Process for preparing triazolyl-o,n-acetals

Fungicide

The invention relates to a fungicide containing novel triazolyl-O, N-acetals as active ingredient.

It is known that trityimidazoles and trithi-1M-triazoles such as triphenylimidazole and triphenyl-1,2,4-tnazole have good fungicidal properties (compare U.S. Patent No. 3,321,366 and Belgian Patent No. 738). 095). However, their performance, especially when used in lower amounts and concentrations, is not always successful. In addition, it is known that zinc ethylene-1,2-bis (dithiocarbamate) has an effective fungicidal effect on carbonates (Phycomycetes), e.g. against Phytophtora infestans, which causes late blight and late blight on tomato fruit, as well as soil fungi, but not always satisfactory when used as a grain stain agent.

It has now been found that the triazolyl-O, N-acetals of the formula 11 wherein R¹ is an alkyl radical, al^kenoyl, iditic, cycloalkydic, or c^ya cloalkenyl, or an aryl or an aralkyl radical, the aryl radical may be substituted in the latter two cases. R², R³ and r⁴represent hydrogen atoms or have the meaning given above for Ri, but R3 and R4 cannot be hydrogen at the same time, and Az is a 1-4 triazohium-1 radical, 1,2,4-triazolyl-4 radical or the radicals they may be optionally substituted, and the salts of these compounds also have strong fungicidal properties.

The compounds of formula 1 have two asymmetric carbon atoms, so they can also exist in the form of erythro and in the form of threo, and in both cases they occur predominantly as racemates.

The novel compounds of formula I, which are the active ingredient of the agent according to the invention, are prepared by reducing the triazole derivatives of formula II, wherein R1, R2, R4 and Az are as defined above, are reduced (a) with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent, or (b) aluminum isopropoxide in the presence of a solvent, or (c) complex hydrides, optionally in the presence of a polar solvent, or (d) formamidine sulfinic acid and an alkali hydroxide optionally in the presence of a polar solvent, or (e) the triazole derivatives of formula 2 are reacted, in the presence of an inert solvent, with organometallic compounds of formula 3 wherein R3 is as defined above Me is an alkali metal or a group of the formula X — Mg— in which Y is chlorine, bromine or iodine.

The compounds of formula 1, which are the active ingredient of the composition according to the invention, have a fungicidal activity significantly greater than the known compounds such as triphenylinudazole, triphenyl-1,2,4-triazole and ethylene-1,2-bis (dithiocarbamate) zinc, so that the above mentioned use is . compounds as active ingredients

780

780 of a fungicide is an enrichment of the prior art.

If 1-femoxy-1- [1,2,4-triazolyl- (r)] - 3,3-dimethylbutanone-2 is used as the starting products, and the course of the reaction is shown in Scheme 1 (variant a).

If 1-phenoxy-1- [1,2,4-triazolylk-1 (Γ)] - 3,3-dimethylbutal non-2 and aluminum isopropoxide are used as starting products, the course of the reaction is shown in scheme 2 (variant b).

If 1-phenoxy-1- [1,2,4-triazolyl-1 (Γ)] 1 -3,3-dimethyl-2-butanone-2 and borosodium hydride are used as the starting products, the course of the reaction is shown in Scheme 3 (variant c).

the starting products are 1-fer | M5Li5ltJX1riazolyl- (r)] - 3,3-dimethylbutanone-2 and formamidine sulfinic acid, and the course of the reaction is shown in Scheme 4 (variant d).

If 1-phenoxy-1- [1,2,4-triazolyl- (r)] - 3,3-dimethylbutanone-2 and methylmagnesium iodide are used as the starting products, the course of the reaction is shown in scheme 5 (variant e).

In formula 2, R.¹ preferably a linear or branched alkyl radical with 1-8, especially 1-4 carbon atoms, a straight or branched alkenyl radical with 2 to 6, especially 3-6 carbon atoms, a straight or branched alkynyl radical with 2 to 6, especially 3 to 6 carbon atoms and also a cycloalkyl or cycloalkenyl radical having 5-7, especially 5-6 carbon atoms, as well as an optionally substituted aryl or aralkyl radical, a straight or branched alkenyl radical having 2 to 6, especially 3 to 6 carbon atoms , a straight or branched alkynyl radical having 2 to 6, especially 3 to 6, carbon atoms, and also a cycloalkyl radical having 5 to 7, especially 5 to 6, carbon atoms, and also optionally substituted aryl or aralkyl radicals having 6 to 10 carbon atoms in an aryl radical and having 1-2 carbon atoms in the alkyl radical. The substituents for the aryl radical are preferably halogens, especially fluorine, chlorine or bromine, straight or branched alkyl radicals with 1-6, especially 1-4 carbon atoms, alkoxy radicals with 1-4, especially 1-2 carbon atoms, haloalkyl radicals with 1-2 carbon atoms and 1-5 halogen atoms, especially fluorine and chlorine, halogenalkylthio radicals with 1-2 carbon atoms and 3-5 halogen atoms, especially fluorine and chlorine, e.g. dichloromethylthio radicals, carboalkoxy groups with 1-4 carbon atoms in the alkoxy radical, phenyl radicals in the ortho or para position and nitro groups.

