RU2127054C1 - Plant fungicide, a method of struggle against fungi - Google Patents

Abstract

FIELD: organic chemistry, agriculture. SUBSTANCE: plant fungicide has two biologically active components. The first (I) component is 1-[3-(tert. -butylphenyl)-2-methylpropyl] -piperidine, 4-(2,2- -difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile or N-(trichloromethylthio)-cyclohex-4-ene-1,2-dicarboximide. The second (II) component is 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidineamine or one of its salts or one of its metallic complexes at weight ratio (I) : (II) = (1:10)-(30:1). EFFECT: enhanced effectiveness of fungicide. 12 cl, 6 tbl

Description

 The present invention relates to new bactericidal mixtures of biologically active substances with a synergistically enhanced effect, containing at least two components of biologically active substances, and a method of plant protection using such mixtures.

где R₁ обозначает фтор или хлор;
R₂ обозначает хлор или трифторметил [см.: европейский патент А-236 272; патент ФРГ 2 927 480];
IE) N-трихлориметилтио/-фталимид {/"фольпет/, см. патент США 2 553 770}.Component I is a compound selected from the group including:
IA) cis-4- {3- / 4-tert. -butylphenyl / -2-methylpropyl} -2,6-dimethylmorpholine / fenpropimorph / and / or 1- {3- / 4-tert-butylphenyl / -2-methylpropyl} -piperidine / fenpropidin /, or one from their salts or complexes with metals [see German patent 2 752 135];
IB) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -IH-pyrrole-3-carbonitrile {/ "fludioxonil"/; see European patent A-206 999};
IC) N- (trichloromethylthio) cyclohex-4-en-1,2-dicarboximide ["captan"];
see US Pat. No. 2,553,770 /;
ID) compound of formula ID

where R ₁ denotes fluorine or chlorine;
R ₂ is chloro or trifluoromethyl [see: European Patent A-236 272; German patent 2,927,480];
IE) N-trichloromethylthio / phthalimide {/ "folpet", see US Pat. No. 2,553,770}.

4-циклопропил-6-метил-N-фенил-2- пиримидинамин, или одну из его солей, или один из его комплексов с металлами /см. европейский патент А-310 550/.Component II is 2-anilinopyrimidine of formula II

4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine, or one of its salts, or one of its complexes with metals / cm. European patent A-310 550 /.

 Of the compounds of formula (IA), preferably 1- {3- / 4-tert.-butyl-phenyl / -2-methylpropyl} -piperidine / "phenpropidine" /.

Of the compounds of formula (ID), preferably the compound wherein R ₁ and R ₂ are chloro: 4- (2,3-dichlorophenyl) -1H-pyrrole-3-carbonitrile ["phenpiclonyl"].

 Of the acids that can be used to obtain salts of the formulas / IA / and / II /, it is necessary to name: hydrohalic acid, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydrochloric acid; as well as sulfuric acid, phosphoric acid, nitric acid; and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, tricyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid , methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalene-disulfo acid.

 The term "salts" also includes metal complexes of the main components / I / and / II /. These complexes can relate, optionally, to only one component or also to both components.

 It is also possible to obtain complexes with metals that bind both biologically active substances / I / and / II / to each other in one mixed complex.

 Metal complexes consist of the underlying organic molecule and inorganic or organic metal salts, for example, halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc., elements of the second the main group, like calcium and magnesium, and the third and fourth main groups, like aluminum, tin or lead, as well as the 1st-8th side groups, like chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. d. Preferred elements of side groups of the 4th period.

 Moreover, metals can be in various valencies inherent in them. Metal complexes can be single or multi-core, i.e. they may contain one or more fractions of organic molecules as ligands.

 Other agrochemical active substances, such as insecticides, acaricides, nematicides, herbicides, growth regulators and fertilizers, in particular, however, other bactericides, can also be added to the inventive mixture of biologically active substances.

 Currently, it turned out to be unexpected that the mixtures of the components / I / and / II / exhibit not only an additive effect in their fungicidal action, but also a distinct synergistically increased effect.

 The present invention therefore represents a very substantial extension of the prior art.

