diethyl ether and dimethylformamide. It can mixtures of the solvents mentioned can also be used.  

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use VIa in an excess based on V ^# .

Alkoxymethylene malonic acid alkyl esters VIa are either commercially available or can be prepared by methods known from the literature.

4) The cyclization of VII ^# to the hydroxypyrazole VIII ^# usually takes place at temperatures from -10 ° C. to 50 ° C., preferably 0 ° C. to 30 ° C., in water or an inert organic solvent in the presence of a base.

Suitable solvents are water, aliphatic hydrocarbons substances such as pentane, hexane, cyclohexane and petroleum ether, aromatic Hydrocarbons such as toluene, o-, m- and p-xylene, halogenated Hydrocarbons such as methylene chloride, chloroform and chlorobes zole, ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetone tril and propionitrile, ketones such as acetone, methyl ethyl ketone, Diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably methanol, ethanol and water. It can too Mixtures of the solvents mentioned are used.

In general, inorganic compounds such as alkali come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate as well as alkali metal hydrogen car Bonate such as sodium bicarbonate, organometallic compounds gene, especially alkali metal alkyls such as methyl lithium, butylli thium and phenyllithium, alkyl magnesium halides such as methylma magnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, also organic Bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri isopropylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well bicyclic amines. Natri are particularly preferred ummethanolat, sodium ethanolate, potassium ethanolate, potassium hydroxide and sodium hydroxide.  

The bases are generally added in catalytic amounts sets, but they can also equimolar, in excess or given can also be used as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the base in an excess based on VII ^# .

5) The saponification of the ester group of VIII ^# and the subsequent decarboxylation of the resulting acid VIIIb ^# to give the hydroxypyrazoles II ^# is usually carried out at from 0 ° C. to 150 ° C., preferably 50 ° C. to 110 ° C., in an inert atmosphere organic solvents in the presence of a base.

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and Propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dime thylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably water, dioxane and dimethylacetamide. It can too Mixtures of the solvents mentioned are used.

In general, inorganic compounds such as alkali come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate as well as alkali metal hydrogen car Bonate such as sodium bicarbonate, organometallic compounds gene, especially alkali metal alkyls such as methyl lithium, butylli thium and phenyllithium, alkyl magnesium halides such as methylma magnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, also organic Bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri isopropylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well  bicyclic amines. Potassium is particularly preferred carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide.

The bases are generally added in catalytic amounts sets, but they can also equimolar, in excess or given can also be used as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the base in an excess based on VIII ^# .

It is also possible to carry out steps 4) and 5) under 5) described reaction conditions run as a one-pot reaction allow.

Compounds of the formula I in which R ^{A is} halogen are advantageously obtained from hydroxypyrazoles of the formula II by a reaction sequence of halogenation and alkylation. The order of implementation is irrelevant.

6) The halogenation of II ^# usually takes place at temperatures from -30 ° C to 50 ° C, preferably 0 ° C to 30 ° C, in an inert organic solvent.

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and  Propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dime thylsulfoxide, dimethylformamide and dimethylacetamide, especially prefers . . . Methylene chloride, methanol and dimethyl form amid. Mixtures of the solvents mentioned can also be used be det.

Chlorine, bromine, iodine and dibromodimethyl come as halogenating agents hydrantoin, N-bromosuccinimide or N-chlorosuccinimide, especially N-bromosuccinimide or N-chlorosuccinimide.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use II ^# in an excess based on the halogenating agent.

7) The substitution of the hydroxypyrazole IX ^# is usually carried out at temperatures from -20 ° C. to 180 ° C., preferably 20 ° C. to 120 ° C., in an inert organic solvent in the presence of a base [cf. Synth. Commun., Vol. 18, p. 2011 (1988); J. Chem. Soc. Chem. Commun., P. 735 (1987)].

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and Propionitrile, alcohols such as methanol, ethanol, n-propanol, isopro panol, n-butanol and tert-butanol, ketones such as acetone, butanone or esters such as ethyl acetate and dimethyl sulfoxide, Dimethylformamide and dimethylacetamide, particularly preferably dime thylformamide, tetrahydrofuran, dimethyl sulfoxide, diethyl ether, Acetone, methanol, ethyl acetate and toluene. It can too Mixtures of the solvents mentioned are used.

In general, inorganic compounds such as alkali come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate as well as alkali metal hydrogen car Bonate such as sodium bicarbonate, organometallic compounds gene, especially alkali metal alkyls such as methyl lithium, butylli  thium and phenyllithium, alkyl magnesium halides such as methyl mag nesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, also organic Bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri isopropylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well bicyclic amines. Natri are particularly preferred umhydrid, sodium hydrogen carbonate, sodium carbonate and sodium and potassium hydroxide.

The bases are generally equimolar or in excess set, but can also in catalytic amounts or given if used as a solvent.

Examples of alkylating agents are alkyl halides, Alkyl sulfonates, alkyl p-toluenesulfonates, alkyl trifluoromethanesul fonates, alcohols, ethers or alkyl-p-bromophenyl sulfonates, esp special methyl or ethyl iodide or dimethyl or diethyl sulfate into consideration. The introduction of the nitrile group is preferred with cyanogen halides, such as cyanogen bromide.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the alkylation agent in an excess based on IX ^# .

8) The alkylation of the hydroxypyrazole II ^# can also take place under the conditions described in section 7). The halogenation of X ^# proceeds analogously to the halogenation of II ^# to IX ^# described in section 6).

Intermediates of formula 1 in which

Q NH-NH-C (R ^B ) = C (COOR ') ₂ or a group Θ 1 or Θ 2,

where # denotes the bond to the phenyl ring and R 'is hydrogen or C ₁ -C ₄ alkyl are new.

Compounds of the formula I in which R ^{A is} cyano, alkyl or halo alkyl can be obtained analogously to known syntheses [R ^A = cyano: J heterocycl. Chem., Vol. 23, 1035ff., 1986; Gazz. Chim. Ital., Vol. 69, pp. 639ff, 1939; ibid., Vol. 77, S, 3ff, 1947; Chem. Ber., Vol. 75, pp. 1214ff, 1942; R ^A = alkyl, haloalkyl: J. Am. Chem. Soc., Vol. 58, pp. 1152ff, 1936; Chem. Ber., Vol. 38, pp. 3275, 1905; ibid., vol. 34, pp. 1301, 1901; J. Prakt. Chem., Vol. 54, pp. 210ff, 1986; J. Chem. Soc. Perkin. Trans., Vol. 2, pp. 969ff, 1987].

Phenylpyrazolones of the formula I '^# are preferably obtained from the compounds of the formula XI'^# . In the formula XI '^# , L' represents a leaving group which is customary for nucleophilic aromatic substitution, such as, for example, fluorine, chlorine, bromine, nitro or alkyl or aryl sulfonates, such as mesylate, tosylate or triflate.

Preferred leaving group is fluorine.

9) This reaction usually takes place at temperatures of -20 ° C to 170 ° C, preferably 0 ° C to 100 ° C, in an inert organic solvents in the presence of a base [cf. WO-A 97 / 24,317; J. Chem. Soc. Perkin Trans., Vol. 1, p. 1727 (1989); Chem. Ber. , Vol. 121, p. 2035 (1988)].

Suitable solvents are aromatic hydrocarbons such as Toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile,  Ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-Bu tylmethyl ketone, and dimethyl sulfoxide, dimethylformamide and Dimethylacetamide, particularly preferably dimethylformamide, dimethyl sulfoxide and tetrahydrofuran. Mixtures of the so-called th solvent.

In general, inorganic compounds, such as alkali, come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compound dungen, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, alkyl magnesium halides such as Methylma magnesium chloride, and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, also organic Bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri isopropylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyrldine as well bicyclic amines. Natri are particularly preferred umhydrid, potassium tert-butanolate and potassium carbonate. The bases are generally equimolar, in excess or, if appropriate used as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use Z-OH in an excess based on XI '^# .

Phenylpyrazoles of the formula I '^# , in which Z represents a group X, can alternatively also be obtained from phenols of the formula XIa'^# . XIa '^# is converted to I'^# with a halide Z-Hal.

10) This reaction usually takes place at temperatures of -20 ° C to 180 ° C, preferably 20 ° C to 160 ° C, in an inert organic solvents in the presence of a base [cf. EP-A 203 608; EP-A 242 081].  

Suitable solvents are aromatic hydrocarbons, such as Toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-Bu tylmethyl ketone, and dimethyl sulfoxide, dimethylformamide and Dimethylacetamide, particularly preferably dimethylformamide and dime ethyl sulfoxide. Mixtures of the solvents mentioned can also be used be used.

In general, inorganic compounds, such as alkali, come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compound dungen, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and alkaline earth metal alcohol latex such as sodium methoxide, sodium ethoxide, potassium ethoxide, Potassium tert-butanolate and dimethoxymagnesium, also organic bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, Tri-isopropylethylamine and N-methylpiperidine, pyridine, substit ized pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well as bicyclic amines. Be particularly preferred Sodium hydride, potassium tert-butanolate and potassium carbonate. The Bases are generally equimolar, in excess or given also used as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use X-Hal in an excess based on XIa '^# .

