GB1559820A

GB1559820A - Fungicidal compositions

Info

Publication number: GB1559820A
Application number: GB50318/75A
Authority: GB
Original assignee: Lilly Industries Ltd
Current assignee: Lilly Industries Ltd
Priority date: 1975-12-09
Filing date: 1975-12-09
Publication date: 1980-01-30
Also published as: IE44318B1; FR2357176A1; OA05505A; AT353546B; DD127276A5; ATA900776A; JPS5270025A; PL107393B1; SE430117B; AU506444B2; FR2357176B1; IT1066726B; SE7613679L; NL7613568A; IL51062A0; DE2655407A1; ZA767306B; NO764183L; AU2029576A; CH602004A5

Description

(54) IMPROVEMENTS OF FUNGICIDAL COMPOSITIONS (71) We, LILLY INDUSTRIES LIMITED, a British company of Henrietta House, Henrietta Place, London, W.l., England, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a method treating or preventing fungal infections in cultivated plants, particularly cereals, and to fungicidal formulations useful in said method.

According to a first aspect of the present invention there is provided a fungicidal formulation which comprises as active ingredients 1 - [Lss - (allyloxy) - 2,4 - dichiorophen- ethyl]imidazole, or a non-phytotoxic salt thereof, and a pyrimidine methanol of formula (I):

where X is halogen; associated with a non phytotoxic carrier therefor.

1 - [P - (Allyloxy) - 2,4 - dichiorophen- ethyl] imidazole, hereinafter abbreviated to "the imidazole", is a compound known to possess antifungal properties-see U.S. Patent Specification No. 3,658,813. The pyrimidine methanols of formula (I) are also known to possess antifungal properties - see U.K.

Patent Specification No. 1,218,623.

It has now surprisingly been discovered that combined treatment with the two active ingredients is particularly effective in controlling mildew, helminthosporium, eyespot, bunt, smut and other fungal infections of cereal crops such as barley, especially winter barley, oats and wheat. For instance, in accordance with the well-known "Colbyequation", see Weeds, 15 20-22 (1967), a synergistic effect has been demonstrated in the treatment of wheat rust. However, the combination of the invention is possibly of greatest value when used as a seed treatment, especially in connection with winter barley. In this connection it has been found that the level of protection obtained by the seed treatment of the invention compares favourably with that hitherto derivable by treatment with organomercury compounds. However, the active ingredients of the invention are far less toxic than such organomercury compounds and thus the formulations and methods of the invention provide a useful addition to the range of antifungal treatments available.

According to a second aspect of the present invention there is provided a method of treating or preventing fungal infections of plants which comprises applying to the leaves or seeds of the plant a pyrimidine methanol of formula (I) and 1 - [d - (allyloxy) - 2,4 - dichloro phenethyl] imidazole, or a non - phytotoxic salt thereof.

Preferred pyrimidine methanols of formula (I) are those in which X is fluorine or chlorine, viz. e - (2 - chtorophenyl) - ez - (4 - chloro- phenyl) - 5 - pyrimidinemethanol, also known by the generic name "fenarimol") and a (2 - chlorophenyl) - a - (4 - fluorophenyl) - 5 pyrimidinemethanol (also known by the generic name "nuarimol"). The imidazole is preferably used in the form of its free base, although non-phytotoxic salts such as the acetate, hydrochloride, nitrate or sulphate may be utilised.

The pyrimidine methanols of use in the present invention are preferably applied to cereal seeds at a rate of from 0.05 to 1.0 g/Kg, preferably 0.1 to 0.3 gK/g. The imidazole is preferably used in the cereal seed treatment aspect of the invention in amounts of from 0.01 to 0.5 g/Kg of seed, preferably 0.02 to 0.1 g/Kg of seed. In the treatment of cereal plants, the pyrimidine methanol is usually applied as a spray in amounts of from 10 to 200 g/hectare, while the imidazole may be used in amounts of from 50 to 1,000 hectare.

In the combined treatment of seeds according to the present invention, it is preferred that the ratio of pyrimidine methanol to imidazole is 20:1 to 1:5, most advantageously 15:1 to 5:1 by weight. In the case of a foliar spray, a preferred ratio of pyrimidine methanol to imidazole is from 1:20 to 1:1 by weight.