 The subject of the present invention is also a method for controlling fungi, characterized in that the affected or endangered fungus is in any place or simultaneously treated with a / biologically active substance of the formula / I / or one of its salts and with b / biologically active substances of the formula / II / or one of its salts, and salts can also be chosen so that both biologically active substances are bound by an acid residue or, in the case of a metal complex, with a central metal thione.

 Favorable ratios of both biologically active substances in the mixture are / I /: / II / = 1:20 - 10: 1, preferably / I /: / II / = 1: 6 - 6: 1.

Particularly favorable ratios of components in the mixture are:
/ IA /: / II / = 1: 4 - 2: 1;
/ IB /: / II / = 5: 1 - 1: 5;
/ IC /: / II / = 5: 1 -1: 2;
/ ID /: / II / = 5: 1 - 1: 5;
/ IE /: / II / = 5: 1 - 1: 2.

 Proposed according to the invention a mixture of biologically active substances / I / + / II / have very preferred therapeutic, protective and systemic fungicidal properties for plant protection.

 Using these mixtures of biologically active substances on plants or parts of plants [fruits, flowers, foliage, stalk, tubers, roots] of various useful crops, it is possible to localize or destroy emerging microorganisms, and later growing parts of plants are not affected by such microorganisms.

 They can also be used as mordants for treating plant propagation material, in particular seed material [fruits, tubers, grains] and plant cuttings [eg graft] for protection against fungal infections, as well as against phytopathogenic fungi in the soil.

 Mixtures of biologically active substances according to the invention are distinguished by particularly good compatibility with plants and environmental safety.

 Mixtures of biologically active substances are effective against phytopathogenic fungi belonging to the following classes: ascomycetes [for example, Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula]; basidiomycetes [for example, the genus Hemileia, Rhizoctonia, Puccinia]; Fungi imperfecti [for example, Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternazia, Pyricularia and especially Pseudocercosporella herpotrichoides]; oomycetes [for example, Phytophthora, Pernospora, Bremia, Pythium, Plasmopara].

 The following plant species are relevant, for example, as target crops for the testimony area disclosed herein within the scope of the present invention: cereals / wheat, barley, rye, oats, rice, sorghum and related crops /; root crops / sugar and fodder beets /; pome fruits, stone fruits and berries (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes / beans, peas, soybeans, lentils /; oil crops / rape, mustard, olives, poppy, sunflower, coconut, castor oil, cocoa, peanuts /; pumpkin / pumpkin, cucumbers, melons /; fiber crops / cotton, flax, hemp, jute /; citrus fruits / oranges, lemons, grapefruit, tangerines /; vegetables / spinach, lettuce, asparagus, types of cabbage, carrots, onions, tomatoes, potatoes, peppers /; laurel / avocado, Cinnamonum, camphor / or plants such as corn, tobacco, nuts, coffee, sugarcane, tea, grapes, hops, bananas and natural rubbers, as well as ornamental plants [palm trees, shrubs, deciduous trees and conifers] . This listing is not a limitation.

Mixtures of active compounds according to the invention are particularly preferred for the following applications:
/ IA / + / II /: in cereals, especially in wheat and barley;
/ IB / + / II /: in vineyards and vegetable crops, as well as for processing plant propagation material, such as seed, tubers and cuttings;
/ IC / + / II /: in fruit and vegetable crops, especially in the case of apples and pears;
/ ID / + / II /: for processing material for propagation of plants, such as, for example, seed, tubers and cuttings;
/ IE / + / 11 /: in root crops and vegetables.

 Mixtures of biologically active substances of the formulas / I / and / II / are usually used in the form of compositions. The biologically active substances of the formula / I / and the biologically active substance of the formula / II / can be applied simultaneously, but also sequentially, on the same day, on the treated areas or plants, together with other, if necessary conventional in the art of formulation, carriers, surface active substances or other additives that contribute to the application.

 Suitable carriers and additives can be solid or liquid and correspond to substances which are appropriate in the art of formulation, such as, for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

 A preferred method of applying a mixture of biologically active substances, which contains at least one of these biologically active substances / I / and / II /, is applying to the aerial parts of plants, especially foliage / applying to leaves /.

