NO862593L - BENZOYL-TRIAZOLYL DIETIC ACID OR TIODE DIETIC ACID DERIVATIVES, PREPARING THEREOF AND BIOCIDE AGENTS CONTAINING THE DERIVATIVES. - Google Patents

Description

The present invention relates to new benzoyl-triazolylacetic acid or thioacetic acid derivatives, methods for their production as well as biocidal agents containing these derivatives, methods for their production and use of the agents.

In EP-A 008458 and in DE-OS 28 31 235, azolylmethylmalonic acid derivatives are described which can be used as agents for combating pests, respectively agents for combating nematodes. However, the effect and duration of action of these compounds are not always satisfactory, especially with certain harmful organisms.

Unexpectedly, new benzoyl-triazolylacetic acid or thioacetic acid derivatives have now been found which exhibit excellent biocidal properties.

Object of the present. invention is consequently benzoyltriazolyl-acetic acid or -thioacetic acid derivatives of the general formula I on the attached formula sheet, in which Rj and R2 independently of each other stand for hydrogen, halogen or an olefinic acid residue with 1-4 C atoms, Y stands for oxygen or sulphur, Z stands for the residues OR4, SR4 or R5NR5, whereby R4 is a straight-chain or branched, saturated or unsaturated, unsubstituted or single- or multi-, with halogen, alkoxy- or alkoxycarbonyl-with 1-4 C atoms in the alkyl chain, phenyl-, halophenyl - or trialkylsilyl residue with 1-4 C atoms in the alkyl chain substituted hydrocarbon residue with 1-20 C atoms or a cyclic hydrocarbon residue which may be substituted with alkyl or alkoxycarbonyl residues with 1-4 C atoms in the alkyl chain and R5 and R5 independently stand for an alkyl, an alkoxycarbonyl residue with 1-4 C atoms in the alkyl chain, a phenyl residue or R5 and R0 can together with the nitrogen atom form a morpholino ring which can be substituted with alkyl residues with 1-4 C atoms, and plant physiologically tolerable salts and metal complexes thereof.

Furthermore, it has been found that the substances according to the invention are obtained by reacting a ketone of the general formula II on the attached formula sheet, in which Rj and R2 have the meanings given in claim 1, with a compound of the general formula III on the attached formula sheet, wherein Y and Z have the meanings given in claim 1 and Hal stands for chlorine or bromine, in the presence of at least an equivalent amount of an acid acceptor and optionally in the presence of a diluent inert under the reaction conditions at a temperature from -20"C to +140 °C, optionally removes the diluent and optionally transfers the reaction product to a plant physiologically tolerable salt or metal complex.

The benzoyl-triazolylacetic acid and -thioacetic acid derivatives according to the invention show excellent biocidal properties and thus constitute a valuable contribution to the technique.

In formula I, R1 and R2 independently of each other mean a hydrogen atom, a halogen atom or an alkoxy acid residue with 1-4 C atoms, preferably a halogen atom or a methoxy acid residue, especially preferably a chlorine atom.

Y stands for oxygen or sulphur, particularly preferred is oxygen.

Z can mean the residues OR4, SR4 or R5NR6, whereby the residues OR4 and SR4 are particularly preferred.

R4 stands for a straight-chain or branched, saturated or unsaturated hydrocarbon residue with 1-20 C atoms. Examples of such residues are saturated hydrocarbon residues, such as methyl, ethyl, n-propyl, i-propyl, butyl, sec-butyl, t-butyl residues, straight-chain or branched pentyl, hexyl, heptyl, octyl -, dodecyl, tridecyl, hexadecyl, nonadecyl residues, ethylenically unsaturated, straight-chain or branched hydrocarbon residues, such as vinyl, allyl, propenyl, i-propenyl, butenyl, pentenyl residues, acetylenically unsaturated hydrocarbon residues, such as ethynyl, propynyl -, 1-butynyl, 2-butynyl or heptynyl residues. Preferred are those compounds in which R4 stands for a saturated alkyl residue with 1-18 C atoms or an ethylenic or acetylenic unsaturated hydrocarbon residue with 1-8 C atoms.

