IE43954B1

IE43954B1 - Fungicidal compositions

Info

Publication number: IE43954B1
Application number: IE2237/76A
Authority: IE
Original assignee: Lilly Industries Ltd
Priority date: 1975-10-29
Filing date: 1976-10-11
Publication date: 1981-07-15
Also published as: AR215605A1; NO763677L; CA1076024A; DD126593A5; SE7612063L; DK152661B; AT353544B; CH602002A5; GR61690B; IE43954L; DE2648705C2; BG27522A3; IL50688A0; DE2648705A1; SU730269A3; BE847771A; DK152661C; GB1561634A; JPS5254029A; ZA766244B

Abstract

A fungicidal formulation which comprises:(a) a pyrimidine methanol of formula (I): (I) where X is a chlorine or fluorine radical, or a non-phytotoxic, acid-addition salt thereof;(b) a co-ingredient selected from the group consisting of dodine,captan, quaternized amine, fatty amine ethoxylates, stearamidopropyldimethyl-.beta.-hydroxyethylammonium nitrate, di-isobutyl cresoxy ethoxy ethyl dimethylbenzyl ammonium chloride, and di-or trimethyl C12-16alkyl benzyl-ammonium chlorides; associated with:(c) one or more non-phytotoxic carrier(s), useful in treating fungal infections in plants.

Description

This invention relates to methods of treating fungal infections of plants and also provides fungicidal formulations for use in such methods.

In Patent Specification No. 32255 there are described inter alia a number of pyrimidinemethanols useful in controlling fungi which attack plants.

It has now been found that two of these pyrimidinemethanols, viz. a-(2chlorophenyl)“a-(4-chlorophenyl)~5-pyrimidinemethanol (known by the generic name 'fenarimol') and a-(2-chlorophenyl)-a-(4-£luorophenyl)-5-pyriraidineniethanol (known by the generic name 'nuarimol'), are particularly active in the control of fungi which are pathogenic to fruit such as apples. Furthermore, it has surprisingly been discovered that these pyrimidinemethanols when used in conjunction with certain co-ingredients, as hereinafter specified, are particularly active against the organisms tiromyces phaseoll var. typica. Venturia inaequalis and Puccihia recondita. The combinations of the invention show a synergistic effect in the control of these organisms, i.e. the fungicidal effect of the combination is greater than the additive effect of the component, as demonstrated by utilisation of the well-known Colbyequation, see Heeds 15, 20-22 (1967). The combinations of the invention also possess value in the control of powdery mildew (Podosphaera leueotricha).

According to one aspect of the present invention there is provided a method of treating or preventing fungal infections of plants which comprises applying to the plant a fungicidal formulation which comprisesi ' (a) a pyrimidinemethaSfitez of formula (I): -2-k. where X is chlorine or fluorine, or a non-phytotoxic, acid-addition 4 39B4 salt thereof; (b) a co-ingredient selected from the group consisting of dodine, captan, cationic quartemized amine surfactants, fatty amine ethoxylates, stearamido- * -propyldimethyl-B-hydro^ethylenmonium nitrate, diisobutylcre'eoxyethoxyethyl- dimethylbenzylammonium. chloride, and di-or trimethyl C^_^g alkylbenzyl .ammonium chlorides; associated with (c) one or more non-phytotoxic carrier(s).

A preferred cationic quartemized amine surfactant is that sold as 10 Quarternary 0. Preferred fatty amine ethoxylates are polyoxyethylene(2) soya amine (sold under the trade name Mazeen S-2), polyoxyethylene(2)coco amine (sold under the trade name Mazeen C-2) and polyoxyethylene(2) mixed fatty amines (sold under the trade name Mazeen T-2). Diisobutylcresoxyethoxyethyldimethylbenzul'ammoniutn —ar- chloride can be obtained as the material sola under the · Trade Mark Hyamine 10-X. Preferred examples of di-or trimethyl C12_lg. alkylbenzylammonium chlorides are : trimethyl artmonium chloride, chloride) -sold under the trade name Hyamine 2389 - and N-C12 alkyldimethylbenzylammonium chloride .(sold under the trade name Hyamine 3500).

