Fungicide

<td>POLAND REPUBLIC CHINA</td><td>PATENT DESCRIPTION</td><td colspan="2"> 115653</td>

<td></td><td>Additional patent to patent no</td><td></td><td></td>

<td>IN</td><td>Reported: 05.01.79 (P. 212674)</td><td colspan="2">Int. Cl 2 A01N 9/22</td>

<td></td><td>Priority: 07.01.78 Federal Republic</td><td></td><td></td>

<td rowspan="2">OFFICE PATENT</td><td>German</td><td></td><td></td>

<td>The application was announced: 14.01.80</td><td>READING ROOM</td><td></td>

<td>POL '</td><td>Patent description published: 30.03.1983</td><td>Patent OfficehlsAiij Ipmtw /</td><td></td>

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

Inventor of the invention _

Patent holder: Bayer Aktiengesellschaft, Leverkusen (Federal Republic of Germany)

Fungicide

The present invention relates to a fungicide containing as active substance new carbomooyl-triazolyl-O, N-acetals.

It is known that acylated triazolyl-O, N-acetals, for example 2-alkylcarbonyloxy-3,3-dimethyl-1-phenoxy-1- (1,2,4-triazolyl-1) -butanes substituted in the phenyl radical, have good fungicidal activity. (German Patent DOS No. 2,600,799), their action, especially at lower levels and concentrations, is not always satisfactory.

Zinc ethylene-1,2-bis-dithio-carbamate has long been used to combat plant fungal diseases (Phytopathology 33, 1113, (1965).

Its use is also limited because at lower doses and concentrations often are not very effective.

New carbamoyl-triazolyl-O, N-acetals of formula 1 have been found in which R is an alkyl radical, haloalkyl, alkoxycarbonyl, alkoxyalkyl, substituted phenyl or alkylsulfonylalkenylcarbamoyl radical, X is halogen, alkyl, cycloalkyl, alkoxy haloalkyl, alkylthio, alkoxycarbonyl, optionally substituted phenyl or phenoxy radical, optionally substituted phenylalkyl radical, amino group, cyano or nitro and n are integers 0-5 and their addition salts with physiologically non-toxic acids and metal complex salts have strong fungicidal activity.

Compounds of formula I have two asymmetric atoms _v carbon may therefore exist in the form of erythro and threo. In both cases they are usually racemates.

New carbamoyl-triazolyl-O, N-acetals are obtained by reaction of triazole derivatives of formula 2 in which ⁵ X and n have the meanings given above.

a) isocyanates of formula 3 in which R is as defined above, in a solvent medium and optionally in the presence of a catalyst, or

b) substituted 1,3,4-dioxazol-2-ones of formula 4, ¹⁰ wherein R is as defined above, in a solvent medium optionally in the presence of a catalyst.

The resulting carbamoyl-triazolyl-O, N-acetals of formula 1 can be converted into salts by reaction with acids or metal complex salts by reaction ¹⁵ with metal salts. ♦

The resulting new carbamoyl-triazolyl-0, N-acetals have much better fungicidal activity than the acylated triazolyl-Ó, N-acetals known in the art, especially those substituted in the phenyl radical with 2 alkyl²⁰ carbonyloxy-3,3-dimethyl-1-phenoxy-1- (1,2,4-triazolyl1) -butanes, which are chemically similar compounds with the same direction of action and known zinc ethylene-1,5-bis-dithiocarbamate with such same course of action.

²⁵ When 1- (4-biphenylyloxy) -3,3-dimethyl-1- (1,2,4-triazolyl-1) -butan-2-ol and methoxymethyl isocyanate are used as starting compounds, the reaction is shown in Scheme 1 (procedure and).

For 1- (4-biphenyl-1-yloxy) -3,3-dimethyl-1³⁰ - (1,2,4-triazolyl -) - butan-2-ol and 5-methoxymethyl-3,4115 653

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-dioxazol-2-one as starting compounds, reaction 2 is shown in scheme 2 (procedure b).