Phenylpyrazoles of the formula I ''^# are preferably obtained from the benzyl compounds of the formula XI ''^# . In the formula XI ''^# L stands for a nucleofugic leaving group, such as halogen or alkyl or aryl sulfonate, preferably bromine, chlorine, iodine, mesylate, tosylate or triflate and E ^# for a group A or a precursor therefor.

11) This reaction usually takes place at temperatures of 0 ° C to 180 ° C, preferably 20 ° C to 60 ° C, in an inert organic solvents in the presence of a base [cf. EP-A 254 426; EP-A 463 488; WO-A 95 / 18,789; WO-A 95 / 29,896].

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and Propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, as well as dime thylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably dimethylformamide, tetrahydrofuran and acetone. It can mixtures of the solvents mentioned can also be used.

In general, inorganic compounds, such as alkali, come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compound dungen, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride, and alkali metal and alkaline earth metal alcohol latex such as sodium methoxide, sodium ethoxide, potassium ethoxide, Potassium tert-butanolate and dimethoxymagnesium, also organic bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, Tri-isopropylethylamine and N-methylpiperidine, pyridine, substi acted pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well as bicyclic amines. Be particularly preferred Sodium hydride, potassium carbonate, potassium tert-butoxide and natri ummethanolat. The bases become generally equimolar, in the over shot or optionally used as a solvent.  

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use Z-OH in an excess based on XI ''^# .

The output required for the preparation of compounds I ' substances Z-OH are known or can according to the cited Litera be manufactured.

12) The benzyl compounds XI ''^# can be obtained from the corresponding tolyl compounds XIa ''^# under generally customary conditions [cf. J. Amer. Chem. Soc., Vol. 71, pp. 2137ff. (1949); ibid., vol. 90, pp. 1797ff. (1968)].

13) Compounds XIb '', in which Hal represents halogen, are advantageous from compounds XIc '', in which Π for subst. Phenyl or another protective group which can be removed under acidic conditions is accessible by reaction with hydrogen halide acids or inorganic acid halides, for example BBr ₃ , under conditions known from the literature [cf. TW Greene, Protective Groups in Organic Chemistry, J. Wiley & Sons, 1981, pp. 89-92].

Phenylpyrazoles of the formula II ''^# can alternatively be obtained from the benzyl alcohols of the formula XId ''^# . In the formula XI ''^# L stands for a nucleofugic leaving group, such as halogen or alkyl or aryl sulfonate, preferably bromine, chlorine, iodine, mesylate, tosylate or triflate and E ^# for a group A or a precursor therefor.

14) Reaction with Z-L, where L is for a nucleofugic finish group, such as halogen or alkyl or aryl sulfonate, preferred is bromine, chlorine, iodine, mesylate, tosylate or triflate, usually takes place at temperatures from 0 ° C to 180 ° C preferably 20 ° C to 60 ° C, in an inert organic solution medium in the presence of a base [cf. EP-A 254 426; EP-A 463 488; WO-A 95 / 18,789; WO-A 95 / 29,896].

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and Propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, as well as dime thylsulfoxide, dimethylformamide and dimethylacetamide, especially preferably dimethylformamide, tetrahydrofuran and acetone. It can mixtures of the solvents mentioned can also be used.

In general, inorganic compounds, such as alkali, come as bases metal and alkaline earth metal hydroxides such as lithium hydroxide, natri Umhydroxid, potassium hydroxide and calcium hydroxide, alkali metal and Alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as Lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, Potassium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compound dungen, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride, and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, also organic Bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri isopropylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well bicyclic amines. Natri are particularly preferred anhydride, potassium carbonate, potassium tert-butoxide and sodium me  thanolate. The bases generally become equimolar, in excess or optionally used as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use ZL in an excess based on XId ''^# .

Compounds XId '' are advantageous from the halides XIb '' by reaction with carboxylates R''COOM, where R '' is an alkyl radical and M is an ion from the group of alkali, alkaline earth or transition metals, and subsequent aminolysis accessible with an amine H ₂ N-R ″, where R ″ is an alkyl radical [cf. EP-A 781 764].

15) The reaction of the halide XIb '' with the carboxylate R''COOM usually takes place at temperatures from 10 ° C to 60 ° C an organic solvent [cf. EP-A 781 764].

Suitable solvents are dimethyl sulfoxide, dimethylformamide and dimethylacetamide. Mixtures of the above can also be used Solvents are used.

16) The aminolysis is usually carried out at from 10 ° C. to 60 ° C. in water or an inert organic solvent in the presence of amines H ₂ N-R '' [cf. EP-A 781 764].

Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane and tetrahydrofuran. It Mixtures of the solvents mentioned can also be used the.

Alternatively, the compounds of the formula XId '' can also be obtained from the Halides XIb '' are represented by the aldehydes XIf ''.  

17) The reaction is usually carried out at temperatures of 10 ° C to 80 ° C, in an inert organic solvent in Ge presence of N-methylmorpholine-N-oxide [cf. Lit. EP-A 422 597].

Suitable solvents are halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, nitriles such as acetone tril and propionitrile as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably acetonitrile, dimethyl sulfoxide and carbon tetrachloride. Mixtures of mentioned solvents are used.

18) The reduction is usually carried out at temperatures of 10 ° C up to 50 ° C, in water or an inert organic solution medium in the presence of reducing agents, for example hydride-transferring agents, such as alkali or alkaline earth boron hydrides, especially sodium borohydride [cf. Lit. EP-A 534 216].

Suitable solvents are water or alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, water is particularly preferred. Mixtures of mentioned solvents are used.

Intermediates of formula 2 in which

L is hydroxyl, CH ₂ OH, CH ₂ L 'or a group L', where L 'is a nucleophilically cleavable group and R ^A , R ^B , R ^C , Y and n have the meanings as in formula I. New.

If individual compounds I are not on the above written ways are accessible through derivatization tion of other compounds I are prepared.

The reaction mixtures are worked up in a conventional manner, e.g. B. by mixing with water, separation of the phases and given if chromatographic purification of the raw products. The intermediate and end products fall e.g. T. in the form of colorless or slightly brown Licher, viscous oils that are under reduced pressure and at moderate at elevated temperatures freed of volatile components or cleaned be inclined. If the intermediate and end products as solids cleaning can also be obtained by recrystallization or digesting.

The compounds I can be produced due to their C = C- and C = N double bonds are obtained as E / Z isomer mixtures which e.g. B. by crystallization or chromatography in the usual way can be separated into the individual connections.

If isomer mixtures are obtained in the synthesis, is generally However, a separation is not absolutely necessary, because the individual isomers partially during the preparation for the Application or during application (e.g. under light, acid or Base action) can convert into each other. Corresponding order Changes can also be made after application, for example during the Treatment of plants in the treated plant or in the controlling harmful fungus or animal pest.

With regard to the -N = C (R ¹ ) -C (R ² ) = NOR ³ double bonds of the substituent Z, the trans, trans isomers of the compounds I are generally preferred with regard to their activity (configuration based on the rest T in relation to the C (R ² ) = NOR ³ group, or based on the rest of OR ³ in relation to the TN = C (R ¹ ) group).

