DE19900571A1 - New oximino substituted phenyl tetrazolinone derivatives, having fungicidal, insecticidal, acaricidal and nematocidal activity - Google Patents

Abstract

1-(2-(N-(1-Oximino-2-alkylidene)-aminooxymethyl)-phenyl)-1,4-dihydro-5 H-tetrazol-5-one derivatives (I) are new. Phenyl tetrazolinones of formula (I) are new. Ra = H, alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylcarbonyl or alkoxycarbonyl; Y = halo, 1-4C alkyl, haloalkyl or alkoxy; n = 0-2; R1 = H, CN, halo, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy or cycloalkoxy; R2 = H, alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkylalkyl, alkoxyalkyl or cycloalkoxyalkyl; R3 = alkoxyalkyl or -C(R3a)=NOR3b; or (all optionally substituted) aryl, heteroaryl, C-bonded 3-, 5- or 6-membered heterocyclyl, aryloxy, heteroaryloxy, arylthio, heteroarylthio, arylsulfinyl, heteroarylsulfinyl, arylsulfonyl, heteroarylsulfonyl, arylalkyl, heteroarylalkyl, 3-, 5- or 6-membered heterocyclylalkyl, aryloxyalkyl, heteroaryloxyalkyl, arylamino, heteroarylamino diarylamino, diheteroarylamino, arylalkylamino or heteroarylalkylamino; R3a = as R3b; or (all optionally substituted) 3-, 5- or 6-membered heterocyclyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl; R3b = H, alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkylakyl, alkoxyalkyl or cycloalkoxyalkyl; alkyl moieties = 1-6C, alkenyl or alkynyl moieties 2-6C and cycloalkyl moieties 3-6C unless specified otherwise. An Independent claim is included for the preparation of (I).

Description

The present invention relates to phenyltetrazolinones of the formula I,

in which the substituents have the following meaning:
R ^{A is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ - Alkynyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl
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;
R ^{1 is} hydrogen, cyano, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or C ₃ -C ₆ cycloalkoxy;
R ^{2 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ -Alkynyl, C ₂ -C ₆ -haloalkynyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or C ₃ -C ₆ - Cycloalkoxy-C ₁ -C ₆ alkyl;
R ³ if necessary subst. Aryl, if necessary subst. Heteroaryl,
if necessary subst. 3-, 5- or 6-membered heterocyclyl which is bonded via a C atom,
if necessary subst. Aryloxy, optionally subst. Heteroaryloxy, optionally subst. Arylthio, if necessary subst. Heteroarylthio, if necessary subst. Arylsulfi nyl, optionally subst. Heteroarylsulfinyl, optionally subst. Arylsulfonyl, optionally subst. Heteroarylsulfonyl,
if necessary subst. Aryl-C ₁ -C ₆ -alkyl, optionally subst. Heteroaryl-C ₁ -C ₆ -alkyl,
if necessary subst. 3-, 5- or 6-membered heterocyclyl-C ₁ -C ₆ -alkyl,
C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, optionally subst. Aryloxy-C ₁ -C ₆ -alkyl, optionally subst - heteroaryloxy-C ₁ -C ₆ -alkyl,
if necessary subst. Arylamino, optionally subst. Heteroarylamino, if necessary subst. Diarylamino, if necessary subst. Diheteroarylamino, if necessary subst. Aryl-C ₁ -C ₆ -alkylamino, optionally subst. Heteroaryl-C ₁ -C ₆ -al kylamino,
C (R ^3a ) = N-OR ^3b , where
R ^3a one of the groups mentioned in R ^3b or, if necessary, subst. 3-, 5- or 6-membered heterocyclyl, optionally subst. Aryl, if necessary subst. Heteroaryl, optionally subst. Aryl- C ₁ -C ₆ alkyl or optionally subst. Heteroaryl-C ₁ -C ₆ alkyl; and
R ^{3b is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ -Alkynyl, C ₂ -C ₆ -haloalkynyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkoxy -C ₁ -C ₆ alkyl be.

In addition, the invention relates to processes and intermediates for the preparation of the compounds I, and agents and the uses of compounds I for combating harmful fungi and tieri pests.

2-phenyl-2,5-dihydro-tetrazolinones with ortho-standing methylene oximino group are disclosed in WO-A 96 / 36,229.

α-phenylacrylic acid and α-phenyl-α-methoximinoacetic acid derivatives with ortho-standing oxime ether grouping are described in DE-A 40 20 384, and likewise those with bisoxime ether grouping in WO-A 95 / 21,154 wrote.

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.  

We have found that this object is achieved by the phenyltetrazolinones of the formula I. Furthermore, intermediate products and processes for the production of the compounds I, and the use of the compounds I and these contain agents to control harmful fungi and tieri pests found. The fungicidal activity is preferred.

The compounds of formula I differ from the compounds known from WO-A 96 / 36,229 mentioned above in the substitution of the oximino group by the specially designed radical R ³ bonded to a double bond. The compounds of the formula I have a higher activity than the known compounds against harmful fungi and animal pests.

The compounds of the formula I per se can be analogous to that in WO-A 96 / 36,229, or WO-A 95 / 21,153 receive methods described be.

The compounds I can be obtained in various ways, it being irrelevant for the synthesis whether the tetrazolyl group or the oxime ether group is built up first. For better clarity, the descriptions are therefore in the following reaction descriptions
Z ^# for the tetrazolyl group, or a suitable precursor for it and
E ^# for the oxime ether group E, # being the point of attachment to the methylene group of the phenyl ring, or used for a suitable precursor of the group E.

The structure of the oxime ether group E is preferred on the stage in which Z ^{# stands} for the nitro group.

Compounds I in which R ¹ stands for halogen are obtained particularly advantageously by first converting a carboxylic acid ester IVc with hydroxylamine to the corresponding hydroxamic acid IVa, then reacting IVa with a benzyl compound Va ^# to the corresponding hydroxamic acid ester VIa ^# and VIa ^# with a halogenating agent [HAL] in IIa ^# transferred [cp. DE note No. 197 08 940.2].

R ^x in formula IVc represents the rest of a normal leaving group. For the purposes of this reaction, customary leaving groups are to be understood in particular as the following groups: C ₁ -C ₄ -alkyl (especially methyl or ethyl) or phenyl.

L in the formula Va ^# stands for a nucleofugic leaving group. For the purposes of this reaction, the following are to be understood in particular: halogen or alkyl or aryl sulfonate, especially chlorine, bromine, iodine, mesylate, tosylate and triflate.

1. The implementation of the carboxylic acid ester IVc with hydroxylamine usually follows at temperatures from -20 ° C to 50 ° C preferably 0 ° C to 20 ° C, in an inert organic solution medium, preferably in the presence of a base (cf. Houben-Weyl, 4th edition, vol.E5, p. 1141 ff.).

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons substances, ethers, alcohols such as methanol, ethanol, n-propanol, Isopropanol, n-butanol and tert-butanol, as well as dimethyl sul foxid, dimethylformamide and dimethylacetamide, especially be prefers alcohols like methanol and ethanol. Ge Mix the solvents mentioned.

