Novel halogenated 1-azolyl-butane derivatives their preparation and their use as fungicides

Start of patent duration: 1980 01 15 Longest possible duration:

t Issued on: 1980 09 10

Inventor:

(60) Dependency: '(5fj) Publications considered to delineate the prior art:

- 2 No.358326

The invention relates to a fungicidal composition containing as active ingredient (s) new halogenated 1-azolyl-butane derivatives.

It has already been disclosed that 1,2,4-triazole derivatives, in particular in the phenyl moiety substituted 3,3-dimethyl-1-phenoxy-l- (l, 2,4-triazol-l-yl) -butan-2-ones and -ole, have good fungicidal properties (cf DE-OS 2201063 and 2324010). It has also become known that imidazole derivatives, in particular substituted in the phenyl moiety 3,3-dimethyl-l- (imidazol-l-yl) -l-phenoxy-butan-2-ones and -ole and in the phenoxy moiety substituted ω - (imidazole-l -yl) -o-phenoxyacetophenone, have good fungicidal properties (cf DE-OS 2325156 and 2333354). The effectiveness of the previously known compounds, however, is not always satisfactory, especially at low application rates and concentrations.

It has been found that the new halogenated 1-azolyl-butane derivatives of the general

formula

<img file="AT358326B_D0001.tif" />

(I) in which YZ n

A

B is halogen, is halogen, nitro, phenyl or halophenyl, is an integer from 0 to 3, and is a keto group or a CH (OH) grouping, and is a nitrogen atom or a CH group, and their physiologically acceptable salts have strong fungicidal properties.

Those compounds of formula (I) in which A is the CH (OH) group have two asymmetric carbon atoms; They can therefore be present in the two geometric isomers (erythro and threo form), which can be obtained in different proportions. In both cases they are present as optical isomers. All isomers are claimed according to the invention.

Furthermore, it has been found that the novel halogenated 1-azolyl-butane derivatives of the formula (I) is obtained when

a) Bromätherketone of the general formula

<img file="AT358326B_D0002.tif" />

CH₃

I

O-CH-CO-C-CH₂YII

Br CH 3 (II) in which

Y, Z and n have the abovementioned meaning, with an azole of the general formula (V)

- 3 Nr.358326 in which

B has the meaning given above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, and if appropriate still

b) reduces the keto derivatives obtained according to a).

Advantageous reaction methods are:

1. with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent, or

2. with aluminum isopropylate in the presence of a solvent, or

3. with complex hydrides optionally in the presence of a polar solvent, or

4. with formamidinesulfinic acid and alkali hydroxide, optionally in the presence of a polar solvent.

Furthermore, the halogenated 1-azolyl-butane derivatives obtainable in this way can be converted into the salts by reaction with acids.

Surprisingly, the new active compounds show a considerably higher fungicidal activity, in particular against rusty mildews and mildews, and against rice diseases, than the 3,3-dimethyl-1-phenoxy-1- (2,4,4-triazole) known from the prior art. l-yl) -butan-2-ones and ols and the corresponding imidazolyl derivatives, which are the closest active ingredients in the same direction of action. These agents thus represent an enrichment of the art.

Using 1-bromo-4-chloro-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one and 1,2,4-triazole

<td colspan="3">as starting materials, the reaction sequence can be by the following (process step a):</td><td>equation</td><td>reproduced</td>

<td></td><td>CHa |</td><td></td><td rowspan="2">base</td><td></td>

<td rowspan="2">^C1- ((</td><td rowspan="2">)) -O-CH-CO-C-CHjCl</td><td>II II</td><td>_</td>

<td>⁺</td><td></td><td></td>

<td>\:</td><td>^u / 1 1 Br CHa</td><td>O N</td><td>- HBr</td><td></td>

<td></td><td></td><td>H</td><td></td><td></td>

<td></td><td rowspan="2"></td><td>CHa</td><td></td><td></td>

<td></td><td>1 DO-C-chacl</td><td></td><td></td>

<td></td><td>N</td><td>CHa</td><td></td><td></td>

<td></td><td>-J</td><td>jj</td><td></td><td></td>

If, on the other hand, l-bromo-4-chloro-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one and imidazole are used as starting materials, the course of the reaction can be represented by the following formula scheme:

<img file="AT358326B_D0003.tif" />

base

->

- HBr

CH ₃

CI - O-CH-COjl-CHiCl CH ₃

<img file="AT358326B_D0004.tif" />

• N

- 4 No.358326

The reduction reactions according to process step b) are shown in the following examples: If 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (l, 2,4-triazol-1-yl) -butane is used. 2-on and

Sodium borohydride as starting materials, the reaction sequence can be represented by the following equation (method step b) / variant 3.):

ClCHa

I

O-CH-CO-C-chacl

II

CHa

NaBH, ->

CI

OH CH₃ - O-CH-CH-Cl

chacl ^XN

CHa

On the other hand, if 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (imidazol-1-yl) -butan-2-one and sodium borohydride are used as starting materials, the reaction sequence can be represented by the following equation become:

<img file="AT358326B_D0005.tif" />

N ·

OH CH_a

-O-CH-CH-C-chacl

I

CH₃

The reduction reactions according to process variant b) / l., B) / 2. and b) / 4. are similar in nature and can be formulated accordingly.

The bromoether ketones to be used as starting materials for process a) are generally defined by formula (II).

The bromo ether ketones of the formula (II) which can be used as starting materials are not yet known, but can be prepared by known processes by, for example, phenols of the general formula ## STR5 ## /

<img file="AT358326B_D0006.tif" />

OH (III)

- 5 Nr.358326 in which

Z and n have the abovementioned meaning, with a bromoketone of the general formula

CH₂X

I

Br-CH₂-CO-C-CH₂Y, (IV)

I

R in which

R, X and Y have the abovementioned meaning, reacted. The still remaining active hydrogen atom is then exchanged in the usual way for bromine (see also the preparation examples).

The phenols of formula (III) are well known compounds in organic chemistry.

The bromoketones of the formula (IV) are likewise generally known compounds of organic chemistry or can be prepared in a generally customary and known manner (cf also the preparation examples).

The azoles to be used as starting materials for process a) are defined by the formula (V). In this formula, B has the meaning given in the definition of the invention preferably. Thus, formula (V) is 1,2,4-triazole and imidazole.

Suitable salts for the compounds of the formula (I) are salts with physiologically tolerated acids. These preferably include the hydrohalic acids, such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, salicylic acid, citric acid, sorbic acid, lactic acid, 1,5-naphthalene-disulfonic acid.

Suitable diluents for the reaction according to process step a) are inert organic solvents. This includes preferably ketones, such as diethyl ketone and in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Alcohols, such as ethanol or iso-popanol; Ethers, such as tetrahydrofuran or dioxane; Benzene; Formamides, in particular dimethylformamide; and halogenated hydrocarbons.

The reaction according to process step a) is carried out in the presence of an acid binder. It is possible to add all customary inorganic or organic acid binders, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, Ν, Ν-dimethylcyclohexylamine, dicyclohexylmethylamine, Ν, Ν-dimethylbenzylamine, furthermore pyridine and diazabicyclooctane.

Preferably, an appropriate excess of triazole is used.

The reaction temperatures can be varied within a broad range in process a). In general, one works between about 20 to about 150 ° C, preferably at 60 to 120 ° C. In the presence of a solvent, it is expedient to work at the boiling point of the particular solvent.

When carrying out process step a), 2 mol of triazole and 1 to 2 mol of acid binder are preferably employed per mole of the compounds of the formula (II). To isolate the compounds of formula (I), the solvent is distilled off, the residue taken up with an organic solvent and washed with water. The organic phase is dried over sodium sulfate and freed from the solvent in vacuo. The residue is purified by distillation or recrystallization.

