CS195319B2 - Fungicide - Google Patents

Abstract

Fungicidal formulations which comprises as active ingredients an .alpha.-(2-chlorophenyl)-.alpha.-(4-halophenyl)-5-pyrimidine methanol in combination with 1-¢.beta.-(allyloxy)-2,4-dichlorophenethyl!imidazole, or a non-phytotoxic salt thereof, methods of making such formulations by admixture and methods of treating fungal infections of cereals with the novel formulations.

Description

The present invention relates to a fungicidal composition for the treatment of crop plants, in particular cereals infected with fungal infections.

The fungicidal composition according to the invention is characterized in that it contains 1- [β- (allyloxy) -2,4-dichlorophenethyl] imidazole or its plants as active ingredient. an acceptable salt and pyrimidylmethanol. of formula I

X

wherein X is a halogen atom, in the range of 20: 1 to 1:20 by weight. parts. The composition further comprises a non-toxic carrier for plants. _;

1- ['/ 3- (Allyloxy) -2,4-Uchl (orphenethyl] imidazole, hereinafter referred to as "imidazole", is a substance known to have fungicidal properties (see U.S. Pat. No. 3,658,813) ).

· '....... 2'

Also, the pyrimidinylmethanol derivatives of formula (I) are. known fungicides (see U.S. Patent No. 1218,632).

It has now surprisingly been found that combinations of both. The active ingredients are particularly effective in combating cereal anthers, wheat anthers, blemishes, barley streaks, wheat rust and others. infections of cereals, especially barley, in particular. winter, oats and. wheat. For example, synergistic. the effect was in accordance with š. the well-known COlby equation [Weeds' 15, s'tr. 20 to 22 1967)]. demonstrated in the treatment of rust. wheat. Combinations of both of these active. However, the compounds according to the invention are of particular importance. in seed dressing, especially in connection with winter barley. was. ..detected that. the degree of 'seed protection' in the manner of the invention is comparable to the 'protection achieved so far only. organomercuric derivatives. However, the active ingredients according to the invention are much less. Toxic non-organomercuric compounds and thus the compositions of the invention and the method themselves constitute a useful contribution to the methods of combating fungal infections currently used.

The method of treating and preventing infections with fungal infections consists of depositing pyrimidinylmetbanol of the formula I and 1- [1H allyloxy) -2,4-di-195319 chlorophenethyl] imidazole or its non-toxic salts on the leaves or seeds of the plants.

Preferred pyrimidinylmethanols of the formula I are those in which X represents a fluorine or chlorine atom, for example N- (2-chlorophenyl) - (2- (4-chlorophenyl) -5-pyrimidinyl) methanol (also known under the generic name "fenarimor") or α- (2-chlorophenyl) - N - (4-fluorophenyl) -5-pyrimidinylmethanol (known by the generic name "nuarimol"). Imldazole is preferably used in the form of the free base, although non-toxic salts such as acetate, hydrochloride, nitrate or sulfate can also be used.

The pyrimidinylmethanols used in the sense of the invention are preferably applied to the cereal seeds in doses of 0.05 to 1.0 g / kg, preferably in the range of 0.1 to 0.3 g / kg. Imidazole is preferably used in seed dressing according to the method of the invention in doses of from 0.01 to 0.5 g / kg of seed, preferably in the range of 0.02 to 0.1 g / kg. In the treatment of plants, pyrimidinylnylmethanol is usually applied in a spray at a rate of from 10 to 200 g / ha and imldazole can be used at a rate of from 50 to 1000 g / ha.

In the combined seed dressing method of the invention, a ratio of pyrimidinylmethanol to imidazole in the range of 20: 1 to 1: 5, preferably 15: 1 to 5: 1 parts by weight is used.

Pyrimidinylmethanol and imidazole may be applied separately or; together for both plants and cereal seeds, in the first case the application is usually repeated at certain intervals up to the time of harvest, the actual frequency and duration of these treatments depending on the extent of the actual or expected infection. In particular, when the conditions for severe infestation have been favorable, it may be desirable, in accordance with the invention, to treat both the seeds of the cereal and their plants. When, as stated above, both pyrimidinylmethanol and imldazole are applied together, a suitable composition is obtained by mixing the two active ingredients directly before use, or preferably both are formulated together in the desired ratio in advance and the composition is only diluted before use. In both cases, dilute compositions containing both active components in the amount and ratio as recited above in the method of the invention are novel and are part of the invention. Besides the active compounds and water ⁽¹ to 100%), these dilute compositions traces of surfactants, inert fillers and similar additives, which were present in the concentrated compositions before diluting. When the cereal plants or seeds are treated with separate doses of pyrimidinylmethanol and imidazole, it is important that both active ingredients are applied at intervals of less than 24 hours.