The above materials are all known compounds which are described in the literature, see for instance, Detergents and Emulsifiers 1975 Annual, publish*)1 by McCutcheon's Division, MC Publishing Company, U.S.A. Stearamidopropyldimethyl-p-hydroxyethylanimonium nitrate is obtainable under the trade name Catenae SN from the American Cyanamid Company. Dodine (n-dodecylguanidine) and its salts and captan[3a,4,7,7a-tetrahydro-N-(trichloromethanesulphenyl) phthalimide] are well-known fungicides which may be used to treat fungal infections of a number of food crops including apples » see for example United States Patent Specifications 2,553,770, 2,553,771, 2,553,776 and 2,867,562.

Use of dodine as the co-ingredient is presently preferred, especially in the form of its acetate. Captan is also extremely useful as the co-ingredient, especially when combined with the 'nuarimol*.

The combination of the invention will normally be applied to the crop to be treated in such a way that from 1 to 80, preferably 10 to 80, grains per l’j hectare of the - .....................................- ......—.....- -------- -.................-........... -3pyriiaidiciemethanol and from 20 to 1,200 grama^hectare of co-ingredient are applied to the area of crop. Clearly the precise amount of active ingredients applied wi1I vary within wide limits, being dependant on variables such as density of cultivation, species of Grop and virulence of the potential or existing infection to be treated, The method, of the invention is particularly useful in connection with the treatment of apple trees to prevent or lower the incidence of scab. (Venturia inaequalis). Dodine acetate is particularly effective as the co-ingredient in such a case. In such treatment the amount of pyrimidinemethanol utilised is preferably from 20 to 80 grams per hectare and the amount of co-ingredient is preferably from 400 to 1200 grams per hectare.

The pyrimidinemethanol and co-ingredient, may be applied separately or together to the apple trees and the treatments will usually be repeated at intervals of from 5 to 20 days commencing at the bud bursting stage or later and continuing up to harvest time, the actual frequency and duration of treatment being determined by the severity of the actual or expected disease.

It may also be desirable in accordance with the method of the present invention to continue treatment of the dormant trees during the winter, particularly where there has been severe infection conditions.

When the pyrimidinemethanol and co-ingredient are applied together to plants requiring treatment, this combined treatment may be accomplished by mixing the two active ingredients in the spray tank 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 aqueous formulation containing both active ingredients is novel and forms a part of this invention. Such a formulation will generally contain from 0.00005 to 0.007%, preferably 0.0005 to 0.004%, most preferably 0.001 to 0.004%, by weight of pyrimidineitethanol and fern 0.001 to 0.1%, preferably 0.001 to 0.06%, most preferably 0.03 to σ.06%, by weight of the coingredient, traces of any surfactants, inert carriers and the like, -443084 which were present in the concentrate compositions used to prepare the diluted formulation, and water to make 1007.. Preferably the diluted formulation in the case of a pyrimidinemethanol /(iodine combination will, contain from 0.001. to 0.005% by weight of the former and 0,005 to 0.05% of the latter.

Although the antifungal combinations of the invention may be applied to the plant to be treated by any conventional technique, such as by spraying, dusting, dipping or dredching, it is preferable to treat the plants by spraying the above aqueous dispersion onto the plants. In this mode of treatment, it is usually sufficient for the infected or susceptible surfaces to be thoroughly wet with the Liquid dispersion employed.

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.

In the case where the active ingredients arc separately formulated, the dodine or captan components may be used in their normal commercially available forms e.g. the dodine may be in the form of a 65% or 80% wettable powder or 207. or 25% aqueous suspension whilst the captan may be in the form of a 50% or 83% wettable powder. Similarly the pyrimidinemithaifti· 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 ingredients.

In the 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 weight ratio of -54 3 9 5 3 coingredient to pyrimidinemethanol of from 2:1 to 25:1. Where a dotline/ pyrimidinemethanol concentrate is concerned, the preferred ratio is 5:1 to 10:1,in each case the pyrimidine methanol most advantageously being present in an 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. The concentrates may be solids, usually known as Wettable powders,or aqueous suspensions. When the coingredient is other than dodine or captan, the co-formulations of the present invention are preferably in the form of emulsifiable concentrates.

