AT351863B

Acylated triazolyl-o,n-acetals and their use as fungicides

Abstract

This record has no abstract on file.

AT351863B, drawing sheet 1 — Sheet 1 of 20

Term

Term ended

Expired 10 January 1997, 29.7 years ago.

7 claims: 2 independent, 5 dependent

1
CLAIMS:1. A fungicidal composition, characterized in that it contains as active ingredient at least one new acyclic triazolyl-O, N-acetal of the general formula O-CO-R /, VO-CH-CH-C (CH,) '/ I az 3'3 5 in which R represents alkyl, haloalkyl, phenoxyalkyl, alkylamino or optionally chlorine-substituted phenylamino, X represents halogen, alkyl, optionally chlorine-substituted phenyl or nitro, n represents integers from 0 to 3, and Az represents the 1,
2
2,4-triazolyl (l) - and the 1,2,4-TriazolyI- (4) radical, in addition to extenders and / or surface-active agents and or, or carriers and optionally other active ingredients. 10 Second Composition according to claim 1, characterized in that it contains as active ingredient a compound of general formula (1) in which R is alkyl of 1 to 8 carbon atoms, haloalkyl of 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenoxyalkyl with bis may be 2 C atoms in the alkyl part, alkylamino having 1 to 4 C atoms in each alkyl part, and optionally phenyl-substituted phenyl, X is halogen, nitro, alkyl having up to 4 C atoms, for optionally chlorine-substituted phenyl, 15 and n represents the numbers 0 to 3.
5
5 5. Composition according Anspruchl, characterized in that it is a compound of the active ingredient formula O-CO-CH. / X_Z X_O-CH-CH-C (CH,) "\ = / \ = / I Λ-ν Contains LJ.

Independent claims3

499 paragraphs in 27 sections, as filed

@ Start of patent period: 1979 01 15

Longest possible duration:

dependency:

@ Pamphlets considered to delineate the prior art:

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The invention relates to fungicidal compositions containing as active ingredient new acylated triazolyl-O, N-acetals, their salts or metal complexes.

It has already been disclosed that triazolyl-O, N-acetal, in particular in the phenyl moiety substituted 1-phenoxy-1- [1,2,4-triazolyl- (l)] - 3,3-dimethylbutan-2-ols, good have fungicidal properties (see 5 DE-OS 2324010). However, their effectiveness is not always quite satisfactory, especially at low application rates and concentrations. In addition, their plant compatibility and seed compatibility when used as seed dressings are not always satisfactory.

It has been found that the new acylated triazolyl-O, N-acetals of the general formula

O-CO-R

in which R represents alkyl, haloalkyl, phenoxyalkyl, alkylamino or optionally chlorine-substituted phenylamino, X represents halogen, alkyl, optionally chlorine-substituted phenyl or nitro, n represents integers from 0 to 3, and Az represents the 1, 2,4-triazolyl- (1) - and the 1,2,4-triazolyl- (4) radical, and their physiologically acceptable salts and MetaUkomplexe have a significantly higher fungicidal activity, in particular against rust and mildew, as the known from the prior art triazolyl-O, N-acetals, which are the closest active ingredients. In addition, they are characterized by a better plant compatibility. The inventive compounds containing these compounds as active ingredients thus represent an enrichment of the art.

The compounds of formula (I) have two asymmetric carbon atoms; they can therefore be in the erythro as in the threo form. In both fäuen they are predominantly as racemates.

The acylated triazolyl-O, N-acetals of the formula (I) are obtained by reacting triazolyl derivatives of the general formula

OH

O-CH-CH-C (CH3)3

Az (II) »in which X, Az and n have the abovementioned meaning,

a) with acid halides of the general formula

Halo-CO-R (ΙΠ), in which R has the abovementioned meaning, and Hal represents halogen, in particular chlorine or bromine, if appropriate in the presence of a solvent, or

b) with acid anhydrides of the general formula

R-CO-O-CO-R (IV), in which R has the abovementioned meaning, if appropriate in the presence of a solvent and if appropriate in the presence of a catalyst, or

c) with ketenes of the general formula

O = C = CH-R '(V) in which R' is hydrogen, alkyl, alkenyl, alkynyl or halomethyl, if appropriate in the presence of a solvent and if appropriate in the presence of a catalyst, or

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d) with isocyanates of the general formula

O = C = N-R (VI) in which R represents alkyl or optionally substituted phenyl, if appropriate in the presence of a solvent and if appropriate in the presence of a catalyst.

The thus obtained acylated triazolyl-O, N-acetals of the formula (I) are converted into the salts by reaction with acids, or the corresponding metal complexes can be obtained by reaction with metal salts.