For the reaction according to process variant b) / l. suitable diluents are polar organic solvents. These include, preferably, alcohols, such as methanol and ethanol, and nitriles, such as acetonitrile. The reaction is carried out in the presence of a catalyst. Preference is given to noble metal, noble metal oxide (or noble metal hydroxide) catalysts or

No. 6,558,326 uses so-called "Raney catalysts", in particular platinum, platinum oxide and nickel. The reaction temperatures can be varied within a substantial range. In general, one works between 20 and 50 ° C, preferably at 20 to 40 ° C. The reaction can be carried out at normal pressure, but also at elevated pressure (eg 1 to 2 atm). In the reaction according to variant 1, 1 mol of the compound of the formula (II) is reacted with about 1 mol of hydrogen and 0.1 mol of catalyst; to isolate the compounds is filtered from the catalyst, freed from the solvent in vacuo and the resulting products of formula (I) are purified by distillation or recrystallization.

If one works according to variant b) / 2., Suitable diluents for the reaction are preferably alcohols, such as isopropanol, or inert hydrocarbons, such as benzene, in question. The reaction temperatures can be varied again within a relatively wide range; in general, one works between 20 and 120 ° C, preferably at 50 to 100 ° C. To carry out the reaction, about 1 to 2 mol of aluminum isopropylate are used per mole of the compound of the formula (II).

To isolate the compounds of the formula (I), the excess solvent is removed by distillation in vacuo and the resulting aluminum compound is decomposed with dilute sulfuric acid or sodium hydroxide solution. The further work-up is carried out in the usual way.

Working according to variant b) / 3., As diluents for the reaction polar organic solvents in question. These include, preferably, alcohols, such as methanol, ethanol, butanol, isopropanol, and ethers, such as diethyl ether or tetrahydrofuran. The reaction is generally carried out at 0 to 30 ° C, preferably at 0 to 20 ° C performed. For this purpose, is used for 1 mole of the compound of formula (II) about 1 mole of a complex hydride, such as sodium borohydride or lithium alanate, a. To isolate the compounds of the formula (I), the residue is taken up in dilute hydrochloric acid, then made alkaline and extracted with an organic solvent. The further work-up is carried out in the usual way.

Suitable diluents for the reaction according to variant b) / 4. polar organic solvents, preferably alcohols, such as methanol and ethanol, but also water, in question. The reaction temperatures can also be varied within a substantial range; one works at temperatures between 20 and 100 ° C, preferably at 50 to 100 ° C. For carrying out the reaction, about 1 to 3 mol of formamidine sulfinic acid and 2 to 3 mol of alkali hydroxide are used per mole of the compounds of the formula (II). To isolate the final products, the reaction mixture is freed from the solvent and the residue extracted with water and organic solvents, worked up in the usual manner and purified.

The compositions of the invention have a strong fungitoxic and a bacteriotoxic effect. They do not damage crops in concentrations necessary to combat fungi and bacteria. For these reasons, they are suitable for use as 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 compositions according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack aboveground plant parts or attack the plants from the ground, as well as against seed-transmissible pathogens.

They have a particularly good activity against parasitic fungi on aboveground plant parts, such as Erysiphe species, Podosphaera species and Venturia species, and against Piricularia and Pellicularia species. Good effects are achieved against the pathogen of apple downy mildew (Podosphaera leucotricha), apple scab (Fusicladium dendriticum), cucumber powdery mildew (Erysiphe cichoracearum) and bean rust (Uromyces phaseoli), as well as the fungi Piricularia oryzae and Pellicularia sasakii. They also show high activity against cereal diseases, such as against powdery mildew and grain rust. It should be emphasized that the active compounds according to the invention not only have a protective effect, but also have a curative effect, ie when applied after infection. Furthermore, the partial systemic effect of the substances should be pointed out. So it is possible to protect plants against fungal infestation, if the active ingredient on the soil and the root or on the seed feeds the aerial parts of the plant.

- 7 No.358326

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 good plant tolerated. They have only low toxicity to warm-blooded animals and, because of their low odor and their good compatibility with human skin, they are not unpleasant to handle.

The active compounds can be converted into the compositions in the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are prepared in a known manner, for example 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, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. 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 example 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; by liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; as emulsifier: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; as a dispersant: eg lignin, liquors and methylcellulose.

The active ingredients may be present in the formulations in admixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, 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% by weight.

The active compounds can be used as such, 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 a conventional manner, for example by pouring, spraying, spraying, dusting, spreading, dry pickling, wet pickling, Naßbeizen, Schlämmbeizen or encrusting.

When used as foliar fungicides, the drug concentrations in the formulations can be varied over a wider range. They are generally between 0.1 and 0.00001 wt .-%, preferably between 0.05 and 0.0001 wt .-%.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, needed.

For soil treatment are amounts of active ingredient of 1 to 1000 g per m³ Soil, preferably from 10 to 200 g, required.

At appropriate application rates, the new substances also show growth-regulating effectiveness.

The versatile uses are shown in the examples below.

Example 1:

Podosphaera test (apple) / Protective. Solvent: 4.7 parts by weight

Emulsifier: 0.3 parts by weight

Water: 95 parts by weight

acetone

Alkylaryl polyglycol ether

Mixing the necessary for the desired drug concentration in the spray liquid amount of active ingredient with the specified amount of the solvent and the concentrate is diluted with

Nr.358326

- 8 of the stated amount of water containing the additives mentioned.

With the spray liquid splashed young apple seedlings, which are in the 4- to 6-leaf stage, 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 apple mildew pathogen (Podosphaera leucotricha) and placed in a greenhouse with a temperature of 21 to 23 ° C and a relative humidity of about 70%.

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

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

Table 1

Podosphaera test (apple) / Protective

<img file="AT358326B_D0007.tif" />

- 9 No.358326

Table 1 (continued)

<td colspan="2" rowspan="2">active substance</td><td colspan="2">Infestation in% at one Active ingredient concentration of</td>

<td>0.01</td><td>0.0025</td>

<td>CI CH, Cl- \ O / -O-CH-CO-C-CHiCl X</td><td>SO, H 1 i «ϊοϊοΊ</td><td></td><td>2</td>

<td>I CH, u</td><td>1 SO, H</td><td></td><td></td>

<td>(18)</td><td></td><td></td><td></td>

Example 2:

Erysiphe test (cucumbers) / Protective.

Solvent:

emulsifier:

Water:

4.7

0.3

Parts by weight parts by weight parts by weight

acetone

Alkylaryl polyglycol ether

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.

The spray liquid sprays young cucumber plants with about three leaves to dripping wet. The cucumber plants remain for drying 24 h in the greenhouse. Then they are pollinated with conidia of the fungus Erysiphe cichoriacearum for inoculation. The plants are then placed at 23 to 24 ° C a relative humidity of about 75% in the greenhouse.

After 12 days, the infestation of cucumber plants is determined. The obtained rating values ​​are converted into% infestation. 0% means no infestation, 100% means that the plants are completely infested.

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

Table 2

Erysiphe test (cucumbers) / Protective

<td rowspan="2">active substance</td><td colspan="4">Infestation in% at one Drug concentration of</td>

<td>0.00062%</td><td>0.0005%</td><td>0.00031%</td><td>0.00025%</td>

<td>(CH,) iC- \ O / ~ ° -CH-CH-C (CH,), 1 0H II N (known)</td><td></td><td></td><td>66</td><td></td>

Nr.358326

Table 2 (continued)

<td colspan="4" rowspan="2">active substance</td><td colspan="4">Infestation in% at one Drug concentration of</td>

<td>0.00062%</td><td>0.0005%</td><td>0.00031%</td><td>0.00025%</td>

<td>CI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Cl- \ O / -O-CK-CH-C (CH,), 1 1 OH ci A «¹¹ 11 N ·</td><td></td><td></td><td></td><td></td><td></td><td>29</td><td></td>

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

<td>(CHj), c- / C) Yo-ch-ch-c (ch,), \ ±. / I 1</td><td></td><td></td><td></td><td>100</td><td>-</td><td>-</td><td>-</td>

<td>1 OH</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(known)</td><td>SO, H</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CH,</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CI \ O / ~0-CH-CO-C-CH, C1 X 1/2</td><td>; groj</td><td></td><td></td><td>-</td><td>-</td><td>-</td><td>10</td>

<td>| CHi</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>JL r [ N--</td><td>SO, H</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(1)</td><td></td><td></td><td>SO, H</td><td></td><td></td><td></td><td></td>

<td>CH,</td><td></td><td></td><td>|</td><td></td><td></td><td></td><td></td>

<td>ci \ o / - \ O /^- 0-CH-CO-C-CH, CI</td><td>x 1/2 |</td><td>Oil</td><td>θΊ</td><td>-</td><td>-</td><td>-</td><td>0</td>

