EP1830643A1

EP1830643A1 - Fungicidal mixtures

Info

Publication number: EP1830643A1
Application number: EP05821560A
Authority: EP
Inventors: Markus Gewehr; Reinhard Stierl; Matthias NIEDENBRÜCK; Udo HÜNGER
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-12-23
Filing date: 2005-12-21
Publication date: 2007-09-12
Also published as: IL183561A0; CA2589787A1; WO2006069713A1; CN101080169A; JP2008525351A; AU2005321579A1; US20080188530A1; BRPI0519234A2; KR20070093119A; AU2005321579B2

Abstract

The inventive fungicidal mixtures contain the following active components: 1) strobilurin derivatives of formula (I), and 2) at least one type of active substance (II) selected from a carboxamide group in a synergistically active quantity. Said invention also relates to a method for controlling harmful fungi by means of the mixtures of the compound (I) and the active substances (II), to the use of the compound (I) and the active substances (II) for producing said mixtures and to agents containing said mixtures.

Description

Fungicidal mixtures

description

The present invention relates to fungicidal mixtures containing as active components

1) the strobilurin derivative of the formula I ₁

and

2) at least one active ingredient II selected from the group of carboxylic acid amides:

Carboxin, benalaxyl, boscalid, fenhexamide, flutolanil, furametpyr, mepronil,

Metalaxyl, mefenoxam, ofurace, oxadixyl,

Oxycarboxine, penthiopyrad, thifluzamide, tiadinil,

3,4-dichloro-N- (2-cyanophenyl) isothiazole-5-carboxamide,

Flumetover, fluopicolide (picobenzamide), zoxamide, carpropamide, diclocymet, mandipropamide,

N- (2- {4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl} -ethyl) -2-methanesulfonylamino-3-methylbutyramide (HA) , N- (2- {4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl} -ethyl) -2-ethanesulfonyl-amino-3-methyl-butyramide (II-B ); and

Amides of formula III,

in the variables and the index have the following meanings: R ¹ and R ² are independently hydrogen, halogen, Ci-C ₆ alkyl or C ₁ -C ₆ haloalkyl, cyano, nitro, methoxy, or trifluoromethoxy, with with the proviso that R ¹ and R ^{2 are} not simultaneously hydrogen, and R ^{3 is} CF ₃ or CHF ₂ ;

in a synergistically effective amount.

In addition, the invention relates to a method for controlling harmful fungi

Mixtures of the compound I with active compounds II and the use of the compound I with active compounds II for the preparation of such mixtures and agents which comprise these mixtures.

The strobilurin derivative of the formula I ₁ 2- {2-, referred to above as component 1

[3- (4-Chlorophenyl) -1-methyl-allylidenaminooxymethyl] -phenyl} -3-methoxy-acrylic acid methyl ester, its preparation and its action against harmful fungi is known from the

Literature known (EP-A 936 213, common name: Enestroburin).

The active ingredients II mentioned above as component 2, their preparation and their

Action against harmful fungi are well known (see: http://www.hclrss.demon.co.uk/index.html); they are commercially available.

Carboxin, 5,6-dihydro-2-methyl-Λ / -phenyl-1, 4-oxathiin-3-carboxamide (US 3,249,499), benalaxyl, methyl Λ / - (phenylacetyl) -Λ / - (2,6 -xylyl) -DL-alaninate (DE 29 03 612),

Boscalid, 2-chloro-Λ / - (4'-chlorobiphenyl-2-yl) nicotinamide (EP-A 545 099);

Fenhexamide, N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (Proc.