The pyrimidine methanol and the imidazole may be applied separately or together to the cereal plants or seeds and the treatments of the former will usually be repeated at intervals up to harvest time, the actual frequency and duration of treatment being determined by the severity of the actual or expected disease. Particularly - where there has been severe infection conditions it may also be desirable in accordance with the method of the present invention to treat both the cereal seeds and plants. When as mentioned above, the pyrimidine methanol and the imidazole are applied together, this combined treatment may be accomplished by mixing the two active ingredients just prior to use or more preferably the two active ingredients are formulated together in the desired proportions and this formulation is merely diluted prior to use. In either case, the diluted formulation containing both active ingredients in the amounts and ratios described above as being usable in the method of the present invention is novel and forms a part of this invention. As well as the active ingredients, such formulations generally contain traces of any surfactants and inert carriers etc, which were present in the concentrate compositions used to prepare the diluted formulation, and water to make 100%.

When the plants or seeds are treated sequentially with the pyrimidine methanol and the imidazole it is important that the active ingredients are applied within 24 hours of each other.

As stated above, the diluted formulations of the present invention may be produced by mixing the active ingredients just prior to use or by diluting a ready-prepared co-formulation of the two active ingredients. In either case, the active ingredients will usually be in the form of concentrate compositions so formulated as to be capable of ready dispersion or dilution in water. Alternatively, the concentrate compositions may be applied direct to the seeds.

In the case where the active ingredients are separately formulated, the imidazole component may be put up in the form of a wettable powder for example one containing 20% by weight of the active ingredient. Similarly the pyrimidine methanol component may be formulated for example as a 4% or 10% wettable powder or as a 5% emulsifiable concentrate. Generally however, any appropriate concentrate compositions may be used and may contain from about 1 to 90% by weight of the individual active ingredient In this case where the active ingredients are formulated together in concentrate compositions, the latter are novel and form a part of this invention. Such concentrates may contain from 5 to 90% total weight of the active ingredients, the latter preferably being present in the ratio of pyrimidine methanol to the imidazole of from 10:1 to 1:5. In the concentrates the pyrimidine methanol is most advantageously present in the amount of 1 to 15% by weight.

The concentrate compositions of the present invention normally comprise the active ingredients in the above stated amounts, one or more inert carriers and optionally one or more surfactants, thickening agents, antifreezing agents and preservatives, and in the case of formulations destined for use in seed dressing, insecticides and bird repellants. The concentrates may be solids, usually known as wettable powders, dusts or liquids which may be aqueous suspensions, solutions or emulsifiable concentrates.

Wettable powders or dusts comprise an intimate mixture of the active ingredients, one or more inert carriers and appropriate surfactants. The inert carrier may be chosen from the attapulgite clays, the montmorillonite clays, the diatomaceous earths, kaolin, micas, talcs and purified silicates. Effective surfactants may be found among the sulfonated lignins, the naphthalene sulfonates and condensed naphthalene sulfonates, the alkyl succinates, the alkylbenzene sulfonates, the alkyl sulfates and nonionic surfactants such as ethylene oxide adducts of phenol. Wettable powder formulations falling within the scope of the invention will normally comprise the following ingredients: (a) For seed dressing use % by weight Pyrimidine methanol 2 to 15 Imidazole 0.5 to 10 Surfactant(s) 2 to 10 Insecticide 0 to 30 Bird-repellent 0 to 30 Inert carrier(s) to 100 (b) For foliar spray use %byweight Pyrimidine methanol 1 to 10 Imidazole 5 to 50 Surfactant(s) 1 to 10 Inert carrier(s) to 100 Dusts falling within the scope of the invention will normally comprise the following ingredients: (c) For seed dressing use % by weight Pyrimidine methanol 2 to 15 Imidazole 0.5 to 10 Insecticide 0 to 30 Bird-repellent 0 to 30 Surfactant(s) 0 to 5 Dust-binding oil 0 to 5 Inert carrier(s) to 100 Aqueous suspensions, solution and emulsifiable concentrates comprise the active ingredients suspended or dissolved in water or suitable solvents respectively together with any desired surfactants, thickening agents, antifreezing agents or preservatives. Suitable surfactants may be chosen from those mentioned above in connection with wettable powders. Thickening agents, if used, are normally chosen from appropriate cellulose materials and natural gums whilst glycols will generally be used when an antifreezing agent is required. Preservatives may be chosen from a wide range of materials such as the various paraben antibacterials, phenol, o - chloro- cresol, phenyl mercuric nitrate and formaldehyde. Suitable solvents include alkyl substituted benzenes, o - chlorotoluene, heavy aromatic naphthalenes, glycol ethers and cyclic ketones. Typical examples of aqueous suspensions, falling within the scope of the invention are: (d) For seed dressing use % weight/volume Pyrimidine methanol 2 to 15 Imidazole 0.5 to 10 Surfactant(s) 1 to 15 Thickening agent 0 to 3 Antifreezing agent 0 to 20 Preservative 0 to 1 Water to 100.