The triazole derivatives used as starting materials are generally represented by formula 2. In this formula, X is preferably a halogen atom, an amino, cyano, nitro group, a straight or branched alkyl radical containing up to 4 carbon atoms, a cycloalkyl group with 5-7 carbon atoms, especially cyclohexyl, a haloalkyl group with up to 2 carbon atoms and up to 5 halogen atoms , especially fluorine and chlorine, furthermore preferably, an alkoxycarbonyl group containing up to 5 carbon atoms in total, an alkoxy group and an alkylthio group up to 2 carbon atoms.

X is further preferably an optionally substituted phenyl or phenoxy radical, the substituents being preferably: halogen, amino, cyano, nitro or an alkyl radical with 1-2 carbon atoms, then preferably represents an optionally substituted phenylalkyl radical with 1 or 2 carbon atoms in the alkyl portion, wherein the substituents in the alkyl portion is preferably a total alkylcarbonyloxy group of up to 3 carbon atoms, and in the phenyl part preferably halogen, nitro and cyano. The index n preferably denotes the numbers 0-3.

Starting compounds of formula 2 are known (DOS 2 324 010) [Le A 14 971].

Still new starting compounds of the formula II can be prepared according to known methods, for example by reduction of the ketone derivative with aluminum isopropylate or complex hydrides in a solvent medium.

The isocyanates used * in procedure (a) as starting compounds are generally represented by formula 3.

In this formula, R is preferably a straight or branched alkyl radical with 5-12 carbon atoms, a halogenoalkyl group containing up to 4 carbon atoms to 5 same or different halogen atoms, especially fluorine and chlorine, and alkoxycarbonyl and alkoxyalkyl groups with 1-4 carbon atoms in the any alkyl radical.

R is further a phenyl radical preferably containing one or more substituents, which are preferably: a straight or branched alkyl radical with 1-4 carbon atoms, an alkoxy group and an alkylthio group with 1 or carbon atoms, a haloalkyl group containing up to 2 carbon atoms and up to 5 the same or different halogen atoms, especially fluorine and chlorine, and a 1-4 alkoxycarbonylalkenyl group carbon atoms in the alkyl radical and 2-4 carbon atoms in the alkenyl radical, R is further preferably an alkylsulfonyl-alkenyl-carbamoyl group with 1-4 carbon atoms in the alkyl portion and 2-4 carbon atoms in the alkenyl portion.

Isocyanates of formula 3 are known or can be prepared according to known methods, e.g. by reacting amines with phosgene and subsequent heating.

Used as starting materials in proceedings (b)

1,3,4-dioxazol12-ones are generally represented by formula 4. In this formula, R is preferably substituents already mentioned as being preferred for isocyanates of formula 3.

1,3,4-Dioxazol-2-ones of formula 4 are known (G. Beck. Chem. Ber. 84, 688 (1951) or can be prepared in a known manner, e.g. by reaction of the corresponding hydrocycarboxylic acids or acid hydazides with phosgene at boiling point.

The solvents used in the procedure (a) are preferably all organic solvents, especially ketones, e.g. acetone and methyl ethyl ketone, nitriles, e.g. propionitrile, especially acetonitrile, ethers, e.g. tetrahydrofuran or dioxane, esters, e.g. ethyl acetate, aromatic hydrocarbons, e.g. benzene or toluene and halogenated hydrocarbons, e.g. methylene chloride, carbon tetrachloride or chloroform.

The catalysts used in the procedure (a) are preferably tertiary bases, e.g. triethylamine and pyridine, or organotin compounds, e.g., dibutyltin dinitrate.

The procedure (a) is carried out over a wide temperature range. Generally at 0-100 ° C, preferably 20-70 ° C.

Preferably reagents in equimolar amounts are used in carrying out procedure (a). To isolate the compounds of formula I, the solvent is distilled off and the residue is worked up in a known manner.

In process (b), inert organic solvents are preferably used as the solvent. They preferably include the liquids mentioned in procedure (a).

The catalyst used in process (b) is preferably tertiary amines, e.g. triethylamine or alkali metal salts of fatty acids, e.g. sodium acetate. The procedure (b) is carried out over a wide temperature range. Generally at a temperature of 60-150 ° C, preferably 80-100 ° C.