<td>| CH,</td><td></td><td>1</td><td></td><td></td><td></td><td></td><td></td>

<td>/ ¼ ! -J</td><td></td><td>SO, H</td><td></td><td></td><td></td><td></td><td></td>

<td>(7)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CH,</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>¢ 0 / - \ Q / -O-CH-CO-C-CH, CI</td><td></td><td></td><td></td><td>-</td><td>-</td><td>-</td><td>22</td>

<td>I CH,</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>_r"-, Lj</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(8th)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

Nr.358326

<img file="AT358326B_D0008.tif" />

- 12 No.358326

Table 2 (continued)

<td colspan="3" rowspan="2">active substance</td><td colspan="4">Infestation in% at one Drug concentration of</td>

<td>0.00062%</td><td>0.0005%</td><td>0.00031%</td><td>0.00025%</td>

<td>"- &lt;o&gt; ·</td><td>CH, 1 -O-CH-CO-C-CH_tCI I |</td><td>SO, H 1 , «(O2o)</td><td></td><td>0</td><td></td><td></td>

<td>(18)</td><td>| CH, X L!</td><td>1 SO, H</td><td></td><td></td><td></td><td></td>

Example 3:

Erysiphe test (cucumbers) / Systemic.

Solvent:

emulsifier:

Water:

4.7

0.3

Parts by weight parts by weight parts by weight

acetone

Alkylaryl polyglycol ether

The amount of active ingredient required for the desired concentration of active substance in the casting 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.

Cucumber plants grown in unit soil are grown in a 1- to 2-leaf stage

Week three times with 100 cm³ Casting liquid in the stated active substance concentration, based on 100 cm³ Earth, poured.

The treated plants are inoculated after treatment with conidia of the fungus Erysiphe cichoracearum. The plants are then placed in the greenhouse at 23 to 24 ° C and a relative humidity of 70%. After 12 days, the infestation of cucumber plants is determined. The obtained rating values ​​are converted into% infestation. 0% means no

Infestation, 100% means that the plants are completely infested.

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

Table 3

Erysiphe Test / Systemic (cucumbers)

<td>active substance</td><td>Infestation in% of infestation of untreated control at a drug concentration of 1ppm</td>

<td>- \ O / - O-CH-CH-C (CH₃) 3 | OH / 'S LJ (known)</td><td>100</td>

- 13 No.358326

<img file="AT358326B_D0009.tif" />

acetone

Alkylaryl polyglycol ether

Example 4:

Fusicladium test (apple) / Protective.

Solvent: 4.7 parts by weight

Emulsifier: 0.3 parts by weight

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 the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

- 14 No.358326

With the spray liquid splashed young apple seedlings, they are in the 4- to 6-leaf stage, to dripping wet. The plants remain for 24 h at 20 ° C and a relative humidity of 70% in the greenhouse. Subsequently, they are inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 16 hours in a moist chamber at 18 to 20 ° C and 100% relative humidity.

The plants then come again for 14 days in the greenhouse.

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

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

Table 4

<img file="AT358326B_D0010.tif" />

Nr.358326

Table 4 (continued)

<td rowspan="2">active substance</td><td colspan="2">Infestation in% at one Drug concentration of</td>

<td>0,025</td><td>0.01</td>

<td>CH₃CI-Z-ZO Z-O-CH-CO-C-CH₂C1 \ O / \ O / I | 1 CH a</td><td>-</td><td>16</td>

<td>ä ii] ° -^H</td><td></td><td></td>

<td>^1.2 IOJ OJ</td><td></td><td></td>

<td>1 so₃H</td><td></td><td></td>

<td>(7)</td><td></td><td></td>

<td>_ _ .CH ₃Z Ο ZZ Ο ZO-CH-CO-l-CHjCl \ _ / \ ϊ ± / 1 1 1 ch₃</td><td>-</td><td>0</td>

<td>/ s II N-¹¹</td><td></td><td></td>

<td>(8th)</td><td></td><td></td>

Example 5:

Uromyces test (bean rust) / Protective.

<td>Solvent:</td><td></td><td>4.7</td><td>Parts by weight</td><td>acetone</td><td></td>

<td>emulsifier:</td><td></td><td>0.3</td><td>Parts by weight</td><td>Alkylaryl polyglycol ether</td><td></td>

<td>Water:</td><td></td><td>95</td><td>Parts by weight</td><td></td><td></td>

<td>You mix</td><td>the</td><td>For</td><td colspan="2">the desired drug concentration in</td><td>the</td>

<td>amount of drug</td><td>With</td><td>the</td><td>specified</td><td>Amount of solvent</td><td>and</td>

with the specified amount of water containing the additives mentioned.

With the spray liquid splashed young bean plants, which are in the 2-leaf stage, to dripping wet. The plants remain for drying 24 h at 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 atmospheric humidity.

The plants are then placed under intense light for 9 days at 20 to 22 ° C and a relative humidity of 70 to 80% in the greenhouse.

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

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

- 16 No.358326

Table 5

Uromyces test / Protective

<img file="AT358326B_D0011.tif" />

Example 6:

Sprout treatment test / Mildew / Protective.

(Leaf destroying mycosis) / Curative.

0.25 parts by weight of active compound in 25 parts by weight of dimethylformamide and 0.06 parts by weight of alkylaryl polyglycol ether are added to produce a suitable active ingredient preparation and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

- 17 No.358326

To test for protective activity, the single-leaf barley young plants of the variety Amsel are sprayed dewatered with the active ingredient preparation. After drying, the barley plants are dusted with spores of Erysiphe graminis var. Hordei.

To test for curative efficacy one proceeds in a similar manner, but in reverse order. The treatment of the one-leaved barley young plants with the active ingredient preparation takes place 48 h after inoculation, if 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% evaluates the stocking of plants with mildew pustules. The degree of infestation is expressed in% of the infestation of the untreated control plants. 10% means no infestation and 100% the same degree of infestation as with 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.

Table £

Sprout Treatment Test / Cereal Mildew / Protective / Curative

<td colspan="2" rowspan="2">drugs</td><td rowspan="2">drug concentration in the spray bottle in% by weight</td><td colspan="2">Infestation in% of untreated control</td>

<td>protective</td><td>curative</td>

<td>untreated</td><td>0H</td><td>-</td><td>100.0</td><td>100.0</td>

<td>&lt;Ö&gt; - ° -</td><td>1/77 \ Hc - &lt;^ 0 / ^x hci 1</td><td>0.01</td><td>66.3</td><td>-</td>

<td>\</td><td>0H</td><td></td><td></td><td></td>

<td>CI</td><td></td><td></td><td></td><td></td>

<td colspan="2">L_J</td><td></td><td></td><td></td>

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

<td>CI</td><td></td><td></td><td></td><td></td>

<td colspan="2">\ O / "C-CH-CO- * ^HC11</td><td>0.01</td><td>-</td><td>50.0</td>

<td colspan="2">u</td><td></td><td></td><td></td>

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

<td colspan="2">/_n\ \ 2 / _ / ^ O ^⁰-^CH-^CH-^C(^CM »</td><td>0.01</td><td></td><td>17.4</td>

<td></td><td>0H</td><td></td><td></td><td></td>

<td>IL</td><td>II -N</td><td></td><td></td><td></td>

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

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<img file="AT358326B_D0012.tif" />

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Table 6 (continued)

<td rowspan="2">drugs</td><td rowspan="2">drug concentration in the spray booth in weight</td><td colspan="2">Infestation in X the untreated control</td>

<td>protective</td><td>curative</td>

<td>ci I CH, 1 CI -O-CH-CO-C-CHi Cl _x 1/2 | 0 | 0 | | CH, 1 SOjH II II ¹¹-N (18) CH, Cl - / θ \ -O-CH-CH-C-CHjCl '-Z 1 | I I OH CH, / k u (6) CH, Cl- \ Ö / ^- O-CH-CO-C-CH, Cl | CH, Lj (2) CH, / ΟVO-CH-CH-C-CH, Cl^x-^z 1 1 1 I OH CH, ! -J (12) CH, Cl- / θ '/ - O-CH-CH-I-CH, Cl x HCl 1 1 1 1 OH CH, II ^NN-1 ' (3)</td><td>0.01 0.01 0.001 0.001 0.001</td><td>21.3 0.0 0.0 0.0 0.0</td><td>0.0</td>

