DE3519453A1 - Herbicidal compositions comprising photosynthesis-inhibitor-type herbicides in combination with vinyl azoles - Google Patents

Abstract

The novel synergistic active substance combinations comprising (1) a photosynthesis-inhibitor-type active substance (herbicide) and (2) a vinyl azole of the general formula (II) (synergist) <IMAGE> in which R<1>, R<2>, R<3>, R<4>, R<5> and R<6> independently of one another in each case represent hydrogen, alkyl, haloalkyl or halogen, where up to not more than 3 of these radicals can represent halogen and/or haloalkyl, or R<1> and R<2> or R<1> and R<3> in each case together represent a divalent alkanediyl radical, R<7> represents hydrogen or halogen, X represents oxygen, sulphur, a sulphinyl group or a sulphonyl group and Az represents pyrazolyl, imidazolyl or triazolyl, or one of their acid addition salts or metal salt complexes display a particularly powerful herbicidal activity. A characteristic example of a photosynthesis-inhibitor-type active substance is metribuzin.

Description

Herbicidal agents containing photosynthesis inhibitor herbic

Zides in Combination with Vinvlazolen The present invention relates to new herbicidal synergistic combinations of active ingredients from known photosynthesis inhibitor herbicides on the one hand and on the other hand from certain, partly known vinyl azoles.

It is already known that certain herbicides, e.g. 4-Amino-6-tert-butyl-3-methylthio or

-ethylthio-1,2,4-triazin-5-oni 1-amino-3- (2,2-dimethylpropyl) -6- (ethylthio) -1 , 3,5-triazine-2,4-dione: 1-methoxy-1-methyl-3- (3,4-dichlorophenyl) urea or 1,3-dimethyl-1- (benzo-1,3-thiazole- 2-yl) urea, have photosynthesis-inhibiting properties (see e.g. Carl Fedkte, Biochemistry and Physiology of Herbicide Action, Springer Verlag, 1982). Disadvantageous with these However, herbicidal compounds are not always found in all weeds and grass weeds are fully covered, or that with correspondingly high application rates some crops are damaged.

It has now been found that the new active ingredient combinations, consisting of a) a photosynthesis inhibitor active ingredient (herbicide) and b) a vinyl azole of the general formula (II) (synergist), in which R1, R2, R3, R4, R5 and R6 each independently represent hydrogen, alkyl, haloalkyl or halogen, up to a maximum of 3 of these radicals being halogen and / or haloalkyl, or also R1 and R2 or R1 and R3 each together represent a doubly linked alkanediyl radical, R7 represents hydrogen or halogen, X represents oxygen, sulfur, a sulfinyl group or a sulfonyl group and Az represents pyrazolyl, imidazolyl or triazolyl or one of their acid addition salts or metal salt complexes that have a particularly high herbicidal effect The compounds of the formula (II) can be present as geometric isomers or isomer mixtures of different composition. Both the use of the pure isomers and that of the isomer mixtures (as respective mixing partners) are claimed according to the invention.

Surprisingly, the herbicidal effectiveness is that according to the invention Combinations of active ingredients are much higher than the sum of the effects of the individual ones Active ingredients. In particular, the partially known vinyl azoles have the general Formula (II) do not produce any herbicidal activity of their own at the usual application rates but an increase in the herbicidal effect of the photosynthesis inhibitor active ingredients. Thus the synergistic effect found here is completely unexpected and over-ratcheting, Since the synergistic effect also affects those weeds that are used by the Photosynthesis inhibitor active ingredients when applied alone at the usual application rates insufficiently damaged or not detected at all the synergistic active ingredient combinations according to the invention are a valuable asset of technology.

Photosynthesis inhibitor active ingredients for the active ingredient combinations according to the invention are preferably the following of the general formulas (IA) to (IJ): (A) Triazinone derivatives of the formula in which X1 stands for amino, optionally substituted alkylideneamino or alkyl with 1 to 2 carbon atoms, X2 for alkylthio with 1 to 2 carbon atoms, alkyl and dialkylamino with 1 to 2 carbon atoms in each alkyl part or alkyl with 1 to 4 carbon atoms and X3 represents tert-8utyl which is optionally substituted by halogen or optionally substituted phenyl; (B) Triazinedione derivatives of the formula in which X4 stands for amino, optionally substituted alkylideneamino or alkyl with 1 to 2 carbon atoms, X5 for alkylthio with 1 to 2 carbon atoms, alkyl and dialkylamino with 1 to 2 carbon atoms in each alkyl part or alkyl with 1 to 4 carbon atoms and X6 represents alkyl having 1 to 6 carbon atoms or optionally substituted phenyl; (C) Triazine derivatives of the formula in which X7 is chlorine, alkoxy or alkylthio each having 1 to 2 carbon atoms, X8 is alkylamino having 1 to 4 carbon atoms and X9 is alkyl having 1 to 4 carbon atoms which is optionally substituted by cyano; (D) urea derivatives of the formula in which X10 represents optionally substituted phenyl, benzothiazolyl or optionally substituted thiadiazolyl, Xll represents hydrogen or methyl, X12 represents methyl and X13 represents hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 2 carbon atoms or alkynyl with 2 to 4 Carbon atoms; (E) Carboxanilide derivatives of the formula X14-C0-NH-X15 (IE) in which X14 represents alkyl with up to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms or cycloalkyl with 3 to 6 carbon atoms and X15 represents optionally substituted phenyl; (F) uracil derivatives of the formula in which X16 stands for alkyl with 1 to 6 carbon atoms or cycloalkyl with 5 to 7 carbon atoms, X17 stands for halogen, X18 stands for alkyl with 1 to 2 carbon atoms or X17 and X18 together stand for an optionally substituted alkylene chain or an optionally substituted fused benzene ring and X19 represents the CO or SO2 group; (G) biscarbamate derivatives of the formula in which X20 is alkyl having 1 to 4 carbon atoms or optionally substituted phenyl and X21 is alkoxy having 1 to 4 carbon atoms or dialkylamino having 1 to 2 carbon atoms in each alkyl part, (H) pyridazinone derivatives of the formula in which X22 represents optionally substituted phenyl, X23 represents amino, alkylamino or dialkylamino each having 1 or 2 carbon atoms in each alkyl part, and X24 represents halogen, and (J) hydroxybenzonitrile derivatives of the formula in which X25 stands for halogen and X26 stands for halogen.