Br. Crop Prot. Conf. - Pests Dis., 1998, vol. 2, p. 327);

Flutolanil, σ, σ, σ-trifluoro-3'-isopropoxy-o-toluanilide (JP 1104514), furametpyr, 5-chloro-Λ / - (1, 3-dihydro-1, 1, 3-trimethyl-4-isobenzofuranyl ) -1, 3-dimethyl-1H-pyrazole-4-carboxamide [CAS RN 123572-88-3],

Mepronil, 3'-isopropoxy-o-toluanilide (US 3,937,840),

Metalaxyl, methyl Λ / - (methoxyacetyl) -Λ / - (2,6-xylyl) -DL-alaninate (GB 15 00 581);

Mefenoxam, methyl Λ / - (2,6-dimethylphenyl) -Λ- (methoxyacetyl) -D-alaninate; Ofurace, (RS) -σ- (2-chloro-Λ / -2,6-xylylacetamido) -κ-butyrolactone [CAS RN 58810-48-3];

oxadixyl; / V- (2,6-dimethylphenyl) -2-methoxy-Λ / - (2-oxo-3-oxazolidinyl) acetamide (GB

20 58 059),

Oxycarboxine, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (US

3,399,214), penthiopyrad, Λ / - [2- (1, 3-dimethylbutyl) -3-thienyl] -1-methyl-3- (trifluoromethyl) -1 / - / - pyrazole

4-carboxamide (JP 10130268),

Thifluzamide,

Tiadinil, 3'-chloro-4,4'-dimethyl-1,2,3-thiadiazole-5-carboxanilide [CAS RN 223580-51-6],

Flumetover, 2- (3,4-dimethoxyphenyl) -Λ / -ethyl-σ, σ, σ-trifluoro-Λ / -methyl-p-toluamide [AGROW No. 243, 22 (1995)], Fluopicolide (picobenzamide) ₎ 2,6-dichloro-N- (3-chloro-5-trifluoromethylpyridin-2-ylmethyl) benzamide (WO 99/42447);

Zoxamide, (f? S) -3,5-dichloro-Λ / - (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -p-toluamide [CAS

RN 156052-68-5]; Carpropamide, 2,2-dichloro-Λ / - [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methylcyclopropane carboxamide [CAS RN 104030-54-8],

Diclocymet, 2-cyano-Λ / - [(1f?) - 1- (2,4-dichlorophenyl) ethyl] -3,3-dimethylbutanamide;

Mandipropamide, (RS) -2- (4-chlorophenyl) -Λ / - [3-methoxy-4- (prop-2-ynyloxy) phenethyl] -2-

(prop-2-ynyloxy) acetamide [CAS RN 374726-62-2].

The carboxylic acid amides without common name, their preparation and their fungicidal action are also known:

3,4-dichloro-N- (2-cyanophenyl) -isothiazole-5-carboxylic acid amide, (WO 99/24413),

N- (2- {4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl} -ethyl) -2-methanesulfonyl-amino-3-methylbutyramide (HA) , N- (2- {4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl} -ethyl) -2-ethanesulfonyl-amino-3-methyl-butyramide (HB ) (WO 04/049804),

R is methyl (M-A) or ethyl (H-B); and amides of the formula III, (WO 03/066609).

With regard to a reduction of the application rates and a broadening of the spectrum of action of the known compounds, mixtures of the present invention were based on an improved effect against harmful fungi, in particular for certain indications, with a reduced total amount of applied active substances.

Accordingly, the mixtures defined above were found. It has also been found that, with simultaneous simultaneous or separate application of the compound I and of an active compound II or, when using the compound I and an active compound II, harmful fungi can be controlled better successively than with the individual compounds (synergistic mixtures). Compound I can be used as a synergist for a variety of different agents. By simultaneous joint or separate application of the compound I with an active compound II, the fungicidal activity is increased to a superadditive extent. The mixtures of the compound I and of an active compound II, or the simultaneous joint or separate use of the compound I and an active compound II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes , Oomycetes and Basidiomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.

They are particularly important for the control of a variety of fungi on various crops such as bananas, cotton, vegetables (eg cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soy, tomatoes , Wine, wheat, ornamental plants, sugar cane and a variety of seeds.