Az preferably represents a group of formula 4, 5, 6, 7, 8, 9 and 10, where Hal in formulas 7, 8, 9 and 10 is halogen, especially chlorine or bromine, and Alkyl in formulas 8 and 9 is the radical methyl.

The starting compounds of formula II are:

[ω- (1,2,4-triazolllo-Γ)] - (kk-enoxy) -a_C.etkfenkn,

[ωkll, l, 4-triazollló-Γ)] - (ω-4'-chlorophenokyy) -acetophenone,

[ω- (1,2,4 - Γίϋζο1ί1ο-Γ)] - (ω-3'-chlorophenox) -acetophenone,> ·. 4

[ω-ll, 2,4-lriazolllo-l ')] - ω-2', 4'-dichlorophenokyy) -acetophenone,

[k- (1,2,4-triazolyl-Γ)] - (ω-2 ', 4'-dichlkrkfenkksy) l4l lchlkrkacetophenone,

[ω- (1,2,4-lriazo-yl-1 ')] - (ω-2', l6-dichlorophenxy) -acetophenone

[ω- (1,2,4-lriazolyl-Γ)] - (ω-4'-methoxyphenxy) -acetphenone, '

[ωo (l, 4₎4-triazckiio-Γ)] l (ω-l4mety-ofhenoxy) -acetkphenone, '

[ω-ll, 2,4-lΓiazo-iio-Γ)] l (ω-2'-methylkphenoxy) -acetkphelon, (ω-methyl) - [ω- (1,2,4-lriazolyl-l ') ] - (ω-4'-chlorophenoxy) -acetophenone,.

(ω-phenyl) - [ω - (-, 4,4-trIazo-iio-Γ)] - (ω-2 ', 4'-dichlorophenoxy) -acetphenone,' (ω-phenyl_ABOUT) - [ω-ll, 2,4-lriazolyl-Γ)] - (ω-2 ', 5'-diflkrOl \ phenoxy) -acetophenone, aldehyde [2- (l, 2,4-lriazolyl-Γ)] - [2- (2 ', 4'-dichlorophene)] - acetic,

[1- (1,2,4-triazolyl-r)] - [1- (2,4,4^,-dichlorophenoxy)] - pi ^ op ^ a ^ r ^^ n ^ - ^ 2,

[2- (1,2,4-triazolyl-Γ)] - (2-phenoxy) -butankn-3, [2- (1,2,4-lriazo-iio-Γ)] - [2- (4 ' -chlorophenoxy)] - 3-butanone,

[2- (1,2,4-triazolyl-1 ')] -. [2- (4'-fluorofenxy)] - butanone- ^ 3,

[2- (1,2,4-lriazolyl-l^,)] - [2 ', 4'-dichlorophenxy)] - 3-butanone,

[1- (1,2,4-triazolyl-1 ')] - [1- (2'4'-dichlorophenoxy)] - 3-methyl-2-butanone,

[2- (1,2,4-triazolyl-l^,)] - [2, (-'- chlorophenoxy)] -4-methylpentanone-3,

[2- (1,2,4-triazolyl-r)] - [2- (2 ', 4'-dichlorophenoxy)] - 4-methylpentanone-3,

[1- (1,2,4-triazolyl- 1 ')] - [1- (4 -' (chlorophenoxy)] - 3,3-dimethyl-2-butankn-2,

[1- (1,2,4-triazolyl-Γ)] - [1- (2 ', 4'-dichlorophenoxy)] - 3,3-dimethyl-2-butanone,

[1- (1,2,4-triazolyl-r)] - [1- (2 ', 5'-dichlorphenoxy)] - 3,

3-dimethylbutanone-2,

[l- (l, 2,4-triazolyl-T)] - [- (2 ', 6l-di-orophenoxy)] - 3,

3-dimethylbutanone-2,

[1- (1,2,4-triazkyl-Γ)] 1 [1- (2^/,-',6^/-trichlkrkfenkkyy)] - 3,3-dimethylbutanone-2,

[1- (1,2,4-triazolyl-1 ')] - [1- (2^/-ch-orophenoxy)] - 3,3-dimethylbutankn-2,

[1- (1,2,4-triazolyl-1 ')] - [1- (4'-bromophenoxy)] - 3,3-dimethyl-2-butanone,

[1-1,2,4-triazkyl-Γ)] - [1- (4'-fluophenoxy)] - 3,3-dimethylbutanone-2,

[l- (l, 2,4-triazolyl-Γ)] - [l- (4l-methyl-oxyphenoxy)] -3,3-dimethylbutanone-2,

[1- (- [1- (4'-methoxyphenofcsy)] - 3,3-dimethylbutanone-2, *,

[1- (1,2,4-triazkyl-l^/)] - [1- (4'-III-IZędbut; ylofenokyy)] - 3,3-dimethylbutanone-2,

