CS195322B2

Fungicide and method of preparing active substances therefor

Abstract

This record has no abstract on file.

CS195322B2, drawing sheet 1 — Sheet 1 of 153

Term

No projected expiry on record.

2 claims: 1 independent, 1 dependent

1
Fungicidní prostředek, vyznačující se tím, že jako účinnou látku obsahuje nejméně jeden acylovaný triazolyl-O,N-acetal obecného vzbrce I O-CO-R ve kterém R znamená alkylovou skupinu s 1 až 4 atomy uhlíku, popřípadě substituovanou chlorem nebo fenoxyskupinou, alkylamlnoskupinu s 1 až 4 atomy uhlíku v alkylové části nebo popřípadě chlorsubstituovanou fenylaminoskupinu, X představuje atom halogenu, nitroskuplnu, methylovou skupinu, trifluormethylovou skupinu, cyklohexylovou skupinu, fenylovou skupinu, chlorfenylovou skupinu nebo ' benzylovou skupinu, která může na methylenové části nést acetoxyskupinu, n je celé číslo o hodnotě 0 až 3 a Az představuje · 1,2,4-trlazol-l-ylový nebo l,2,4-triazol-4-ylový zbytek, nebo jeho . -fyziologicky snášitelnou sůl nebo kovový komplex.
2
'Způsob výroby účinných látek obecného vzorce I podle bodu 1, vyznačující se tím, že se triazolylderiváty obecného vzorce II OH . I ο-γι-снA? ve kterém X, Az a .n mají shora uvedený význam, nechají reagovat s halogenidy kyselin, obecného vzorce III Hal—CO—R (III), ve kterém R má shora uvedený význam a Hal znapená atom halogenu, zejména chloru nebo bromu, v přítomnosti rozpouštědla, při teplotě mezi 0 a 100 °C.

Independent claims2

647 paragraphs in 35 sections, as filed

The present invention relates to novel acylated triazolyl-O, N-acetals, their salts and metal complexes, to processes for their preparation and to their use as fungicides.

It is already known that trlazolyl-O, N-acetals, especially the phenyl substituted 1-phenoxy-1- (1,2,4-triazolyl) -3,3, dimethylbutan-2-oles, exhibit good fungicidal properties. properties (see DOS No. 2 324 010). However, the efficacy of these substances, in particular when applied in lower amounts and concentrations, is not always entirely satisfactory. Furthermore, these substances are not always tolerated satisfactorily by plants and seeds (when used as seed dressings).

It has now been found that the novel acylated triazolyl-δ, N-acetals of formula I

O <OR o-ch-ch-c (ch3)3 Az db

X represents a halogen atom, a nitro group, a methyl group, a trifluoromethyl group, a cyclohexyl group, a phenyl group, a chlorophenyl group or a benzyl group which can carry an acatoxy group on the methylene moiety, n is an integer of 0 to 3;

Az represents a 1,2,4-triazol-1-yl or a 1,2,4-triazol-4-yl moiety, and their physiologically tolerable salts as well as metal complexes exhibit potent fungicidal properties.

The compounds of formula I contain two asymmetric carbon atoms and can therefore exist in both erythro and threo forms. In both these cases they occur predominantly as racemates.

It has further been found that the acylated triazolyl-Ο, ΝΙ-acetals of the above general formula (I) are obtained by the formation of triazolylderivatives of the general formula (II) in which:

R is (C 1 -C 4) alkyl optionally substituted by chlorine or phenoxy, (C 1 -C 4) alkylamino, or optionally chloro-substituted phenylamino,

in which

X, Az and n are as defined above, and do not react with the acid halides of formula III

Hal — CO — R (III) wherein

R is as defined above and

Hal represents a halogen atom, especially chlorine or bromine, in the presence of a solvent.

Furthermore, the acylated triazolyl-O, N-acetals of the formula I obtained by the process according to the invention can be converted into the corresponding metal complexes by reaction with acids or with metal salts.

Surprisingly, the acylated triazolyl-O, N-acetals of the present invention exhibit significantly higher fungicidal activity, especially against various types of rust and powdery mildew than the prior art triazolyl-O, N-acetals, which are the closest related active ingredients. In addition, the compounds according to the invention are characterized by a better tolerance to plants. The active compounds according to the invention thus represent an enrichment of the prior art.

1- (4-Chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-ol and acetyl chloride are used as starting materials. by the following reaction scheme

The starting materials of the aforementioned general formula (II) are known (see DOS No. 2 324 010). The hitherto unknown starting materials of the formula (II) can be prepared as described above, for example by reducing the corresponding ketoderrates with aluminum isopropoxide or complex hydrides in the presence of a solvent. . ·,

Halides, acids. The compounds of formula III are known or can be prepared in a conventional manner, for example by reacting carboxylic acids or their salts with alkali metals with phosphorus halides or sulfur. This method is known from. all organic chemistry textbooks.

Suitable salts of the compounds of the formula I are salts with physiologically tolerated acids, which preferably include hydrohalic acids, for example hydrochloric and hydrobromic acids, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, monobasic and dibasic carboxylic acids, and the like. hydroxycarbolic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid and 1,5:naphthalenedisulfone.