If one uses l- (4-chlorophenoxy) -l- [l, 2,4-triazolyl (l)] - 3,3-dimethyl-butan-2-ol and acetyl chloride as starting materials, the reaction sequence by the following formula scheme to be reproduced [method a)]:

OH

CI_

O-CH-CH-C (CH-), I 3 3 + CH3-CO-Cl

Cl-o-co-ch3

O-CH-CH-C (CH3) j

^ N

When using 1- (4-chlorophenoxy) -1-, 2,4-triazolyl- (1)] - 3,3-dimethylbutan-2-ol and acetic anhydride as starting materials, the reaction can be carried out by the following Formula scheme [method b)]:

OH

O-CO-CH, // "W" + (CH«O · I

Cl- / -O-CH-CH-C (CH3)3 -> Cl - // \ O-CH-CH-C (CH3)3 '3 \ = / • N

• N

If l- (2,4-dichlorophenoxy) -l- [l, 2,4-triazolyl- (l) [- 3,3-dimethylbutan-2-ol and 4-chlorophenyl isocyanate are used as starting materials, the reaction sequence is represented by the following formula scheme [Method d) J:

OH ci_ / O-CH-CH-C (CH3>3 \=

O-CO-NH _ // \ _Cl / I \ = / + C1_ / X-N = C = O - / I \ == / Cl_ ^ O-CH-CH-C (CH3)3

SN

n_l1

I

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4 reactions of triazolyl derivatives of the formula (II) with a ketene of the formula (V) can be formulated in a corresponding manner [process c) J. Chem.

The triazolyl derivatives to be used as starting materials are generally defined by the formula (Π). In this formula, X preferably represents halogen, nitro, straight-chain or branched alkyl having up to 4 carbon atoms, or represents optionally chlorine-substituted phenyl.

The subscript n stands for the numbers 0 to 3, and Az has the meaning given above.

The starting materials of the formula (II) are known (cf., DE-OS 2324010). Not yet known starting materials of the formula (H) can be obtained by the methods already described by z. For example, the resulting ketone derivatives are reduced with aluminum isopropylate or with complex hydrides in the presence of a solvent.

The acid halides required for the preparation of the compounds which can be used according to the invention according to process variant a) are generally defined by the formula (ΠΙ). Here, R preferably represents straight-chain or branched alkyl having 1 to 8, in particular 1 to 6, carbon atoms; Haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, in particular fluorine and chlorine; Phenoxyalkyl with up to 2 carbon atoms in the alkyl part. Furthermore, R preferably represents alkylamino having 1 to 4, in particular 1 or 2 carbon atoms in each alkyl moiety, as well as optionally substituted by chlorine phenylamino.

The acid halides of the formula (III) are known or can be prepared by customary processes; for example, by reacting carboxylic acids or their alkali metal salts with acid halides of phosphorus or sulfur. These methods are known from the general textbooks of organic chemistry.

The acid anhydrides further required for process variant b) are generally defined by formula (IV). Here, R preferably represents the substituents which have already been mentioned as preferred in the case of the acid halides of the formula (III).

The acid anhydrides of the formula (IV) are known or can be prepared by known processes;

so z. B. by the action of acid chlorides on the alkali metal salts of carboxylic acids. These methods are well known.

The ketenes additionally required for process variant c) are generally defined by the formula (V). Here, R 'is preferably hydrogen, alkyl having 1 to 7, in particular 1 to 5 carbon atoms, alkenyl and alkynyl each having bis.zu 3 carbon atoms, and preferably Halo30 genmethyl with 1 to 3 halogen atoms, in particular fluorine and chlorine. The usable for the reaction ketenes are also known or can be prepared by known methods, such. Example by thermolysis of ketones or by dehydration of carboxylic acids (see Houben-Weyl, Methods of Organic Chemistry, Volume 7/4, Georg Thieme Verlag).

The further required for process variant d) isocyanates are generally defined by the formula (VI). In this formula, R preferably represents alkyl having 1 to 4, in particular 1 or 2, carbon atoms, as well as optionally substituted phenyl, with halogen, nitro or cyano being the preferred substituents.

Suitable salts for the compounds of the formula (I) are salts with physiologically tolerated acids. This preferably includes the hydrohalic acids, such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, monound and bifunctional Carbonsänren and Hydroxycarhonsäuren, such as Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, 1,5-naphthalenedisulfonic acid.

The salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving the base in ether, for example diethyl ether, and adding the acid, for example nitric acid, and in known manner, for. B. isolated by filtration and optionally purified.

Suitable complexes for the compounds of the formula (I) are complexes with metal salts. Hiebei are preferably metals of Π. to IV. Main and I., H., IV. to VHI. Subgroup, in particular 50 copper, zinc, manganese, magnesium, tin, iron and nickel called. Suitable salts are salts with physiologically tolerated acids. These include, preferably, the hydrohalic acids, such as z, B,

Hydrochloric acid and hydrobromic acid, phosphoric acid, nitric acid and sulfuric acid.