[l- (l, 2,4-triazolyl-l ')] - [l- (4l-isopropylphenoxy)] -3,3-dimethylbutankn 2,

[1 - 1,2,4-triazolyl-Γ)] - [1 - (2'-methyl-4'-chlorophenoxy)] - 3,3-dimethylbutanone-2,

[1- (1,2,4-triazolylk-1 ')] - [1- (4''trifluoromethylphenoxy)] - 3,3-dimethylbutanone-2,

[l - l, 2,4-triazkyl-Γ)] - [l- (4'-nitrophenoxy)] - 3,3-dimethylbutanone-2,

780

[l- (l, 2,4-triazolyl-l ')] - [l- (2'-nitrophenoxy)] - 3,3-dimethylbutanone-2,

[1- (1,2,4-triazolyl-r] - [1- (4'-chloromethylmercaptophenoxy)] - 3,3-dimethylbutanone-2,

[1- (1,2,4-triazolyl-1 ')] - [1- (p-diphenoxy)] - 3,3-dimethylbutanone-2,

[1- (1,2,4-triazolyl-r)] - [1- (o-diphenoxy)] - 3,3-dimethylbutanone-2,

[2- (1,2,4-triazolyl-1 ')] - (2-phenoxy) - 4,4-dimethylpentanone-3,.

[2- (lL2L4-triazolyl-l ')] - [2- (4-fluorophenoxy)] - 4,4-dimethylpentanone-3,

[2- (1L2,4-triazolyl-1 ')] - [2- (2', 4'-dichlorophenoxy)] - 4L

4-dimethylpentanone-3,

[1-phenyl (-) 1- (1,2,4-triazolyl-1 ')] r (1-phenoxy) -3,3-dimethylbutanone-2,

[1-phenyl (-) 1- (1,2,4-triazolyl-1 ')] - [1- (4'-fluorophenoxy)] - 3,3-dimethylbutanone-2,

[1-phenyl (-) 1,2,4-triazolyl-1 ')] - [1- (2', 4'-dichlorophenoxy)] - 3,3-dimethylbutanone-2,

[2- (1,2,1 ^^ l ')] - [2- (2', 4 '- (^ 5 ^ i ^ c ^ l ^ llDi ^ (^ f ^ i ^ ol ^ ss ^)) - ^: i-cyclohexylacetate-1,

[2- (1,2,4-triazolyl-1 ')] - [2- (2', 4'-dichlorophenoxy)] -1-cyclopentylactanone-1,

[2- (1,2,4-triazolyl-1 ')] - [2- (2', 4'-dichlorophenoxy)] - 3-cyclohexylpropanone-3.

The triazole derivatives of the formula II used are not known compounds and are in part the subject of German patent application P 22 01 063.3 They are prepared, for example, by reacting a halogen ether ketone with 1,2,4-triazole, or the presence of a solvent or diluent and an acid-binding agent, preferably at a temperature of 80-120 ° C, using both reaction components in stoichiometric amounts. Another method of preparation consists in reacting the hydroxyether ketones with 1,2,4-triazoles in the presence of a water-extracting agent and optionally in the presence of a diluent, preferably at a temperature of 140 ° -200 ° C.

Depending on the method of preparation and processing, depending on the tautomeric nature of the 1,2,4-triazole, which is present as a compound of formula 11 or 12, the triazole derivatives of formula 2 are obtained as 4- (1,2,4-triazole) derivatives or 1- (1,2,

4-triazole). Often a mixture of both is obtained.

Salts of the compounds of formula I are those with physiologically acceptable acids. These preferably include hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, monobasic carboxylic acid and hydroxycarboxylic acid, e.g. cetric acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid and naphthalene disulfonic 1.5.

As diluents in the process according to process variant a), polar organic solvents, preferred alcohols, such as methanol or ethanol, or nitriles, e.g. acetonitrile, are used. The reaction is carried out in the presence of a catalyst, preferably a noble metal, a noble metal oxide or hydroxide, or a Raney catalyst, especially platinum, platinum oxide or nickel. The reaction temperature can vary widely, but a temperature is generally 20-50 ° C, preferably 20-40 ° C. The reaction can be carried out under normal or increased (1-2 atmospheres) pressure. When carrying out the process according to variant a), about 1 mole of hydrogen and 0.1 mole of catalyst are used per mole of the compound of formula II. The product was isolated by filtering the catalyst and evaporating the filtrate under reduced pressure. The obtained compound of formula I is purified by recrystallization. If necessary, the product is converted into a salt in a known manner.