Salts of the compounds of formula (I) may be prepared in a simple manner by conventional salt-preparation methods, for example by dissolving the base in an ether such as diethyl ether and adding an acid, for example nitric acid. The resulting salts can be isolated in a known manner, for example by filtration, and optionally purified.

Suitable complexes of the compounds of the formula I are metal salt complexes. In this context, metals II are preferred. to IV. main groups and I., II. and IV · to VIII. side groups of the Periodic Table of the Elements, in particular copper, zinc, manganese, magnesium, tin, iron and nickel. Suitable salts are those with physiologically compatible acids, which preferably include hydrohalic acids such as hydrochloric and hydrobromic acids, phosphoric acid, nitric acid and sulfuric acid.

The metal complexes of the compounds of formula I can be obtained in a simple manner using conventional methods, for example by dissolving the metal salt in an alcohol, for example ethanol, and adding the solution to the base. The resulting complex can be isolated in a known manner, for example by filtration, and optionally purified by recrystallization.

Suitable solvents for the reaction according to the invention are preferably all inert organic solvents, preferably ketones, such as diethyl ketone; and in particular acetone and methyl ethyl ketone, nitriles such as propionitrile and especially acetonitrile, ethers such as etherahydrofuran and dioxane, esters such as ethyl acetate, aromatic hydrocarbons, and the like.

such as benzene or toluene and halogenated hydrocarbons such as methylene chloride, carbon tetrachloride or chloroform; 1

The reaction temperatures of the process according to the invention can be varied within a wide range. In general, the reaction is carried out at a temperature between 0 to 100 ° C, preferably at a temperature between 20 and 85 ° C. If a solvent is used, the solvent is expediently boiled.

In the process according to the invention, the starting materials are preferably used in molar amounts. The compounds of formula I result in the form of their hydrohalides and as such can be isolated by precipitation by addition of an organic solvent, for example hexane, suctioned off and optionally purified by recrystallization. The compounds of formula (I) may also be isolated in the free form. Aqueous sodium bicarbonate solution is added to the reaction mixture and the base is isolated in a conventional manner.

Alternatively, the active compounds of the formula I can also be prepared by reacting the triazolylderivatives of the abovementioned general formula II with acid anhydrides of the formula IV

R-CO-O-CO-R (IV), wherein, R is as defined above, in the presence of a solvent and optionally in the presence of a catalyst, or with ketones of formula V

O = C = GH-R '(V) in which

R 'represents a hydrogen atom, an alkyl or halomethyl group, in the presence of a solvent and optionally in the presence of a catalyst or with isocyanates of the general formula VI

O = C = N-R '(VI), in which

R 1 represents an alkyl group or an optionally chloro-substituted phenyl group, in the presence of a solvent and optionally in the presence of a catalyst.

The acid anhydrides of the general formula (IV) are known or can be prepared in a known manner, for example by treating the alkali metal salts of the acid salts with acid chlorides. This method is generally known. The ketenes of the formula V are also known or can be prepared in a known manner, for example by thermal decomposition to tons or by dehydration of carboxylic acids (see Houben-Weyl, & quot; Methoden der órganischem Chemie & quot ;, Vol.

Suitable diluents for the reaction with anhydrides of the formula IV are preferably all inert organic solvents, preferably those mentioned in the description of the reaction with the halides of the formula III, as well as the anhydrides of the formula IV used.

The catalysts used in the reaction with anhydrides of the formula (IV) are preferably all customary acidic and basic catalysts, such as, for example, sulfuric acid, hydrogen chloride, hydrogen bromide, boron trifluoride. magnesium chloride, sodium acetate, sodium bezoate, sodium carbonate, calcium oxide and magnesium oxide.

The reaction temperatures for this reaction can be varied within a wide range. In general, the reaction is carried out at a temperature between 0 and 150 ° C, preferably at a temperature between 80 and 120 ° C.

r In the reaction with anhydrides of the formula IV, the starting materials are preferably used in molar amounts. For simplicity, the starting acid anhydride of formula IV may also serve as a solvent. In this case, of course, this anhydride is required in an appropriate excess. The isolation of the compounds of the formula I is carried out in the usual manner.

Suitable diluents for reaction with the ketenes of formula (V) are preferably all inert organic solvents, preferably the solvents mentioned above.

The reaction temperatures in this reaction may be within a certain range. In general, the reaction is carried out at a temperature between -10 and 70 ° C, preferably at 0 and 40 ° C.

Suitable diluents for the reaction with the isocyanates of the formula (VI) are preferably all inert organic solvents, preferably those mentioned above.

Tertiary bases such as triethylamine and pyridine or organic tin compounds such as dibutyltin dilaurate are preferably used as catalysts in this reaction.

The reaction temperatures for the reaction with the isocyanates of the formula VI can be varied within a wide range. In general, the reaction is carried out at a temperature between 0 ° C and 100 ° C, preferably at a temperature between 20 ° C and 40 ° C.

In this reaction, the starting materials are preferably used in molar amounts. To isolate the compounds of formula (I), the solvent is distilled off from the reaction mixture and the residue is worked up in a conventional manner.