When carrying out procedure (b), it is preferred to use equimolar quantities. To isolate the compounds of formula I, the solvent is distilled off and the residue is processed in a known manner.

Plant-tolerated acids are used to prepare the acid addition salts of compounds of formula I.

These include hydrohalic acids, e.g. hydrochloric and hydrobromic, especially hydrochloric, in addition, phosphoric, nitric, sulfuric, monofunctional carboxylic and hydroxycarboxylic acids, e.g. acetic, maleic, succinic, fumaric, tartaric, citric, salicylic, sorbic, and sulfonic acids, e.g. p-toluenesulfonic and 1,5-naphthalene disulfonic acids. φ

Salts of compounds of formula 1 can be prepared in a known manner in that the compounds of formula 1 are dissolved in a suitable inert solvent, an acid, e.g. hydrochloric acid is added, filtered off and optionally purified by washing with an inert organic solvent.

For the preparation of the metal complex salt of the compounds of the formula - preferably metal salts of II-IV main groups I and II and IV-VIII side groups, preferably copper, zinc, manganese, magnesium, tin, iron and nickel are used. The anions of these salts are derived from physiologically tolerable acids, preferably hydrohalic, e.g. hydrochloric and hydrobromic, in addition phosphoric, nitric and sulfuric.

Metal complex salts of compounds of formula I can be prepared in a known, simple manner, for example, by dissolving a metal in an alcohol, e.g. ethanol, and adding a compound of formula 1. Metal complex salts can be isolated in a known manner, e.g. by filtration, and optionally purified by recrystallization.

Examples of particularly active active compounds of formula 1 sq m, in addition to those given in the preparation examples and table, are the following compounds:

1- (4-ch! Orofenoksy) -3,3-dimethyl-2-methoxymethyl-carbamoyloxy-1- (1,2,4-triazol-1) butane,

1- (2,4-dichlorophenoxy) -3,3-dimethyl-2-metoksymetylokarbamoiloksy-1- (1,2,4-triazol-1) butane,

1- (4-chlorophenoxy) -3,3-dimethyl-2-trójfluorometylokarbamoiloksy-1- (1,2,2-triazol-1) -butan_f

1- (4-bifenyliloksy) -3,3-dimethyl-2-trójfluorometylokarbamoi! Oxy-1- (1,2,4-triazol-1) -butan.

The active substances according to the invention have strong fungicidal activity.

In the concentrations used to combat fungi they do not damage crop plants. For these reasons, they can be used. use in the form of plant protection products to combat fungi. Fungitoxic agents in plant protection are used to combat Plasmodiophoromycetes, Ascomycetes, Omycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The active substances according to the invention have a broad spectrum of activity and can be used to control parasitic pathogens infesting aerial parts of plants, infecting plants from soil and transmitted by seeds, especially infesting aerial parts of plants.

In plant protection, the active substances according to the invention can be used to control Venturia species_tfor example potogen of the scab Fusicladium dendriticum, species of uromyces, e.g. pathogen of bean rust (Uromyces phaseoli), Phytophtora and cereal diseases.

Active substances in the form of plant protection products can be used to treat seeds or soil and treat aerial parts of plants.

The active substances can be converted into ordinary preparations in the form of solutions, emulsions, wetted powders, suspensions, powders, powdered powders, foams, pastes, soluble powders, granules, aerosols, suspoemulsion concentrates, seed treatment powders, introduced into natural and artificial substances impregnated active substances, microcapsules in polymeric substances, seed coatings, for fumigation preparations such as cargo and smoke candles, and preparations used in the ULV method.

These preparations are obtained in a known manner, e.g. by mixing the active substances with diluents, i.e. liquid solvents, pressurized gases and / or solid carriers, optionally using surface-active substances such as emulsifiers and / or dispersants and / or foaming agents.

When using water as the diluent, organic solvents serving as auxiliary solvents can be used, for example.

As liquid solvents, essentially aromatic compounds can be used, e.g. xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylates or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins e.g. petroleum fractions, alcohols such as butanol or glycol and its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, high polarity solvents such as dimethylformamide and dimethyl sulfoxide, and

water; wherein the liquefied gaseous diluents or carriers are liquids that are gases at normal temperature and pressure, e.g., aerosol gases such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.