The metal complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the meta-salt in alcohol, for example ethanol, and adding to the base. 55 They can be purified in a known manner, for example by filtration, isolation and optionally by recrystallization.

Suitable solvents for the reaction according to process variant a) preferably all inert organic solvents in question. This includes preferably ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ether, such as tetrahydrofuran

No. 351863 or dioxane; Esters, such as ethyl acetate; aromatic hydrocarbons such as benzene or toluene and halogenated hydrocarbons such as methylene chloride, carbon tetrachloride or chloroform.

The reaction temperatures can in carrying out the process variant a) in a larger

Range can be varied. In general, one works between 0 and 100 ° C, preferably between 20 and

85 ° C. In the presence of a solvent, it is expedient to work at the boiling point of the particular solvent.

When carrying out process variant a), preference is given to working in molar amounts. The compounds of the formula (I) are obtained in the form of their hydrohalides and can be isolated as such by precipitation by addition of an organic solvent, for example hexane, filtered off and optionally purified by recrystallization. The compounds of the formula (I) can also be isolated in the form of their free base by adding aqueous sodium bicarbonate solution to the reaction mixture and isolating the base by customary methods.

Suitable diluents for the reaction according to process variant b) are preferably all inert organic solvents. This preferably includes the solvents counted in the process variant a) auf15 and the acid anhydrides of the formula (IV) used in each case.

As catalysts, in process variant b), it is possible to use preferably all customary acidic and basic ones

Catalysts are used, such as sulfuric acid, hydrogen chloride, hydrogen bromide, boron trifluoride, zinc chloride, sodium acetate, sodium benzoate, sodium carbonate, calcium oxide, magnesium oxide.

The reaction temperatures can in carrying out the process variant b) in a larger

Range can be varied. In general, one works between 0 and 150 ° C, preferably between 80 and 120 ° C.

When carrying out process variant b), preference is given to working in molar amounts. For the sake of simplicity, the acid anhydride of the formula (IV) used can also be used as solvent, with which a corresponding excess is required. The isolation of the compounds of formula (I) is carried out in the usual manner.

Suitable diluents for the reaction according to process variant c) are preferably all inert organic solvents. This preferably includes the solvents listed in process variant a).

The reaction temperatures can be varied within a certain range when carrying out the process variant c). In general, one works between -10 and 70 ° C, preferably between 0 and

40 ° C.

Suitable diluents for the reaction according to process variant d) are preferably all inert organic solvents. This preferably includes the solvents listed in process variant a).

As catalysts, d) may preferably be used in the process: tertiary bases, such as triethylamine and pyridine or tin-organic compounds, such as dibutyltin dilaurate.

The reaction temperatures can be varied within a relatively wide range when carrying out process variant d). In general, one works between 0 and 100 ° C, preferably between 20 and 40 ° C.

When carrying out process variant d), preference is given to working in molar amounts. To isolate the compounds of the formula (I), the solvent is distilled off and the residue is worked up by customary methods.

The active compounds which can be used according to the invention have a potent fungitoxic and bacteriotoxic action. They do not damage crops in the concentrations necessary to combat fungi and bacteria. For these reasons, they are suitable as active ingredients in crop protection agents for controlling fungi and bacteria. Fungitoxic agents in crop protection are used to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,

Deuteromycetes.

The active compounds which can be used in the present invention have a broad spectrum of activity and can be used against parasitic fungi that infest above-ground parts of plants or attack plants from the ground, as well as against seed-borne pathogens.

As already mentioned in part, the active ingredients have a particularly good activity against parasitic fungi on above-ground parts of plants, such as Erysiphe species and Venturia species, also against Pyricularia and Pellicularia species. Good effects are achieved against the pathogen of the bean rust (Uromyces 55 phaseoli) and against those fungi that cause powdery mildew diseases, such as against the causative agent of cereal powdery mildew (Erysiphe graminis) and apple powdery mildew (Podosphaera leucotricha). Particularly noteworthy is that the active ingredients not only have a protective effect, but are also curatively effective, so when applied after infection. Furthermore, on the systemic effect of the substances

No.351863. So it is possible to protect plants against fungal attack, if one. delivers the active substance to the aerial parts of the plant via the soil and the root or via the seed.

As plant protection agents, the compositions according to the invention can be used for soil treatment, for seed treatment and for the treatment of above-ground parts of plants.

The compositions of the invention are well tolerated by plants. They have only a low toxicity to warm-blooded animals and are not unpleasant to the skin because of their low odor and their good compatibility.

