WO2025031851A1

WO2025031851A1 - Fungicidal compositions comprising carboxamides

Info

Publication number: WO2025031851A1
Application number: PCT/EP2024/071422
Authority: WO
Inventors: Markus Gewehr; Tim Short; Lutz Brahm
Original assignee: Basf Se
Priority date: 2023-08-09
Filing date: 2024-07-29
Publication date: 2025-02-13

Abstract

The present invention relates to fungicidal compositions comprising carboxamide (compounds I) and at least one active compounds II. The invention also relates to an agrochemical composition comprising the composition and a solvent of solid carrier. Further, the invention relates to a non-therapeutic use of the inventive compositions controlling phytopathogenic harmful fungi.

Description

Fungicidal compositions comprising carboxamides

Description

The present invention relates to a fungicidal composition comprising as active component 1)

(1-1) 2-(cyano-(5-fluoro-3-pyridyl)-amino)-N-cyclobutyl-5-methyl-thiazole-4-carboxamide,

(I-2) 2-(cyano-(2,6-difluoro-3-pyridyl)-amino)-N-cyclobutyl-5-methyl-thiazole-4-carboxamide,

(I-3) 2-(N-cyano-(3,5-difluoro-anilino)-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide,

(I-4) 2-(cyano-(5-fluoro-3-pyridyl)-amino)-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide,

(I-5) 2-(cyano-(2,6-difluoro-4-pyridyl)-amino)-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide,

(I-6) 2-(cyano-(2,6-difluoro-4-pyridyl)-amino)-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide,

(I-7) 2-(cyano-(2,6-difluoro-4-pyridyl)-amino)-5-methyl-N-spiro[3.3]heptan-3-yl-thiazole-4-carboxamide,

(I-8) 2-(N-cyano-(3,5-difluoro-anilino)-5-methyl-N-(1-methylcyclopentyl)thiazole-4-carboxamide,

(I-9) 2-(cyano-(2,6-difluoro-4-pyridyl)-amino)-5-methyl-N-(1-methylcyclopentyl)thiazole-4-carboxamide,

(1-10) 2-(cyano-(2,6-difluoro-4-pyridyl)-amino)-N-hexyl-5-methyl-thiazole-4-carboxamide,

(1-11) 2-(cyano-(2,6-difluoro-4-pyridyl)-amino)-N-(2,2-dimethylpropyl)-5-methyl-thiazole-4-carboxamide, as active component 2) at least one azole, or an N-oxide, or an agriculturally useful salt thereof, selected from the group consisting of

(11-1) (2RS)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 H-1 ,2,4-triazol-1-yl)propan-2-ol,

(il-2) (RS)-2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-1 ,2,4-triazole-3-thione, wherein the weight ratio of compound I to compound II is from 20:1 to 1:20.

The invention also relates to an agrochemical composition comprising the composition and a solvent of solid carrier. Further, the invention relates to a non-therapeutic use of the inventive compositions controlling phytopathogenic harmful fungi.

The compounds 1-1 to 1-11 defined above for component 1) are herein collectively referred to as "compound of the formula I” or "compounds I”. The compounds 11-1 to II-2 as defined above for component 2) is herein collectively referred to as "compounds of the formula II” or "compounds II”.

The compounds 1-1 to 1-11 are known from WO 2021/241100. Further, the compound 11-1 and 11-2 are disclosed in are known from http://www.bcpcpesticidecompendium.org/.

One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.

In regard to the present invention the term pests embrace harmful fungi and animal pests.

Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of harmful fungi and harmful animal pests.

There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.

Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natural or adapted resistance against the active compounds In question. Therefore, there is a need for pest control agents that help prevent or overcome resistance.

Especially controlling fungicidal diseases in soybeans is a challenge and already now, more than one active ingredient is needed to achieve sufficient activity. It is expected, that in future all products will consist of at least two active ingredients (binary compositions).

Therefore, it is an object of the present invention to provide, with a view to effective resistance management and effective control of phytopathogenic harmful fungi, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful fungi (synergistic compositions) and a broadened activity spectrum.

We have accordingly found that this object is achieved by the compositions, defined herein, comprising compounds I and at least one compounds II.

Especially, it has been found that the compositions as defined in the outset show markedly enhanced action against pests compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.

