WO2004039157A1

WO2004039157A1 - Fungicide mixtures containing oxazinone

Info

Publication number: WO2004039157A1
Application number: PCT/EP2003/011226
Authority: WO
Inventors: Joachim Rheinheimer; Thomas Grote; Eberhard Ammermann; Reinhard Stierl; Siegfried Strathmann; Ulrich Schöfl
Original assignee: Basf Aktiengesellschaft
Priority date: 2002-10-28
Filing date: 2003-10-10
Publication date: 2004-05-13
Also published as: AU2003278066A1

Abstract

The invention relates to fungicide mixtures containing a) an oxazine of formula (I), in which R1 represents n-propyl or n-butyl; R2 represents methyl, ethyl or n-propyl; R3 represents fluorine, chlorine, bromine or iodine and at least one compound b) to g) of formulas (II) to (VII), as cited in the description.

Description

Fungicidal mixtures containing oxazinones

description

The present invention relates to fungicidal mixtures comprising

a) an oxazine of the formula I,

in the

R ^{1 is} n-propyl or n-butyl; R ^{2 is} methyl, ethyl or n-propyl; R ^{3 represents} fluorine, chlorine, bromine or iodine;

and

b) an amine II selected from the group Ila to Ile:

- (R, S) cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2, 6-dimethylmorpholine

(R, S) -1- [3- (4-fcerfc-butylphenyl) -2-methylpropyl] piperidine

(E, Z) -4- [3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) -l-oxo-2-propenyl] morpholines

- 4-tridecyl-2, 6-dimethylrrιorpholine

H, C —— ((CCHH 2 ",)) 'Ild,

8-fcerfc-butyl-1,4-doxaspiro [4,5] decan-2-ylmethyl (ethyl) (propyl) amine

Ile,

and or

an azole III selected from the group of the compounds purple to Ille:

(2RS, 3SR) -1- [3- (2-chlorophenyl) -2- (4-f luorophenyl) oxiran-2-ylmethyl] -1H-1, 2, 4-triazole

(lRS, 5RS; lRS, 5SR) -5- (4-chlorobenzyl) -2,2-dimethyl-l- (lH-l, 2,4-triazol-l-ylmethyl) cyclopentanol

(R, S) -1- [2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-ylmethyl] -lH-l, 2,4-triazole

(R, S) -1- (4-chlorophenyl) -4, 4-dimethyl-3- (1H-1, 2, 4-triazol-1-ylmethyl) pentan-3-ol

(R, S) -1- (2-chlorophenyl) -2- (1-chlorocyclopropyl) -3- (5-mer-capto-lH-l, 2,4-triazolyl) propan-2-ol

and or

d) an oxime IV selected from the group of compounds IVa and IVb:

2,3-difluoro-6-difluoromethoxy-N-phenacetylbenzamide-O-cyclopropylmethyloxime

2,3-difluoro-6-trifluoromethyl-N-phenacetylbenzamide-O-cyclopropylmethyloxime

and or

trobilurin V selected from the group of compounds is Vf:

Methyl -E-methoxyimino- [alpha- (o-tolyloxy) -o-tolyl] acetate

Methyl E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate

Methyl -E-methoxyimino- [alpha- (o-2,5-dimethylphenoxy) -o-tolyl] acetamide

Methyl E-2- {2- [(2-trifluoromethylpyridyl-6-) oxymethyl] phenyl} -3-methoxyacrylate

Methyl-E, E-methoximino- {2- [1- (3-trifluoromethyl-phenyl) ethyl idenaminooxymethyl] phenyl} acetate

Methyl -N- (2- {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} phenyl) -N-methoxycarbamate

and or

f) 5-Bromo-2 ', 6-dimethyl-2, 4', 5 ', 6' -tetramethoxybenzophenone VI:

and or

g) N- (4 'chlorobiphenyl-2) nicotinamide VII:

In addition, the invention relates to methods for combating harmful fungi with mixtures of the compounds I and II to VII and to agents which are conditioned in two parts and contain the compounds I and II to VII.

The compounds of the formulas II to VII are described in the literature as detailed below. The amine derivatives of the formula II, their preparation and their action against harmful fungi are known from the literature:

Ila common name: Fenpropimorph, DE-A 2752096; Ilb common name: Fenpropidin, GB 1584290; Ile common name: Dirnethomorph, EP-A 120 321; Ild common name: Trideorph, DE-A 1164152; Ile common name: Spiroxamine, EP-A 281 842.

The azole derivatives of the formula III, their preparation and their action against harmful fungi are known to the person skilled in the art from the literature:

purple: common name epoxiconazole, EP-A 196 038; Illb: common name metconazole, Proc. Br. Crop Prot. Conf. - Pests Dis., 5-4, 419 (1992);

IIIc: common name: propiconazole, GB-A 1,522,657; Illd: common name tebuconazole, EP-A 40 345; Here: common name prothioconazole, WO-A 96/16048.