In general, inorganic compounds such as Al come as bases potash and alkaline earth metal hydroxides such as lithium hydroxide, Sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metals metal carbonates, alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, Ka lium-tert-butanolate and dimethoxymagnesium, also orga African bases, e.g. B. tertiary amines, pyridine, substituted Pyridines and bicyclic amines are also considered. Especially be Alkali metal hydroxides such as sodium and potassium are preferred hydroxide, and alkali metal alcoholates such as sodium methoxide and sodium ethanolate. The bases are generally equimo lar or used in excess.  

The starting materials are generally in equimolar amounts implemented each other. It can be beneficial for the yield be hydroxylamine in an excess based on IVc put.

The carboxylic acid esters IVc required for the preparation of the compounds I are known in the literature [DE-A 28 08 317; DE-A 22 65 234; J. Chem. Soc. PT 1, 2340 ff. (1975); Chem. Ber. 16, 2987 ff. (1883); J. Org. Chem. 37, 139 (1972)] or can be prepared according to the literature cited.

2. The reaction of the hydroxamic acid IVa with the benzyl compound Va ^# usually takes place at temperatures from 0 ° C. to 130 ° C., preferably 10 ° C. to 60 ° C., in an inert organic solvent in the presence of a base [cf. Liebigs Ann. Chem. 10, 997 ff. (1992); Synth. Commun. 19, 339 ff. (1989)].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons substances, ethers such as diethyl ether, diisopropyl ether, tert-Bu tylmethyl ether, dioxane and tetrahydrofuran, nitriles such as Ace tonitrile and propionitrile, ketones and dimethyl sulfoxide, di methylformamide and dimethylacetamide, particularly preferably Te trahydrofuran, acetonitrile and dimethylformamide. It can mixtures of the solvents mentioned can also be used.

In general, inorganic compounds such as Al come as bases Potash and alkaline earth metal hydroxides, alkali metal and Alkaline earth metal oxides, alkali metal and alkaline earth metal hy dride such as lithium hydride, sodium hydride, potassium hydride and Cal ziumhydrid, alkali metal amides, alkali metal and alkaline earths tall carbonates such as lithium carbonate, potassium carbonate and calzi umcarbonate and alkali metal bicarbonates such as sodium hy bicarbonate, organometallic compounds, in particular Alkali metal alkyls, alkyl magnesium halides and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, Sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxymagnesium, also organic bases, e.g. B. ter tertiary amines, pyridine, substituted pyridines and bicycli chemical amines. Sodium are particularly preferred methanolate, potassium carbonate and sodium hydride. The bases who  generally equimolar, in excess or given if 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 IVa in an excess based on Va ^# .

The benzyl compounds required for this reaction are known from the literature cited at the outset or can be prepared according to this literature.

3. The halogenation of the hydroxamic acid ester VIa ^# usually takes place at temperatures from -20 ° C to 100 ° C, preferably -10 ° C to 80 ° C, in an inert organic solvent [cf. Houben-Weyl, 4th ed., Vol. E5, p. 631 ff .; J. Org. Chem. 36, 233 (1971); Synthesis 9, 750 ff. (1991); Tetrahe dron 52 (1), 233 ff. (1996)].

Suitable halogenating agents in this reaction are the customary inorganic and organic halogenating agents, e.g. B. thionyl chloride, oxalyl chloride, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus triiodide, triphenylphosphine / CCl ₄ , triphenylphosphine / CBr ₄ , triphenylphosphine / iodine, preferably thionyl chloride or the triphenylphosphine reagents mentioned.

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-Xy lol, halogenated hydrocarbons, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and Tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Ketones as well as dimethyl sulfoxide, dimethylformamide and dimethy lacetamide, particularly preferably acetonitrile, toluene and tetra hydrofuran. Mixtures of the solutions mentioned can also be used tel can be used.

The halogenating agents are generally used at least in equimolar amounts. It can be advantageous for the yield to be used in an excess of up to 10 mol based on 1 mol VIa ^# , preferably up to 5 mol, in particular up to 3 mol.

4. The compounds VIa ^# can alternatively be obtained by reacting a carboxylic acid IVd with a benzylhydro xylamine Ve ^# .

This reaction usually takes place at temperatures of -10 ° C to 120 ° C, preferably 0 ° C to 50 ° C, in an inert organic solvents in the presence of an activation rea gens [cf. Houben-Weyl, 4th ed., Vol. E5, p. 1141 ff .; J. Antibiot. 39, 1382 (1986)].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane and tetrahydrofuran, nitriles, ketones and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably tetrahydrofuran and methylene chloride. It can too Mixtures of the solvents mentioned are used.

Acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride or oxalyl chloride are suitable as activation reagents; Anhydride formers such as ethyl chloroformate or methanesulfonyl chloride; Carbodiimides such as N, N'-dicyclohexylcarbodiimide or other conventional agents such as N, N'-carbonyl diimidazole or triphenylphosphine in CCl ₄ . Thionyl chloride, oxalyl chloride and N, N'-carbonyl diimidazole are particularly preferred.

The activation reagents generally become equimolar or used in excess.

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

The carboxylic acids IVd required for this reaction are off known in the literature [J. Pharm. Sci. 57, 688 ff. (1968); DE-A 22 23 375; DE-A 22 65 234] or according to the citation literature are produced.

5. In addition, the compounds VIa ^{# are} also obtained by reacting a carboxylic acid ester of the formula IVc with the benzylhydroxylamine Ve ^# under the conditions described above for the conversion of IVc to IVa in section 1.

According to a further process, the compounds I are advantageously obtained by converting an amidoxime IVe with a benzyl compound Va ^# into the corresponding compound of the formula VIb ^# and exchanging the amino group of VIb ^# for halogen by diazoation.

6) The reaction of the amidoxime IVe with the benzyl compound Va ^# usually takes place at temperatures from 0 ° C. to 130 ° C., preferably before 10 ° C. to 60 ° C., in an inert organic solvent in the presence of a base [cf. Lit. Heterocycles 36, 1027 ff. (1993)].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons substances, ethers such as diethyl ether, diisopropyl ether, tert-Bu tylmethyl ether, dioxane and tetrahydrofuran, nitriles such as Ace tonitrile and propionitrile, ketones, alcohols and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably tetrahydrofuran, acetonitrile and dimethylformamide. Mixtures of the solvents mentioned can also be used become.

In general, inorganic compounds such as Al come as bases Potash and alkaline earth metal hydroxides, alkali metal and Alkaline earth metal oxides, alkali metal and alkaline earth metal hy dride such as lithium hydride, sodium hydride, potassium hydride and Cal  ziumhydrid, alkali metal amides, alkali metal and alkaline earths tall carbonates such as lithium carbonate, potassium carbonate and calzi umcarbonate and alkali metal bicarbonates such as sodium hy bicarbonate, organometallic compounds, in particular Alkali metal alkyls, alkyl magnesium halides and alkali metals tall and alkaline earth metal alcoholates such as sodium methoxide, Sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxymagnesium, also organic bases, e.g. B. ter tertiary amines, pyridine, substituted pyridines and bicycli chemical amines. Sodium me are particularly preferred thanolate, potassium carbonate and sodium hydride. The bases will be generally used in equimolar amounts or in excess.