 The number of applications and the rate of application are selected depending on the biological and climatic living conditions for the pathogen. Biologically active substances, however, also enter the plants through the soil / systemic effect / by the fact that the locality of the plants is impregnated with a liquid composition, or substances in solid form are introduced into the soil, for example, in the form of granulate / soil application /.

 The compounds of the formulas / I / and / II / for seed treatment can also be applied to grains [Coating] in that the tubers, respectively, grains are either sequentially soaked in the liquid composition of the biologically active substance, or they are coated with an already combined, wet or dried composition.

 Moreover, in special cases, other types of application are possible in the case of plants, for example, as targeted treatment of buds or fruit.

 The combination compounds are hereby used in unchanged form or preferably together with adjuvants customary in the art of formulation and therefore, for example, are processed in a known manner to emulsifiable concentrates capable of spreading pastes, directly sprayable or dilute solutions, dilute emulsions, wettable powders, soluble powders, preparations for dusting, granules or by encapsulation, for example, in polymeric substances.

 Methods of application, such as spraying, misting, dusting, scattering, spreading or watering, as well as the type of product, are selected depending on the goals to which they are striving, and the given ratios.

 Favorable consumption rates for a mixture of biologically active substances are generally from 50 g to 2 kg of active substance / ha, in particular 100-1000 g of active substance / ha, particularly preferably 400-1000 g of active substance / ha.

 For the treatment of seed, the consumption rate is 0.5-1000 g, preferably 5-100 g of active substance per 100 kg of seed.

 The formulations are prepared in a known manner, for example, by thoroughly mixing and / or grinding the biologically active substances with additives, such as, for example, with solvents, solid carriers and, if necessary, surface-active compounds.

Suitable solvents include: aromatic hydrocarbons, preferably C ₈ -C ₁₂ fractions, such as, for example, xylene mixtures or substituted naphthalenes; phthalic acid esters such as dibutyl or dioctyl phthalate; aliphatic hydrocarbons, such as cyclohexane, or paraffins, alcohols and glycols, as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ketones like cyclohexanone; strongly polar solvents like N-methyl-2-pyrrolidone; dimethyl sulfoxide or dimethylformamide, and, if necessary, epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil; or water.

 As solid carriers, for example, for dusting preparations and dispersible powders, stone flour is generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite.

 To improve physical properties, finely divided silicic acid or finely dispersed absorbent polymers can also be added.

 As granular, adsorbing granular carriers, porous types, such as pumice, brick bricks, sepiolite, or bentonite, as well as non-sorbing carriers, for example, calcite or sand, are taken into account.

 Moreover, many pre-granular materials of inorganic or organic nature can be used, such as, in particular, dolomite or crushed plant residues.

 As surface-active compounds, depending on the kind of formulated biologically active substances of the formulas / I / and / II /, nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties are taken into account. Surfactants also need to be understood as mixtures of surfactants.

The surfactants conventional in the art of formulation are indicated, inter alia, in the following publications:
- "MC Cutcheon's Detergents and Emolsifiers Annual" MC Publishing Corp., Glen Rock, New Jersey, 1988;
- M. and J. Ash "Encyclopedia oj Surfactants" vol. I-III, Chemical Publishing Co., New York, 1980-1981.

 Particularly preferred, facilitating application additives are further natural or synthetic phospholipids from the series of mullet and lecithin, such as, for example, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, lysolecithin.

 Agrochemical compositions contain, as a rule, 0.1-99%, in particular 0.1-95%, of biologically active substances of the formulas / I / and / II /; 99.9-1%, in particular 99.9-5%, of a solid or liquid additive and 0-25%, in particular 0.1-25%, of a surfactant.

 While concentrated means are preferred as a means of trading, the final consumer, as a rule, uses diluted means.

 Such / agro / chemicals are an integral part of the present invention.

 The following examples (see table. 1) serve to illustrate the invention, with the "biologically active substance" means a mixture of compound / I / and compound / II / in a certain ratio in the mixture.

 The active ingredient is well mixed with additives and well milled in a suitable mill. Wettable powders are obtained which can be diluted with water to suspensions of any desired concentration.