Natural solid minerals, such as kaolins, alumina, talc, chalk, quartz attapulgite, montmoryionite or diatomite, and synthetic inorganic flours such as high-grade silicic acid, alumina and silicates are used as solid carriers.

As solid carriers for granules, crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours as well as granules of organic material, e.g. sawdust, coconut shells, corn cobs and tobacco stems are used .

Non-ionic and anionic emulsifiers such as polyoxide and fatty acid esters, polyethylene oxide and fatty acid ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates are used as emulsifiers and / or foaming substances. As dispersants, for example, lignin, sulfite lye and methyl cellulose are used. *

The preparations may contain adhesives such as carboxymethyl cellulose, natural and synthetic polymers, powdered and granular or in the form of latexes such as acacia, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian blue, and organic dyes, e.g., alizarin, azo, metal-phthalocyanion dyes, and trace substances such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts can be used.

The formulations usually contain 0.1-95%, preferably 0.5-90%, by weight of active ingredients.

The preparations may contain additives of other known active substances such as fungicides, indicides, acaricides, nematocides, herbicides, repelling birds foraging, growth substances, plant nutrients and soil conditioners. .

The active substances can be used alone, in the form of concentrates or prepared from them by diluting working preparations, such as ready-to-use solutions, emulsions, suspensions, powders and granules. The agents are applied in known manner, e.g. by watering, spraying, nebulizing, dusting, spreading, dry, wet, slurry or encrusting.

When used as nalistic fungicides, the active substance concentrations in the preparations may be different. In general, the concentration is 0.00001-0.1% by weight, preferably 0.0001-0.05% by weight.

For seed dressing, a dose of active substances of 0.001-50 g / kg of seed is generally used, in particular 0.01-10 g. For soil treatment, a dose of active substance of 1-100 g / m³ soils, especially 10-200 g. Various application possibilities result from the following examples.

Example I. Fusicladium (apple) testing as a preventive measure.

Solvent: 4.7 parts by weight of acetone p

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Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

Water: 95 parts by weight.

In order to obtain a spray liquid with the desired concentration of active substance, the required amount of active substance is mixed with the given amount of solvent and the concentrate is diluted with the given amount of water containing the said additives.

Young apple seedlings at a 4- to 6-leaf stage are sprayed with liquid for spraying. Plants are kept in the greenhouse for 24 hours at 2G ° C and a relative humidity of 70%. It is then filled with an aqueous suspension of apple scab (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18-20 ° C and a relative air humidity of 100%.

The plants are put back into the greenhouse for 14 days. After 15 days after inoculation, seedling infestation is determined in%. The obtained bonitation values ​​are converted into paralysis in%, with 0% meaning no paralysis and 100% total paralysis. Tests have shown that the compounds obtained according to examples IV, V, XI, XIX, XX show good effects exceeding those of other compounds.

Example II Uromyces testing (bean rust) preventively.

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

Water: 95 parts by weight.

In order to obtain a spray liquid with the desired concentration of active substance, the required amount of active substance is mixed with the indicated amount of solvent, the concentrate is diluted with water containing the given additives.

The resulting spray liquid is sprayed onto the young bean shoots at 2-leaf development until reflux. The plants remain dry for 24 hours in a greenhouse at 20-22 ° C and a relative humidity of 70%.

Next, the rust pathogen (Uromyces phaseoli) is inoculated with an aqueous suspension of uredospores and incubated for 24 hours in a dry humid chamber at 20-22 ° C and 100% humidity.

The plants are left for 9 days in a greenhouse under intense light at 20-22 ° C and a relative humidity of 70-80%. 10 days after inoculation, plant infection is established. The obtained bonitation values ​​are converted into paralysis in% where 0% means no paralysis and 100% total paralysis.

Tests have shown that the compounds obtained according to examples IV, V, VI, VII, VIII IX, X, XI, XII, XIII, XIV, XVI, XVII, XVIII, XIX, XX show good activity clearly better than that of known compounds.

