KR20010032654A - Fungicidal combinations comprising thieno[2,3-d]pyrimidin-4-one - Google Patents

Abstract

The present invention provides a component (a) which is thieno [2,3-d] pyrimidin-4-one of the general formula (I), an anilinopyrimidine fungicide (II), an azole fungicide (III), and a morpholine fungicide (IV). ), Strobilurine compound (V), pyrrole compound (VI), phenylamide (VII), dithiocarbamate fungicide selected from mancozeb, maneb, metiram and geneb, copper hydroxide, copper oxychloride, copper sulfate And copper compounds selected from auxin-copper, phthalimide compounds (VIII), prochloraz, triflumizol, pyridoxox, acibenzola-S-methyl, chlorothalonil, cymoxanyl, dimethomorph, Pamoxadon, phenhexamide, phenarimol, fluzinam, phosphetyl-aluminum, quinoxyphene, phenpropidine, spiroxamine, carbendazim, thibendazole, etirimol, triazoside or guazinin A novel fungicidal composition having a synergistically increased activity comprising component (b).

Formula I

In Formula I above,

R ₁ is halogen,

R ₂ is C ₁ -C ₅ -alkyl or -CH ₂ -cyclopropyl,

R ₃ is C ₁ -C ₅ -alkyl or —CH ₂ -cyclopropyl.

Description

Fungicidal combinations comprising thieno [2,3-d] pyrimidin-4-one}

The present invention relates to novel fungal compositions against infection of plant propagation stock or other plant material, in particular against phytopathogenic fungi, and to crops for the treatment of phytopathogenic diseases of crops. A method for combating phytopathogenic diseases or for seed dressing.

It is known that certain pyrimidin-4-one derivatives have biological activity against phytopathogenic fungi, for example, as known from WO 97/33890 where their properties and methods of preparation are described. On the other hand, anilinopyrimidine, azole fungicides, phthalimide, phenylamide, strobiliurine, pyrrole, dithiocarbamate and morpholine are well known as plant fungicides for application to various crops of cultivated plants. have. Crop tolerance and activity for phytopathogenic plant fungi, however, do not always meet the demands of agricultural practice in many cases and aspects.

In the present invention,

With thieno [2,3-d] pyrimidin-4-one (a) of formula (I),

Anilinopyrimidines of formula II; Azoles of formula III and salts of these azole fungicides; Morpholine fungicides of formula IV and salts of these morpholine fungicides; Strobiliurine compounds of formula V; Pyrrole compounds of formula VI; Phenylamide of formula VII; Dithiocarbamate fungicides selected from mancozeb, maneb, metiram and geneb; Copper compounds selected from copper hydroxide, copper oxychloride, copper sulfate and auxin-copper; sulfur; Phthalimide compounds of formula VIII; A compound of Formula IX; A compound of Formula X; Compounds of formula (XI); Compounds of formula (XII); A compound of Formula (XIII); A compound of Formula XIV; A compound of Formula XV; A compound of Formula (XVI); A compound of Formula (XVII); Compounds of formula (XVIII); A compound of Formula XIX; A compound of formula XX; A compound of Formula XXI; A compound of formula XXII; A compound of formula XXIII; A compound of Formula XXIV; A compound of Formula XXV; A compound of Formula XXVI; A compound of formula XXVII; Or the use of a compound of formula XXVIII has been found to be particularly effective in combating or preventing fungal diseases of crops.

In the above formulas (I) to (XXVIII),

R ₁ is halogen,

R ₂ is C ₁ -C ₅ alkyl or —CH ₂ -cyclopropyl,

R ₃ is C ₁ -C ₅ alkyl or —CH ₂ -cyclopropyl,

R ₄ is methyl, 1-propynyl or cyclopropyl,

A is selected from formulas i to xv, wherein β-carbon is bonded to the benzene ring of formula III,

R ₅ is H, F, Cl, phenyl, 4-fluorophenoxy or 4-chlorophenoxy,

R ₆ is H, Cl or F,

R ₁₃ is C _8-15 cycloalkyl, C _8-15 alkyl or C _1-4 alkylphenyl-C _1-4 alkyl,

X is NH or 0,

Y is CH or N,

R ₁₄ is 2-methylphenoxy-methyl, 2,5-dimethylphenoxy-methyl, 4- (2-cyanophenoxy) -pyrimidin-6-yloxy or 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl,

R ₁₅ and R ₁₆ are independently halo or together form a perhalomethylenedioxo bridge,

R ₁₇ is benzyl, methoxymethyl, 2-furanyl, chloromethyl or ego,

R ₁₈ is 1-methoxycarbonyl-ethyl or (Wherein Z is CH or N),

R ₁₉ and R ₂₀ together form a four-membered bridge -CH ₂ -CH = CH-CH ₂ -or -CH-CH = CH-CH =,

R ₂₁ is hydrogen or methyl,

R ₂₂ is hydrogen or methyl,

n is 0, 1 or 2, etc.

R is hydrogen or -C (= NH) NH ₂ .

In the above formulas i to xv,

R ₇ and R ₈ are independently H or CH ₃ ,

R ₉ is C _1-4 alkyl or cyclopropyl,

R ₁₀ is 4-chlorophenyl or 4-fluorophenyl,

R ₁₁ is phenyl,

R ₁₂ is alkyloxy, C _1-4 alkyl or 1,1,2,2-tetrafluoroethoxy-methyl.

Such combinations exhibit synergistic fungicidal activity.

The combinations according to the invention may also comprise one or more of the active ingredients (b) when it is necessary to broaden the extent of disease inhibition. For example, it may be advantageous in agricultural practice to combine two or three components (b) with any compound of formula (I), or with any desired member of the group of compounds of formula (I).

From WO 97/33890 the following specific species of formula I are known:

Compound number R ₁ R ₂ R ₃ (I.01) Cl n-propyl n-propyl (I.02) Br n-propyl n-propyl (I.03) Cl n-propyl n-butyl (I.04) Br n-propyl n-butyl (I.05) Cl n-butyl n-propyl (I.06) Br n-butyl n-propyl (I.07) Cl i-butyl n-propyl (I.08) Br i-butyl n-propyl (I.09) Cl n-propyl i-butyl (I.10) Br n-propyl i-butyl

Preferred embodiments of the present invention comprise as component (a) R ₁ is chloro or bromo, R ₂ is n-propyl, n-butyl, i-butyl and R ₃ is n-propyl, n-butyl, i-butyl Represented by a combination comprising a compound of formula (I).

Most preferred among the mixtures of the present invention are compounds (I.01), (I.02), (I.03), (I.04), (I.05), (I.06), (I.07) Or a mixture of (I.08) with a compound of component (b), in particular a commercially available product within a given range, ie commercially mentioned throughout the literature.

Salts of azole, amine and morpholine active ingredients can be acid, for example hydrohaloic acid (e.g. hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid) or sulfuric acid, phosphoric or nitric acid, or organic acids (e.g. acetic acid, Trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfoic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid And 1,2-naphthalenesulfonic acid).