Furthermore, the hydrocarbon residue can be singly or polysubstituted with halogen atoms, alkoxy or alkoxycarbonyl residues with 1-4 C atoms in the alkyl chain, or with optionally single or multi-halogenated phenyl residues or with trialkylsilyl residues with 1-4 C atoms in the alkyl chain. Examples of such substituted hydrocarbon residues are single or polyhalogenated alkyl residues, such as 1-chloroethyl-, 1-chloropropyl-, 1-bromomethyl-, 2-bromopropyl-, 1-bromopropyl-, dichloromethyl-, 1,1-dichloroethyl-, 1, 1,1-trichloroethyl and the various trichlorobutyl residues, further with alkoxy or alkoxycarbonyl-substituted alkyl residues, such as methoxyethyl, methoxypropyl, methoxybutyl, ethoxypropyl, ethoxyheptyl, propoxyhexyl, methoxycarbonylpropyl, ethoxycarbonylbutyl, propoxycarbonylbutyl residues . Examples of alkyl radicals substituted with optionally halogenated phenyl radicals are benzyl, 4-butylphenyl, 4-ethylphenyl, monochlorobenzyl, dichlorobenzyl, bromobenzyl radicals, examples of alkyl radicals substituted with trialkylsilyl radicals are trimethylsilylpropyl, triethylsilylethyl or tripropylsilylhexyl radicals.

Preferred are those compounds in which R4 stands for an alkyl radical with 1-18 carbon atoms mono- or polysubstituted with halogen atoms, an aldehyde radical with 1-4 carbon atoms or optionally a halogenated phenyl substituted alkyl radical with 1-18 carbon atoms.

Particularly preferred are those compounds in which R4 stands for an optionally single or multiple, with chlorine atoms, substituted alkyl radical with 1-15 C atoms or benzyl or 2,4-dichlorobenzyl radical.

Furthermore, R4 can stand for a cyclic hydrocarbon residue, such as e.g. a cyclohexyl residue, a phenyl residue, an alkyl residue substituted cyclic hydrocarbon residue, such as 4-methylcyclohexyl, 4-ethylcyclohexyl or 4-butyl cyclohexyl residue or an alkylcarbonyl substituted cyclic hydrocarbon residue, such as methylcarbonylphenyl residue or ethylcarbonylphenyl residue.

Preferred are compounds in which R4 stands for a cyclohexyl residue.

R5 and R5 can be the same or different and stand for an alkyl radical with 1-4 C atoms, such as a methyl, ethyl, propyl or butyl radical, an alkoxycarbonyl radical with 1-4 C atoms in the alkyl chain, such as e.g. a methoxycarbonyl, ethoxycarbonyl or propoxycarbonyl residue.

Preferred are those compounds in which R5 and R0 both mean an alkyl radical with 1-4 C atoms.

R5 and R5, together with the nitrogen atom, can further form a morpholino ring which is singly or polysubstituted with alkyl residues with 1-4 C atoms, such as a 3,5-dimethylmorpholino residue.

The compounds according to the invention can be prepared by reacting a ketone of the general formula II with an equal molar amount of a compound of the general formula III in the presence of at least the equivalent amount of an acid acceptor.

Usually, a salt of the ketone of the general formula II is first prepared with an acid acceptor, and this salt is then reacted with a compound of the general formula III. However, it is also possible to prepare the compounds according to the invention in one step by the simultaneous use of the reaction partner and the acid acceptor.

As acid acceptors serve strongly basic compounds, such as e.g. inorganic bases, such as sodium hydride or potassium hydride, or organic bases, such as e.g. trialkylamine compounds, such as trimethylamine, triethylamine, tripropylamine or triphenylamine compounds.

