CA1076024A

CA1076024A - Fungicidal compositions

Info

Publication number: CA1076024A
Application number: CA263,290A
Authority: CA
Inventors: Leonardo Calvani
Original assignee: Lilly Industries Ltd
Current assignee: Lilly Industries Ltd
Priority date: 1975-10-29
Filing date: 1976-10-13
Publication date: 1980-04-22
Also published as: AR215605A1; JPS5254029A; DE2648705C2; BE847771A; SE7612063L; DK152661C; AT353544B; NL188139C; DE2648705A1; IE43954L; ZA766244B; IL50688A; DK152661B; JPS6117803B2; SU730269A3; BG27522A3; PL106521B1; CH602002A5; GR61690B; NZ182331A

Abstract

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

1076024 ~ ' This invention relates to methods of treating fungal infections of plants and also provides fungicidal formulations for use in such methods.
In United Kingdom Patent Specification No. 1,218,632 there are described _ter alia a number of pyrimidinemethanols useful in controlling i fungi which attack plants.
It has now been found that two of these pyrimidinemethanols, viz. a-(2-chlorophenyl)-~-~4-chlorophenyl)-5-pyrimidinemethanol (known by the generic na~e 'fenarimol') and a-(2-chlorophenyl)--(4-fluorophenyl)-5-pyrimidinemeth- t anol (known by the generic name 'nuarimol'), are particularly active in the LO 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 Uromyces phaseoli var. _yP-ca, Venturia inaequalis and Puccinia recondita. The combinationsof the invention ¦ show a synergistic effect in the control of these organisms, i.e. the fungicidal effect of the combination is greate. than the additive effect of ¦ the components, as demonstrated by utilisation of the well-known "Colby-¦ equation," see ~eeds 15, 20-22 (1967). The combinations of the invention ¦ also possess value in the control of powdery mildew (Podosphaera leucotricha).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 comprises: -¦
(a) a ~imidine ~ethanol of formula (I):

Cl Oh N ~ N
~i, \/ ~

~) l -2-10761)24 where g is a chlorine or fluorine radical, or a nan-phytotoxic, acid-addition salt thereof;
(b) a co-ingredient selected from the group consisting of dodine, captan, quaternized amine, fatty amine ethoxylates, stearamidopropyldimethyl- ~ -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).
According to another aspect of the present invention there is provided a fungicidal formulation which comprises:

(a) a pyrimidine methanol of formula (I):

; ~ I ~ X (I) N
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-~-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).

, 107~024 A preferred quaternized amine is that sold under the trade mark "Quaternary 0". Preferred fatty amine ethoxylates are polyoxyethylene(2) soya amine (sold under the trade mark '~azeen S-2"), polyoxyethylene (2)coco amine (sold under the trade mark '~azeen C-2") and polyoxyethylenet2) mixed fatty amines (sold under the trade mark 't~lazeen T-2"). Di-isobutyl cresoxy ethoxy ethyl dimethylbenzyl ammonium chloride can be obtained as the material sold by the trade mark "Hyamine 10-X". Preferred examples of di-or trimethyl C12 16alkyl ammonium chlorides are methyl dodecylbenzyl trimethyl ammonium chloride, methyl dodecyl xylene bis (trimethyl ammonium chloride) -sold under the trade mark "Hyamine 2389" - and N-C12 14 16alkyl dimethyl-benzyl ammonium chloride (sold under the trade mark "Hyamine 3500").
The above materials are all known compounds which are described in the literature, see for instance, Detergents and Emulsifiers 1975 Annual, published by ~cCutcheon;s Division, YC Publishing Company, IIS.A. Stear-amidopropyldimethyl-~-hydroxyethylammonium nitrate is obtainable under the trade mark "Catanac SN" from the American Cyanamid Company. Dodine (n-dodecylguanidine) and its salts and captan 3a, 4,7,7a-tetrahydro-N-(tri-chloromethanesulphenyl)phthalimide are well-known fungicides which may be used to treat fungal infections of a number of food crops including applies see for example Ulited States Patent Specifications, 2,553,770, 2,553,771,

2,553,776 and 2,867,562.
rse 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 normaliy be applied to the crop to be treated in such a way that from l to 80, preferably lO to 80, grams per hectare of the -3a-pyrim;dinemetllallol and i r0o7 ~ ~ ~o~ ,200 gram~hectare of co-ingredient are applied to the area of crop. Clearly the precise amount of active ingredients ~Z applied will vary within wide limits, being dependant on variables such as Il density oE cultivation, species of crop and virulence oF the potential or 1 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 (Vent~lria 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 ; 15 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 inventio~
~ to continue treatment of the dormant trees during the winter, particularly ¦I where there has been severe infection conditions.
I .
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 ¦l 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 !l ingredients is novel and forms a part of this invention Such a formulation will contain from 0.00005 to 0.007%, preferably 0.0005 to 0.004%, most preferably 0.001 to 0.004%, by weight of pyrimidinemethanol and from 0.001 to ¦
1, 0.1, preferably 0.001 to 0.06%, most preferably 0.03 to 0.06%, by weight of I the coingredient, traces of any surfactants, inert carriers and the li~e, ' I

