JPH07165509A - Disinfectant mixture and method for controlling harmful fungi - Google Patents

Abstract

PURPOSE: To obtain a fungicidal mixture that comprises a combination of an oxime ether carboxamide and an oxime ether carboxylic ester or a methoxyacrylate ester and brings about improved effect on fungi with reduced application amount. CONSTITUTION: This fungicidal mixture comprises a combination of an oxime ether carboxamide of formula I with an oxime ether carboxylic ester of formula II or a methoxyacrylate ester. The formulation weight ratio of the compound of formula I to the compound of formula II or formula III is 10/1-0.1 1. Among these fungicidal components, the compound of formula I is applied in an amount of 0.005-0.5 kg/hectare and the compound II or III is in an amount of 0.01-0.5 kg/hectare. This mixture is used to treat the destructive fungi, their growing spaces, plants, seeds, soil, ground surface or a variety of material to be protected from destructive fungi. As the compounds of formula I - formula III, an E/Z-isomer mixture or E-isomer, particularly E-isomer is preferably used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention comprises (a) the following formula I:

[0002]

[Chemical 4] An oxime ether carboxylic acid amide represented by
1) The following formula II

[0003]

[Chemical 5] An oxime ether carboxylic acid ester represented by: or (b2) the following formula III

[0004]

[Chemical 6] The present invention relates to a bactericide mixture characterized by containing a methoxyacrylic acid ester represented by

The present invention also relates to a method for controlling with the above-mentioned compounds I and II or a mixture of the above-mentioned compounds I and III and the use of the compounds I, II and III for the preparation of this synergistic mixture.

[0006]

2. Description of the Related Art The compound of formula I, its production method and its control effect against fungi are known from the literature (for example, European Patent Publication No. 477631). In the same manner, compound II (ibid., No. 253213) and compound III
(Ibid., No. 38237), their manufacturing methods and sterilizing effects are also known.

[0007]

However, in view of the fact that the required amount of each of these known compounds is relatively large and the effective range of application is relatively narrow, a smaller amount of the compound is used against fungi. It is an object of the present invention to bring about further improved effects, which is a technical problem in this field.

[0008]

However, it has been found by the present inventors that the above-mentioned problems can be solved by the bactericide mixture (synergistic mixture) described at the beginning of the present specification. Furthermore, by applying the compounds I and II, or the compounds I and III simultaneously, together or separately, or the compounds I and II or III before or after, the phytopathogenic fungi control effect can be obtained by each of these compounds alone. It has been found by the present inventors that it is significantly improved over that used in.

Compounds I, II, III may exist in the E-configuration or the Z-configuration (with respect to the carboxylic acid function) in view of their C = X double bond. For this,
The mixture of the present invention can be used as a pure E-isomer or a pure Z-isomer alone or as a mixture of E / Z-both isomers.
However, it is preferred to use the E / Z-isomer mixture or the E-isomer, in particular the E-isomer.

Due to the basicity of its NH group, compound I forms salts or adducts with inorganic or organic acids or with metal ions.

Examples of the inorganic acid include hydrofluoric acid, hydrobromic acid, hydrochloric acid, hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.

As the organic acid, formic acid, carbonic acid, alkanoic acid such as acetic acid, trifluoroacetic acid, trichloro acid,
Propionic acid, further glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acid (sulfonic acid having a linear or branched alkyl group having 1 to 20 carbon atoms), Aryl sulfonic acid or disulfonic acid (1 or 2
Aromatic compounds such as phenyl and naphthyl having 1 sulfonic acid group), alkylphosphonic acid (phosphonic acid having a linear or branched alkyl group having 1 to 20 carbon atoms), arylphosphonic acid, or diphosphonic acid (1
Aromatic compounds such as phenyl and naphthyl having one or two phosphonic acid groups). The alkyl or aryl may further have a substituent. For example, p-toluenesulfonic acid, salicylic acid, p-
Aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, dodecylbenzenesulfonic acid and the like.

The metal ions include, in particular, elements of the second main group, especially ions of calcium and magnesium, and third,
4th main group elements, especially aluminum, tin and lead ions,
1st to 8th subgroup elements, especially chromium, manganese, iron,
Examples include ions of cobalt, nickel, copper, and zinc. Especially preferred are the 4th period subgroup metal element ions. In this case, the metals may have different intrinsic valences.

In preparing the pure compounds I and II or the mixture of I and III, if necessary, fungicides and / or other pests such as insects, arachnids, nematodes, or herbicides, A plant growth control agent and a fertilizer can be added.

Compounds I and II, or compounds I and II
A wide range of phytopathogenic fungi, especially ascomycetes and basidiomycetes, by using a mixture of I or compounds I and II or I and III simultaneously, together or separately Excellent bactericidal effect. They partially show a seepage effect and can therefore be used as foliar and soil fungicides.

Importantly, various cultivated plants such as cotton, vegetables (eg, melons, beans, pumpkins), barley, grass, oats, coffee, corn, fruit trees,
It is possible to control a wide variety of harmful fungi against rice, rye, soybeans, grapes, wheat, ornamental plants, sugar cane, and many seeds.

