NO762585L - - Google Patents

Description

The invention relates to a new combination of known fungicidally active 1,2,4-triazole derivatives and the known gibberellins, which are plant growth factors, which are distinguished by the fact that, by maintaining the fungicidal effect, it is avoided by 1,2,4- triazole derivatives possible growth influence.

It is already known that 1,2,4-triazole derivatives, namely especially l-/_—1' , 2 ' , 4 '-triazolyl-(1'2~~l~aryloxyalka-

nones have an excellent fungicidal action (compare here DOS 2.2OI.O63). On the other hand, however, it is also known that triazole derivatives can be used as growth regulators, namely especially as growth inhibitors (compare here DOS 1,964,995). However, this inhibitory effect can in some cases also be undesirable and affect the applicability of triazoles as plant protection fungicides.

It has now been found that the new combination of (A) 1,2,4-triazole derivatives of formula

in which

R"*" means frenyl, which may optionally be substituted with halogen, nitro, trifluoromethyl, alkyl with up to 6 carbon atoms, alkoxy with up to 4 carbon atoms and phenyl,

R means hydrogen, alkyl with up to 4 carbon atoms or phenyl,

r<3>means alkyl with up to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, phenyl or 4-chlorophenyl and

Y means the CO group, the group

C(OH)2 or CH(OH) as well as their salts and (B) the gibberellins of formula

and optionally also (C) alkali, ammonium and alkaline earth salts of inorganic acids by maintaining the fungicidal effect have no growth effects.

It is to be regarded as surprising that the addition of gibberellins strongly cancels the growth inhibition caused by the triazole derivatives and thereby the fungicidal preparation retains its activity against phytopathogenic fungi. The effective substance combination thus means a valuable enrichment of the technique.

The 1,2,4-triazole derivatives to be used in the combination are defined by the general formula I. In this formula, halogen preferably means mono- or multiple-substituted phenyl, R<2> preferably means hydrogen and R^ preferably the tertiary butyl group , Y preferably means the carbonyl group. The preparation and properties of the compounds of formula I are known from the literature (compare e.g. DOS 2,201,063 and 2,401,715). Examples of compounds of formula I can be mentioned: 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 1-( 2,4-dichlorophenoxy)-3 >3~ dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one.

The gibberellins to be used further in the combination are denoted by formula II. As substances that preferably fall under formula II, mention should be made of gibberellin GA 3 (the so-called "Gibberellic acid"), gibberellin GA 4 and gibberellin GA 7- The gibberellins are known (compare the entries in R. Wegler, "Chemie der Pflanzenschutz- und Schådlingsbekåmpfungs-mittel ", volume 2, pages 401-412, Springer-Verlag, Berlin/Heidel-berg/New York _/<_>19707, further J.L. Andus, "Plant Growth Sub-stances", volume I, Chemistry and Physiology, Leonhard Hill , London _ l19727 and further the contribution by E. Kreuz in Archiv f. Acker- und Pflanzenbau und Bodenkunde, Berlin, 18, pages 593-604 /~19747).

The alkali and alkaline earth salts of inorganic acids which can possibly be used further are preferably nitrates, phosphates, sulphates, chlorides and carbonates of sodium, potassium, ammonium, magnesium and calcium.

The weight ratios of the components in the combination can fluctuate within relatively large areas. Generally, 10 to 10,000 parts by weight of 1,2,4-triazole derivatives of formula I, preferably 10 to 100 parts by weight of 1,2,4-triazole derivative, fall on 1 part by weight of gibberellin of formula II. Also the ratio between gibberellin with formula II and the inorganic alkali- or ammonium resp', alkaline earth salts can be varied in a large area. Usually 1 to 100, preferably 2 to 10 parts by weight of salt is used for 1 part by weight of gibberellin.

Instead of gibberellins with formula II, such substances can also be used which trigger plant physiologically equivalent effects as gibberellins; to mention here are ethylene-bis-nitrourethanes, phaseolic acid and helmintosporol.

As already mentioned, the combination according to the invention has a strong fungitoxic effect. They do not damage cultivated plants in the concentrations necessary to combat fungi and bacteria and have little warm blood toxicity.

For these reasons, they are suitable for use as a plant protection agent to combat fungi and bacteria. Fungitoxic agents in plant protection are used to combat plasmo-dioforomycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes, deuteromycetes.

The combinations according to the invention can be used against parasitic fungi and bacteria, which attack plant parts above ground or attack the plants from the ground, as well as against seed-transmissible pathogens.