According to the invention, the active compounds are converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are prepared in a known manner, eg

by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, as emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene,

Toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. B. Petroleum fractions, 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, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. B. Aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorhlonite, or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; as emulsifier: nonionic and anionic emulsifiers, such as Polyoxyäthy25 len fatty acid esters, polyoxyethylene fatty alcohol ether, eg Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates; as a dispersant: eg lignin, liquors and methylcellulose.

The compositions according to the invention may also contain other known active substances, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth substances, plant nutrients and soil conditioners.

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

The agents are used in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is done in übUcher way, z. By pouring, spraying, spraying, dusting, spreading, dry pickling, wet pickling, wet pickling, blushing or encrusting.

When used as foliar ficides, the drug levels in the formulations can be varied within a wide range. They are generally between 0.1 and 0.00001 wt .-%, preferably between 0.05 and 0.0001%.

In the case of seed treatment, the amount of active ingredient used must be from 0.001 to 50 g per kg of seed, preferably from 0.01 to 10 g.

For soil treatment, amounts of active ingredient, from 1 to 1000 g / m.3 soil, preferably from 10 to 200 g, required.

The versatility and good Pflanzverträgliehkeit the inventive compositions will be apparent from the following examples.

Example 1: Uromyces test (bean rust) / protective

Solvent: 4.7 parts by weight acetone

Emulsifier: 0, 3 parts by weight of alkyl aryl polyglycol ether

Water: 9 5 parts by weight

The amount of active substance required for the desired active substance concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount

Amount of water containing these additives.

, With the spray liquid splashed the young bean plants, which are in the 2-leaf stage, to dripping wet. The plants remain for drying 24 h to 20 to 22 ° C and a relative humidity of 70% in the greenhouse. They are then inoculated with an aqueous uredospore suspension of the bean rust pathogen (Uromyces phaseoli) and incubated for 24 hours in a dark moist chamber at 20 to 22 ° C and 100% relative humidity.

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The plants are then grown under intense light for 9 days at 20 to 22 ° C and a relative

Humidity of 70 to 80% placed in the greenhouse.

Days after inoculation, infestation of plants is determined. The obtained rating values are in percent. Infestation converted. 0% means no infestation, 100% means that the plants are completely infested.

Drugs, drug concentrations and results are shown in the table below:

Table I

Uromyces test / protective

<td>active substance</td><td>Infestation in% of the infestation of the untreated control at one Active substance concentration of 0.005%</td>

<td>Cl _ // \ _O-CH-CH-C (CH,), \ _ / | · 1 II (known) /1 OH</td><td>59</td>

<td>z J Cl_ /% _O-CH-CH-C (CH-), > = / 1 / N f \ N01 II (known) OH</td><td>59</td>

<td>ch3 O-CH-CH-C (CH3) 3-N11 1 N II (known)</td><td>54</td>

<td>Cl_fl \ -O-CH-CH-C (CH,), WH nHOh ll 5, (known)</td><td>50</td>

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Solvent: 4, 7 parts by weight of acetone

Emulsifier: 0, 3 parts by weight of alkyl aryl polyglycol ether

Water: 95 parts by weight

The amount of active ingredient required for the desired active substance concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

With the spray liquid splashed young apple seedlings, which are in the 4- to 6-leaf stage, 10 to the dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. They are then inoculated by dusting with conidia of the powdery mildew pathogen (Podosphaera leucotricha) and in a greenhouse with a temperature of 21 to 23 ° C and a relative

Humidity brought by about 70%.

Days after inoculation infestation of seedlings is determined. The rating values obtained are converted to the percentage of infestation. 0% means no infestation, 100% means that the plants are completely infested.

Drugs, drug concentrations and results are shown in the table below:

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Table II

Podosphaera test (apple) / Protective

<td>active substance</td><td>Infestation in% at an active substance concentration of 0, 00031%</td>

<td>OH (CH3)3C-Z-O-CH-CH-C (CH3)3Lj (known) _z r Z Χ__Ο-ΟΗ-ΟΗ-Ο (ΟΗ,), \ = / | /n-n 1! II N_II (known)ZC1 O-CO-CH ( Cl is -O-CH-CH-C (CH3)3IUI O-CO-CH - 1 Cl__O-CH-CH-C (CH3)3"Α * ul Cl O-CO-NH Z _C1_ / | V / C1_Z_O-CH-CH-C (CH3)3n / '' N ul</td><td>94 95 44 36 27</td>

- 12 No.351863

Table II (continued)

<td>active substance</td><td>Infestation in% at an active substance concentration of 0.00031%</td>

<td>Cl_ /% _O-CH-CH-C (CH,), \ = / | \ i Λ II N_II (known) O-CO-CH</td><td>27</td>

Example 3: Sprout Treatment Test / Powdery Mildew / Protective (Foliar Mycosis)

To prepare a suitable preparation of active compound, 0.25 parts by weight of active compound are taken

Parts by weight of dimethylformamide and 0, 06 parts by weight of alkyl-aryl-polyglycol ether and are 975 parts by weight of 5 parts of water. The concentrate is diluted with water to the desired final concentration of

Spray mixture.

