CS214842B2 - Fungicide means - Google Patents

Abstract

N-Phenylpropyl-substituted azoles of the formula <IMAGE> in which R<1> denotes an alkyl radical or halogen, R<2> denotes hydrogen, or an alkyl radical or aralkyl radical which can be substituted by halogen, m denotes the numbers 0 to 3 and X denotes CH or N, and their phytophysiologically tolerable acid addition salts and metal complexes, process for their preparation and fungicides containing them.

Description

The invention discloses novel valuable N-phenylpropyl substituted azoles, as well as their salts and metal complexes, and fungicidal compositions containing these compounds as active ingredients.

It is already known that N-phenyl-substituted morpholines, for example N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine, are used as active ingredients of fungicidal agents (cf. However, the effect of the above-mentioned substance is not sufficient.

It has now been found that the novel N-phenylpropylsubstituted azoles of formula I,

in which

R ¹ represents a methyl group or a halogen atom,

R ² represents a hydrogen atom, an alkyl group containing up to 6 carbon atoms or benzyl optionally substituted with halogen, m is an integer of 0 to 3, and

X is CH or N, and their plant-compatible acid addition salts and metal complexes have surprisingly good fungicidal activity.

(R ¹ ) _m means, for example, methyl, chlorine or bromine, such as, for the special substituents on the phenyl moiety, 4-chloro, 2,4-dichloro, 2,3,4-trichloro, 3,4-dichloro, 2,4,5-trichloro, 2-chloro, 4-bromo, 2-methyl-4-chloro.

The symbol R ² represents for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, benzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl, 4-bromobenzyl.

Typical plant tolerable editorial salts of the novel phenylpropylazoles of the invention are the chlorides, bromides, iodides, fluorides, sulfates, nitrates, phosphates, acetates, citrates, oxalates, tartrates, malic acid salts, and maleate salts.

The novel phenylpropylazoles are obtained by reacting compounds of formula II,

R ^1, R ² and m have the above meanings, and

X represents a halogen atom (chlorine, bromine or iodine) or another nucleofugic group, such as OSO3R, where R is an alkyl radical, a p-methylbenzenesulfonyl group or a p-methoxybenzenesulfonyl group, reacted with 1,2,4-triazole or imidazole.

This reaction is carried out, for example, in high boiling organic solvents or in the absence of a solvent, at a temperature in the range of from 80 to 200 ° C, optionally with the addition of an acid binding agent, at normal or elevated pressure.

Suitable solvents are, for example, ethanol, methanol, acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide or N-methylpyrrolidone.

Suitable acid binding agents are, for example, sodium methoxide, sodium ethoxide, sodium hydride, sodium carbonate or potassium carbonate. An excess of the starting trlazole or imidazole may also serve as the acid binding agent.

Preferably, the reaction is carried out in the absence of a solvent or in acetonitrile or dimethylformamide, at a temperature of 80 to 160 ° C under normal pressure.

The starting materials of formula (II) above are obtained by generally known reactions in the sense of the following reaction scheme, wherein R ¹ and R ^{2 are} as defined above:

o-tn

Lx сн- »он

К ->

Raney-

soct _from рву

The following examples illustrate the preparation of the novel compounds of formula (I).

Example 1

N- (3- (4-chlorophenyl) -2-isopropylpropyl) imidazole

A mixture of 33 g of 1-bromo-3- (4-chlorophenyl) -2-isopropylpropane and 25 g of imidazole was heated at 150 ° C for 5 hours. After cooling, the reaction mixture was dissolved in chloroform, washed first with dilute aqueous sodium hydroxide solution and then with water, dried over sodium sulfate and evaporated. Distillation of the crude product gave 23.5 g of N- (3- (4-chlorophenyl) -2-isopropylpropyl) imidazole.

The product has a boiling point of 152-156 ° C / 100 Pa (active substance No. 10).

Example 2

1- (3- (4-chlorophenyl) -2-isopropylpropyl) -1,2,4-triazole

A solution of 50 g of 1-bromo-3- (4-chlorophenyl) -2-isopropylpropane and 32 g of 1,2,4-triazole in 300 ml of dimethylformamide was refluxed for 5 hours, then allowed to cool and the solvent was distilled off. in a water pump vacuum. The residue was dissolved in chloroform, washed first with dilute aqueous sodium hydroxide solution and then with water, dried over sodium sulfate and evaporated. Distillation of the crude product gave 25 g of 1- [3- (4-chlorophenyl) -2-isopropylpropyl] -1,2,4-triazole.