Preferably, the reaction takes place in a diluent that is inert under the reaction conditions, e.g. in halogenated or non-halogenated hydrocarbons, such as petroleum ether, toluene, chloroform, methylene chloride or in ethereal diluents, such as diethyl ether, dioxane or tetrahydrofuran.

The reaction can also take place with an excess of the liquid acid acceptor, which in this case also serves as a dissolving or diluting agent.

The reaction is carried out at temperatures from approx. -20°C to +140°C, preferably at temperatures from -10°C to +80°C, particularly preferably at temperatures from 0°C to 35°C.

Depending on the reactivity of the starting compounds, the activity of the acid acceptor and the reaction temperature, the reaction duration amounts to approx. 30 minutes to 5 hours, usually approx. 1 to 2 hours.

After completion of the reaction, the produced inorganic or organic salt is removed by washing with water or filtration. The volatile components of the reaction mixture are then evaporated at atmospheric pressure or reduced pressure at room temperature or elevated temperature.

Optionally, the remaining product can be purified by suitable methods, such as e.g. recrystallization, extraction or chromatographic separation.

The compounds of the general formulas II and III used as starting materials are known, or can be prepared by methods known per se. Consequently, compounds of the general formula II can for example be prepared according to DE-OS 26 53 420.

To prepare the salts or metal complexes, the free base of the general formula I is reacted in the presence of an inert diluent with at least the stoichiometric amount of a corresponding acid or a corresponding metal salt. Preferably, the individual reactants are used in solution.

The resulting precipitate is separated, e.g. by filtration, possibly during cooling, then washed and dried.

The products usually occur with high purity and can possibly be further purified by recrystallization.

The compounds according to the invention and salts and metal complex compounds thereof are effective against a wide spectrum of plant pathogenic fungi, algae and bacteria, e.g. against fungi from the class phycomycetes, ascomycetes, basidomycetes and deuteromycetes.

The good plant tolerance and the partly systemic activity in the concentration necessary for the treatment of plant diseases enable a treatment of the plant parts above the iodine, of plants and seeds and of the soil.

Particularly interesting are the fungicidal compounds for combating a variety of fungi on various cultivated plants and their seeds, such as e.g. wheat, rye, barley, oats, rice, maize, cotton, soya, coffee, sugar cane, fruit and ornamental plants for horticulture as well as vegetables such as cucumbers, beans or pumpkin plants.

The new compounds can be used with particularly advantageous results, e.g. for the treatment of the following plant diseases:

In similar quantities, the substances can also be used as a wood preservative against fungi that discolour wood and decay fungi, such as e.g. for the control of Merulius lacrimans, Polyporus vaporarius, Poria placenta and Polystictus cinnabarinus.

The fungicidal agents generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active substance.

The amount used is, depending on the type of the desired effect, between 0.02 and 3.00 kg of active substance or more per hectares.

Depending on the area of application, the active substances can be transferred to the usual preparations, such as solutions, spray powders, emulsion concentrates, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active substances, microencapsulations in polymers substances and in encasing compounds for seeds, further in compositions with burning rates, such as smoke cartridges, cans, spirals etc., as well as ULV cold and warm fog preparations.

These formulations are produced in a manner known per se, e.g. by mixing the active substances with emulsifiers, i.e. liquid solvents, liquefied gases under pressure and/or solid carriers, possibly using surfactants, i.e. emulsifiers and/or dispersing and/or wetting agents and/or foaming agents. If water is used as a suspending agent, e.g. organic solvents are also used as auxiliary solvents. As a liquid solvent, the following are mainly mentioned: aromatics, such as xylene, toluene or alkylnaphthalene, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffin, e.g. petroleum fractions, alcohols, such as butanol or glycol, as well as ethers and esters thereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water. By liquefied, gaseous suspending agents or carrier substances are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide; as solid carrier substances come into question, e.g. natural stone flours, such as kaolin, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic products, such as highly dispersed silica, alumina and silicates; as solid carrier substances for granules come into question, e.g. decomposed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, as well as synthetic granules of inorganic and organic flours, as well as granules of inorganic material, such as sawdust, coconut shells, corn cobs two tobacco stalks; as an emulsifier and/or foaming agent comes into question, e.g. nonionic and ionic surfactants, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkyl aryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates and aryl alkyl sulphonates as well as egg white hydrolysates; as dispersants come into question, e.g. lignin sulfonate or condensation products of aryl sulfonates with formaldehyde.