(e) For foliar spray use % weight/volume Pyrimidine methanol 1 to 10 Imidazole 5 to 50 Surfactant(s) 1 to 15 Thickening agent 0 to 3 Antifreezing agent 0 to 20 Preservative 0 to 1 Water to 100.

Typical examples of solutions and emulsifiable concentrates are: (f) For seed dressing use % weight/volume Pyrimidine methanol 2 to 15 Imidazole 0.5 to 10 Surfactant(s) 0 to 15 Organic solvent(s) to 100.

(g) For foliar spray use % weight/volume Pyrimidine methanol 1 to 10 Imidazole 5 to 50 Surfactant(s) 1 to 15 Organic solvent(s) to 100.

Whilst the foregoing general examples will adequately demonstrate to those skilled in the art the types of concentrate compositions of use in the present invention, the following specific examples are given to further illustrate the invention but are not to be construed as limiting the invention in any way. In these examples, fenarimol is the compound a - (2- chlorophenyl) - a - (4 - chlorophenyl) - 5 pyrimidine methanol and nuarimol is the compound a - (2 - chlorophenyl) - a - (4 - fluorophenyl) - 5 - pyrimidine methanol. Examples 1 to 8 illustrate the preparation of wettable powders.

EXAMPLE 1 % by weight Nuarimol 10 midazole nitrate 2.5 Ethoxylated nonyl phenol 4 Sodium lignin sulfate 3 Silica 8 Clay 10 The active ingredients, Nuarimol and the imidazole nitrate, were milled and then blended with other ingredients in conventional mixing equipment. The blend was then milled in a fluid energy mill to a size range of from 1 to 10 microns and finally the mixture was reblended and deaerated prior to being packaged.

Similarly, the following other wettable powders were prepared: EXAMPLE 2 % by weight Fenarimol 8 Imidazole sulphate 1.25 Sodium lauryl sulfate 4 Sodium lignin sulfonate 2 Kaolin to 100.

EXAMPLE 3 % by weight Nuarimol 4 Imidazole nitrate 40 Sodium succinate 8 Mica 5 Clay to 100.

EXAMPLE 4 % by weight Fenarimol 3 Imidazole nitrate 50 Sodium lignin sulfonate 4 Sodium succinate 2 Clay to 100.

EXAMPLE 5 % by weight Fenarimol 5 Imidazole nitrate 20 Sodium lauryl sulfate 7 Silica 8 Clay to 100.

EXAMPLE 6 % by weight Nuarimol 10 Imidazole sulphate 5 Sodium alkyl succinate 3 Sodium lignin sulfate 2 Clay to 100.

EXAMPLE 7 % by weight Nuarimol 10 Imidazole base 2 Polyvinylpyrrolidone 1.5 Sodium alkyl aryl sulphonate 2.

Sodium silico aluminate 7.5 Clay to 100.

In this example, the imidazole base was impregnated onto sodium silico aluminate as a 25% concentrate before use.

EXAMPLE 8 % by weight Nuarimol 10.0 Imidazole nitrate 2.0 Polyvinylpyrrolidone 1.5 Bio Terge AS-9OF* 1.0 Silica 1.5 Permanent Red R 5.0 Clay to 100.

*Tradename of a blend of sodium C14 olefin and sodium Cl d - olefin sulphonates.

Examples 9 to 12 illustrate the preparation of aqueous suspensions of the invention EXAMPLE 9 % weight/volume Nuarirnol 10 Imidazole nitrate 50 Sodium naphthalene sulfonate 8 Sodium lauryl sulfate 4 Gum arabic 1 o - chlorocresol 0.5 Water to 100.

Both active ingredients, size reduced by conventional means, if necessary, were dispersed in water containing the surfactant system, preservative and parts of the thickening agent. The particle size of both toxicants was further reduced by liquid milling, the balance of the thickening agent added, the mixture allowed to hydrate and the product diluted to volume with water Similarly, the following other aqueous sus pensions were prepared: EXAMPLE 10 % weight/volume Fernarimal 10 Imidazole sulphate 5 Calcium dodecylbenzene sulfonate 1 Ethoxylated nonylphenol blend 8 Xanthan gum 0.2 Water to 100.

