DK161006B - VINYLTRIAZOL DERIVATIVES, FUNGICID CONTAINING THESE AND PROCEDURES TO COMBAT FUNGI - Google Patents

Abstract

1. Claims (for the Contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE) A ketene O,N-acetal of the general formula I see diagramm : EP0056125,P9,F3 where X is halogen, alkyl of 1 to 4 carbon atoms or phenyl, and n is an integer from 1 to 3. 1. Claims (for the Contracting State AT) A fungicide containing a ketene O,N-acetal of the general formula I see diagramm : EP0056125,P10,F2 where X is halogen, alkyl of 1 to 4 carbon atoms or phenyl, and n is an integer from 1 to 3.

Description

in

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The invention relates to novel vinyl triazole derivatives, a fungicide containing them, and a method for controlling fungi.

It is known to use 1- (21 - [2,4-dichlorophenyl] -21 -5 [2-propenyloxy] ethyl-1H-imidazole (GB-PS 1,318,590) and zinc-ethylene bisdithiocarbamate (Chemical Week, July 26, 1972, page 41) as fungicides, but their effects are unsatisfactory.

It is thus the object of the invention to provide new compounds which exhibit a better fungicidal activity than the known fungicides.

The vinyl triazole derivatives according to the invention are characterized by the characterizing part of claim 1.

Surprisingly, it has been found that the novel vinyl triazole derivatives of the invention exhibit a better fungicidal activity than the known compounds mentioned above.

It is known from DK 678/80 and US 4 182 862 compounds which also exhibit fungicidal activity. However, these known compounds differ substantially from the 20 new vinyl triazole derivatives as far as the chemical constitution is concerned.

The vinyl triazole derivatives of the invention can be prepared by decomposing a sulfonate of the general formula 2

A

(H3O3C - C - CH2,

i, '° XH

2

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wherein X and n are as defined in claim 1 and R is hydrogen, halogen, alkyl of 1 to 4 C atoms or alkoxy of 1 to 4 C atoms, and m is 1 to 3, in the presence of an

C

solvent and a catalyst, at temperatures "between 10 and 100 ° C.

The decomposition is carried out in the presence of a solvent, e.g., acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphoric acid triamide, preferably dimethylsulfoxide, and of basic catalysts such as alkali hydroxides, sulfides and carbonates, preferably C . The sulfonates of formula 2 required for the decomposition can be recovered from the corresponding metal alcohols 15 3, which can be prepared according to known processes there and described in the literature by reaction with the sulfonic acid chlorides 4.

A

? O / = Λ (H3C, 3 '?' CB ^ + C1 -? - * 20 C) _ Or 1 Χ, ΚχΝ n

Me | i Ί ~ Χη 3 4

The compounds of formula 1 may exist as E or Z isomers, depending on the arrangement of the groups at the C bonds of the double bond. Both the pure isomers and mixtures thereof are encompassed by the invention.

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Preparation Example a) Tosylate_af_1-triazyl-1-γΙ) -1- (4-chloro-ghenox®) -3 L-dimethyl-butane-g-ol 44.6 g (0.15 mol) 1- (1.2 (4-Triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethyl-butan-2-ol (as diastereomeric mixture) is dissolved in 500 ml of absolute tetrahydrofuran (THF) and mixed with stirring. at room temperature with 4.5 g of sodium hydride (about 80%) (wt%). Then stir for 6 to 8 hours at -40 ° C to 50 ° C and after cooling 28.5 g of 10 are dropped. (0.15 mol) p-toluenesulfochloride, dissolved in as little THF as possible. The mixture is stirred for an additional 5 to 6 hours at room temperature, then hydrolyzed with water, extracted several times, each time with 500 ml of methylene chloride, dried over the organic phase over sodium sulfate and the solvent is evaporated off in vacuo. The residual residue is fractionally crystallized by vinegar ester to yield 23.5 g (35% theoretical to diastereomer mixture) tosylate as diastereomer mixture, mp 155 to 157 ° C.