The following photosynthesis inhibitor active ingredients of the general formulas (IA) to (IJ) are particularly preferred: (A) Triazinone derivatives of the formulas (IA-1) (metribuzin) (IA-4) (Metamitron) 0 (CH3) 3CIkY "= CH-CH (CH3) 2 + (IA-5) SCH3 (isomethiocine) (B) Triazinedione derivative of the formula (IB-1) (Ametridione) (C) Triazine derivatives of the formulas C1 (IC-1) (Atrazine) C2H5-NH NH-CH (CH3) 2 SCH3 (IC-2) (Ametryn) C2H5 NH ffi NH-CH (CH3) 2 OCH3 (IC-3) (Atraton) C2H5-NH + NH-CH (CH3) 2 C1 (IC-4) C = N- <(cyanazine) CH3-C1-NHNH-C2H5 CH3 OCH2 (IC-5) <(Prometon) (CH3) 2CH-NH + NH-CH (CH3) 2 NS 3 (IC-6) (Promettyn) (CH3) 2CH-NH ffi NH-CH (CH3) 2 C1 (IC-7) <(Propazine) (OH3) 2CH-NHNH-CH (CH3) 2 (IC-8) (Simazine) (IC-9) (Simeton) (IC-10) (Simetryn) SCH3 (1-0-11) (Terbutryn) C2H5-NHNH-C (OH3) 3 (IC-12) (Trietazine) (D) Urea derivatives of the formulas (ID-1) (Linuron) (ID-2) (Methabenzthiazuron) (ID-3) (isoproturon) (ID-4) (Benzthiazuron) (ID-5) (Buthiuron) (ID-6) (Buturon) (ID-7) (Chlorbromuron) (ID-8) (chloroxuron) (ID-9) (Chlortoluron) (ID-10) (Diuron) (ID-11) (Ethidimuron) (ID-12) (Fenuron) (Fluometuron) (ID-14) (Metoxuron) (ID-15) (Monolinuron) (ID-16) (Monuron) (ID-17) (Neburon) (ID-18) (Tebuthiuron) (Thiochloromethyl) (E) carboxanilide derivatives of the formulas (IE-1) (Chloranocryl) (IE-2) (Cypromid) (IE-3) (Karsil) (IE-4) (Pentanochlor) (IE-5) (Propanil) (IE-6) (Swep) (F) Uracil derivatives of the formulas (IF-1) (Lenacil) (IF-2) (Bromacil) (IF-3) (Isocil) (IF-4) (Terbacil) (IF-5) (Bentazone) (G) Biscarbamate derivatives of the formulas (IG-1) (Desmedipham) (IG-2) (Carbutilate) (IG-3) (Phenmedipham) (H) Pyridazinone derivatives of the formulas (IH-1) (Pyrazone) (IH-3) (Metflurazon) (IH-3) (Norflurazon) (J) Hydroxybenzonitrile derivatives of the formulas (IJ-1) (Bromoxynil) (IJ-2) (Chloroxynil) (IJ-3) (iodoxynil) The photosynthesis inhibitor active ingredients of the formulas (IA to IJ) are known (cf., for example, Carl Fedtke, Biochemistry and Physiology of Herbicide Action , Springer-Verlag, 1982).

The vinyl azoles still to be used as a component of the mixture are generally defined by the formula (II).

Preference is given to compounds of the formula (II) in which R1, R2, R3, R4, R5 and R6 each independently represent hydrogen, fluorine, chlorine, bromine, straight-chain or branched alkyl with 1 to 4 carbon atoms or for straight-chain or branched haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, with a maximum of up to 3 of these radicals for Fluorine, chlorine, bromine and / or stand for haloalkyl, or also R1 and R2 or R1 and R3 each together for a straight-chain or branched twofold link Alkanediyl radical having 2 to 10 carbon atoms, R7 represents hydrogen, chlorine or Bromine is bromine, X is oxygen, sulfur, a sulfinyl group or a sulfonyl group stands and Az for pyrazol-1-yl, imidazol-1-yl or 1,2,4-triazol-1-yl stands.

Particularly preferred are compounds of the formula (II) in which R1, R2, R3, R4, R5 and R6 independently of one another each represent hydrogen, methyl, ethyl, Fluorine * chlorine, bromine, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, Trifluoromethyl, dichlorofluoromethyl or difluorochloromethyl stand, with a maximum of up to 3 of these radicals for fluorine, chlorine, bromine, chloromethyl, dichloromethyl, trichloromethyl, Fluoromethyl, difluoromethyl, trifluoromethyl, dichlorofluoromethyl and / or difluorochloromethyl stand, or R1 and R2 stand for butane-1,4-diyl or pentane-1,5-diyl, or R1 and R3 together represent propane-1,3-diyl or butane-1,4-diyl, R7 represents hydrogen, Is chlorine or bromine, X is oxygen, sulfur, a sulfinyl group or a Is a sulfonyl group and Az is pyrazol-1-yl, imidazol-1-yl or 1,2,4-triazol-i-yl stands.