The active compounds according to the invention show a strong fungitoxic and battery-toxic effect. The substances in concentrations necessary for combating fungi and bacteria do not damage crop plants. For these reasons, they are suitable for use as agents for protecting plants against fungi and bacteria. Fungitoxic agents are used to control organisms of the classes Plasmodiopiwromyeetee, Oomycetes, Chytridlomycetes, Zygemycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. .

The active compounds according to the invention have a broad spectrum of action and can be used against parasitic fungi attacking the aerial parts of the canopy or attacking plants from the soil, as well as agents of seed-borne fungal diseases. .

As already mentioned above, the active compounds according to the invention show particularly good activity against parasitic fungi on above-ground parts of plants, such as Erysjphe and Venturia, and also against Pyricnlaria and Pellicularia. Good effects are obtained against the agent of bean rust (Uromycetes phaseoli), as well as against fungi inducing true powdery mildew, such as the agent of powdery mildew (Erysiphe graminis) and powdery mildew (Podosphaera leucotricha). It is particularly advantageous that the active compounds according to the invention exhibit not only a protective effect, alo, but also a curative effect, i.e. they act only after the plants have been infected. Further, it is necessary to consider the systemic effect of the disclosed substances, which makes it possible to protect plants against fungal infections by supplying the active substance to the above-ground parts of the plants - through the soil and root system or through seeds.

As plant protection agents, the active compounds according to the invention can be used for the treatment of soil, for the treatment of seeds and for the treatment of aerial parts of plants.

The plants of the present invention are well tolerated. Said compounds have little toxicity to warm-blooded animals and, due to their low odor and good compatibility to human skin, there are no difficulties in handling them.

The active compounds according to the invention can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with surfactants, emulsifiers and / or dispersants and / or In the case of using water as a filler, organic solvents can also be used as auxiliary solvents. Essentially, liquid solvents include: aromatics such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, as well as water. By liquefied gaseous fillers or carriers is meant those liquids which are at ambient temperature and gaseous at normal pressure, for example aerosol propellants, for example dichlorodifluoromethane or trichlorofluoromethane. Suitable solid carriers are: natural stone meal, such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable emulsifiers are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, for example, alkyl aryl polyglycol ether, alkylsulfonates, alkylsulfates and arylsulfonates, and dispersants, for example, lignin, sulfite waste liquors and methylcellulose.

The active compounds according to the invention may be present in the formulations in admixture with other active substances, such as fungicides, insecticides, acaricides, nematicides, herbicides, preservatives against birds, growth agents, nutrients. for plants and soil conditioners.

The concentrates according to the invention generally contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90% by weight.

The active compounds according to the invention can be applied as such, in the form of concentrates or further dilution forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is carried out in a conventional manner, for example by watering, spraying, dusting, tossing, dry, wet, pickled, wet or in suspension or incrustation.

When active compounds are used as foliar fungicides, their concentrations in the applied compositions can be varied within a wide range. These concentrations generally lie between 0.1 and 0.00001% by weight, preferably between 0.05 and 0.0001% by weight.

In the treatment of seed, it is generally necessary to use from 0.001 to 50 g, preferably 0.01 to 10 g, of active compound per kilogram of seed.

To treat the soil it is necessary to use on each m5 1 to 1000 g, preferably 10 to 20 g of active ingredient.

The versatility of the active compounds according to the invention and their good tolerance to plants can be seen from the following examples:

P-UcladA .:

Test for bean rust (Uromyces phaseoli) - protective effect,

Solvent:.

4.7 parts by weight of acetone

Emulsifier:

19S32.2

0.3 part by weight of alkylaryl polyglycol ether

Water:

parts by weight

The amount of active ingredient required to achieve the desired concentration of active ingredient in the liquid spray is mixed with the stated amount of solvent and the concentrate is diluted with the specified amount of water containing the above ingredients.

Young bean plants are sprayed in the two-leaf stage until liquid is sprayed. The treated plants are kept in a greenhouse at 20-22 ° C for 24 hours to dry

Table A and relative humidity of -7d%, then inoculated with an aqueous suspension of uredospore bean rust - (Uroniyces · phaseoli) - · and incubated for 24 hours - in a dark humid chamber at 20 ° to 22 ° C and · 100% - -relative humidity. .

The plants are then kept in a greenhouse under intensive illumination at 20-22 ° C, and 70-80% humidity for 9 days.

days after inoculation, the percentage of infestation of the plants was determined.

% represents no infestation, 100% means complete infestation of plants.

The active substances, active substance concentrations and results obtained are shown in the following table;

Test for bean rust (Uromyces phaseoli) - protective effect

Active - 'Infestation' in% '' attack of untreated control plants at a concentration of ·.-Ύδίη ^ ΙάΐΚγβ, Ο05%

(znama!