In the compositions, adhesives and thickeners can be used, such as carboxymethyl cellulose, methyl cellulose, natural and synthetic powder-like, granular and latex-like polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and inorganic or organic dyes can be added.

The compositions generally contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90% by weight.

The active substances can be used as such in the form of the compositions or as forms of use prepared from them by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application takes place in the usual way, e.g. by pouring, dipping, spraying, sprinkling, misting, evaporation, injection, slurrying, coating, dust application, spreading, dry pickling, wet pickling, wet pickling, mud pickling or incrustation.

When treating plant parts, the concentration of active substance in the application forms can be varied within a larger range. It is generally between 1 and 0.001% by weight, preferably between 0.5 and 0.001% by weight.

When treating seeds, amounts of active substance from 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g.

When treating the soil, concentrations of active substance from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight at the site of action are required.

EXAMPLE 1:

In a reaction flask, 14.08 g (0.055 mol) of 2-(2,4-dichloro-phenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one were dissolved in 150 ml tetrahydrofuran and 1.32 g (0.055 mol) of sodium hydride were added. After stirring for 2 hours at room temperature, 6.0 g (0.055 mol) of chloroformic acid ethyl ester in 50 ml of tetrahydrofuran was added dropwise. After 1 hour the solvent was removed at room temperature under reduced pressure, the residue was taken up in chloroform, washed with water, the organic phase was dried and the solvent was evaporated. The oily residue was dissolved in tetrachloromethane/acetonitrile (volume/volume: 3/1) and purified by means of column chromatography over silica gel with tetrachloromethane/acetonitrile as mobile phase. After removal of the eluent, 9.9 g (0.03 mol) of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid ethyl ester were obtained in the form of an oil.

EXAMPLE 2:

In a reaction flask, 15.36 g (0.06 mol) of 2-(2,4-dichlorophenyl)-1-(1,2,3-triazol-1-yl)-ethan-2-one were dissolved in 400 ml methylene chloride and 6.1 g (0.06 mol) of triethylamine. After cooling to 5°C, 7.11 g (0.06 mol) of chloroformate (2-propyne) ester in 50 ml of methylene chloride were added dropwise at constant temperature. After completion of the reaction, the reaction solution was washed with water, the solvent was evaporated and the remaining residue was purified by column chromatography. 17 g (0.05 mol) of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid propyl ester with a freezing point of 76-81°C were obtained.

EXAMPLE 3:

14.08 g (0.055 mol) of 2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one was slurried in 100 g (0.98 mol) triethylamine and cooled to 10 "C. Then 5.2 g (0.055 mol) methyl chloroformic acid was added dropwise. After the reaction was complete, the solution was evaporated and the residue was taken up in diethyl ether, after which the insoluble residue was filtered off. After evaporation of the solvent, 15 .5 g (0.05 mol) 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid methyl ester with freezing point 105°C.

EXAMPLE 4:

To a solution of 10.1 g (0.0295 mol) of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid propyl ester in 100 ml of diisopropyl ether, at a temperature at 5°C with stirring, an HCl-saturated diisopropyl ether solution was added dropwise until the formation of the precipitate had ended. The crystalline precipitate was filtered off with cooling, washed with diisopropyl ether and dried at room temperature. 6.5 g (0.017 mol) of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid propyl ester hydrochloride with a freezing point of 105-108 °C were obtained .