To test for protective efficacy, the single-leafed barley seedlings of the variety Amsel are sprayed with the active compound in a dewy manner. After drying, the barley plants are dusted with spores of Erysiphe graminis var. Hordei.

After 6 days residence time of the plants at a temperature of 21 to 22 ° C and a humidity of 80 to 90% is evaluated, the stocking of plants with mildew pustules. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infestation and 100% the same degree of infestation as in the untreated control. The lower the powdery mildew case, the more effective the active ingredient.

Active ingredients, drug concentrations in the spray mixture and infestation levels are shown in the table below.

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Table III

Shoot treatment test / powdery mildew / protective

<td colspan="2">drugs</td><td>Active substance concentration in the spray mixture in wt.%</td><td>Infestation% of untreated control</td>

<td>untreated</td><td>OH I</td><td>-</td><td>100.0</td>

<td colspan="2">(known)</td><td></td><td></td>

<td colspan="2">(known)</td><td></td><td></td>

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Example 4: Sprout Treatment Test / Cereal Mildew / Curative (Leaf Destroying Mycosis)

To prepare a suitable preparation of active compound, 0.25 part by weight of active compound is taken up in

Parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier alkyl arylpolyglykoläther and 5 975 parts by weight of water added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for curative efficacy, the procedure is reversed in the same way as for testing for protective efficacy. The treatment of the single-leaved barley seedlings with the preparation of the active ingredient takes place 48 hours after inoculation, when the infection is already manifest.

After 6 days residence time of the plants at a temperature of 21 to 22 ° C and a humidity of 80 to 90% is evaluated, the stocking of plants with mildew pustules. The degree of affection is expressed as a percentage of the infestation of the untreated control plants. 0% means no infestation and 100% the same degree of infestation as in the untreated control. The lower the powdery mildew case, the more effective the active ingredient.

Active ingredients, drug concentrations in the spray mixture and infestation levels are shown in the table below.

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Table IV

Sprout Treatment Test / Cereal Mildew / Curative

<td>drugs</td><td>Active substance concentration of the spray mixture in% by weight</td><td>Infestation in% of untreated control</td>

<td rowspan="2">untreated OH (CH3)3C - ^ O - CH - CH - C (CH3)3LJ (known) /C1 o-co-ch3</td><td></td><td>100.0</td>

Example 5: Barley powdery mildew test (Erysiphe graminis var.hordei) / systemiseh (fungal cereal disease)

The application of the active ingredients is carried out as a powdered seed treatment agent. They are prepared by stripping the respective active compound with a mixture of equal parts by weight of talc and diatomaceous earth to give a finely powdered mixture having the desired active ingredient concentration.

For seed treatment, barley seed is shaken with the stripped active ingredient in a sealed glass bottle. The seed is sown with 3 x 12 seeds in flower pots 2 cm deep in a mixture of one part by volume of Fruhstorfer unit earth and one vol. Part of quartz sand. Germination and casserole are carried out under favorable conditions in the greenhouse. 7 Days after sowing, when the barley plants have unfolded their first leaf, they are dusted with fresh spores of Erysiphe graminis var. Hordei and further cultivated at 21 to 22 ° C and 80 to 90% relative humidity and 16 hours exposure. Within 6 days the typical mildew pustules develop on the leaves.

The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. Thus, 0% indicates no infestation and 100% the same degree of infestation as with the untreated control. The active ingredient is the more effective the lower the mildew case is.

Active ingredients, active substance concentrations in the seed treatment agent as well as its application rate and the percentage of powdery mildew cases are shown in the following table.

No.351863 unpickled

Table V

Barley powdery mildew test (Erysiphe graminis var.hordei) / systemic

drugs

Active ingredient concentration in the mordant in% by weight

Quantity of application in g / kg of seed

Infestation in% of untreated

control

100.0

OH (CH,), C - / - - O - CH - CH \ = / I \

Jf C (CH3)a '' 'N (known) .Cl

OH

Cl / -O-CH-CH-C (CH3)3

0 /

N_ (known)

O-CO-CH

Cl_ / \ O-CH-CH-C (CH) "\ = / I KN

O-CO-CH

CL

F ~ \.