Diluted compositions of the invention may, as mentioned above, be prepared either by mixing the active ingredients directly before use, or by diluting a pre-formulated composition containing both active ingredients. In both cases, the active ingredients are usually in the form of concentrated mixtures formulated so as to ensure easy dispersion or dilution with water. Concentrated mixtures can also be used directly for seed treatment.

When formulated separately, the imidazole component may be prepared in the form of a wettable powder containing, for example, 20 weight percent of the active ingredient. Similarly, the pyrimidinyl methyl alcohol component may be formulated as, for example, 4% or 5% by weight of a compound. 10% wettable powder, not more than 5%. emulsifiable concentrate. In general, however, any suitably concentrated mixture containing 1 to 90 weight percent of the individual active agent can be used.

When the active ingredients are formulated together in concentrated mixtures, these are novel and form part of the invention. Such concentrates may contain 5 to 90% of the active ingredients (based on the total weight of the composition), wherein the ratio of pyrimidinylmethanol to imidazole may be in the range 10: 1 to 1: 5. Pyrimidinylmethanol is most preferably present in the concentrates in an amount of 1 to 15% by weight.

The concentrated compositions according to the invention usually contain the abovementioned amounts of active substances, one or more inert carriers and optionally one or more surfactants, fillers, antifreeze agents and preservatives, and if the composition is to be used for seed dressing, it may also contain insecticides and bird repellent substances. The concentrates may be solids, known as wettable powders and dusts, or liquids, which may be substantially aqueous suspensions, solutions or emulsifiable concentrates.

Wettable powders and dusts include mixtures of the active ingredients, one or more carriers, and a suitable surfactant. Atapulgite, montmorillonite, dlatomic soils, kaolins, mica, talc and purified silicates can be used as inert carriers. Active surfactants are, for example, sulfonated lignins, alkyl succinates, alkylbenzene sulfonates, but also nonionic surfactants such as phenol adduct and ethylene oxide. Wettable powders which are also included in the present invention usually contain the following components:

a] For seed dressing

Pyrimidininylmethanol

Imidazole

Surfactant (s) Insecticide

Bird repellent

Inert carrier

1 · 9 .s & is

Weight % to 15

0.5 to 10 to 100 - to 30 to 30 to 100

Weight,%

b) For spraying leaves

Pyrlmidinylmethanol 1 to 10

Imidazole 5-50

The surfactant (s) 1 to 10

Inert - carrier up to 100

The dusts according to the invention usually comprise the following components:

c) Pro. seed dressing %

Pyrimidylmethanol 2 to -15

Imidazole 7 0.5 to 10

Insecticide -. . - 0-. áž 30

Bird repellent 0 - to 30

Surfactants 0 to 5

Oil-like binder

Inert carrier up to 100

Aqueous suspensions, solutions and emulsifiable concentrates contain the active substances suspended - or - dissolved - in water or in water. in suitable solvents together with - the necessary surfactants, - thickeners, - antifreeze agents - and protective substances. Suitable surfactants may be selected from those mentioned in connection with the preparation of comminutable powders. When used, the thickening agents are usually selected from suitable surfactants; -cellulose materials and natural gums, while glycol is usually used as, frost-resistant. an additive, if desired. The preservatives can be selected from a variety of compounds such as antibacterial paraben, phenol, o-chlorocresol, nitrate; - phenylmercury and - formaldehyde. Suitable solvents include alkyl, substituted benzenes, o-chlorotoluene, naphthalene derivatives, glycol-derived ethers. and cyclic ketones. Typical examples of aqueous suspensions according to the invention are as follows:.

Percent

d) For seed dressing (w / v)

Pyrimidinylmethano-1 2 to 15 Dec Imidazole ,, 0.5 to 10 Surfactant (s) 1 to 15 Dec Thickener 0 to. - 3 Frost resistant admixture . - 0 up to - 20 May Protective substance 0 to 1 Water to 100 ALIGN!

6 ' Percent ej For spraying leaves (w / v) Pyrimidinylnylmethanol 1 to 10 Imidazole 5 to 50 Surfactant (s) 1 to 15. . Thickener 0 to 3 Frost-resistant additive. 0 to 20 Protective substance ^; . 0 to 1 Water: do -100 Typical examples of solutions and emulsifiable concentrates are: f) For seed dressing Percent (w / v) Pyrlmidinylmethanol 2 to 15 Imidazole 0.5 to 10 Surfactant (s) 0 to 15 Organic solvent (s) to 100 (g) - For - spraying of leaves Percent (w / v) Pyrimidinylmethanol 1 to 10 Imidazole 5 to 50 Surfactant (s) 1. to 15 ..... Organic solvent (s) to 100

The above general examples demonstrate the types of concentrated compositions of the invention in a manner sufficient to those skilled in the art. The following are specific examples which are intended to illustrate the invention in greater detail, but are not to be construed as limiting the scope of the invention in any way. In these examples, - the name fenarlmol - is used. N- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine. nylmethanol - and nuarimol instead of (N- (4-chlorothenyl) -α-4-fluorophenyl) -S-pyrimidinylmethanol. - '.