The active ingredient combination is effective against phytopathogenic fungi belonging to the following classes: cyst fungi (eg, Venturia, Podosphaera, Erysiphe, Monilinia, Sclere) Sclerotinia, Mycosphaerella, Uncinula], Basidiomycetes (e.g., Hemileia genus, Rhizoctonia, Tiletia, Puccinia ), Incomplete fungi (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alterna Alternativeria, Pyricularia and Pseudocercosporella herpotrichoides, fungi (e.g. Phytophthora, Peronospora, Bremia ), Pythium, Plasmopara].

Target crops for the indicated regions described herein include, for example, the following plant species within the scope of the present invention: cereals (wheat, barley, rye, oats, rice, soorghum and related crops), sugar beet (beet) [sugar beet and fodder beet], fruit, nucleus and confection (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry), legume ( Beans, lentils, peas, soybeans), oil plants (flat, mustard, poppy, olive, sunflower, coconut, castor oil, cacao seeds, peanuts), cucumber plants (western pumpkin, cucumber, melon), fiber plants (cotton, Flax, hemp, jute), citrus fruits (orange, lemon, grapefruit, mandarin), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers), camphor (avocados, cinnamon, camphor) ), Or corn, tobacco, nuts, coffee, sugar cane, tea, vine, hops, grass Plants such as, bananas and natural rubber plants, as well as ferns (flowers, shrubs, broad-leaved trees and evergreens such as conifers) and their seeds. This list does not represent any limitation.

The combinations of the present invention can also be used in the field of protecting technical substances against fungal attack. Technical areas include wood, paper, leather, structures, cooling and heating systems, ventilation and air conditioning systems. The formulations according to the invention can prevent adverse effects such as corrosion, discoloration or molding.

The combination according to the invention is suitable for powdery fungi and fungi, pyrenophora, rhynchosporium and leptosphaeria fungi, in particular of monocotyledons (such as cereals including wheat and barley). It is particularly effective against pathogens. It is further particularly effective against Downey fungal species, especially against Plasmopara of the vine.

The application amounts of the combinations of the invention can be determined by the compound used, the agent to be treated (plants, soil, seeds), the type of treatment (eg spraying, dusting, seed dressing), the purpose of the treatment (prevention or treatment), the type of fungi to be treated and the application It depends on various factors such as time.

Particularly preferred mixing partners of compounds of formula II are those wherein R ₄ is methyl or cyclopropyl. Such compounds are generally known as pyrimethanyl and cyprodinyl.

Especially preferred mixing partners of compounds of formula III are those in which R ₅ is Cl, R ₆ and R ₇ are H, R ₈ is CH ₃ , R ₉ is cyclopropyl, and A is residue (i) (generally Known as cyproconazole); Compounds wherein R ₅ and R ₆ are Cl, R ₇ and R ₈ are H, R ₉ is propyl, and A is residue (i) (commonly known as hexaconazole); A compound in which R ₅ is 4-chlorophenoxy, R ₆ is Cl, R ₇ , R ₈ and R ₉ are H, and A is residues (ii) (commonly known as diphenoconazole); Compounds wherein R ₅ and R ₆ are Cl, R ₇ and R ₈ are H, R ₉ is ethyl, and A is residue (ii) (commonly known as etaconazole); Compounds wherein R ₅ and R ₆ are Cl, R ₇ and R ₈ are H, R ₉ is propyl, and A is residues (ii) (commonly known as propiconazole); Compounds wherein R ₅ is Cl, R ₆ is H, R ₇ , R ₈ and R ₉ are CH ₃ , and A is residue (iii) (commonly known as tebuconazole); Compounds wherein R ₅ is Cl, R ₆ is H and A is residue (iv) (commonly known as triticazole); Compounds wherein R ₅ is H, R ₆ is F, R ₁₀ is 4-fluorophenyl and A is residue (v) (commonly known as fluturiapol); Compounds in which R ₅ is H, R ₆ is Cl, R ₁₀ is 4-fluorophenyl, and A is residue (vi) (commonly known as epoxyconazole); Compounds in which R ₅ is Cl, R ₆ is H, R ₁₁ is phenyl, and A is residue (vii) (commonly known as fenbuconazole); Compounds wherein R ₅ and R ₆ are Cl and A is residue (viii) (commonly known as bromuconazole); Compounds wherein R ₅ and R ₆ are Cl, R ₁₂ is propyl and A is residue ix (commonly known as fenconazole); Compounds wherein R ₅ and R ₆ are Cl, R ₁₂ is allyloxy and A is residue ix (commonly known as imazalyl); Compounds wherein R ₅ and R ₆ are Cl, R ₁₂ is 1,1,2,2-tetrafluoroethoxymethyl and A is residue ix (generally known as tetraconazole); Compounds wherein R ₅ is F, R ₆ is H, R ₉ is CH ₃ , R ₁₀ is 4-fluorophenyl, and A is residue (x) (commonly known as flusilazole); Compounds wherein R ₅ is chloro, R ₆ is hydrogen, R ₇ and R ₈ are methyl and A is residue (xi) (commonly known as metconazole); Compounds in which R ₅ and R ₆ are chloro, R ₇ and R ₈ are H, R ₉ is t-butyl, and A is residue (xii) (commonly known as diconazole); Compounds in which R ₅ and R ₆ are chloro and A is residue (xiii) (commonly known as fluquinconazole); Compounds wherein R ₅ is chloro, R ₆ , R ₇ and R ₈ are H, R ₉ is n-butyl, and A is residue (xiv) (commonly known as michaelrobutanyl); Compounds wherein R ₅ is chloro, R ₆ is H, R ₇ , R ₈ and R ₉ are methyl and A is residue (xv) (commonly known as triadimenol); And compounds wherein R ₅ is phenyl, R ₇ , R ₈ and R ₉ are methyl and A is residue (xv) (commonly known as bitteranol).

Particularly preferred mixing partners of compounds of formula IV are compounds in which R ₁₃ is cyclododecyl (commonly known as dodemorph), compounds in which C _10-13 alkyl (commonly known as tridemormo) or 3- ( 4-tert-butylphenyl) -2-methylpropyl (generally known as phenpropimod). Primarily, the cis habitat of the methyl group of the morpholine ring is present in the compound of formula IV when used in the combination of the present invention.

Particularly preferred mixing partners of compounds of formula V are those wherein X and Y are O and R ₁₄ is 2-methylphenoxy-methyl; X is 0, Y is LH, and R ₁₄ is 4- (2-cyanophenoxy) -parimidin-6-yloxy (commonly known as creoxime-methyl); X is NH, Y is N, and R ₁₄ is 2,5-dimethylphenoxy-methyl; X is 0, Y is CH and R ₁₄ is 4- (2-cyanophenoxy) -pyrimidin-6-yloxy (commonly known as azoxystrobin); Or X is O, Y is N and R ₁₄ is 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-pentenyl.

Particularly preferred mixing partners of compounds of formula VI are compounds in which R ₁₅ and R ₁₆ are both chloro (generally known as fenpiclonyl) or R ₁₅ and R ₁₆ together bridge -O-CF ₂ -O- Compound, commonly known as fludioxonyl.

