Fungicide means and method of making the active substances

DESCRIPTION OF THE IMPLEMENTATION

TO THE PATENT OF THE CZECHOSLOVAK SOCIALIST

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204043 (11) (B2) (51) Int. Cl.3 A 01 N 43/82 (22) Registered 04 01 79 (21) (PV 134-79) (32) (31) (33) Right of priority from 07 01 78 (P 28 00 544.9) German Federal Republic 40) Published 30 06 80

OftAD PRO IMPRESSIONS AND OBJECTS (45) Published 15 12 83 (72) .Author of the invention BUCHEL KARL HEINZ prof. Dr. KRAMER WOLFGANG dr, WUPPERTAL and BRANDES WILHELM dr., LEICHLINGEN (NSR)

BAYER AKTIENGESELLSCHAFT, LEVERKUSEN (NSR) Patent Owner (54) Fungicide Agent and Method for the Production of Active Ingredients 1

The present invention relates to fungicidal compositions comprising as active ingredient new carbamoyltriazolyl O, N-acetals. Further, the invention relates to a process for the production of these novel fungicidal active compounds.

It is already known that acylated triazolyl-O, N-acetals such as, in particular, phenyl-substituted 2-alkylcarbonyloxy-3,3-dimethylphenoxy- 1- (1,2,4- triazol- butanes, have good fungicidal properties (see DOS2 600 799). However, their effect is not always satisfactory, especially with lower applied concentrations of concentrations. It has now been generally known for a long time that zinc ethylene-l, 2-bis-dithiocarbamate is a good means of controlling fungal plant growth [cf. Phytopathology 33, 1113 (1963) j. However, it is only possible to use it on a limited scale, because it is less effective at low application rates and concentrations.

It has now been found that the novel carbamoyl-triazolyl-O, N-acetals of formula I, O-CO-NHRO-CH-CH-

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2 wherein R represents a C 5 -C 12 alkyl group, a C 1 -C 4 haloalkyl group and from 1 to 5 same or different halogen atoms, in particular fluoro and chloro, an alkoxyalkyl group Alkyl of 1 to 4 carbon atoms, a phenyl group which is substituted by one or more straight-chain or branched C1-C4-alkyl, C1-C2-alkoxy, as well as alkoxycarbonyl-alkenyl having 1 to 4 C 1 -C 4 alkyl and C 2 -C 4 alkenyl, said substituents being the same or different and furthermore alkylsulfonylalkenylcarbamoyl of 1-4 carbon atoms in the alkyl (C 2 -C 4) alkenyl, X is halogen or phenyl and integers are from 0 to 5,as well as their physiologically acceptable acid addition salts and complex compounds with co-salts have strong fungicidal properties.

The compounds of the formula I have two asymmetric carbon atoms and can therefore be present in erythro- and threo form. In both cases, they are predominantly as racemates.

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(I) 204043 204043

According to the invention, the novel carbamoyltriazolyl-O, N-acetals of formula I are prepared by making the triazolyl derivatives of general formula II,

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in which X and Y are as defined in formula (I), are reacted with isocyanates of general formula III,

In which R is as defined in formula (I), in the presence of a solvent and optionally in the presence of a catalyst, whereupon the obtained compounds are optionally converted by addition of the acid or salts of the metals to the corresponding salts, optionally to the complex metal compounds.

The process according to the invention will be referred to hereinafter as process a).

The compounds of formula (I), their physiologically acceptable acid addition salts or complexes with solemics can be further prepared by reacting the triazolyl derivatives of the formula (II) with a substituted 1,3,4-dioxa Zol-2-ones of the formula IV,

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(IV) in which R is as hereinbefore defined, in the presence of a solvent and optionally in the presence of a catalyst, whereupon the carbamyltriazolyl-O, N-acetals obtained may be converted to acids with salts or by reaction with metal salts to the corresponding complex compounds with metals. This procedure will hereinafter be referred to as process b). Surprisingly, the carbamoyl-O, N-acetals of the present invention exhibit a much higher fungicidal activity than the acylated triazolyl-O, N-acetases known in the art, especially in the phenyl portion of the substituted 2-alkylcarbonyloxy- dimethyl-1-phenoxy-1- (1,2,4-triazol-1-yl) butanes which are the pharmacologically and physically related compounds and zinc ethylene-1,2-bis-dithiocarbamate is a known substance with the same type of effect.