Example III. Testing Phytoptora (tomatoes) preventive action.

Solvent: 4.7 parts by weight of acetone;

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether;

Water: 95.0 parts by weight.

In order to obtain a spray liquid with the desired concentration of active substance, the required amount of active substance is mixed with the given amount of solvent and the concentrate is diluted with the given amount of water containing the said additives. Young tomatoes with 2 to 4 assimilation leaves are sprayed for reflux with the obtained spray liquid. The plants are left in the greenhouse for 24 hours at a temperature of 20 ° C and a relative humidity of 70%.

Tomatoes are then inoculated with a Phytophtora 'infestanc spore suspension. Plants are introduced into a humid chamber with 100% air humidity and 20 ° C.

After 5 days, tomato infestation is determined. The obtained bonitation values ​​are converted into infestation in%, with 0% meaning no infestation, and 100% that the plants are completely infected.

Active substances, the active substance concentrations and the results obtained are determined. .

The tests confirmed that the compounds obtained according to examples IV, VIII, XI, XIX, XX far outweigh the known compounds from the prior art.

Production examples

Example IV (Procedure a). 505 g (1.5 mole) 1- (4-biphenylyloxy) -3,3-dimethyl-1- (1,2,4-triazolyl-1) -butan-2-ol (form A) and 140 g (1 , 6 mole) methoxymethyl isocyanate is refluxed for 48 hours in 2.5 liters tetrahydrofuran versus 40 ml triethylamine and 1 ml dibutyltin dinaurate.

The solvent is then distilled off under reduced pressure, and the residue is treated with 3 liters of petroleum ether. The resulting crystalline precipitate is mixed with 1.5 liters of diisopropyl ether. 528 g (82.5% of theory) of 1- (4-biphenylyloxy) -3,3-dimethyl-2-methoxymethylcarbamoyloxy-1- (1,2,4-triazolyl-1-butane (form A) is obtained, formula 5, with a melting point of 95-98 ° C.

The compounds listed in the table are obtained analogously.

Table

Compounds of formula 1

<td>Example</td><td>Xn</td><td>R</td><td>Melting point (° C)</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>V</td><td>formula 6</td><td>- (CH₂)₂Cl</td><td>138-141 (form A)</td>

<td>VI</td><td>formula 6</td><td>-co-oh₂</td><td>184-185 (form B)</td>

<td>VII</td><td>formula 6</td><td>—CO ^ - OC2H5</td><td>164-166 (post B)</td>

<td>VIII</td><td>formula 6</td><td>- (CH₂)₂-c</td><td>103-105 (form A)</td>

<td>IX</td><td>formula 6</td><td>-co-oh₃</td><td>120 (form A)</td>

<td>X</td><td>formula 6</td><td>-CO-OC₂H₅</td><td>100 (form A)</td>

<td>XI</td><td>formula 6</td><td>analysis₂-0-CH₃</td><td>141-144 (form B)</td>

<td>XII</td><td>formula 6</td><td>—CO — N (CH2 — CH = CH₂) SO₂CH₃</td><td>141-144 (form B)</td>

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<td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>XIII</td><td>formula 6</td><td>- (CH₂)₂—CH (CH ₃) —C (C h ₃)₃-h₂</td><td>109-115 (form B)</td>

<td>XIV</td><td>formula 6</td><td>formula 7</td><td> 194—200</td>

<td>XV</td><td>formula 6</td><td>formula 8</td><td> 158—165</td>

<td>XVI</td><td>formula 6</td><td>formula 9</td><td> 193—206</td>

<td>XVII</td><td>formula 6</td><td>formula 10</td><td> 148—155</td>

<td>XVIII</td><td>formula 6</td><td>-CO-OCH₃</td><td>151-154 (form A)</td>

<td>nineteenth</td><td>formula 6</td><td>_ch₂-O-C₂h₅</td><td>140 (xHCI)</td>

<td>XX</td><td>formula 6</td><td>- (CH₃)₃-O-CH₃</td><td>100 (XHCl)</td>

Form A and Β = one of two possible geometric isomers in each case