The product has a boiling point of 150-170 ° C / 100 Pa (active substance No. 45).

The distilled product was dissolved in ethyl acetate and concentrated nitric acid was added dropwise at 10 ° C. The crystallized product is filtered off with suction, washed with ethyl acetate and dried under vacuum at 50 ° C. 20 g of 1- [3- (4-chlorophenyl) -2-isopropylpropyl] -1,2,4-triazole nitrate are obtained (active substance No 46).

Example 3

N- [3- (4-bromophenyl) propyl] imidazole

A mixture of 3- (4-bromophenyl) -1-chloropropane (70 g) and imidazole (61 g) was heated at 150 ° C for 5 hours. After cooling, the reaction mixture was dissolved in chloroform, washed first with dilute aqueous sodium hydroxide solution and then with water, dried over sodium sulfate and evaporated. Distillation of the crude product gave 50 g of N- [3- (4-bromophenyl) propyllimidazole, b.p. 176 ° C / 200 Pa (active ingredient no. 4).

Example 4

1- (3- (2,4-dichlorophenyl) propyl] -1,2,4-triazole-1/2 CuCl 2

A solution of 46 g of 1- [3- (2,4-dichlorophenyl) propyl] -1,2,4-triazole and 26.4 g of copper (II) chloride dihydrate in 300 ml of ethanol was heated to reflux for 10 minutes. The reaction mixture was allowed to cool and 500 ml of water were added thereto to precipitate an oily product which was decanted off and triturated with ether to crystallize the desired copper complex.

30 g of light green crystals of melting point 132 DEG C. (decomposition) are obtained.

The following active substances are obtained in an analogous manner:

Effective (R ¹ ) ™ R ² X Y Boiling point Melting point substance no. (° C / Pa) (° C) 1 4-Br H N N03 132 (decomposition) 2 4-Br H CH 176/200 3 4-Cl n-propyl N Nose 130 4 4-Cl n-butyl N N03 116 5 4-Cl n-hexyl N 170/100 6 4-Cl isopropyl CH 152–156 / 100 7 4-Cl n-propyl CH 171–176 / 100 8 2,4-Cl СНз N N03 142 9 2,4-Cl СНз N 160-170 / 100 10 2,4-Cl isopropyl CH 160/100 11 2,4-Cl isopropyl N N03 130 12 2,4-Cl isopropyl N 164-170 / 200 13 2,4-Cl n-propyl N N03 100 ALIGN! 14 2,4-Cl n-propyl N 170–173 / 300 15 Dec 2,4-Cl n-propyl CH 176-180 / 200 16 2,4-Cl n-butyl N N03 106 17 2,4-Cl n-butyl N oil 18 2,4-Cl n-butyl CH 200—204 / 200 19 Dec 2,4-Cl n-pentyl N N03 109 20 May 2,4-Cl n-pentyl N oil 21 2,4-Cl benzyl N N03 130 (decomposition) 22nd 3,4-Cl n-butyl N N03 23 2,4,5-Cl H N N03 140 24 - n-butyl N 130-140 / 100 25 - n-butyl N N03 78 26 4-Cl isopropyl N 150-170 / 100 27 Mar: 2,3,4-Cl n-butyl N 212–219 / 200 28 2,3,4-Cl n-butyl N N03 122 29 2,4-Cl n-propyl N Cu-complex 132 30 2,4-Cl isopropyl N Cu-complex 120

The novel compounds according to the invention and their salts and metal complex compounds are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. The disclosed compounds are partially systemically active and can be used as foliar and soil fungicides. Furthermore, they can also be used to protect materials (for example, wood).

Of particular interest is the applicability of fungicidally active compounds to combat numerous fungi on various crop plants or their seeds, such as, in particular, wheat, rye, barley, oats, rice, corn, cotton, soy, coffee, sugarcane, fruit and ornamental plants in garden architecture as well as vegetables such as cucumbers, beans, beans and tuna.

The novel compounds described are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) on cereals,

Erysiphe cichoracearum (Powdery mildew) on cucurbits,

Podosphaera leucotricha (apple powdery mildew) on apple trees,

Uncinula necator (powdery mildew) on grapevine,

Erysiphe polygoni (powdery mildew) on beans and beans,

Sphaerotheca pannosa on powdery mildew, Puccinia on rust, Rhizoctonia, solani on cotton, Helminthosporium on helium, Ustilago on cereals and sugar cane,

Rhynchosporium secale (rhynchosporia) on cereals,

Venturia inaequalis (apple scab).