- 20 No.358326

Table 6 (continued)

<td rowspan="2">drugs</td><td rowspan="2">Hirkstoffkonzentration in the spray booth in weight S</td><td colspan="2">Infestation in% of untreated control</td>

<td>protective</td><td>curative</td>

<td>S0, H CH, |^cl- \ Ö / - ^ Oy-O-CH-CO-C-CHiCl x 1/2 | 0 1 O | t^CH&gt; 1 ll ll N (7) CH, \O/^- O-CH-CO-C-CH, Cl (CH, for N! ' (8th) CH, l Cl - O-CH-CO-C-CH, Br _x HCl | CH, U (13) CH, Cl- \ O / - O-CH-CH-C-CHisulfo OH CH, / 'S ll N-¹(14)</td><td>0.001 0.001 0.00025 0.00025</td><td>0.0 0.0 21.3, 0.0</td><td>-</td>

Example 7:

Barley powdery mildew test (Erysiphe graminis var. Hordei) / Systemic (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 ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered mixture with 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 1 part by volume of Fruhstorfer unit earth and 1 part by volume of quartz sand. Germination and

No.358326 the casserole done under favorable conditions in the greenhouse. 7 days after sowing, when the barley plants have unfolded their first leaf, they are pollinated with fresh spores of Erysiphe graminis var. Hordei and at 21 to 22 ° C from 80 to 90% rel. Humidity and 16-hour exposure further cultivated. Within 6 days the leaves form the typical ones

Mildew pustules.

The degree of infestation is expressed in% of the infestation of the untreated control plants. Thus, 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, active substance concentrations in the seed treatment agent as well as its application rate 10 and the percentage of powdery mildew are shown in the table below.

Table 7

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

<td>drugs</td><td>drug concentration in the pickling agent in weight SS</td><td>Beizmittelaufwandmenge in g / kg of seed</td><td>Infestation in% of untreated control</td>

<td>unstained CI J 1^C1 II N " (known) (CH,), C - O / --O - CH - CH - C (CH,), J 0H A! -1 (known) ci _l \ O ^ -0-CH-C0-C (CH,), "I "-N (known) Cl- / θ '/ - O-CH-CH-C (CH,), - | i, f'i "--b (known)</td><td>10 25 25 25</td><td>2 10 10 10</td><td>100.0 100.0 100.0 100.0 48.8</td>

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Table 7 (continued)

<td colspan="2">drugs</td><td>Hirkstoffkonzentration in mordant in weight</td><td>Beizmittelaufwandmenge in g / kg of seed</td><td>Infestation in% of untreated control</td>

<td colspan="2"></td><td></td><td></td><td></td>

<td>CI</td><td>CH,</td><td></td><td></td><td></td>

<td colspan="2">CI - / (QO-CH-CO-C-CH, Cl</td><td>10</td><td>2</td><td>0.0</td>

<td rowspan="2">1 II N-</td><td>CH,</td><td></td><td></td><td></td>

<td>"B jl</td><td></td><td></td><td></td>

<td>'0)</td><td>CH,</td><td></td><td></td><td></td>

<td></td><td>1 1H-C0-C-CH, CI I</td><td>10</td><td>2</td><td>0.0</td>

<td></td><td>1 ch₃</td><td></td><td></td><td></td>

<td>II B-</td><td>J</td><td></td><td></td><td></td>

<td>(10)</td><td>CH,</td><td></td><td></td><td></td>

<td colspan="2">/ f) \ - O-CH-CO-C-CH, CI \ / I Ϊ</td><td>10</td><td>2</td><td>0.0</td>

<td></td><td>CH,</td><td></td><td></td><td></td>

<td>, &lt;η</td><td></td><td></td><td></td><td></td>

<td>N "</td><td>SO, H</td><td></td><td></td><td></td>

<td>x 1/2</td><td>ioYo) Ύ '' '</td><td></td><td></td><td></td>

<td></td><td>1 SO, Η</td><td></td><td></td><td></td>

<td>(11)</td><td>CH,</td><td></td><td></td><td></td>

<td colspan="2">CI - \ O / -O-CH-CO-C-CH; CI</td><td>25</td><td>10</td><td>0.0</td>

<td></td><td>CH,</td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td><td></td>

<td>ll_</td><td>II | ° '^H</td><td></td><td></td><td></td>

<td>x 1/2</td><td>ιοΊ'οΊ</td><td></td><td></td><td></td>

<td></td><td>SO, H</td><td></td><td></td><td></td>

<td>(15)</td><td></td><td></td><td></td><td></td>

- 23 Nr.358326

Table 7 (continued)

drugs

Active substance concentration in the mordant in wt. 8

Pickling agent quantity in g / kg seed

Affected in% of the untreated control

CH, «Ν-ζθ / - Ο '¹

CH-CO-C-CH, C1

CH,

S0, H

1/2 IOI o

SO, H

0.0 (17)

CH,

Cl- (Π> - O-CH-CH-C-CH.C1 \ id / I | |

OH CH,

0.0 (6)

Example 8:

Sprout Treatment Test / Grain Freeze / Protective (leaf destroying mycosis)

0.25 parts by weight of active compound in 25 parts by weight of dimethylformamide and 0.06 parts by weight of alkylaryl polyglycol ether are added to produce a suitable active ingredient preparation and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for protective activity inoculate einblättrige wheat young plants of the variety Michigan Amber with a Uredosporensuspension of Puccinia recondita in 0, l% water agar. After the spore suspension has dried on, the wheat plants are dewatered with the active compound preparation and placed in a greenhouse for incubation at about 20.degree. C. for 24 h at 100% atmospheric humidity.

After 10 days residence time of the plants at a temperature of 20 ° C and an air humidity of 80 to 90%, one evaluates 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 active ingredient is the more effective, the lower the rust attack.

Active ingredients, active substance concentrations in the spray mixture and degrees of infestation are shown in the following table.

- 24 Table 8

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<img file="AT358326B_D0013.tif" />

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Table 8 (continued)

drugs

Concentration of active substance in spray mixture in% by weight

Infestation in X of the untreated control

CI

CH,

O-CH-CO-C-CH, Cl

I CH,

0,025

33.8 (9)

ON - / 1 o> CH,

I

O-CH-CO-C-CH, Cl

II

CH,

N (10)

0,025

41.3

SO, H

CH, -O-CH-CO-C-CH, Cl x 1/2 j Ο | O | CH,

0,025

50.0

SO, H (11)

CH,

CI - (O - O - CH - CO - C - CH, CI II

CH,

0,025

0.0 (2)

CH, -O-CH-CH-C-CHiCl III

OH CH,

0,025

0.0 (12)

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<img file="AT358326B_D0014.tif" />

- 27 No.358326

Table 8 (continued)

<td>drugs</td><td>Hirkstoffkonzentration in the spray booth in weight-S!</td><td>Infestation in% of untreated control</td>

<td>CH, C1- / Q \ -O-CH-CO-C-CH, Cl | CH, ύ r^{x 1/2}SO, H (15) CH, CI - / Q - O-CH-CO-C-CH, CI 1 ! 1 CH, X II II SO.H - " X 1/2 foTo] 1 ' SO, H (18)</td><td>0,025 0,025</td><td>40.0 0.0</td>

Example 9:

Piricularia and Pellicularia test,

<td></td><td>Solvent:</td><td>11.75</td><td>Parts by weight</td><td>acetone</td>

<td>5</td><td>dispersants:</td><td>6.75</td><td>Parts by weight</td><td>Alkylaryl polyglycol ether</td>

<td></td><td>Water:</td><td>987.50</td><td>Parts by weight</td><td></td>

<td></td><td>other additives:</td><td>-</td><td></td><td></td>

The amount of active ingredient required for the desired active substance concentration in the spraying liquid is mixed with the specified amount of solvent and dispersing agent, and the concentrate is diluted with the specified amount of water.