Particularly preferred mixing partners of compounds of formula (VII) are those in which R ₁₇ is benzyl, R ₂₁ and R ₂₂ are methyl and R ₁₈ is 1-methoxycarbonyl-ethyl (commonly known as benalexyl); A compound in which R ₁₇ is 2-furanyl, R ₂₁ and R ₂₂ are methyl and R ₁₈ is 1-methoxycarbonyl-ethyl (commonly known as furalaxyl); R ₁₇ is methoxymethyl, R ₂₁ and R ₂₂ are methyl, and R ₁₈ is 1-methoxycarbonyl-ethyl or (R) -1-methoxycarbonyl-ethyl (generally metallaxyl and R Known as metallaxyl); R ₁₇ is chloromethyl, R ₂₁ and R ₂₂ are methyl, and R ₁₈ is Compounds wherein Z is CH (generally known as orfurace); R ₁₇ is methoxymethyl, R ₂₁ and R ₂₂ are methyl and R ₁₈ is Compounds wherein Z is N (generally known as oxadixyl); Or R ₁₇ And R ₁₈ , R ₂₁ and R ₂₂ are hydrogen (generally known as carboxy).

Particularly preferred mixing partners of compounds of formula (VIII) are those in which R ₁₉ and R ₂₀ together form a bridge —CH ₂ —CH═CH—CH ₂ — (commonly known as captan); Or R ₁₉ and R ₂₀ together form a bridge = CH-CH = CH-CH = (commonly known as a polpet).

Compounds of formula (IX) are generally known as procollaz.

Compounds of formula (X) are generally known as triflumizol.

Compounds of formula (XI) are generally known as pyriphenox.

Compounds of formula (XII) are generally known as acibenzola-S-methyl.

Compounds of formula (XIII) are generally known as chlorothalonil.

Compounds of formula (XIV) are generally known as cyoxanyl.

Compounds of formula (XV) are generally known as dimethomorph.

Compounds of formula (XVI) are generally known as paroxadon.

Compounds of formula (XVII) are generally known as phenhexamides.

Compounds of formula (XVIII) are generally known as phenarimol.

Compounds of formula (XIX) are generally known as fluazinam.

Compounds of formula (XX) are generally known as pocetyl-aluminum.

Compounds of formula (XXI) are generally known as quinoxyphene.

Compounds of formula (XXII) are generally known as fenpropidine.

Compounds of formula (XXIII) are generally known as spiroxamine.

Compounds of formula (XXIV) are generally known as carbendazim.

Compounds of formula (XXV) are generally known as thiabendazoles.

Compounds of formula (XXVI) are generally known as etirimole.

Compounds of formula (XXVII) are generally known as triazoxides.

Compounds of formula (XXVIII) are generally known as guazatin.

Certain compounds (b) mentioned in the preceding paragraph are commercially available. Compounds within the range of various groups of component (b) can be obtained following processes similar to those known for preparing commercially available compounds.

The use of compounds of formulas (II) to (XXVIII) in combination with compounds of formula (I) surprisingly substantially enhances the effectiveness of formula (I) against fungi and vice versa. In addition, the methods of the present invention, when used alone, are effective against a broader range of such fungi that can be combated by the active ingredients of the method.

Particularly preferred mixtures according to the invention are combinations of the active ingredient of formula (I), any subgroup of formula (I), or pymethanyl, cyprodinyl, cyproconazole, hexaconazole, diphenoconazole, Etaconazole, propiconazole, tebuconazole, triticazole, flutriafol, epoxyconazole, fenbuconazole, bromuconazole, fenconazole, imazaryl, tetraconazole, flusilazole, metconazole , Diconazole, fluquinconazole, michaelrobutanyl, triadimenol, bitteranol, dodemorph, tridemorph, fenpropormfe, mancozeb, maneb, metiram, geneb, copper hydroxide , Copper oxychloride, copper sulfate, auxin-copper, sulfur, creoxime-methyl, azoxystrobin, 2- [2- (2,5-dimethylphenoxy-methyl) -phenyl] -2-methoximino-acetic acid N -Methyl-amide, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -phenyl}- 2-methoxyimino-acetate, fenpiclonyl, fludioxonil, benalacyl, furalacyl, metallaxyl, R-metallaxyl, orpulace, oxadixyl, carboxycin, captan, polpet, prochloraz , Triflumizol, pyridenox, acibenzola-S-methyl, chlorothalonil, cymoxanyl, dimethomorph, pamoxadon, phenhexamide, phenarimol, fluazinam, pocetyl-aluminum As a specifically mentioned member with a second fungicide selected from the group comprising quinoxyphene, phenpropidine, spiroxamine, carbendazim, thiabendazole, etirimole, triazoside and guazatin It is figured out.

From this group, cyproconazole, hexaconazole, diphenoconazole, propiconazole, tebuconazole, flutriafol, epoxyconazole, fenbuconazole, bromuconazole, fenconazole, tetraconazole, flu Preference is given to subgroups (b1) comprising combinations with silazole, metconazole, diconazole, triadimenol, fluquinconazole and prochloraz.

From this group, combinations with propiconazole, difenoconazole, fenconazole, tebuconazole, prochloraz, epoxyconazole and cyproconazole are of particular importance as preferred embodiments of the invention as subgroup (b1a). Do.

Further preferred subgroups (b2) are cyprodinyl, tridemorph, phenpropmorph, creazosim-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl)- 3-aza-2-oxa-3-pentenyl] -phenyl} -2-methoxyimino-acetate, acibenzola-S-methyl, chlorothalonil, pamoxadon, quinoxyphene, phenpropidine and carbene Combination with compaction.

Cyprodinyl, fenpropormoff, creoxime-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-4-phene from this group Combinations with tenyl] -phenyl} -2-methoxyimino-acetate, acibenzola-S-methyl, and phenpropidine are of particular importance as preferred embodiments of the invention as subgroup (2ba).

Further important formulations are:

A combination of compound (I.01) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.02) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.03) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.04) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.05) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.06) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.07) with groups (b1) and (b2) or any member of groups (b1a) and (b2a),

A combination of compound (I.08) with groups (b1) and (b2) or any member of groups (b1a) and (b2a).

The weight ratio of (a) :( b) is chosen to provide synergistic fungicidal action. In general, the weight ratio of (a) :( b) is 100: 1 to 1: 400. The synergistic action of the composition is evident from the fact that the fungicidal action of the composition of (a) + (b) is greater than the sum of the fungicidal action of each of (a) and (b).

When component (b) is anilinopyrimidine of formula (II), the weight ratio of (a) :( b) is for example 1: 2 to 1:36, in particular 1: 2 to 1:18, more preferably 1: 3 and 1: 8.

When component (b) is an azole fungicide of formula III, the weight ratio of (a) :( b) is for example 10: 1 to 1:20, in particular 5: 1 to 1:10, more preferably 2 : 1 to 1: 4.

When component (b) is a morpholine fungicide of formula IV, the weight ratio of (a) :( b) is for example 1: 2 to 1:30, in particular 1: 3 to 1:15, more preferably 1: 3 to 1:10.

When component (b) is a strobiliurin fungicide of formula V, the weight ratio of (a) :( b) is for example 1: 2 to 1:10, in particular 1: 1 to 1: 8, more preferably Is 1: 2 to 1: 5.