Moreover, we have found that simultaneous, that is joint or separate, application of compounds I and compounds II or successive application of compounds I and of compounds II allows better control of harmful fungi than is possible with the individual compounds alone (synergistic compositions). Therefore, the term "composition” in the context of the present invention shall mean a physical composition of the components prior to application or the result of a simultaneous, i.e. joint or separate, application of compounds I and of compounds II on the fungi, their habitat or the seed, the soil or the plants to be protected against fungal attack. Compounds I and/or the compounds II can be present in different crystal modifications, which may differ in biological activity.

The scope of the present invention includes compositions of the (R)- and (S)-isomers and the racemates of compounds I and/or II having one or more chiral centers. As a result of hindered rotation of asymmetrically substituted groups, atrope isomers of active compounds I and/or II may be present. They also form part of the subject matter of the invention.

Agriculturally acceptable salts of the active compounds I, II encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the active compounds. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry 1 to 4 C1-C4- alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4- alkyljsulfonium, and sulfoxonium ions, preferably tri (Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

In the binary mixtures the weight ratio of the component 1) and the component 2) generally depends from the properties of the components used, usually it is in the range of from 1 :10,000 to 10,000:1, often from 1 :100 to 100:1, regularly from 1:50 to 50:1, preferably from 1 :20 to 20:1, more preferably from 1 :10 to 10:1, even more preferably from 1 :4 to 4: 1 and in particular from 1 :2 to 2: 1 . According to further embodiments, the weight ratio of the component

1) and the component 2) usually is in the range of from 1000:1 to 1 :1, often from 100: 1 to 1 :1, regularly from 50:1 to 1:1, preferably from 20:1 to 1 :1, more preferably from 10:1 to 1 :1, even more preferably from 4:1 to 1 :1 and in particular from 2:1 to 1 :1. According to further embodiments, the weight ratio of the component 1) and the component

2) usually is in the range of from 20,000:1 to 1:10, often from 10,000:1 to 1:1, regularly from 5,000:1 to 5:1, preferably from 5,000:1 to 10:1, more preferably from 2,000:1 to 30:1, even more preferably from 2,000:1 to 100:1 and in particular from 1,000:1 to 100:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1 :1 to 1:1000, often from 1 :1 to 1 :100, regularly from 1 :1 to 1 :50, preferably from 1 :1 to 1 :20, more preferably from 1 :1 to 1 :10, even more preferably from 1 :1 to 1 :4 and in particular from 1 :1 to 1 :2.

According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1 :20,000, often from 1 :1 to 1 :10,000, regularly from 1:5 to 1 :5,000, preferably from 1:10 to 1:5,000, more preferably from 1:30 to 1 :2,000, even more preferably from 1:100 to 1 :2,000 to and in particular from 1 :100 to 1:1,000. According to further embodiments, the compound I and the compound II are usually present in the ratios from 20:1 to 1:20, often from 15:1 to 1:15, more often from 10:1 to 1:10, even more often from 9:1 to 1:9, regularly from 8:1 to 1:8, preferably from 7:1 to 1:7, more preferably from 6:1 to 1:6, even more preferably from 5:1 to 1:5, most preferably from 4:1 to 1:4, especially preferably from 3:1 to 1:3, in particular from 2:1 to 1:2, specifically 1:1. The compound I and the compound 11 can be also present in the ratios from 20: 1 to 1 : 1 , often from 15: 1 to 1 : 1 , more often from 10:1 to 1:1, even more often from 9:1 to 1:1, regularly from 8:1 to 1:1, preferably from 7:1 to 1:1, more preferably from 6:1 to 1:1, even more preferably from 5:1 to 1:1, most preferably from 4:1 to 1:1, especially preferably from 3:1 to 1:1, in particular from 2:1 to 1:1.

The compound I and the compound II can be further present in the ratios from 1:1 to 1:20, often from 1:1 to 1:15, more often from 1:1 to 1:10, even more often from 1:1 to 1:9, regularly from 1:1 to 1:8, preferably from 1:1 to 1:7, more preferably from 1:1 to 1:6, even more preferably from 1:1 to 1:5, most preferably from 1:1 to 1:4, especially preferably from 1:1 to 1:3, in particular from 1:1 to 1:2.

In a preferred aspect the present invention relates to fungicidal compositions M.1 to M.110 that are each identified in one row of table M below, wherein component 1) and component 2) are identified together with their relative amounts (weight ratio).

Table M

Some of the binary compositions and agrochemical compositions thereof according to the invention are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants. The binary compositions and agrochemical compositions thereof according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as oilseed rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, oilseed rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

Preferably, binary compositions and agrochemical compositions thereof according to the invention are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

More preferably, binary compositions and agrochemical compositions thereof according to the invention are used for controlling a multitude of fungi on cereals, corn, fruits, vegetables, rice, soybean.