When starting from 1- (4-biphenylyloxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol and methoxymethylisocyanate, the course of the reaction according to the invention (process a) is illustrated by the following reaction scheme:

OH

CH3 -CH2-W.-C = O-O-CO-NH-CH2 O-CH2 O-CH-

When starting from 1- (4-biphenylyloxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol and 5methoxymethyl- , 4-dioxal-2-one, the course of the reaction according to process b) can be illustrated by the following reaction scheme: 204043 6

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Triazolyl derivatives used as starting materials; substances are generally defined by Formulation II. In this formula, the symbol Xhalogen or phenyl group and the index denote integers ranging from 0 to 5, preferably integers ranging from 0 to 3. The starting materials of formula II are known (cf. DOS 2 324 010). Hitherto unknown starting materials of formula II can be obtained according to the processes already described by reducing, for example, the corresponding ketone derivatives with aluminum isopropoxide or complex hydrides in the presence of a solvent.

The isocyanates used as starting materials for the process according to the invention are generally defined by formula III In this formula, the symbol R is a straight-chain or branched alkyl group having from 5 to 12 carbon atoms, haloalkyl of up to 4 carbon atoms and up to 5 identical or different halogen atoms, especially fluorine and chlorine atoms, and an alkoxyalkyl group each having 1 to 4 carbon atoms in each of the alkyl moieties. Symbool R is additionally preferably one or more times substituted phenyl, with the substituents as preferably, straight chain or branched alkyl of 1 to 4 carbon atoms, alkoxy of 1 or 2 carbon atoms, and alkoxycarbonyl of 1 to 4 carbon atoms in the alkyl part and 2 to 4 carbon atoms in the alkenyl moiety.The symbol R is further preferably C 1-4 alkylsulfonylalkenylcarbamoyl and 2 to 4 carbon atoms in the alkenyl moiety.

The isocyanates of the formula III are known or can be produced according to generally conventional procedures. This can be done, for example, by reaction of amines with phosgene and subsequent heating. 1,3,4-dioxazol-2-ones, used as starting materials for process b), are generally defined by formula IV. In this formula, the symbol R is preferably those residues which have been preferred for isocyanates of the formula III. 1,3,4-dioxazol-2-ones of formula IV are known (see G. Beck, Chem Ber, 84, 688 (1951)) or can be prepared according to generally conventional and known procedures. For example, they can be prepared by reacting the corresponding hydroxycarboxylic acids or hydrazides of the acids with phosgene while heating to room temperature.

Suitable solvents for the reactant according to the invention (process a) are preferably all inert organic solvents. These include, preferably, ketones such as diethyl ketone, especially acetone and methyl ethyl ketone; nitriles, such as propionitrile, in particular acetonitrile; ethers, such as tetrahydrofuran or dioxane; esters, such as ethyl acetate; aromatic hydrocarbons, such as benzene or toluene, and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.

As catalysts, the tertiary bases, such as triethylamine and pyridine, or organotin compounds such as dibutyltindulaurate can be used in the process of the present invention (process a).

Reaction temperatures may vary over a wide range in the process according to the invention (process a). Generally, the temperature is from 0 to 100 ° C, preferably between 20 and 70 ° C. The process according to variant a) is preferably carried out using a molar quantity. To isolate the compounds of formula I, the serose solvent is distilled off and the residue is worked up using conventional methods.

Suitable solvents for the process variant b) are preferably inert organic solvents. These preferably include the solvent already mentioned for process variant a).

As catalysts, preferably tertiary amines, such as triethylamine or alkali metal fatty acids such as sodium acetate, may be used in the process of variant b) above.

Reaction temperatures may vary widely in the process of variant b). Generally, it is operated at temperatures of 60 to 150 ° C, preferably 80 to 100 ° C. In the process according to variant b), it is preferably employed in molar amounts. To isolate the compounds of formula I, the solvent 204043 is distilled off and the residue is worked up by conventional methods.

All physiologically acceptable acids are contemplated for the production of the acid addition salts of the compounds of the formula (I). Examples include hydrohalic acids such as hydrochloric and brominic acids, in particular hydrochloric acid, phosphoric acid, nitric, sulfuric, monobasic and dibasic carboxylic acids and hydroxycarboxylic acids such as acetic, maleic, succinic, fumaric, tartaric, citric, salicylic acid, sorbic acid, lactic acid as well as sulfonic acids such as p-toluenesulfonic acid and 1,5-disulfonic acid.

Salts of the compounds of formula (I) may be obtained in a simple manner by customary methods for the preparation of salts, for example by dissolving the compound of the formula (I) in a suitable mineral solvent and adding an acid such as hydrochloric acid and is isolated in a known manner, and optionally washed with a mineral organic solvent.