When component (b) is a pyrrole fungicide of formula VI, the weight ratio of (a) :( b) is for example 1: 3 to 1:30, in particular 1: 1.5 to 1: 7, more preferably 1 : 2 to 1: 5.

When component (b) is a phenylamide fungicide of formula VII, the weight ratio of (a) :( b) is for example 3: 1 to 1:12, in particular 2.5: 1 to 1: 6, more preferably 2: 1 to 1: 3.

When component (b) is a dithiocarbamate fungicide, the weight ratio of (a) :( b) is for example 1: 3 to 1: 120, in particular 1: 4 to 1:60, more preferably 1 : 7 to 1:25.

When component (b) is a copper compound fungicide, the weight ratio of (a) :( b) is for example 1: 1.5 to 1: 100, in particular 1: 2 to 1:50, more preferably 1: 5 To 1:30.

When component (b) is a sulfur fungicide, the weight ratio of (a) :( b) is for example 1: 6 to 1: 400, in particular 1: 8 to 1: 200, more preferably 1:10 to 1: 100.

When component (b) is a phthalimide fungicide of formula VIII, the weight ratio of (a) :( b) is for example 1: 3 to 1:80, in particular 1: 4 to 1:40, more preferably Is 1: 8 to 1:20.

When component (b) is a compound of formula IX, the weight ratio of (a) :( b) is for example 1: 2 to 1:25, in particular 1: 4 to 1:12, more preferably 1: 5 To 1: 8.

When component (b) is a compound of formula X, the weight ratio of (a) :( b) is for example 3: 1 to 1:16, in particular 2.5: 1 to 1: 8, more preferably 1: 1 To 1: 4.

When component (b) is a compound of formula (XI), the weight ratio of (a) :( b) is for example 8: 1 to 1: 4, in particular 2.5: 1 to 1: 2, more preferably 2: 1 To 1: 1.

When component (b) is a compound of formula XII, the weight ratio of (a) :( b) is for example 6: 1 to 1: 2, in particular 6: 1 to 2: 1, more preferably 5: 1 To 2: 1.

When component (b) is a compound of formula XIII, the weight ratio of (a) :( b) is for example 1: 3 to 1:40, in particular 1: 4 to 1:20, more preferably 1: 5 To 1:10.

When component (b) is a compound of formula XIV, the weight ratio of (a) :( b) is for example 3: 1 to 1: 8, in particular 2.5: 1 to 1: 4, more preferably 2: 1 To 1: 2.

When component (b) is a compound of formula XV, the weight ratio of (a) :( b) is for example 1.5: 1 to 1:12, in particular 1: 1 to 1: 6, more preferably 1: 1 To 1: 4.

When component (b) is a compound of formula XVI, the weight ratio of (a) :( b) is for example 1.5: 1 to 1:10, in particular 1: 1 to 1: 5, more preferably 1: 1 To 1: 3.

If component (b) is a compound of formula XVII, the weight ratio of (a) :( b) is for example 2: 1 to 1:30, in particular 1.5: 1 to 1:15, more preferably 1: 1 To 1: 5.

When component (b) is a compound of formula XVIII, the weight ratio of (a) :( b) is for example 8: 1 to 1: 4, in particular 2.5: 1 to 1: 2, more preferably 2: 1 To 1: 1.

When component (b) is a compound of formula XIX, the weight ratio of (a) :( b) is for example 1.5: 1 to 1:12, in particular 1: 1 to 1: 6, more preferably 1: 1 To 1: 4.

When component (b) is a compound of formula XX, the weight ratio of (a) :( b) is for example 1: 3 to 1:80, in particular 1: 4 to 1:40, more preferably 1: 1 To 1:25.

When component (b) is a compound of formula XXI, the weight ratio of (a) :( b) is for example 2: 1 to 1: 5, in particular 1.5: 1 to 1: 2.5, more preferably 1: 1 To 1: 2.

When component (b) is a compound of formula XXII, the weight ratio of (a) :( b) is for example 1: 2 to 1:30, in particular 1: 3 to 1:15, more preferably 1: 3 To 1:10.

If component (b) is a compound of formula (XXIII), the weight ratio of (a) :( b) is for example 1: 2.5 to 1:30, in particular 1: 3 to 1:15, more preferably 1: 3 To 1:10.

When component (b) is a compound of formula XXIV, the weight ratio of (a) :( b) is for example 1.5: 1 to 1:10, in particular 1: 1 to 1: 5, more preferably 1: 2 To 1: 4.

When component (b) is a compound of formula (XXV), the weight ratio of (a) :( b) is for example 40: 1 to 1:10, in particular 20: 1 to 1: 5, more preferably 10: 1. To 1: 2.

When component (b) is a compound of formula XXVI, the weight ratio of (a) :( b) is for example from 1: 1 to 1:10, in particular from 1: 1 to 1: 5, more preferably 1: 1 To 1: 2.

When component (b) is a compound of formula XXVII, the weight ratio of (a) :( b) is for example 10: 1 to 100: 1, in particular 5: 1 to 50: 1, more preferably 2: 1 To 20: 1.

When component (b) is a compound of formula XXVIII, the weight ratio of (a) :( b) is for example 5: 1 to 1: 4, in particular 3: 1 to 1: 2, more preferably 2: 1 To 1: 1.

The process of the present invention comprises the application of a fungicidally effective total of a compound of formula (I) and a compound of component (b) in admixture or separately to the plant or its locus to be treated.

The term "habitat" as used herein is intended to include the tillage from which the treated crop is grown, the tillage of the seed of the cultivated plant, or the place where the seed is placed in the soil. The term “seed” is intended to include plant reproductive materials such as barley branches, seedlings, seeds, germinated or invasive. The novel formulations are extremely effective against a wide range of phytopathogenic fungi, particularly fungi from asymptomatic fungi and basidiomycetes. Some of these have tissue activity and can be used as thin and soil fungicides.

Fungicidal combinations include a variety of crops or seeds thereof, in particular wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, fruit and flavor plants in the field of coffee, sugar cane, horticulture and grape growing, and cucumbers, beans And fungi of the majority of vegetables, such as gourds.

The combination is applied by treating seeds, plants or substances or soil threatened by fungal or fungal attack with a fungicidally effective amount of active ingredient.

The formulations may be applied before or after infection of the substance, plant or seed by the fungus.

The new formulations are particularly useful for suppressing the following plant diseases: Erysiphe graminis of cereals, Erysiphe cichoracearum of gourds and Sphaerotheca. fuliginea), apple grapes, Podosphaera leucotricha, uncinula necator of vines, puccinia species of cereals, cotton, rice and paddy lizartonia species, utilites of cereals and sugarcane Ustilago species, Venturia inaequalis (apple spot) of apples, Helmintosporiium species of cereals, Septoria nodorum of wheat, Septoria tritici of wheat , Rhyncosporium secalis of barley, Pseudocercosporella herpotrichoides of wheat and barley, Pyricularia oryzae of rice, potato and The pie Saratov Torah inpe Afghanistan's (Phytophthora infestans), a variety of plants in Mato Fusarium (Fusarium) and Bertie room Solarium (Verticillium), of Playa sumo para Beatty Cola (Plasmopara viticola) of grape fruit and vegetables Alterna Leah species.

