GB2242131A

GB2242131A - Synergistic fungicidal active compound combinations

Info

Publication number: GB2242131A
Application number: GB9105766A
Authority: GB
Inventors: Stefan Dutzmann; Heinz-Wilhelm Dehne; Hans Scheinpflug; Wolfgang Kraemer; Detlef Wollweber
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1990-03-20
Filing date: 1991-03-19
Publication date: 1991-09-25
Anticipated expiration: 2011-03-19
Also published as: GB2242131B; FR2659832A1; DE4008867A1; GB9105766D0

Abstract

The new active compound combinations of A) 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1, 2, 4-triazol-1-ol)-4-butan-2-ol (I> <IMAGE> and/or 1-4-phenyl-phenoxy)-3,3-dimethyl-1-(1, 2, 4-triazol-1-ol)-butan-2-ol (II> <IMAGE> and B) 3-cyano-4-(2-fluoro-3-chloro-phenyl)-pyrrole (III> <IMAGE> and/or 3-cyano-4-(2, 4-difluoro-3-chloro-phenyl)-pyrrole (IV> <IMAGE> and/or 3-cyano-4-(2, 3-dichloro-phenyl)-1-(N-methyl-N-fufuryl-aminomethyl)-pyrrole (V> <IMAGE> have very good fungicidal properties.

Description

A j - 1 FUNGICIDAL ACTIVE COMPOUND COMBINATIONS is 2 -->.4:> l- a l- The

present application relates to new active compound combinations consisting of the known active compounds 1-(4-chlorophenoxy)-3i3-dimethyll-(112,4-triazol-l-yl)-butan-2-ol or 1-(4-phenyl-phenoxy)-3,3-dimethyl-l(l,214-triazol-l-yl)-butan-2-ol on the one hand and, on the other hand, of cyano-pyrrole derivatives#, which are likewise known, these new active compound combinations being very suitable for combating fungi.

it is already known that 1-(4-chlorophenoxy)-3,3dimethyl-l-(1,2,4-triazoll-yl)-butan-2-ol and 1-(4phenyl-phenoxy)-3,3-dimethyl-l-(li2i4-triazol-lyl)butan-2-ol have fungicidal potency (cf. German Patent Specification 2, 324,010). The activity of these substances is good; however, when low amounts are used, it leads something to be desired in some cases.

it has furthermore already been disclosed that 3cyano-4-(2-fluoro-3chloro-phenyl)-pyrrole, 3-cyano-4(2,4-dif luoro-3-chlorophenyl)-pyrrole and 3-cyano-4-(2,3dichlorophenyl)-1-(N-methyl-Nfurfurylaminomethyl)pyrrole can be employed for combating fungi (cf. DEOS (German Published Specification) 3,737,984 and EP-OS (European Published Specification) 0.281.731). However. the action of these substances Is likewise not always satisfactory when low amounts are used.

It has now been found that the new active compound combinations of A) 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1,2,4-triazoll-yl-)-butan-2-ol of the formula 2 - OH H-C (CH3) 3 andlor (I) 1-(4-phenyl-phenoxy)-3,3-dimethyl-l-(li2,4-triazoll-yl)-butan-2-ol of the formula OH ........... 1 and r-"IN 1 1 iL J1 B) 3-cyano-4-(2-fluoro-3-chloro-phenyl)-pyrrole of the formula C 1 CN H (III) andlor 3-cyano-4-(2,4-difluoro-3-chlorophenyl) pyrrole of the formula Le A 27 255 J i i j cl N (IV) and/or 3-cyano-4-(2,3-dichloro-phenyl)-1-(N-methylN-furfuryl-aminomethyl)pyrrole of the formula &1 1 Z131 __CN cl (V) 1 ICH3 CH2-N 1. 1 1 CHe-11Q have very good fungicidal properties.

Surprisingly, the fungicidal action of the active compound combinations according to the invention is considerably higher than the sum of the actions of the individual active compounds. This means that a true synergistic effect exists which could not have been predicted, and not only a completion of action.

The active compounds contained in the active compound combinations according to the Invention have already been disclosed (cf. German Patent Specification 2,324j010, DE-OS (German Published Specification) 3.737,, 984 and EP-OS (European Published Specification) 0j281,731).

The synergistic effect Is particularly pronounced when the active compounds in the active compound combinations according to the invention are present in certain ratios by weight. However.. the ratios by weight of the is Le A 27 255 1 ---4 - active compounds in the active compound combinations can be varied within a substantial range. In general, 0.1 to 2 0 parts by weight, preferably 0. 2 to 15 parts by weight, of active compound of the formulae (III), (IV) andlor (V) are employed per part by weight of active compound of the formula (I) and/or (II).