Wettable powders comprise an-intimate mixture of the active ingredients, one or more inert carriers and appropriate surfactants. The inert carrier may, for example, be chosen fran the attapulgite clays, the montmorillonite clays, the diatomaceous earths, kaolins, 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. In general wettable powder fomulations contain frcm 1 to 15% by weight of pyrimidinemethanol, 10 to 75% by weight of co-ingredient and 1 to 10% by weight of(Surfactant, a typical formulation being as follows:% by weight (a) Pyrimidinemethanol χ to 15 Coingredient 10 to 75 Surfactant(s) 1 to 10 Inert carrier to 100 Aqueous suspensions comprise the active ingredients suspended or dissolved in water 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 « 6 43854 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-chlorocresol, phenyl mercuric uliraic ami formaldehyde. In general, aqueous suspensions contain iron 1 to 15% by weight pyrimidinemethanol, 10 to 75% by weight of co-lngredr ient and 0.5 to 25% by weight of surfactant(s), a typical fornnulaticn being as follows:- Pyr imid inemethanol % weicjht/volurre 1 to 15 Coingredient 10 to 75 Surfactant(s) 0.5 to 25 Thickening agent 0 to 3 Antifreezing agent 0 to 20 Preservative 0 to 1 Water to 100 -743 9½ ^following non-limitative examples will further illustrate the invention.

Examples 1 to 5 illustrate the preparation of wettable powders containing the combination of the invention.

EXAMPLE 1 7, by weight Fenarimol 6 Dodine acetate 30 Sodium alkyl succinate 2 Sodium lignin sulfonate ' 3 Silica 8 Clay to 100 EXAMPLE 2 % by weight Fenarimol 6 Dodine acetate 45 Sodium lauryl sulfate 4 Sodium lignin sulfonate 2 Kaolin to 100 EXAMPLE 3 % by weight Nuarimol 4 Dodine acetate 40 Sodiumalkyl succinate 8 Mica 5 Clay to 100 EXAMPLE 4 , ,,.

Nuarimol 3 Captan 60 Sodium lignin sulfonate 4 Sodium alkyi succinate 2 Clay to 100 EXAMPLE 5 7. by weight Fenarimol 4 Dodine acetate 35 Alkaryl polyether alcohol 3 Silica 3 China clay to 100 -843954 Wettable powders were prepared having the above compositions. In each case, the active, ingredients were milled and then blended with the specified excipients in conventional mixing equipment. The blend was then further milled in a fluid energy mill to a size range of from 1 to 10 microns and finally the mixture reblended and deaerated prior to being packaged.

Examples 6 to 8 illustrate the preparation of aqueous suspensions containing the combination of the invention.

EXAMPLE 6 Aqueous Suspensions % welght/volume Fenarimol Dodine acetate Sodium naphthalene sulfonate Sodium lauryl sulfate Gum arabic o-cblorocresol Water 0.5 to 100 EXAMPLE 7 % welght/volume 7.0 Nuarimol Dodine acetate Sodium alkyl succinate Sodium lignin sulphonate Propylene glycol Formaldehyde Water 0.2 to 100.0 :io EXAMPLE 8 Fenarimol Captan Sodium naphthalene sulfonate Sodium lignin sulfonate Ethylene glycol Phenol Water 7, weight/volume S 0.5 to 100 Aqueous suspensions containing the components listed in Examples 6 to 8 were prepared. Both active ingredients, size reduced by conventional means, if necessary, were dispersed in water containing the surfactant system, -9«3 ii *·β preservative and part of the thickening agent. The particle size of both toxicants was further reduced by liquid milling, the balance of the thickening agent added, allowed to hydrate and the product diluted to volume with water.

Examples 9 and 10 illustrate the preparation of emulsifiable concentrates containing the combination of the invention.

EXAMPLE 9 7. weight/volume - Fenarimol 2 Mazeen C-2* (co-ingredient) 20 Ethylene oxide/Propylene oxide block co-polymer (surfactant) 5 Dimethylnaphthalene (solvent) to 100 EXAMPLE 10 7, we ight/volume Nuarimol 4 Hyamine 2389* (co-ingredient) 30 Alkylaryl poiyether alcohol (surfactant) 4 2-Ethosyethanol (solvent) 10 Xylene (solvent) to 100 *· Trade name The active ingredients were added to the appropriate solvent (s) with stirring and optional heating to facilitate solubilisation of the active materials. The surfactants were then added. After solubilisation the solution was filtered to remove insoluble impurities.

EXAMPLES 11 to 17 Similar emulsifiable concentrates to that described in Example 9 were prepared by using Quaternary 0*, Catanac SN*, Mazeen S-2*, Mazeen T-2*, Hyamine 10-X*, and Hyamine 3500* as the co-ingredient.