B) IIlirazi-triazol-1-yl ^ -1U-chlorophenoxy ^ -S ^ S-dimethyl-butane ^ l 22.4 g (0.05 mol) of the tosylate obtained is dissolved in 250 ml dimethyl sulfoxide and mixed with 30 g of sodium sulfide. The mixture is stirred at room temperature (20 ° C) for 1 hour, then the reaction mixture is mixed with 500 ml of diethyl ether, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. 11.8 g (85% theory) of very pure 1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethyl-butene-1 (E, Z) are obtained. isomer mixture) m.p. 75 to 76 ° C (Compound No. 1).

Analysis for C ^ HH g gClN ^O (277,754):

Calculated: C 60.5 - H 5.9 - Cl 12.8 - N 15.1

Found: C 60.4 - H 6.1 - Cl 12.5 - N 15.0.

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The following compounds appear in similar fashion:

ISLAND

CH-,, CH- \ X J \ / C \ \

CE <C ------ C

Ηκ '

V X

(E-isomer) n

Compound Physical Data No. X n Isomer 1 H NMR (ppm) in CDCl3

Melting point: 75-76 ° C

5 & = 1.0 (s, 9H) 5.5 (s, 1H) 7.1 (AA'BB ', 4H) 7.95 (s, 1H) 8.2 (s, 1H)

Melting point: 92.5 ° C

δ = 1.0 (s, 9H) 5.55 (s, 1H) 7.2 (ΑΑ, 'ΒΒ', 4H) 8 (s, 1H) • 8.25 (s, 1H) 4 2-Cl 1 Z Oil δ = 1.15 (s, 9H) 5.9 (s, 1H) 6.75-7.5 (m, 4H) 7.89 (s, 1H) 8.15 (s, 1H) tert. -butyl 1 E-Z mixture Oil δ = 1.0 (s, 9H) 5.5 (s, 1H) 7.1 (AA'BB ', 4H) 7.98 (s, 1H)

8.2 (s, 1H) E

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5

Compound No. X n Isomer Physical Data 5 δ = 1.15 (s, 9H) (cont.) 1.25 (s, 9H) δ 5.89 (s, 1H) 7.08 (AA'BB ', 4H) 7.9 ( s, IH)

8.1 (s, 1H) Z

6 3.5-Cl 2 E 6 = 0.95 (s, 9H) 5.55 (s, 1H) 10 6.9 (m, 3H) 7.9 (s, 1H) 8.15 (s, 1H)

Oil 15 7 2,4-Cl 2 Z δ = 1.25 (s, 9H) 5.85 (s, 1H) 6.7- 7.4 (m, 3H) 7.85 (s, 1H) 8.1 (s, 1H) 8 2 , 4-Cl 2 E Oil 20 δ = 0.95 (s, 1H) 5.3 (s, 1H) 7.1-7.3 (m, 3H) 7.9 (S, 1H) 8.25 (s, 1H) 9 9 3-CFQ 1 E δ = 1.0 (s, 9H) 0 5.5 (s, 1H) 7.2 (m, 4H) 7.9 (s, 1H) 8.15 (s, 1H) 10 4-Phenyl 1 Oil δ = 1.2 (s, 9H) 5.85 (s, 1H) 6.7-7.5 (m, 9H) 7.85 (S, 1H) 8.05 (s, 1H)

Mp 82-84 ° C

11 2,4,5-Cl 3 E δ = 0.95 (s, 9H) 5.4 (s, 1H) 7.4 (s, 1H9 7.5 (s, 1H) 7.95 (s, 1H) 8, 45 (s, 1H)