In addition to the compounds mentioned in the preparation examples, the following compounds of the general formula may be specifically mentioned. (II) named: (Az is respectively Table 1 R¹ R² R³ R4 R5 R6 R7 X CH3 CH3 HHHH Cl O C2H5 C2H5 HHHHHO C2H5 C2H5 HHHHH SO C2H5 HHHHHHS CH3 CH3 HHHH Br SO2 CH3 CH3 HHHH cl SO2 C2H5 C2H5 HHHHH SO2 F-HHO- CH2- HHHHHO F-CH2- F-CH2- HHHHH S02 F-CH2- CH3 HHHHH 802 ClCH2- CH3 HHHHHO ClCH2- CH3 HHHHH S02 F-CH2- CH3 HHHH Cl O F-CH2- CH3 HHHH Br O F-CH2- f -CH2- HH HH Cl O Table 1 (continued) R1 R2 R3 R4 R5 R6 R7 X F-CH2- F-CH2- HHHH Br O F-CH2- CH3 HHHH Cl SO2 F-CH2- CH3 HHHH Br SO2 F-CH2 - F-CH2- HHHH Cl SO2 F-CH2- F-CH2- HHHH Br SO2 F-CH2- F-CH2- HHHHH SO F-CH2- CH3 HHHHH SO F-CH2- F-CH2- HHHHHS F-CH2- CH3 HHHHHS CH3 CH3 H Br HH Cl O CH3 CH3 H Br HH Br O CH3 CH3 H Cl HH Cl O CH3 CH3 H Cl HH Br O CH3 CH3 HH H -CH2Br H SO2 CH3 CH3 HHH -CH2Cl HO CH3 CH3 HHH -CH2Cl H SO2 CH3 CH3 HHH -CH2Cl Br O CH3 CH3 HHH -CH2Cl Cl O CH3 CH3 HHH -CH2Br Br O CH3 CH3 HHH -CH2Br Cl O - (CH2) 5- HHHHHO - (CH2) 5- HHHHH SO - (CH2) 5- HHHHHO - (CH2) 5- H HHHH SO2 Table 1 (continued) R1 R3 R4 R5 R6 R7 X - (CH2) 4- CH3 HHHHO - (CH2) 4- CH3 HHHH SO2 - (CH2) 4- CH3 HHH Cl O - (CH2) 4- CH3 HH H Br O - (CH2) 4- CH3 HHH Cl SO2 - (CH2) 4- CH3 HHH Br SO2 - (CH2) 4- CH3 HHHH S Preferred mixing partners which can be used according to the invention are also addition products of acids and those vinyl azoles of the formula (II) in which the substituents R1, R2, R3, R4, R5, R6, R7, X and Az have the meanings that are already preferred for these Substituents were mentioned.

The acids that can be added preferably include hydrohalic acids, such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, Tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as p-toluenesulphonic acid and 1,5-naphthalenesilphonic acid.

Mixing partners which can be used according to the invention are also preferred Addition products from salts of metals of the II. To IV. Main and the 1. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those Vinyl azoles of the formula (II) in which the substituents R1, R2, R3, R4, R5, R6, R7, X and Az have the meanings which are already preferred for these substituents were named, here are salts of copper, zinc, manganese, magnesium, tin, Iron and nickel are particularly preferred. The anions of these salts are those into consideration that are derived from acids that are too plant-contracted Lead addition products. Particularly preferred such acids are in this Together menhang the hydrohalic acids, such as, for example, the hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid.

The vinyl azoles of the formula which can be used according to the invention as mixing partners (II) are partly known (cf.

DE-OS 3 204 795, DE-OS 3 229 734, DE-OS 3 336 861, DE-OS 3 336 859); they can be produced by the processes described there.

Vinylazoles of the formula (IIa) are not yet known in which R1, R2, R3t, R4, R5, R6, X and Az have the meanings given above and Hal stands for halogen. The same applies to their acid addition salts and metal salt complexes.

The compounds of the formula (IIa) are obtained if vinyl azoles of the formula (IIb) in which R1, R2, R3, R4, R5, R6, X and Az have the meaning given above, are reacted with halogens, optionally in the presence of a diluent, and then the halogenated azole compounds of the formula (III) obtained in this way, in which R1, R2, R3, R4, R5, R6, X and Az have the meaning given above and Hal stands for halogen, either after previous isolation in a 2nd

Stage or directly after the 1st stage in a so-called One-pot process with strong bases, also optionally in the presence of one Diluent, dehydrohalogenated.

Inorganic or inorganic diluents are used for this reaction organic solvents in question. Water, alcohols, such as methanol or ethanol or their mixtures with water1 or chlorinated hydrocarbons, such as dichloromethane, chloroform or carbon tetrachloride.

The bases used are preferably alkali metal hydroxides, such as sodium or potassium hydroxide or alkali metal alcoholates, such as sodium methylate, sodium ethylate or potassium tert-butoxide.

The reaction can be carried out over a wide temperature range will. In general, one works between OC and 1000C, preferably between 20iC and 50es, possibly also under pressure.

To carry out the reaction, one uses per mole of vinyl azole of the formula (IIb) generally 1.0 to 1.5 mol, preferably equimolar amounts of halogen and base a. The conduct of the reaction, work-up and isolation of the reaction products of the formula (IIa) takes place according to generally known processes.