The active compound combinations according to the invention have very good fungicidal properties and can be employed for combating phytopathogenic fungi, such as Plasmodiophoromycetest Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes. Deuteromycetes etc.

The active compound combinations according to the invention are particularly suitable for combating Botrytis species in viticulture, in soft fruit and in vegetable growing, and for combating cereal diseases such as Fusarium.

The good tolerance by plants of the active compound combinations at the concentrations required for combating plant diseases permits treatment of aboveground parts of plants, of propagation stock and seeds, and of the soil.

The active compound combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions. powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixing the active compounds. or active compound combinationsi with extenders. that is. liquid solvents, liquefied gases under pressure, andlor solid carriers. optionally with the use of surf ace-active agents that is, emulsifying agents and/or dispersing agents andlor foam-forming agents. In the case of the use of water as an extender,, organic solvents can, for Le A 27 255 - example. also be used as auxiliary solvents. As liquid solvents. there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenest chlorinated aromatics or chlorinated aliphatic hydrocarbons. such as chlorobenzenesi chloroethylenes or methylene chlorider aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions,, alcohols,, such as butanol or glycol as well as their ethers and eaters# ketones,, such as acetone,. methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone strongly polar sol- vents, such as dimethylformamide and dimethyl sulphoride,' as well as water. By liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure. for example aerosol propellantsi such as butane. propane, nitrogen and carbon dioxide. As solid carriers there are suitable:

for example ground natural minerals, such as kaoline, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals,, such as highly-disperse silica, alumina and silicates. As solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite. as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells. maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers. such as polyoxyethylene fatty acid eaters, polyoxyethylene fatty alcohol ethers. for example alkylaryl polyglycol ethers.

alkylsulphonates, alkyl sulphatesi aryleulphonates as well as albumen hydrolysis products. As dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulosei natural and synthetic polymers in the form of powders, granules Le A 27 255 or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipidst can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese. boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can be present in the formulations as a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, as well as in mixtures with fertilizers, or plant growth regulators.

The active compound combinations can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-touse solutions, emulsifiable concentrates, emulsions, suspensions. wettable powders, soluble powders and granules. They are used in the customary manner, for example by watering, spraying, atomizing. scattering, brushing on, dry dressing, moist dressing, wet dressing. slurry dressing or incrusting.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight,, preferably between 0.5 and 0. 001%.

In the treatment of seed,, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

Le A 27 252 W is For the treatment of soil, active compound concentrations of 0.00001 to 0. 1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.

The good fungicidal action of the active compound combinations according to the invention can be seen from the examples which follow. While the Individual active compounds have weak points in the fungicidal actionj the combinations have an action which exceeds a simple sum of actions.

A synergistic effect In fungicides is always present when the fungicidal action of the active compound combinations is greater than the sum of the actions of individually applied active compounds.

Example 1 Fusarium nivale test (rye)/seed treatment The active compounds are applied as agents for dry-dressing. They are prepared by extending the particular active compound, or active compound combinatio, with ground minerals to give a finely pulverulent mixture which guarantees uniform distribution on the seed surface.

For seed dressing, the infected seed and the seed-dressing agent are shaken for 3 minutes in a sealed glass flask.

2 x 100 rye grains are sown in standard soil at a depth of 1 cm and grown in the greenhouse at a temperature of about 10C and a relative atmospheric humidity of about 95% in seed boxes which are exposed to light for 15 hours per day.

The plants are assessed for snow-mould symptoms about 3 weeks after sowing.

The active compoundsi active compound concentrations and test results can be seen from the Table below.

Le A 27 255 Table 1 is Fusarium nivale test (rye)lseed treatment Active compound Amount of active compound in mglkg of seed Untreated - 0 Degree of effectiveness in % relative to the untreated control known:

OH L;m-CH-C(CH3) N ri'i 1 c 1 F- 1 N 1 1 1 N 1 H (M 3 74 74 Accordinc to the invention:

(II) (M 7,5) 2.5) Le A 27 255 - 9 Example 2 Erysiphe test (barley) 1 protective To produce a suitable preparation of active compound, in each case a sprayable, commercially available formulation of active compound is diluted with water to the desired concentration To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried onj the plants are dusted with spores of Erysiphe graminis f.sp.

hordei.