Oil 6

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12 2-phenyl in E / Z mixture δ = 1.2 (9H) 5.8 (1H) 6.7-7.9 (m, 11H) 5 13 4-phenoxy 1 E / Z mixture δ = 1.0 (9H) 5.5 (s, 1H) 6.7-7.5 (m, 9H) 8.0 (s, 1H) 8.2 (s, 1H) 15 20 25 30 35

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The new active substances have a good fungicidal effect. They are particularly suitable for the control of fungal diseases in various crop plants, eg Erysiphe graminis in cereals,

Uncinula necator in wine, Podosphaera leucotricha in apples, 5 Erysiphe cichoracearum in bananas, Phytophthora infestans in tomatoes and potatoes, Plasmopara viticola in wine and Pseudoperonospora hum.uli in hops.

Some of the active substances are systemically active on the plants attacked by fungi? the amounts used to control 10 phytopathogenic fungi are between 0.025 and 2 kg of active substance / ha of culture surface.

The new active substances are also suitable for the protection of wood against attack by wood-destroying fungi, such as Coniophora puteana, Lenzites trabea and Trametes versicolor. Depending on the nature of the desired effect, the amounts used are between 0, OD1 and 5% (wt.%), Calculated in relation to the weight of the material to be protected, however preferably between 0.01 and 3%.

The use as a fungicide is, for example, in the form of 20 directly extrudable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powdering agents, emulsifiers, granules by spraying, spraying, impregnation, mist formation, spraying or spraying. The dispensing forms are directed entirely to the uses; they must in each case ensure the finest possible distribution of the active substances.

For the preparation of direct sprayable solutions, emulsions, pastes and oil dispersions, medium to high boiling mineral oil fractions such as petroleum or diesel oil, in addition coal oils, etc., as well as vegetable or mineral origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.

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benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, e.g., methanol, ethanol, propanol, butanol, chloroform, tetrachlorocarbon, cyclohexanol, cyclohexanone, chlorobenzene, iso-phosphorone, etc., highly polar solvents, e.g. -formamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc., in consideration.

Aqueous applications can be prepared from emulsion concentrates, pastes or wettable powders (spray powders) and oil dispersions by the addition of water.

For the preparation of emulsions, pastes or oil dispersions, the substances as such or the substances dissolved in an oil or solvent can be homogenized in water by wetting, adhesive, dispersing or emulsifying agents. But concentrates may also be made up of active substance, wetting, adhesive, dispersing or emulsifying agent and optionally solvent or oil which are suitable for dilution with water.

For example, the fungicides contain 5 to 95% (weight percent) of active substance, especially between 10 and 80% of active substance.

Examples of surfactants are: alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acids, phenylsulfonic acids, alkylarylsulfonates, alkylsulfates, alkylsulfonates, alka limetal, sulfates, sulfates - and alkaline earth metal salts, sulphated hexadecanols salts, heptadecanols, octadecanols, sulphated fatty alcohol glycol ethers salts, sulphonated naphthalene and naphthalene ethylsulfene condensation products

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9 octylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkyl arylpolyether alcohols, isotridecylalcohol ether alcohol polyethylene oxide ethylene oxide condensates, ethoxylated castor oil ether and methyl cellulose.

Powders, scatters and powders can be prepared by mixing or co-grinding the active substances 10 with a solid carrier.

Granules, e.g., envelope, impregnation and homogeneous granules, can be prepared by bonding the active substances to solid carriers. Solid carriers are, for example, mineral soils, such as silicas, silicates, talc, kaolin, lime, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, milled plastics, fertilizers such as, for example, ammonium sulfate, ammonium phosphate, ammonium phosphate, urea and vegetable products such as cereal flour, wood bark, wood 20 and nut shell flour, cellulose powder and other solid carriers.

Example a

90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution suitable for use in the form of very small drops is obtained.

Example b 10 parts by weight of compound 2 are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-30 mono-ethanolamide, 2 parts by weight of calcium salt of dodecylbenzene.