* Trade name

Claims

CLAIMS 43854

I. A method of preparing a fungicidal formulation which comprises admixing: (a) a pyrimidinemethanol·. of formula (I): (I) where X is chlorine or fluorine, or a non-chytotoxic, acid-addition salt thereof; 5 (b) a co-ingredient selected from the group consisting of dodine,captan, cationic quartemized amine surfactants, fatty amine ethoxylates, stearamido-projyldimethyl-8-hydroxyethylanrioinium nitrate, diisobutylcresoxyethyldimethylbenzyl ammonium chloride, and cW-or trimethyl C 12 ~16 alkylbenzyl-ammonium chlorides; and 10 (c) one or more non-phytotoxic carrier(s).
2. A method according to claim 1, wherein the fungicidal formulation comprises from 5 to 90%, by weight of active ingredients.
3. A method according to claim 1 or 2, wherein the ratio of the coingredient to tha pyrimidinemethanol is from 2:1 to 25:1 by weight. 15
4. , A method according to any one of claims 1 to 3 for preparing a wettable powder which comprises admixing from 1 to 15% by weight of the pyrimidine-methanol, frcm 10 to 75% by wei^it of the coingredient, and from 1 to 10% by weight of surfactant.
5. A method according to any one of claims 1 to 3 for preparing an aqueous 20 suspension which comprises admixing frcm 1 to 15% by weight of the pyrimidlne•methanol, from 10 to 75% by weight of the coingredient and from 0.5 to 25% by wei^it of surfactant.
6. A method according to any one of claims 1 to 5 wherein the co-ingredient is dodine acetate and the pyrimidinemethanol is fenarimoi. 25
7. A fungicidal formulation whenever prepared by a method according to any one of claims 1 to 6. -1143S54
8. A fungicidal formulation which comprises: (a) a pyrimidine methanol of formula (I): where X is chlorine or fluorine, or a non-phytotoxic, acidaddition salt thereof; (b) a co-ingredient selected from the group consisting of dodine, captan, cationic quarternized amine surfactants, fatty amine ethoxylates, stearamidopropyldimethyl8-hydroxyethylammonium nitrate, disiobutylcrexoxyethoxyethyldiigethyl0 benzylammonium chloride, and di-or trimethyl C 12-16 alk 7 lbenz 7 laramotlium chlorides; associated with: (c) one or more non-phytotoxic carrier(s).
9. A fungicidal formulation as claimed in claim 8, in the form of a dilute aqueous formulation and which 5 comprises from 0.00005 to 0.007% by weight of the pyrimidinemethanol of formula (I) and from 0.001 to 0.1% by weight of the co-ingredient.
10. A fungicidal formulation as claimed in claim 9, which comprises from 0.0005% to 0.004% by weight of the ι pyrimidinemethanol and from 0,001 to 0.6% by weight of the coingredient.
11. A fungicidal formulation as claimed in claim 8, in the form of a concentrate and which comprises from 5 to 90% by weight of active ingredients. 43934
12. A fungicidal formulation as claimed in any one of claims 8 to 11, wherein the ratio of the coingredient to the pyrimidinemethanol is from 2:1 to 25:1 by weight.
13. A fungicidal formulation as claimed in claim 10 or 12 which is a wettable powder which comprises from 1 to 15% by weight of pyrimidinemethanol, from 10 to 75% by weight of coingredient and from 1 to 10% by weight of surfactant.
14. A fungicidal formulation as claimed in claim 11 or 12, which is an aqueous suspension which comprises from 1 to 15% by weight of the pyrimidinemethanol, from 10 to 75%, by weight of the co-ingredient and from 0.5 to 25% by weight of surfactant.
15. A fungicidal formulation as claimed in any one of claims 8 to 14, wherein the pyrimidinemethanol is fenarimol and the coingredient is dodine acetate.
16. A fungicidal formulation as claimed in claim 8, substantially as hereinbefore described with reference to any one of the foregoing Examples.
17. A method of treating or preventing fungal infections of plants which comprises applying to the plant a fungicidal formulation as claimed in claim 8, 9 or 10.
18. A method according to claim 17 for treating or preventing fungal infections caused by one or more organisms selected from the group consisting of Uromyces phaseoll var. typica, Venturia inaequalis and Puccinla recondita.
19. A method according to claim 17 or 18 for treating or preventing fungal infections of apples.
20. A method according to any one of claims 17 to 19 wherein the pyrimidinemethanol is fenarimol and the coingredient is dodine acetate.