The oxime derivatives of the formula IV, their preparation and their action against harmful fungi are known from the literature:

IVa: EP-A 1 017 670 and EP-A 1 017 671; IVb: common name: Cyflufenamide, WO-A 96/19442.

The strobilurin derivatives of the formula V, their preparation and their action against harmful fungi are known from the literature:

Va common name Kresoxim-methyl, EP-A 253 213;

Vb common name azoxystrobin, EP-A 382 375;

Vc common name dimoxystrobin, EP-A 477 631;

Vd common name picoxystrobin, EP-A 278 595;

Ve common name trifloxystrobin, EP-A 460 575;

Vf common name pyraclostrobin, WO-A 96/01256.

The benzophenone of formula VI, its production and its action against harmful fungi is known from the literature:

VI: EP-A 897 904.

The anilide of formula VII, its production and its action against harmful fungi is known from the literature:

VII; common name: Nicobifen, EP-A 545 099. The compounds of formula I, their preparation and their action against harmful fungi are known from the subsequently published document DE-A 101 24 798.2. It is also mentioned in this document that compounds which generally have an oxazine structure can be used together with other pesticides, for example fungicides. However, no specific mixture combinations are specified in the script.

In the present invention, the mixture combinations mentioned at the outset were found, which bring numerous advantages in terms of application. In many cases, the mixture increases the fungicidal spectrum of activity. By applying the mixture according to the invention, the farmer can effectively combat the infestation caused by different harmful fungi. As a rule, application of suitable fungicide mixtures can also prevent the development of resistance to one of the solo active ingredients.

In a particularly preferred embodiment, the individual active ingredient components are used in the mixture in a synergistically effective amount. In this way, the total amount of active ingredients applied can be significantly reduced.

It has also been found that with simultaneous, joint or separate use of the compounds I and the compounds II to VII or when the compounds I and the compounds II to VII are used in succession, harmful fungi can be controlled better than with the individual compounds alone.

The following compounds of the formula I are preferred as mixing partners, the individual preferences taken on their own and to be read in combination.

Compounds I in which R ^{1 is} n-propyl are preferred.

In addition, compounds I are preferred in which R ^{2 represents} methyl or ethyl.

Compounds I are particularly preferred in which R ^{3 represents} iodine.

In particular, the mixtures according to the invention can contain the following compounds of the formula I in which the substituents have the meanings given in the table below:

Preferred components a) are the compounds of the formulas 1-4, 1-8, 1-12, 1.16 and 1.20. Fungicidal mixtures which contain the compound 1-4 as component a) are particularly preferred.

Because of the basic character of the nitrogen atoms contained in them, the compounds I are capable of forming salts or adducts with inorganic or organic acids or with metal ions. Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.

Examples of suitable organic acids are formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-benzoic acid, 2-phenol acid or 2-benzoic acid Acetoxybenzoic acid into consideration.

In particular, the ions of the elements of the first to eighth subgroups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and in addition the second main group, especially calcium and magnesium, of the third and fourth main group come as metal ions Aluminum, tin and lead are considered. The metals can optionally be present in different valences.

When preparing the mixtures, preference is given to using the pure active ingredients I and II to VII, to which further active ingredients can be admixed against harmful fungi or against other pests such as insects, arachnids or nematodes or else herbicidal or growth-regulating active ingredients or fertilizers.

With regard to their action against harmful fungi, the binary mixtures comprising a) an oxazinone of the formula I and, as the second component, an active ingredient selected from the group: b) an amine of the formula II, c) an azole of the formula III and e) proven a strobilurin of formula V.

With regard to their action against harmful fungi, in particular the ternary mixtures comprising a) an oxazinone of the formula I, b) an amine of the formula II and c) an azole of the formula III have been found. At the same time, ternary mixtures comprising a) an oxazinone of the formula I, c) an azole of the formula III and e) a strobilurin of the formula V have been found to be advantageous.

The mixtures of the compounds I and II to VII or the compounds I and II to VII used simultaneously, together or separately, are distinguished by an excellent action against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes , Phycomycetes and Deuteromycetes from. Some of them are systemically effective and can therefore also be used as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (eg cucumber, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye , Soy, wine, wheat, ornamental plants, sugar cane and a variety of seeds. In particular, fungal diseases on cereals and grapevines can be combated with the mixtures according to the invention.