Emulsifiable concentrate:
biologically active substance {/ I /: / II / = 1: 6} - 10%
octylphenolpolyethylene glycol ether / 4 - 5 mol of ethylene oxide / - 3%
calcium dodecylbenzenesulfonate - 3%
castor oil polyglycol ether / 35 mol ethylene oxide / - 4%
cyclohexanone - 30%
xylene mixture - 50%
From this concentrate, by dilution with water, emulsions of any desired concentration can be prepared that can be used to protect plants (see table. 2).

 Ready-to-use dusting preparations are obtained in that the biologically active substance is mixed with a carrier and ground in a suitable mill. Such powders can also be used for dry dressing of seed.

Extruded granulate
biologically active substance {/ I /: / II / = 1: 1,5} - 15%
sodium ligninsulfonate - 2%
carboxymethyl cellulose - 1%
kaolin - 82%
The biologically active substance is mixed with additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

Shell granulate
biologically active substance {/ I /: / II / = 3: 5} - 8%
polyethylene glycol / m. weight 200 / - 3%
kaolin - 89%
/ m weight = molecular weight /
The finely ground biologically active substance is uniformly applied in a mixer onto kaolin moistened with polyethylene glycol. Thus, dust-free granulate in the shell is obtained.

Suspended Concentrate
biologically active substance {/ I /: / II / = 3: 7} - 40%
propylene glycol - 10%
nonylphenolpolyethylene glycol ether / 15 mol ethylene oxide / - 6%
sodium ligninsulfonate - 10%
carboxymethyl cellulose - 1%
silicone oil / as a 75% aqueous emulsion / - 1%
water - 32%
Finely ground biologically active substance is thoroughly mixed with additives. In this way, a suspending concentrate is obtained from which suspensions of any desired dilution can be prepared by dilution with water.

 Using such dilutions, live plants, as well as plant material for propagation by spraying, watering or dipping, can be treated and protected against damage by microorganisms.

Biological Examples
The synergistic effect in the case of fungicides is always there when the fungicidal effect of the combination of biologically active substances is greater than the sum of the actions of individually applied biologically active substances.

 The expected action "E" for a given combination of biologically active substances, for example, of two fungicides, obeys the so-called COLBY formula and can be calculated as follows [COLBY S.R. "Calculating synergistic and antagonistic reponses of herbicide combination" Weeds, vol. 15, p. 20-22, 1967].

ppm = milligram of biologically active substance [= WS] per 1 liter of broth for spraying;
X =% action due to fungicide (I) when using "p" ppm biologically active substance;
Y =% action due to fungicide (II) when using "q" ppm biologically active substance;
E = expected effect of the sum of fungicides (I) + (II) when applying "p + q" ppm biologically active substance [additive effect];
then according to COLBY E = X + Y - X • Y / 100.

 If the actually observed action / 0 / is greater than the expected / E /, then the combination is super-additive in its action, i.e. there is a synergistic effect. 0 / E = synergy factor [= SF].

 In the following examples, the damage to untreated plants is assumed to be 100%, which corresponds to the action of 0%.

Example 1:
Action against Botrytis cinerea on apples
Artificially damaged apples are treated by spraying the broth [30 μl of biologically active substance, respectively, of a combination of biologically active substances] into the place of damage.

The processed fruits are then inoculated with a spore suspension of the fungus and incubated for a week at high humidity and at a temperature of about 20 ^o C.

 The fungicidal effect of the test substance is determined from the number and magnitude of decayed damage sites. At the same time, the results indicated in the table are achieved. 3.

Example 2:
Action against Botrytis cinerea on vines
Grape seedlings at the age of 5 weeks are sprayed with a suspension prepared from the formulated test substance and after 2 days they are infected with a suspension of conidia B. cinerea.

After an incubation for 4 days at 21 ^o C and a relative humidity of 95-100% in a greenhouse, damage is assessed. At the same time, the results indicated in the table are achieved. 4.

Example 3:
Action against Venturia inaequalis on apple trees
Apple cuttings with fresh shoots 10-20 cm long are sprayed before being picked up by spraying broth prepared from a formulated biologically active substance, respectively, a combination of biologically active substances.