EXAMPLE 5:

8.42 g (0.025 mol) of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid n-propyl ester was dissolved in 40 ml of ethanol and with stirring at room temperature 1.18 g (0.0123 mol) of zinc chloride dissolved in 50 ml of ethanol are added dropwise. After approx. After 1 hour, the precipitate formed was filtered off, washed with ethanol and dried. 6.8 g (0.0082 mol) of [2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid-n-propyl ester] 2 * ZnCl2 with freezing point was obtained 120-125.5°C.

By one of the methods described, the compounds summarized in the table and characterized by the melting point were produced (<*->decomposition).

EXAMPLE 50:

1 part of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid ethyl ester was dissolved in 3 parts of xylene and mixed with 1 part of a mixture of 50% Ca-dodecylbenzenesulfonate and 50% ethoxylated nonylphenol with an average content of 10 mol ethylene oxide/1 mol nonylphenol. This concentrate, containing 20% by weight of active substance, could be diluted with water to an emulsion of the desired concentration.

EXAMPLE 51:

1 part 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid ethyl ester was pulverized with 2 parts attack clay, 6 parts kaolin and 1 part Na-oleylmethyl tauride and ground in a planetary ball mill in 1 hour. The produced wettable powder could be dispersed in water to a spray mixture of the desired concentration.

EXAMPLE 52:

1 part of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid n-propyl ester was dissolved in 3 parts of xylene and mixed with 1 part of a mixture of 40% Ca-dodecylbenzenesulfonate and 60% of a polyoxyethylene sorbitan fatty acid ester. By mixing with water, an emulsion of the desired concentration could be obtained.

EXAMPLE 53:

1 part of 2-(2,4-dichlorobenzoyl)-2-(1,2,4-triazol-1-yl)-acetic acid n-propyl ester was mixed with 2 parts of highly dispersed precipitated silicic acid, 6 parts of kaolin and 1 part of a mixture of 30% dialkylnaphthalenesulfonic acid Na salt and 70% Na oleylmethyl tauride and melt for 1 hour in a planetary ball mill. The resulting wettable powder was diluted in water to a spray mixture of the desired concentration.

Example A:

Prophylactic effect of the compounds against powdery mildew (Erysiphe cichoracearum) on cucumbers by treating the leaves of 10-day-old cucumber plants sprayed with an aqueous dilution of the composition of the active substance. After drying the spray liquid, the plants were inoculated with spores recovered from infected plants. The cucumber plants were then left in a greenhouse at around 60% humidity. 14 days after the artificial infection, the attack with Erysiphe cichoracearum was assessed according to the following assessment form:

The active substance, the concentration of active substance and the assessment values appear in the following table.

j Example B:

Prophylactic effect of the compounds against grain powdery mildew (Erysiphe graminis) on wheat by treating the leaves Ca. 10 cm wheat plants were sprayed with an aqueous dilution of - the compound active substance on all sides. After 48 hours, the treated plants were pollinated with conidiospores of the fungus Erysiphe graminis var.tritici recovered from infected plants.

The infected plants were allowed to stand in greenhouses at around 22 °C. 10 days after the artificial infection, the infestation was assessed.

The compounds of Example 1, Example 2, 22, 26, 40, 24, 36, 8, 38, 34 and 35 completely prevented the growth of the fungus.

Example C:

Prophylactic effect of the compounds against powdery mildew (Podosphaera leucotricha) on apple seedlings

Young apple seedlings were sprayed with an aqueous dilution of the compound active substance on all sides and then allowed to stand for 24 hours in a greenhouse.

Then the treated plants were inoculated with conidiospores recovered from diseased apple seedlings.

After the outbreak of the disease on the control plants, the attack by Podosphaera leucotricha was assessed.

For example, the compounds according to example 1 and according to example 2 at a concentration of active substance of 0.005% prevented the growth of the fungus completely, with compounds 33 and 24 being approx. 3% of the leaf surface attacked.

Example D:

Prophylactic action against wheat brown rust (Puccinia recondita) on wheat

To investigate the protective activity, young wheat plants were inoculated with an aqueous spore suspension of Puccinia recondita.