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

The amide required for this preparation of the compounds I. oxime IVe are known in the literature [DE-A 44 42 732; Gazz. Chim. Italian 55, 327 (1925)] or can according to the zi be prepared literature.

7) The diazotization and halogenation of VIb ^# to I ^# is usually carried out at temperatures from -20 ° C to 50 ° C, preferably 0 ° C to 20 ° C, in water or in an aqueous inert organic solvent [cf. Lit. J. Org. Chem. 45, 4144 ff. (1980); Chem. Ber. 26, 1567 ff. (1893)].

Fluorine is used as the halogenating agent in this reaction hydrogen, hydrogen chloride, hydrogen bromide and iodine water substance, especially hydrogen chloride.

The halogenating agents are generally in excess or optionally used as a solvent.

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons substances, ethers such as diethyl ether, diisopropyl ether, tert-Bu tylmethyl ether, dioxane and tetrahydrofuran, nitriles, ketones, Alcohols as well as dimethyl sulfoxide, dimethylformamide and dime  Thylacetamide, in addition to water, mixtures are particularly preferred of dioxane and water and / or tetrahydrofuran and water.

The benzyl compounds Va ^# -Vd ^# required for the preparation of the compounds I, in which E ^{# represents} a leaving group L, are known from the literature [cf. WO-A 96 / 36,229]. The compounds Va ^# -Vd ^# , in which E ^{# stands} for the oxime ether group E, correspond to the formulas IIa, IIb and IIc. The Tetrazo linon group can be built up using the following synthetic route:

This route is not only suitable for the production of the benzyl compounds Va-Vd, but in principle for the synthesis of the tetrazolinone group at each synthesis stage of the oxime ether group E ^# . The group E is particularly preferably set up at the level of the compounds Va.

8) The reduction of the nitro group of Va ^# 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 [ see. 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, aromatic hydrocarbons, halogenated coal water substances, ethers, alcohols such as methanol, ethanol, n-propanol, Isopropanol, n-butanol and tert-butanol, as well as dimethyl sulfoxide, Dimethylformamide and dimethylacetamide, particularly preferably metha nol, ethanol and water. Mixtures of the above can also be used Solvents are used.

Can be found as catalysts in catalytic hydrogenation 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 1% 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 Right. Usually hydrogenation is carried out at a hydrogen pressure, which is between normal pressure and 10 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, he generally follows in the presence of a base. Come as bases generally alkali metal amides and alkali metal and alkaline earths tall alcoholates, also organic bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-Me thylpiperidine, pyridine, substituted pyridines such as collidine, Lu tidine and 4-dimethylaminopyridine and bicyclic amines in Be dress. Ammonia and primary amines are particularly preferred. The bases are generally equimolar, in excess or ge optionally used as a solvent.

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

9) The reaction of Vb ^# with phosgene or a phosgene equivalent, such as, for example, di- or triphosgene, is usually carried out at temperatures from -10 ° C. to 250 ° C., preferably 10 ° C. to 110 ° C., in an inert organic solvent in the presence of a base or a catalyst [cf. Chem. Ber., Vol. 72, p. 457 (1972); Chem. Soc. Rev., Vol. 3, p. 209 (1974); Appl. Chem., Vol. 107, p. 2746 (1995)].

Suitable solvents are aliphatic hydrocarbons, 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 so such as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, be particularly preferably tetrahydrofuran, dimethylformamide, chlorobenzene and toluene. 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, alkali metal and alkaline earth metal limetalloxides, alkali metal and alkaline earth metal hydrides, alkali metallamides, alkali metal and alkaline earth metal carbonates and Al potassium metal bicarbonates, organometallic compounds, ins special alkali metal alkyls, alkyl magnesium halides and au also organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, tri-isopropylethylamine and N-methylpiperidine, Pyri din, substituted pyridines such as collidine, lutidine and 4-dimethy laminopyridine and bicyclic amines. Especially be triethylamine and pyridine are preferred. The bases are in space common equimolar, in excess or, if appropriate, as a solution medium used.

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

10) The reaction of the isocyanate Vc ^# with the azide IIIa, it usually takes place at temperatures from -10 ° C to 200 ° C, preferably 20 ° C to 140 ° C, in an inert organic solvent, optionally in the presence of a base or an acid [cf. J. Org. Chem., Vol. 45, p. 5130 (1980); J. Am. Chem. Soc., Vol. 81, p. 3076 (1959); Tetrahedron, Vol. 31, p. 765 (1975); J. Org. Chem., Vol. 38, p. 675 (1973)].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, nitriles and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially before adds toluene, xylene, dimethylformamide and chloroform. If that Azid IIIa used is liquid, it can also be used as a solvent be used. Mixtures of the solutions mentioned can also be used means are used.

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

In formula IIIa, M stands for a cation from the group of Al potash or alkaline earth metals, trialkylsilyl or alkyl. Prefers trimethylsilyl azide is used.

Compounds of the formula Vf ^# in which R ^{B is} C ₁ -C ₆ alkyl, C ₁ -C ₆ -Ha logenalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ - Haloalkenyl, C ₂ -C ₆ alkynyl or C ₂ -C ₆ haloalkynyl are obtained from tetrazo linones of the formula Vd ^# by alkylation. If E ^# in formula Vf ^{# stands} for a group TZ, the compounds Vf ^# correspond to the compounds Ia.

11) The alkylation of the tetrazolinones Vd ^# to Vf ^# usually takes place 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, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers such as diethyl ether, diiso propyl ether, tert-butyl methyl ether, dioxane and tetrahydrofuran, Nitriles, alcohols and dimethyl sulfoxide, dimethylformamide and Dimethylacetamide, particularly preferably dimethylformamide, tetrahy drofuran, dimethyl sulfoxide, diethyl ether and toluene. 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, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides, alkali metal and alkaline earth metal carbonates such as Lithium carbonate, potassium carbonate and calcium carbonate as well as alkali metal bicarbonates such as sodium bicarbonate, metallorga African compounds, especially alkali metal alkyls, alkyl magne sodium halides and alkali metal and alkaline earth metal alcoholates and dimethoxymagnesium, also organic bases, e.g. B. tertiary Amines, pyridine, substituted pyridines and bicyclic amines in Consideration. Sodium hydride and sodium hydro are particularly preferred gene 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, Al alkyl sulfonates, alkyl p-toluenesulfonates, alkyl trifluoromethanesulfo nates, alcohols, ethers or alkyl-p-bromophenyl sulfonates, in particular methyl iodide or dimethyl sulfate.