They are particularly suitable for combating the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cotton, cereals, Ähi2 Rice and lawn, üstilagσ species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosphorium species on cereals, Septoria nodorum on wheat, Botrytis ci - nera (gray mold) on strawberries, vegetables, ornamental plants and vines , Cercospora arachidicola on peanuts, Pseudocercosporella hezpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara vi ticola on vines, Pseudoperonospora atates in hops and cucumbers, Al eraaria species on vegetables and Al Obstaia species on vegetables Species in bananas as well as Fusarium and Verticilli um species. The mixtures according to the invention have proven to be particularly advantageous in combating the group of powdery mildew fungi.

They can also be used in material protection (e.g. wood protection), for example against Paecilomyces variotii.

The compounds I and II to VII can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the success of the control measures.

The compounds I and II to VII are usually used in a weight ratio of 20: 1 to 1:20, in particular 10: 1 to 1:10, preferably 5: 1 to 1: 5.

The following mixing ratios have proven to be particularly advantageous, particularly with regard to a synergistic effect, in the case of binary mixtures: 1 part by weight of oxazine of the formula I is used

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight amine II;

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of azole III;

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of oxime IV;

0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight of strobilurin V;

0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight of benzophenone VI; 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of anilide VII;

In the binary and ternary mixtures, the compounds I, II and / or III (I, III and / or V) are used such that the respective mixing ratios of the compounds I and II (I and V), I and III, and II and III (III and V) are each 20: 1 to 1:20 and in particular 10: 1 to 1:10.

The application rates of the mixtures according to the invention, especially for agricultural crop areas, are from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.1 to 3.0 kg / ha, depending on the type of effect desired ,

The application rates for the compounds I are 0.005 to 5 kg / ha, preferably 0.08 to 3 kg / ha, in particular 0.06 to 2.0 kg / ha.

The application rates for the compounds II are accordingly from 0.01 to 3 kg / ha, preferably 0.05 to 2 kg / ha, in particular 0.1 to 1 kg / ha.

The application rates for the compounds III are accordingly from 0.01 to 2 kg / ha, preferably 0.05 to 1 kg / ha, in particular 0.05 to 0.5 kg / ha.

The application rates for the compounds IV are accordingly 0.005 to 1 kg / ha, preferably 0.01 to 0.5 kg / ha, in particular 0.01 to 0.2 kg / ha.

The application rates for the compounds V are accordingly from 0.01 to 3 kg / ha, preferably 0.05 to 2 kg / ha, in particular 0.1 to 1 kg / ha.

The application rates for the compounds VI are accordingly 0.005 to 1 kg / ha, preferably 0.01 to 0.5 kg / ha, in particular 0.01 to 0.2 kg / ha. The application rates for the compounds VII are accordingly from 0.01 to 3 kg / ha, preferably 0.05 to 2 kg / ha, in particular 0.1 to 1 kg / ha.

In the case of seed treatment, application rates of the mixture of 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg, are generally used.

If pathogenic harmful fungi are to be combated for plants, the compounds are applied separately or jointly

I and II to VII or the mixtures of the compounds I and

II to VII by spraying or dusting the seeds, plants or soil before or after sowing the plants or before or after emergence of the plants.

The fungicidal mixtures according to the invention or the compounds I and II to VII can be used, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, old-dispersions, pastes, dusts, spreading agents or granules processed and applied by spraying, atomizing, dusting, scattering or pouring. The form of application depends on the intended use; in any case, it should ensure as fine and uniform a distribution of the mixture according to the invention as possible.

The formulations are prepared in a manner known per se, e.g. by adding solvents and / or carriers. Inert additives such as emulsifiers or dispersants are usually added to the formulations.

The surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol Isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose.

Powders, materials for spreading and dusts can be prepared by mixing or jointly grinding the compounds I or II or the mixture of the compounds I, II and optionally III with a solid carrier.

Granules (e.g. coating, impregnation or homogeneous granules) are usually produced by binding the active ingredient or ingredients to a solid carrier.

Mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics and fertilizers are used as fillers or solid carriers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations in general contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and II to VII or of the mixture of the compounds I and II to VII used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum).

The compounds I and II to VII, the mixtures or the corresponding formulations are used in such a way that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them are mixed with a fungicidally effective amount of the mixture, or the compounds I and II to VII treated separately.

The application can take place before or after the infestation by the harmful fungi.

example

The advantageous fungicidal activity of the mixtures according to the invention was demonstrated by the following tests:

The active ingredients were prepared separately or together as a 10% emulsion in a mixture of 63% by weight cyclohexanone and 27% by weight emulsifier and in accordance with the desired concentration diluted with water.

The synergistic effect of the mixtures according to the invention was demonstrated by the following experiments:

The evaluation was carried out by determining the affected leaf areas in percent. These percentages were converted into efficiencies. Efficiency (W) was determined using Abbot's formula as follows:

W = (1 - α / β) -100

α corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants showed no infection.