In the definitions of the symbols given in the formulas above, collective terms were used which generally represent the following substituents:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: saturated, straight-chain or branched hydrocarbon residues with 1 to 4, 6 or 10 carbon atoms, e.g. B. C ₁ -C ₆ alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1- Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1 , 2,2-trimethyl propyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
Haloalkyl: straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, e.g. B. C ₁ -C ₂ haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- Di fluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Alkoxy: straight-chain or branched alkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-O-);
Haloalkoxy: straight-chain or branched haloalkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-O-);
Alkylthio: straight-chain or branched alkyl groups with 1 to 10 or 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-);
Alkylamino: a straight-chain or branched alkyl group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via an amino group (-NH-);
Dialkylamino: two independent, straight-chain or branched alkyl groups each having 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via a nitrogen atom;
Alkylcarbonyl: a straight-chain or branched alkyl group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Alkoxycarbonyl: an alkoxy group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Alkylthiocarbonyl: an alkylthio group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Alkylaminocarbonyl: an alkylamino group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Dialkylaminocarbonyl: a dialkylamino group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Alkylcarbonyloxy: a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyloxy group (-CO ₂ -);
Alkylsulfonyl: a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-SO ₂ -);
Alkoxysulfonyl: an alkoxy group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-SO ₂ -);
Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and a double bond in any position, e.g. B. C ₂ -C ₆ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1- propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3- Methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-pro penyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2 -pro penyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4- Methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl- 3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl , 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1- butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2- butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl- 2-methyl-2-propenyl;
Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon residues with 2 to 10 carbon atoms and a double bond in any position (as mentioned above), the hydrogen atoms in these groups being partially or completely counteracted by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine , can be replaced;
Alkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 10 carbon atoms and a double bond in any position (as mentioned above) which is not adjacent to the hetero atom and which are bonded to the structure via an oxygen atom (-O-);
Haloalkenyloxy: unsaturated, straight-chain or branched alkenyloxy groups with 3 to 10 carbon atoms (as mentioned above), in which the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
Alkenylthio: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 10 carbon atoms and a double bond in any position (as mentioned above) which is not adjacent to the hetero atom and which are bonded to the skeleton via a sulfur atom (-S-);
Alkenylamino: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 10 carbon atoms and a double bond in any position (as mentioned above) which is not adjacent to the hetero atom and which are bonded to the skeleton via an amino group (-NH-);
Alkenylcarbonyl: unsaturated, straight-chain or branched hydrocarbon residues with 2 to 10 carbon atoms and a double bond in any position (as mentioned above) which are bonded to the skeleton via a carbonyl group (-CO-);
Alkenyloxycarbonyl: straight-chain or branched alkenyloxy groups with 3 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via a carbonyl group (-CO-);
Alkenylthiocarbonyl: straight-chain or branched alkenylthio groups with 3 to 10 carbon atoms (as mentioned above), which are bonded to the skeleton via a carbonyl group (-CO-);
Alkenylaminocarbonyl: straight-chain or branched alkenylamino groups with 3 to 10 carbon atoms (as mentioned above), which are bonded to the skeleton via a carbonyl group (-CO-);
Alkenylcarbonyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and a double bond in any position (as mentioned above) which is bonded to the skeleton via a carbonyloxy group (-CO ₂ -);
Alkynyl: straight-chain or branched hydrocarbon groups with 2 to 4, 6, 8 or 10 carbon atoms and a triple bond in any position, e.g. B. C ₂ -C ₆ alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3- Pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1- Ethyl 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentinyl, 2-methyl-4-pentinyl, 3-methyl-1-pentinyl, 3-methyl-4-pentinyl, 4-methyl-1-pentinyl, 4-methyl-2-pentinyl, 1, 1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1- Ethyl 2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Haloalkynyl: unsaturated, straight-chain or branched hydrocarbon residues with 2 to 10 carbon atoms and a triple bond in any position (as mentioned above), in which groups the hydrogen atoms are partially or completely counteracted by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine , can be replaced;
Alkynyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 10 carbon atoms and a triple bond in any position (as mentioned above) which is not adjacent to the heteroatom and which are bonded to the structure via an oxygen atom (-O-);
Haloalkynyloxy: unsaturated, straight-chain or branched alkynyloxy groups having 3 to 10 carbon atoms (as mentioned above), in which the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
Cycloalkyl: monocyclic, saturated hydrocarbon groups with 3 to 6, 8, 10 or 12 carbon ring members, e.g. B. C ₃ -C ₈ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclo hexyl, cycloheptyl and cyclooctyl;
Cycloalkoxy: monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are bonded to the structure via an oxygen atom (-O-);
Cycloalkylthio: monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-);
Cycloalkylamino: monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above) which are bonded to the structure via an amino group (-NH-);
Cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups with 3 to 12 carbon ring members (as mentioned above), which are bonded to the skeleton via a carbonyl group (-CO-);
Cycloalkoxycarbonyl: a monocyclic cycloalkoxy group with 3 to 12 carbon ring members (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Cycloalkylthiocarbonyl: a monocyclic cycloalkylthio group with 3 to 12 carbon ring members (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
saturated or partially unsaturated cyclic radical which, in addition to carbon atoms as ring members, can contain heteroatoms from the group consisting of oxygen, sulfur or nitrogen: cycloalkyl having 3 to 12 carbon ring members as mentioned above or containing 5- or 6-membered heterocycles (heterocyclyl) in addition to carbon ring members up to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, e.g. B. 2-tetrahydrofuranyl, 3-tetra hydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiaziazinyl Isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazo lidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1, 2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolini din-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2 , 4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thia diazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3- Dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3- Dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2,3-pyrrolin-2-yl, 2,3-pyrrolin-3-yl, 2,4- Pyrrolin-2-yl, 2,4-pyrrolin-3-yl, 2,3-isoxazolin-3-yl, 3,4-isoxazolin-3-yl, 4,5-isoxazolin-3-yl, 2,3- Isoxazolin-4-yl, 3,4-isoxazolin-4-yl, 4,5-isox azolin-4-yl, 2,3-isoxazolin-5-yl, 3,4-isoxazolin-5-yl, 4,5-isoxazolin-5-yl, 2,3-isothiazolin-3-yl, 3,4- Isothiazolin-3-yl, 4,5-isothiazolin-3-yl, 2,3-isothiazo lin-4-yl, 3,4-isothiazolin-4-yl, 4,5-isothiazolin-4-yl, 2,3 -Isothiazolin-5-yl, 3,4-isothiazolin-5-yl, 4,5-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2, 3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3rd , 4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl , 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-di hydrooxazol-5-yl, 3,4-dihydrooxazol-2 -yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4 -Tetrahy dropyranyl, 2-tetrahydrothia nyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-te trahydro-triazin-2-yl and 1,2,4-tetrahydro -3-yl;
Aryl: a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. B. phenyl, naphthyl and anthracenyl;
Aryloxy: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an oxygen atom (-O-);
Arylthio: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a sulfur atom (-S-);
Arylamino: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an amino group (-NH-);
Arylcarbonyl: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Aryloxycarbonyl: a mono- to trinuclear aryloxy group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Arylthiocarbonyl: a mono- to trinuclear arylthio group (as mentioned above) which is bonded to the structure via a carbonyl group (-CO-);
Arylaminocarbonyl: a mono- to trinuclear arylamino group (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
Arylcarbonyloxy: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonyloxy group (-CO ₂ -);
Arylcarbonylthio: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonylthio group (-COS-);
Arylcarbonylamino: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a carbonylamino group (-CONH-);
Arylsulfonyl: a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-SO ₂ -);
Aryloxysulfonyl: a mono- to trinuclear aryloxy group (as mentioned above) which is bonded to the skeleton via a sulfonyl group (-SO ₂ -);
aromatic ring system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen: aryl as mentioned above or one or two nuclear heteroaryl, e.g. B.

• - 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or Oxygen atom: 5-ring heteroaryl groups, which in addition to carbon Substance atoms one to four nitrogen atoms or one to three Nitrogen atoms and a sulfur or oxygen atom as a ring may contain members, for. B. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imida zolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5- yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-tria zol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl;
• - Benzo-condensed 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one acid Substance or sulfur atom: 5-ring heteroaryl groups, which in addition to carbon atoms one to four nitrogen atoms or one up to three nitrogen atoms and one sulfur or oxygen atom can contain as ring links, and in which two contiguous bearded carbon ring members or a nitrogen and a adjacent carbon ring member by a buta-1,3-diene-1,4- diyl group can be bridged;
• - Containing 5-membered heteroaryl bound via nitrogen one to four nitrogen atoms, or nitrogen bound benzo-fused 5-membered heteroaryl containing one to three nitrogen atoms: 5-ring heteroaryl groups, which next to Carbon atoms one to four nitrogen atoms or one to can contain three nitrogen atoms as ring members, and in which two adjacent carbon ring links or a stick fabric and an adjacent carbon ring member by a Buta-1,3-diene-1,4-diyl group can be bridged, this Tied rings over one of the nitrogen ring links to the frame are;
• - 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups, which next to Carbon atoms one to three or one to four nitrogen may contain atoms as ring members, for. B. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyri  midinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5- Triazin-2-yl and 1,2,4-triazin-3-yl;

The addition "possibly subst." with respect to alkyl, alkenyl and alkynyl groups is intended to express that these groups can be partially or completely halogenated [ie the hydrogen atoms of these groups can be partially or completely replaced by the same or different halogen atoms as mentioned above (preferably fluorine, chlorine or Bromine) can be replaced] and / or can carry one to three (preferably one) of the following radicals:

• - cyano, nitro, hydroxy, alkoxy, haloalkoxy, alkoxycarbonyl, Alkylcarbonyloxy, the alkyl groups being present in these residues preferably 1 to 6 carbon atoms, in particular 1 to 4 Contain carbon atoms;
• - Unsubstituted or substituted by usual groups Cycloalkyl, cycloalkoxy, heterocyclyl, heterocyclyloxy, where the cyclic systems 3 to 12 ring members, preferably 2 to Contain 8 ring links, in particular 3 to 6 ring links and the alkyl groups in these residues are preferably 1 to 6 carbons contain atoms, in particular 1 to 4 carbon atoms;
• - Unsubstituted or substituted by usual groups Aryl, aryloxy, arylalkoxy, arylalkyl, hetaryl, hetaryloxy, het arylthio, hetarylamino, hetarylalkoxy, hetarylalkyl, the Aryl radicals preferably 6 to 10 ring members, in particular 6 Contain ring members (phenyl), the hetaryl residues in particular 5 or contain 6 ring members and the alkyl groups in them Residues preferably 1 to 6 carbon atoms, in particular 1 contain up to 4 carbon atoms.