The spray liquid is sprayed 2 x 30 about 2 to 4 weeks old rice plants to dripping wet. The plants remain until dry in a greenhouse at temperatures of 22 to 24 ° C and a relative humidity of about 70%. Thereafter, one part of the plants is inoculated with an aqueous suspension of 100,000 to 200,000 spores / ml of Piricularia ory15 zae and placed in a room at 24 to 26 ° C and 100% relative humidity. The other part of the plants is infected with a Malzagar grown culture of Pellicularia sasakii and placed at 28 to 30 ° C and 100% relative humidity.

until 8 days after inoculation, the infestation in all leaves existing at the time of inoculation with Piricularia oryzae is determined as a percentage of the untreated but also inoculated 20 control plants. In the case of plants infected with Pellicularia sasakii, the infestation after the same time on the leaf sheaths is also determined in relation to the untreated but infected control. The evaluation takes place in value numbers from 1 to 9. 1 means 100%

Effect, 3 = good effect, 5 = moderate effect and 9 = no effect.

- 28 No.358326

Table 9

Piricularia (a) and Pellicularia (b) test

<td rowspan="2">active substance</td><td colspan="2">Infestation in% of the infestation the untreated control at an active substance concentration (in%) of 0.025</td>

<td>a)</td><td>b)</td>

<td>CI- (OO-CH-CH-C (CH₃)₃\ ^ / 1 1</td><td>9</td><td>9</td>

<td>1 OH II Ϊ N-</td><td></td><td></td>

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

<td>ch₃CI- / () \ O-CH-CO-C-CHjCl \ / / 1 | ch₃N-II SO₃H</td><td>3</td><td></td>

<td>•^1.2 photo!</td><td></td><td></td>

<td>1 SO_aH</td><td></td><td></td>

<td>(1)</td><td></td><td></td>

<td>_ CH 3 -O-CH-CO-C-CHaCl | CH 3</td><td>3</td><td></td>

<td>!! i</td><td></td><td></td>

<td>(8th)</td><td></td><td></td>

<td>ch₃Cl-O-O-CH-CO-C-CHaCl</td><td>5</td><td>1</td>

<td>1 ch₃</td><td></td><td></td>

<td>N ) 1 N-¹¹</td><td></td><td></td>

<td>(2)</td><td></td><td></td>

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Example 10:

Mycelial growth test. Used culture medium:

<td></td><td>20</td><td>Parts by weight</td><td>Agar Agar</td>

<td>5</td><td>200</td><td>Parts by weight</td><td>Kartoffeldekokt</td>

<td></td><td>5</td><td>Parts by weight</td><td>malt</td>

<td></td><td>15</td><td>Parts by weight</td><td>dextrose</td>

<td></td><td>5</td><td>Parts by weight</td><td>peptone</td>

<td></td><td>2</td><td>Parts by weight</td><td>disodium</td>

<td>10</td><td>0.3</td><td>Parts by weight</td><td>calcium nitrate</td>

<td></td><td colspan="2">Ratio of solvent mixture to</td><td>Fertile soil:</td>

<td></td><td>2</td><td>Parts by weight</td><td>Solvent mixture</td>

<td></td><td>100</td><td>Parts by weight</td><td>agar medium</td>

Composition solvent mixture:

<td>15</td><td>0.19</td><td>Parts by weight</td><td>DMF or acetone</td>

<td></td><td>0.01</td><td>Parts by weight</td><td>Emulsifier alkylaryl polyglycol ether</td>

<td></td><td>1.80</td><td>Parts by weight</td><td>water</td>

<td></td><td>2</td><td>Parts by weight</td><td>Solvent mixture</td>

The amount of active ingredient required for the desired active ingredient concentration in the nutrient medium is mixed with the stated amount of the solvent mixture. The concentrate is thoroughly mixed with the liquid, cooled to 42 ° C culture medium in said ratio and poured into Petri dishes with a diameter of 9 cm. Furthermore, control plates are added without adding the preparation.

When the medium has cooled and solid, the plates are inoculated with the fungus species listed in the table and incubated at about 21 ° C.

The evaluation takes place according to the growth rate of the fungi after 4 to 10 days. In the evaluation, the radial mycelium growth on the treated nutrient media is compared with the growth on the control media. The assessment of fungal growth is done with the following key figures:

no fungal growth to 3 very strong inhibition of growth to 5 moderate inhibition of growth to 7 weak inhibition of growth

Growth equal to the untreated control

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

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Hyzelwachstums test

<img file="AT358326B_D0015.tif" />

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Table 10 (continued)

<td></td><td>xxjjbsbs exjBjnoxjPd</td><td></td><td colspan="4">CT 1</td>

<td></td><td>Ejooxsni »ejjajaeqdsooÄn</td><td></td><td>CT</td><td></td><td>t-1</td><td></td>

<td></td><td>uinouxuiejss uinxjodsoq4uxüi [8y</td><td></td><td>CT</td><td></td><td>tn</td><td></td>

<td></td><td>suaasajauxo EJoqdoqEiqd</td><td></td><td>in</td><td></td><td>tn</td><td></td>

<td></td><td>aezAjo exjEqnaxjxd</td><td></td><td colspan="4">CT 1</td>

<td></td><td>uinjqeoqje iDruj jxoxqjo / \</td><td></td><td>CT</td><td></td><td>in</td><td></td>

<td></td><td>eajauto sxqÄjqog</td><td></td><td>CT</td><td></td><td>in</td><td></td>

<td></td><td>snuEaqeÄxu snqoqoxqqaog</td><td></td><td colspan="4">CT 1</td>

<td>O</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>i-1 O_</td><td>wnuxqqn uinxqqXd</td><td></td><td>CT</td><td></td><td>CM</td><td></td>

<td></td><td>xubjos exuorpozxqy</td><td></td><td>CT</td><td></td><td>tn</td><td></td>

<td></td><td>uinuBojjoo iunq0TJ40Q9t {03</td><td></td><td colspan="4">CT 1</td>

<td></td><td>SJBAXU UiniJESnj</td><td></td><td colspan="4">CT 1</td>

<td></td><td>uinjox; ojeps exux ^ ojsps</td><td></td><td>CT</td><td></td><td>m</td><td></td>

<td></td><td>wnjouqno uinxaBsnj</td><td></td><td colspan="4">CT 1</td>

<td></td><td>"St.</td><td></td><td>O</td><td></td><td>O</td><td></td>

<td></td><td>uoxqBjquszuo&gt; jjjo; s&gt; | JX (i |</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td>= / - \</td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td>$ - (p)</td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td>CM</td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td>ΣΕ O</td><td></td><td>X</td><td></td>

<td colspan="2"></td><td></td><td>O 1</td><td></td><td>O</td><td></td>

<td colspan="2"></td><td></td><td>ΣΕ o</td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td>n: / J</td><td></td><td>o - O o</td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td>o _</td><td></td>

<td colspan="2"></td><td></td><td>T</td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td>z \</td><td></td><td rowspan="2">tu</td><td></td>

<td colspan="2"></td><td></td><td>101</td><td></td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td>z \</td><td></td>

<td colspan="2">44-</td><td></td><td>1</td><td>4J</td><td>101</td><td></td>

<td colspan="2">O rt tn</td><td></td><td></td><td>C c</td><td>\ z</td><td></td>

<td colspan="2">L ·</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">SB</td><td></td><td>O</td><td></td><td>O</td><td></td>

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Tabe ll 10 (continued)

<td rowspan="15">mushrooms</td><td>-Ilveses BtjejnoTjPd</td><td></td><td>in t</td>