As starting materials for the production of the vinyl azoles described above The vinyl azoles of the formula (IIb) required for the formula (IIa) are known in some cases (cf. e.g. DE-OS 3 336 861).

Vinylazoles of the formula (IIc) are not yet known, in which R1, R2, R3, R4, R5, R6 and Az have the meaning given above and Y stands for sulfur, a sulfinyl group or a sulfonyl group.

The same applies to their acid addition salts and metal salt complexes. The compounds of the formula (IIc) can be prepared by (a) vinyl chloride derivatives of the formula (IV) in which R1, R2, R3, R41, R5 and R6 have the meaning given above and yl represents a sulfinyl or sulfonyl group, with azoles of the formula (V), Az-H (V) in which Az has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, or if (b) the sulfinyl vinyl azoles of the formula (IId) obtainable by process (a), in which R1, R2, R3, R4, R5, R6 and Az have the meaning given above * either a) oxidized on the sulfur of the sulfinyl group by customary processes, if appropriate in the presence of a diluent, or ß) likewise by customary processes, if appropriate in the presence of a diluent Sulfur of the sulfinyl group is reduced.

The vinyl chloride derivatives of the formula (IV) required as starting materials for carrying out production process (a) are also not yet known. They are obtained if 1-pentene derivatives of the formula (VI), in which R1, R2, R3, R4, R5 and R6 have the meaning given above, initially in a 1st stage with thioacetic acid of the formula (VII), optionally in the presence of a diluent such as N, N-dimethylformamide and optionally in the presence of a base such as sodium methylate at temperatures between + 50 ° C. and + 2000 ° C., and the tetrahydrothiophene derivatives of the formula (VIII) obtainable in this way in which R1, R2, R3, R4, R5 and R6 have the meaning given above, by customary methods, for example with hydrogen peroxide, optionally in the presence of a diluent such as glacial acetic acid at temperatures between -200C and 70C either partially (up to sulfoxide -Stage ie with stoichiometric amounts of oxidizing agent, temperature -200C to + 300C) or completely (up to the sulfone stage; ie with an excess of oxidizing agent, temperature 20 ° C to 700C, optionally using a catalyst such as ammonium molybdate).

The 1-pentene derivatives of the formula (VI) are known (cf.

e.g. DE-OS 3 336 861). The thioacetic acid of the formula (VII) and the to carry out the manufacturing process (a) still required as starting materials Azoles of the formula (V) are generally known compounds of organic chemistry, Inert diluents can be used for carrying out preparation process (a) organic solvents in question. Preference is given to using aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example Petrol, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, Chloroform, carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone, Butanone or methyl isopropyl ketone, nitriles such as acetonitrile or propionitrile, amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoric acid triamide, esters such as ethyl acetate, or alcohols such as Methanol, ethanol or propanol.

The preparation process (a) is optionally in the presence of a Acid binder carried out, as such come all the usual inorganic or organic bases in question. Alkali metal hydroxides are preferably used, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, Potassium carbonate or sodium hydrogen carbonate, as well as tertiary amines such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), Diazabicyclonones (DBN) or Diazabicycloundecene (DBU).

You can also use a corresponding excess at the same time as Use reaction partner employed azole of formula (V) as acid binder.

The reaction temperatures can vary when carrying out the manufacturing process (a) can be varied over a wide range. In general, one works at temperatures between 200C and 150in, preferably at temperatures between 60iC and 1200C.

To carry out the preparation process (a), per mole of vinyl chloride derivative of the formula (IV) generally 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol of azole of the formula (V) and optionally 1.0 to 5.0 mol of acid binder a. Carrying out the reaction, working up and isolating the reaction products of the formula (IIc) is carried out by customary processes.

As an oxidizing agent for carrying out the manufacturing process (b-) all oxidizing agents commonly used for sulfur oxidations come in question. Peroxides such as hydrogen peroxide, peracetic acid, Perpropionic acid or optionally substituted perbenzoic acids, such as m-chloroperbenzoic acid or p-nitroperbenzoic acid.

The manufacturing process (b- «) is optionally in the presence of a suitable diluent carried out Preference is given to using hydrocarbons, such as gasoline, benzene, toluene, hexane or petroleum ether; chlorinated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene; Carboxylic acids or anhydrides, such as acetic acid, propionic acid or acetic anhydride or dipolar aprotic solvents such as acetonitrile, acetone, ethyl acetate or dimethylformamide.

The reaction temperatures can be used in the preparation process (b-a) can be varied in certain areas.

Generally one works at temperatures between -20 * C and + 70-C, preferably between O'C and + 50in.

To carry out the preparation process (b-oc), one sets per mole of sulfinyl vinylazole of the formula (IId) in general from 0.8 to 1.5 mol, preferably 1.0 to 1.2 moles of oxidizing agent. The conduct of the reaction, work-up and The oxidized end products of the formula (IIc) are isolated by customary processes.

As a reducing agent for carrying out the manufacturing process (b-g) all inorganic and commonly used for sulfoxide reductions come organic reducing agents in question. Hydroiodic acid may be mentioned by way of example and 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-dithione (Lawesson's Reagent) (val, also Houben-Weyl "Methods of Organic Chemistry, Volume IX, 8.218off, 4th edition, Thieme Verlag, Stuttgart 1955).

As a diluent for carrying out the manufacturing process (b-ß) are inert organic or inorganic solvents. For this include in particular aliphatic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, Ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, amides, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide, alcohols such as methanol, ethanol or propanol or their mixtures with water. If necessary, pure water can also be used as a diluent into consideration The reaction temperatures can be used when carrying out of the manufacturing process (b-ß) can be varied over a wide range. In general one works at temperatures between OC and + 150'C, preferably between + 200C and + 120'C.

