FR2574626A1 - Selective oomycetes control fungicides - Google Patents

Abstract

Selective fungicide compsns. contain alkylbenzenesulphonates of formula (I) (where M = alkali(ne earth) metal or opt. substd. ammonium; R = alkyl). Pref. the compsns. contain 10-100 wt.% of (I) where M = Na, K, Mg, Ca or ethanolammonium, opt. together with an ethoxylated aralkylphenol of formula (III) (where R1 = lower (esp. 1-4C) alkyl; A = lower (esp. 1-4C) alkylene; m = 2-7, esp. 2-5; n = 1-30, esp. 15-30).

Description

 The present invention relates to the use of known salts of benzenesulfonic acids as selective fungicides.

 Salts of benzenesulfonic acids are known as emulsifiers, their use in formulations for the protection of plants is common. It is also known that they have bactericidal and fungicidal properties. Thus, they produce an effect for example against the agent responsible for the disease of the spots of the leaves of rice (see for example the Japanese patent published under the number 55111-403) or against the virus of the cucumber mosaic (see by example the Japanese patent published under the number 54-117-025) -.

It is also known that certain dithiocarbamates, in particular zinc (N, N'-propylene-1, 4-bis-dithio-carbamate), have a fungicidal action and they are used in particular to combat oomycetes (see R. Wegler, "Chemie der Pflanzenschutz
und Schadlings-bekampfungsmittel "tome 6, pages 395396 (1981), Springer-Verlag, Berlin, Heidelberg, New
York).

 Compared with these compounds, the substances used in accordance with the invention are advantageous in that they act selectively against oomycetes and in that only one third of the applied amount of benzenesulfonic acid salts is used to achieve in magnitude the effect produced by known carbamates.

dans laquelle
M est un équivalent de métal alcalin, de
métal alcalino-terreux ou d'ammonium éven
tellement substitué et
R est un groupe alkyle à chaîne droite ou
ramifié, présentent des propriétés fongicides
sélectives prononcées, éventuellement en
présence d'ethers d'alkylarylpolyglycols. The Applicant has discovered that the known salts of benzenesulfonic acids of formula (I)

in which
M is an equivalent of alkali metal,
alkaline earth metal or even ammonium
so substituted and
R is a straight chain alkyl group or
branched, have fungicidal properties
pronounced selective, possibly in
presence of alkylarylpolyglycol ethers.

dans laquelle
R1 est un groupe alkyle inférieur à charnue
droite ou ramifié, alkylène désigne un groupe alkylène inférieur à chaine droite ou ramifié, m est un nombre de 2 à 7 et n est un nombre allant jusqu'à 30, sont considérés à cette fin.The alkylarylpolyglycol ethers of formula (II)

in which
R1 is a lower fleshy alkyl group
straight or branched, alkylene denotes a lower or straight chain alkylene group, m is a number from 2 to 7 and n is a number up to 30, are considered for this purpose.

 It is surprising to note that the salts of benzenesulfonic acids possibly show, compared to ethers of alkylarylpolyglycols, a much more pronounced selective fungicidal action, when combating oomycetes, than (N, N'propylene-1,2 -bis-dithiocarbamate) of zinc which is the agent known in the prior art used against oomycetes.

 The benzenesulfonic acid salts and, where appropriate, the alkylarylpolyglycol ethers which must be used in accordance with the invention are exactly defined by the respective formulas (I) and (II) and are already known (see the published Japanese patent 55-111-403). These compounds can also be purchased on an industrial scale. The salts of benzenesulfonic acids can be obtained in a simple manner by common methods from benzenesulfonic acids, by reaction with corresponding salts.

 The benzenesulfonic acids can be obtained, for example, from the corresponding alkylbenzene with chlorosulfonic acid (see the Japanese patent published under No. 55-111-403).

 In formula (I), M preferably represents an equivalent of sodium, potassium, magnesium or calcium or an equivalent of substituted ammonium, such as 2-hydroxyethylammonium, and R represents a straight or branched chain alkyl group having 4 to 14 carbon atoms, especially decyl, undecyle and dodecyl.

In formula (II), R1 preferably represents a straight chain or branched alkyl group having 1 to 4 carbon atoms, in particular the methyl group, alkylene denotes a straight chain or branched alkylene group having 1 to 4 carbon atoms , in particular methylene and 1-methylmethylene, m is a number from 2.0 to 5.0 and n is an integer from 15 to 30, in particular
from 17 to 27.

As examples of active substances which can be used in accordance with the invention, the following compounds are mentioned: 1. Monoethanolamine salt of p-docecylbenzene acid
sulfonic of formula

2) 16% de n-butanol, 3) 4% de xylène et 4) 48X d'éther d'alkylarylpolyglycol de formule

and 2. A mixture of
1) 32% of the calcium salt of p-docecylbenzene acid
sulfonic of formula

2) 16% n-butanol, 3) 4% xylene and 4) 48X alkylarylpolyglycol ether of formula

 The active substances which can be used in accordance with the invention produce pronounced selective fungicidal effects in the fight against oomycetes. They can therefore be used as selective fungicides.

By way of nonlimiting examples, mention is made of some agents responsible for mycoses belonging to the class of oomycetes
Pseudoperonospora cubensis and Phytophthora infestans.

 The good compatibility of the active substances with plants at the concentrations necessary to combat plant diseases allows treatment of aerial parts of plants and plants.

 The active substances are generally applied in dilution with water. However, they can also be incorporated into conventional formulations such as solutions, powders and pastes, as well as very low volume formulations.

 These formulations are prepared in a known manner, for example by mixing the active substances with diluents, that is to say liquid solvents and / or solid supports, optionally using other surfactants, that is to say emulsifiers and / or dispersants and / or agents producing foam.