<td>EjooTsniii ejpjseqdsooÄH</td><td></td><td>-</td>

<td>luneuxuiBjß unxJodsoqpxupH</td><td></td><td>σ&gt; »-d</td>

<td>suaasauauio EJoqdoqExqd</td><td></td><td>1 in</td>

<td>aezÄjo eiJEinoiJTd</td><td></td><td>1 t</td>

<td>lanjjeoqp unx "[jppj9 / \</td><td></td><td>1</td>

<td>eajaup sxqXjqog</td><td></td><td>1 in</td>

<td>snueaqelii »snjoqoxjqoog</td><td></td><td>in i</td>

<td>uinuxqqn «inxqqXg</td><td></td><td>in &lt;-i</td>

<td>xuejos exuo; oozxqy</td><td></td><td>in in</td>

<td>tunueajjoa anqoxj ^ o ^ ajpg</td><td></td><td>1 1</td>

<td>ajeAxu anxjesnj</td><td></td><td>1 1</td>

<td>tunjopojajos exupojaps</td><td></td><td>mm</td>

<td>uinjoupo tunxjBsnj</td><td></td><td>in i</td>

<td>H^dl uopejquazuoqjjopjjjxfl</td><td></td><td>o</td>

<td colspan="2">drugs</td><td></td><td>O «&gt; O« = ci □ = -i o - o - o o i «« © z O == i η O · « 1 / Ä 1 □ = = / 0 - 0 - · Ο O '- z 1 A \ 8 = - y, γ = _A Λ io, ' (° J, Y 'o -</td>

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Table 10 (continued)

<td rowspan="15">mushrooms</td><td>u&gt; Jeses</td><td>in -i</td>

<td>etooisnw ejjaj8BqdsooÄ (|</td><td>-</td>

<td>uinauTiije j6 wniJOdsoq utuipH</td><td>ΙΛ rt</td>

<td>suaosajsuxo ejoqdoyeTqj</td><td></td>

<td>aezÄJo exje ^ noxjTd</td><td>1 1</td>

<td>uinj ^ BoqjB unxjjTopjsA</td><td>rt rt</td>

<td>E8J9UiD sxqÄjqog</td><td>in rt</td>

<td>snueaqeAiii snjoqoiiqaog</td><td>in »ί</td>

<td>unnitqp lanxqqAj</td><td>CM ^ -1</td>

<td>xueps exuopozxqy</td><td>rt - «</td>

<td>uinueajjoo uinqoxj ^ oqaypQ</td><td>1 1</td>

<td>apAxu ujnxjesnj</td><td>1</td>

<td>uinjopojdfos exutqojeps</td><td>in rt</td>

<td>uinjouqno uiniJBsnj</td><td>l in</td>

<td>"dl UOpBJ ^ USZUO ^ J ^ O ^ S ^ JIH</td><td>oo</td>

<td colspan="2">drugs</td><td>O n: X "-H O s λ O « ι-t Ä | Ä oo ^ - o - o N { = C HZ ZC moo - o == sr. HZ 1 HZ 1 / O-O-O 3 = / 1 CJ - 3C 1 s_g ₌_ ä \ 1 i / I '= O¹ z 1 1 = \ _L z \ Λ "i ° i ιοι _π Υ \ / -1 f-4 rt -'Ο -</td>

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Table 10 (continued)

<td rowspan="15">mushrooms</td><td>xxjjbsbs epepoppd</td><td>CO i-1</td>

<td>ejooTsnia eqpjaEqdsooÄti</td><td>rH - (</td>

<td>uinauiuiBjß uinxjodsoqquxiupH</td><td>in -1</td>

<td>sueossjeuxo euoqdofexqd</td><td></td>

<td>sezÄJo exjefnojjid</td><td>CO -i</td>

<td>uinjqBoqp uirnnppjaA</td><td>mm</td>

<td>eejauxo sxqXjqog</td><td>CO it</td>

<td>snueaqeXia sntoqoijip &lt;&gt; 3</td><td>CM CO</td>

<td>uinuixqp unxqqÄy</td><td>CO -i</td>

<td>xueps exuoqoozxqy</td><td>·"· -1</td>

<td>jnuesjjoo uinqoxjqopjpg</td><td>in cm</td>

<td>sjbaxu uinxjesnj</td><td>co in</td>

<td>uinjopouaps etuxqojspg</td><td>CO,</td>

<td>uinuouipo uinpesnj</td><td>co co</td>

<td>H^di uopej; uazuo&gt; | jjo; s&gt;} JXH</td><td>© ©</td>

<td colspan="2">44O in c_ • ri 9</td><td>^s~ \ 2 / , d -^X- "" (Ο) s, == - (Ο) -^wi / I x "'-' © ........ ze I 1 n © « O \ 1 π: l zz cm I ⁵- © _-o-o Λ s: IOI i-J \ z ° \ = l zk Z \ IOI IOI \ z \ z 1 1 Ϊ7 r4 · -1 «-t «Sz O '</td>

Nr.358326

Table 10 (continued)

<td rowspan="15">mushrooms</td><td>ujfeses eTjejnonPd</td><td>-</td>

<td>Epapniu EjpjaEqdsoaXw</td><td>-</td>

<td>Nauruiejb unpodsoqquiupH</td><td>W CO</td>

<td>suaasajaup Ejoqdoppj</td><td>w in</td>

<td>sbzjojo epeynapTd</td><td>-</td>

<td>uinj ^ eoqie ιηΐμρμαδ ^</td><td>in co</td>

<td>Eajaup spXjgog</td><td>rH CM</td>

<td>snuEaqBÄiiu snpqopqaog</td><td>* -t I</td>

<td>βηωρχη luniqqXjj</td><td>-</td>

<td>lueps eiuo ^ ooziqy</td><td>F-. CO</td>

<td>uinuea ^ joo unqotJ ^ o ^ aipo</td><td>-</td>

<td>apAxu lunyjesnj</td><td>-</td>

<td>uinjopojdps exupojafos</td><td>r «CSJ</td>

<td>uinjotujno wnTjesnj</td><td>FH |</td>

<td>H ^ i uopejquazuo ^ joqsijjiM</td><td>© ©</td>

<td colspan="2">drugs</td><td>* '- ©,: · / a \ "P" X · - &lt;o) - ° =? Ϊ = S ü S&gt; -! O Cj&gt; o - _£Ο __ η «n CM 7 / -T x S_0-5 o se o j o l_,^{/ _}T " A = \ _J i. i \ A / \ 1 IO | 101 1 \ / - 3 3</td>

Nr.358326

Table 10 (continued)

<td></td><td>XXJjBSBS BXJBjnOXftSd</td><td></td><td>-</td>

<td></td><td>ejootsniu ejjajaeqdsoeXq</td><td></td><td></td>

<td></td><td>mnauTaej6 mxjodsoqquiwjaq</td><td></td><td>-</td>

<td></td><td>suaossjsuio ejoqdopiqd</td><td></td><td>CN</td>

<td></td><td>obzXjo eijeinoTJiti</td><td></td><td>-</td>

<td></td><td>ünj ^ eoqte ωηχ ^ χορυθή</td><td></td><td>-</td>

<td></td><td>esjaup spXjqog</td><td></td><td>-</td>

<td></td><td>snuBoqeÄiw snpqopqoog</td><td></td><td>-</td>

<td>ft)</td><td></td><td></td><td></td>

<td>N</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td>

<td>O.</td><td>Dinupp nniqqXg</td><td></td><td></td>

<td></td><td>xuejos exuoqooziqy</td><td></td><td>-</td>

<td></td><td>wnmjjoo uinipxjqoqsjfOQ</td><td></td><td>-</td>

<td></td><td>a ^ BAXu wnxjesnj</td><td></td><td>m</td>

<td></td><td>uinjopojeps exuxqojaps</td><td></td><td>-</td>

<td></td><td>uinjouijno uinxjBsnj</td><td></td><td>&lt;* 5</td>

<td></td><td>H^dl</td><td></td><td></td>

<td></td><td></td><td></td><td>O</td>

<td></td><td>uoxqejquszuo ^ ^ joqs jx ^</td><td></td><td></td>

<td colspan="2"></td><td></td><td></td>

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

<td colspan="2"></td><td></td><td>\ ° / -^Ä</td>

<td colspan="2"></td><td></td><td></td>

<td colspan="2"></td><td></td><td>X</td>

<td colspan="2"></td><td></td><td>η Ο n CN</td>

<td colspan="2"></td><td></td><td>□ = 1 = ---</td>

<td colspan="2"></td><td></td><td>O- C_5 ~ CJ r-1</td>

<td colspan="2"></td><td></td><td>O</td>

<td colspan="2"></td><td></td><td>«. = == X</td>

<td colspan="2"></td><td></td><td>A /</td>

<td colspan="2"></td><td></td><td>oz 1</td>

<td colspan="2"></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td>

<td colspan="2"></td><td></td><td>\ ä</td>

<td colspan="2">qq.</td><td></td><td>101</td>

<td colspan="2">*&gt; w</td><td></td><td></td>

<td colspan="2">.24</td><td></td><td>1 -'</td>

<td colspan="2"></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td>

<td colspan="2">ae</td><td></td><td>OK-*</td>

- 37 No.358326

Requirements for the production of the active substances:

SoAH

1.