After drying, the plants were sprayed with the preparation of active substance until they were dripping wet. The plants were then inoculated for 24 hours at 20°C and approx. 95% humidity in a climate room. Until the outbreak of the disease on the control plants, the test plants were kept in greenhouses at around 20°C and 70% humidity.

Active substances, concentrations of active substances and assessment values (assessment forms 1-9 from example 1) appear in the following table.

Example E:

Fungicidal activity in agar plate tests

The active substances dissolved in acetone were added in specific concentrations to liquefied soil.

The agar was poured into the Petri dishes and, after cooling, inoculated with the test organism. As soon as the control of the test organism had grown, the results were assessed.

In the following table, the minimum inhibitory concentration (MIC) is the lowest concentration in the soil (in % by weight) of the substance at which fungal growth was completely inhibited.

Example F:

Fungicidal and bactericidal activity in agar diffusion experiments

Aqueous dispersions were prepared from the formulations of active substance. Sheets of filter paper were immersed in these and then placed on the inoculated soil.

For example, compound 29 at a concentration of active substance of 0.0016% completely prevented the growth of Alternaria tenuis, at a concentration of 0.008% 35 and 34. With a concentration of active substance of 0.04%, the growth of Penicillium glaucum was completely blocked by the compounds 29, 22, 26, 28, 24 and of the compound according to example 2.

The growth of the bacterium Xanthomonas ssp. was, for example, completely prevented by a concentration of active substance of 0.04% of compound 35.

Example G:

Effect of the active substance on the growth of the algae Chlorella fusca

To 70 ml algae suspension, corresponding to 0.1 mg algae/l ml nutrient solution, the substance to be examined, dissolved in acetone, was added.

The algal suspension was kept for 48 hours under artificial lighting and aeration.

The percentage value (P) = algae concentration (in mg) in the test solution in relation to the control (= 100%) was assessed.

At a concentration of active substance of 10 ppm, for example, in the compound according to example 2, P was less than 1%.

Claims (11)