The novel compounds are particularly suitable for controlling the following plant diseases:

Grain Erythipe Graminis (Erys)
iphe graminis; Erysiphe cic of the family Cucurbitaceae
horacearum) and Spherotetheca fuliginea,
Podosfera leukotrica (Podosph) of apple
aera leucotricha), cereals Puccinia species, cotton and turf Rhizoctonia species, cereals and sugarcane Ustilago species, apple Venturia ricequaria (Venturia)
qalis), cereals Helminthosporium, wheat Septoria nodoru
m), strawberries and grapes of Botrytis cinerea (Bo)
trytis cinerea; peanut cercospora arachizicola (Cercospo)
Ra arachdicola), Wheat and Barley Pseudokercosporella herpotricoides (Ps)
eudocercosporella herpotr
ichoides), rice Pyricularia oryzae potato and tomato Phytopitra infestans (Phy)
tophthora infestans, Plasmopara viticola (Plasmopara vi)
ticola, fruit and vegetable alternaria (Al
ternaria) and Fusarium (Fusar)
ium) and Verticillium (Verticilli)
um) species.

They are also used for protection of various materials (eg wood), eg Paecilomyces variot.
It can be used for protection against ti bacteria.

Compounds I and II or I and III are
It can be applied simultaneously, together or separately, or one after the other. The order in which they are applied separately does not generally affect the fungal control effect.

The compounds I and II or I and III are generally 10: 1 to 0.1: 1, preferably 5: 1 to 0.2: 1, especially 3: 1 to 0.3: 1. Used in proportion.

The amount of the mixture according to the invention used is generally 0.02 to 1 kg / ha, preferably 0.05 to 1 kg / ha, depending on the intended effect.
It is 1 to 0.8 kg. The amount of compound I used is generally 0.005 to 0.5 kg, preferably 0.005 to 0.3 kg, per one hectare, compound II or II.
The amount of I used is generally 0.01 to 0.5 kg, preferably 0.01 to 0.3 kg.

In the case of seed disinfection, 0.001 to 50 g, preferably 0.01 to 10 g, especially 0.01 to 5 g of fungicide mixture are used per kg of seed. Separate or simultaneous use of compounds I and II or compounds I and III for controlling plant pathogens, compounds I and I
The use of I or the mixture of compounds I and III is carried out by spraying and spraying the seeds, plants or soil before or after sowing and before or after the growth of the fungus.

Mixtures having a bactericidal synergistic effect according to the invention, compounds I and II, or compounds I and II
I is for example a directly sprayable solution, powder, suspension,
Highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oily dispersions, pastes, dusting agents,
It can be applied in the form of dusts or granules by spraying, misting, dusting, dusting or pouring. The application form depends entirely on the intended use; in each case, the finest possible distribution of the active substances according to the invention should be ensured.

The application form can be manufactured by a known method such as addition of a solvent and / or a carrier. The formulations are prepared by the addition of customary inert additives, such as emulsifiers or dispersants.

The surface-active substances include the following: Aromatic sulphonic acids, for example alkali salts of lignin sulphonic acid, phenol sulphonic acid, naphthalene sulphonic acid, dibutylnaphthalene sulphonic acid,
Alkaline earth salts, ammonium salts, and fatty acids, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates,
Alkali salts and alkaline earth salts of fatty alcohol sulphates, ammonium salts, and salts of sulfated hexadecanol, heptadecanol and octadecanol, salts of fatty alcohol glycol ethers, sulfonated naphthalene and naphthalene derivatives and formaldehyde , A condensation product of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene-octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl Polyether alcohol, isotridecyl alcohol, fatty alcohol ethylene oxide-condensate, ethoxyl Castor oil, polyoxyethylene alkyl ethers, or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin - sulfite waste liquors and methylcellulose.

Powders, dusting agents and sprinkling agents can be obtained by mixing compound I or II, I or III, or a mixture of compounds I and II, or a mixture of I and III with a solid carrier substance or grinding them together. Can be manufactured by.

Granules (for example coated, impregnated and homogeneous granules) can be prepared by binding the active substances to solid carrier substances.

Examples of fillers or solid carrier substances are mineral soils, such as silica gel, silicic acid, silicic acid gels, silicates, talc, kaolin, limestone, lime, chalk, agglomerate granules,
Calcareous yellow clay, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic resin, fertilizer such as ammonium sulfate, ammonium phosphate,
Ammonium nitrate, urea and vegetable products such as cereal flour, bark, wood and walnut flour, cellulosic flour and other solid carrier materials.

The dosage form is usually compound I or II, or compound I or II, or a mixture of compounds I and II, or a mixture of compounds I and III.
To 95% by weight, in particular 0.5 to 90% by weight. In this case, the active substance has a purity of 90 to 100%, especially 95 to 100%.
Used at 100% (according to NMR spectrum, HPLC spectrum).

The compounds I, II or I and III, or the mixtures or the corresponding preparations, are applied in fungicidally effective amounts to the fungi, the plants to be protected, the seeds, the soil, the ground, the materials and the spaces. . The treatment can take place before or after infection with the fungus.