For the preparation of complex salts with metals removed from the compounds of formula I, the metal salts II are contemplated. to IV. main groups I and II as well as IV. to VIII. side groups of the periodic system, with examples being copper, zinc, manganese, magnesium, tin, iron and nickel. Salts anions are also contemplated and anions derived from physiologically acceptable acids are contemplated. Preferably, hydrohalic acids such as hydrochloric and bromoacetic acids, phosphoric, nitric and sulfuric acids are preferred.

The complexes of the compounds of the formula I with the metals are obtained in a simple manner, for example by dissolving the metal salt in an alcohol, for example in methanol, and adding this solution to the compound of the formula I. The complex metal compounds can be isolated in a known manner, for example by filtration, and, if desired, by crystallisation.

Fungitoxic plant protection agents use Flasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes to control the fungus. The active ingredients according to the invention have a broad spectrum of action and can be used for parasitic fungi that attack the over-ground parts of plants and against fungus-infesting plants as well as against seed-borne diseases. Particularly good effect these agents have on the mushrooms that parasite on the above-ground parts of plants. as well as against transporters of porcine diseases. Particularly good effect these agents have on the mushrooms that parasite on the above-ground parts of plants. as well as against transporters of porcine diseases. Particularly good effect these agents have on the mushrooms that parasite on the above-ground parts of plants.

As a plant protection agent, the active compounds of the invention can be used particularly successfully to combat Venurian fungi such as Fusicladlum dendritlcum, Uromyces counterparts such as Uromyces phaseoli ), the fight against Phytophthora species and the treatment of cereal diseases.

As a plant protection agent with the active substance of the invention, seed dressing or soil care and the treatment of the above-ground parts of plants can be used. The active ingredients may be formulated into conventional formulations, such as solutions, emulsions, wettable powders, suspensions, powders, powders, foams, pastes, soluble powders, granules, aerosols, suspension concentrates, and emulsions, powders for seed treatment, natural and synthetic substances impregnated with active substances, small particles coated with polymeric substances and coating of the mass of propellant, furthermore with means of flammable additives, such as smoke cartridges, smoke dies, smoke spirals, etc. concentrates in the form of concentrated cold or hot melt active ingredients.

These formulations are prepared in a known manner, for example by mixing the active compound with a plurality of liquid solvents, liquefied gases under vacuum and / or solid carriers, optionally using surface-active agents, such as emulsifiers and / or dispersants, and / or foaming agents. In the case of the use of water as a filler, for example, such organic solvents can be used as useful solvents. Suitable solvents include, for example, aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or propanolamines, for example petroleum fractions, alcohols such as butanol or glycol, ethers and esters, ketones such as acetone, methyl ethyl ketone, methylisobutylketone, cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, as well as water. Liquefied gaseous vapors or carrier substances means those liquids that are behind. normal temperature and normal gaseous pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers include: natural stone flours such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or non-cast iron, and synthetic stone flours such as highly disperse silicic acid, alumina and silicates. The solid and fractionated natural stone materials, such as limestone, marble, pumice, sepiolite and dolomite, are suitable for the preparation of granules, as well as synthetic granules of organic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Emulsifiers and / or foaming agents include non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene ethers of fatty alcohols, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates, and as dispersants, for example lignin, sulfite waste liquors, and methylcellulose.

The compositions of the invention may contain adhesives such as carboxymethyl cellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. In addition, the compositions may contain coloring agents such as organic pigments, for example ferric oxide, titanium dioxide and ferricyanide blue, and organic dyes such as alizarin dyes and metal azo-phthalocyanine dyestuffs as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of the active ingredient. The active compounds according to the invention can be included in the compositions of the present invention in admixture with other active ingredients, such as fungicides, insecticides, acaricides, nematocides, herbicides, avian pests, growth promoters, nutrients for plants and soil soil improvers. The active compounds according to the invention may be applied as such, in the form of concentrates or by further dilution of the prepared dosage forms, such as directly applicable solutions, emulsions, suspensions, powders, pastes and granulates. The application is carried out in a conventional manner, for example by dressing, by spraying, dusting, scrubbing, dry, wet, wet or slurrying or incrustation. When using the active substances as foliar fungicides, their concentrations of the formulations may vary over a wide range. These concentrations are generally 0.1 to 0.00001% by weight, preferably 0.05 to 0.0001% by weight. In seed treatment, it is generally desirable to use each kilogram of seed from 0.001 to 50 g, preferably from 0.01 to 10 g of active ingredient. For soil treatment, 1 to 1000 g, preferably 10 to 200 g, of active substance should be used per m3 of soil.

The versatility of the disclosed compounds is illustrated by the following examples.

Example A

Protective test for apple scab (Fusicladium)

Solvent: 4.7 parts by weight of acetone.

Emulsifier: 0.3 parts by weight of alkylene aryl polyglycol ether.