If the process is carried out according to variant b), alcohols, e.g. isopropanol, or neutral hydrocarbons, e.g. benzene, are preferably used as solvents. The reaction temperature can be varied within a wide range, preferably from 20 to 120 ° C, preferably from 50 to 100 ° C. 1-2 moles of aluminum isopropoxide are used per mole of the compound of formula II. To isolate the compound of formula I, excess solvent is distilled off under reduced pressure, the aluminum compound obtained is decomposed with sulfuric acid or sodium hydroxide, and the product is isolated in the usual manner.

In carrying out the process according to variant c), polar organic solvents, preferably alcohols, e.g. methanol, ethanol, butanol, isopropanol, or ethers, e.g. diethyl ether or tetrahydrofuran, are used as diluents. The reaction temperature is preferably 0-30 ° C, preferably 0-20 ° C. For 1 mole of the compound of formula II, approximately 1 mole of a complex hydride, e.g. sodium hydride or lithium aluminum hydride, is used. To isolate the compound of formula I, the residue is dissolved in dilute hydrochloric acid, then made alkaline and extracted with an organic solvent, followed by further processing in the usual manner.

In the process according to variant d), polar organic solvents, preferably alcohols, e.g. methanol or ethanol, or also water are used as diluents. The temperature may vary widely, but is usually between 20 and 100 ° C, preferably 50-100 ° C. About 1 to 3 moles of formamidine sulfinic acid and 2 to 3 moles of alkaline hydroxide are used per mole of Formula II. Solvents are removed to isolate the final product, the residue is extracted with water and organic solvents, then worked up and purified by conventional methods. Optionally, the product is salified.

In the process according to variant e), the compounds of formula I are prepared in which R8 is not hydrogen. In contrast, reactions a) -d) are reduction reactions and · the products give compounds of formula I which are secondary alcohols, in which R8 always represents only a hydrogen atom.

Proceeding according to variant e), in addition to the starting products of the formula 2, organometallic compounds of the formula 3 are used. In this formula, R 8 preferably represents an alkyl, alkenyl or alkynyl radical having up to 8, in particular up to 4

780 carbon atoms, and preferably also a cycloalkyl radical with 5 to 6 carbon atoms, in particular a cyclhexyl radical, and preferably also an aryl or aralkyl radical with 6-10 carbon atoms, in the aryl radical with 1-2 atoms in the alkyl radical The aryl radical preferably contains the substituents such as fluorine, chlorine, an alkyl or alkoxy radical of 1-4 carbon atoms, Me in formula III is preferably lithium or sodium, or the so-called Grignard moiety of the formula Mg-X, where X is chlorine, bromine or iodine. The organometallic compounds of formula III are known compounds and a compilation and review of numerous publications on the subject can be found, for example, in the section GE Coates, Organo-Metalie Compounds, 2nd edition, Methuen. and Co. (1960).

. In the process according to variant e), anhydrous ethers are preferably used as diluents, for example diethyl ether or dibutyl ether. The reaction is carried out at a temperature of 0-80^aboutC preferably 30-60 ° C, using, per 1 mole of the compound of the formula II, about 1 mole of the organometallic compound of the formula 3. The resulting reaction mixture is processed by the usual methods.

The compositions according to the invention have strong fungicidal properties and, at the concentrations used to control the fungi, they do not harm crops, and are therefore suitable for use as a fungicide plant protection agent. Fungicides in plant protection are used to control primary fungi (Archimycetes), algae (Phycomycetes), saccharides (Ascomycetes), basidiomycetes (Rasidiomycetes) and imperfect fungi (Fungi 'imperfecti).

The agent according to the invention has a wide range of action and can be used against parasitic fungi which attack the aerial parts of plants or attack the plants from the soil, as well as against seed-borne pathogenic fungi. The compositions according to the invention are particularly effective against fungi which parasitize the above-ground parts of plants, such as those from the species Erysiphe, Podosphaera, Sphaerotheca and Venturia, and also from the species Piricularia Pellicularia. They are also highly effective against fungus and fungi, e.g. against wheat blight fungi. It should be emphasized that the agents according to the invention not only exhibit a protective effect, but also a curative effect, i.e. they can also be used after the plants have been attacked by fungi. Their systemic action should also be emphasized. For example it is possible to protect plants from attack by fungi if the agent of the invention is applied to the aerial parts of the plants via soil, plants or seeds. As plant protection agents, they can be used to treat soil, seeds and above-ground parts of plants.

The agent of the invention is well tolerated by plants and is only slightly toxic to warm-blooded, and due to its low odor and no effect on human skin, it is not difficult to use. The active ingredients of the agent according to the invention can be converted into the usual means, such as solutions, emulsions, suspensions, powders, pastes and granular preparations. Such agents are prepared by known methods, e.g. by mixing the active ingredients with diluents, also liquid solvents, liquefied gases under increased pressure and / or solid carriers, optionally with the addition of surfactants, emulsifiers and / or dispersants and / or foaming agents. If water is used as an extender, organic co-solvents can, for example, be used.