 In the case of the use of water as diluent, it is possible, for example, also to use organic solvents as auxiliary solvents. As liquid solvents, the following are mainly considered: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example 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, highly polar solvents such as dimethylformamide and dimethyl sulfoxide.

 As solid supports, the following are considered: for example natural mineral powders such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral powders such as silica , aluminum oxide and highly dispersed silicates.

 As emulsifiers and / or agents producing a foam, the following are considered: for example nonionogenic and anionic emulsifiers such as polyoxyethylene esters of fatty acids, polyoxyethylene ethers of fatty alcohols, for example alkylarylpolyglycol ethers, alkylsulfonates, alkyl sulfates, aryl sulfonates as well as albumin hydrolyses.

The following are considered to be dispersants: for example lignosulphite waste liquors and methylcellulose.

 Adhesives such as carboxymethylcellulose, natural and synthetic polymers in powder, granular or latex form, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and also natural phospholipids, can be used in the formulations. than cephalins and lecithins and synthetic phospholipids.

Other additives can be mineral and vegetable oils.

 Dyes can be used such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue and organic dyes such as dyes-derivatives of alizarin, azo dyes and derivatives metallic phthalocyanines, and trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts.

 The active substances according to the invention can be present in the formulations in admixture with other known active substances such as fungicides, insecticides, acaricides and herbicides as well as in admixtures with fertilizers and growth substances.

 The active substances can be used as such, in the form of their formulations or in the application forms prepared from them, such as solutions, emulsifiable concentrates, emulsions, foams, sprayable powders, pastes, soluble powders and powders. powder ready to use.

The application is carried out in a conventional manner, for example by watering, spraying, sprinkling, diffusion, dusting, foaming, whitewashing, etc. It is also possible to apply the active substances by the very low volume process.

 The selective fungicidal compositions according to the invention generally contain 10 to 100% by weight, preferably 30 to 100% by weight of salts of formula (I) as active substance.

 When treating plant parts, the concentrations of active substances in the application forms can vary between wide limits.

They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

(N,N'-propylène-1 ,2-bis-dithiocarbamate) de zinc. Application example
The following compound, which has long been known as an active substance for combating oomycetes, is used as a comparison substance:

(N, N'-propylene-1, 2-bis-dithiocarbamate) of zinc.

Example
Test on the downy mildew of cucurbits.

Test on Pseudoperonospora cubensis (cucumber)
The desired concentration of active substance is established by dissolving the necessary quantity of substance in a predetermined quantity of water.

With the sprayable liquid, spray cucumber plants until spray drops and then expose them to the natural conditions of infection. The treatment is repeated twice more at intervals of one week each time. One week after the last treatment, the attack on the plants is determined. The evaluation scores obtained are expressed as a percentage of attack. 0% means zero attack, 100% indicates that the plants are fully attacked. BOARD
Test on Pseudoperonospora cubensis (cucumber)
Attack Concentration as% of At
Active substance in millionths of the untreated control
No treatment - 100
CH3 (S-CS-NH-CH2-CH-NH-CS-S-) 2Zn 1350 0.1 (known)
Active substance according to Example 2 # 400 2.0
Active substance according to example 1 # 400 0.5 # For composition, see text, page 4

Claims (10)

 1. Selective fungicidal compositions, characterized in that they contain at least one salt of benzenesulfonic acids of formula (I)

 in which M is an equivalent of alkali metal, metal  alkaline earth or ammonium if necessary  substituted, and R is a straight chain alkyl group or  branched.  2. Selective fungicidal compositions according to claim 1, characterized in that they contain compounds of formula (I)

 in which M is an equivalent of sodium, potassium,  magnesium or calcium or a group  2-hydroxyethylammonium and R is a straight chain alkyl group or  branched having 4 to 14 carbon atoms.  3. Selective fungicidal compositions according to claims 1 and 2, characterized in that they contain 10 to 100% by weight of the active substances.  4. Use of salts of benzene ~ sulfonic acids of formula (I)

 in which M is an equivalent of alkali metal,  alkaline earth metal or even ammonium  tually substituted and R is an alkyl group S straight hate or  branched, to fight oomycetes.  5. Method for preparing selective fungicidal compositions, characterized in that the salts of benzenesulfonic acids of formula (I) according to claim 1 are mixed with diluents and / or surfactants.  6. Method for combating oomycetes, characterized in that salts of benzenesulfonic acids of formula (I) according to claim 1 are made to act on oomycetes and / or on their medium.  7. A process for the preparation of selective fungicidal compositions according to claims 1 to 5, characterized in that the salts of benzenesulfonic acids of formula (I) are mixed with ethers of alkylarylpolyglycols of formula (II) and, where appropriate, with diluents and / or surfactants.  8. Method for preparing selective fungicidal compositions according to claim 7, characterized in that the ethers of alkylarylpolyglycols are defined by formula (II)

 in which R1 is a lower alkyl group  straight or branched, alkylene is a lower chaste or branched alkylene group, m is a number from 2 to 7 and n is a number up to 30.  9. Process for the preparation of selective fungicidal compositions according to Claims 7 and 8, characterized in that in formula (II) R1 is a straight chaste alkyl group or  branched having 1 to 4 carbon atoms, alkylene is a straight or branched alkylene group having 1 to 4 carbon atoms, m is a number from 2.0 to 5.0 and n is a number from 15 to 30.  10. Use of the monoethanolamine salt of p-dodecylbenzenesulfonic acid or of the mixture of the salt. Calcium from p-dodecylbenzenesulfonic acid and an alkylarylpolyglycol ether in butanol and xylene according to claim 4 for combating oomycetes.