Even more preferably, binary compositions and agrochemical compositions thereof according to the invention are used for controlling a multitude of fungi on wheat, barley, corn (Zea mays), tomato, potato, rice, melon, cucumber, squash, pumpkin, pepper, grapes, soybean.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on wheat.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on barley.

According one preferred embodiment of the invention, the compositions M.1 to M. 110 are used for controlling phytopathogenic harmful fungi on corn (Zea mays).

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on tomato.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on potato.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on melon.

According one preferred embodiment of the invention, the compositions M.1 to M. 110110 are used for controlling phytopathogenic harmful fungi on cucumber.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on squash. According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on pumpkin.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on pepper.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on grapes.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling phytopathogenic harmful fungi on soybean.

Preferably, the binary compositions and agrochemical compositions thereof according to the invention are used for controlling the following causal agents of plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and sunflowers (e.g. A. tragopogonis),' Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e.g. A. solani, A. grandis or A. alternata), tomatoes (e.g. A. solani or A. alternata) and wheat (e.g. A. triticina),' Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e.g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (8. zeicola) on corn, e.g. spot blotch (8. sorokiniana) on cereals and e.g. 8. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages); 8. sguamosa or 8. allii on onion family), oilseed rape, ornamentals (e.g. 8 eliptica), vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae- maydis), rice, sugar beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice; Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum

(formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph: 8. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae),' Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C. lindemuthianum), soybeans (e.g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liriodendrf. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e.g. D. teres, net blotch) and wheat (e.g. D. tritici- repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa,' Elsinoe spp. on pome fruits (E pyri), soft fruits (E veneta: anthracnose) and vines (E ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E betae), vegetables (e.g. E pisi), such as cucurbits (e.g. E cichoracearum), cabbages, oilseed rape (e.g. E cruciferarum),' Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e.g. E turcicum),' Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as E graminearum or E culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), E oxysporum on tomatoes, E solani (f. sp. glycines now syn. E virguliforme ) and E tucumaniae and E brasiliense each causing sudden death syndrome on soybeans, and E veriicillioides on corn; Gaeumannomyces graminis (take- all) on cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gym nosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes and rice; Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M. laxa, M. fructicola and M. fructigena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e.g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis: black Sigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M. arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), oilseed rape (e.g. P. parasitica), onions (e.g. P. destructor), tobacco (P. tabacina) and soybeans (e.g. P. manshurica),' Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans (e.g. P. gregata: stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans: root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum),' Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight) and broad-leaved trees (e.g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, oilseed rape, radish and other plants; Plasmopara spp., e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e.g. P. leucotricha on apples) and curcurbits (P. xanthii)', Polymyxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, 0. acuformis: eyespot, teleomorph: Tapesia yallundae) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e.g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e.g. P. tiiticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. horde! (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus;

Pyrenopeziza spp., e.g. P. brassicae on oilseed rape; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea: rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e.g. P. ultimum or P. aphani- dermatum) and P. oligandrum on mushrooms; Ramularia spp., e.g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e.g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis and R. commune (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (e.g. S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucked) on vines; Setosphaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana, syn. Ustilago reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthii: powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases;

Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans),' Tilletia spp. (common bunt or stinking smut) on cereals, such as e.g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms,' Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus, syn. U. phaseoli), sugar beets (e.g. U. betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae),' Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae), corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V. inaegualis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e.g. V. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicola on mushrooms; Zymoseptoria tritici on cereals.

More preferably, binary compositions and agrochemical compositions thereof according to the invention are used for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necatoron vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Zymoseptoria tritici.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Septoria nodorum synonym Parastagonospora nodorum.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Puccinia recondita.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Puccinia striiformis.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Puccinia sorghi.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Puccinia polysora.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Blumeria graminis.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Blumeria graminis f.sp.tritici.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Phakopsora pachyrhizi.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Sclerotinia sclerotiorum.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Alternaria solani. According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Pyrenophora teres.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Cercospora spp. like C. beticola, C. sojina, C. kikuchii, C. zea-maydis.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Corynespora cassiicola.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Pyricularia oryzae.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of anthracnose = Colletotrichum spp. like C. graminicola, C. sojae aka C. truncation, C. orbiculare aka C. lagenarium.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Botrytis cinerea.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Ramularia spp. like R. colo-cygni.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Rhynchosporium secale.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Podosphaera fuligena.