The combination according to the invention can be transferred

in the usual formulations, such as solutions, emulsions, suspensions, powders, pastes, granules. These are produced in a known manner, e.g. by mixing the active substances with emollients, i.e. liquid solvents, pressurized liquefied gases and/or solid carriers, possibly using surface-active agents, i.e. emulsifiers and/or dispersants. In the case of using water as a suspending agent, it can e.g. organic solvents are also used as auxiliary solvents. As

liquid solvents are essentially: Aromatics such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; by liquefied gaseous suspending agents or carriers, such liquids are meant

which at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants, such as halogenated hydrocarbons, e.g. freon; as solid carriers: natural stone flour, such as kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic stone flour, such as highly dispersed silica, aluminum oxide and silicates; as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates; as a dispersant: e.g. lignin, sulphite liquor and methyl cellulose.

The combination according to the invention can be present in the formulations in admixture with other known active substances such as other fungicides, but also acaricides, insecticides and fertilisers'.

The formulations usually contain between 0.1 and 95% by weight of the combination according to the invention, preferably between 0.5 and 90.

The combination according to the invention can be used as such in the form of their formulations or the application forms prepared from them, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application takes place in the usual way, e.g. by pouring, spraying, showering, pre-dusting, spreading, dry pickling, wet pickling, wet pickling, sludge pickling, incrustation or pilling.

With pickling, it usually comes into use

per kg of seed material amounts from 10 mg to 10 g of the combination according to the invention, preferably 100 mg to 3 g. For soil treatment that can be carried out completely flat, strip-shaped or point-shaped, concentrations from 1 to 1000 g of the combination according to the invention are required at the site for the expected effect per

3 • . 'in

m soil, preferably 10 to 200 g per m.

The following examples explain the application possibilities.

Application examples 1 to 5-

Pickling of winter wheat.

Seed: Winter wheat, type "Jubilar".

mordant-

effectively

substance: 1-(4-chlorophenoxy)-353-dimethyl-1,2,4-(triazol-1-yl)-butan-2-one

Used

quantity: 200 mg of a 25% active substance formulation (containing 50 mg of active substance) is used on 100 g of seed material.

Test location: Veksthus.

The seed material used in the experiment is stained with the i

the table indicated mordant amounts in the usual way. The stained seed material is laid out in 20 x 20 cm plastic bowls with a depth of

5 cm to every 100 pieces per toast. The seed material is covered after laying out with a 2 cm layer of soil. The dishes are kept during the experiment at temperatures between 22 and 25°C at a humidity suitable for the culture. For each type of treatment, at least 6 repetitions were set up, i.e. 6 bowls with 100 grains and assessed. The assessment appears in the tables.

Assessment.

Example 1 shows the following:

a) With increasing gibberellic acid additions from 0.6 to 1 mg per 100 mg of seed material to the pickling powder, an increasing weakening of the inhibitory effect caused by the pickling was achieved. This is above all expressed in the initial rate of emergence and growth height of the seedlings. b) Additions of gibberellic acid in combination with potassium nitrate in a weight mixture ratio of 1:2 also worked to reduce inhibition, as a lower gibberellic acid concentration (0.6 mg per 100 g of seed) was necessary to achieve an optimal value. This fact shows that potassium nitrate manages to effectively support the action of gibberellic acid.

Assessment.

The following appears from example 2: ,.'

a) Increasing additions of gibberellic acid in combination with potassium dihydrogen phosphate in a weight mixture ratio of 1:2 to

mordant powders, compared to the gibberellic acid addition alone, also had an inhibitory effect, rather than

all at the growth height of the seedlings.

b) At a lower amount of gibberellic acid of 0.6 mg gibberellic acid per 100 g of seed stock shows a growth mixture ratio of 1:4

as beneficial, since, in addition to inhibiting the growth height, the single sprout fresh weight was also considerably reduced. This shows that potassium dihydrogen phosphate partially replaces the biochemical functions of gibberellic acid and can even be synergistically supported.

Assessment.

The following appears from example 3:

a) With increasing additions of gibberellic acid to dry pickling, the growth inhibition caused by the latter allows itself to increase

degree partially cancel, especially from 2.5 mg gibberellic acid

per 100 g seed material and upwards.

b) With wet pickling, the same tendency can be observed, however with the difference that already from 1.5 mg of gibberellic acid per 100 g of seed, a clear inhibitory-decreasing effect is visible when observing growth height and

single sprout fresh growth.

c.) With additions of mixtures of gibberellic acid and potassium nitrate in a weight ratio of 1:2 to moisture stain, a clear weakening of inhibition was observed already at lower gibberellic acid parts, which again shows a complementary resp. synergistic effect.

Assessment.

The following appears from example 4:

a) Increasing gibberellic acid.e addition to the dry and wet mordant has an inhibitory effect on the initial emergence rate, growth height of the seedling and single sprout fresh weight. b) With wet pickling, less gibberellic acid additions are needed than with dry pickling to achieve a

specific inhibition attenuation.

c) The inhibition by the mordant was significantly stronger in quartz sand than in soil. This seems to be reason

to the fact that the reduction in inhibition by the addition of gibberellic acid to the mordant in the case of seeds in the soil is less than in the case of such quartz sand.