They are advantageously suitable for controlling the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphae- rotheca fuliginea on cucurbits, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia arias on cereals, Rhizoctonia species Cotton, Rice and Turf, Ustilago A anen on cereals and sugar cane, Venturia inaequalis on apples, Bipolaris and Drechslera Aύeu on cereals, rice and turf, Sepfor / a species on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and vines, mycosophaerella arias on bananas, peanuts and cereals, Pseudocercosporella herpotri- chides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora on cucurbits and hops, Plasmopara viticola on vines, Alternaria -Aeas of vegetables and fruits as well as Fusarium and Verticillium Aύen.

The compound I and active compounds II can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally having no effect on the control result.

In the definitions of the symbols given for formula III collective terms were used, which stand for the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 6 carbon atoms, for example C _r C ₄ alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl; Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, where in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular C ₁ -C ₂ -HaIo- genalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl , Difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoro-ethyl, 2-chloro-2-fluoroethyl , 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.

With regard to the use of the amides of the formula III in the mixtures according to the invention, the following compounds of the formulas IIIa to IIIf are particularly suitable:

Particularly preferred are the compounds of the formula IMd. Particular preference is given to the compounds compiled in the following tables:

Table 1

Compounds 1.1 to 1.22: Compounds of the formula IIIa in which R ^{1 is} fluorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 2

Compound 2.1 - 2.22: Compounds of the formula IIIa in which R ^{1 is} chlorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Compound 3.1 - 3.22: Compounds of the formula IIIa in which R ^{1 is} bromine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 4

Compound 4.1 - 4.22: Compounds of the formula IIIa in which R ^{1 is} iodine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 5

Compounds 5.1 to 5.22: Compounds of the formula IIIa in which R ^{1 is} methyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 6

Compound 6.1 - 6.22: Compounds of the formula IIIa in which R ^{1 is} methoxy and the combination of R ² and R ^{3 is} in each case one row of Table A. Table 7

Compound 7.1 - 7.22: Compounds of the formula IIIa in which R ^{1 is} trifluoromethyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 8

Compound 8.1 - 8.22: Compounds of the formula IIIa in which R ^{1 is} trifluoromethoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 9 Compound 9.1 - 9.22. Compounds of the formula IIIa in which R ^{1 is} cyano and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 10

Compound 10.1-10.22: Compounds of the formula IIIa in which R ^{1 is} nitro and R ^{2 is} in each case one row of Table A.

Table 11

Compound 11.1-11.20: Compounds of the formula IIIa in which R ^{1 is} hydrogen and the combination of R ² and R ^{3 is} in each case one of the rows 2 to 21 of Table A.

Table 12

Connection 12.1 - 12.22. Compounds of the formula IIIb in which R ^{1 is} fluorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 13

Compounds 13.1-13.22: Compounds of the formula IIIb in which R ^{1 is} chlorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 14 Compound 14.1-14.22: Compounds of the formula INb in which R ^{1 is} bromine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 15

Compounds 15.1-15.22: Compounds of the formula IHb in which R ^{1 is} iodine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 16

Compound 16.1-16.22: Compounds of the formula IIIb in which R ^{1 is} methyl and the combination of R ² and R ^{3 is} in each case one row of Table A. Table 17

Compound 17.1-17.22: Compounds of the formula INb in which R ^{1 is} methoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 18

Compound 18.1-18.22: Compounds of the formula NIb, in which R ^{1 is} trifluoromethyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 19 Compound 19.1-19.22 Compounds of the formula IUb in which R ^{1 is} trifluoromethoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 20

Compound 20.1 - 20.22: Compounds of the formula INb, in which R ^{1 is} cyano and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 21

Compounds 21.1-21.22: Compounds of the formula IUb in which R ^{1 is} nitro and the combination of R ² and R ^{3 is} each one of the meaning of Table A.

Table: 22

Compound 22.1-22.20: Compounds of the formula IIIb in which R ^{1 is} hydrogen and the combination of R ² and R ^{3 is} in each case one of the rows 2 to 21 of Table A.