The compounds of the invention are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. The application is carried out before or after infection of the plants or seeds by the fungus.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms depend entirely on the intended use, but in any case are intended to ensure a fine and uniform distribution of the active ingredient. These compositions are prepared in a manner known per se, for example by mixing the active ingredient with solvents and / or carriers, optionally with emulsifiers and dispersants, whereby organic solvents can also be used as co-solvents when water is used as a diluent. Suitable carriers and auxiliaries are, in particular, solvents: aromatics (e.g. xylene or benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol or butanol), amines (e.g. ethanolamine), dimethylformamide and water; carriers such as natural stone meal (for example kaolins, alumina, talc or chalk) and synthetic stone meal (for example highly disperse silicic acid or silicates); emulsifiers such as non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to about 95-mass / ₀ active compound, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the type of effect desired, the active substance consumption is between 0.1 and 3 kg or more of active substance per hectare.

The novel active compounds can also be used for the protection of materials, inter alia for controlling wood-destroying fungi such as Coniophora puteana and Polystictus versicolor.

When active substances are used for the protection of materials, for example as fungicides for paints and plasticized polyvinyl chloride, the consumption amounts to 0.05 to 5% by weight of the active substance, based on the total weight of the preserved paint or polyvinyl chloride with a microbicidal treatment. The novel active compounds can also be used as fungicidally active components of oily formulations to protect wood against wood coloring fungi. In the present case, the application is effected by treating the wood, for example by impregnation or painting.

Concentrates; and optionally applicable compositions prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, pickling or dressing.

The following preparations are exemplified by the above compositions:

I. 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone to give a solution which is suitable for application as small droplets.

II. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per mole of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid. parts of the addition product of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

III. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol and 20 parts by weight of the addition product of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210-280 ° C and 10 parts by weight of an adduct of 40 moles ethylene oxide per mole castor oil. An aqueous dispersion containing 0.02% by weight of the active ingredient is obtained by finely distributing the solution in 100,000 parts by weight of water.

V. 20 parts by weight of the compound of Example 3 are mixed well with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from waste sulphite lyes and 60 parts by weight of powdered silica gel and milled in a hammer mill. . By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

VI. 3 parts by weight of the compound of Example 1 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

VII. 30 parts by weight of the compound of Example 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective composition with good adhesion is obtained.

VIII. 40 parts by weight of the compound of Example 3 are mixed intimately with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion. By diluting this dispersion with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of the active ingredient is prepared.

IX 20 parts of the compound of Example 1 are intimately mixed with 2 parts calcium dodecylbenzenesulfonic acid calcium, 8 parts fatty alcohol polyglycol ether, 2 parts phenol sulfonic acid, urea and formaldehyde condensation sodium salt, and 68 parts paraffinic mineral oil fraction to obtain a stable oil dispersion .

The active compounds according to the invention can be present in these compositions, together with other active substances, such as herbicides, insecticides, growth regulators and fungicides, or they can also be mixed with fertilizers and applied in this form. When mixed with fungicides, in many cases the spectrum of activity is broadened.

The following list of fungicides with which the compounds of the invention may be combined illustrates these combination possibilities in greater detail, but is not intended to limit them in any way.

Fungicides with which the compounds of the invention may be combined are, for example:

sulfur, dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate, zinc dimethyldi thiocarbamate, manganese ethylenedi-bis-dithiocarbamate, manganatosinium ethylenediamine-bis-dithiocarbamate, zinc ethylenebis-dithiocarbamate, and N, N'-polyethylene-bis- (thiocarbamoyl) disulfide.

Zinc N, N‘-propylene-N-bis-dithiocarbamate, zinc ammoniacal complex of N, N pr-propylene-bis-dithiocarbamate and N, N‘-propylene-bis- (thiocarbamoyl) disulfide; nitro derivatives, such as dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate,

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate;

heterocyclic compounds such as N-trichloromethylthio-tetrahydrophthalimide, N- (1,1,2,2-tetrachloroethylthio} tetrahydrophthalimide,

N-trichloromethylthiophthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine,

O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,

2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio [4,5-b] quinoxaline, 1-butylcarbamoyl-2-benzimidazolecarbamic acid methyl ester,

2-methoxycarbonylaminobenzimidazole, 2-thiocyanatomethylthiobenzthiazole,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxyquinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

2- (2-furyl) benzimidazole, piperazine-1,4-diylbis [1- (2,2,2-trichloroethyl) formamide],

2- (4-thiazolyl) benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) pyridine methanol,