Rating:

The following appears from example 5:

From the table it can be seen that the part in the area of around 2.5 mg potassium dihydrogen phosphate of mordant added to the mixture with 1325 and 2.5 mg gibberellic acid per 100 g of seed material reduces the inhibition of sprout growth caused by the mordant most strongly. Example 6.

Treatment of young cotton plants/growth influence.

Young cotton plants are grown in pots containing 500 cm^ of soil and mixed with an aqueous suspension of the fungicide alone or in combination with gibberellic acid (GA-^). Calculated on soil volume, the concentration specified in the table is used. Fungicidal active substance: 1-(4-chlorophenoxy)-3,3-dimethyl-1,2,4-(triazol-1-yl)-butan-2-one.

Example 7-

Barley powdery mildew sample (Erysiphe graminis var. hordei)/systemic (fungal grain sprout disease).

Application of the active substance took place as a powdered or liquid seed treatment agent. The powdered seed dressing (TB) is produced by grinding the possible active substance with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered mixture with the desired active substance concentration. The liquid seed dressing (FB) is produced by dissolving the possible active substance in a solvent mixture of glycol monoethyl ether and dimethylformamide (active substance + 15% dimethylformamide + the rest glycol monoethyl ether.

For seed treatment, barley seed is shaken with the delayed active substance in a closed glass bottle. The seed is sown with 3 x 12 grains in flower pots 2 cm deep in a mixture of one part by volume Fruhstorfer unit soil and one part by volume quartz sand. Germination and emergence take place under favorable conditions in greenhouses. 7 days after sowing, when the barley plants have unfolded their first leaf, they are pollinated with fresh spores of Erysiphe graminis var. hordei and is further cultivated at 21 to 22°C and 80 to 90% relative humidity and 16 hours of lighting. Within 6 days, the typical powdery mildew pustules form on the leaves.

The degree of attack is expressed as a percentage of the attack of untreated control plants. Thus, 0% means no attack and 100$ means the same degree of attack as in untreated controls. The active substance is all the more effective the less the mildew grip is.

Active substances, active substance concentrations in the seed treatment agent as well as the amounts used and the percentage powdery mildew attack are shown in the following table:

Assessment.

Example 7 shows:

The results show that the effect of the active substance used against barley powdery mildew is not affected by the addition of gibberellic acid to the mordant.

Example 8.

Plant f oren similar to sp-r øve / forage treatment/wheat .

The active substance was used as a powdered or liquid seed treatment agent. The powdered seed dressings (TB) are produced by grinding the possible active substance with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered mixture with the desired active substance concentration. The liquid seed dressing agents (FB) are produced by dissolving the possible active substance in a solvent mixture of glycol monoethyl ether and dimethylformamide (active substances + 15% dimethylformamide + the rest glycol monoethyl ether).

For pickling, wheat seed material is shaken with a water content of approx. 16% with the mordant in a closed glass bottle. The seed material is sown with 2 x 100 grains in seed boxes 1 cm deep in sterile quartz sand. The boxes are set up in greenhouses at a temperature of 15°C and are normally kept moist. 7 days after sowing, the number of sprouting plants is determined as a % of the seeds laid out. Compared to unstained controls, they reveal preparation-related run-up delays and possibly also run-up accelerations. The number of grown plants on the 14th day characterizes the germination capacity of the seed stock under the influence of the preparation. The average fresh weight of the single sprout can be shown by the impact on growth intensity. If these 3 individual values are clearly lower than for untreated control boxes, then there is a phytotoxic effect of the preparation.

Claims (3)

1. Fungicidal agent characterized by a content of a combination of (A) 1,2,4-triazole derivatives with the formula in which R1 means phenyl, which may optionally be substituted with halogen, nitro, trifluoromethyl, alkyl with up to 6 carbon atoms, alkoxy with up to 4 carbon atoms and phenyl, R <2> means hydrogen, alkyl with up to 4 carbon atoms or phenyl, R-^ means alkyl with up to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, phenyl or 4-chlorophenyl and Y means the CO group, the group or C(OH) 2 or CH(OH), as well as their salts and (B) gibberellins with formula and possibly also (C) alkali, ammonium and alkaline earth salts of inorganic acids. 2. Fungicidal agent according to claim 1, characterized in that in the combination the weight ratio between (A) (1,2,4-triazole derivatives) and (B) (gibberellins) is between 10:1 and 1,000:1 and the weight ratio between present salts (C) and (B) (gibberellins) between 1 : 1 and 100 : 1. 3. Use of a combination according to claim 1 or 2 for combating fungi.