To carry out the preparation process (b-ß), per mole of sulfinyl vinylazole of the formula (IId) in general 1.0 to 15.0 mol, preferably 1.0 to 10.0 moles of reducing agent. The implementation of the reaction, work-up and the end products of the formula (IIc) are isolated by customary processes (cf. in this context, for example, Org.Prep.Prod.Int. Volume 16, 8.171-198 (1984); Synthesis 1984, 827-829; Houben-Weyl "Methods of Organic Chemistry", Volume IX, 8. 218ff, 4th edition, Thieme Verlag Stuttgart 1955).

For the production of acid addition salts that are tolerated by plants Compounds of the formula (II) are preferably the following acids: hydrogen halide acids, such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, e.g.

Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, Salicylic acid, sorbic acid, lactic acid and sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

The acid addition salts of the compounds of the formula (11) can be used in simply by using common salt formation methods, such as by loosening a connection of formula (II) in a suitable inert solvent and adding the acid, such as. Hydrochloric acid, and in a known manner, e.g. Filter off, isolated and optionally by washing with an inert organic Solvent cleaned.

For the preparation of metal salt complexes of the compounds of the formula (II) are preferably salts of metals from II. To IV. Main and 1. and II. And IV. To VIII. Subgroup of the periodic table of the elements in question, where Copper, zinc, manganese, magnesium, tin, iron and nickel may be mentioned by way of example.

Suitable anions of salts are those which are preferably derived from the following acids: hydrohalic acids such as hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of compounds of the formula (II) can in can easily be obtained by conventional methods, for example by dissolving the Metal salt in alcohol, e.g. ethanol, and adding to the compound of the formula (II). Metal salt complexes can be isolated in a known manner, e.g. by filtering off and, if necessary, purify by recrystallization.

The weight ratios of the active ingredients in the new active ingredient combinations can fluctuate in relatively large areas. Generally it accounts for one part by weight Photosynthesis inhibitor active ingredient (herbicidal active ingredient) 0.25 to 100, preferably 5 to 50, in particular 10 to 20 parts by weight of vinyl azole of the formula (II) (synergist).

The photosynthesis inhibitor active ingredients have strong herbicidal effects on. Nevertheless, they have against some weeds, such as Galium aparine, Ipomoea hederacea, Datura stramonium, Cirsium arvense, Convolvulus arvensis or Solanum nigrum and some grass weeds, e.g.

Agropyron repens, Avena fatua, Cynodon dactylon, Cyperus ssp. and Lolium rigidum does not always have an adequate effect. The active ingredient combinations according to the invention extend the spectrum of activity of the compounds of the formulas (I-A to I-J) and enable thereby combating these weeds, which are difficult or impossible to control or weed.

The active ingredient combinations according to the invention can e.g.

be used in the following plants: dicot weeds the Genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dikotvle cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucurnis, Cucurbita.

Monocot weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotvle cultures of the Gattunaen: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the use of the active ingredient combinations according to the invention is in no way restricted to these genera, but extends in the same way also on other plants.

The active ingredient combinations according to the invention show in particular in addition to a good effect against monocotyledon (grassy) weeds also a good herbicidal Effect on dicotyledonous (broad-leaved) weeds.

The active ingredient combinations according to the invention can be converted into the usual Formulations such as solutions, emulsions, wettable powders, suspensions, Powder, Dusting agents, pastes, soluble powders, granulates, suspension emulsion concentrates, Active ingredient-impregnated natural and synthetic materials, fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. Mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally with the use of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-producing agents.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

The following can be used as solid carriers: e.g. ammonium salts and natural ones Ground rock, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly dispersed silica, Alumina and silicates, as solid carriers for granulates come into question: e.g. broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegatable oils.

In the formulations, dyes such as inorganic Pigments such as iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%, the active ingredient combinations according to the invention are generally used in the form of finished formulations. the However, active ingredients contained in the active ingredient combinations can also be used as individual formulations mixed in use, i.e. applied in the form of tank mixes will.

The new active ingredient combinations can be used as such or in their formulations continue to be used as a mixture with other known herbicides, with turnkey formulations or tank mixes are possible. Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, Protective substances against bird damage, growth substances, plant nutrients and soil structure improvers is possible.

The new active ingredient combinations can be used as such, in the form of their Formulations or the application forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granulates can be applied. It is used in the usual way, e.g. by pouring, Splashing, spraying, dusting or scattering.

The active ingredient combinations according to the invention can both before as also after sowing as well as after Emergence of the plants can be applied together or in separate applications. This is where the The order of the applications does not matter.

When using the synergists according to the invention, the usual application rate can be used the herbicides of the formulas (I-A to I-J) are reduced. The application rate of herbicidal Photosynthesis inhibitor active ingredient is between 0.01 and 3.0 for surface treatment kg / ha, preferably between 0.05 and 2.0 kglha.

The application rate of synergistic vinyl azole of the formula (II) is for surface treatment between 0.1 and 10 kg ha, preferably between 0.5 and 3 kg / ha.

The good herbicidal action of the active compound combinations according to the invention can be seen from the following examples. While the individual active ingredients in the herbicidal effect show weaknesses, the combinations show a weed effect, which goes beyond a simple summation of effects.

With herbicides there is always a synergistic effect when the herbicidal effect of the active ingredient combinations is greater than the sum of the effects of the applied active ingredients.