<img file="AT358326B_D0016.tif" />

O-CH-CO-C-CHaCl x

CH a

CHa

<img file="AT358326B_D0017.tif" />

SoAH ^1.2 IO I o

N,

<img file="AT358326B_D0018.tif" />

N (process step a)

368.3 g (0.79 mol) of crude 1-bromo-4-chloro-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one are dissolved in 2 liters of absolute acetonitrile. To this is added 190 g (2.7 mol) of 1,2,4-triazole and heated for 20 h at reflux. It is then concentrated by distilling off the solvent in vacuo and the residue taken up in 1000 ml of methylene chloride. It is washed three times with 250 ml of water, dried over sodium sulfate and concentrated again in vacuo. The residual oil is dissolved in 1000 ml of acetone and treated with a solution of 140 g (0.48 mol) of naphthalene disulfonic acid in 500 ml of acetone. After 30 minutes, the resulting precipitate is filtered off with suction. This gives 285 g (76.6% of theory) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (1, 2,4-triazol-1-yl) -butan-2 on-naphthalenedisulfonat- (l, 5) of melting point 245 ° C (decomposition).

Production of the starting material.

<img file="AT358326B_D0019.tif" />

O-CH-CO-C-CHjCl

CH ₃

Br CH₃

213.5 g (1 mol) of 1-bromo-4-chloro-3,3-dimethyl-butan-2-one are added to a boiling suspension of 128.5 g (1 mol) of 4-chlorophenol and 140 g (1 mol ) Potassium carbonate is added dropwise in 1000 ml of absolute acetone. The mixture is stirred for 15 h under reflux, then allowed to cool, the inorganic residue is filtered off and washed with acetone. The filtrate is concentrated by distilling off the solvent in vacuo and the residue taken up in 1000 ml of methylene chloride, washed three times with 250 ml of water, dried over sodium sulfate and distilled. This gives 210 g (80.7% of theory) of 4-chloro-l- (4-chlorophenoxy) -3,3-dimethyl-butan-2-one of boiling point 125 to 127 ° C / 0.1 mm.

210 g (0.81 mol) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one are dissolved in 1000 ml of carbon tetrachloride. At room temperature, 41 ml (0.81 mol) of bromine are added dropwise so that steady consumption occurs. Then allowed to stir for 30 min at room temperature. After distilling off the solvent in vacuo, 268.3 g (98% of theory) of crude 1-bromo-4-chloro-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one, which is further reacted directly ,

Production of precursors.

CH₃

a)

BrCH₂-CO-C-CH₂Cl

CH_a

134.5 g (1 mol) of 1-chloro-2,2-dimethyl-butan-3-one are dissolved in 500 ml of ether. At room temperature, 51 ml (1 mol) of bromine are added dropwise with gentle cooling so that steady consumption occurs. Thereafter, the solution is stirred into 1000 ml of ice water, the organic phase separated, washed with 250 ml of water, dried over sodium sulfate and distilled. You get

- 38 Nr.358326

169 g (80% of theory) of 1-bromo-4-chloro-3,3-dimethyl-butan-2-one of melting point 95 to 106 ° C / 13 mm.

CH₃

I

CH₃-CO-C-CH₂C1

I ch₃

11.6 g (0.1 mol) of 2,2-dimethyl-1-hydroxy-butan-3-one are at 50 to 60 ° G (ice cooling) 5 to 20.5 g (0.1 mol) of N, N -Diethyl-l, 2,2-trichlorovinyl-amine dropped. After two hours of stirring at 60 ° C is distilled in a water jet vacuum. This gives 8.1 g (60% of theory) of 1-chloro-2,2-dimethyl-butan-3-one of melting point 60 to 62 ° C / 12 mm. (The l-chloro-2,2-dimethyl-butan-3-one is obtained in a yield of 90%, when equimolar amounts of 2,2-dimethyl-l-hydroxybutan-3-one and triphenylphosphine in ten times the amount of carbon tetrachloride Heated under reflux for 12 h, the

Distilled solvent, the residue taken up in ether, filtered and distilled.)

CH₃

I

CH₃-C0-C-CH₂0H

I ch₃

To 172 g (2 mol) of methyl isopropyl ketone in 1000 ml of methanol are added dropwise 66 g (2.2 mol) of paraformaldehyde and 1 g of potassium hydroxide in 10 ml of methanol. The mixture is heated under reflux for 15 h and then distilled off the methanol via a column at 82 ° C internal temperature. The residue is distilled in a water-jet vacuum. This gives 152.7 g (68% of theory) of 2,2-dimethyl-l-hydroxy-butan-3-one of boiling point 80 to 82 ° C / 12 mm.

Second

CI / n \.

\ w

CH_S • O-CH-CO-C-CH₂C1

CHs

285 g (0.6 mol) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (1, 2,4-triazol-1-yl) butan-2 obtained according to procedure 1 on-naphthalenedisulfonat- (l, 5) are neutralized with aqueous sodium hydroxide solution. This gives 221.7 g [67.5% of theory, based on 1-bromo-4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-butan-2-one] 4-chloro-1 used - (4-chlorophenoxy) -3,3-dimethyl-1- (l, 2,4-triazol-1-yl) -butan-2-one as a colorless oil of refractive index nff = 1.546.

OH GH ₃II

1-CH-C-CHaCl x HCl I

CH_a

Ο1-ζθ / - ΟΙ Process stage b)

96.5 g (0.244 mol) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (l, 2,4-triazol-1-yl) -butan-2-one 25 (Example 2) are dissolved in 300 ml of methanol. At 5 to 10 ° C, 12 g (0.3 mol) of sodium borohydride are added in portions. The mixture is stirred at room temperature for 15 h, 30 ml of concentrated hydrochloric acid are added and the mixture is stirred at room temperature for a further 15 h. Subsequently, the reaction mixture is stirred into 500 ml of saturated sodium bicarbonate solution, extracted three times with 150 ml of methylene chloride and the combined organic phases washed twice with 100 ml of water, dried over sodium sulfate and concentrated by distilling off the solvent in a water-jet vacuum. The residue is dissolved in acetone, mixed with 100 ml of ethereal hydrochloric acid and concentrated in a water-jet vacuum. The residue is taken up in 100 ml of ethyl acetate and allowed to crystallize out at 0 ° C. 41.4 g (38% of theory) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (1, 2,4-triazol-1-yl) -butan-2 are obtained. ol-hydrochloride (erythro and threo form) of melting point 157 ° C.

SO₃H

4th

⁰¹ - \ O / - \ O / -O-CHLJ ch₃ co-c-ch₃c i ch₃

1.2

OIO

SO_aH (process step a)

20.8 g (0.05 mol) of crude 1-bromo-4-chloro-1- [4- (4'-chlorophenyl) -phenoxy] -3,3-dimethyl-butan-2-one are dissolved in 120 ml of absolute Acetonitrile dissolved. To this is added 12 g (0.175 mol) of imidazole and heated for 40 h under reflux. It is then concentrated by distilling off the solvent in vacuo and the residue taken up in 300 ml of methylene chloride. It is washed three times with 100 ml of water, dried over sodium sulfate and concentrated again in vacuo. The residue is taken up in 100 ml of acetone and treated with a solution of 9 g (0.038 mol) of 1,5-naphthalenedisulfonic acid in 50 ml of acetone. After 2 h, the precipitate formed is filtered off with suction and dried. 19.6 g (72% of theory) of 4-chloro-1- [4- (4'-chlorophenyl) -phenoxy] -3,3-dimethyl-1- (imidazol-1-yl) -butane are obtained. 2-on-naphthalenedisulfonate (l, 5) of melting point 246 ° C.

Production of the intermediate.