When applied to plants, the compounds of formula (I) may be selected from 25 to 150 g / ha, in particular from 50 to 125 g / ha, for example 75, 100 or 125 g / ha, depending on the type of species used as component (b). 20 to 3000 g / ha, in particular 20 to 2000 g / ha, for example 20 g / ha, 30 g / ha, 40 g / ha, 75 g / ha, 80 g / ha, 100 g / ha, 125 g / ha, 150 g / ha, 175 g / ha, 200 g / ha, 300 g / ha, 500 g / ha, 1000 g / ha, 1200 g / ha, 1500 g / ha, 2000 g / ha or in some cases up to 10000 g / ha of sulfur, Apply with compound.

When component (b) is an anilinopyridine of formula (II), for example 300 to 900 g a.i. (active ingredient) / ha is applied together with the compound of formula (I). If component (b) is an azole fungicide of formula III, for example 20 to 350 g a.i./ha is applied together with the compound of formula I. If component (b) is a morpholine of formula IV, for example 300 to 750 g a.i./ha is applied together with the compound of formula I. When component (b) is strobiliurin of formula (V), for example 75 to 250 g a.i./ha is applied together with the compound of formula (I). If component (b) is a pyrrole of formula VI, for example 200 to 750 g a.i./ha is applied together with the compound of formula I. If component (b) is a phenylamide of formula (VII), for example 50 to 300 g a.i./ha is applied together with the compound of formula (I). If component (b) is dithiocarbamate, for example 500 to 3000 g a.i./ha is applied with the compound of formula (I). If component (b) is a copper compound, for example 250 to 2500 g a.i. are applied together with the compound of formula (I). When component (b) is sulfur, for example 1000 to 10000 g a.i. are applied together with the compound of formula (I). If component (b) is a phthalimide of formula (VIII), for example 500 to 2000 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula (IX), for example 400 to 600 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula (X), for example 50 to 400 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula (XI), for example 20 to 100 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XII, for example 20-40 g a.i./ha is applied together with the compound of formula I. If component (b) is a compound of formula (XIII), for example 500 to 1000 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XIV, for example 50 to 200 g a.i./100 kg are applied together with the compound of formula I. If component (b) is a compound of formula XV, for example 100 to 300 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XVI, for example 125 to 250 g a.i./ha is applied together with the compound of formula I. If component (b) is a compound of formula XVII, for example 100 to 750 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XVIII, for example 20 to 100 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XIX, for example 100 to 300 g a.i./ha is applied together with the compound of formula I. If component (b) is a compound of formula (XX), for example 500 to 2000 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XXI, for example 75 to 125 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula (XXII), for example 300 to 750 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula (XXIII), for example, 375 to 750 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XXIV, for example 125 to 250 g a.i./ha is applied together with the compound of formula (I). If component (b) is a compound of formula XXV, for example 5 to 200 g a.i./100 kg is applied for seed dressing with the compound of formula (I). If component (b) is a compound of formula (XXVI), for example, 200 g a.i./100 kg is applied for seed dressing with the compound of formula (I). If component (b) is a compound of formula (XXVII), for example, 2 g a.i./100 kg is applied for seed dressing with the compound of formula (I). If component (b) is a compound of formula (XXVIII), for example 40 to 80 g a.i./100 kg is applied for seed dressing with the compound of formula (I).

In industrial practice, the application rate of the combination depends on the type of effect required and ranges from 0.02 to 4 kg of active ingredient per hectare.

When the active ingredient is used to treat the seed, a ratio of 0.001 to 50 g a.i./kg, preferably 0.01 to 10 g / kg, is generally sufficient.

The present invention also provides a fungicide composition comprising a compound of formula (I) and a compound of component (b).

The compositions of the present invention can be used in any conventional form, for example in the form of twin packs, instant granules, flowable or wettable powders and agriculturally acceptable auxiliaries. Such compositions can be prepared by conventional methods, for example by mixing the active ingredient with a suitable adjuvant (diluent or solvent, and optionally other formulation ingredients such as surfactants).

The term "diluent" as used herein refers to any agriculturally acceptable, including carriers that can be added to the active ingredient to bring the active ingredient to the active strengths available or desired, respectively, in an easy or improved application form. Means a liquid or solid substance. Suitable solvents are aromatic hydrocarbons, preferably fractions of 8 to 12 carbon atoms, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, cycloaliphatic hydrocarbons such as cyclohexane or Paraffin), alcohols and glycols and their ethers and esters (e.g. ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether), ketones (e.g. cyclohexanone), strong polar solvents (e.g. N-methyl-2 -Pyrrolidone, dimethyl sulfoxide or dimethyl formamide), as well as vegetable oils or epoxidized vegetable oils such as epoxidized coconut oil or soybean oil, or water. For example, solid carriers used as dust and dispersible powders are typically natural mineral fillers such as calcinate, talcum, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acid or highly dispersed absorbent polymers may be added to improve physical properties. Suitable granular adsorptive carriers are of the porous type, eg pumice, broken brick, sepiolite or bentonite, and suitable nonhygroscopic carriers are, for example, calsite or sand. In addition, many inorganic or organic natural substances, such as dolomite or ground plant residues, can be used. Depending on the nature of the compound of formula I and the compound of component (b) being formulated, suitable surface active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. The term "surfactant" is also understood to include mixtures of surfactants. Particularly advantageous application facilitating aids are also natural or synthetic phospholipids of the cephalin and lecithin family, such as phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol and risolecithin.

Particularly applied in spray form, such as water dispersible concentrates or wettable powders, are wetting and dispersing agents, for example formaldehyde and naphthalene sulfonates, alkylarylsulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols. And surfactants such as condensation products with ethoxylated fatty alcohols.

Seed dressing formulations are applied to seeds in a manner known per se, using the inventive formulations and diluents in the form of suitable seed dressing formulations, for example, as an aqueous suspension or in the form of a dry powder with good adhesion to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a sustained release capsule or microcapsules.

Formulations generally comprise from 0.01 to 90% by weight of activator, from 0 to 20% of agriculturally acceptable surfactants and from 10 to 99.99% of solid or liquid auxiliaries, the activator together with at least the compound of formula (I) And optionally other activators, in particular fungicides or preservatives.

The concentrated form of the composition generally contains from 2 to 80%, preferably from about 5 to 70% by weight of activator. Application forms of the formulations contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of activator.

The following examples are used to illustrate the present invention, where the "active ingredient" refers to a mixture of specific mixing ratios of the compound of formula I and the compound of component (b).

Formulations can be prepared, for example, similar to those described in WO 97/33890.

Sustained-release capsule suspension

A combination of a compound of formula (I) with a compound of component (b), or 28 parts of these individual compounds, is mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylenepolyphenylisocyanate mixture (8: 1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.