The plants are placed in a greenhouse at a temperature of about 200C and a relative atmospheric humidity of about 80%, in order to promote the develop ment of powdery mildew pustules.

Evaluation is carried out 7 days after the inocu lation.

The active compounds, active compound concen trations and results can be seen from the following table:

Le A 27 255 - Table 2 Erysiphe test (barley) 1 protective Active compound Active Degree of compound activity concen- in % rela tration tive to the in g/ha untreated control (untreated) 0 known:

is OH 1 CY-CY-O - CH-CH-C(CH3)3 100 91 1 cl CN 100 88 H (III) According to the invention:

(11) (III) (1: 1) Le A 27 255 so + 100 so - 11 Example 3

Erysiphe test (wheat) 1 protective To produce a suitable preparation of active compound, in each case a sprayable, commercially available formulation of active compound is diluted with water to the desired concentration.

To feat for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on# the is plants are dusted with spores of Erysiphe graminis f.9p. tritici.

The plants are placed in a greenhouse at a temperature of about 2CPC and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and results can be seen from the following table:

Le A 27 255 12 Table 3 5 Erysiphe test (wheat) 1 protective Active compound is Active compound concentration in g/ha Degree of activity in % relative to the untreated control (untreated) 0 known:

OH 1 -CH-CH-C(CH3)3 (II) cl 61 1 1 CN 1 N H (III) 75 75 AccordinQ to the invention:

(11) (III) (1: 1) Le A 27 255 - 12 so + 100 so Example 4

Pyrenophora teres test (barley) 1 protective.

To produce a suitable preparation of active compound$ in each case a sprayable, commercially available formulation of active compound is diluted with water to the desired concentration.

To test for protective activityp young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on# the is plants are sprayed with a conidia suspension of Pyreno phora teres.

The plants then remain in an incubation cabin at 20'DC and 100% relative atmospheric hurnidityfor 48 hours.

The plants are placed in a greenhouse at a temperature of about 2010C and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inocu lation, The active compounds, active compound concentra ions and results can be seen from the following table:

Le A 27 255 Table 4 Pyrenopora teres (barley) 1 protective Active compound is z Active compound concentration in g/ha Degree of activity in % relative to the untreated control (untreated) 0 known:

c 1 61 1 wi CN N H ( 111) OH \1 - 1 CH-CH-ukCH3)3 300 75 300 75 According to the invention:

( I) ( I I I) (1: 1) Le A 27 255 + 100 -p - is - Example 5

Erysiphe test (barley) curative To produce a suitable preparation of active compound, in each case a sprayable, commercially available formulation of active compound is diluted with water to the desired concentration.

To test for curative activity, young plants are dusted with spores of Erysiphe graminis f.sp. hordei. 48 hours after the inoculation# the plants are sprayed is with the preparation of active compound until dewmoist.

The plants are placed in a greenhouse at a temperature of about 200C and a relative atmospheric humidity of about 80%, in order to promote the develop- ment of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and results can be seen from the following table.

Le A 27255 - is - 16 - Table 5 Erysiphe test (barley) 1 curative Active compound is Active compound concentration in g/ha Degree of activity in % relative to the untreated control (untreated) 0 known:

OH 1 CH-CH-ukUM3)3 100 84 N cl 6l CN N H ( 111) 75 According to the invention:

(11) (III) (1: 1) Le A 27 255 so + 100 so - 17 Example 6

Erysiphe test (wheat) 1 curative To produce a suitable preparation of active compound, in each case a sprayable, commercially available formulation of active compound is diluted with water to the desired concentration, To test for curative activity, young plants are dusted with spores of Erysiphe graminis f.sp. tritici. 48 hours after the inoculation, the plants are sprayed with the preparation of active compound until dewmoist.

The plants are placed in a greenhouse at a temperature of about 200C and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentra tions and results can be seen from the following table.

Le A 27 255 - 18 Table 6 Erysiphe test (wheat) 1 curative Active compound is Act ive compound concentration in g/ha Degree of activity in % relative to the untreated control (untreated) 0 known:

OH 1 -CH-CH-C (CH3) 3 (II) &1 IM: 131-CN IM H (III) so 41 Accordinc to the invention:

(11) (III) (1: 1) Le A 27 255 so so - 18 + 75 4 Example 7

Cochliobolus sativus test (barley)lcurative To produce a suitable preparation of active compound, in each case a sprayables commercially available 10 formulation of active compound is diluted with water to the desired concentration, To test for curative activity, young Plants are sprayed with a conidia suspension of CochlioboIus sativus The plants then remain in an incubation cabin is at 20PC and 100% relative atmosphaeric humidity for 48 hours. The plants are then sprayed with the preparation of active compound until dew-moist.