.O-CH-CH-C (CH3)3

JL

N

ΓΊ

O-CO-CH-O

100.0

66.3

0.0

CI_ /

--O-CH-CH-C (CH3)3

N2.5

33.8

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Table V (continued)

<td colspan="4">drugs</td><td>Actively in the mordant in% by weight -%</td><td>Pickling agent quantity in g / kg seed</td><td>Infestation in% of untreated control</td>

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T e e 11 e V (continued)

<td>drugs</td><td>Active ingredient concentration in the mordant in% by weight</td><td>Pickling agent quantity in g / kg seed</td><td>Infestation in% of untreated control</td>

Example 6: Sprout Treatment Test / Grain Freeze / Protective (Foliar Mycosis)

To prepare a suitable preparation of active compound, 0.25 parts by weight of active compound in 25 parts by weight of dimethylformamide and 0, 06 parts by weight of alkyl-aryl-polyglycol ether on and 975 wt. Added 5 parts of water. The concentrate is diluted with water to the desired final concentration of

Spray mixture.

In order to test for protective activity, one cultivars single-leaved wheat varieties of Michigan Amber with a Uredosporensuspension of Puceinia recondita in 0, l% water agar. After the spore suspension has dried on, the wheat plants are dewatered with the preparation of active compound and incubated for 24 h at about 20 ° C. and 100% humidity in a greenhouse.

After 10 days residence time of the plants at a temperature of 20 ° C and a humidity of 80 to 90% is evaluated, the stocking of plants with rust pustules. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infestation and 100% the same degree of infestation as in the untreated control. The less active the active substance is the more effective

Rust is.

Active ingredients, drug concentrations in the spray mixture and infestation levels are shown in the table below.

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Table VI

Shoot treatment test / cereal rust / protective

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Example 7: Driving Force Testing / Seed Treatment / Wheat

To prepare a two-stage dry mordant, the active ingredient is stretched in a mixture of equal parts by weight of talc and diatomaceous earth to give a fine powdery mixture having the desired active ingredient concentration.

For dressing, shake wheat seed with the mordant in a sealed glass bottle. The seeds are sown with 2 x 100 seeds in seed boxes on sterile quartz sand. The top layer used is 5 cm of sterile brick burr. The boxes are placed in the greenhouse at a temperature of + 15 ° C and kept normally moist.

The number of accumulated plants on the 21st day characterizes the motive power of the seed under the influence of the preparations. If this value is significantly lower than that of the untreated control boxes, there is an impairment of the driving force.

Table VII

Driving force test / seed treatment / Wheat

<td>active substance</td><td>Quantity of active ingredient in mg / kg of seed</td><td>Number of accumulated plants in% on the 21st day</td>

<td>unheated</td><td>-</td><td>83.0</td>

<td>(known)</td><td></td><td></td>

<td>(known)</td><td></td><td></td>

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Example 8: Phytotoxicity Test / Cucumbers

Solvent: 4, 7 parts by weight of acetone

Emulsifier: 0, 3 parts by weight of alkyl aryl polyglycol ether

Water: 95.0 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned. With the spray liquid splashed young cucumber plants to drip hazards. After drying, the plants are placed in the greenhouse at a temperature of + 20 ° C and about 70% relative humidity.

The plants are repeatedly evaluated for damage. The evaluation is carried out according to a Boniturschema 1 to 9. 1 means no damage, 9 means that the plant is totally damaged or dead. The observation period is usually 10 days.

Active ingredients, drug concentrations and results are shown in the table below.

Table VIII

Phytotoxicity Test

<td>active substance</td><td>Damage at drug concentration of 0, 2%</td>

<td>j Cl_ / -O-CH-CH-C (CH3)3IUI (known) / * r</td><td>5</td>

<td>Cl _ / \ _O-CH-CH-C (CH,)3(known) OH</td><td>5</td>

<td>J Br_ / -O-CH-CH-C (CH-) \ = / | xn^ n II II N_II (known) o-co-ch3</td><td>5</td>

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T of hurry VIII (continued)

<td>active substance</td><td>Damage at drug concentration of 0.2%</td>

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Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 part by weight of alkyl-arylpolyalkylolether

Water: 95 parts by weight

With the spray liquid young tomato plants are sprayed with 2 to 4 leaves to the dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. Subsequently, the tomato plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humidity chamber with 100% humidity and a temperature of 18 to 20 ° C.

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After 5 days, the infection of tomato plants is determined. The obtained rating values are on

Percent infestation converted. 0% means no infestation, 100% means that the plants are completely infested.

Active substance, active substance concentration and results are shown in the following table:

Table IX

Phytophthora test (tomato) / Protective

active substance

Infestation in% at an active substance concentration of 0.0025%

CH2--NCS

Zn ch2NH-cs

S (known)

O-CO-NH-CH / -O-CH-CH-C (CH3)3

JI

N ^

-N

OH o_o - O-CH-CH-C (CH3)3 .N

N_ (known)

..... O-CO- (CH2)2-CH3 // \ _ /% _O-CH-CH-C \ = r \ = /

-C (CH3)

100 • N

O-CO-C (CH3)3 oo _O-CH-CH-C (CH3)3

N /3^ x

-N

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Table IX (continued)

<td>active substance</td><td>Infestation in% at an active substance concentration of 0.0025%</td>

Example 10: Phytophthora test (tomatoes) / curative

Solvent: 4.7 parts by weight acetone

Dispersant: 0.3 parts by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

Young tomato plants with 2 to 4 leaves are inoculated with an aqueous spore suspension of 10 Phytophthora infestans. The plants remain for 7 h at 20 ° C and a relative humidity of

100% stand.