The resulting capsule suspension is stabilized by adding 0.25 part thickener and 3 parts dispersant. Capsule suspension formulations contain 28% active ingredient. The median capsule diameter is 8 to 15 microns. The formulation obtained is applied to the seed as an aqueous suspension in a device suitable for that purpose.

Seed dressing formulation

25 parts of a combination of the compounds of formulas (I) and (II), 15 parts of dialkylphenoxypoly (ethyleneoxy) ethanol, 15 parts of fine silica, 44 parts of fine kaolin, 0.5 parts of rhodamine B as colorant and 0.5 parts of xanthan gum are mixed and Grind to an average particle size of less than 20μ in a contrastplex mill at 10000rpm. The formulation obtained is applied to the seed as an aqueous suspension in a device suitable for that purpose.

Commercially available products are preferably formulated as concentrates, while end users typically use dilute formulations.

Biological Example

A synergistic effect exists whenever the action of the active ingredient combination is greater than the sum of the actions of the individual ingredients.

The expected action E for a given active ingredient combination can be calculated according to the so-called COLBY formula and calculated as follows: COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967].

ppm = milligrams of active ingredient (a.i.) per liter of spray mixture,

X =% action by active ingredient (I) using p ppm of active ingredient,

Y =% action by active ingredient (II) using q ppm of active ingredient.

According to Colby, the expected (additional) action of active ingredient (I) + (II) using p + q ppm of the active ingredient is to be.

If the actually observed action (O) is greater than the expected action (E), then the action of the blend is hyperadditive, ie there is a synergistic effect.

In another method synergy may be measured from dose response curves according to the so-called WADLEY method. In this way the efficacy of ai is measured by comparing fungal attack against treated plants to fungal attack against untreated, similarly inoculated and cultured test plants. Each ai is tested at 4-5 concentrations. Dose response curves are used to achieve EC90 of a single compound (ie, the concentration of ai providing 90% disease control) as well as EC90 of the combination (EC90 _observation ). This experimentally found value of the mixture at a given weight ratio is compared with the value found to be the only complementary potency of the component [EC90 (A + B) _expected ]. EC90 (A + B) _projections are calculated according to Waldley (Levi et al., EPPO- Bulletin 16, 1986, 651-657).

[Where a and b are the weight ratios of compounds A and B in the mixture and symbols (A), (B) and (A + B) represent the observed EC90 values of compound A, B or a given combination A + B EC90 (A + B) _expected / EC90 (A + B) _observation ratio represents the factor of interaction (F). In the case of synergy, F is greater than one.

Example B-1: eryrecipe graminis f.sp. Efficacy in Tritici

About 10 days old wheat plant "Arina" is sprayed with an aqueous suspension of the active ingredient or mixture thereof. After 1 day, the plants are inoculated by dusting with spores of E. recipe graminis. The test can also be carried out in a therapeutic application, ie 1 to 3 days after the artificial inoculation of the plant. The plants are incubated in a greenhouse or climate chamber at 20 ° C., 70% relative humidity. At 7-10 days post inoculation, the fungal attack on the first leaves is assessed.

result:

Example B-2: eryrecipe graminis f.sp. Holiday Efficacy on

a) protective or therapeutic activity

Barley plants "Golden Promise" are used. The test process is the same as described in Example B-1.

b) organizational activity

An aqueous spray mixture of the active ingredient or mixtures thereof is poured after the barley plants about 8 cm high. Care should be taken that the spray mixture does not come into contact with the air portion of the plant. After 48 hours, the plants are dusted with fungi conidia. Infected plants are placed in a greenhouse at 22 ° C. Disease attack on leaves is assessed 12 days after infection.

Example B-3 Activity against Grapespaera rucotica in Apples

Apple heads with fresh branches 10 cm long are sprayed with an aqueous spray mixture of the active ingredient or mixtures thereof. Treated plants are inoculated with fungal congenital magnetic suspension after 24 hours and placed in a climatic chamber at 70% relative humidity and 20 ° C. The test can also be performed as a therapeutic application two days after inoculation. Disease attack is assessed 12-14 days after inoculation.

Example B-4: Activity against Uncinula Necaptor in Grapes

In the 4-5 leaf stage, grape plants grown from seed (“Gutedel”) are sprayed with an aqueous spray mixture of the active ingredient or mixtures thereof. After 1 day, the treated plants are inoculated with a spore suspension of Uncinula necaptor and then incubated in a growth chamber at + 24 ° C. and 70% relative humidity. The test may also be performed using therapeutic applications 2 days after inoculation. Disease attack is assessed 14 days after inoculation.

Example B-5: Activity against Spaeroteca Pullignia in Cucumber

About two weeks (Cotyledon stage) cucumber heading "chinesische Schlange" is sprayed with an aqueous spray mixture of the active ingredient or mixtures thereof. After 1 day, the treated plants are inoculated with a spore suspension of Spaeroteca fulginia, and then incubated in a growth chamber at + 24 ° C. and 70% relative humidity. The test may also be performed using therapeutic applications 2 days after inoculation. Disease attack is assessed 10 days after vaccination.

Example B-6 Activity against Venturia Equalis in Apples

Apple seedlings with about 10 cm fresh branches are sprayed with an aqueous spray mixture of the active ingredient or mixtures thereof. Treated plants are inoculated with a fungal congenital suspension after 24 hours. The plants are incubated in the greenhouse at + 20 ° C. and 95-100% relative humidity for 2 days, followed by an additional 20-24 ° C. and 80% relative humidity. Disease attack is assessed in the youngest leaves treated.

Example B-7 Activity against Puccinia Recondita in Wheat

About 10 days old wheat plant “Arina” is sprayed with an aqueous suspension of the active ingredient or mixture thereof. After 1 day, the plants are inoculated with a fungal spore suspension. The test may also be carried out as a therapeutic application, ie 1 to 3 days after the artificial inoculation of the plant. The plants are incubated in the growth chamber for 2 days at 20 ° C. and 95-100% relative humidity, followed by 10 days at 20 ° C. and 70% relative humidity. Fungal attack on the first leaf is assessed.

Example B-8: Activity against Septoria nodorum on Wheat

About 10 days old wheat plant “Zenith” is sprayed with an aqueous suspension of the active ingredient or mixtures thereof. After 1 day, the plants are inoculated with a fungal spore suspension. The test may also be carried out by application at the timing of treatment, ie 1 to 3 days after artificial inoculation of the plants. The plant is subsequently incubated in a growth chamber at a relative atmospheric humidity of 95-100%. Disease attack is assessed 10 days after inoculation.

Example B-9: Activity against Plasmopara Viticola in Grapevines

In the 4 to 5 leaf stage, grape plants grown from seeds ("Gutedel") are sprayed with an aqueous spray mixture of the active ingredient or mixtures thereof. After 1 day, the treated plants are inoculated with a fungal spore suspension. Plants are incubated in a growth chamber for 2 days at 22 ° C. and 95-100% relative humidity followed by 4 days at 22 ° C. and 70% relative humidity, followed by one day at high humidity to induce sporulation. Disease attack is evaluated 7 days after inoculation.