As liquid solvents, there are mainly used aromatic hydrocarbons, such as xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, e.g. chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, as well as alcohols, such as butanol or glycol and its ethers and esters, ketones, e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulfoxide, or else water. Liquefied gaseous diluents or carriers are those which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons, for example freon. As solid carriers, it is used. ground natural minerals like. kaolin, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth as well as ground synthetic mineral products, e.g. highly dispersed silica, alumina and silicates. As emulsifiers and / or foaming agents. ion-forming or anion-forming emulsifiers are used, such as condensation products of polyoxyethylene with fatty acid esters or fatty alcohol ethers, e.g. alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysis products. >

The dispersing agents used are, for example, lignin, post-sulfuric lyes or methylcellulose.

The composition according to the invention may be in a mixture with other known active substances, such as fungicides, insecticides, acaricides, nematocides, herbicides, anti-bird protection substances, growth promoters, plant nutrients and soil conditioners. .

The fungicides according to the invention usually contain from 1 to 95% by weight, preferably 5 to 90% by weight, of the active compound of the formula 1. The compositions according to the invention are used in the form of preparations or in the form of formulations prepared from them by further dilution, e.g. emulsion solutions, suspensions, powders, pastes and granules. These measures are used in the usual way, e.g. by dripping, spraying, fogging, dusting, spreading, dry, wet, wet or mud dressing, or by. inlay.

When using the compositions according to the invention for controlling leaf fungus, the content of the substance. hours may fluctuate. with broader limits and is generally 0.1-0.00001% by weight,. ko88 788

19 also 0.05-0.0001%. For the treatment of seed, the usual amounts are 0.001 to 50 g, preferably J), 01 to 10 g of active compound per kg of grain. For the treatment of GIfcby, 1 to 1,000 g, preferably 10 to 200 g, per 1 m 2 are required⁸ soil.

The agent according to the invention also effectively inhibits the growth of microorganisms. The various possible uses of the agents according to the invention are illustrated in the following examples:

Example A. Protective effect against Erysiphe.

Solvent: 4.7 parts by weight of acetone, Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether,

Water: 95 cleans by weight.

The amount of active ingredient necessary to obtain the desired concentration in the spray liquid is mixed with the specified amount of solvent, and the concentrate is diluted with the desired amount of water containing the emulsifier. The obtained liquid is sprayed on young cucumber plants with about 3 true leaves so that the liquid drips dropwise, and the plants are left in the greenhouse for 24 hours to dry, and then inoculated by dusting the conidial spores of the fungus Erysiphe cichoreacearum. The plants are then kept in a greenhouse at a temperature of 23 to 24 ° C and a relative air humidity of about 75%. After 12 days, the degree of infestation of the cucumber plants is compared with the controls of the inoculated but treated plants, giving the results as a percentage, 0% being no infection and 100% being the control plants. The compounds tested, the concentration of active substance and the results are given in Table I.

Table I Study on Erysiphe

<td></td><td>Paralysis in%</td>

<td></td><td>sample paralysis</td>

<td>The active substance</td><td>control,. concentrated</td>

<td></td><td>the substance</td>

<td></td><td>active 0.00025 °%</td>

<td>Formula 13 (known compound)</td><td> 41</td>

<td>Formula 14</td><td> 0</td>

<td>Formula 15</td><td> 10</td>

<td>Formula 16</td><td> 29</td>

<td>Formula 17</td><td> 2</td>

<td>Formula 18</td><td> 2</td>

Example B. Systemic Operation on Erysiphe. *

Solvent: 4.7 parts by weight of acetone

Dispersant: 0.3 parts by weight of alkylaryl polyglycol ether, Water: 95 parts by weight.

The active substance in an amount necessary to obtain the desired concentration in the liquid. for irrigation, mix with the stated amount of liquid solvent, and the concentrate is mixed with the stated amount of water containing the dispersant. Plants. Cucumbers at the 1-2 leaf stage, grown in uniform soil, are watered three times a week with the irrigation liquid described above, using 20 ml of liquid per 100 ml of soil. Then for⁵ the plants are inoculated with conidial spores of the fungus Erysiphe cichoreacearum and kept in a greenhouse in air with a relative humidity of 70% and a temperature of 23-24 ° C. ;

After 12 days, the degree of infestation is compared ¹⁰ plants with plant controls also include-? vaccinated but not treated with the test substance, giving the results as a percentage, where 0% is no contamination and 10 (0% is contamination as in the controls.¹⁵ The active substances, their concentrations and the test results are given in Table II.