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10 zenesulfonic acid and 2 parts by weight of the preparation product of 40 moles of ethylene oxide to 1 mole of castor oil.

Example c 20 parts by weight of compound 3 are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutane-ol, 5 parts by weight of the product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 5 parts by weight of the product of 40 moles of ethylene oxide. 1 mole of castor oil.

Example D 20 parts by weight of compound 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 ° C, and 10 parts by weight of the preparation product of 40 moles of ethylene oxide 15 to 1 mole of castor oil.

Example e 80 parts by weight of the active substance 1 is thoroughly mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel and ground in a hammer mill.

Example f 5 parts by weight of compound 1 is thoroughly mixed with 95 parts by weight of finely divided kaolin. In this way, a powder containing 5% by weight of the active substance is obtained.

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Example g 30% by weight of compound 1 is thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. In this way, a preparation of the active substance with good adhesiveness is obtained.

Example h 40 parts by weight of the active substance 1 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active substance.

Example in 20 parts of the active substance 1 is thoroughly mixed with 12 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol-polyglycol ether, 2 parts of sodium salt of a phenolic sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.

The fungicides in these applications may also be present with other active substances such as, for example, herbicides, insecticides, growth regulators and fungicides, or also mixed and applied together with fertilizers. By mixing with fungicides, an increase in the fungicidal spectrum of action is thereby achieved in many cases.

The following experiments explain the good fungicidal action of the active substances in comparison with known active substances.

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The following known compounds were used as comparative agents: 1 - [(2 '- (2 ", 4" -dichlorophenyl) -2' - (2 "-propenyloxy) ethyl] -5H-imidazole of the formula:

CH-N ^ N

CH 2 * = CH-CH 2 O-CH 2 (Compound A) 10

Cl 15

Zinc-ethylene bis-dithiocarbamate (Compound B) In the tables, attacks on the leaves after treatment with emulsions of active ingredient in various concentrations are indicated on a scale of 0-5, where 0 = no fungal attack and incremental to 5 = total attack.

Activity of herb seed-driven wheat seedlings of the "Jubilar" variety are sprayed with aqueous emulsions of 80% 25 (wt.%) Of active substance and 20% emulsifier (based on dry matter), and after the initial drying of the spray coating, they are sprayed with oidium (spores). wheat mildew (Erysiphe graminis var. tritici). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and at a relative humidity between 75 and 80%. After 10 days the extent of mildew development is assessed. The results are shown in the following table:

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Table 1

Fungal attack on the leaves after treatment with Nr. 0.025 wt% 0.012 wt% 0.006 wt% 5 active ingredient emulsion 2 0 12 3 0 0 0 4 0 0 0 10 5 2 2 2 A 2 3 4 Untreated 5 15 In this experiment the new compounds showed 2, 3 , 4 and 5 show a better fungicidal activity against wheat mildew, especially at lower concentrations than the known comparative agent A.

Experiment 2

Activity against Erysiphe cichoracearum; cucumbers

Leaves of cucumber-driven cucumber seedlings are sprayed with aqueous emulsions of 80% active substance and 20% emulsifier (based on dry matter) and are sprayed after the initial drying of the spray coating with oidia (spores) of cucumber mildew (Erysiphe cichoracearum). The test plants are then set up in greenhouses at temperatures between 20 and 22 ° C and at relative humidity between 75 and 80%. After 10 days, the extent of the development of mildew fungus is assessed. The result is shown in Table 2: 35 below

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Table 2

Fungal attack on the leaves after treatment with Nr. 0.025% by weight emulsion of active ingredient 5-i-3 0 4 0 5 0 A 2 10 untreated 5

In this experiment, the active substances 3, 4 and 5 showed far better fungicidal activity against Erysiphe cichoracearum 15 than the known active comparator A.