(xnai / riaí)

Active substance . Infestation in% attack of untreated control plants at active compound concentration of 0.005%

O-CO-CWj

19’5·3^2

Active substance

Attack in ° / o. infestation of untreated control plants at 0.005%

о-со- (сн2)2-сн3

Q- {yo-?-H «cV3

q-CO-NH-CH3 o-ch-lh-ci3)3

. 11

Example в

Protective test for apple powdery mildew (Podosphaera)

Solvent:

4.7 parts by weight of acetone

Emulsifier:

0.3 part by weight of alkyl polyglycol ether

Water:

95.0 parts by weight

The amount of active ingredient required to achieve the desired concentration of active ingredient in the spray is mixed with the indicated amount of solvent and the concentrate is diluted with the indicated amount.

Table В

Protective test for apple powdery mildew (Podosphaera) '

................... ............. 12.............. ...........

amount of water containing the above ingredients.

By spraying, young apple seedlings having 4-6 leaves are sprayed until wet. The plants are kept in a greenhouse at 20 ° C and 70% relative humidity for 24 hours, then inoculated by dusting with spores of Podosphaera leucotricha (apple mildew) and placed in a greenhouse at 21-23 ° C and a relative air humidity of about 70%.

days after the inoculation, the infected seedlings were infected.

% means that no infection occurred, 10Q% represents complete infestation of plants.

The active substances, the active substance concentrations and the results obtained are given in the following table:

Г—

Active substance

Infestation in% at active substance concentration 0.00031%

OH (сн3)3 c - ^^ o ~ ch-ch <(ch3)3 (znarraí)

O-CO-Cfy

0 <Н-СН3

3β

Active substance

Infestation in% at active substance concentration 0.00031%

(known from U.S. Patent No. 3,952,002)

Example Ci

Protective test (shoot treatment) for Erysiphe graminis var. hordei (leaf-destroying mycosis)

To prepare a suitable active ingredient, 0.25 part by weight of the active ingredient is mixed in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether as emulsifier, and 975 parts by weight of water are added. The concentrate obtained is then diluted with water to the desired final concentration.

To determine the protective effect, young barley plants (Amsel species) in the single leaf stage are sprayed to moisten with the active ingredient prepared and sprayed with spores of Erysiphe graminis var. hordei.

After six days of cultivation at 21-22 ° C and 80-90% air humidity, the extent of disease on the plants is evaluated. The degree of infestation is expressed as the percentage of infestation of untreated control plants, with 0% indicating no infestation and 100% the same infestation as untreated control plants. The lower the degree of attack, the more effective the test substance is.

The following table shows the active substances, the concentration of the active substances in the spray and the extent of the disease:

<td>Table Ci Thickness test</td><td>(treatment of shoots) on Erysiphe graminis var. hordei (mycosis</td>

<td>Active substance</td><td>Concentration Effective Infestation in% substances in the spray-attack of the untreated control (% by weight) of plants</td>

<td>untreated</td><td> — 100,0</td>

OH

0,001 - 60,0 (known)

<td>n <activity_of .... .</td><td> , ..... -------T.... Concentration effective</td><td>% Attack</td>

<td></td><td>substances in the spray</td><td>infestation</td>

<td></td><td>suspension</td><td>control</td>

<td></td><td>(% by weight)</td><td>plant</td>

0.001 82.5 (Known)

0 <0 <H3

O & lt; H-CH-C (CH3)3 o-what-ch3

O - CH - CH - C (CH3)3

O-CO-NH-CH 3

O & lt; H-CH-C (GH3)3 __ 0 <0-NH <H3

O & lt; 1 & gt;

С /

0,001 ..... . 0,0

0,001 3,8

0,001 . 50,0

0,001 50,0

0,001 41,3

0,001 25,0

J9S322

Active substance

Concentration of the active ingredient in the spray suspension (w / w). ° / o)

Infestation in% attack of untreated control plants

0,001

0,0

55,0

Си

O-CO 2 CH 2 CH3

O - CH - CH - C (CH3)3

0,001

11,3

0,001

11,3

frCO-CH3

O'CH ~ CH ~ C (CH3)3

0,001

0,0

33,8

0,0005

25,0

.......16.

<td>Active substance</td><td>Concentration effective</td><td>% Attack</td>

<td></td><td>substances in the spray</td><td>infestation</td>

<td></td><td>suspension</td><td>control</td>

<td></td><td>(% by weight)</td><td>plant</td>

<td>α-phyo-m H -thooj t 4 —il</td><td> 0,001</td><td> 6,3</td>

Example C2

Curative test (treatment of shoots) for Erysiphe graminis var. hordei (leaf-destroying mycosis)

The determination of the curative effect is as for the determination of the protective effect, but in the reverse order. In this case, young barley plants at single leaf stage are treated with the active agent 48 hours after inoculation, when the infection is already obvious.