The addition "optionally subst" with respect to the cyclic (saturated, unsaturated or aromatic) groups is intended to express that these groups can be partially or completely halogenated [ie the hydrogen atoms of these groups can be partially or completely replaced by identical or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine, in particular fluorine or chlorine in particular) can be replaced] and / or can carry one to four (in particular one to three) of the following radicals:

• - cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbo nyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy, Alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino, Dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfo xyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,  Dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothio carbonyl, the alkyl groups in these radicals being preferred 1 to 6 carbon atoms, especially 1 to 4 carbon atoms contain and the alkenyl or alkynyl groups mentioned in these residues 2 to 8, preferably 2 to 6, in particular 2 to Contain 4 carbon atoms;

and / or one to three (in particular one) of the following radicals:

• unsubstituted or substituted cycloalkyl, cycloalkoxy, Heterocyclyl, heterocyclyloxy, the cyclic systems 3 up to 12 ring links, preferably 2 to 8 ring links, in particular containing 3 to 6 ring members and the alkyl groups in the sen radicals preferably 1 to 6 carbon atoms, in particular Contain 1 to 4 carbon atoms;
• unsubstituted or substituted aryl, aryloxy, arylthio, arylalkoxy, arylalkyl, hetaryl, hetaryloxy, hetarylthio, where the aryl radicals preferably contain 6 to 10 ring members, in particular 6 ring members (phenyl), the hetaryl radicals contain in particular 5 or 6 ring members and the alkyl groups in these Radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms,
  the above-mentioned cyclic groups in turn can be partially or completely halogenated and / or can carry 1 to 3 of the following substituents:
  • - Cyano, nitro, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ - C ₆ -Ha logenalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, C ₂ -C ₆ alkenyl, C ₂ -C ₆ -alkenyl oxy, C ₃ -c ₆ -alkynyloxy and C ₁ -C ₄ -alkylenedioxy, which may be halogenated,
  and / or can carry one or two (in particular one) of the following radicals:
  • - C (= NOR ^d ) -Γ ₁ -R ^d ', where R ^{d is} hydrogen or C ₁ -C ₆ alkyl, Γ is oxygen, sulfur or NR ^d and 1 is 0 or 1;
  and / or in which two adjacent C atoms of the cyclic systems can carry an oxy-C ₁ -C ₃ -alkyleneoxy, oxy-C ₂ -C ₄ -alkenylene, or butadiene diyl group, these bridges in turn halogenating partially or completely could be.

Typical groups are in particular the following substituents: cyano, halogen, nitro, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ - Haloalkoxy.

With regard to their intended use of the phenylpyrazoles of the formula I, the following meanings of the substituents, in each case individually or in combination, are particularly preferred:
Compounds of the formula I in which T is oxymethylene are particularly preferred.

In addition, particular preference is given to compounds of the formula I, in where n = zero (0).

Likewise, particular preference is given to compounds I in which Z represents N = C (R ¹ ) -C (R ² ) = NOR ³ .

In addition, compounds I are particularly preferred in which Z is N = CWR ¹ .

In addition, compounds I are particularly preferred in which W represents optionally substituted phenyl.

In particular, compounds I are preferred in which Z is a group X stands.

In addition, compounds 1 are particularly preferred in which R ^{2 represents} a group W.

Likewise, particular preference is given to compounds I in which R ^{2 represents} a group W which is bonded via oxygen.

In addition, compounds I are particularly preferred in which X for subst. Aryl or optionally subst. Hetaryl stands.

Furthermore, compounds 1 are particularly preferred in which R ^{1 represents} methyl or ethyl.

In addition, compounds I are particularly preferred in which R ^{3 is} C ₁ -C ₃ alkyl, C ₃ -C ₅ alkenyl or C ₃ -C ₅ alkynyl.

In addition, compounds I are particularly preferred in which R ^{3 represents} methyl, allyl or propargyl.

Furthermore, particular preference is given to compounds of the formula I in which T is oxygen or oxymethylene, Z is a group X, N = CWR ¹ or N = C (R ¹ ) -C (R ² ) = NOR ³ , where
X heterocyclyl, which can be completely or partially halogenated and / or can carry 1 to 3 of the following radicals:
Cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxy;
Aryl, hetaryl, arylmethylene or hetarylmethylene, where the cyclic radicals can be partially or completely halogenated and / or can carry one to three of the following groups:
Cyano, nitro, hydroxy, mercapto, amino, carboxyl, amino carbonyl, aminothiocarbonyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ -halogen alkyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkyl sulfoxyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkyl thio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkyl aminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C ₆ -alkyl aminothiocarbonyl, di-C ₁ - C ₆ alkylaminothiocarbonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy, hetero arylthio, C ₃ -C ₆ alkynyloxy, C ₁ -C ₄ -alkylenedioxy, which can be halogenated, or C (= NOR ^d ) -Γ ₁ -R ^d ', wherein
R ^{d is} hydrogen or C ₁ -C ₆ alkyl;
Γ represents oxygen, sulfur or NR ^d ;
l is 0 or 1 and
the cyclic groups in turn can be partially or completely halogenated and / or can carry 1 to 3 of the following substituents: cyano, nitro, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ - Alkylcarbonyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylamino, Di-C ₁ -C ₆ alkylamino, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy and C ₁ -C ₄ alkylenedioxy, which can be halogenated,
W is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl,
these groups being completely or partially halogenated and / or having 1 to 3 of the following radicals:
Cyano, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₃ -C ₆ cycloalkyl, heterocyclyl, aryl or hetaryl, where
the cyclic groups in turn can be partially or completely halogenated and / or can carry 1 to 3 of the following radicals:
Cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy; or
for C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl or heterocyclyl,
these groups being completely or partially halogenated and / or having 1 to 3 of the following radicals:
Cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxy; or
for aryl or heteroaryl,
wherein these residues can be partially or completely halogenated and / or can carry one to three of the following groups:
Cyano, nitro, hydroxy, mercapto, amino, carboxyl, amino carbonyl, aminothiocarbonyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ -halogen alkyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkyl sulfoxyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkyl thio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkyl aminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C ₆ -alkyl aminothiocarbonyl, di-C ₁ - C ₆ alkylaminothiocarbonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy, hetero arylthio, C ₃ -C ₆ alkynyloxy, C ₁ -C ₄ -alkylenedioxy, which can be halogenated, or C (= NOR ^d ) -Γ ₁ -R ^d ', wherein
R ^{d is} hydrogen or C ₁ -C ₆ alkyl;
Γ represents oxygen, sulfur or NR ^d ;
l is 0 or 1 and
the cyclic groups in turn can be partially or completely halogenated and / or can carry 1 to 3 of the following substituents:
Cyano, nitro, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ -halogen alkyl, C ₁ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ - C ₆ -haloalkoxy, C ₁ -C ₆ -alkoxy carbonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy and C ₁ -C ₄ alkylenedioxy, which may be halogenated;
R ^{2 is} hydrogen, cyano, halogen, C (R ^d ) = NOR ³ or W, OW, SW or NR ^c W, where
R ^{c is} hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl;
R ^{d is} hydrogen or C ₁ -C ₄ alkyl; and
R ^{3 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ cyanoalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkoxy-C ₁ -C ₆ - alkyl or C ₃ -C ₆ cycloalkyl- C ₁ -C ₄ alkyl, wherein
these groups can be partially or completely halogenated and the cycloalkyl groups can additionally carry 1 to 3 C ₁ -C ₄ -alkyl radicals; mean.

In particular, compounds I are preferred in which R ^{A is} halogen.

In addition, compounds I are particularly preferred in which R ^{A represents} chlorine or bromine.

Likewise, particular preference is given to compounds I in which R ^{B is} hydrogen.

Compounds of the formula I in which R ^{C is} alkyl or haloalkyl are furthermore preferred.

In addition, compounds of formula I are particularly preferred in which R ^{C is} methyl or ethyl.

In particular, compounds I are preferred in which Z is optionally substituted phenyl, pyridinyl, pyrimidinyl, Quinazolinyl, furanyl, thienyl, pyrrolyl, benzofuranyl, benzo thiophenyl, indolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxazo lyl, thiazolyl, imidazolyl, triazolyl, tetrazolyl, thiadiazolyl, Benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzisothiazolyl or indazolyl.  

In particular, compounds I.1 'are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl and Z is optionally substituted phenyl, pyridinyl, pyrimidi nyl, quinazolinyl, furanyl, thienyl, pyrrolyl, benzofuranyl , Ben zothiophenyl, indolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, tetrazolyl, thiadiazo lyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazo lyl or indazolyl.

In addition, compounds I.1 'are particularly preferred in which Z for substi by halogen, methyl, trifluoromethyl or methoxy tuated phenyl.

Compounds I.1 ″ are also preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl and Z is optionally substituted phenyl, naphthyl, pyridinyl, pyrimidinyl, quinolyl, triazolyl, pyrazinyl, Thienyl, quinoxalinyl, benzoxazolyl, benzthiazolyl or pyrazolyl.