1,2-bis (3-ethoxycarbonyl-2-thloureido) benzene,

1,2-bis (3-methoxycarbonyl-2-thioureido) benzene;

and various other substances such as dodecylguanidine acetate,

3- (3- (3,5-Dimethyl-2-hydroxycyclohexyl) -

-2-hydroxyethyl] glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N ‘, N‘-dlmethyl-N-phenyldiamide sulfuric acid,

2,5-dimethylfuran-3-carboxanilide, cyclohexylamide 2,5-dimethylfuran-

-3-carboxylic acids, 2-cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) acetamide, 2-methylbenzoic acid anilide, 2-iodobenzoic anilide, 1- (3,4-dichloroanilino] -1-formylamino-2, 2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

D, L-methyl-N- (2,6-dimethylphenyl) -N-2-furoylalaninate, D, LN- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, 5-nitroisophthalic acid diisopropyl ester acid, 1- (1 ', 2', 4'-triazol-1'-yl) -1- (4'-chlorophenoxy-3,3-dimethylbutan-2-one),

1- (1‘, 2 2, 4‘-triazol-1--yl) -1- (4‘-chlorophenoxy) -3,3-dimethylbutan-2-ol,

N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,

N- (n-Propyl) -N- (2,4,6-trichlorophenoxyethyl) -N‘-imidazolylurea.

The following examples illustrate the biological activity of the novel compounds of the invention. N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-di-methylmorpholine (active ingredient A), known from DOS No. 26 56 747, is used as reference.

Example A

Activity against powdery mildew Erysiphe graminis var. tritlci

The leaves of potato sprouts of wheat (Jubilar species) are sprayed with aqueous emulsions containing 80% by weight of the active ingredient and 20% emulsifier in the dry matter and, after drying of the spray coating, are dusted with spores (oidiemi) of Erysiphe graminis var. tritici (powdery mildew). The plants are then kept in a greenhouse at 20-22 DEG C. and at 75 to 80 ° / ₀ relative humidity. After 10 days, the extent of the mildew infestation is evaluated.

The results are summarized in the following table, with values from 0 to 5, where 0 means no fungus occurrence and 5 represents complete fungal attack.

TABLE

Active substance number

Infestation of leaves after spraying with active substance concentration (%)

0.025 0.012 0.006

2 0 0 5 0 0 7 0 0 13 0 0 16 0 0 17 0 1 18 0 0 19 Dec 0 0 20 May 0 0 22nd 0 0 23 0 0 24 0 0 25 0 0 control 5 (untreated)

2—3

Example В

Efficacy against Puccinia recondita

Leaves of wheat plants grown in the greenhouse are artificially infected with spores of wheat rust (Puccinia recondita), the plants are kept in a water-saturated chamber at 20-25 ° C for 48 hours, then sprayed with aqueous suspensions prepared by dissolving or emulsifying the 80% tested effective ingredient and 20% of sodium ligninsulphonate in water and transferred to a greenhouse at 20 to 22 ° C and 75o / ₀ to 80% relative humidity. After 10 days, the value of attack of the plants by rust.

The results are shown in the following table, expressed on a scale of 0 to 5, where 0 means no fungal growth and 5 represents complete fungal attack.

TABLE

active substance no. infestation of leaves after spraying with active substance concentration (%) 0.025 0.012 0.006

130

160

180

190 control (untreated) 5

Example C

Activity against powdery mildew of Erysiphe cichoracearum on cucumbers

The leaves of germinant cucumber plants ('Chinensische Schlangen') grown in a greenhouse are sprayed at two leaf stage with aqueous emulsions containing 80 why in the dry matter, the active ingredient and 20% emulsifier, and after spray coating has dried on Erysiphe powdery mildew cichoracearum. The test plants are then transferred to a greenhouse where they are stored at 20-22 ° C and 70-80% relative humidity. To determine the efficacy time of the new active substances, the extent of the mildew infestation is evaluated after 21 days.

The results are summarized in the following table, expressed on a scale of 0 to 5, where 0 means no fungal growth and 5 represents complete fungal attack. The ⁺ sign indicates slight damage to the leaves.

active substance no.

A (reference substance control (untreated)

TABLE of infestation of leaves after spraying with a concentration of active substance of 0.025%.

Claims (1)

OBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and, as active ingredient, an N-phenylpropyl substituted azole of the formula I in which: R ¹ represents a methyl group or a halogen atom, R ² represents a hydrogen atom, an alkyl group containing up to 6 carbon atoms or benzyl optionally substituted with halogen, m is an integer of 0 to 3 and X is CH or N, or a plant-tolerable acid addition salt or metal complex thereof.