Table II

Systemic action on Erysiphe

<td rowspan="2"> 25</td><td rowspan="2">The active substance</td><td colspan="2">Infection in% infection of the control sample, concentration of the active substance in parts per million</td>

<td> 100</td><td> 1</td>

<td></td><td>Formula 13 (known compound)</td><td> 91</td><td></td>

<td> 30</td><td>Pattern 19 (Treo Character)</td><td></td><td> 0</td>

<td></td><td>Pattern 29 (erythro form)</td><td></td><td> 0</td>

<td></td><td>Pattern 21</td><td></td><td> 0</td>

<td></td><td>Formula 14</td><td></td><td> 0</td>

ExampleC. Protective action against Podosphaera (apple mealworm).

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 necessary to obtain the desired concentration in the spray liquid is mixed with the specified amount of solvent, and the resulting concentrate is diluted with the specified amount of water containing the emulsifier. Young apple seedlings at the 4-6 true leaf stage are sprayed with the liquid obtained until the liquid drips dropwise, and then the plants. kept for 24 hours in a greenhouse with a relative air humidity of 70% and a temperature of 20 ° C, then inoculated by sprinkling them with conidia spores of apple mealworm (Podosphaera 'leucotricha Saln.) and kept in a greenhouse with relative humidity. , air of 70% and a temperature of 21-23 ° C. After. 10 days after inoculation, the degree of infection of the seedlings is compared with the control samples of plants that were vaccinated, but treated with the test suti: concentration, giving the results as a percentage, with 0%. mean none. infestations, and 100% means time: same as in 'control samples. , .. ..;

: Active substance and their concentration as well as pa65 results were given. in. array ΪΙΙ. _ '

780

T ab 1i ca III

Protective effect on Podosphaera

<td rowspan="2">The active substance</td><td colspan="2">Infection in% infection of the control sample, concentration of active substance in%</td>

<td> 0,00062</td><td> 0,00031</td>

<td>Formula 13 (known compound)</td><td> 52</td><td> 79</td>

<td>Formula 14</td><td> 5</td><td> 16·</td>

<td>Pattern 19 (Treo Character)</td><td> 0</td><td> —</td>

<td>Formula 20 (erythro form)</td><td> 0</td><td> —</td>

<td>Pattern 21</td><td> 0</td><td></td>

<td>Pattern 22</td><td> 4</td><td></td>

Example D. Protective effect of cereal mildew - mycosis destroying leaves - examination on shoots.

For the preparation of an active ingredient, 0.25. parts by weight of active ingredient are dissolved in 25 parts by weight of dtoumyylformamide and 0.06 parts by weight of emulsifier W, and 975 parts by weight of water are added. This concentrate is diluted with water so as to obtain the spray liquid of the desired concentration. In order to determine the protective effect, young barley plants of the Amsel variety. in the one-leaf stage, it is moistened to grow with the prepared liquid and, after drying, it is dusted with spores of Erysiphe graminis var hordei. Plants are kept for 6 days in air at a relative humidity of 80-9 ° C and a temperature of 21-22 ° C, and the degree of infection with powdery mildew is assessed, giving a percentage assessment in comparison with the infestation of plants also inoculated but not treated with the test subjects relationship. 0% means no infection and 100%. means contamination as in the controls. An active substance is more effective the lower the degree of contamination. The active substances and their concentration in the spray liquid and the degree of infection are given in Table IV.

* Table IV Protective effect on powdery mildew in cereals, examination on shoots

<td>The active substance</td><td>Concentration of active substance in the spray liquid (% by weight)</td><td>Infection in% infection of the control sample</td>

<td>Not treated</td><td> —</td><td> 100</td>

<td>Formula 23 (known compound)</td><td> 0,3</td><td> 64,0</td>

<td></td><td> 0,1</td><td> 80,5</td>

<td>Formula 14</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 0,0</td>

<td>Pattern 24</td><td> 0,01</td><td> 6,3</td>

<td></td><td> 0,001</td><td> 10,8</td>

<td>Formula 20 (erythro form)</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 0,0</td>

cont. tab. IV

<td>The active substance</td><td>Concentration of active substance in the spray liquid (% by weight)</td><td>Infection in% infection of the control sample</td>

<td>Pattern 19 (Treo Character)</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 0,0</td>

<td>Formula 18</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 0,0</td>

<td>Pattern 25</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 23,8</td>

<td>Pattern 21</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 0,0</td>

<td>Pattern 26</td><td> 0,01</td><td> 0,0</td>

<td></td><td> 0,001</td><td> 6,3</td>

Example E. Systemic action on barley mildew (Erysiphe graminis var. Hordei), a fungus causing cereal shoot disease.

The active ingredients are used in the form of a powdered seed treatment agent. These compositions are prepared by diluting the active ingredient in question with a mixture of equal amounts of talc and silica and mixing it so as to obtain a powdered product with the desired active ingredient concentration.