Furthermore, compounds I.1 ″ are particularly preferred in which Z represents phenyl substituted by halogen, methyl, trifluoromethyl or C (= NOR ^d ) R ^d ′.

Equally preferred are compounds I.2 'in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl and Z is optionally substituted phenyl, naphthyl, pyridinyl, pyrimidinyl, quinolyl, pyrazinyl, thienyl, quinoxalinyl, Benzoxa zolyl, benzthiazolyl or pyrazolyl.

In addition, compounds I.2 'are particularly preferred in which Z represents phenyl substituted by halogen, methyl, trifluoromethyl or C (= NOR ^d ) R ^d '.

Equally particularly preferred are compounds I.3 'in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, as well as C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl and R ^{1 represents} methyl or methoxy.

In addition, compounds I.3 ″ are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, as well as C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl and R ^{1 represents} methyl or methoxy.

Furthermore, compounds I.4 'are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, R ^{1 is} methyl or methoxy, R ^{2 is} halogen, cyano, C (= NOR ^d ) R ^d ', if necessary subst. C ₁ -C ₄ alkyl, C ₁ -C ₄ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ cycloalkoxy, C ₁ -C ₄ alkylamino, C ₂ -C ₄ alkenyl or phenyl and R ³ for hydrogen, propargyl or allyl or optionally subst. C ₁ -C ₄ alkyl.

In addition, compounds I.4 ″ are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, R ^{1 is} methyl or methoxy, R ^{2 is} halogen, cyano, C (= NOR ^d ) R ^d 'if necessary subst. C ₁ -C ₄ alkyl, C ₁ -C ₄ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ cycloalkoxy, C ₁ -C ₄ alkylamino, C ₂ -C ₄ alkenyl or phenyl and R ³ for hydrogen, propargyl or allyl or optionally subst. C ₁ -C ₄ alkyl.

Furthermore, compounds I.5 'are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, and also C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl.

In particular, compounds I.5 ″ are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, and also C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl.

In addition, compounds I.6 'are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, and also C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl.

Equally preferred are compounds I.6 ″ in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, and also C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl.

In addition, compounds I.7 'are preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, and also C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl.

Compounds 1.8 'are also preferred in which R ^{A is} chlorine or bromine, R ^{B is} hydrogen, R ^{C is} methyl or ethyl, T is nitrogen or carbon and W is optionally subst. Phenyl, naphthyl, anthryl, benzyl, phenylethyl, phenylpropyl, pyridinyl, pyrimidinyl, thienyl, furyl, thiazolyl, benzothiazolyl, dioxanyl, C ₃ -C ₆ cycloalkyl, and also C ₁ -C ₄ alkyl, allyl, propargyl or trifluoromethyl .

In particular, with regard to their use, those shown in fol Compounds I compiled in the tables preferred. The  groups in the tables for a substituent also considered individually, regardless of the combination, in  of which they are called, a particularly preferred embodiment of the relevant substituents.

Table 1

Compounds of the general formula I.1 ', in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl and Z for each compound corresponds to one row of Table A.

Table 2

Compounds of the general formula I.1 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl and Z for each compound corresponds to one row of Table B.

Table 3

Compounds of the general formula I.2 'in which R ^A for chlorine, R ^B for hydrogen, R ^C for methyl and Z for a compound corresponds in each case to one line of Table B.

Table 4

Compounds of the general formula I.3 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 5

Compounds of the general formula I.3 ″ in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 6

Compounds of the general formula I.4 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and the combination of the radicals R ² and R ³ for a compound in each case one row of Table D corresponds.

Table 7

Compounds of the general formula I.4 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ³ for a compound in each case one row of Table D corresponds.

Table 8

Compounds of the general formula I.4 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and the combination of the radicals R ² and R ³ for a compound is in each case one row of the table D corresponds.

Table 9

Compounds of the general formula I.4 '' in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methoxy 51517 00070 552 001000280000000200012000285915140600040 0002019756115 00004 51398 and the combination of the radicals R ² and R ^{3 is} one connection corresponds to one row of Table D.

Table 10

Compounds of the general formula I.5 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 11

Compounds of the general formula I.6 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 12

Compounds of the general formula I.6 ″ in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 13

Compounds of the general formula I.7 ', in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 14

Compounds of the general formula I.1 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl and Z for a compound corresponds in each case to one line of Table A.

Table 15

Compounds of the general formula I.1 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl and Z for each compound corresponds to one row of Table B.

Table 16

Compounds of the general formula I.2 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, and Z for each compound corresponds to one row of Table B.

Table 17

Compounds of the general formula I.3 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 18

Compounds of the general formula I.3 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 19

Compounds of the general formula I.4 'in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and the combination of the radicals R ² and R ^{3 is} in each case one row of the table D corresponds.

Table 20

Compounds of the general formula I.4 'in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ^{3 is} in each case one row of the table D corresponds.

Table 21

Compounds of the general formula I.4 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methyl and the combination of the radicals R ² and R ^{3 is} in each case one line of the compound Table D corresponds.

Table 22

Compounds of the general formula I.4 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ^{3 is} in each case one line of the compound Table D corresponds.

Table 23

Compounds of the general formula I.5 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 24

Compounds of the general formula I.6 'in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 25

Compounds of the general formula I.6 ″ in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 26

Compounds of the general formula I.7 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} methyl and W for each compound corresponds to one row of Table C.

Table 27

Compounds of the general formula I.1 ', in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl and Z for each compound corresponds to one row of Table A.

Table 28

Compounds of the general formula I.1 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl and Z for each compound corresponds to one row of Table B.

Table 29

Compounds of the general formula I.2 ', in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, and Z for each compound corresponds to one row of Table B.

Table 30

Compounds of the general formula I.3 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 31

Compounds of the general formula I.3 ″ in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 32

Compounds of the general formula I.4 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and the combination of the radicals R ² and R ³ for a compound is in each case one row of the table D corresponds.

Table 33

Compounds of the general formula I.4 ', in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ³ for a compound corresponds in each case to one line of Table D. corresponds.

Table 34

Compounds of the general formula I.4 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and the combination of the radicals R ² and R ^{3 is} in each case one line of the compound Table D corresponds.

Table 35

Compounds of the general formula I.4 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ³ for a compound is in each case one row of the table D corresponds.

Table 36

Compounds of the general formula I.5 ", in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 37

Compounds of the general formula I.6 'in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 38

Compounds of the general formula I.6 ″ in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 39

Compounds of the general formula I.7 ', in which R ^{A is} chlorine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 40

Compounds of the general formula I.1 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl and Z for each compound corresponds to one row of Table A.

Table 41

Compounds of the general formula I.1 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl and Z for each compound corresponds to one row of Table B.

Table 42

Compounds of the general formula I.2 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, and Z for a compound corresponds in each case to one part of Table B.

Table 43

Compounds of the general formula I.3 'in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 44

Compounds of the general formula I.3 ″ in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and W for each compound corresponds to one row of Table C.

Table 45

Compounds of the general formula I.4 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and the combination of the radicals R ² and R ³ for a compound is in each case one row of the table D corresponds.

Table 46

Compounds of the general formula I.4 'in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ³ for a compound is in each case one row of the table D corresponds.

Table 47

Compounds of the general formula I.4 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methyl and the combination of the radicals R ² and R ^{3 is} in each case one line of the compound Table D corresponds.

Table 48

Compounds of the general formula I.4 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl, R ^{1 is} methoxy and the combination of the radicals R ² and R ^{3 is} in each case one line of the compound Table D corresponds.

Table 49

Compounds of the general formula I.5 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 50

Compounds of the general formula I.6 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 51

Compounds of the general formula I.6 ", in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table 52

Compounds of the general formula I.7 ', in which R ^{A is} bromine, R ^{B is} hydrogen, R ^{C is} ethyl and W for each compound corresponds to one row of Table C.

Table A

Table B

Table C.

Table D

The compounds I are suitable as fungicides. You stand out due to its excellent effectiveness against a wide range of phytopathogenic fungi, in particular from the class of Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes, out. Some of them are systemic and can be used in plants protection can be used as foliar and soil fungicides.

They are particularly important for combating a large number of mushrooms on various crops such as wheat, rye, Barley, oats, rice, corn, grass, bananas, cotton, soy, coffee fairy, sugar cane, wine, fruit and ornamental plants and vegetables like cucumbers, beans, tomatoes, potatoes and squash, as well as on the seeds of these plants.

They are particularly suitable for combating the following plant diseases:

• - Alternaria species in vegetables and fruits,
• - Botrytis cinerea (gray mold) on strawberries, vegetables, ornaments plants and vines,
• - Cercospora arachidicola on peanuts,
• - Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin grow,
• - Erysiphe graminis (powdery mildew) on cereals,
• - Fusarium and Verticillium, species on different plants,
• - Helminthosporium species on cereals,
• - Mycosphaerella species on bananas and peanuts,
• - Phytophthora infestans on potatoes and tomatoes,
• - Plasmopara viticola on vines,
• - Podosphaera leucotricha on apples,
• Pseudocercosporella herpotrichoides on wheat and barley,
• - Pseudoperonospora species on hops and cucumbers,
• - Puccinia species on cereals,
• - Pyricularia oryzae on rice,
• - Rhizoctonia species on cotton, rice and lawn,
• - Septoria nodorum on wheat,
• - Uncinula necator on vines,
• - Ustilago species on cereals and sugar cane, as well
• - Venturia species (scab) on apples and pears.