Example A Pre-emergence test solvent: 5 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of herbicidal active ingredient or

Synergists or a mixture of herbicidal active ingredient and synergists with the specified amount of solvent, the specified amount of emulsifier is added and dilutes the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after 24 hours with a herbicide preparation or

with the synergist preparation or with the preparation from synergists and herbicidal active ingredient watered.

The amount of water per unit area is expediently kept constant. The concentration of the active substance in the preparation does not matter, it is decisive is only the application rate of the active ingredient per unit area. After three weeks it will the degree of damage to the plants rates in X damage in comparison to development the untreated control.

The figures denote: O X = no effect (like untreated control) 100 X = total destruction of active ingredients, application rate and results are based on the following Table.

Table A Synergistic effect of vinyl azoles of the formula (II) (= Svnersist S) and 4-Amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one (I-A-1) (= Herbicide H) on Ipomoea hederacea. The application rate in kglha refers to the Active ingredient content.

Structure of the (S) (H)% effect with Synergist (II) Kg / ha Kg / ha Ipomoea hedercea HS H + S 0.5 0.05 0 0 30 2 0.05 0 0 50 0.5 0.15 10 0 100 2 0.15 10 0 100 0.5 0.05 10 0 20 2 0.05 10 0 50 0, 5 0.15 20 0 70 2 0.15 20 0 80 Table A - Frortsetzuna structure of (S) (H) X Effect on synergists (II) kg / ha kg / ha Ipomoea hederacea HS H + S 0.01 0.07 10 - 30 0.03 0.07 10 - 30 0.1 0.07 10 - 30 0.3 0.07 10 - 90 1.0 0.07 10 0 90 0.03 0, 1 10 - 30 0.1 0.1 10 - 80 0.3 0.1 10 - 50 1.0 0.1 10 - 90 2.0 0.1 10 0 80 0.01 0.07 10 - 0 0 , 03 0.07 10 - 10 0.1 0.07 10 - 30 0.3 0.07 10 - 50 1.0 0.07 10 0 80 The sole application of the herbicide (IA-1) in a concentration of 0 , 5 and 2.0 kglha leads to 80 and 95% damage in Ipomoea hederacea.

Preparation examples Example 1 17.9 g (0.1 mol) of (3,3-dimethyl-tetrahydrofuran-2-ylidene) - (1,2,4-triazol-1-yl) methane in 150 ml of chloroform are added dropwise with stirring at room temperature 16 g (0.1 mol) of bromine were added. After the addition has ended, the mixture is stirred for a further hour and the reaction mixture is concentrated under reduced pressure. The remaining residue is taken up in water. It is adjusted to pH 7 with 2 normal aqueous sodium hydroxide solution and extracted several times with ether. The combined ether phases are washed with water, dried over sodium sulfate and freed from the solvent under reduced pressure.

4.7 g (14% of theory) of (3,3, -dimethyltetrahydrofuran-2-ylidene) - (1,2,4-triazol-1-yl) -bromomethane are obtained of melting point 122C.

EXAMPLE 2 85 g (1.23 mol) 1,2,4-triazole and 464 g (33.6 mol) potassium carbonate are placed in 2.5 1 acetone. At room temperature, 220 g (1.12 mol) of 1,5-dichloro-3,3-dimethyl-2-pentanone are added dropwise with stirring without cooling. After the addition is complete, the mixture is stirred for a further 2 hours at the reflux temperature.

The reaction mixture is cooled, suctioned off through a suction filter, and the mother liquor is concentrated under reduced pressure. The residue will taken up in methylene chloride. The solution is washed with water over sodium sulfate dried and concentrated. The remaining residue is stirred in petroleum ether, suctioned off and dried in vacuo at 50 ° C., 145.3 g (56.5% of theory) are obtained (3,3-Dimethyltetrahydrofuran-2-ylidene) - (1,2,4-triazol-1-yl) methane, melting point 47-C.

Preparation of the starting compounds A vigorous stream of hydrogen chloride gas from a bomb is introduced into 476 g (3.25 mol) of 2-chloromethylene-3,3-dimethyltetrahydrofuran while cooling with ice. The gas is completely absorbed and the temperature of the reaction mixture rises to 30C. After complete saturation with hydrogen chloride, the reaction mixture is stirred for 2 hours at room temperature, excess hydrogen chloride is first drawn into the water pump; then it is distilled under a good vacuum.

531 g (90% of theory) of 1,5-dichloro-3,3-dimethyl-2-pentanone with a boiling point of 85-90 * Cl0.3 mbar are obtained.

806 g (4 mol) of 1,1,5-trichloro-3,3-dimethyl-1-pentene are mixed with 360 ml (4.4 mol) of anhydrous sodium acetate in 1 l of dimethylformamide for 6 hours Heated to reflux, after cooling to 1000 ° C., 1.6 l (8 mol) of 30% sodium methylate solution are added dropwise in methanol and refluxed for a further 4 hours. The cold solution will poured into water and extracted several times with methylene chloride. After drying the organic phase and removal of the solvent by distillation, 654 g of product remain, which is fractionated via a column.

522 g (89% of theory) of 2-chloromethylene-3,3-dimethyl-tetrahydrofuran are obtained from the boiling point 84-87 * C / 20 mbar.

Example 3 73.6 g (0.378 mol) 3,3-dimethyl-2-chloromethylene tetrahydrothiophene-1,1-dioxide, 38.6 g (0.57 mol) imidazole and 78.4 g (0.57 mol) potassium carbonate in 200 ml Dimethylformamide is stirred at 140 ° C. for 15 hours. For working up, the cooled reaction mixture is poured into water, extracted several times with methylene chloride, the combined organic phases are washed with water and dried over sodium sulfate and the solvent is removed under reduced pressure.