The starting materials are generally reacted with one another in equimolar amounts. It can be advantageous for the yield to use the alkylation agent in an excess based on IVd ^# . Compounds of the formula Vg ^# in which R ^{c is} C ₁ -C ₆ -alkylcarbonyl or C ₁ -C ₆ -alkoxycarbonyl are obtained from tetrazolinones of the formula Vd ^# by reaction with alkylating agents, such as carboxylic acid halides, carboxylic acid anhydrides, carboxylic acid esters or chlorocarbonic acid esters .

The acylation of Vd ^# takes place under conditions which are known per se in the literature, in which an inert mixture is used with carboxylic acid derivatives such as carboxylic acid, halides, anhydrides or active esters at temperatures of from -20 ° C. to 120 ° C., preferably from 0 ° C. to 60 ° C. organic solvent, if appropriate in the presence of a base [cf. Organikum, 17th edition, Berlin 1988, pp. 409 and 412].

In particular, compounds of the formula I.1 are obtained

in which R ^3a one of the groups mentioned in R ^3b or, if necessary, subst. 3-, 5- or 6-membered heterocyclyl, optionally subst. Aryl, if necessary subst. Heteroaryl, optionally subst. Aryl-C ₁ -C ₆ alkyl or optionally subst. Heteroaryl-C ₁ -C ₆ -alkyl and R ^3b hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -Ha logenalkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ -alkenyl, C ₂ - C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy-C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₆ -alkyl mean, for example, by reacting a benzyl compound of the formula Va ^# with an oxime of the formula IVh and the obtained oxime ether of the formula VII ^# halogenation in the halogen compound of formula VIII ^# transferred ^# VIII is reacted with a hydroxyl amine ether of the formula IIIb the bisoxime ether of the formula IX ^# Ix ^# oxidized to the carbonyl compound of formula X ^# X ^# and reacted with a hydroxylamine ether of the formula IIIc.

13. The reaction of the benzyl compound Va ^# with the oxime of the formula IVh is carried out in a manner known per se at temperatures from -10 ° C. to 100 ° C., preferably 10 ° C. to 85 ° C., in an organic solvent in the presence a base [cf. WO-A 97 / 02,255].

Suitable solvents are ethers such as diethyl ether, diiso propyl ether, tert-butyl methyl ether, dioxane and tetrahydrofu ran, nitriles such as acetonitrile and propionitrile, ketones, alcohol hole as well as dimethyl sulfoxide, dimethylformamide and dimethyla cetamide, particularly preferably tetrahydrofuran, acetonitrile and Dimethylformamide. Mixtures of the mentioned Lö be used.

In general, inorganic compounds, such as Al Potash and alkaline earth metal hydroxides, alkali metal and Alkaline earth metal hydrides such as lithium hydride, sodium hydride, Ka lium hydride and calcium hydride, alkali metal and alkaline earths tall carbonates such as lithium carbonate, potassium carbonate and calzi umcarbonate, as well as alkali metal bicarbonates, such as sodium hydrogen carbonate, alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, Ka lium-tert-butanolate and dimethoxymagnesium, also orga African bases, e.g. B. tertiary amines, pyridine, substituted Py ridine and bicyclic amines. Especially before sodium hydride, potassium carbonate and sodium methano are added lat. The bases are generally in catalytic amounts used, but they can also 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 IVh in an excess based on Va ^# .

The oximes of the formula IVh are also known from the literature [cf. WO-A 95 / 21,153] or can be prepared according to the literature cited.

14. The halogenation of the oxime ether VII ^# is usually carried out at temperatures from -10 ° C. to 80 ° C., preferably 0 ° C. to 65 ° C., in an inert organic solvent, if appropriate in the presence of an acid [cf. J. Org. Chem., P. 2532 (1981); Org. Synth., Vol. 55, p. 24 (1976); Tetrahe dron p. 5611 (1970)].

Suitable halogenating agents are bromine, chlorine, pyridine.HBr ₃ , CuBr ₂ and SO ₂ Cl _2, in particular bromine, CuBr ₂ and SO ₂ Cl ₂ . They are generally reacted with one another in equimolar amounts. It can be advantageous for the yield to use them in a 1.2- to 2.5-fold excess, based on the compound VII ^# .

Suitable solvents are aromatic hydrocarbons, such as toluene, o-, in- and p-xylene, halogenated hydrocarbons substances such as methylene chloride, chloroform and chlorobenzene, and Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, particularly preferably cyclohexane, Methylene chloride, chloroform, chlorobenzene and methanol. It mixtures of the solvents mentioned can also be used become.

Inorganic acids are found as acids and acidic catalysts such as hydrochloric acid, hydrobromic acid and sulfuric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin-IV-chloride, titanium-IV-chloride and zinc-II-chloro rid, as well as organic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, citric acid and trifluoroacetic acid Use. The acids are generally used in catalytic Amounts used, but they can also be equimolar, in excess 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 the halogenating agent in an excess based on VII ^# .

15. The reaction of the oxime ether VIII ^# with the hydroxylamine ether of the formula IIIb to the bisoxime ether IX ^# takes place in a known manner at temperatures from 0 ° C. to 85 ° C., preferably at 20 ° C. to 65 ° C., in an inert organic solvent.

16. The oxidation of bisoxime ether IX ^# is carried out in a known manner at temperatures from 20 ° C. to 160 ° C., preferably at 20 ° C. to 100 ° C., in an inert organic solvent, if appropriate in the presence of a base [cf. Houben-Weyl, Methods of Organic Chemistry, Volume E3, pp. 247-265, Georg Thieme Verlag, Stuttgart 1983].

Examples of oxidizing agents are N-methylmorpholine N-oxide, 2-benzoyl-1-trifluoromethanesulfonyl hydrazine, trime thylamine-N-oxide and pyridine-N-oxide in question, in particular N-methylmorpholine-N-oxide, trimethylamine-N-oxide and pyridine- N-oxide.

In general, inorganic compounds such as Al come as bases potash and alkaline earth metal hydroxides such as lithium hydroxide, Sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Ka lium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates such as sodium bicarbonate, also organic Bases, e.g. B. tertiary amines, pyridine, substituted pyridines as well as bicyclic amines. Particularly preferred who the sodium hydroxide, sodium hydrogen carbonate and potassium carbo nat. The bases are generally in catalytic amounts used, but they can also 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 the oxidizing agent in an excess based on IX ^# .

17. The reaction of the carbonyl compound X ^# in the trisoxime ether I.1 ^# is usually carried out at from 10 ° C. to 120 ° C., preferably from 20 ° C. to 85 ° C., in an inert organic solvent, if appropriate in the presence of a base [cf. . EP-A 386 561].

Suitable solvents are ethers such as diethyl ether, diiso propyl ether, tert-butyl methyl ether, dioxane, anisole and Tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, as well as dimethyl sulfoxide, dime thylformamide and dimethylacetamide, particularly preferably metha nol and ethanol. Mixtures of the mentioned Lö be used.

In general, inorganic compounds, such as Al potash and alkaline earth metal carbonates and alkali metal hydrogen carbonates such as sodium bicarbonate, alkali metal and Alkaline earth metal alcoholates and dimethoxymagnesium, except the organic bases, e.g. B. tertiary amines such as trimethylamine, Triethylamine, triisopropylethylamine and N-methylpiperidine, Pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and bicyclic amines. Sodium bicarbonate and pyridine are particularly preferred and triethylamine. The bases are generally in cataly used amounts, but they can also be equimolar, in Excess or optionally used as a solvent become.