The compounds I are also suitable for combating harmful substances mushrooms like Paecilomyces variotii in material protection (e.g. wood, Paper, dispersions for painting, fibers or fabrics) and in Storage protection.  

The compounds I are applied by using the mushrooms or the plants, seeds, materials to be protected from fungal attack s or the soil with a fungicidally effective amount of active fabrics treated. The application can be done both before and after Infection of materials, plants or seeds by the fungi respectively.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.

The application rates are depending on the application in crop protection Depending on the desired effect, between 0.01 and 2.0 kg of active ingredient fabric per ha.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 0.1 g, preferably 0.01 to 0.05 g per kilogram Seed needed.

When used in the protection of materials or stocks, the application rate of active ingredient according to the type of application and the desired effect. Usual application rates are in Material protection, for example 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.

The compounds of formula I are also suitable for effectively combating animal pests from the class of insects, arachnids and nematodes. They can be used in crop protection as well as in the hygiene, storage protection and veterinary sectors to control animal pests. They are particularly suitable for controlling the following animal pests:

• - Insects from the order of the butterflies (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argilla cea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, cirphis unipuncta, cydia pomonella, dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insu lana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersi cella, Lambdina fiscellaria, Laphygma exigua, Leucoptera cof feella, Leucoptera scitella, Lithocolletis blancardella, lobe sia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra  brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseu doplusia includens, Rhyacionia frustrana, Scrobipalpula abso luta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumato poea pityocampa, Tortrix viridana, Trichoplusia ni and Zeira phera canadensis,
• - Beetles (Coleoptera), e.g. B. Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Bla piniperda stophagus, Blitophaga undata, Bruchus rufimanus, Bru chus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebu losa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorr hynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica l2-punc tata, Diabrotica virgifera, Epilachna varivestis, Epitrix hir tipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera fountain tennis, hypera postica, ips typographus, lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californi cus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,
• - Two-winged (Diptera), e.g. B. Aedes aegypti, Aedes vexans, Anas trepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macella ria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pi piens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, fan nia canicularis, Gasterophilus intestinalis, glossina morsi tans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifo lii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lyco ria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagole tis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula ole racea and tipula paludosa,  
• - Thrips (Thysanoptera), e.g. B. Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
• - Hymenoptera, e.g. B. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testu dinea, Monomorium pharaonis, Solenopsis geminata and'Solenopsis invicta,
• Bugs (Heteroptera), e.g. B. Acrosternum hilare, Blissus leucop terus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus in termedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Ne zara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
• - Plant suckers (Homoptera), e.g. B. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopa lomyzus ascalonicus, Rhopa, losiphum maidis, Sappaphis mala, Sap paphis mali, Schizaphis graminum, Schizoneura lanuginosa, Tria leurodes vaporariorum and viteus vitifolii,
• - Termites (Isoptera), e.g. B. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis,
• - Straight wing aircraft (Orthoptera), e.g. B. Acheta domestica, Blatta orien talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melano plus femur rubrum, Melanoplus mexicanus, Melanoplus sanguini pes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,
• - Arachnoid such as arachnids (Acarina), e.g. B. Amblyomma america num, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoeni cis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius magnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllo  coptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetra nychus pacificus, Tetranychus telarius and Tetranychus urticae,
• - Nematodes such as root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming Nematodes, e.g. B. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, heterodera schachtii, heterodera trifolii, Stick and leaf flakes, e.g. B. Belonolaimus longicaudatus, Dity lenchus destructor, Ditylenchus dipsaci, Heliocotylenchus mul ticinctus, Longidorus elongatus, Radopholus similis, Rotylen chus robustus, Trichodorus primitivus, Tylenchorhynchus clay toni, Tylenchorhynchus dubius, Pratylenchus neglectus, Praty lenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.

The amount of active ingredient used to combat animal Pests are 0.1 to 2.0 in free field conditions preferably 0.2 to 1.0 kg / ha.

The compounds I can in the usual formulations leads, z. B. solutions, emulsions, suspensions, dusts, Powders, pastes and granules. The application form depends according to the respective purpose; in any case, it should be fine and uniform distribution of the verbin invention guarantee.

The formulations are prepared in a known manner, e.g. B. by stretching the active ingredient with solvents and / or Carriers, if desired using emulsifier agents and dispersants, where in the case of water as Ver other organic solvents as auxiliary solvents can be used. Coming as auxiliaries essentially considered for this: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. Kaolins, clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene Fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and Disper greed such as lignin sulfite and methyl cellulose.  

Alkali, alkaline earth, ammonium come as surface-active substances salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsul fonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, Alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and fatty acids as well as their alkali and alkaline earth salts, salts of sulfated Fatty alcohol glycol ether, condensation products of sulfonated Naphthalene and naphthalene derivatives with formaldehyde, condensate onproducts of naphthalene or naphthalene sulfonic acid Phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxy lated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl poly ether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates sate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxy lated polyoxypropylene, lauryl alcohol polyglycol ether acetal, Sor bitester, lignin sulfite and methyl cellulose.

For the production of directly sprayable solutions, emulsions, Pastes or oil dispersions come from medium oil fractions rem to high boiling point, such as kerosene or diesel oil, further Coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated Naphthalenes or their derivatives, methanol, ethanol, propanol, Butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclo hexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. B. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, into consideration.

Powders, materials for spreading and dusts can be mixed or joint grinding of the active substances with a solid Carrier are manufactured.

Granules, e.g. B. coating, impregnation and homogeneous granules te, can by binding the active ingredients to solid carriers getting produced. Solid carriers are e.g. B. mineral soils, such as silica gel, silicas, silica gels, silicates, talc, Kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolo with, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as. B. ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and herbal pro products such as cereal flour, tree bark, wood and nutshell flour, Cellulose powder and other solid carriers.  

The formulations generally contain between 0.01 and 95 % By weight, preferably between 0.1 and 90% by weight of the active ingredient. The active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are:

• I. 5 parts by weight of a compound according to the invention 95 parts by weight of finely divided kaolin intimately mixed. Man receives a dusting agent that contains 5% by weight of the Contains active ingredient.
• II. 30 parts by weight of a compound according to the invention are with a mixture of 92 parts by weight of powdered pebble acid gel and 8 parts by weight paraffin oil, which is on the surface this silica gel was sprayed, mixed intimately. Man receives a treatment of the active ingredient in this way good adhesion (active substance content 23% by weight)
• III. 10 parts by weight of a compound according to the invention are in dissolved a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mol of oleic acid-N-monoethanolamide, 2 parts by weight of calcium salt the dodecylbenzenesulfonic acid and 2 parts by weight of the plant tion product of 40 moles of ethylene oxide with 1 mole of castor oil exists (active ingredient content 9% by weight).
• IV. 20 parts by weight of a compound according to the invention are in dissolved a mixture consisting of 60 parts by weight of cyclohexanone, 030 parts by weight of isobutanol, 5 parts by weight of the addition pro product of 7 moles of ethylene oxide with 1 mole of isooctylphenol and Parts by weight of the adduct of 40 moles of ethylene oxide 1 mol of castor oil (active ingredient content 16% by weight).
• V. 80 parts by weight of a compound of the invention 3 parts by weight of the sodium salt of diisobutylnaphthalene-al pha-sulfonic acid, 10 parts by weight of the sodium salt Lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight powdered silica gel well mixed and in one Hammer mill ground (active ingredient content 80% by weight)
• VI. 90 parts by weight of a Ver according to the invention are mixed bond with 10 parts by weight of N-methyl-α-pyrrolidone and receives a solution for use in the form of tiny drops is suitable (active ingredient content 90% by weight).  
• VII. 20 parts by weight of a compound according to the invention are described in dissolved a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide on 1 mole of castor oil. By pouring and fine Distribute the solution in 100,000 parts by weight of water an aqueous dispersion containing 0.02% by weight of the active ingredient contains.
• VIII. 20 parts by weight of a compound according to the invention are with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight pul deformed silica gel well mixed and in a ham grind grinder. By finely distributing the mixture in 20,000 parts by weight of water are obtained from a spray mixture which Contains 0.1% by weight of the active ingredient.

The active ingredients as such, in the form of their formulations or the application forms prepared from it, e.g. B. in the form of directly sprayable solutions, powders, suspensions or dispersers sions, emulsions, oil dispersions, pastes, dusts, litter averaging, granules by spraying, atomizing, dusting, ver sprinkle or pour. The application forms rich depending on the purposes; they should be in everyone If possible, the finest distribution of the active ingredient according to the invention ensure fabrics.