Example B-10 Activity against Phytophthora infestans in Tomato

About 4 weeks old tomato plant "Baby" is sprayed with an aqueous spray mixture of the active ingredient or mixtures thereof. After 1 day, the treated plants are inoculated with a fungal suspension of fungi. The plants are incubated in a humid chamber for 6 days at 18 ° C. and 100% relative humidity. After this period, disease attack is assessed.

The efficacy of the test combination and single active ingredient in the above test is measured by comparing fungal attack to fungal attack on untreated, similarly cultured test plants.

Example B-11 Activity against Gelatinia nivalis in wheat

G. Nivalis infected wheat seeds are harvested from the crop. The seed is treated with either active ingredient (I) or (b) or with a mixture of active ingredients. The active ingredient is first dispersed in water and then the dispersion is sprayed onto seeds on the rotating disk. This process corresponds to the conditions found in practice. Untreated seeds from the same raw material are used for comparison purposes. A batch of 100 grains is sown into seed trays (45 × 35 × 10 cm) in sterile soil 2 cm deep. Repeat the test three times. The seed tray is kept moist for 21 days at 5 ° C. excluding light. It is then transferred to a controlled environment cabinet (day / night: 16/8 hours; 10 ° C.) with the roughness at which germination occurs. Germination does not occur with grains heavily infected with G. nivalis. After 10 days, the tray is covered with a plastic film and kept at 10 ° C. without light. Due to the high atmospheric humidity under cover, mycelium becomes evident at the root base of plants infected with G. nivalis. About 60 days after sowing, the number of plants present and the number of infected plants are measured. The sum of ungerminated grain and infected grain forms the total infection rate. This ratio is compared to the total infection rate of the comparative seed tray containing untreated seeds and expressed as the total percent infection rate.

Example B-12 Activity against Helmintosporium Gramineum in Barley

Harvest barley seeds infected with H. gramineum from the field. The seed is treated with either active ingredient (I) or (b) or with a mixture of active ingredients. The active ingredient is first dispersed in water and then the dispersion is sprayed onto seeds on the rotating disk. This process corresponds to the conditions found in practice. Untreated seeds from the same raw material are used for comparison purposes. A batch of 100 grains is sown into seed trays (45 × 35 × 10 cm) in sterile soil 2 cm deep. Repeat the test three times. The seed tray is kept moist for 28 days at 2 ° C. excluding light. It is then transferred to a greenhouse (day / night: 18/12 ° C.). About 60 days after sowing, the number of plants present and the number of infected plants is measured. Symptoms appear as the typical striped dots of the first leaf. The total infection rate is compared to the total infection rate of the comparative seed tray including untreated seeds and expressed as the total percent infection rate.

Example B-13: Activity against Septoria nodorum on Wheat

Wheat seeds infected with S. nordorum are harvested from the field. The seed is treated with either active ingredient (I) or (b) or with a mixture of active ingredients. The active ingredient is first dispersed in water and then the dispersion is sprayed onto seeds on the rotating disk. This process corresponds to the conditions found in practice. Untreated seeds from the same raw material are used for comparison purposes. Test methods are described in Homes and Colhoun, Ann. of appl. Biolg., 1973, 225-232]. A batch of 100 grains is sown into seed trays (45 × 35 × 10 cm) in sterile soil 2 cm deep. Repeat the test three times. The seed tray is kept moist for 14 days at 8-10 ° C. excluding light. It is then transferred to a greenhouse (20 ° C.) for an additional 14 day period. The seedlings are then removed from the soil, washed with water and then evaluated for infection. The total infection rate is compared to the total infection rate of the comparative seed tray including uninfected seeds and expressed as the total percent infection rate.

Example B-14: Activity against Erycife Graminis in Barley or Wheat

Cereal seeds are treated with either active ingredient (I) or (b), or with a mixture of active ingredients. The active ingredient is first dispersed in water and then the dispersion is sprayed onto seeds on the rotating disk. This process corresponds to the conditions found in practice. Untreated seeds from the same raw material are used for comparison purposes. A batch of 100 grains is sown into seed trays (45 × 35 × 10 cm) in sterile soil 2 cm deep. Repeat the test three times. Seeds are germinated under controlled conditions (day / night: 15/10 ° C.). In the two to three leaf germination stages, the plants are artificially inoculated by shaking the heavily infected plants across the test tray. The seed tray is then maintained at elevated temperature (day / night: 22/18 ° C.). Percentage of infected leaf area is assessed at regular intervals. The total infection rate is compared to the total infection rate of the comparative seed tray including uninfected seeds and is expressed as the total percent infection rate.

The mixture according to the invention shows good activity in this example.

Claims (10)