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

The Aus required for the preparation of compounds I. Starting materials of the formula IVh are known in the literature [J. Org. Chem., P. 2605 (1991); Bull. Soc. Chim. Fr., p. 1452 (1973)] or can be prepared according to the literature cited become.

Compounds of formula I in which R ^{1 is} C ₁ -C ₄ alkoxy, it is obtained, for example, by adding a compound of formula I ^# in which R ^{1 is} halogen with an alcoholate of formula IIId , in which M is a cation from the group of alkali metals, such as lithium, potassium or sodium, and R ^{1 is} C ₁ -C ₆ alkyl.

18. The reaction is usually carried out at temperatures of 20 up to 120 ° C, preferably at 20 to 80 ° C, in an inert or ganic solvent [cf. J. Org. Chem., 50, p. 993 (1985); Tetrahedron Lett., 35, p. 15 (1994)].

Suitable solvents are ethers, such as dioxane or tetrahy drofuran, nitriles, such as acetonitrile, alcohols, such as methanol, Ethanol, n-propanol, isopropanol, n-butanol or tert-buta nol, as well as dimethyl sulfoxide, dimethylformamide and dimethyl acetamide. Mixtures of the solvents mentioned can also be used be used.

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

The compounds of the formula I in which R ^{1 is} C ₁ -C ₆ -alkoxy are also obtained, in which a benzyl compound of the formula Va ^# with an oxime of the formula IVb in which R ^{1 is} C ₁ -C ₆ - Alkoxy stands under the conditions described for the reaction of Va ^# with IVe in section 6.

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

The oximes of the formula IVb are obtained, for example, by reacting an oxime of the formula IVf, in which Hal represents halogen, with an alcoholate of the formula IIId under the conditions described in section 16. [cf. EP-A 158 153; US 4,339,444] or can be prepared according to the literature cited.

20. The oximes of the formula IVf are obtained, for example, by reacting a ketoxime of the formula IVg with a hydroxylamine ether of the formula IIIb.

The ketoximes of the formula IVg are known in the literature [cf. Ber. German Chem. Ges. 88, p. 130 (1955); J. Org. Chem., P. 4570 (1987)], or can be prepared according to the literature cited become.

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 z. 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 in the preparation 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 be fighting harmful fungus or animal pest.

With regard to the -N = CR ¹ -C (CR ³ ) = NOR ² double bonds, the E, E isomers of the compounds I are generally preferred with regard to their effectiveness (configuration based on the residue -CH ₂ O- in the ratio to the -C (CR ³ ) = NOR ² group, or based on the radical -OR ² in relation to the -C (R ¹ ) -N = OCH ₂ 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 6 carbon atoms methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 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-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl propyl and 1-ethyl-2-methylpropyl;
Alkenyl:
unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 6 carbon atoms and a double bond in any position, 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-propenyl, 1,2-dimethyl-2-propenyl, 1- Ethyl-1-propenyl, 1-ethyl-2-propenyl, 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-meth yl-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-eth yl-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;
Alkynyl:
straight-chain or branched hydrocarbon groups with 2 to 6 carbon atoms and a triple bond in any position, 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-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4- Methyl-2-pentynyl, 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;
3-, 5- or 6-membered heterocyclyl:
e.g. B. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 4-isothiazolidinyl, 4-isothiazolidinyl, 4-isothiazolidinyl, 4-isothiazolidiazine , 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazideinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2 , 4-oxadiazolidin-3-yl, 1,2,4-oxadiazoli 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-dihydrothiene -3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2,3-pyrrolin-2-yl, 2,3-pyrrolin-3-yl, 2,4-pyrroline -2-yl, 2,4-pyrrolin-3-yl, 2,3-isoxazolin-3-yl, 3,4-isoxazolin-3-yl, 4,5-isoxazolin-3-yl, 2,3-isoxazoline -4-yl, 3,4-isoxazolin-4-yl, 4,5-isoxa zolin-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-ihydrooxazol-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-tetrahydrothien yl, 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 one to three-ring aromatic ring system containing tend 6 to 14 carbon ring members, z. B. phenyl, naphthyl and anthracenyl;
Heteroaryl:

• - 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-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadia zol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-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 ne ben carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as Ring members can contain, and in which two adjacent Carbon ring members or one nitrogen and one neighboring carbon ring member through 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-py ridinyl, 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;

organic rest:
if necessary subst. Alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl or hetaryl.

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, amino, formyl, carboxyl, aminocarbonyl, Alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylamino, Dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, Alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, Alkoxycarbonylamino, alkylcarbonyl-N-alkylamino and alkylcarbo nyl-N-alkylamino, the alkyl groups being present in these radicals preferably 1 to 6 carbon atoms, in particular 1 to 4 Contain carbon atoms;
• - Unsubstituted or substituted by usual groups Cycloalkyl, cycloalkoxy, cycloalkylthio, cycloalkylamino, cy cloalkyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocy clylthio, heterocyclylamino or heterocyclyl-N-alkylamino where in the cyclic systems 3 to 12 ring members, preferably 2 up to 8 ring links, in particular 3 to 6 ring links included and the alkyl groups in these residues are preferably 1 to 6 Contain carbon atoms, in particular 1 to 4 carbon atoms ten;
• - Unsubstituted or substituted by usual groups Aryl, aryloxy, arylthio, arylamino, aryl-N-alkylamino, arylal koxy, arylalkylthio, arylalkylamino, arylalkyl-N-alkylamino, Hetaryl, hetaryloxy, hetarylthio, hetarylamino, hetaryl-N-alky lamino, hetarylalkoxy, hetarylalkylthio, hetarylalkylamino and Hetarylalkyl-N-alkylamino, the aryl radicals preferably 6 Contain up to 10 ring members, especially 6 ring members (phenyl) ten, the hetaryl residues contain in particular 5 or 6 ring members  ten and the alkyl groups in these radicals preferably 1 to 6 Contain carbon atoms, in particular 1 to 4 carbon atoms ten.