The lower the degree of attack, the more effective the test substance is. '

The following table shows the active substances, the concentration of the active substances in the spray and the extent of the disease:

1959^2

<td>17 Table Cz ........ Curry..te.st- ,, (treatment of shoots.) On Eryšiphé graminis var. hordei (mycosis - destructive leaves) - ·· ... ... '.....:</td><td colspan="2"> 18</td>

<td>Active substance '··.·'·</td><td>Concentration</td><td>% Attack</td>

<td></td><td>active substance</td><td>nepadení neoset-</td>

<td> , ' ' ...... . , ... . · ........</td><td>. in spray</td><td>plant</td>

<td></td><td>suspension (w / w)</td><td></td>

<td>untreated</td><td> —</td><td> 100,0</td>

он о-сн <н ~ асн3>3

0.0025 25.0 (sign

0,0025 0,0

0,0025

0,0

Example 1 D *

Test for systemic action on powdery mildew (Erysiphe graminis var hordei) - fungal disease of shoots

The active ingredient is used in the form of powdered seed dressings. The mordant is prepared by mixing the respective active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to form a finely divided powder containing the active ingredient at the desired concentration. ·

Barley seed shall be treated by shaking with prepared mordant in a closed glass container. The seed is then sown (3X12 grains) 2 centimeters deep into pots containing a mixture of one part by volume of standard peat soil and one part by volume of quartz sand. Germination and - emergence of plants takes place under favorable conditions in the greenhouse. 7 days after sowing, when barley plants unfold their first leaf, they are dusted with fresh spores of Erysiphe graminis var. hordei and further cultured at 21-22 ° C and 80-90% relative humidity under 16 hour illumination per day. Typical powdery mildew spots are formed on the leaves of the plants within 6 days.

The degree of infestation is expressed as the percentage of infestation of the untreated control plants, with 0% indicating no infestation and 100% the same infestation as untreated control plants. The more active the active substance, the lower the extent of the disease.

Active substances, concentration of active substances in mordants, consumption of meals and percentage of disease content are given in the following table:

Table D

Systemic effect test on Erysiphe graminis var. hordei

<td>Active substance</td><td>Active substance concentration in mordant (w / w)</td><td>Mordant consumption in grams per kilogram of seed</td><td>Attack. -in,0infestation of untreated control plants</td>

<td>nemořeno ......</td><td> ....... —</td><td> —</td><td> 100,0 . .</td>

100,0

__ о-со-сн2с / а- ^ у-о-сн-сн-с (сн ^3

Účinná iátRa

Active substance concentration in the mordant f wt. %]

Mordant consumption in grams per kilogram of seed

Infestation in% attack of untreated control plants

2,5

0,0

2,5

25,0

0,0

0,0

2,5

0,0

2,5

0,0

0 <Н-С ^ С (СН ^

4 — n

0,0

Example Е

Rust test Puccmia recondita - (leaf-destroying mycosis) - treatment of plant shoots - (protective effect)

To prepare a suitable active ingredient, 0.25 part by weight of the active compound is stirred in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether as emulsifier and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final spray suspension concentration.

In order to determine protective activity, Michigan Amber wheat plants are inoculated in a single leaf stage with a suspension of uredospores of Puccinia recondita rust in 0.1% aqueous agar. After the spore suspension has dried, the plants are sprayed until moistened with the active preparation and placed in a greenhouse for 24 hours at a temperature of about 20 ° C and 100% relative humidity.

After 10 days of growing at 20 ° C and 80-90 percent relative humidity, rust control of the plants was evaluated. The degree of infestation is expressed as% infestation of untreated control plants. In this case, 0% means no infestation and 100% the same degree of infestation as in untreated control plants. The more active the active substance, the lower the rust attack.

The active substances, the concentration of the active substance in the spray suspension and the degree of attack are shown in the following table:

Table E ;

Protective test (treatment of shoots) for rust of Puccinia recondita

<td>Active substance</td><td>Concentration effective</td><td>Attack in% per-</td>

<td></td><td>substances in the spray</td><td>do not treat</td>

<td></td><td>[in mass % ·]</td><td>control</td>

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

untreated

100,0

OH (CH3)3 C ^ - ^ ^ 0-CH <H <(CH3)3

0,025 75,0

0,025 0,0

0,025 0,0

and

0,025 13,8

0,01 8,821

19-S-3.2 1

Р'г-Ϊ Klad F '

Germination test (seed treatment) - wheat

To prepare a suitable dry dressing, the active ingredient is admixed with a mixture of equal parts by weight of talc and diatomaceous earth to form a finely powdered mixture containing the active ingredient at the desired concentration. '

Wheat seed with the prepared dressing is soaked in a sealed glass container and the soaked seed is then distributed in seed boxes (twice 100 grains each) onto sterile quartz sand. A sterile brick pulp (5 cm) serves as a cover layer. The cabinets are transferred to a greenhouse where they are maintained at ψ-15 degrees Celsius and normal humidity.

Seed germination, possibly influenced by the action of the test preparation,. characterizes the number. of plants emerging until · · 21st day of experiment. If the number of emerged plants from the treated seeds is significantly lower than the number of plants from the untreated control seeds, the test preparation affects germination.

The active substances, consumption and results are shown in the following table:

Table

<td>Active substance</td><td>Active substance consumption in mg / kg of seed</td><td>Number of emerging plants in% 21</td>

<td>infested</td><td> —</td><td> 83,0</td>

OH '

500 32,5

(known)

500 60,0

500 82,0

500 72,0

Example G

Cucumber phytotoxicity test

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether Water: 95.0 parts by weight

The amount of active ingredient required to achieve the desired concentration of active ingredient in the spray liquid is mixed with the indicated amount of solvent and the concentrate is diluted with the specified amount of water containing said ingredients.