Thieno [2,3-d] pyrimidin-4-one derivatives of Formula I (a) anilinopyrimidines of Formula II that synergistically enhance the effective amount and activity against phytopathogenic diseases; Azoles of formula III and salts of these azole fungicides; Morpholine fungicides of formula IV and salts of these morpholine fungicides; Strobiliurine compounds of formula V; Pyrrole compounds of formula VI; Phenylamide of formula VII; Dithiocarbamate fungicides selected from mancozeb, maneb, metiram and geneb; Copper compounds selected from copper hydroxide, copper oxychloride, copper sulfate and auxin-copper; sulfur; Phthalimide compounds of formula VIII; A compound of Formula IX; A compound of Formula X; Compounds of formula (XI); Compounds of formula (XII); A compound of Formula (XIII); A compound of Formula XIV; A compound of Formula XV; A compound of Formula (XVI); A compound of Formula (XVII); Compounds of formula (XVIII); A compound of Formula XIX; A compound of formula XX; A compound of Formula XXI; A compound of formula XXII; A compound of formula XXIII; A compound of Formula XXIV; A compound of Formula XXV; A compound of Formula XXVI; A compound of formula XXVII; Or applying an effective amount of compound (b) of formula (XXVIII) to a crop infected with a phytopathogenic disease or a habitat thereof. Formula I Formula II Formula III Formula IV Formula V Formula VI Formula VII Formula VIII Formula IX Formula X Formula XI Formula XII Formula XIII Formula XIV Formula XV Formula XVI Formula XVII Formula XVIII Formula XIX Formula XX Formula XXI Formula XXII Formula XXIII Formula XXIV Formula XXV Formula XXVI Formula XXVII Formula XXVIII In the above formulas (I) to (XXVIII), R ₁ is halogen, R ₂ is C ₁ -C ₅ alkyl or —CH ₂ -cyclopropyl, R ₃ is C ₁ -C ₅ alkyl or —CH ₂ -cyclopropyl, R ₄ is methyl, 1-propynyl or cyclopropyl, A is selected from formulas i to xv, wherein β-carbon is bonded to the benzene ring of formula III, R ₅ is H, F, Cl, phenyl, 4-fluorophenoxy or 4-chlorophenoxy, R ₆ is H, Cl or F, R ₁₃ is C _8-15 cycloalkyl, C _8-15 alkyl or C _1-4 alkylphenyl-C _1-4 alkyl, X is NH or 0, Y is CH or N, R ₁₄ is 2-methylphenoxy-methyl, 2,5-dimethylphenoxy-methyl, 4- (2-cyanophenoxy) -pyrimidin-6-yloxy or 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl, R ₁₅ and R ₁₆ are independently halo or together form a perhalomethylenedioxo bridge, R ₁₇ is benzyl, methoxymethyl, 2-furanyl, chloromethyl or ego, R ₁₈ is 1-methoxycarbonyl-ethyl or (Wherein Z is CH or N), R ₁₉ and R ₂₀ together form a four-membered bridge -CH ₂ -CH = CH-CH ₂ -or -CH-CH = CH-CH =, R ₂₁ is hydrogen or methyl, R ₂₂ is hydrogen or methyl, n is 0, 1 or 2, etc. R is hydrogen or -C (= NH) NH ₂ . Formula i Formula ii Formula iii Formula iv Chemical formula v Chemical formula vi Formula vii Chemical formula viii Formula ix Chemical formula x Formula xi Chemical formula xii Formula xiii Chemical formula xiv Chemical formula xv In the above formulas i to xv, R ₇ and R ₈ are independently H or CH ₃ , R ₉ is C _1-4 alkyl or cyclopropyl, R ₁₀ is 4-chlorophenyl or 4-fluorophenyl, R ₁₁ is phenyl, R ₁₂ is alkyloxy, C _1-4 alkyl or 1,1,2,2-tetrafluoroethoxy-methyl. The compound of claim 1 wherein component (a) is R ₁ is chloro or bromo, R ₂ is n-propyl, n-butyl or i-butyl, and R ₃ is n-propyl, n-butyl or i-butyl Which is a compound of formula (I). The method according to claim 1 or 2, wherein component (b) is pyrimethanyl, cyprodinyl, cyproconazole, hexaconazole, diphenocazole, etaconazole, propicoconazole, tebuconazole, tritico. Nazol, Flutriapol, Epoxyconazole, Penbuconazole, Bromuconazole, Penconazole, Imazalyl, Tetraconazole, Flusilazole, Metconazole, Diniconazole, Fluquinconazole, Michaelobutanyl , Triadimenol, bitteranol, dodemorph, tridemorph, fenpropormoff, mancozeb, maneb, metiram, geneb, copper hydroxide, copper oxychloride, copper sulfate, auxin-copper, sulfur, cre Foot-methyl, azoxystrobin, 2- [2- (2,5-dimethoxyphenoxy-methyl) -phenyl] -2-methoximino-acetic acid N-methyl-amide, methyl 2- {2- [4 -(3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -phenyl} -2-methoxyimino-acetate, fenpiclonyl, fludioxosonyl, benalacyl, fural Lock room, metal lock , R-metallaxyl, orfurrace, oxadixyl, carboxycin, captan, polpet, prochloraz, triflumizol, pyriphenox, acibenzola-S-methyl, chlorothalonil, cymoxanyl, dimetho Morphs, pamoxadons, phenhexamides, phenarimol, fluazinam, pocetyl-aluminum, quinoxyfen, phenpropidine, spiroxamine, carbendazim, thibendazole, etirimol, triazosides and Group consisting of guazatin; Preferably, cyproconazole, hexaconazole, diphenoconazole, propiconazole, tebuconazole, flutriafol, epoxyconazole, fenbuconazole, bromuconazole, fenconazole, tetraconazole, flusila The group consisting of sol, metconazole, diconazole, triadimenol, fluquinconazole and prochloraz; In particular propiconazole, diphenoconazole, fenconazole, tebuconazole, prochloraz, epoxyconazole and cyproconazole, and more specifically, cyprodinil, tridemorph, pen Propimorph, creoxime-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -phenyl} -2- Group consisting of methoxyimino-acetate, acibenzola-S-methyl, chlorothalonil, pamoxadon, quinoxafen, phenpropidine and carbendazim; In particular cyprodinyl, fenpropimod, creoxime-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -Phenyl} -2-methoxyimino-acetate, acibenzola-S-methyl and phenpropidine. 4. Compound (I) according to claim 3, wherein component (a) comprises compound (I.01), compound (I.02), compound (I.03), compound (I.04), compound (I.05), compound (I. 06), compound (I.07) and compound (I.08). A fungicide composition comprising a fungicidally effective combination of component (a) and component (b) as defined in claim 1 present in an amount that synergistically enhances activity against phytopathogenic diseases. The composition of claim 5 wherein the weight ratio of component (a) to component (b) is between 100: 1 and 1: 400. The compound of claim 5, wherein component (a) is R ₁ is chloro or bromo, R ₂ is n-propyl, n-butyl or i-butyl, and R ₃ is n-propyl, n-butyl or i-butyl A compound of formula (I). 8. Component (b) according to claim 6 or 7, wherein component (b) is pyrimethanyl, cyprodinyl, cyproconazole, hexaconazole, difenoconazole, etaconazole, propiconazole, tebuconazole, tritico Nazol, Flutriapol, Epoxyconazole, Penbuconazole, Bromuconazole, Penconazole, Imazalyl, Tetraconazole, Flusilazole, Metconazole, Diniconazole, Fluquinconazole, Michaelobutanyl , Triadimenol, bitteranol, dodemorph, tridemorph, fenpropormoff, mancozeb, maneb, metiram, geneb, copper hydroxide, copper oxychloride, copper sulfate, auxin-copper, sulfur, cre Foot-methyl, azoxystrobin, 2- [2- (2,5-dimethoxyphenoxy-methyl) -phenyl] -2-methoximino-acetic acid N-methyl-amide, methyl 2- {2- [4 -(3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -phenyl} -2-methoxyimino-acetate, fenpiclonyl, fludioxosonyl, benalacyl, fural Lock room, metal lock , R-metallaxyl, orfurrace, oxadixyl, carboxycin, captan, polpet, prochloraz, triflumizol, pyriphenox, acibenzola-S-methyl, chlorothalonil, cymoxanyl, dimetho Morphs, pamoxadons, phenhexamides, phenarimol, fluazinam, pocetyl-aluminum, quinoxyfen, phenpropidine, spiroxamine, carbendazim, thibendazole, etirimol, triazosides and Group consisting of guazatin; Preferably, cyproconazole, hexaconazole, diphenoconazole, propiconazole, tebuconazole, flutriafol, epoxyconazole, fenbuconazole, bromuconazole, fenconazole, tetraconazole, flusila The group consisting of sol, metconazole, diconazole, triadimenol, fluquinconazole and prochloraz; In particular propiconazole, diphenoconazole, fenconazole, tebuconazole, prochloraz, epoxyconazole and cyproconazole, and more specifically, cyprodinil, tridemorph, pen Propimorph, creoxime-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -phenyl} -2- Group consisting of methoxyimino-acetate, acibenzola-S-methyl, chlorothalonil, pamoxadon, quinoxafen, phenpropidine and carbendazim; In particular cyprodinyl, fenpropimod, creoxime-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] -Phenyl} -2-methoxyimino-acetate, acibenzola-S-methyl and phenpropidine. A compound according to claim 8, wherein component (a) comprises compound (I.01), compound (I.02), compound (I.03), compound (I.04), compound (I.05), compound (I. 06), a compound selected from the group consisting of compound (I.07) and compound (I.08). A method according to claim 1 for treating plant reproductive material, preferably seed.