Table 23

Compound 23.1-23.22: Compounds of the formula IHc in which R ^{1 is} fluorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 24 Compound 24.1 - 24.22: Compounds of the formula IIIc in which R ^{1 is} chlorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 25

Compound 25.1-25.22: Compounds of the formula NIc, in which R ^{1 is} bromine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 26

Compound 26.1-26.22: Compounds of the formula IHc in which R ^{1 is} iodine and the combination of R ² and R ^{3 is} in each case one row of Table A. Table 27

Compound 25.1-25.22: Compounds of the formula IHc in which R ^{1 is} methyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 28

Compound 28.1-28.22: Compounds of the formula IHc in which R ^{1 is} methoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Compound 29.1-29.22: Compounds of the formula Never in which R ^{1 is} trifluoromethyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 30

Compound 30.1 - 30.22: Compounds of the formula IHc in which R ^{1 is} trifluoromethoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 31

Compound 31.1-31.22: Compounds of the formula IIIc in which R ^{1 is} cyano and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 32

Compound 32.1-32.22: Compounds of the formula IIIc in which R ^{1 is} nitro and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 34

Compound 34.1-34.22: Compounds of the formula HId in which R ^{1 is} fluorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Compound 35.1 -35.22: Compounds of the formula HId in which R ^{1 is} chlorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 36

Compound 36.1-36.22: Compounds of the formula HId in which R ^{1 is} bromine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 37

Compound 37.1 - 37.22: Compounds of the formula IHd in which R ^{1 is} iodine and the combination of R ² and R ^{3 is} in each case one row of Table A. Table 38

Compounds 38.1-38.22: Compounds of the formula IHd ₁ in which R ^{1 is} methyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 39

Compound 39.1-39.22: Compounds of the formula IHd in which R ^{1 is} methoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 40 Compound 40.1 - 40.22: Compounds of the formula IMd, in which R ^{1 is} trifluoromethyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 41

Compound 41.1-41.22: Compounds of the formula IHd in which R ^{1 is} trifluoromethoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 42

Compound 42.1-42.22: Compounds of the formula HId in which R ^{1 is} cyano and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 43

Compound 43.1-43.22: Compounds of the formula HId in which R ^{1 is} nitro and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table: 44

Compounds 44.1-44.20: Compounds of the formula IHd in which R ^{1 is} hydrogen and the combination of R ² and R ^{3 is} in each case one of lines 2 to 21 of Table A.

Table 45 Compound 45.1-45.22: Compounds of the formula IIIe in which R ^{1 is} fluorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 46

Compound 46.1-46.22: Compounds of the formula IH in which R ^{1 is} chlorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 47

Compound 47.1-47.22: Compounds of the formula Never in which R ^{1 is} bromine and the combination of R ² and R ^{3 is} in each case one row of Table A. Table 48

Compound 48.1 - 48.22: Compounds of the formula Never in which R ^{1 is} iodine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 49

Compound 49.1-49.22: compounds of the formula Never in which R ^{1 is} methyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Compound 50.1 - 50.22: Compounds of the formula Never in which R ^{1 is} methoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 51

Compound 51.1 - 51.22: compounds of the formula Never in which R ^{1 is} trifluoromethyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 52

Compound 52.1-52.22: Compounds of the formula INe in which R ^{1 is} trifluoromethoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 53

Compound 53.1-53.22: Compounds of the formula IMe, in which R ^{1 is} cyano and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 54

Compound 54.1-54.22: Compounds of the formula IH in which R ^{1 is} nitro and the combination of R ² and R ^{3 is} in each case one row of Table A.