After a short drying time, the plants are sprayed with the spray liquid prepared in the manner described above, dripping wet and then placed in a humid chamber with 100% humidity and 18 to 20 ° C temperature.

After 5 days, the infection of tomato plants is determined. The obtained rating values are converted to percent infestation. 0% means no infestation, 100% means that the plants are completely infested.

Drugs, drug concentrations and results are shown in the following table:

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Table X

Phytophthora test (tomatoes) / curative

<td>active substance</td><td>Infestation in% at an active ingredient concentration of 0, 025%</td>

<td>S 1 CH-NH-CS.2 \ Zn CH.-NH-CS ^ II s (known) O-CO-NH-CH, - - 1 / \ _ / \ O-CH-CH-C (CH,), \ _ / \ _ / | II 111! N</td><td>70 17</td>

Example 11: Fusicladium test (Apfelsehorf) / Protective

Solvent: 4.7 parts by weight acetone

Emulsifier: 0.3 part by weight of albyl-aryl polyglycol ether

Water: 95 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

Young apple seedlings in the 4th to 6th leaf stage were sprayed with the spray until they were dripping wet. Subsequently, the seedlings were stored in a glasshouse for 24 hours at 20 ° C and a relative humidity of 70%. Then they were inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dentriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C and 100% relative humidity. The plants were then kept in a greenhouse again for 14 days.

15 Days after inoculation, the infestation of the seedlings was determined. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants, where 0% means no infestation and 100% the same infestation level as in the untreated control.

Active substance, active substance concentration and results are shown in Table XI below:

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Table XI

Fusicladium test (apple scab) / Protective

<td>active substance</td><td>Infestation in% at an active ingredient concentration of 0.0025%</td>

<td>F_ / -O-CH-CH-C (CH,), W | | x ^ NOH Ii II n-y (known) O / VO-0H-OC (CH,), \ _ / || H_! (known) F_ / X-O-CH-CH-C (CH,) " \s/ | l ι OC-CHj , r 1 · N '1 O / oco-nh-ch3/ \ _O-CH-CH-C (CH, k \ = / | .N Ν</td><td>54 56 9 37</td>

Instructions for the preparation of active substance compounds: Regulation 1:

O-CO-CH

Cl_ / O-CH-CH-C (CH3)3

A, y

N_II

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Production according to process variant a)

To 29.5 g (0.1 mol) of 1- (4-chlorophenoxy) -1- [l, 2,4-fcriazolyl (1)] - 3,3-dimethylbutan-2-ol in 100 ml of ethyl acetate 8.0 g (0.1 mol) of acetyl chloride are added at room temperature. Thereafter, it is heated under reflux for 4 h. It is allowed to cool and concentrated by distilling off the solvent in vacuo. The residue is taken up in benzene, washed with aqueous sodium bicarbonate solution and dried over sodium sulfate. The solvent is distilled off in a water-jet vacuum and the residue is recrystallized from n-hexane. This gives 15 g (44, 5% of theory) of 2-acetoxy-l- (4-chlorophenoxy) -l- [l, 2,4-triazolyl (l)] - 3,3-dimethyl-butane as a mixture of isomers of Melting point 86 to 93 ° C.

By recrystallization from ethyl acetate, a pure stereoisomer of melting point 153 to 10 154 ° C can be isolated.

Production according to process variant b)

591 g (2 mol) of 1- (4-chlorophenoxy) -l- [l, 2,4-triazolyl- (l)] - 3,3-dimethyl-butan-2-ol are dissolved in 1.2 l of acetic anhydride with 10 g Sodium acetate heated at 100 ° C for 16 h. Thereafter, the solution is cooled and stirred into 5 1 of ice water, the temperature is maintained at 20 to 25 ° C. It precipitates a greasy, crystalline mass, which is taken up in 2, 5 1 Methylenehlorid. It is washed with water and sodium bicarbonate solution, dried over sodium sulfate and concentrated in vacuo by distilling off the solvent. This gives 674 g (100% of theory) of 2-acetoxy-l- (4-chlorophenoxy) -l- [l, 2,4-triazolyl- (l)] - 3,3-dimethyl-butane as isomer engemisch of the melting point 88 to 95 ° C.

When recrystallized from 500 ml of ethyl acetate, a pure stereoisomer of melting point 149 to 153 ° C can be isolated.