Phase of the mixture according to the invention against harmful fungi
Example of Multiplicative Effect The following experiment shows the bactericidal effect of the compound according to the present invention, or the mixture thereof.

70% by weight of cyclohexanone, Nekanil® LN, individually or together with the active substances
(Lutensol: AP6, a wetting agent with emulsifying and dispersing action on the base of ethoxylated alkylphenols) 20% by weight, and Emulph
or (registered trademark) EL (Emulan: registered trademark, emulsifier for ethoxylated fatty alcohol base) 10
Treated as an emulsion with a concentration of 20% in a mixture consisting of wt.% And diluted with water to the desired concentration.

An effective substance was applied to the damaged leaf surface, and the effect was evaluated in%. The value by this% was converted as an effect. With the mixture of active substances, the expected effect is S.
R. Colby (Weeds, 15, 20-22, (19
67)) was calculated by the following formula and compared with the effect actually observed.

E = X + Y−Y · Y / 100 The definition of the code is as follows.

E is the active substance A of concentration [a] and [b]
And the expected effect of using the mixture of B and the untreated control (%), X being the effect of the active substance A at the concentration [a], the effect of the untreated control (%) , Y means the effect (%) observed by using the active substance B at the concentration [b], respectively, as compared with the untreated control.

Effect 0 indicates that the treated plants were as damaged as untreated plants, and effect 100 indicates that the treated plants were not damaged at all.

Fusarium culmoru of wheat
Action on m The seedling leaf surface of wheat (Kanzler species) cultivated in a flowerpot was sprayed with an aqueous spray solution containing 80% of the active substance and 20% of an emulsifier in a desiccant to the extent that water droplets drip. The next day, it was infected with a filamentous fungal suspension of Fusarium culmorum and then kept at> 90% high humidity, 22-24 ° C. in a temperature controlled room. After 6 days, the degree of occurrence of symptoms was visually evaluated.

[0039]

[Table 1] From the experimental results, it was found that the obtained effect exceeds the effect calculated in advance by Colby's formula at all the mixture contents.

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[Procedure amendment]

[Submission date] November 15, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

The definition of the E = x + y−x · y / 100 code is as follows.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

E is the active substance A of concentration [a] and [b]
The expected effect of the use of the mixture of B and B (%) over the untreated control, x is the effect of the active substance A at the concentration [a] observed over the untreated control (%) , Y means the respective effects (%) observed by the use of the active substance B at the concentration [b], as compared with the untreated control.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hubert, Sauter Germany, 68167, Mannheim, Necarpromenade, 20 (72) Inventor Eberhard, Ammermann Germany, 64646, Hepenheim, von-Gagern-Strasse, 2 (72) Invention Giesela, Lorenz Germany, 67434, Neustadt, Erlenweg, 13 (72) Inventor Reinhold, Saul Germany, 67459, Beer-Igelheim, Königsberger, Strasse, 9 (72) Inventor Klaus, Schellberg Germany, 67161 , Genheim, Traminerweg, 2 (72) Inventor Manfred, Hampel Germany, 67435, Neustadt, Im, Weingarten, 15

Claims (11)

[Claims] 1. (a) Formula I below: An oxime ether carboxylic acid amide represented by
1) The following formula II: An oxime ether carboxylic acid ester represented by: or (b2) the following formula III: And a methoxyacrylic acid ester represented by 2. An oxime ether carboxylic acid amide of formula I in claim (1) and a formula I in claim (1).
The bactericide mixture according to claim 1, characterized in that it contains a synergistic effect of the oxime ether carboxylic acid ester of I. 3. An oxime ether carboxylic acid amide of formula I in claim (1) and a formula I in claim (1).
The bactericide mixture according to claim 1, characterized in that it contains a methoxyacrylic acid ester of II in a synergistic amount. 4. Fungicidal mixture according to claim 1, characterized in that the weight ratio of compound I to compound II or compound III is from 10: 1 to 0.1: 1. 5. A compound of formula I according to claim (1),
The compound of formula (II) or formula (III) in claim (1) is used to treat harmful fungi, their growth space, plants, seeds, soil, ground, spaces or materials to be protected from harmful fungi. , How to control fungi. 6. A compound of formula I according to claim (1),
Process according to claim (5), characterized in that the compound of formula II or formula III in claim (1) is applied simultaneously, together or separately or before or after. 7. From 0.005 to 0.1 per hectare.
5. Treating harmful fungi, their growth space, plants, seeds, soil, ground, space or various materials to be protected from harmful fungi with 5 kg of the compound of formula I in claim (1) The method according to claim (5). 8. 0.01 to 0.5 per hectare
Kg of formula II or formula III in claim (1)
The method according to claim (5), which comprises treating a harmful fungus, its growth space, a plant, a seed, a soil, a ground, a space, or various materials to be protected from the harmful fungus with the compound represented by 9. Use of a compound of formula I according to claim (1) for preparing a germicidal synergistic mixture according to claim (1). 10. Use of a compound of formula II in claim (1) for the preparation of a germicidal synergistic mixture according to claim (1). 11. Use of a compound of formula III according to claim (1) for the preparation of a germicidal synergistic mixture according to claim (1).