Water: 95 parts by weight.

The amount of active compound required to achieve the desired active substance spray concentration is mixed with the amount of water that contains the above-mentioned additives.

Spraying is sprayed until grinding with the apple tree seedlings in stage 4 to 6 leaves. The plants are kept for 24 hours at 20 ° C and atmospheric humidity 70, and then inoculated with Fusicladium den- driticum sponge water suspension and incubated 18 hours in a humid chamber at 18 to 20 ° C and 100 % relative humidity.

The plants are then transferred to the greenhouse for 14 days. 15 days after inoculation, sedation is detected. The values ​​obtained are recalculated by nanowires in%. 0% means no attack, 100% is a complete attack on plants. In this test, for example, the following compounds exhibit a very good effect, which clearly outweighs the effect of the compounds of the prior art: compounds according to examples illustrating the production of active substances 1, 2, 8, 16 and 17.

ExampleB

Bean cut test (Uromyces phaseolt), 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. 204043 11 12

The amount of active compound required to achieve the desired active compound concentration by spraying is mixed with the specified amount of solvent and the concentrate is diluted with the stated amount of water containing the aforementioned additives.

By liquid spraying, young bean plants are sprayed in the stale leaves until they are sprayed. The treated plants are kept for 24 hours in the greenhouse at 20-22 ° C and 70% relative humidity, then inoculated with Uromyces pha-seoli aqueous uredospor suspension and incubated for 24 hours in a dark, humid chamber at a temperature of 20 to 22 ° C and 100% relative humidity.

The plants are then kept in the greenhouse for 9 days under intensive illumination at 20-22 ° C and 70-80% humidity. 10 days after inoculation, the infestation of the plants is determined. The values ​​obtained are converted to% of the attack. 0% means no attack and 100 o / o means complete attack on plants. In this test, for example, the following compounds exhibit a very good effect which clearly outweighs the effect of the compounds known in the art:

compounds according to examples illustrating the preparation of active substances 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17. Example C

Phytophthora test (Phytophthora) - protective effect / tomato

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 compound required to achieve the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent and the concentrate with the diluted amount of water containing the additives.

The spraying liquid is sprayed with young plants of 2 to 4 leaf tomatoes until they are wetted. The plants are left for 24 hours at 20 ° C and 70% relative humidity for the greenhouse. The tomato plants are then inoculated with an aqueous suspension of Phytophthora infestans (Phytophthora infestans). Plants are transferred to a humid chamber where they are kept at 100% relative humidity and at a temperature of 18 to 20 ° C.

After 5 days, rape-infestation of the plants is detected and percentages are calculated from the obtained results. 0% means no attack, 100% means complete attack on plants. In this test, for example, the following compounds exhibit a very good effect which clearly outweighs the effect of the compounds known in the art: the compounds of Examples 1, 5, 8, 16 and 17. Examples illustrating the method of producing the active compounds Example 1 O-CO (1,5) of 1- (4-biphenylyloxy) -3,3-dimethyl-1- (1,2,3,4- 4-triazol-1-yl) butan-2-ol (A form) and 140 g (1.6 moles) of methoxymethyl isocyanate are heated in 2.5 liters of tetrahydrofuran in the presence of 40 ml of triethylamine and 1 ml of dibutyltin dilaurate The solvent was evaporated under vacuum and 3 liters of petroleum ether was added to the residue. The resulting crystalline precipitate is stirred with 1.5 l of diisopropyl ether. There is obtained 528 g (82.5% of theory) of 1- (4-biphenylyloxy) -3,3-dimethyl-2-methoxymethylcarbamoyloxy-1- (1,2,4- form) with a melting point of 95 to 98 ° C.

Analogously, the compounds listed in Table 1 were obtained. 204043 TABLE 1 O-CO-NHR4-Q-O-CH-CH-C (CH3)

Az

A 33 Example number

Xn

4-CO-OC2 H5 164-166 (B-form) 3-CO-OCHs 184-185 (B-form) ) 5 - (CH 2) 2 -C 1 103-105 (A-form) 6 -CO-OCH 3 103-105 (A-form) (CH2) 2 -CH (CH3) 2-CH3 141-144 (B-form) 9-4- form) 10 C (CH3) 3 109-115 (B-form) 11 4- [194-200] h-ch-cooch3 Cf 12 12 4- 193-206 14 4-ol 148-155 och3 15 4-C1-CO-OCH3 151-154 (A-form) 16 4-C2H5-C2H5 140 (xHCl) 17 4- &gt; - (CH2) 3-O-CH3 100 (xHCl) and B-form = always one of the two possible geometric isomers