Preparation of the starting product

OH

Cl_ / \ _O-CH-CH-C (CH) \ == / I

587 g (2 mol) of 1- (4-chlorophenoxy) -l- [l, 2,4-triazolyl- (l)] - 3,3-dimethyl-butan-2-one are dissolved in 3 l of methanol. For this purpose, 80 g of 25 (2 mol) of sodium borohydride are added at 0 to 10 ° C with stirring and ice cooling in portions of 5 g and stirred for 2 h at 5 to 10 ° C, then 12 h at room temperature. It is then cooled to 10 ° C and concentrated at 10 to 20 ° C 300 g (3 mol) of conc. aqueous hydrochloric acid was added. After stirring for 6 hours at room temperature, the suspension obtained is diluted with 3.8 l of water containing 400 g (4.8 mol) of sodium bicarbonate. The resulting precipitate is filtered off. This gives 502 g (85% of theory) of 1- (4-chlorophenoxy) -1- [2,4-triazolyl (1)] - 3,3-dimethylbutan-2-ol of

Melting point 112-117 ° C.

Regulation 2:

Cl /

-OO-CO-NH_

I

O-CH-CH-C (CH3)3

O-CI

Production according to process variant c)

To 6.6 g (0.02 mol) of 1- (2,4-dichlorophenoxy) -1- [1,2,4-triazolyl (1)] -3,3-dimethylbutan-2-ol in 30 ml

Ethyl acetate and 50 ml abs. Ether is added to a solution of 3.1 g (0.02 mol) of 4-chlorophenyl isocyanate in 50 ml

Ether and 3 drops of triethylamine. The mixture is allowed to stand at room temperature for 48 h, the solvents are distilled off in vacuo and the residue is recrystallized from petroleum ether / ether (1: 1). This gives 4.8 g (50% of

Theory) 2- (4-chlorophenylcarbamoyl) -1- (2,4-dichlorophenoxy) -1- [2,4-triazolyl (1)] - 3,3-dimethyl-butane

Isomer mixture of melting point 183 to 184 ° C.

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Regulation 3:

/ O-CO-CH,

O-CH-CH-C (CH3)3

SO.H

SO.H

salt formation

4.9 g (0.014 mol) of 1- (2-phenyl-phenoxy) -H, 2,4-triazolyl- (1)] - 3,3-dimefl-butan-2-ol are dissolved in 30 ml of acetic anhydride with 0.1 g Sodium acetate heated at 100 ° C for 15 h. Then allowed to cool, stirred in 300 ml of 5 water and shaken with 200 ml of chloroform. The chloroform solution is washed 4 times with 50 ml of water and Imal with 100 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and concentrated by distilling off the solvent in vacuo. The residue is treated with 50 ml of acetone in which 1.44 g of 1,5-naphthalenedisulfonic acid are dissolved, whereby the salt precipitates in crystalline form. This gives 3.1 g (42% of theory) of 2-acetoxy-1- (2-phenylphenoxy) -l- [l, 2,4-triazolyl- (l)] - 3,3-dimethyI-butane 10 -1.5 -naphthalenedisulfonate as a stereoisomer of melting point 213 ° C.

Regulation 4:

O-CO-CH

CI

x CuCl,

complexation

8.8 g (0.03 mol) of 1- (3-chlorophenoxy) -1- [l, 2,4-triazolyl (1)] - 3,3-dimethylbutan-2-ol are dissolved in 45 ml of 15 Acetic anhydride with 0.1 g sodium acetate stirred at 100 ° C for 15 h. The cooled solution in 450 ml of water, stirred for 15 h at room temperature and extracted with 3 times 100 ml of methylene chloride. The combined organic phases are washed with 100 ml of water and 100 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and concentrated by distilling off the solvent in vacuo. The residue is dissolved in 50 ml of ethanol. For this purpose, 2.4 g (0.014 mol) of copper dichloride in 7 ml of water. The mixture is concentrated in a water-jet vacuum, the residue is combined with 100 ml of ethyl acetate and the resulting crystalline precipitate is filtered off with suction. This gives 8.1 g (67% of theory) of bis [2-acetoxy-1- (3-chlorophenoxy) -1-] -1,2,4-triazolyl- (I)] - 3,3-dimethylbutane ] -Copper (I]) - chloride as a mixture of isomers of melting point 181 to 183 ° C.

Analogously to the above instructions, the following consecutively numbered compounds of the general formula are obtained

O-CO-R

X

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<td rowspan="2">connection No.</td><td rowspan="2">X n</td><td rowspan="2">R</td><td rowspan="2">Indication of whether 1,2,4-TriazolylResfc in (1) - or (4) -SteIlung is linked</td><td colspan="2">Melting point (° C)</td>