Experiment 3

Activity against Phytophthora infestans in tomatoes 20

Leaves of tomato plants of the "Professor Rudloff" variety are sprayed with aqueous suspensions containing 80% (wt.%) Of the active substance to be tested and 20% sodium lignin sulfonate, calculated in relation to dry weight. 0.012 and 0.06% syringes are used. After the initial drying of the spray coating, the leaves are infected with a zoospore slurry of the fungus Phytophthora infestans. The plants are then placed in a water vapor-saturated chamber at temperatures between 16 and 18 ° C. After 5 days, the disease has developed so strongly on the untreated but infecting control plants that you can judge the fungicidal activity of the substances, cf. the following table: 35

Table 3

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15

Fungal attack on the leaves after treatment with 0.012 wt% 0.06 wt% 5 Nr. active substance emulsion 3 1 2-3 5 1 1 B 2-3 4 10 untreated 5 In this experiment, active substances 3 and 5 showed a better fungicidal activity against Phytophthora infestans than 15 the known active comparator B.

Experiment 4

Under open-air conditions, the following compounds 20 were tested for activity against wheat dust: E / Z-Isomer mixture of compounds 7 and 8 \ of the present '' XX, invention [= ¾1 Comparative substance C (no.

38 in DE-A 2 201 063)

(H3C) 3C-C-CH

0 Well

The lightly infested wheat plants were treated once with the active substance in the pollination phase. Twenty days later, the extent of the fungal attack was assessed. In the table means: 1 = without attack or mildew killed, incrementally

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16 9 = very strong attack (60% of the leaves surface attacked).

Table 4 5

Quantity of wheat varieties used

No. [kg / ha] "Caribo" "Caribo" "Free Gold" 7 + 8 0.12 1.7 2.0 2.7 10 0.16 1.3 1.3 1.7 c 0.12 3.7 5 , 3 6.7 0.16 3.7 4.3 6.3 untreated 6.3 7.1 8.0 15

The results of three independent experiments show that, especially at low concentrations, the isomer mixture of compounds 7 and 8 has a better fungicidal effect than the known comparator C.

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Experiment 5

In an agar plate test, the following compounds were tested for activity against various woody fungi which impair the properties of the wood: .

Comparative D

tø ^ clothesjJ (connection with Xn =

35 (H3O3C-C-CH 2,4-Dichloro of EP-A

H0 1414) cXlc,

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The active substances, dissolved in acetone, were added in various amounts to a hot malt extract agar. This mixture was distributed in Petri dishes. The contents of each dish were inoculated centrally with mycelium or spores 5 of the fungi "Coniophara puteana", "Chaetomium globosum" and "Trichoderma viride" and then grown for 14 days at 25 ° C. Next, the extent of fungal growth on the agar dishes was assessed.

10 In the table: 0 = no growth 1 = strong inhibition of growth 2 = clearly detectable growth 15 3 = medium growth 4 = strong growth 5 = uninhibited growth

The results are shown in the following table: 20

Table 5

Active ingredient in Coniophora Chaetomium Trichoderma malt textile

No. puteana globosum viride funnel agar 7 + 8 1 1 1 40 ppm D 2-3 2 2-3 40 ppm 30 7 + 8 0 0 0 80 ppm

Dl 1 2 80 ppm untreated 5 5 5- 35 The results show that the isomer mixture of compounds 7 and 8 has a better fungicidal effect than comparator D.

Claims (4)

1. Vinyl triazole derivatives, characterized in that it has the general formula 1 (H3O3C1f in C = C -LO / \ H O. \\ "T7 ~ X // n wherein 15 X is halogen, C -C ^ alkyl, CF CF, phenoxy or phenyl, and n is an integer from 1 to 5. Fungicide, characterized in that it contains a vinyl triazole derivative according to claim 1. A fungicide, characterized in that it contains a solid or liquid carrier and a vinyl triazole derivative according to claim 1. Method for controlling fungi, characterized in that the fungi or articles to be protected from fungal attack are treated with a vinyl triazole derivative according to claim 1. 35