33.8 g (40% of theory) of 3,3-dimethyl-1,1-dioXo-tetrahydrothiophen-2-ylidene) - (imidazol-1-yl) methane are obtained of melting point 78-C.

Manufacture of the Ausaanasverbindungen To 85 g (0.52 mol) of 3,3-dimethyl-2-chloromethylene-tetrahydrothiophene in 1000 ml of glacial acetic acid, 296 g (2.8 mol) of 30 percent aqueous hydrogen peroxide solution are added with stirring at room temperature. When the addition is complete, the mixture is stirred for 20 hours at 50 ° C., the cooled reaction mixture is poured into 3000 ml of water, extracted several times with dichloromethane, the combined dichloromethane phases are washed with water, dried over sodium sulfate and the solvent is removed under reduced pressure. The residue is recrystallized from diisopropyl ether.

78.4 g (74.2% of theory) of 3,3-dimethyl-2-chloromethylene-tetrahydrothiophene-1,1-dioxide with a melting point of 62 ° C. are obtained.

806 g (4.0 mol) of 3,3-dimethyl-1,1,5-trichloro-1-pentene, 344 g (4.4 mol) of thioacetic acid and 880 ml (4.4 mol) of 30 percent strength methanolic sodium methylate solution in 4000 ml of dimethylformamide heated under reflux for 3.5 hours. A further 440 ml (2.2 mol) of 30 percent strength methanolic sodium methylate solution are then added and the mixture is refluxed for a further 7 hours. To work up, most of the solvent is distilled off under reduced pressure, the residue is taken up in water, extracted several times with dichloromethane, the combined dichloromethane phases are washed with water, dried over sodium sulfate and the solvent is removed under reduced pressure. The residue is fractionated in a high vacuum, 466 g (72% of theory) of 3,3-dimethyl-2-chloromethylene-tetrahydrothiophene with a boiling point of 389-45 ° C. at 0.1 mbar as an E / Z isomer mixture, Z isomer: NMR (CDCl3): 6 1.2 (s, 6 H), 1.95 (t, 5 = 6.5 Hz, 2 H), 3.05 (t, J = 6.5 Hz, 2 H), 5.85 (s, 1 H) E-isomer: NMR (CDCl3): # 1.35 (s, 6 H), 2.05 (t, 5 = 6.5 Hz, 2 H), 3.0 ( t, J = 6.5 Hz, 2 H), 5.75 (s, 1 H) Example 4 21.5 g (0.12 mol) 3,3-dimethyl-2-chloromethylene-tetrahydrothiophene-1-oxide, 12.3 g (0.18 mol) imidazole and 24.9 g (0.18 mol) potassium carbonate stirred in 130 ml of dimethylformamide for 12 hours at 00C. For working up, 300 ml of water are added, the mixture is extracted several times with dichloromethane, the combined dichloromethane phases are washed with water, dried over sodium sulfate and the solvent is removed under reduced pressure. The residue is purified by chromatography on a silica gel column (mobile solvent: ethyl acetate / cyclohexane 3: 1).

11 g (46% of theory) of (3,3-dimethyl-1-oxo-tetrahydrothiophen-2-ylidene) - (imidazol-1-yl) methane with a refractive index of n20 1.580 are obtained, D Preparation of the starting compound To 110 g (0.678 mol) of 3,3-dimethyl-2-chloromethylene-tetrahydrothiophene in 110 ml of glacial acetic acid, 55 ml (62.6 g, 0.65 mol) of a 35 percent aqueous hydrogen peroxide solution are added dropwise with stirring at 0 ° C. to 5 ° C. after the addition has ended, stir for a further hour at 0 to 5 ° C. and then for 4 hours at room temperature. For working up, the reaction mixture is poured into water, neutralized with aqueous sodium hydroxide solution and extracted several times with dichloromethane. The combined dichloromethane phases are washed with water, dried over sodium sulfate and freed from the solvent under reduced pressure. The residue is recrystallized from 500 ml of diisopropyl ether. 72.6 g (40% of theory) of 3,3-dimethyl-2-chloromethylene-tetrahydrothiophene-1-oxide with a melting point of 78 ° -79 ° C. are obtained.

Example 5 2.1 g (0.01 mol) of (3,3-dimethyl-1-oxo-tetrahydrothiophen-2-ylidene) - (imidazol-1-yl) methane are stirred in 10 ml of concentrated hydroiodic acid at 70 ° C. for 4 hours. For working up, 100 ml of water are added to the cooled reaction mixture, adjusted to pH 6 with dilute aqueous sodium hydroxide solution, extracted several times with dichloromethane, the combined dichloromethane phases are washed with water, dried over sodium sulfate, the solvent is removed under reduced pressure and the residue is purified by chromatography ( Silica gel; mobile phase: ethyl acetate / cyclohexane = 3: 1).

1.5 g (77% of theory) of (3,3-dimethyltetrahydrothiophen-2-ylidene) - (imidazol-1-yl) methane are obtained of the refractive index nD20 = 1.646.