After 24 hours, the treated plants are infected with a suspension of conidia of the fungus, then the treated plants are incubated for 3 days at a relative humidity of 90-100% and at 20 ^o C and for the next 10 days they are kept in a greenhouse at 20-24 ^o C. After 14 days after infection, the fungus lesion is assessed. At the same time, the results indicated in the table are achieved. 5a, 5b.

Example 4:
Action against Puccinia recondita on wheat
Wheat plants at the age of 10 days are sprayed before dripping using a spray broth prepared from a formulated biologically active substance, respectively, a combination of biologically active substances.

After 24 hours, the treated plants are infected with a suspension of conidia of the fungus, then the treated plants are incubated for 2 days at a relative humidity of 90 - 100% and a temperature of 20 ^o C. After 2 weeks after infection, the fungal infection is assessed. At the same time, the results indicated in the table are achieved. 6.

Example 5:
Action against Erysiphe graminis on barley
Barley plants at the age of 6 days are sprayed before dripping with spray broth prepared from a formulated biologically active substance, respectively, a combination of biologically active substances.

After 1 day, the plants are inoculated with conidia of Erysiphe graminis and incubated in a greenhouse at 21 ^o C and a relative humidity of 50-80%. After a week, the fungus lesion is assessed. In this case, the following results are achieved, indicated in table. 7.

Example 6:
Action against Pyrenophora teres on barley
Barley plants at the age of 6 days are sprayed before dripping with spray broth prepared from a formulated biologically active substance, respectively, a combination of biologically active substances.

After 2 days, the plants are inoculated with a spore suspension of Pyrenophora teres and incubated in a greenhouse at 21 ^° C and an air humidity of 90-100%. After a week, the fungus lesion is assessed. At the same time, the results indicated in the table are achieved. eight.

Claims (12)

1. A fungicide for plants containing two biologically active components, characterized in that component 1 is a compound selected from the group including
1A) 1- [3- (4-tert-butyl-phenyl) -2-methylpropyl] -piperidine ("phenpropidine"), or one of its salts, or one of its metal complexes;
1B) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile ("fludioxonil");
1B) N- (trichloromethylthio) cyclohex-4-en-1,2-dicarboximide ("captan"), and
that component II is 2-anilinopyrimidine of formula II

4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine, or one of its salts, or one of its metal complexes, the weight ratio of 1: II being 1: 10 to 30: 1.  2. The fungicide according to claim 1, characterized in that component 1 is compound 1A) 1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine (2-phenpropidine).  3. The fungicide according to claim 1, characterized in that component 1 is compound 1B) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile ("fludioxonil") .  4. The fungicide according to claim 1, characterized in that component 1 is compound 1B) N- (trichloromethylthio) cyclohex-4-en-1,2-dicarboximide ("captan").  5. The fungicide according to claim 1, characterized in that the weight ratio of 1: II is 1: 5 to 3: 1.  6. A method of combating fungi and protecting plants from them, characterized in that the place affected or at risk of being affected by fungi is treated in any sequence on the same day or simultaneously with component 1 and component II according to claim 1 in an amount of from 50 g to 2 kg biologically active substances per hectare or from 0.5 to 1 kg of biologically active substance per 100 kg of seed. 7. The method according to claim 6, in which component 1 is a compound selected from the group including
1A) 1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine ("phenpropidine") or one of its salts or one of its metal complexes;
1B) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile ("fludioxonil");
1B) N- (trichloromethylthio) cyclohex-4-en-1,2-dicarboximide ("captan").  8. The method according to claim 6, in which component 1 is compound 1A 1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine ("phenpropidine").  9. The method of claim 6, wherein component 1 is compound 1B of 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile (“fludioxonil”).  10. The method according to claim 6, in which component 1 is compound 1B N- (trichloromethylthio) cyclohex-4-en-1,2-dicarboximide ("captan").  11. The method according to claim 6, characterized in that they process plant propagation material.  12. The method according to claim 11, in which, as component 1, a compound of formula 1C ("fludioxonil") is used. Priority on points:
06/28/93 - according to claims 1 - 5, 7, 8, 9, 10, 12;
07/16/93. - according to claims 6, 11.

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