Barley seed is shaken with this agent in a closed glass bottle and then sown by placing 3 × 12 grains in pots to a depth of 2 cm in a mixture of 1 volume of Fruhstorfer earth and 1 volume of quartz sand. Germination and breeding take place under favorable conditions in a greenhouse. Seven days after sowing, when the barley plants have developed their first leaf, they are dusted with fresh spores of Erysiphe graminis var. hordei and grown at 21-22 ° C and 80-90% relative air humidity, with 16 hours of light per day. Typical powdery mildew bubbles form on the leaves within 6 days. The degree of infection is defined as the percentage of infection of the plants from the controls, where 0% means no infection, and 100% means infection as in the control, in which the test substance is not used. The active substances and their concentration in the seed treatment agent and the amount of active substance per kg of grain as well as the percentage of infection are given in Table V.

Example F. Protective effect on Fusicladium (apple scab).

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 substance necessary to obtain the desired concentration in the spray liquid is mixed with the above-mentioned amount of solvent, and the obtained concentrate is diluted with the above-mentioned amount of water with the addition of an emulsifier. The obtained liquid is sprayed on young apple seedlings at sta88 788 u

Table V

Systemic action on barley mildew (Erysiphegraminis var.hordei)

<td>The active substance</td><td>Concentration of active ingredient in the treatment agent (% by weight)</td><td>The amount of the product used in g / kg of grain</td><td>Contamination in ° / c of control sample contamination</td>

<td>No seasoning</td><td> —</td><td> —</td><td> 100</td>

<td>Pattern 27</td><td></td><td></td><td></td>

<td>(relationship known '</td><td> 30</td><td> 10</td><td> 100</td>

<td>Pattern 23</td><td></td><td></td><td></td>

<td>(relationship known '</td><td> 30</td><td> 10</td><td> 100</td>

<td>Formula 14</td><td> 25</td><td> 10</td><td> 0,0</td>

dium 4 to 6 suitable leaves, so that the liquid drips in droplets and the plants are kept in the greenhouse at a temperature of 20 ° C and a relative air humidity of 70%. After 24 hours, the plants are inoculated with an aqueous suspension of apple scab (Fusicladium dendriticum Fuck.) Conidia and cultivated for 18 hours in a chamber temperature of 18-20 ° C and a relative air humidity of 100%. The plants are then kept back in the greenhouse for 14 days, and on the fifteenth day the degree of infection of the plants is established in percentage of the control plants, which were also inoculated but not treated with the test substance. A degree of infection of 0% means no infection, and 100% means an infection as in the control plants. The active substances tested and their concentration as well as the test results are given in Table VI.

Table VI

Protective effect on Fusicladium

<td rowspan="2">The active substance</td><td colspan="2">Infection in% infection of the control sample at the concentration of the active substance</td>

<td> 0,025%</td><td> 0,00125%</td>

<td>Formula 13 (known compound) Formula 14 Pattern 19 Formula 20 Formula 18 Pattern 21</td><td> 97</td><td> 16 7 5 0 12</td>

Examples of the preparation of the new compounds according to the invention are given below.

EXAMPLE 1 31.4 g (0.1 mol) of c- (4'-chlorophenoxy) - (1,2,4-triazol-r) -acetophenone were dissolved in 300 ml of methanol, the solution was cooled with ice and, while stirring, added. 3 g (0.08 mol) of borosodium hydride are then stirred for 1 hour at room temperature, and then the solvent is distilled off under reduced pressure. The residue is dissolved in dilute hydrochloric acid, heated for a short time and filtered. The filtrate makes it alkaline. with SO hydroxide⁵ The resulting precipitate is filtered off with suction and dissolved in ethyl acetate, the ethyl acetate is distilled off and the oily residue is crystallized by trituration with petroleum ether. After recrystallization from a mixture of petroleum ether and isopropanol, it is kept at 25 g. (98 ° / theoretical yield) 1- (4'-chlorophenoxy) - (- (1,2,4, -triazolyl-1 ') - 2-phenylethanol of formula 28. The product melts at 117 ° C .

Used in this example as a starting product ω- (4 '- Chorolenoxy) -ω- (4,2,4-triazolllo-1') - acetophenone is prepared on this. way that 32.5 g (0.1 mol) of ω-bromo-ω- (4'-chlorolenoxy) -acetophenone and 30 g (0.44 mol) of 1,2,4-triazole are dissolved in 240 ml of acetonitrile and it is refluxed for 48 hours. The solvent was then distilled off and the residue was dissolved in 800 ml of water, the solution was extracted several times with methylene chloride, the extract was washed with 2 portions of 200 ml of water, dried over sodium sulfate and the solvent was distilled off under reduced pressure. The residue which crystallizes can be recrystallized from a mixture of ligroin with isopropanol (2: 1) to give o - 3 - cblorophenoxy) t α&gt; (4,2,4-triazolyl-1 ') - acetophenone, mp 98-100 ° C.