The vinyl azoles of the formula (II) listed in Table 2 are obtained using the methods described in the preceding examples and in accordance with the general information on preparation: Table 2 Table 2 Example physical No. R¹ R² R³ R4 R5 R6 R7 X Az Properties 6 CH3 CH3 HHHHHO # nD20 1.5038 7 CH3 C2H5 HHHHHO # nD20 1.5237 8 CH3 C2H5 HHHHHO # nD20 1.5364 9 CH3 CH3 HHHHHO # nD20 1.5018 *) 10 CH3 CH3 HHHHH SO2 # Mp 128 ° C 11 H3 CH3 HH CH2Br HHO # nD20 1.5452 *) E / Z isomer ratio deviating from example (2) Table 2 (continued) Example physical No. R¹ R² R³ R4 R5 R6 R7 X Az Properties 12 CH3 CH3 HHHH Cl O # Mp 100 ° C 13 CH3 CH3 HHHHH SO # nD20 1.547 14 CH3 CH3 HHHHHS # nD20 1.635 15 CH3 CH3 HHHHH SO # Mp: 58 ° C 16 CH3 CH3 HHHHH SO2 # Mp 128 ° C

Claims (10)

Claims 1. herbicidal agents, characterized by a content of an active ingredient combination, consisting of (a) a photosynthesis inhibitor active ingredient (herbicide) and (b) a vinyl azole of the general formula (II) (synergist), in which R1, R2, R3,, R5 and R6 each independently represent hydrogen, alkyl, haloalkyl or halogen, up to a maximum of 3 of these radicals being halogen and / or haloalkyl, or also R1 and R2 or R1 and R3 each together represents a doubly linked alkanediyl radical, R7 represents hydrogen or halogen, X represents oxygen, sulfur, a sulfinyl group or a sulfonyl group and Az represents pyrazolyl, imidazolyl or triazolyl or one of their acid addition salts or metal salt complexes. 2. Herbicidal agents according to claim 1, characterized in that they contain as photosynthesis inhibitor active ingredients (herbicides) compounds from the active ingredient groups of the formulas (IA) to (IJ) mentioned below: (A) triazinone derivatives of the formula in which X1 stands for amino, optionally substituted alkylideneamino or alkyl with 1 to 2 carbon atoms, X2 for alkylthio with 1 to 2 carbon atoms, alkyl and dialkylamino with 1 to 2 carbon atoms in each alkyl part or alkyl with 1 to 4 carbon atoms, and X3 represents tert-butyl optionally substituted by halogen or optionally substituted phenyl, (B) triazinedione derivatives of the formula in which X4 stands for amino, optionally substituted alkylideneamino or alkyl with 1 to 2 carbon atoms, X5 for alkylthio with 1 to 2 carbon atoms, alkyl and dialkylamino with 1 to 2 carbon atoms in each alkyl part or alkyl with 1 to 4 carbon atoms , and X6 represents alkyl having 1 to 6 carbon atoms or optionally substituted phenyl, (C) triazine derivatives of the formula in which X7 is chlorine, alkoxy or alkylthio each having 1 to 2 carbon atoms, X8 is alkylamino having 1 to 4 carbon atoms, and X9 is alkyl having 1 to 4 carbon atoms which is optionally substituted by cyano, (D) urea derivatives of the formula in which x10 represents optionally substituted phenyl, benzothiazolyl or optionally substituted thiadiazolyl, represents hydrogen or methyl, represents methyl, and X13 fi represents hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 2 carbon atoms or alkynvl with 2 to 4 in which X16 stands for alkyl with 1 to 6 carbon atoms or cycloalkyl with 5 to 7 carbon atoms, X17 stands for halogen, X18 stands for alkyl with 1 to 2 carbon atoms or X17 and X18 together stand for an optionally substituted alkylene chain or an optionally substituted fused benzene ring and X19 represents the CO or SO 2 group, (G) biscarbamate derivatives of the formula in which X20 is alkyl having 1 to 4 carbon atoms or optionally substituted phenyl and X21 is alkoxy having 1 to 4 carbon atoms or dialkylamino having 1 to 2 carbon atoms in each alkyl part, (H) pyridazinone derivatives of the formula in which X22 represents optionally substituted phenyl, X23 represents amino, alkylamino or dialkylamino each having 1 or 2 carbon atoms in each alkyl part, and X24 represents halogen, and (J) hydroxybenzonitrile derivatives of the formula in which X25 stands for halogen and X26 stands for halogen. 3. Herbicidal agents according to claim 1, characterized in that they are the photosynthesis inhibitor active ingredient (herbicide) 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one of the formula (IA -1) (metribuzin) contain. 4, herbicidal agents according to claim 1, characterized in that in the active ingredient combination the weight ratio of (1) photosynthesis inhibitor active ingredient (Herbicide) to (2) the vinyl azole of the formula (11) (synergist) between 1: 0.25 and 1: 100 lies. 5, use of active ingredient combinations according to claims 1 to 4 to control weeds, 6. Process for the preparation of herbicidal agents, characterized in that an active ingredient combination according to Claims 1 to 4 mixed with extenders and / or surfactants. 7. Use of vinyl azoles of the formula (11) according to claim 1 as Synergists in combination with photosynthesis inhibitor herbicides. 8. Use of vinyl azoles of the formula (1I) according to claim 1 as Synergists in combination with the herbicidal active ingredient 4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5-one (Metribuzin) of the formula (I-A-1) according to Claim 3. 9. Vinyl azoles of the formula (IIa) in which R1, R2, R3, R4, R5 and R6 each independently represent hydrogen, alkyl, haloalkyl or halogen, up to a maximum of 3 of these radicals being halogen and / or haloalkyl, or also R1 and R2 or R1 and R3 each together represent a doubly linked alkanediyl radical, X represents oxygen, sulfur, a sulfinyl group or a sulfonyl group, Az represents pyrazolyl, imidazolyl or triazolyl and Hal represents halogen. 10. Vinyl azoles of the formula (IIc) in which R1, R2, R3, R4, R5, R6 and Az have the meaning given in claim 9 and Y stands for sulfur, a sulfinyl group or a sulfonyl group.