1, ' :

1076~24 which were present in the concentrate compositions used to prepare the diluted formulation, and water to make 100%. Preferabl~ the diluted formulation in the case of a pyrimidine methanol/dodine combination will I contain from 0.001 to 0.005% by weight of the former and 0.005 to 0.05% of 1 5 1 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 drenching, it is preferable to treat the plants by spray-~ ing the above aqueous dispersion onto the plants. In this mode of treatmPnt, ~ 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 ]ust 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 concen-trate compositions so formulated as to be capable of ready dispersion or dilution in water.
In the case where the active ingredients are 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 20% or 25% aqueous suspension whilst the c~ptan may be in the form of a 50% or 83% wettable powder. 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 ~ 25 I concentrate compositions may be used and may contain from about 1 to 90% by ¦ I weight of the individual active ingredients.
In this case where the active ingredients are formulated together in concentrate compositions, the latter are novel and form a part of this 1 invention. Such concentrates may contain from 5 to 90% total weight of the ,0 ¦ active ingredients, the latter preferably being present in the ratio of i .

i -5- ~

coingredient to pyrimidine methanol of from 2:1 to 25:1 Where a dodine/
pyrimidinemethanol concentrate is concerned, the preferred ratio is 5:1 to 10:1 ;n each case the pyrimidine methanol most advantageously being Il present in an amount of 1 to 15% by weight.
I The concentrate compositions of the present invention normally comprise ¦¦ the active ingredients in the above stated amounts, one or more inert I I 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 co-`~ 10 ll ingredient 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 1 may be chosen from the attapulgite clays, the montmorillonite clays, the ¦I diatomaceous earths, kaolins, micas, talcs and purified silicates. Effective ¦¦ surfactants may be found among the sulfonated lignlns, the naphthalene sulfonates and condensed naphthalene sulfonates, the alkyl succinates, the alkylbenzene sulfonates, the alkyl sulfates and nonionic surfactantssuch as 1 ethylene oxide adducts of phenol. Examples of wettable powder formulations ~ falling within the scope of the invention are % bv weight I (a) Pyrimidine methanol 1 to 15 I Coingredient 10 to 75 ¦ Surfactant(s) 1 to lO
¦ Inert carrier to 100 - ¦¦ Aqueous suspensions comprise the active ingredients suspended or ¦l 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 ~l agents, if used, are normally chosen from appropriate cellulose materials 1~ 1 ! I
1.
1. 1 _ 6 --i, . and natural gums whilst glycols will generally be used when an antifreezing agent is required. Preservat;ves may be chosen from a wide range of materials¦
such as the various paraben antibacter;als, phenol, o-chlorocresol, phenyl I mercuric nitrate and formaldehyde. Examples of aqueous suspensions falling 1I within the scope of the invention are % weight/volume ¦I Pyrimidine methanol l to 15 Coingredient lO to 75 I Surfactant(s) 0.5 to 25 Thickening agent 0 to 3 Antifreezing agent . 0 to 20 ¦ Preservative 0 to 1 Water to 100 , .' .

~076~Z4 The following non-limitative examples will further illustrate the invention.

Examples 1 to 5 illustrate the preparation of wettable powders containing ¦
!!
I the combination of the invention.
' I
; 5 1'1 EXAMPLE 1 . ¦1 % by wei~ht . - .
i Fenarimol 6 ! Dodine acetate 30 : Sodium alkyl succinate 2 : 10 Sodium lignîn sulfonate 3 I Silica . 8 I Clay to 100 I

li % by weight 15l l Fenarimol 6 ¦ - Dodine acetate 45 Sodium lauryl sulfate 4 Sodium lignin sulfonate 2 Kaolin to 100 i % by weight ~ Nuarimol 4 :~ I Dodine acetate 40 .. -.
Sodiumalkyl succinate 8 ~ 25 ' Mica 5 : ~ Clay ` to 100 , EXAMPLE 4 .' l ~ ~ Nuarimol 3 .~ I Captan 60 : 30 ~! Sodium lignin sulfonate 4 1. Sodium alkyl succinate 2 1~ ¦ Clay to 100 . I . EXAMPLE 5 ¦ % by weight I Fenarimol 4 I Dodine acetate 35 11 Alkaryl polyether alcohol 3 I' Silica 3 China clay to 100 ,, I