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) can be replaced] and / or can carry one to four (in particular one to three) of the following radicals:

• Cyano, nitro, hydroxy, amino, carboxyl, aminocarbonyl, alkyl, Haloalkyl, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, Alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxy, halo genalkoxy, alkylthio, haloalkylthio, alkylamino, dialkyl amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkyl aminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, alk oxycarbonylamino, alkylcarbonyl-N-alkylamino and alkylcarbonyl- N-alkylamino, the alkyl groups in these radicals preferred have 1 to 6 carbon atoms, especially 1 to 4 carbons Contain atoms and the alkenyl or alkynyl mentioned groups in these residues 2 to 8, preferably 2 to 6, ins contain particular 2 to 4 carbon atoms;

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

• - Unsubstituted or substituted by usual groups Cycloalkyl, cycloalkoxy, cycloalkylthio, cycloalkylamino, cy cloalkyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocy clylthio, heterocyclylamino or heterocyclyl-N-alkylamino where in the cyclic systems 3 to 12 ring members, preferably 2 up to 8 ring links, in particular 3 to 6 ring links included and the alkyl groups in these residues are preferably 1 to 6 Contain carbon atoms, in particular 1 to 4 carbon atoms ten;
• - Unsubstituted or substituted by usual groups Aryl, aryloxy, arylthio, arylamino, aryl-N-alkylamino, arylal koxy, arylalkylthio, arylalkylamino, arylalkyl-N-alkylamino, Hetaryl, hetaryloxy, hetarylthio, hetarylamino, hetaryl-N-alky lamino, hetarylalkoxy, hetarylalkylthio, hetarylalkylamino and Hetarylalkyl-N-alkylamino, the aryl radicals preferably 6 Contain up to 10 ring members, especially 6 ring members (phenyl) ten, the hetaryl residues contain in particular 5 or 6 ring members ten and the alkyl groups in these radicals preferably 1 to 6 Contain carbon atoms, in particular 1 to 4 carbon atoms ten;

and / or can carry one or two (in particular one) of the following radicals:

• - formyl,
• CR ⁱⁱⁱ = NOR ^iv [where R ^{iii is} hydrogen, alkyl, cycloalkyl and aryl and R ^{iv is} alkyl, alkenyl, haloalkenyl, alkynyl and arylalkyl (the alkyl groups mentioned preferably containing 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, said cycloalkyl groups, alkenyl groups and alkynyl groups preferably contain 3 to 8, in particular 3 to 6, carbon atoms) and aryl, in particular phenyl, which is unsubstituted or can be substituted by customary groups] or
• - NR ^v -CO-DR ^vi [where R ^{v is} hydrogen, hydroxy, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy- C ₁ -C ₆ -alkoxy and C ₁ - C ₆ alkoxycarbonyl, R ^{vi is} hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl , Aryl, aryl-C ₁ -C ₆ -alkyl, hetaryl and hetaryl-C ₁ -C ₆ -alkyl and D is a direct bond, oxygen or nitrogen, where the nitrogen can carry one of the groups mentioned at R ^vi ] ,

and / or in which two adjacent C atoms of the cyclic systems are a C ₃

-C ₅

-Alkylene-, C ₃

-C ₅

-Alkenylene, oxy-C ₂

-C ₄

-alkylene-, oxy-C ₁

-C ₃

-alkyleneoxy, oxy-C ₂

-C ₄

-alkenylene, oxy-C ₂

-C ₄

can carry alkenyleneoxy or butadienediyl group, these bridges can be partially or completely halogenated and / or can carry one to three, in particular one or two of the following radicals:

• - C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ halo alkoxy and C ₁ -C ₄ alkylthio.

With regard to their intended use of the phenylte trazolinones of formula I are the following meanings of sub stituents, individually or in combination, particularly preferred:

The particularly preferred embodiments of the intermediates in terms of the variables correspond to those of the radicals R ^A , Y _n , R ¹ , R ² and R ^{3 of} the formula I.

Compounds of formula I in which R ^{A is} C ₁ -C ₆ alkyl are particularly preferred.

Also preferred are compounds of formula I in which n = is zero (0).

Compounds of the formula I in which R ^{A is} methyl or ethyl are particularly preferred.

In addition, compounds I are particularly preferred in which R ^{1 is} C ₁ -C ₆ alkyl.

Likewise, particular preference is given to compounds I in which R ^{1 is} C ₁ -C ₆ alkoxy.

In addition, compounds I are particularly preferred in which R ^{1 is} halogen.

Similarly, compounds I are preferred in which R ^{1 is} C ₁ -C ₂ haloalkyl.

In particular, compounds I are particularly preferred in which R ³ for optionally subst. Phenyl stands.

Furthermore, compounds I are particularly preferred in which R ^{3 represents} the following optionally substituted groups: aryloxy, heteroaryloxy, arylthio, heteroarylthio, arylsul finyl, heteroarylsulfinyl, arylsulfonyl, heteroarylsulfonyl, aryl-C ₁ -C ₆ -alkyl, heteroaryl- C ₁ -C ₆ alkyl, 3-, 5- or 6-membered heterocyclyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, aryloxy- C ₁ -C ₆ -alkyl, heteroaryloxy-C ₁ -C ₆ -alkyl, arylamino, heteroaryl amino, diarylamino, diheteroarylamino, aryl-C ₁ -C ₆ -alkylamino, He teroaryl-C ₁ -C ₆ -alkylamino or C (R ^3a ) = N -OR ^3b stands.

Furthermore, compounds I are particularly preferred in which R ^{3 is} pyridinyl.

Also preferred are compounds of formula I in which R ^{3 is} C (R ^3a ) = N-OR ^3b .

In particular, compounds I are preferred in which R ^{3 is} benzyl, which can be partially or completely halogenated in the aryl part and / or can carry one to three of the following radicals: cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy.

Likewise, particular preference is given to compounds I in which R ^{3 is} phenoxy, which can be partially or completely halogenated and / or can carry one to three of the following radicals: cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ - Haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy.

In addition, compounds I are particularly preferred in which R ^{3 is} pyrimidinyl.

Compounds of the formula I.1 'are also preferred.  

Likewise, particular preference is given to compounds I.1 'in which R ^{1 is} chlorine, R ^{3a is} methyl, Y _{n is} hydrogen and R ^{2 is} methyl or ethyl.

In addition, compounds I.1 'in which Y _{n is} 6-methyl are particularly preferred.

Particularly preferred are compounds of formula I 'in which R ^{A is} methyl, ethyl or isopropyl, R ^{1 is} chlorine, trifluoromethyl, methyl, ethyl or methoxy, R ^{2 is} methyl or ethyl and R ^{3 is} C ₁ - C ₃ alkoxy-C ₁ -C ₃ alkyl or optionally substituted pyridyl, pyrimidinyl, oxazolyl, isoxazolyl or pyrazo lyl.

Also particularly preferred are compounds I.1 in which R ^{A is} methyl, ethyl or isopropyl, R ^{1 is} chlorine, trifluoromethyl, methyl, ethyl or methoxy, R ^{2 is} methyl or ethyl, R ^{3a is} hydrogen, methyl or Ethyl and R ^{3b is} C ₁ -C ₄ alkyl, C ₃ alkenyl or C ₃ alkynyl.

Also particularly preferred are compounds I.2 in which R ^{A is} methyl, ethyl or isopropyl, R ^{1 is} chlorine, trifluoromethyl, methyl, ethyl or methoxy, R ^{2 is} methyl or ethyl and R ^{3c is} hydrogen, halogen or methoxy stands.

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 'in which R ^{A is} methyl and the combination of the radicals R ¹ , R ² and R ³ for a compound corresponds in each case to one line of Table A.

Table 2

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

Table 3

Compounds of the general formula I 'in which R ^{A is} isopropyl and the combination of the radicals R ¹ , R ² and R ³ for a compound corresponds in each case to one line of Table A.