With the prepared spray, young cucumber plants are sprayed until dripping. when dried, the plants are kept 'in' greenhouses at a temperature of - (- 20¾ and about 70% relative humidity).

Treated plants are repeatedly assessed for degree of damage, the observation period usually being 10 days.

Evaluation is carried out using a scale of 1 to 9, where 1 means no damage and 9 represents total damage or destruction of the plants, respectively.

The active substances, the active compound concentration and the results obtained are given in the following table:

Table G

Cucumber phytotoxic test

Active substance

Degree of damage at active substance concentration of 0.2%

OH

Q 1 -CH 2 O-CH-cH-C (CH3)3 (known) Ij | l. N --- Cl

........ / ........... OH .....

& сн-ан-0щНз

Λν (known) ___ У

O-CO-CHy

O-CH-CH'C (Cty3

Cl '

ΓΛ

O 'CO CHg chicho O-CH-CH-CiChfy №

• O & lt; O- (H3-cch-ccch3)3 AN—— 02

S-5 3 2 2

Active substance

Degree of damage at 0.2% active substance concentration

Cl O-CO-Nhland а- /

AND

O-CO-NH-CH 2 O-cH-bi-diacetes

Example H

Test for potato late blight (Phytophthora) - protective effect

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether Water: 95 parts by weight

The amount of active ingredient required to achieve the desired concentration in the fluid is mixed with the indicated amount of solvent, and the concentrate is diluted with the specified amount of water containing said ingredients.

Young tomato plants in the 2 to 4 leaf stage are sprayed with the spray liquid until wet. The plants are left for 24 hours

185322

<td>at 20 ° C 'and 70 ° / o relative humidity - in the greenhouse. Then the tomato plants are inoculated with an - aqueous - suspension of spores of the late blight (Phytophthora infestans). The plants are transferred to a humid chamber where they are maintained at 100% relative humidity and 18-20 ° C. After 5 days, infestation of the tomato plants is detected.</td><td>chats and the results obtained are calculated - attack in%. ' 0% means no attack, 100% means complete attack. The active substances, active substance concentrations and results are given in the following table:</td>

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

<td>Active substance</td><td>Infestation in% at active substance concentration 0.0025 -%</td>

<td>fznama)</td><td></td>

<td>Active substance ·</td><td>Infestation in% at an active compound concentration of 0.005%</td>

100 ALIGN! (known from U.S. Pat. No. 3,952,002)

......39 .19 5 3 22

<td>Active substance</td><td>- .... - '·: λ' - </td><td>Infestation in% at active ingredient concentration 0.005%</td>

Example I

Test for potato late blight (Phytophthora) - curative effect (tomato)

Solvent: 4.7 parts by weight aceDisperser: ton

0.3 part by weight of alkyl water: aryl polyglycol ether of parts by weight

The amount of active ingredient required to achieve the desired concentration of active ingredient in the spray liquid is mixed with the indicated amount of solvent, and the concentrate is diluted with the specified amount of water containing the above ingredients.

Young tomato plants having 2-4 leaves are inoculated with an aqueous suspension of spores of Phytophthora infestans (potato late blight) and the plants are then left to rest at 20 ° C and 100% relative humidity for 7 hours.

After a brief drying time, the plants are sprayed with the spray liquid prepared as described above and transferred to a humid chamber containing 100% air humidity and a temperature of 18-20 ° C.

After 5 days, the infestation of tomato plants is determined and the infestation is calculated in%. 0% means no infestation, 100% means complete infestation of plants.

The active substances, the active substance concentrations and the results obtained are given in the following table:

Table I

Test for potato late blight (Phytophtora) - curative effect / tomato

Active substance Attack in% at active substance concentration 0,025% * Zn ch2-nh-enof with

(known)

19’532.2

Ex. 1. and d. J .....

Protective. test ·· apple scab (Fusicladium)

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl; arylpolyglycol ether

Water: 95 parts by weight

5 ^ - 'I'

By spraying, young apple seedlings in the 4-6 leaf stage are sprayed until dew. The plants are kept for 24 hours in a greenhouse at 20 ° C and relative. 70% air humidity, then · inoculated · with water-suspension · fungal spore · Fusicladium dendriticum (apple scab) · · and incubated for 18 hours in a humid chamber at 18 to 20 ° C and · 100% relative · Humidity. · Air.

The plants are then replanted for 14 days in a greenhouse. days after inoculation, infestation of treated seedlings, expressed as a percentage of infestations of untreated but equally inoculated control plants, is detected;

0% means no infestation, 100% means that infestation is as high as in control plants. .

The active substances, active substance concentrations and results obtained are given in Table J below:

'Table J Protective test for apple scab (Fusicladium)' ·

Active substance Infestation in% at active substance concentration 0,0025%

(known from U.S. Patent No. 3,952,002)

(known from U.S. Patent No. 3,952,002)

The preparation of the active compounds according to the invention, however, is not limited to the following examples.