A pre-product for the preparation of the starting product, ω-bromo-ω- (4'-chlorophenoxy) -acetophenone, is prepared by the condensation of 4-chloro * phenol with ω-chloroacetophenone and bromination of the obtained o - ^ - chlorophenoxy acetophenone . The resulting pre-product melts at 71^ABOUTC.

Example II. 587 g (2 moles) of 1- (4'-chlorophenoxy) -1- (1,2,4-tria from olyl --'-- 3,3-dimethylbutanone-2) are dissolved in 3 liters of methanol, the solution is cooled with ice and at 0-10 ° C, add, with stirring, 5 g in total, 80 g (2 mol) of borosodium hydride, with stirring, and stir for 2 hours at 5-10 ° C, and then for 12 hours at room temperature. The mixture is then cooled to 10 ° C and, maintaining the temperature at 10-20 ° C, add 300 g (3 mol) of concentrated aqueous hydrochloric acid solution and then stirred for 6 hours at room temperature. and the obtained suspension is diluted with 3.8 liters of water containing 400 g (4.8 mol) of sodium bicarbonate. After filtering off the precipitate, 502 g (85% theoretical yield) of '1- (4'-chlorophenoxy) -1- (1,2,4-triazolyl-' (- 3,3-dimethylbutanol-2 of the formula 14) are obtained. The product melts at temperature

112-117 ° C.

Example III. A solution of 31.2 g (0.22 mol) of methyl iodide in 100 ml in dry ether is added dropwise to a suspension of 4.8 g (0.22 mol) of magnesium turnings in 50 ml of anhydrous ether, while stirring under reflux, the solvent begins to boil. . After completion of the dropwise addition, the solution is added dropwise to the obtained Grignard solution

29.4 g (0.1 mol) of 1- 4 -'-chlorophenoxy) -1- (1,2, - thiazolyl-1) -3,3-dimethylbutanone-2 in 100 ml of anhydrous ether and It is refluxed for 18 hours. After cooling the mixture, a solution of 80 g of ammonium chloride in 600 ml of water and then 250 ml of ethyl acetate is added to the mixture and the mixture is stirred for 15 minutes. The organic phase is separated and the aqueous phase is re-extracted with ethyl acetate. The combined organic solutions are washed with 2 x 100 ml portions of water, dried over sodium sulphate and the solvent is evaporated off under reduced pressure. The crystalline residue is treated with hot petroleum ether and the undissolved product is filtered off while hot. 11 g (3β · / ο theoretical) of 1- (4'-chlorophenoxy) -1- (1,2,4-triazolyl ') - 2,3,3-trimethylbutanol-2 of the formula 29 are obtained. The product melts to temperature 158-160 ° C.

Example IV. Dissolve 33.6 'g (0.1 mol) of 1- (4'-bromophenoxy) -1- (1,2,4-triazolyl-1') - 2-dimethylbutanone-2 in 300 ml of ethanol and add the solution to the solution. 8 g (0.2 mol) of sodium hydroxide in 40 ml of water, then 32.4 g (0.3 mol). formamidine sulfinic acid. The mixture is refluxed for 3 hours, then the mixture is filtered, and the solvent is distilled off the filtrate under reduced pressure. The oily residue is taken up in 100 ml of water and extracted with two 100 ml portions of methylene chloride. The combined organic solutions are washed with 100 ml of water each time, dried over sodium sulphate and the solvent is evaporated off under reduced pressure. The oily residue is boiled with petroleum ether, whereupon the product crystallizes. After draining, it receives food

26.5 g (79% of theory) of 1- (4'-bromo88 780 at 0-5 ° C under reflux condenser, add 5.8 g (0.15 mol) borosodium hydride in portions. hours at room temperature, then, as described in example II, it is treated with 20 ml of concentrated hydrochloric acid and 250 ml of saturated sodium bicarbonate solution. The sodium bicarbonate suspension is extracted with 2 '150 ml portions of methylene chloride and the combined organic extracts are washed with 2 100 ml portions of water until neutral, dried and the solvent is evaporated off under reduced pressure. The oily residue is boiled with hot petroleum ether to give a crystalline solid (I) which is filtered hot and dried. The filtrate is evaporated under reduced pressure to dryness. The residue (II) is triturated with petroleum ether and a little ether. A total of 23.4 g (79^&lt;^% of theory) 1-phenoxy-1- (1,2,4-triazo-1-yl-1 ') - 3,3-dimethylbutanone-2 of the formula 44, including (I) 4.1 g of the erythro compound at a temperature of melting 132^ABOUTC and (II) 19.3 'g of threo, m.p. 88-94 ° C.

Compounds of formula I in which R1, R2, R®, R4 and Az are as defined in Table VII, which also shows the melting point, are prepared analogously.