Table 4

Compounds of the general formula I.1 where R ^A and R ^{2 are} methyl and the combination of the radicals R ¹ , R ^3a and R ^3b for a compound corresponds in each case to one line of Table B.

Table 5

Compounds of the general formula I.1, in which R ^{A is} methyl, R ^{2 is} ethyl and the combination of the radicals R ¹ , R ^3a and R ^3b for a compound corresponds in each case to one line of Table B.

Table 6

Compounds of the general formula I.1 where R ^{A is} ethyl, R ^{2 is} methyl and the combination of the radicals R ¹ , R ^3a and R ^3b for a compound corresponds in each case to one line of Table B.

Table 7

Compounds of the general formula I.1 where R ^A and R ^{2 are} ethyl and the combination of the radicals R ¹ , R ^3a and R ^3b for a compound corresponds in each case to one line of Table B.

Table 8

Compounds of the general formula I.1, in which R ^{A is} isopropyl, R ^{2 is} methyl and the combination of the radicals R ¹ , R ^3a and R ^3b for a compound corresponds in each case to one line of Table B.

Table 9

Compounds of the general formula I.1, in which R ^{A is} isopropyl, R ^{2 is} ethyl and the combination of the radicals R ¹ , R ^3a and R ^3b for a compound corresponds in each case to one line of Table B.

Table 10

Compounds of the general formula I.2, in which R ^A and R ^{2 are} methyl and the combination of the radicals R ¹ and R ^3e for a compound corresponds in each case to one line of Table C.

Table 11

Compounds of the general formula I.2 in which R ^{A is} methyl, R ^{2 is} ethyl and the combination of the radicals R ¹ and R ^3e for a compound corresponds in each case to one line of Table C.

Table 12

Compounds of the general formula I.2, in which R ^{A is} ethyl, R ^{2 is} methyl and the combination of the radicals R ¹ and R ^3e for a compound corresponds in each case to one line of Table C.

Table 13

Compounds of the general formula I.2, in which R ^A and R ^{2 are} ethyl and the combination of the radicals R ¹ and R ^3e for a compound corresponds in each case to one line of Table C.

Table 14

Compounds of the general formula I.2, in which R ^{A is} isopropyl, R ^{2 is} methyl and the combination of the radicals R ¹ and R ^3e for a compound corresponds in each case to one line of Table C.

Table 15

Compounds of the general formula I.2, in which R ^{A is} isopropyl, R ^{2 is} ethyl and the combination of the radicals R ¹ and R ^3e for a compound corresponds in each case to one line of Table C.

Table 16

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

Table 17

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

Table 18

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

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, like that like 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 12-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 eguestris, 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, Ce rosipha 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, Rhopalosiphum 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 me Gnini, 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, He terodera 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 Ver ensure loyalty.

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. As auxiliary agents come there for essentially: 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 what ser; Carriers such as natural rock powder (e.g. kaolins, Clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates); Emulsifiers like not ionogenic and anionic emulsifiers (e.g. polyoxyethylene fatty al alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants agents such as lignin sulfite liquor and methyl cellulose.

Alkali, alkaline earth, ammonium come as surface-active substances salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsul fonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, Al 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 mixed 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, Kao lin, attackclay, limestone, lime, chalk, bolus, loess, clay, dolomite, Diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ge ground plastics, fertilizers, such as. B. aminonium sulfate, amino nium phosphate, ammonium nitrate, ureas and herbal products such as cereal flour, tree bark, wood and nutshell flour, Cel Loose 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 used 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 he in this way holds a dusts that 5 wt .-% of 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 ingredient 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 Divide 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 approximately 40 moles of ethylene oxide to 1 mole of castor oil stands (active ingredient content 9 wt .-%).
• 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, 30 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 5 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 that is used 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 pro 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 of 1 mole of castor oil. By pouring and fine Ver dividing the solution in 100,000 parts by weight of water is obtained 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 20000 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 di 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, dis Powder or emulsifier can be homogenized in water. It can also wetting, adhering, dispersing or Emulsifier and possibly solvent or oil de 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 processing driving (ULV) can be used, it is possible to use 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 ferridimes ethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bis dithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine bis-dithiocarbamate, tetramethylthiuram disulfide, Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), Am monia complex of zinc (N, N'-propylene-bis-dithiocarbamate), Zinc (N, N'-propylene bis-dithiocarbamate), N, N'-polypropylene bis- (thiocarbainoyl) 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- (dimethylamino) - phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioane thrachinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (butylcar bamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycar bonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazo lyl- (4)) - benzimidazole, N- (1,1,2,2-tetrachloroethylthio) tetrahy drophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide;
• - N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-09366 00070 552 001000280000000200012000285910925500040 0002019900571 00004 092473-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-di hydro-5-carboxanilido-6-methyl-1,4-oxathiin, 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-car bonsäureanilid, 2,5-dimethyl-furan-3-carbonsäureanilid, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-fu ran-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy- 2,5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid ani lid, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2- trichloroethyl acetal, piperazine-1,4-diylbis-1- (2,2,2-trichlor ethyl) formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2- trichloroethane;
• Amines such as 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-Butylphenyl) -2-methylpropyl] cis-2,6-dimethyl morpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperi din, (8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxa spiro [4.5] decane-2-methanamine;
• Azoles such as 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl ethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-pro pyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-Pro pyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2- butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole- 1-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophen nyl) -oxiran-2-ylmethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophene nyl) pentyl] -1H-1,2,4-triazole, 2,4'-difluoro-a- (1H-1,2,4-tri azolyl-1-methyl) -benzhydryl alcohol, 1 - ((bis- (4-fluorophenyl) -me thylsilyl) methyl) -1H-1,2,4-triazole, 1- [2RS, 4RS; -2RS, 4SR) -4-  bromo-2- (2,4-dichlorophenyl) tetrahydrofuryl] -1H-1,2,4-triazole, 2 - (4-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-triazol-1-yl) -bu tan-2-ol, (+) - 4-chloro-4- [4-methyl-2- (1H-1,2,4-triazol-1-ylme thyl) -1,3-dioxolan-2-yl] phenyl-4-chlorophenyl ether, (E) - (R, S) -1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1H-1,2,4-tri azol-1-yl) pent-1-en-3-ol, 4- (4-chlorophenyl) -2-phenyl-2- (1H-1,2,4, -triazolylmethyl) butyronitrile, 3- (2,4-dichlorophene nyl) -6-fluoro-2- (1H-1,2,4-triazol-1-yl) quinazolin-4 (3H) -one, (R, S) -2- (2,4-dichlorophenyl) -1-H-1,2,4-triazol-1-yl) hex ano-2-ol, (1RS, 5RS; 1RS, 5SR) -5- (4-chlorobenzyl) -2,2-dime thyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol, (R, S) -1- (4- chlorophenyl) -4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pen tan-3-ol, (+) - 2- (2,4, -dichlorophenyl) -3- (1H-1,2,4-triazolyl) - propyl-1,1,2,2-tetrafluoroethyl ether, (E) -1- [1- [4-chloro-2-tri fluoromethyl) phenyl] imino) -2-propoxyethyl] -1H-imidazole, 2- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-ylmethyl) hexanenitrile;
• - 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-thio ureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benz zol;
• - 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-phe noxyphenyl)] - acetamide, methyl-E-methoxyimino- [α- (2,5-dimethyl phenoxy) 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 morpholide;
• - and various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, N-methyl, N-ethyl- (4-trifluoromethyl, -2- [3 ', 4'-dimethoxyphe nyl] -benzoic acid amide, hexachlorobenzene, DL-methyl-N- (2,6-dime thyl-phenyl) -N-furoyl (2) -alaninate, DL-N- (2,6-dimethyl-phe nyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dime thylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2,6- Dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl 5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazoli din-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydane toin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicar boximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methox  imino] acetamide, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phe nyl) -5-trifluoromethyl-3-chloro-2-aminopyridine.