The expected efficacies of the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and bx the efficiency, expressed in% of the untreated control, when using active ingredient A in concentration ay der Efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b

Example of use 1 - Activity against powdery mildew (Erysiphe graminis f. Sp. Tri tici)

Leaves of potted wheat seedlings of the variety

"Chancellors" were sprayed to runoff point with aqueous preparation of active compound, which was prepared from a stock solution consisting of 10% active compound, 63% cyclohexanone and 27% emulsifier, and 24 hours after the spray coating had dried on, with spores of the powdery mildew (Erysiphe graminis forma specialis tritici ) pollinated. The test plants were then grown in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity set up. After 7 days, the extent of mildew development was determined visually in% attack on the entire leaf area.

Claims

claims

Fungicidal mixtures containing

a) an oxazine of the formula I,

in the

R ^{1 is} n-propyl or n-butyl;

R ^{2 is} methyl, ethyl or n-propyl;

R ^{3 represents} fluorine, chlorine, bromine or iodine;

and

b) an amine II selected from the group Ila to Ile:

(R, S) cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2, 6-dimethylmorpholine

(R, S) -1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine

(E, Z) -4- [3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -l-oxo-2-propenyl] morpholines

-tridecyl-2, 6-dimethylmorpholines

ild,

- ert-butyl-1,4-doxaspiro [4,5] decan-2-ylmethyl (ethyl) (propyl) amine

and or

an azole III selected from the group of the compounds purple to Ille:

(lRS, 5RS; lRS, 5SR) -5- (4-chlorobenzyl) -2,2-dimethyl-1- (lH-l, 2,4-triazol-l-ylmethyl) cyclopentanol

Cl (R, S) -l- (4-chlorophenyl) -4,4-dimethyl-3- (1H-l, 2,4-triazol-1-ylmethyl) pentan-3-ol

and or

an oxime IV selected from the group of compounds IVa and IVb:

2,3-difluoro-6-difluoromethoxy-N-phenacetylbenzamide-O-cy-c1opropyImeth 1oxime

2,3-difluoro-6-trifluoromethyl-N-phenacetylbenzamide-O-cy-c1opropyImethy1oxime

and or

a strobilurin V selected from the group of compounds Va to Vf:

Methyl -E-methoxyimino- [alpha- (o-tolyloxy) -o-tolyl] acetate

Methyl-E-methoxyimino- [alpha- (o-2,5-dimethylphenoxy) -o-tolyl] acetamide

Methyl E-2- {2- [(2-trifluoromethylpyridyl-6-) oxymethyl] phenyl} -3 - ethoxyacrylate

Methyl-E, E-methoximino- {2- [1- (3-trifluoromethylphenyl) ethylideneaminooxymethyl] phenyl} acetate

Methyl N- (2- {[1- (4-chlorophenyl) -IH-pyrazol-3-yl] oxymethyl} -phenyl) -N-methoxycarbamate

and or

f) 5-Bromo-2 ', 6-dimethyl-2, 4', 5 ', 6' -tetramethoxybenzophenone VI:

and or

g) N- (4 'chlorobiphenyl-2) nicotinamide VII:

2. Fungicidal mixtures according to claim 1, wherein in formula I

R ^{3 represents} iodine.

3. Fungicidal mixture according to claim 1, characterized in that the weight ratio of the oxazinones I to the compounds II to VII is 20: 1 to 1:20.

4. A fungicidal mixture as claimed in claims 1 to 3, comprising, in addition to component a), one or two of the following components b) and c):

b) an amine of formula II;

10 c) an azole derivative of the formula III.

5. Fungicidal mixture according to claims 1 to 3, comprising in addition to component a) one or two of the following components

15 ten c) and e):

c) an azole of the formula III;

e) a strobilurin of formula V. 20

6. A method of combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free by them are mixed with a fungicidal mixture

25 treated one of claims 1 to 5.

7. The method according to claim 6, characterized in that an oxazinone of formula I according to claim 1 and a compound of formulas II to VII in a synergistically effective

30 quantity used.

8. The method according to claim 6, characterized in that the oxazinone of the formula I according to claim 1 is used in an amount of 0.08 to 3 kg / ha.

35

9. The method according to claims 6 to 8, characterized in that the compounds of the formulas II to VII according to claim 1 in an amount of 0.02 to 2 kg / ha.

10. A composition according to claim 1 which is conditioned in two parts, one part containing an oxazinone of the formula I according to claim 1 in a solid or liquid carrier and the other part a compound of the formulas II to VII according to claim 1 in one contains solid or liquid carrier.

45