According one preferred embodiment of the invention, the compositions M.1 to M.110 are used for controlling of Podospheara xanthii.

In one aspect of the present invention the amount of compounds 1-1 in compositions M.1 to M.110 is in the range between 40 and 200 g/ha, preferably between 60 and 120 g/ha, more preferably 100 g/ha.

The binary compositions and agrochemical compositions thereof according to the invention can, in the use form as fungicides, also be present together with further active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immediately prior to use (tank mix).

Mixing the active compounds I, II and the compositions comprising the compositions, respectively, in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.

The binary compositions according to the invention can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and compositions thereof. Examples for composition types are suspensions (e. g. SC, CD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EC, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6^th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

The binary compositions of active compounds described herein can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given herein for the compositions of compounds I. Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 1 and 70%, and in particular between 10 and 60%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The compositions in question give, after two-to-tenfold dilution, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compounds I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, binary composition according to the invention or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active compound of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amount of active compound applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated material.

By applying binary composition according to the invention a synergistic effect can be obtained, i.e. more than simple addition of the individual effects is obtained (synergistic compositions).

This can be obtained by applying the binary composition according to the invention either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active compound applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.

When applying binary composition according to the invention sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1 .5 hours to 5 days, even more preferred from 2 hours to 1 day.

Biological tests

Microtest

The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.

Example 1 - Activity against the Colletotrichum orbiculare in the microtiterplate test

A spore suspension of Colletotrichum orbiculare in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.

The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.

An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.

The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations",

Example 2 - Activity against the Septoria tritici in the microtiterplate test

A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.

Claims

Claims:

1. A fungicidal composition comprising as active component 1 )

2. The composition according to claim 1, wherein active component 1) is compound (i-5).

3. The composition according to claim 1, wherein active component 1) is compound (i-6).

4. The composition according to claim 1, wherein active component 1) is compound (1-10).

5. The composition according to any one of claims 1 to 4, wherein active component 2) is (11-1) (2RS)-2- [4- (4-ch lorophenoxy)-2- (tr if I uoromethy I) pheny I] - 1 -(1 H-1 ,2,4-triazol-l -y I )propan-2-ol .

6. The composition according to any one of claims 1 to 5, wherein active component 2) is

(il-2) (RS)-2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-1 ,2,4-triazole-3-thione.

7. The composition according to any one of claims 1 to 6, comprising compounds I and compounds II in a weight ratio of from 5:1 to 1 :5.

8. The composition according to any one of claims 1 to 7, comprising compounds I and compounds II in a weight ratio of from 4:1 to 1 :4.

9. The composition according any one of claims 1 to 8, comprising compounds I and compounds II in a weight ratio of from 2:1 to 1 :2.

10. An agrochemical composition, comprising a solvent or solid carrier and the composition according to any one of claims 1 to 9.

11 . The agrochemical composition according to claim 10 further comprising seed in an amount of from 1 g to 1000 g active components per 100 kg of seed.

12. The non-therapeutic use of the composition as defined in any one of claims 1 to 11 for controlling phytopathogenic harmful fungi.

13. The non-therapeutic use as defined in claim 12 for controlling phytopathogenic harmful fungi on cereals, corn, fruits, vegetables, rice, soybean.

14. The non-therapeutic use according to any one of claims 12 to 13 for controlling phytopathogenic harmful fungi on wheat, barley, corn (Zea mays), tomato, potato, rice, melon, cucumber, squash, pumpkin, pepper, grapes, soybean.

15. The non-therapeutic use according to any one of claims 12 to 14, for controlling of diseases selected from the group consisting of: Zymoseptoria tritici, Septoria nodorum synonym Parastagonospora nodorum, Puccinia recondita, Puccinia striiformis, Puccinia sorghi, Puccinia polysora, Blumeria graminis, Blumeria graminis f.sp.tritici, Phakopsora pachyrhizi, Sclerotinia sclerotiorum, Alternaria solani, Pyrenophora teres, Cercospora spp. like Cercospora beticola, C. sojina, C. kikuchii, C. zea-maydis, Corynespora cassiicola, Pyricularia oryzae, anthracnose = Colletotrichum spp. like C. graminicola, C. sojae aka C. truncatum, C. orbiculare aka C. lagenarium, Botrytis cinerea, Ramularia spp. like R. colo-cygni, Rhynchosporium secale, Podosphaera fuligena, Podospheara xanthii.