EXAMPLE 11 % weight/volume Nuarimol 10.0 Imidazole base 2.5 Sodium silico aluminate 7.5 Polyoxyethylene - polyoxy propylene glycol block co polymer 2.0 Xantham gum 0.3 Acrylic polymer 2.0 Permanent Red R 5.0 Water to 100.

EXAMPLE 12 % weight/volume Nuarimol 10.0 Imidazole sulphate 2.5 Fatty alcohol polyglycol ether 2.0 Xanthan gum 0.3 Polyvinyl pyrrolidone 2.0 Water to 100.

Examples 13 and 14 illustrate the preparation of dusts according to the invention.

EXAMPLE 13 ' by weight Nuarimol 10.0 Imidazole base 2.5 Iron oxide (red) 5.0 Sodium silico aluminate 7.5 Clay (75% < 2ss) 10.0 Mineral oil 1.5 Slate powder (50% < 10 to 100.

EXAMPLE 14 % by weight Fenarimol 10 Imidazole base 2.5 Permanent Red R 5.0 Sodium silico aluminate 7.5 Mineral oil 2.0 Talc (50% < 20,a) to 100.

The imidazole base was absorbed onto sodium silico aluminate and the combined.

material, together with pyrimidine methanol was milled to a particle size in the range of from 1 to 10 microns in a fluid energy mill.

The milled material was then blended with the other dry ingredients and the oil sprayed onto the blend.

Examples 15 and 16 illustrate the preparation of solutions of the invention.

EXAMPLE 15 % weight/volume Fenarimol 10 Imidazole base 2 Dimethylformamide 8 Xylene to 100.

EXAMPLE 16 % weight/volume Nuarimol 8 Imidazole base 2.5 Dimethylformamide 10 Xylene to 100.

The active ingredients were dissolved with stirring in the dimethylformamide in the presence of half the aromatic solvent. After dis- solution of the active ingredients the remainder of the aromatic solvent was added and the solution thus formed filtered and packaged.

Examples 17 and 18 illustrate the preparation of emulsifiable concentrates of the invention.

EXAMPLE 17 % weight/vdume Fenarimol 5 Imidazole base 10 Ethoxylated nonyl phenol 3 Calcium dodecylbenzene sulphonate 2 2 - Ethoxylethanol 20 Xylene to 100.

EXAMPLE 18 % weight/volume Nuarimol 10 Imidazole base 10 Polyoxyethylene glyceride 2.5 ester Calcium dodecylbenzene 2.5 sulphonate 2 - Methoxyethanol 25 Heavy aromatic naphtha to 100.

The active ingredients and surfactants were dissolved in the aliphatic solvents and the aromatic solvents were then added to the solution thus formed. After filtration the emulsifiable concentrate was packaged.

WHAT WE CLAIM IS:- 1. A fungicidal formulation which comprises as active ingredients 1 - [,$ - (allyloxy) - 2,4 - dichlorophenethyl]imidazole, or a nonpnytotoxic salt thereof, and a pyrimidine methanol of formula (I):

where X is halogen; associated with a nonphytotoxic carrier therefor.

2. A fungicidal formulation according to claim 1, wherein the pyrimidine methanol of formula (I) is one in which X is chlorine or fluorine.

3. A fungicidal formulation according to claim 1 or 2, wherein the ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is from 20:1 to 1:20 by weight.

4. A fungicidal formulation according to claim 3 for seed treatment and wherein the weight ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is from 20:1 to 1:5.

5. A fungicidal formulation according to claim 4, wherein said weight ratio is in the range of from 15 : 1 to5:1.

6. A fungicidal formulation according to claim 3 for use as a foliar spray and wherein the weight ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is froml:20to1:1.

7. A fungicidal formulation according to claim 1, substantially as hereinbefore described with reference to any one of the foregoing Examples 1 to 18.

8. A method of preparing a fungicidal formulation according to any one of the preceding claims, which comprises admixing the components.

9. A fungicidal formulation whenever prepared by the method of claim 8.

10. A method of treating or preventing fungal infections of plants which comprises applying to the leaves or seeds of the plant a pyrimidine methanol of formula (I), stated in claim I, and 1 - CE - (allyloxy) - 2,4 dichlorophenethyl J imidazole, or a non-phytotoxic salt thereof.

11. A method according to claim 10 wherein the pyrimidine methanol of formula (I) is one in which X is chlorine or fluorine.