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 table below with physical details listed.

example 1 Preparation of 1- (2-tolyl) -1,4-dihydro-5H-tetra zol-5-one

64.9 g of trimethylsilyl azide were added to 50 g of tolyl isocyanate, the mixture was refluxed for 3 hours and about 16 hours at 20 to Stirred at 25 ° C. After distilling off the volatile constituents the residue was mixed with methanol. The precipitation was filtered off at about 0 ° C, then dried. 62.7 g of the were obtained Title compound as colorless crystals.

Example 2 Preparation of 1-methyl-4- (2-tolyl) -1,4-dihydro-5H-th trazol-5-one

A mixture of 52.8 g of 1- (2-tolyl) -1,4-dihydro-5H-tetrazol-5-one and 6.2 g of potassium carbonate in 60 ml of dimethylformamide was mixed with 6.4 g of methyl iodide, then about 66 Stirs at 20 to 25 ° C ge. After the addition of dilute sodium chloride solution, the mixture was extracted with ethyl acetate. After drying and distilling off the solvent, 5.7 g of the titanium compound were obtained from the organic phase as colorless crystals of mp. 51-53 ° C.
IR: 1730, 1505, 1422, 1384, 1147, 756, 748, 710, 580 cm ^-1 .

Example 3 Preparation of 1- (2-bromomethylphenyl) -4-methyl-1,4-di hydro-5-H-tetrazol-5-one

A solution of 5 g of 1-methyl-4- (2-tolyl) -1,4-dihydro-5H-tetra zol-5-ion in 70 ml of carbon tetrachloride was treated with 5.85 g of N-bromosuc cinimid and 0.1 g of azobisisobutyronitrile. The mixture was irradiated with UV light during 30 minutes of refluxing. Then was extra water after dilution with 100 ml of methylene chloride here. After drying and drying, the organic phase style the solvent by digesting with diisopropyl ether 4.2 g of the title compound as colorless crystals of Mp 79-81 ° C.  

Example 4 Production of [I-1]

A solution of 1.13 g of 1- (4-fluorophenyl) -1-oximmethyl ether-2-oxime-1,2-propanedione in 25 ml anhydrous Dimethylformamide (DMF) was added after adding 0.18 g of sodium hydride for about 1 hour. stirred at 20 to 25 ° C. After adding a solution of 1.88 g of the Tetrazolones from Example 3 in 15 ml water. DMF became more Stirred at 20 to 25 ° C for 16 hours. Then after adding ver thin saline solution extracted with ethyl acetate. From the orga African phase was obtained after drying and distilling off the Solvent 1.8 g of the title compound as colorless crystals m.p. 139-141 ° C.

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 were separated or together as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight .-% Wetto® EM (non-ionic emulsifier based on ethoxylated ricinus oil) prepared and diluted with water according to the desired concentration.

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 tests still 80 to 100% inhibition or cause mortality (threshold of action or minimum concentration tion).

Claims (6)

1. phenyltetrazolinones of the formula I,
in which the substituents have the following meaning:
R ^{A is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ -Alkynyl, C ₂ -C ₆ -haloalkynyl, C ₁ -C ₆ -alkylcarbonyl, C ₁ -C ₆ -alkoxy carbonyl;
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;
R ^{1 is} hydrogen, cyano, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ halo alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or C ₃ -C ₆ cycloalkoxy;
R ^{2 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ -Alkynyl, C ₂ -C ₆ -haloalkynyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or C ₃ -C ₆ -cycloalkoxy -C ₁ -C ₆ alkyl;
R ³ if necessary subst. Aryl, if necessary subst. Heteroaryl,
if necessary subst. 3-, 5- or 6-membered heterocyclyl which is bonded via a C atom,
if necessary subst. Aryloxy, optionally subst. Heteroaryloxy, optionally subst. Arylthio, if necessary subst. Heteroarylthio, if necessary subst. Arylsulfinyl, optionally subst. Heteroarylsulfinyl, optionally subst. Arylsulfonyl, optionally subst. Heteroarylsulfonyl,
if necessary subst. Aryl-C ₁ -C ₆ -alkyl, optionally subst. Heteroaryl-C ₁ -C ₆ -alkyl,
if necessary subst. 3-, 5- or 6-membered heterocyclyl-C ₁ -C ₆ -alkyl,
C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, optionally subst. Aryloxy-C ₁ -C ₆ alkyl, optionally subst. Heteroaryloxy-C ₁ -C ₆ alkyl,
if necessary subst. Arylamino, optionally subst. Heteroarylamino, if necessary subst. Diarylamino, if necessary subst. Diheteroarylamino, if necessary subst. Aryl-C ₁ -C ₆ -alkylamino, optionally subst. Heteroaryl C ₁ -C ₆ alkylamino
C (R ^3a ) = N-OR ^3b , where
R ^3a one of the groups mentioned in R ^3b or, if necessary, subst. 3-, 5- or 6-membered heterocyclyl, optionally subst. Aryl, if necessary subst. Heteroaryl, optionally subst. Aryl-C ₁ -C ₆ alkyl or optionally subst. Hetero aryl-C ₁ -C ₆ alkyl; and
R ^{3b is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkylene, C ₂ -C ₆ -Alkynyl, C ₂ -C ₆ -haloalkynyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or C ₃ -C ₆ - Cycloalkoxy-C ₁ -C ₆ alkyl mean. 2. Process for the preparation of compounds of the formula Ia,
in which
R ^B C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl or Is C ₂ -C ₆ haloalkynyl,
and Y, n, R ¹ , R ² and R ^{3 have} the meaning as in formula I,
characterized in that an isocyanate of the formula IIc
by reaction with an azide of the formula IIIa,
MN ₃ IIIa
in which M is a cation from the group of alkali or alkaline earth metal, trialkylsilyl or alkyl, to form a tetra zolinone of the formula Ib
cyclized, which is converted by alkylation into tetrazolinones of the formula Ia. 3. 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. 4. Use of the compounds I according to claim 1 for the manufacture for the control of animal pests or Suitable fungi suitable agent. 5. 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 An spell 1 treated. 6. 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 Formula I treated according to claim 1.