The plants are placed in a greenhouse at a temperature of about 200C and a relative atmospheric 20 humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

s, 0 Le A 27 255 i - 20 Table 7 Cochliobolus sativus test (barley) curative Active compound is Active Degree of compound activity concen- in % relatration tive to the in g/ha untreated control (untreated) 0 known:

( 111) cl 61 1 m1 CN N H OH cl;H-CH-C (CH3) 3 300 68 300 so According to the invention:

(1) (III) (1:

Le A 27 255 - + 75

Claims

1. Fungicidal compositions, characterized in that they contain an active compound combination consisting of A) 1-(4-chlorophenoxy)-3#3-dimethyl-l-(1,,2,4-triazol- I-yl-)-butan-2-ol of the formula OH 1 cl -0-0 -CH-CH-C (CH3) 3 1 N -jl andlor 1 1 (I) -(4-phenyl-phenoxy)-3$3-dimethyl-l-(1,2,4-triazol-yl)-butan-2-ol of the formula OH 1 CH-C(CH3)3 (II) and B) 3-cyano-4-(2-fluoro-3-chloro-phenyl)-pyrrole of the formula Le A 27 255 is -:- 22 - cl 61 1 Ir CN H (III) andlor 3-cyano-4-(214-difluoro-3-chlorophenyl) pyrrole of the formula cl F-" -1 1 1 1 1 CN H (IV) andlor 3-cyano-4-(2,3-dichloro-phenyl)-1(NmethylN-furfuryl-aminomethyl)-pyrrole of the formula cl 1 N 1 1 1 1 --- N Le A 27 255 (V) j.-CH3 CH2-N '--CH2"O ' - 22 t e 2. Compositions according to Claim 1, characterized in that$ in the active compound combinations$ the ratio by weight of active compound of the formula (1) andlor (1;) to active compound of the formulae (Ill)# OV) andlor (V) is between 1:0,1 and 1:20, 3, Method of combating fungi# characterized in that active compound combinations according to Claim 1 are allowed to act on the fungi andlor their environment.

4, Use of active compound combinations according to Claim 1 for combating fungi.

51 Process for the preparation of fungicidal compo sitions, characterized in that active compound combina tions according to Claim 1 are mixed with extenders andlor surface-active substances.

6. Compositionsaccording to claim 1, as hereinbefore identified in any one of the Examples.

Le A 27 255 - 23 i )-4- Amendments to the claims have been filed as follows t 1. Fungicidal compositions, characterized in that they contain an active compound combination consisting of A) 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1,2,4-triazoll-yl-)-butan-2-ol of the formula OH 1 cl -CY-O -CH-CH-C(CH3)3 ( I) is andlor 1-(4-phenyl-phenoxy)-3,3-dimethyl-l-(1,2,4-triazol- lyl)-butan-2-ol of the formula OH 1 3) 3 and B) 3-cyano-4-(2-fluoro-3-chloro-phenyl)-pyrrole of the formula 4 Le A 27 255 -1 L is - z- - cl &1 1 1 N H (III) andlor 3-cyano-4-(294-difluoro-3chlarophonyl) pyrrole of the formula cl N 716 11 1 H (M andlor 3-cyano-4-(213-dichloro-phenyl)-1-(N-methylN-turfuryl-aminomethyl)-pyrrole of the formula cl 1 CH3 CH2-N 1 1 CH2,.Q Le A 27 255 (V) 1 1 - Z6 - in which the ratio by weight of active compound of the formula (I) andlor (II) to active compound of the formulae (III), (IV) andlor (V), in the active compound combination, is between 1:0.1 and 1:20.

2. Method of combating fungi, characterized in that active compound combinations according to Claim 1 are allowed to act on the fungi and/or their environment.

3. Use of active compound combinations according to Claim 1 for combating fungi.

4. Process for the preparation of fungicidal compositions, characterized in that active compound combinations according to Claim 1 are mixed with extenders andlor surface-active substances.

5. Compositions according to claims 1, as hereinbefore identified in any one of the Examples.

Le A 27 255 -21G_ Published 1991 at The Patent Of-,;,c. Concept House. Cardiff Road. Newport. Gwent NP9 I RH Further copies maybe obtained from Sales Branch. U 1!! 6, Nine Mile Point. C,&Ti-,..^el;nfach. Cross Keys, New-port. NPI 7HZ. Printed by Multiplex techniques ltd. St Marv Crav Kent.