Aqueous application forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) through Zu set of water to be prepared. For the production of emulsions, Pastes or oil dispersions can contain the substances as such or dissolved in an oil or solvent, using wetting, adhesive, Dispersants or emulsifiers are homogenized in water. But it can also be made of an effective substance, wetting, sticking, dispersing yaw or emulsifier and possibly solvent or oil existing concentrates are made that can be diluted with Water are suitable.

The active ingredient concentrations in the ready-to-use preparation cations can be varied in larger areas. In general NEN they are between 0.0001 and 10%, preferably between 0.01 and 1%.  

The active ingredients can also be used successfully in ultra-low-volume Procedure (ULV) can be used, where it is possible to form stungen with more than 95 wt .-% active ingredient or even the active ingredient without applying additives.

Oils of various types, herbicides, fun gicides, other pesticides, bactericides, given if necessary, only immediately before use (tank mix) be set. These agents can be used with the invention be mixed in a weight ratio of 1:10 to 10: 1.

The agents according to the invention can be used as Fungicides are also present together with other active ingredients e.g. B. with herbicides, insecticides, growth regulators, fungicides that or with fertilizers. When mixing the connections I or the agents containing it in the application form as fun In many cases, one obtains gicides with other fungicides Enlargement of the fungicidal spectrum of activity.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

• - Sulfur, dithiocarbamates and their derivatives, such as Ferridi methyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bis-dithiocarbamate, tetramethylthiuram disulfide, Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), Zinc (N, N'-propylene bis-dithiocarbamate), N, N'-polypropylene bis- (thiocarbamoyl) disulfide;
• Nitroderivatives, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-Bu tyl-4,6-dinitrophenyl-isopropyl carbonate, 5-nitro-isophthalic acid re-di-isopropyl ester;
• - Heterocyclic substances, such as 2-heptadecyl-2-imidazolin-ace tat, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl phthalimidophosphonothioate, 5-amino-1- [bis- (dimethylami no) -phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-di thioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benz imidazole, 2- (thiazolyl- (4)) benzimidazole, N- (1,1,2,2-tetra chloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-te trahydrophthalimide, N-trichloromethylthio-phthalimide,  
• - N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanme thylthiobenzthiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, Pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dime thyl-furan-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-me thoxy-2,5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid re-anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpho lin-2,2,2-trichloroethyl acetal, piperazin-1,4-diylbis-1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -1-formy lamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpro pyl] cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) - 2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl- 1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichloro phenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-tri azol-1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H- 1,2,4-triazol-1-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophene nyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H-1,2,4-triazole, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol, 5-Bu tyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis (p-chloro phenyl) -3-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2- thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thio ureido) -benzene,
• - Strobilurins such as methyl-E-methoxyimino- [α- (o-tolyloxy) -o-to lyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl oxy] -phenyl} -3-methoxyacrylate, methyl-E-methoxyimino- [α- (2- phenoxyphenyl) acetamide, methyl-E-methoxyimino- [α- (2,5-dime thylphenoxy) -o-tolyl] -acetamide,
• Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-Me thyl-6-cyclopropyl-pyrimidin-2-yl] aniline,
• Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyr rol-3-carbonitrile,  
• - Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphe nyl) acrylic acid morpholide,
• - and various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, Hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-fu royl (2) alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyace tyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chlorace tyl-D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phe nylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlor phenyl) -2,4-dioxo-1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-me thyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione, 3- (3,5-dichlor phenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) - 1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4- Dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H- 1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2,6- dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2- aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) - 1H-1,2,4-triazole.

Synthesis examples

The examples given in the synthesis examples below Writings were made with a corresponding modification of the output compounds used to obtain further compounds I. The Compounds thus obtained are in the tables below listed with physical details.

Example 1a

Production of

A solution of 11.8 g (36 mmol) of 2- [1 '- (4' '- chlorophenyl) pyrazole- 3-yloxymethyl] nitrobenzene [Lit .: WO-A 93 / 15,046] in 60 ml of metha nol was activated with 25 mg of iron (III) chloride hexahydrate and 2 g coal added. This mixture was at reflux temperature 3 ml (60 mmol) of hydrazine hydrate were added within one hour. After a further 5 hours of reflux and cooling, the mixture became filtered and the filtrate concentrated in vacuo. After Chromatogra On silica gel (methylene chloride) 6.5 g of the title were obtained compound in the form of colorless crystals (mp. 75-78 ° C).  

Example 1b

Production of

A mixture of 21 g (70 mmol) of the aniline from Example 1a in 125 ml of water and 20 ml of conc. A solution of 7 g of NaNO ₂ in 25 ml of water was added dropwise to hydrochloric acid at 0 ° C. After stirring at 0 ° C. for about 30 minutes, it was added dropwise to a suspension of 75 g of SnCl ₂ .H ₂ O at about -5 ° C. After stirring for about 14 hours at 20-25 ° C, the precipitate was filtered off and washed with water. It was taken up in dilute sodium hydroxide solution. The solution was treated with methyl tert. Butyl ether (MTBE) and extracted with ethyl acetate. After drying the combined organic phases and separating off the solvent, 22 g of the title compound were obtained in the form of yellow crystals.
¹ H NMR (CDCl ₃ , δ in ppm): 3.6 (s, br, 3H); 5.25 (s, 2H); 5.9 (d. 1H); 6.8 (t, 1H); 7.1 (d, IH); 7.3 (m. 2H); 7.4 (d. 2H); 7.5 (d. 2H); 7.7 (d. 1H).

Example 1c

Production of

A mixture of 21.5 g (68 mmol) of the hydrazine from Example 1b and 14 g (65 mmol) of diethyl ethoxymethylene malonate in 400 ml of diethyl ether was stirred at 20-25 ° C. for about three days. The resulting precipitate was filtered off, taken up in methylene chloride and filtered through silica gel. After elution with cyclohexane / ethyl acetate mixture (1: 1), the solvent mixture was distilled off. The residue was digested in diisopropyl ether. 21.5 g of the title compound 1c were obtained as colorless crystals.
¹ H NMR (CDCl ₃ , δ in ppm): 1.2 (t, 3H); 1.3 (t, 3H); 4.2 (q, 2H); 4.3 (q, 2H); 5.3 (s, 2H); 5.9 (d. 1H); 6.9 (m, 2H); 7.25 (m. 2H); 7.3 (d. 2H); 7.5 (d. 2H); 7.7 (m. 2H); 8.2 (d. 1H); 10.0 (d, 1H).

Example 1d

Production of

A mixture of 20 g (41 mmol) of the malonic ester from Example 1c and 24 g of sodium hydroxide in 200 ml of water was refluxed for about four hours. At about 20-25 ° C was neutralized with dil. Hydrochloric acid. The precipitate was filtered off, then taken up in ethyl acetate. After drying and distilling off the solvent, the residue was chromatographed on silica gel (cyclohexane / ethyl acetate mixture 1: 1). 5 g of the title compound were obtained as pale yellow crystals.
¹ H NMR (DMSO-d ₆ , δ in ppm): 5.3 (s, 2H); 5.7 (s, br, 1H); 6.2 (d. 1H); 7.6 (m, 4H); 7.7 (d. 2H); 7.85 (m. 2H); 7.9 (d. 2H); 8.5 (d. 1H); 11.6 (s, br, 1H).

Example 1e

Production of

A mixture of 1.5 g (4 mmol) of the hydroxypyrazole from Example 1d and 0.75 g (4.2 mmol) of N-bromosuccinimide in 30 ml of methylene chloride was stirred at 20-25 ° C. for about three hours. The resulting precipitate was filtered off, taken up in ethyl acetate. After washing with water and drying the organic phase, the solvent was distilled off. The residue was digested in diisopropyl ether. 1.75 g of the title compound were obtained as pale yellow crystals.
¹ H NMR (DMSO-d ₆ , δ in ppm): 5.2 (s, 2H); 6.0 (d. 1H); 7.4 (d. 1H); 7.5 (m, 4H); 7.7 (m. 4H); 8.3 (d. 1H); 11.6 (s, br, 1H).

Example 1f

Production of

A mixture of 900 mg (2 mmol) of the hydroxypyrazole from example 1e, 420 mg (3 mmol) of K ₂ CO ₃ and 310 mg (2.5 mmol) of dimethyl sulfate in 10 ml of acetone was stirred for about three hours at about 20- Stirred at 25 ° C. The solvent was distilled off and the residue was dissolved in methylene chloride. After washing with water and drying, the organic phase was freed from the solvent. After chromatography on silica gel (cyclohexane / ethyl acetate mixture 1: 1), 150 mg of the title compound were obtained as a yellow oil from the residue.
¹ H NMR (CDCl ₃ , δ in ppm): 3.1 (s, 3H); 5.3 (dd, 2H); 6.9 (d, 1H); 7.1 (d. 1H); 7.3 (d. 2H); 7.4 (m, 5H); 7.7 (m, 2H).