CH

<img file="AT358326B_D0020.tif" />

Br CH ₃

42.7 g (0.2 mol) of 1-bromo-4-chloro-3,3-dimethyl-butan-2-one are added to a boiling suspension of 41 g (0.2 mol) of 4- (4'-chlorophenyl) - phenol and 28 g (0.2 mol) of potassium carbonate in 300 ml of absolute acetone. The mixture is stirred for 15 h under reflux, then allowed to cool, the inorganic residue is filtered off and washed with acetone. The filtrate is concentrated by distilling off the solvent in vacuo. The residue crystallizes after addition with 50 ml of diisopropyl ether. This gives 37.5 g (55% of theory) of 4-chloro-4- (4'-chlorophenyl) phenoxy-3,3-dimethyl-butan-2-one of melting point 67 to 68 ° C.

33.7 g (0.1 mol) of 4-chloro-1- [4- (4'-chlorophenyl) -phenoxy] -3,3-dimethyl-butan-2-one are dissolved in 250 ml of carbon tetrachloride. At room temperature, 5.1 ml (0.1 mol) of bromine are added dropwise so that steady consumption occurs. Then allowed to stir for 30 min at room temperature. After distilling off the solvent in vacuo, crude 1-bromo-4-chloro-l- [4- (4'-chlorophenyl) -phenoxy] -3,3-dimethyl-butan-2-one is obtained in quantitative yield, which continues directly is implemented.

- 40 No.358326

5th

_ / n \ \ S ± / ./n\_

CH 3 I

O-CH-CO-C-CHjCl II

I CH 3

The 4-chloro-l- [4- (4'-chlorophenyl) -phenoxy] -3,3-dimethyl-1- (imidazol-1-yl) -butan-2-one-naphthalene-disulfonate obtained according to Example 1 (l, 5) is neutralized with sodium bicarbonate solution. 4-Chloro-1- [4- (4'-chlorophenyl) -phenoxy] -3,3-dimethyl-1- (imidazol-1-yl) -butan-5-one of melting point 97.degree.-99.degree. C. is obtained quantitatively ,

CI./n \.

\ X /

OH CHA II

-O-CH-CH-C-CHaCl II | CHa

X '- N (process step b)

18.8 g (0.04 mol) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (imidazol-1-yl) -butan-2-one-naphthalenesulfonate (1: 5) (= Example 4, preparation according to Example 1 in 81% yield) are suspended in 100 ml of methylene chloride and treated with 100 ml of sodium bicarbonate solution. The¹⁰ organic phase is separated, dried over sodium sulfate and concentrated by distilling off the solvent in vacuo. The base thus obtained is taken up in 100 ml of isopropanol and at 5 to 10 ° C 2 g (0.05 mol) of sodium borohydride are added in portions. The mixture is stirred for 15 h at room temperature and then distilled off the isopropanol. The residue is taken up in 100 ml of methylene chloride and after addition of 100 ml of water for another 15 h at room¹⁵ temperature stirred. Subsequently, the organic phase is separated, washed twice with 50 ml of water, dried over sodium sulfate and concentrated. The remaining oil is boiled in 100 ml of petroleum ether, where it comes to crystallization. This gives 9.8 g (75% of theory) of 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (imidazol-1-yl) -butan-2-ol as mixture of isomers (erythrocyanide). and threo-form) of melting point 120 to 125 ° C.

²⁰ Analogously to the abovementioned examples, in each case starting from corresponding compounds (II) and (III), the following compounds of the general formula

chax

<img file="AT358326B_D0021.tif" />

receive:

Nr.358326

<img file="AT358326B_D0022.tif" />

Nr.358326

<img file="AT358326B_D0023.tif" />

- 43 Nr.358326

<td>example No.</td><td>z RI</td><td>A</td><td>X</td><td>Y</td><td>R</td><td>B</td><td>Melting point (° C)</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>30</td><td>2-Cl</td><td>CO</td><td>H</td><td>CI</td><td>CH,</td><td>N</td><td>210 (xl / 2 NDS) **</td>

<td>31</td><td>4-C1, 2-CH,</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>N</td><td>104 - 110</td>

<td>32</td><td>2,4-Cl</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>N</td><td>96 - 102</td>

<td>33</td><td>2-Cl</td><td>CH (OH)</td><td>H</td><td>br</td><td>CH,</td><td>N</td><td>132-140 (A-shape) ***</td>

<td>34</td><td>'- &lt;ö&gt;</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>N</td><td>115 - 120 (A-form) ***</td>

<td>35</td><td>'- &lt;ö&gt;</td><td>CH (OH)</td><td>H</td><td>8r</td><td>CH,</td><td>N</td><td>147 - 150</td>

<td>36</td><td>2-Cl</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>N</td><td>132 (A-shape) ***</td>

<td>37</td><td>4-C1, 2-CH,</td><td>CO</td><td>H</td><td>CI</td><td>CH,</td><td>CH</td><td>91</td>

<td>38</td><td>2,4-Cl</td><td>CO</td><td>H</td><td>CI</td><td>CH,</td><td>CH</td><td>165 - 168 (x HCl)</td>

<td>39</td><td>2-Cl</td><td>C0</td><td>H</td><td>br</td><td>CH,</td><td>CH</td><td>192 - 196 (x 1/2 NDS) **</td>

<td>40</td><td>2-Cl</td><td>C0</td><td>H</td><td>CI</td><td>CH,</td><td>CH</td><td>197 (x 1/2 NDS) **</td>

<td>41</td><td>2-Cl</td><td>CH (OH)</td><td>H</td><td>br</td><td>CH,</td><td>CH</td><td>119-124 (A-form) ***</td>

<td>42</td><td>4-CI, 2-CH,</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>CH</td><td>116 - 129</td>

<td>43</td><td>2,4-Cl</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>CH</td><td>92-95 (A-form) ***</td>

<td>44</td><td>2-Cl</td><td>CH (OH)</td><td>H</td><td>CI</td><td>CH,</td><td>CH</td><td>97 (A-form) ***</td>

** = NDS = 1,5-naphthalene-disulfonic acid *** = A-form = one of the two possible geometric isomers

Production of further precursors.

CH₃

I

ß) BrCH_a-CO-C-CH_abr

CH 3

To 47.6 g (0.25 mol) of p-toluenesulfonyl chloride in 100 ml of chloroform, 34.8 g (0.3 mol) of 5 2,2-dimethyl-l-hydroxy-butan-3-one and at 0 to 5 ° C 40 ml (0.5 mol) of pyridine added dropwise. The mixture is stirred at room temperature for 15 h and then added to 200 g of ice and 70 ml of concentrated hydrochloric acid. The organic phase is separated, washed with 100 ml of water three times, dried over sodium sulfate and concentrated by distilling off the solvent in a water-jet vacuum. The residue is treated with 200 ml of petroleum ether, with 48 g (71% of theory) of 2,2-dimethyl-3-keto-butoxy10-p-toluenesulfonic acid ester of melting point 49 to 52 ° C precipitate.

Dissolve 44.sup.38326 g (0.1 mol) of this p-toluenesulfonic acid ester in 100 ml of methyl ethyl ketone and reflux for 48 hours with 52 g (0.6 mol) of lithium bromide. It is suctioned off, the solvent is distilled off under atmospheric pressure, the residue is dissolved in methylene chloride and washed four times with 100 ml of water. The organic phase is dried over sodium sulfate and concentrated in a water jet 5 vacuum. This gives 15 g (84% of theory) of 1-bromo-2,2-dimethyl-butan-3-one which, corresponding to the 1-chloro-2,2-dimethyl-butan-3-one (cf., in Example 1 ) is reacted with bromine to 1,4-dibromo-3,3-dimethyl-butan-2-one.

CHsCl

I

γ) BrCH₂-CO-C-CH₂Cl

I ch₃

According to Example 1 α), the preparation of the 2,2-bis-hydroxymethyl-butane-310-one is first carried out by formylation of methyl ethyl ketone; Subsequently, the reaction of 2,2-bis-hydroxymethyl-butan-3-one with two equivalents of N, N-diethyl-l, 2,2-trichlorvinyl-amine to 2,2-bis-chloromethyl-butan-3-one performed.

Finally, then the reaction of the 2,2-bis-chloromethyl-butan-3-one with bromine to 1-bromo-3,3-bis-chloromethyl-butan-2-one.