12. A method according to claim 10 or 11 wherein the ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is from 20: 1 to 1: 20 by weight.

13. A method according to any one of claims 10 to 12, which comprises applying to cereal seeds the pyrimidine methanol at a rate of from 0.05 to 1.0 g/kg of seed.

14. A method according to claim 13, wherein said rate is from 0.1 to 0.3 g/kg of seed.

15. A method according to any one of claims 10 to 14, which comprises applying to cereal seeds the imidazole at a rate of from 0.01 to 0.5 g/kg of seed.

16. A method according to claim 15, wherein said rate is from 0.02 to 0.1 g/kg of seed.

17. A method according to any one of claims 10 to 12 which comprises applying to cereal plants, as a spray, from 10 to 200

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

The active ingredients were dissolved with stirring in the dimethylformamide in the presence of half the aromatic solvent. After dis- solution of the active ingredients the remainder of the aromatic solvent was added and the solution thus formed filtered and packaged.

Examples 17 and 18 illustrate the preparation of emulsifiable concentrates of the invention.

EXAMPLE 17 % weight/vdume Fenarimol 5 Imidazole base 10 Ethoxylated nonyl phenol 3 Calcium dodecylbenzene sulphonate 2

2 - Ethoxylethanol 20 Xylene to 100.

EXAMPLE 18 % weight/volume Nuarimol 10 Imidazole base 10 Polyoxyethylene glyceride 2.5 ester Calcium dodecylbenzene 2.5 sulphonate

2 - Methoxyethanol 25 Heavy aromatic naphtha to 100.

The active ingredients and surfactants were dissolved in the aliphatic solvents and the aromatic solvents were then added to the solution thus formed. After filtration the emulsifiable concentrate was packaged.

WHAT WE CLAIM IS:- 1. A fungicidal formulation which comprises as active ingredients 1 - [,$ - (allyloxy) - 2,4 - dichlorophenethyl]imidazole, or a nonpnytotoxic salt thereof, and a pyrimidine methanol of formula (I):

where X is halogen; associated with a nonphytotoxic carrier therefor.
2. A fungicidal formulation according to claim 1, wherein the pyrimidine methanol of formula (I) is one in which X is chlorine or fluorine.
3. A fungicidal formulation according to claim 1 or 2, wherein the ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is from 20:1 to 1:20 by weight.
4. A fungicidal formulation according to claim 3 for seed treatment and wherein the weight ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is from 20:1 to 1:5.
5. A fungicidal formulation according to claim 4, wherein said weight ratio is in the range of from 15 : 1 to5:1.
6. A fungicidal formulation according to claim 3 for use as a foliar spray and wherein the weight ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is froml:20to1:1.
7. A fungicidal formulation according to claim 1, substantially as hereinbefore described with reference to any one of the foregoing Examples 1 to 18.
8. A method of preparing a fungicidal formulation according to any one of the preceding claims, which comprises admixing the components.
9. A fungicidal formulation whenever prepared by the method of claim 8.
10. A method of treating or preventing fungal infections of plants which comprises applying to the leaves or seeds of the plant a pyrimidine methanol of formula (I), stated in claim I, and 1 - CE - (allyloxy) - 2,4 dichlorophenethyl J imidazole, or a non-phytotoxic salt thereof.
11. A method according to claim 10 wherein the pyrimidine methanol of formula (I) is one in which X is chlorine or fluorine.
12. A method according to claim 10 or 11 wherein the ratio of pyrimidine methanol to imidazole, or non-phytotoxic salt thereof, is from 20: 1 to 1: 20 by weight.
13. A method according to any one of claims 10 to 12, which comprises applying to cereal seeds the pyrimidine methanol at a rate of from 0.05 to 1.0 g/kg of seed.
14. A method according to claim 13, wherein said rate is from 0.1 to 0.3 g/kg of seed.
15. A method according to any one of claims 10 to 14, which comprises applying to cereal seeds the imidazole at a rate of from 0.01 to 0.5 g/kg of seed.
16. A method according to claim 15, wherein said rate is from 0.02 to 0.1 g/kg of seed.
17. A method according to any one of claims 10 to 12 which comprises applying to cereal plants, as a spray, from 10 to 200

g/hectare of the pyrimidine methanol and from 50 to 1,000 g/hectare of the imidazole.
18. A method according to claim 10, wherein a formulation, as claimed in any one of claims 1 to 7 is employed.
19. A method according to claim 10, substantially as hereinbefore described.