1. Benzoyl-triazolyl-acetic acid or -thioacetic acid derivatives of the general formula I on the formula sheet, characterized in that R^ and Pv2 independently of each other stand for hydrogen, halogen or an olefinic acid residue with 1-4 C atoms, Y stands for oxygen or sulphur, Z stands for the residues OR4, SR4 or R5NR5, in which R4 is a straight-chain or branched, saturated or unsaturated, unsubstituted or single- or multiple-, with halogen, alkoxy- or alkoxycarbonyl- with 1-4 C atoms in the alkyl chain, phenyl-, halophenyl or trialkylsilyl residue with 1-4 C atoms in the alkyl chain, substituted hydrocarbon residue with 1-20 C atoms or a cyclic hydrocarbon residue, which may be substituted with alkyl or alkoxycarbonyl residues with 1-4 C atoms in the alkyl chain and R5 and R5 are independent of each other for an alkyl, an alkoxycarbonyl residue with 1-4 C atoms in the alkyl chain, a phenyl residue or R5 and R5 together with the nitrogen atom form a morpholino ring which can be substituted with alkyl residues with 1-4 C atoms, and plant physiologically tolerable s altars and metal complexes thereof. 2. Benzoyl-triazolyl-acetic acid or -thioacetic acid derivatives according to claim 1 of the general formula I, characterized in that R^ and R2 independently of each other stand for a halogen atom or a methoxy acid residue, Y stands for oxygen or sulphur, Z stands for the residues OR4, SR4 or R5NR5, in which R4 is a straight-chain or branched, saturated or unsaturated, unsubstituted or mono- or multi-, with halogen atoms, 1-4 C-atom alkoxy radicals or halogenated phenyl radicals, substituted 1-18 C-atom hydrocarbon radicals or a cyclohexyl radical and R5 and R5 are both for an alkyl residue with 1-4 C atoms and plant physiologically tolerable salts and metal complexes thereof. 3. Benzoyl-triazolyl-acetic acid or -thioacetic acid derivatives according to claim 1 of the general formula I, characterized in that R^ and R2 both stand for a chlorine atom, Y stands for oxygen, Z stands for the residues OR4, SR4, in which R4 is an unsubstituted or with chlorine single - or polysubstituted alkyl residue with 1-15 C atoms, a benzyl residue or a 2,4-dichlorobenzyl residue and plant physiologically tolerable salts and metal complexes thereof. 4. Process for the preparation of compounds of the general formula I, characterized in that a ketone of the general formula II on the formula sheet, in which Pq and R2 have the meanings specified in claim 1, is reacted with a compound of the general formula III on the formula sheet, in which Y and Z have the meanings given in claim 1 and Hal stands for chlorine or bromine, in the presence of at least the equivalent amount of an acid acceptor and optionally in the presence of a diluent inert under the reaction conditions at a temperature from -20 °C to +140 °C, optionally removes the diluent and optionally transfers the reaction product to a plant physiologically tolerable salt or metal complex. 5. Method according to claim 4, characterized in that a compound of the general formula II is first reacted with an acid acceptor and then with a compound of the general formula III. 6. Method according to claim 4, characterized in that sodium hydride or a tertiary amine is used as acid acceptor. 7. Biocidal agent, characterized by the content of at least one compound of the general formula I on the formula sheet, in which R\ and R2 independently of each other stand for hydrogen, halogen or an carboxylic acid residue with 1-4 C atoms, Y stands for oxygen or sulphur, Z stands for the residues OR4, SR4 or R5NR5, in which R4 is a straight-chain or branched, saturated or unsaturated, unsubstituted or mono- or poly-, with halogen, alkoxy or alkoxycarbonyl with 1-4 C atoms in the alkyl chain, phenyl, halophenyl or trialkylsilyl residues with 1-4 C atoms in the alkyl chain, substituted hydrocarbon residue with 1-20 C atoms or a cyclic hydrocarbon residue which may be substituted with alkyl or alkoxycarbonyl residues with 1-4 C atoms in the alkyl chain, and R5 and R5 are independent of each other >for an alkyl, an alkoxycarbonyl residue with 1-4 C atoms in the alkyl chain, a phenyl residue or R5 and R5 together with the nitrogen atom form a morpholino ring which can be substituted with alkyl residues with 1-4 C atoms and plant physiologically tolerable salts and metal complexes thereof. 8. Fungicidal agent, characterized by the content of at least one compound of the general formula I on the formula sheet, in which Rj and R2 independently of each other stand for hydrogen, halogen or an carboxylic acid residue with 1-4 C atoms, Y stands for oxygen or sulphur, Z stands for the residues OR4, SR4or R5NR5, in which R4 is a straight-chain or branched, saturated or unsaturated, unsubstituted or mono- or multi-, with halogen, alkoxy or alkoxycarbonyl- with 1-4 C atoms in the alkyl chain, phenyl, halophenyl or trialkylsilyl residues with 1-4 C atoms in the alkyl chain, substituted hydrocarbon residue with 1-20 C atoms or a cyclic hydrocarbon residue, which may be substituted with alkyl or alkoxycarbonyl residues with 1-4 C atoms in the alkyl chain, and R5 and R0 are independent of each other for an alkyl, an alkoxycarbonyl residue with 1-4 C atoms in the alkyl chain, a phenyl residue or R5 and R5 together with the nitrogen atom form a morpholino ring which can be substituted with alkyl residues with 1-4 C atoms, and plant physiologically tolerable s altars and metal complexes thereof. 9. Method for combating harmful organisms, characterized in that at least one compound of the general formula I is allowed to act on the harmful organisms and/or their life frame. 10. Use of the compounds of general formula I for the control of harmful organisms. 11. Process for the production of biocidal agents, characterized by mixing the compounds of the general formula I with emollients and/or surfactants.