Examples 1 to 8 illustrate the production of wettable powders. ·

Ex - k - 1 - and d - - 1

Weight percent

Nuarimol ... 10 Imidazole nitrate '  2.5 Ethoxylated nonylphenol 4 Sodium lignin sulphonate 3 Silica gel 8 Hlinka - -. . - 10

The active substances, nuarimol and imidazole nitrate are ground and mixed with the other ingredients of the mixture in a conventional mixer. Similarly, the other wettable powders are prepared:

5 319

Example 2 Weight percent Example Nuarímol Weight. percent 10.0 Fenarimol 8 Lmidazole nitrate 2,0 Lmidazole sulphate 1,25 Polyvlnylpyrrolidone . 1.5 Sodium lauryl sulfate .4 Bio Terge AS-90F 1.0 Sodium lignin sulphonate 2 Sillkagel 1.5 Kaolin to 100 Permanent red R 5.0 Hlinka to 100 Example3. . *) Trademark of a mixture of Ci4- and Cie-olefin- Weight - «- sodium sulphonates. Examples 9 to 12 percent production of aqueous suspensions according to the invention. lezu. Naurimol 40 Imldazole nitrate 40 Example 1 a d 9 Sodium succinate 8 Percent Mica 5 (weight / Hlinka to 100 /volume) Example 4 Nuarímol 10 Weight Imldazole nitrate 50 percent Sodium naphthalenesulfonate 8 Sodium lauryl sulfate 4 Fenarimol 3. Arabic gum Ι- Imldazole nitrate 50 o-Chlorocresol 5, 5 Sodium lignin sulphonate. . 4 Water to 100 Sodium succinate 2 Hlinka to 100 Both active substances were if necessary

ground in conventional ways and then were

Example 5 dispersed in water containing the topcoat active ingredient, protective substances and part of Weight hušťovadla. Part size active substances percent was further reduced by grinding of this suspension, The lever has added the rest of the thickener, the mixture is Fenarimol. 5 let it hydrate and finally dilute the water Lmidazole nitrate 20 May dou. Sodium lauryl sulfate 7 ·. Similarly, other aqueous dry- Sillkagel 8 pension: Hlinka to 100 Example 10 ... ·. ·. · Example 6 · '·, · - ·; Percent (w / w) Weight /volume) percent Fenarimol Imidazole sulphate 10 Nuarímol 10 Dodecylbenzenesulfonate 5 Imldazole sulphate 5 Calcium Sodium alkyl succinate 3 Mixture of ethoxylated 1 Sodium lignin sulphonate 2 nonylphenols 8 Hlinka to 100 Xanthan gum 0.2 Water to 100 Example 7 Weight Example 11 percent Percent Nuarímol 10 .. (w / w) /volume) Imidazole 2 Nuarímol Polyvinylpyrrolldone 1.5 Imidazole 10.0 Sodium alkylarylsulfonate 2 Sodium silicate 2.5 Sodium silicate 7.5 Polyoxyethylene-polyoxypro- 7.5 Hlinka to 100 pylene copolymer 2,0 Xanthan gum 0.3 In this example, the silicate was first Polyacrylate 2,0 Sodium yellow impregnated with free imidazo- Permanent red R 5.0 (in 25% solution). Water to 100

Example I a d 12 Example 1 a d 16

Percent (w / v)

Percent . (w / v)

Nůarimol 10, Imidazole sulphate 2.5 Polyglycol et fatty alcohol 2,0 Xanthan gum 0.3 Polyvinylpyrrolidone 2,0 Water to 100

Examples 13 and 14 illustrate the production of dusts according to the invention:

Example 13

Weight. percent of Narimol8

Imidazole2,5

Dimethylformamide 10

Xylene. '. to 100

The active substances are dissolved with stirring in dlmethylformamide and half the volume of aromatic solvent. After dissolution of the solids, the remainder of the aromatic solvent is added and the solution thus formed is filtered and filled.