,, , ' I -8-Wettable powders were prepared hav;ng the above composition. In each case, the active ingredients were milled and then blended with the specified excipients in conventional mixing equipment. The blend was then further ll milled in a fluid energy mill to a size range of from 1 to 10 microns and 1I finally ~he mixture reblended and deaerated prior to being packaged.
¦I Examples 6 to 8 illustrate the preparation of aqueous suspensions ¦¦ containing the combination of the invention.
I .
¦ EX~MPLE 6 Aqueous Suspensions % weight/volume ~ lo Fenarimol ~ 10 I Dodine acetate 50 I Sodium naphthalene sulfonate 8 Sodium lauryl sulfate 4 Gum arabic o-chlorocresol 0.5 Water to 100 weight/volume I Nuarimol 6 ; Dodine acetate 40 Sodium alkyl succinate 2 I Sodium lignin sulphonate 2 -~ Propylene glycol 8 ` Formaldehyde 0.2 Water to 100.0 ` EXAMPLE 8 ;- % weight/volume ~; I Fenarimol 2 Captan 40 ! Sodium naphthalene sulfonate 5 I Sodium lignin sulfonate 8 I Ethylene glycol 4 Phenol 0 5 Water to 100 ¦1 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, 1~ i 1 Ii .
_9_ .~

1076~24 ~ !! preservative and part of the thickening a2ent. The particle size of bo~h ¦ toxicants was further reduced by liquid milling, the balance of the thickeningj ¦ 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.

,~, % weiRht/volume ., Fenari~ol 2 Mazeen C-2~- (co-ingredient) 20 0 Ethylene oxide/Propylene oxide block co-polymer (surfactant) 5 Dimethylnaphthalene (solvent) to 100 . .' ~ weight/volume Nuarimal 4 Hyamine 2389~ (co-ingredient) 30 Alkylaryl polyether alcohol (surfactant) 4 2-Ethoxy ethanol (solvent) 10 ¦ Xyleae (solvent) to 100 ¦ ~, * Tsade mark 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 .~ I
¦ Similar emulsifiable concentrates to that described in Example 9 were ` ! prepared by usin~ "Quaternary 0_", "Catanac SN~", 'Mazeen S-2-", "Mazeen T-2_"j "Hyamine 10-X-.", and "Hyamine 3500~ as the co-ingredient.

~ Trade marL

I' . , ~' , `' ' 10- , _.. . _ .. __. _ . . , . ... _ _ . __ . ,_ .. _ _ . _ ,

Claims

CLAIMS (A) A method of preparing a fungicidal formulation which comprises admixing:
(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;
and (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 wherein the ratio of the coingredient to the pyrimidinemethanol is from 2:1 to 25:1 by weight.
4. A method according to any one of claims 1 to 3 for preparing a wettable powder which comprises from 1 to 15% by weight of the pyrimidinemethanol, from 10 to 75% by weight 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 suspension which comprises from 1 to 15% by weight of the pyrimidinemethanol, from 10 to 75% by weight of the coingredient and from 0.5 to 25% by weight of surfactant.
6. A method according to any one of claims 1 to 3 wherein the co-ingredient is dodine acetate and the pyrimidinemethanol is fenarimol.
7. 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).
8. A fungicidal formulation as claimed in claim 7, which comprises from 5 to 90% by weight of active ingredients.
9. A fungicidal formulation as claimed in claim 7, wherein the ratio of the coingredient to the pyrimidinemethanol is from 2:1 to 25:1 by weight.
10. A fungicidal formulation as claimed in claim 7, 8 or 9 which is a wettable powder which comprises from 1 to 15% by weight of pyrimidine-methanol, from 10 to 75% by weight of coingredient and from 1 to 10% by weight of surfactant.
11. A fungicidal formulation as claimed in claim 7, 8 or 9 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.
12. A fungicidal formulation as claimed in claim 7, 8 or 9 wherein the pyrimidinemethanol is fenarimol and the coingredient is dodine acetate.
13. An aqueous dilution of the fungicidal formulation as claimed in claim 7 which 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.
14, A method of treating or preventing fungal infections of plants which comprises applying to the plant a fungicidal formulation as claimed in claim 7.
15. A method according to claim 14 for treating or preventing fungal infections caused by one or more organisms selected from the group consisting of Uromyces phaseoli var. typica, Venturia inaequalis and Puccinia recondita.
16. A method according to claim 14 or 15 for treating or preventing fungal infections of apples.
17. A method according to claim 14 or 15 wherein the pyrimidinemethanol is fenarimol and the coingredient is dodine acetate.