Compound 56.1-56.22: Compounds of the formula HIf ₁ in which R ^{1 is} fluorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 57

Compound 57.1-57.22: Compounds of the formula Nif in which R ^{1 is} chlorine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 58

Connection 58.1. - 58.22: Compounds of the formula IIIf in which R ^{1 is} bromine and the combination of R ² and R ^{3 is} in each case one row of Table A. Table 59

Compound 59.1-59.22: Compounds of the formula IIIf in which R ^{1 is} iodine and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 60

Compound 60.1-60.22: Compounds of the formula IIIf in which R ^{1 is} methyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 61 Compound 61.1 - 61.22: Compounds of the formula IIIf in which R ^{1 is} methoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 62

Compound 62.1-62.22: Compounds of the formula HIf in which R ^{1 is} trifluoromethyl and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 63

Compound 63.1-63.22: Compounds of the formula IIIf in which R ^{1 is} trifluoromethoxy and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 64

Compound 64.1-64.22: Compounds of the formula IIIf in which R ^{1 is} cyano and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 65

Compound 65.1-65.22: Compounds of the formula IIIf in which R ^{1 is} nitro and the combination of R ² and R ^{3 is} in each case one row of Table A.

Table 66 Compound 66.1-66.20: Compounds of the formula IIIf in which R ^{1 is} hydrogen and the combination of R ² and R ^{3 is} in each case one of the rows 2 to 21 of Table A.

Table A

A preferred embodiment of the mixtures according to the invention relates to the combination of the compound of the formula I and one of the active compound from the group: carboxylic anilides, in particular fenhexamide, benalaxyl, boscalid, penthiopyrad, an anilide of the formula III.

Preference is given to providing the mixtures, the pure active ingredients, which can be added as needed further active ingredients against harmful fungi or other pests such as insects, spider animals or nematodes, or herbicidal or growth-regulating agents or fertilizers as further active components.

Usually, mixtures of compound I with an active ingredient II are used. Under certain circumstances, however, mixtures of compound I with two or optionally several active components may be advantageous.

As further active components in the above sense, especially the above-mentioned active compounds II and in particular the above-mentioned preferred active ingredients in question.

The compound I and the active compound II are usually employed in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10. If desired, the further active components are added to the compound I in a ratio of from 20: 1 to 1:20.

Depending on the nature of the compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g / ha to 2000 g / ha, preferably from 50 to 900 g / ha, in particular from 50 to 750 g / ha.

The application rates for the compound I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

The application rates for the active compound II are correspondingly generally 1 to 2000 g / ha, preferably 10 to 900 g / ha, in particular 40 to 500 g / ha.

In seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg, are generally used.

The method for controlling harmful fungi is carried out by the separate or combined application of the compound I and the active compound II or the mixtures of the compound I and the active ingredient II by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants.

The mixtures according to the invention or the compound I and the active compound II can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

- water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used

- Carriers such as ground natural minerals (eg kaolins, clays, talc, crayons) and ground synthetic minerals (eg fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell meal, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredients. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum). For seed treatment, the formulations in question give, after dilution of from two to ten times, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.

Examples of formulations according to the invention are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC) 20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C. Emulsifiable Concentrates (EC) 15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.

D emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC ₁ OD, FS)

20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active ingredients are mixed with the addition of 50 parts by weight of dispersing and Wetting agents finely ground and produced by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP ₁ SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations

In a ball mill, 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent milled to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, usually water-soluble concentrates (LS), suspensions (FS), dusts (DS) ₁ water-dispersible and water-soluble powders (WS, SS) ₁ emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are used. These formulations may be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing. Preference is given to using FS formulations for seed treatment. Typically, such formulations contain 1 to 800 g / l active ingredient, 1 to 200 g / l surfactants, 0 to 200 g / l antifreeze, 0 to 400 g / l binder, 0 to 200 g / l dyes and solvents, preferably water.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. However, it is also possible to prepare from active substance wetting, adhesion, dispersing or emulsifying agents and any solvents or oil concentrates which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, possibly also just immediately before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. Eg Pluro- never RPE 2035 and Genapol ^® B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®.