19532 2

Í33 34

Example 1

а) 29.5 g (0.1 mpl) of 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutane-2-

In ethyl acetate (100 ml), acetyl chloride (8.0 g, 0.1 mol) was added at room temperature. The residue was taken up in benzene, the solution was washed with aqueous sodium bicarbonate solution and dried over sodium sulfate. The solvent was distilled off under water pump vacuum and the residue was recrystallized from n-hexane. 15 g (44.5% of theory) of 2-acetoxy-1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutane are obtained in the form of a mixture. 86-193 ° C.

The pure stereoisomer of m.p. 153-154 ° C can be isolated by recrystallization from ethyl acetate.

b) 591 g (2 mol) of 1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-ol was added in

1.2 liters of acetic anhydride were heated to 100 ° C with 10 g of sodium acetate for 16 hours. The resulting solution was cooled and added with stirring to 5 liters of ice water while maintaining the temperature at 20-25 ° C. A viscous crystalline mass precipitates, which is taken up in 2.5 liters of methylene chloride, washed with water and aqueous sodium bicarbonate solution, dried over sodium sulfate and the solvent is distilled off in vacuo. 674 g (100% of theory) of 2-acetoxy-1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutane are obtained in the form of a mixture of isomers having a temperature of mp 88-95 ° C.

Recrystallization from 500 mL of ethyl acetate gave the pure stereoisomer, m.p. 149-153 ° C.

Preparation of starting material:

587 g (2 mol) of 1- (4-Clorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-one is dissolved in 3 liters of methanol to the solution at room temperature 0 to 10 ° C with a total of 80 g (2 moles) of sodium borohydride are added in 5 g portions with stirring and ice-cooling, the reaction mixture is first stirred for 2 hours at 5 to 10 ° C, then for 12 hours at room temperature. 300 g (3 mol) of concentrated aqueous hydrochloric acid are added thereto at a temperature of 10 to 20 ° C. After stirring at room temperature for 6 hours, the resulting suspension is diluted with 3 (8 liters of water containing 400 g (4.8 mol) of sodium bicarbonate). - (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-ol, m.p. 112-117 ° C.

Example 2

[Preparation according to variant c) of the process according to the invention]

К 6.6 g (0.02 mol) 1- (2?4-Dichlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-ol in 30 ml of ethyl acetate and 50 ml of absolute ether is added a solution of 3.1 g (0.02) mol) of 4-chlorophenylisocyanate in 50 ml of ether and 3 drops of triethylamine. The mixture is allowed to stand at room temperature for 48 hours, then the solvent is distilled off in vacuo and the residue is recrystallized from a mixture of equal parts of ether and petroleum ether. 4.8 g (50% of theory) of 2- (4-chlorophenylcarbamoyl) -1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3 were obtained. dimethylbutane as a mixture of isomers, m.p. 183-184 ° C.

(Salt preparation)

4.9 g (0.014 mol) of 1- (2-phenylphenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutan-2-ol in 30 ml of acetic anhydride together with 0, 1 g of sodium acetate is heated at 100 ° C for 15 hours, then the mixture is allowed to cool, stirred with 300 ml of water and the resulting mixture is shaken with 200 ml of chloroform. The chloroform solution is washed four times with 50 ml of water each time and once with 100 ml of saturated sodium bicarbonate solution, dried over sodium sulfate.

The solvent is distilled off under vacuum and 50 ml of acetone in which 1.44 g of 1,5-naltalenedisulphonic acid is dissolved are added to the residue. the desired salt precipitates in the crystalline llama.

3.1 g - (42% of theory) of 2-acetoxy-1- (2-enyl-enoxy) -1- (1,2,4-riazol-1-yl) -3,3- are obtained. Dimethylbutane-1,5-naltalenedisullonate in the lemma stereoisomer, m.p. 213 ° C.

(Preparation of complex)

8.8 g (0.03 mol) 1- (3-chloro-oxyoxy) -1- (1,2,

4-Triozo-1-yl) -3,3-dimethylbutan-2-ol, 45 ml of acetic anhydride together with 0.1 g of sodium acetate are stirred at 100 ° C for 15 hours. The resulting solution was cooled, added to 450 ml of water, stirred for 15 hours at room temperature, and then extracted three times with 100 ml of methylene chloride. The combined organic base is washed with 100 ml of water and 100 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and the solvent is distilled off in vacuo. The residue is dissolved in 50 ml of ethanol and added

2.4 g (0.014 mol) of copper chloride in 7 ml of water. The resulting mixture was evaporated in a water-jet vacuum, 100 ml of ethyl acetate were added to the residue and the precipitated crystalline precipitate was filtered off with suction. 8.1 g (67% of theory) of bis [2-acetoxy-1- (3-chloro-ethoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutane] copper (II) chloride are obtained in the lorum mixture. 181 DEG-183 DEG.