Example 2a

Production of

A solution of 500 mg (1.4 mmol) of the hydroxypyrazole from Example 1d in 10 ml of methylene chloride was mixed with 185 mg (1.4 mmol) of N-chlorosuccinimide (NCS) at about 20-25 ° C. After about two hours of stirring, 100 mg of NCS were added and the mixture was stirred for a further 14 hours. The precipitate was filtered off, washed with methylene chloride and dried. 100 mg of the titanium compound were obtained as colorless crystals of mp 156 ° -159 ° C.
¹ H NMR (DMSO-d ₆ , δ in ppm): 5.2 (s, 2H); 6.0 (d. 1H); 7.4 (d. 1H); 7.5 (m, 4H); 7.7 (m. 4H); 8.3 (d. 1H); 11.7 (s, br, 1H).

Example 2b

Production of

A mixture of 450 mg (1.1 mmol) of the hydroxypyrazole from example 2a, 200 mg of K ₂ CO ₃ and 180 mg (1.4 mmol) of dimethyl sulfate in 10 ml of acetone was at about 20-25 ° C for about two hours touched. The solvent was distilled off and the residue was dissolved in methylene chloride. After washing with water and drying, the organic phase was freed from the solvent. After chromatography on silica gel (cyclohexane / ethyl acetate mixture), 70 mg of the title compound were obtained from the residue as a yellow crystal mass.
¹ H NMR (CDCl ₃ , δ in ppm): 3.1 (s, 3H); 5.3 (dd, 2H); 6.9 (d, 1H); 7.15 (d. 1H); 7.3 (d. 2H); 7.45 (m. 5H); 7.7 (d. 1H); 7.75 (d. 1H).

Table I

Examples of the action against harmful fungi

The fungicidal activity of the compounds of the general formula I was demonstrated by the following tests:
The active ingredients are separated or together as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Neka nil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) and diluted with water to the desired concentration.

Application example 1 Efficacy against Plasmopara viticola

Leaves of pot vines of the "Müller-Thurgau" variety were washed with aq active ingredient preparation, which contains a 10% stock solution Active ingredient, 63% cyclohexanone and 27% emulsifier was sprayed to dripping wet. To the long-term effect of To be able to assess substances, the plants were after the Dry the spray coating for 7 days in the greenhouse on ge poses. Only then were the leaves covered with an aqueous zoo spore inoculation of Plasmopara viticola inoculated. After that the vines initially for 48 hours in a steam saturated Chamber at 24 ° C and then in the greenhouse for 5 days Temperatures between 20 and 30 ° C set up. After this time the plants were used to accelerate the sporangic carrier broke again in a humid chamber for 16 hours. Then the extent of infestation on the leaf was under pages determined visually.

In this test, those with 250 and 63 ppm showed the compound I-3 treated plants 5% infestation, while the untreated too 80% were infected.

Example of use 2 Efficacy against Pyricularia oryzae (protective)

Leaves of "Tai-" rice seedlings grown in pots Nong 67 "were treated with an aqueous active ingredient preparation, which with a Stock solution of 10% active ingredient, 63% cyclohexanone and 27% emul yeast was applied until dripping wet. On fol On the same day, the plants were treated with an aqueous spore suspension sion of Pyricularia oryzae inoculated. Then the Test plants in climatic chambers at 22-24 ° C and 95-99% rela  tive humidity set up for 6 days. Then that became The extent of the development of infestation on the leaves was determined visually.

In this test, those with 250 and 63 ppm showed the compound 1-3 treated plants no infestation, while the untreated were 90% infected.

Examples of the action against animal pests

The activity of the compounds of the general formula I against animal pests was demonstrated by the following experiments:
The active ingredients were

• a. as a 0.1% solution in acetone or
• b. as a 10% emulsion in a mixture of 70% by weight cyclohex anon, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with Emulsifying and dispersing action based on ethoxylated Alkylphenols) and 10% by weight Wettol® EM (non-ionic emuls gator based on ethoxylated castor oil)

processed and in accordance with the desired concentration Acetone in the case of a. or with water in the case of b. diluted.

After the end of the tests, the lowest Kon center determined at which the connections compared to untreated control trials still an 80 to 100% Hem cause or mortality (threshold or minimum conc centering).

Claims (10)

1. Substituted phenylpyrazolones of the formula I,
in which the substituents have the following meaning:
Y halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxy;
n is 0, 1 or 2, where the radicals Y can be different if n = 2;
E a group A,
where # denotes the bond with the phenyl ring,
R ^{A is} halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;
R ^{B is} hydrogen or C ₁ -C ₄ alkyl;
R ^C cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ haloalkyl;
T is a direct bond, oxygen or oxymethylene;
Z a) when T is oxygen or oxymethylene, a group X, N = CWR ¹ or N = C (R ¹ ) -C (R ² ) = NOR ³ , where
X if necessary subst. Heterocyclyl, optionally subst. Aryl, if necessary subst. Hetaryl, possibly subst. Arylmethylene or optionally subst. Hetarylmethylene;
W if necessary subst. Alkyl, optionally subst. Alkenyl, if necessary subst. Alkynyl, optionally subst. Cycloalkyl, optionally subst. Cycloal kenyl, optionally subst. Heterocyclyl, optionally subst. Aryl or optionally subst. Hetaryl;
R ^{1 is} hydrogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C _6- cycloal kyl;
R ^{2 is} hydrogen, cyano, halogen, C (R ^d ) = NOR ³ or W, OW, SW or NR ^C W, where
R ^{c is} hydrogen, alkyl, alkenyl or alkynyl;
R ^{d is} hydrogen or alkyl;
R ³ hydrogen, optionally subst. Alkyl, optionally subst. Alkenyl or subst. Mean alkynyl and
b) if T stands for a direct bond,
a group W, CH ₂ -CH ₂ -W, CH = CH-W, C∼CW, SW, CH ₂ -SW, CH = NO-CH ₂ -W, CH ₂ -OC (= O) -W or CH ₂ -OC (CH ₃ ) = NN = C (CH ₃ ) -W means. 2. phenylpyrazolones of the formula I according to claim 1, in which
W is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl,
these groups being completely or partially halogenated and / or carrying 1 to 3 of the following radicals:
Cyano, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkoxycarbonyl, C ₃ -C ₆ cycloalkyl, heterocyclyl, aryl or hetaryl, the cyclic groups in turn being substituted by conventional groups can be acted on;
for C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl or heterocyclic, it being possible for these groups to be substituted by customary groups;
for subst. Aryl or optionally subst. Heteroaryl;
R ² for hydrogen, cyano, halogen, C (R ^d ) = NOR ³ or W, OW, SW or NR ^C W, where
R ^{c is} hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl;
R ^{d is} hydrogen or C ₁ -C ₄ alkyl; and
R ^{3 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ cyanoalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkoxy-C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, where
these groups can be partially or completely halogenated and the cycloalkyl groups can additionally carry 1 to 3 C ₁ -C ₄ alkyl radicals;
stands. 3. Process for the preparation of compounds of the formula Ia
in which
Hal for halogen and
T represents oxygen or oxymethylene,
R ^B , R ^C , Y, n and Z have the meaning given in claim 1,
characterized in that anilines of the formula IV,
in the
L * CH ₂ L 'or a group L', where
L 'represents a nucleophilically removable group,
with compounds Z-OH to anilines of the formula IVa
implemented and converted with nitrite into the corresponding diazonium salts, which by reduction in the hydrazines of formula V
be transferred and with alkoxymethylene malonic acid alkyl esters of the formula VIa,
in which R "stands for C ₁ -C ₄ alkyl, to dicarboxylic acid esters of the formula VII
are implemented in basic medium via hydroxypyrazo le of formula VIII
with ester cleavage and decarboxylation in hydroxypyrazoles of the formula II
are transferred to compounds of formula IX
are halogenated and converted into the pyrazolones of the formula Ia by alkylation. 4. intermediates of formula X,
in which R ^B , R ^C , Y, n, T and Z have the meaning given in claim 1. 5. intermediates of formula 1,
in the
Q NH-NH-C (R ^B ) = C (COOR ') ₂ or a group Θ 1 or Θ 2,
# denotes the bond to the phenyl ring and R 'represents hydrogen or C ₁ -C ₄ alkyl,
mean and
R ^B , Y, n, T and Z have the meaning given in claim 1. 6. intermediates of formula 2,
L is hydroxy, CH ₂ OH, CH ₂ L 'or a group L', where L 'is a nucleophilically cleavable group
and R ^A , R ^B , R ^C , Y and n have the meanings given in claim 1. 7. To control animal pests or harmful fungi suitable agent containing a solid or liquid Carrier and a compound of formula I according to claim 1. 8. Use of the compounds I according to claim 1 for the manufacture for the control of animal pests or Suitable fungi suitable agent.   9. A method of combating harmful fungi, characterized records that one should protect the mushrooms or those from fungal attack materials, plants, soil or seeds an effective amount of a compound of formula I according to Claim 1 treated. 10. A method for controlling animal pests, thereby characterized in that the animal pests or the materials, plants, the soil to be protected from them or seeds with an effective amount of a compound of the general formula I treated according to claim 1.