The compounds I and II, or the mixtures or the corresponding formulations, are applied by mixing the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free of them with a fungicidally effective amount of the mixture Compounds I and II with separate application, treated. The application can be made before or after the attack by the harmful fungi.

The fungicidal activity of the compound and of the mixtures was demonstrated by the following experiments:

The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control:

The efficiency (W) is calculated according to the formula of Abbot as follows:

W = (1 - σ /)) - 100

a corresponds to the fungal infestation of the treated plants in% and ß corresponds to the fungal infestation of the untreated (control) plants in%

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

The expected efficiencies for drug combinations were determined according to the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicidal combinations), Weeds, 15, pp. 20-22, 1967) and compared with the observed efficiencies. Colby formula:

E = x + y - x-y / 100

expected efficiency, expressed as% of untreated control, using the mixture of active substances A and B at concentrations a and b, expressed as% of untreated control, using active substance A at concentration a, efficiency in% of the untreated control, when using the active substance B in the concentration b

Application Example 1 - Efficacy against the net blotch of barley caused by Pyrenophora teres

Leaves of potted barley seedlings of the cultivar "Igri" were sprayed to drip point with aqueous suspension in the concentration of active compound specified below. 5 days after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ⁰ C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

Use Example 2 - Activity against tomato late blight on tomatoes caused by Phytophthora infestans in protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below. Five days later, the leaves were infected with an aqueous sporangium suspension of Phytophthora infestans. Subsequently, the plants were saturated in a water vapor Chamber placed at temperatures between 18 and 20 ⁰ C. After 6 days, the late blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

From the results of the experiments, it is clear that the mixtures according to the invention are considerably more effective due to the synergism than predicted by the CoI by formula.

Claims

claims

1. Fungicidal mixtures for controlling phytopathogenic harmful fungi containing two active components:

1) the strobilurin derivative of the formula I,

and

Carboxin, benalaxyl, boscalid, fenhexamide, flutolanil, furametpyr, meprilil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxine, penthiopyrad, thifluzamide, tiadinil,

3,4-Dichloro-N- (2-cyanophenyl) -isothiazole-5-carboxylic acid amide, flumetover, fluopicolide (picobenzamide), zoxamide, carpropamide, diclocymet, mandipropamide,

N- (2- {4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl} -ethyl) -2-methanesulfonyl-amino-3-methyl-butyramide (HA), N - (2- {4- [3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl} -ethyl) -2-ethanesulfonylamino-3-methylbutyramide (HB); and

Amides of the formula IM,

in which the variables and the index have the following meanings: R ¹ and R ² independently of one another are hydrogen, halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -haloalkyl, cyano, nitro, methoxy or trifluoromethoxy, with the proviso that R ¹ and R ^{2 are} not simultaneously hydrogen, and R ^{3 is} CF ₃ or CHF ₂ ; in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing the compound of formula I and an active ingredient II in a weight ratio of 100: 1 to 1: 100.

3. A composition containing a liquid or solid carrier and a mixture according to claims 1 or 2.

4. A method for controlling phytopathogenic harmful fungi, characterized in that treating the fungi, their habitat or to be protected against fungal attack plants, the soil or seeds with an effective amount of the compound I and an active ingredient II according to claim 1.

5. Method according to claim 4, characterized in that the compounds I and II according to claim 1 are applied simultaneously, namely jointly or separately, or successively.

6. The method according to claims 4 or 5, characterized in that the compounds I and II according to claim 1 or the mixture according to claims 1 or 2 in an amount of 5 g / ha to 2000 g / ha expends.

7. The method according to claims 4 or 5, characterized in that applying the compounds I and II according to claim 1 or the mixture according to claims 1 or 2 in an amount of 1 to 1000 g / 100 kg of seed.

8. Seed containing the mixture according to claims 1 or 2 in an amount of 1 to 1000 g / 100 kg.

9. Use of the compounds I and II according to claim 1 for the preparation of a suitable agent for controlling harmful fungi.