Examples 17 and 18 illustrate the preparation of emulsifiable concentrates according to the invention:

Example 17

Nůarimol10,0

Imidazole

Iron oxide5,0

Sodium aluminum silicate7,5

Clay (75%, particle size below 2 nm) 10.0

Mineral oil1,5

Slate meal (50%, grain size below 10 nm) up to 100

Example 14

Weight percent

Percent (w / v)

Fenarimol 5Imidazole10

Ethoxylated nonylphenol3

Calcium dodecylbenzenesulfonate2

2-Ethoxyethanol20

Xylene do100

Example 18

Fenarimol10

Imidazole2,5

Permanent red R5,0

Sodium aluminum silicate. 7.5 Mineral oil2.0

Talc (50 ° / o, particle size at nm) to 100

The free imidazole is absorbed on .... Sodium aluminum silicate and this material is then milled with pyrimidinylmethanol to a particle size in the range of 1 to 10 nm. The mixture is mixed with other dry ingredients and finally with oil .............

Examples 15 and 16 illustrate the production of solutions according to the invention:

Percent

- · weight / volume)

Nůarimol10

Imidazole 10

Polyoxyethylene glyceride2,5

Dodecylbenzenesulfonate

Calcium2,5

2-Methoxyethanol25

Heavy aromatic diesel up to 100. The active substances and surfactants are dissolved in aliphatic solvents, and aromatic solvents are added to the solution thus formed. After emulsification, this emulsifiable concentrate is adjusted. ,

Example 15

Percent (w / v) Fenarimol 10 Imidazole 2 Dimethylformamide 8 Xylene to 100

The unexpected effects of the combination of the invention in combating pathogenic fungi on plants have been demonstrated by greenhouse testing. In one such assay, imazoilil and α- (2-chlorophenyl) -α- (4-fluorophenyl) -5-pyrimidinemethanol were tested alone and in combination against wheat rust. The monon wheat seed was sown in round pots of 6.2 x 5.8 cm containing greenhouse soil and covered with sand. Eight days after sowing, the wheat plants were sprayed with everyone

191319 with a single solution, and the plants were allowed to dry. The test plants were inoculated with a suspension of wheat spores (Puccinia recondita ' tritici) and. the plants were incubated in a cold humid chamber for 40 hours. The plants were then transferred to a greenhouse and observed 9 days after. inoculation with respect to disease symptoms. Treated plants were compared to untreated control plants and the percentage of disease recorded. Test solutions were prepared by dissolving 70 milligrams of test compound in 2 ml of a mixture prepared from 500 ml acetone, 500 ml ethanol and 100 ml Tween 20 and diluting with deionized water to the desired concentration.

Tween 20 is polyoxyethylene sorbitan monolaurate.

The results of this experiment are summarized in Table I below.

Table 1

Checking rust of wheat

Percentage of disease incidence

Compound Dose ppm Group 1 Group 2 Diameter disease control CFPM 10 45 45 45 25 20 May 30 40 35 42 40 15 Dec 15 Dec 15 Dec 75 Imazolll 100 ALIGN! 50 50 50 17 200 40 35 37.5 17.5 37 400 20 May 15 Dec . 72 CFPM + Imazolil 10 - 100 30 30 30 50 10-- 200 20 May 20 May 20 May 67 -4- 400 5 5  5 92 20-J-100 15 Dec 20 May 17.5 72 20-- 200 2 5 3.5 94 20-b 400 0 1 0.5 99 40 -.100 25 5 15 Dec . 75 40 + 200 5 5 5 92 401 · 400 0 1 0.5 99 Comparison, 1% ethanol / / acetone 4 * 0.1 -% Tween 20 60 50 55 8 Comparison, untreated 60 60 60 0

The above experiment was repeated except that the treatments were not repeated. The results are summarized in Table 2.

Table 2

Control - rust 'wheat

Compound Dose ppm Percentage of disease incidence Percentage of disease control CFPM ' 10 50 17 20 May 25 58 40 25 58 Imazolil 100 ALIGN! 50 17 200 10 83 400 10 83 CFPM + - - Imazolil 10 - - 100 15 Dec 75 10 - - 200 15 Dec 75 10 - - 400 5 92 20 - r 100 25 58 20 - - 200 15 Dec 75 20 - - 400 2 97 40 - - 100 15 Dec 75 40 - - -200 10 83 40- - 400 5 92 Comparison, 1%. ethanol / / acetone - f - - 0.1 -% Tween 60 0 Comparison - not saved · 60 0

Claims (2)

BACKGROUND OF THE INVENTION A fungicidal composition, characterized in that it contains, as active substances, 1 - [[3- (allyloxy) -2,4-dichlorophenethyl] imidazole or its non-toxic salt for plants and pyrimidinylmethanol of the formula I Wherein X is a halogen atom in admixture with a carrier which is nontoxic to plants, wherein the ratio of pyrimidinylmethanol to imidazole or its nontoxic salt plants is in the range of 20: 1 to 1:20 parts by weight. 2. A fungicidal composition as claimed in claim 1, which comprises pyrimidinylmethanol of the formula I in which X represents a chlorine or fluorine atom.