In analogy to the previous examples, the compounds of the following examples are summarized in the table below:

í о φ

Рн

(V) О ю.2 ой

со cd

Give it to me

LO

CO rd

1-C 4 H 9 (1),. 145

CM Ml Mi ss

H «.CU> q

CO ID Ьч 00

CD

O

·—<

\ ι — I t i CA 4Ό OX

P_ | > CJ- -

rH rH rH

P> И ю ki ю to

o ю sjf

CM *

CM

OQ τε — οετ (τ) T io-f о ~гйэ ~

Example? Xn R Position at which the melting point (C °) of the pure stereoisomer is bound by the 1,2,4-tri-isomer mixture of the isolyl isomer residue _________________________________________________________ - '____________________, _______________________________________ (1) or (.4) _________________ · ___________________'_______________'__________ 27 4-C1 C2H5 (1) 112-14 o

<td>lili 0 CM rH SK</td><td>1 oo</td><td>1 CD</td><td>1 oo</td><td>1 1 About CM</td><td></td><td>1II1 About 10 sC CD</td>

tH that's it

XX XX □ ω ω o to xo it

X it

X o

CT>

X ťj it U, .X + O it

X ω to to XXXX CJ.QO CJ 't

I sK

O) CM

ABOUT WHAT

I CM

ŠK

SK

OJ ω

** I CM + Π

ÍH PQ

SK ω

AND

CD 'Ф Рн

CM SK

PQ

AND

CO rH CO

CM CO

CO CQ

SK

Cď - s oo oo by n

CD - O rH CM Π sK Til sK

1^5322

Example Xn R Position at which the 1,2,4-tri-isomer mixture of the isomer of the azolyl isomer is attached to the melting point (C °) of the pure stereoisomer.

____________ ____________________________________________________ [1] or (.4) ________ ____________ what co • ts

CD

CD ОТ

CM

NH — C2H5 (1) 109–122 (Form A)

CM

o 4 cd cd o> ~ III

00 'Φ

CD i

CD

CD <

T 5P

OO 'T ^ UOCDt ^ opCDO-lCMOO ^ LiOCDO.COCDQ r4. 04 /

CD CO

CO CD

CD

Example Xn R Position which is the Melting Point of Net,:Stereo number bound 1,2,4-tri-isomer mixture isomers of azolyl residue _____________________________________________________________________________________ (1) or (4) __________________

<td>CO CM</td><td>About CM</td><td>Ф <m</td><td>Ю 4—4</td><td>CM CM</td>

'ф

CD

rH CM 00195322

Contents35

38 members in 29 offices

This recordMember, by publication datePriority claim19 more offices are in the list below

Priority claims4

Priority claims
Document	Office	Kind	Date
2600799	Germany	A	1976-01-10
2600799	Germany	A	1976-01-10
762600799	–	–	–
DE19762600799	–	–	–

Members38

Family members, oldest first
Document	Office	Kind
PT66046A	Portugal	A	1977-02-01
IL51230A0	Israel	A0	1977-03-31
BE850239A	Belgium	A	1977-07-11
DK5877A	Denmark	A	1977-07-11
FI770045A	Finland	A	1977-07-11
FI770045A7	Finland	A7	1977-07-11
SE7700065L	Sweden	L	1977-07-11
NL7700143A	Netherlands (Kingdom of the)	A	1977-07-12
DE2600799A1	Germany	A1	1977-07-14
JPS5287170A	Japan	A	1977-07-20
FR2337719A1	France	A1	1977-08-05
BR7700076A	Brazil	A	1977-09-06
ZA77101B	South Africa	B	1977-11-30
TR18945A	Türkiye	A	1977-12-20
DD129395A5	German Democratic Republic (until 1990)	A5	1978-01-18
GB1505241A	United Kingdom	A	1978-03-30
PT66046B	Portugal	B	1978-06-22
AU2109477A	Australia	A	1978-07-13
SU621302A3	Soviet Union (until 1991)	A3	1978-08-25
PL101196B1	Poland	B1	1978-12-30
ATA7877A	Austria	A	1979-01-15
GR62062B	Greece	B	1979-02-19
NZ183028A	New Zealand	A	1979-03-16
US4145428A	United States of America	A	1979-03-20
EG12330A	Egypt	A	1979-03-31
AU502450B2	Australia	B2	1979-07-26
AT351863B	Austria	B	1979-08-27
CS195322B2This record	Czechoslovakia (until 1993)	B2	1980-01-31
IL51230A	Israel	A	1980-02-29
CA1077943A	Canada	A	1980-05-20
PH14133A	Philippines	A	1981-03-03
HU176915B	Hungary	B	1981-06-28
CH629078A5	Switzerland	A5	1982-04-15
FI61699B	Finland	B	1982-05-31
FR2337719B1	France	B1	1982-07-09
FI61699C	Finland	C	1982-09-10
IT1077110B	Italy	B	1985-05-04
JPS6224425B2	Japan	B2	1987-05-28

Abstract

Term

19S32.2

OH

O-CO-NH-CH 3

J9S322

19-S-3.2 1

OH '

OH

S-5 3 2 2

AND

LO

1-C 4 H 9 (1),. 145

CD

CD

O

CM

O) CM

ABOUT WHAT

I CM

SK

AND

CM SK

PQ

AND

CM CO

CO CQ

SK

CD

CM

CM

CD

T 5P

CD CO

CO CD

CD

CD

Priority claims4

Members38

Numbers

Titles

Classification