CZ20001998A3 - Fungicidal composition containing thieno[2,3-d]pyrimidin-4-one - Google Patents

Abstract

Fungicidal compositions having synergistic effects, comprising component a) which is thieno [2,3-d] pyrimidin-4-one of formula I, wherein R b R 2 and R 3 have a specific meaning; in conjunction with component b) which is either an anilopyrimidine fungicide (II) or an azole fungicide (III) or a morpholine fungicide (IV) or a strobilurin compound (V) or a pyrrole compound (VI) or a phenylamide (VII) or a dithiocarbamate fungicide selected from a group consisting of mancozeb, maneb, metiram and zineb, or a copper compound selected from the group consisting of copper hydroxide, copper oxychloride, copper sulfate and oxine-copper or a phthalimide compound (VIII) or prochloraz or triflumizole or pyrifenox or acibenzolar-S methyl or chlorthalonil or cymoxanil or dimethomorph or famoxadone, or fenhexamide or phenarimol or fluazinam or fosetyl-aluminum, orquinoxyfen or fenpropidine or spiroxamine or carbendazim or thiabendazole or ethirimol or triazoxide or quazatin, in synergistically effective amounts.

Description

Qblast ..techniky

The present invention relates to novel fungicidal compositions for the treatment of plant phytopathogenic diseases and against attack of plant propagating material or other plant material, in particular phytopathogenic fungi, and furthermore the invention relates to a method for combating phytopathogenic diseases of crops or seed dressings.

BACKGROUND OF THE INVENTION

Certain pyrimidin-4-one derivatives are known to be biologically active against phytopathogenic fungi. for example WO 97/33890, where their properties and methods of preparation are described. On the other hand, anilinopyrimidines, azole fungicides, phthalimides, phenylamides, strobilurins, pyrroles, dithiocarbamates and morpholines are generally known plant fungicides for use on various crops of crop plants. However, plant tolerance and activity against phytopathogenic plant fungi does not always meet the needs of agricultural practice in many cases and aspects.

SUMMARY OF THE INVENTION

Now it has surprisingly been found to use

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

where

Ri is a halogen atom, • is a halogen atom, • is a halogen atom, or is a halogen atom; ···· ···· ····· ·· · ·

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

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

in connection with

b) either anilinopyrimidine of formula II

where

R ₄ is methyl, 1-propynyl or cyclopropyl;

or with an azole of formula III

OH

-C- CH.— β ι

CR _? R _and R _g

--- C - CH / \ o o

CRjRgRg (i) (ii) 9 9 9 9 9 9 9 9 9 98 9 ·

• 9 9 • 9 9 '9

9 9 9

9 9 9

9 9 9

OH (iii). -CH ₂ - CH ₂ -, -CH C - β I

CR ₇ R _and R ₉

(IN)

OH

C-CH.

(vi)

R <

(vii)

CN

CH 2 C - CH ₂ β R "

R ₉

O-CH-—

AND

CH — OH CR ₇ R ₈ R ₉ (XV)

9 9 9 «99 · · · · · 9 9 ··· · * 9 φ 99999 9 999 99 ·

9 9 9 9999

99999 »999999999 where β-carbon binds to the benzene ring of formula III and goes

R ₅ is hydrogen, fluoro, chloro, phenyl, 4-fluorophenoxy or 4-chlorophenoxy;

R 5 is hydrogen, chlorine or fluorine;

R ₇ and R ₈ are independently hydrogen or CH ₃ ;

R ₉ is C 1 -C 4 alkyl or cyclopropyl; '

R ₁₀ is 4-chlorophenyl or 4-fluorophenyl;

R 11 is a phenyl group, and

R ₁₂ is allyloxy, C 1 -C 4 alkyl or 1,1,2,2-tetrafluoroethoxymethyl, and salts thereof or with these azole fungicides;

a morpholine fungicide of formula IV

H ₃ C

NR (iv) h ₃ c wherein

R ₁₃ is C 8 -C 15 cycloalkyl, C 8 -C 15 alkyl, or C 1 -C 4 alkylphenylalkyl, and salts of these morpholine fungicides;

or with a strobilurin compound of formula V

444 • · · · ···

4 · 4 ·

4 4 4 4

where

X is NH or O,

Y is CH or N and

R 14 is 2-methylphenoxymethyl, 2,5-dimethylphenoxymethyl, 4- (2-cyanophenoxy) pyrimidin-6-yloxy, or 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl ; '.

or with a pyrrole compound of formula VI

(VI) where

Ris and R _{1 S} are each independently halogen or together form a perhalomethylendioxo bridge;

or with a phenylamide of formula VII

(Vil) where φφ ·· ♦ · ···· · ». Φ · · ♦ · * * * * * * 4 4 4 4 4 4 φ φ φ φ φ 4

Λ Ο · · ·· «φφφ

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

R ₁₃ is 1-methoxycarbonylethyl, or group II / o 0

Z is CH or N,

R ₂₁ is a hydrogen atom or a methyl group,

R ₂₂ is hydrogen or methyl;

or a dithiocarbamate fungicide selected from the group consisting of mancozeb, maneb, metiram, and zineb;

or with a copper compound selected from copper hydroxide, copper oxychloride, copper sulfate, and copper oxide;

or with sulfur;

or with a phthalimide compound of formula VIII

where

R ₁₉ and R _{20 taken} together form a four-membered bridge -CH ₂ -CH = CH-CH ₂ - or = CH-CH = CH-CH =;

or with a compound of the formula IX • 8 8 *

8 9 8 9 • ··· · · φ · · · 9

8

8

9 8 8 9'8 8

8 8 9 9 9 • · · · 9 «· 9 89 88 or se or se

a compound of formula X

a compound of formula XI

Cl

N-OCH ₃ (IX);

(XI);

or with a compound of formula XII

COSCH,

(XII) 'or a compound of formula XIII

or with a compound of formula XIV • 4 4 4 4 4 • 4 4 4 4 44 4 «4«

4 4 4 4

44444 4 4 · 4 4

4 4 4 4 · · · 4

4444 44 4 4. <44 44 4 4

O O CN

II II I (XIV);

H ₃ c-CH ₂ -NH-c-NH-C-C = N-OCH ₃ or with a compound of formula XV

(XV) or with a compound of formula XVI

or with a compound of formula XVII

CH,

WHAT

OH (XVII)

Cl Cl or with a compound of formula XVIII

φ · · · · · Φ · Φ · Φ · 9 · 9 φ

Φ Φ Φ 9 9 9 9 Φ Φ · Φ

999 9 9 Φ φ φ Φ φ • Φ ΦΦ Φ Φ φφφφ 99 «Φ« 99. ·· ·· f ₃ c

CF, (XIX);

or with a compound of formula XX

O.

II

H ₃ C - CH - P - OH ^{J 2} I

H

Al (XX);

or with a compound of formula XXI

Cl

(XXI), or with a compound of Formula XXII

(XXII);

or with a compound of formula XXIII

CH, h ₃ cCH

CH (XXIII);

, N.

CH, or with a compound of formula XXIV

9 ·

999 •. ·

9 9

9 9

9 · · * or se

• 9 · «• 9 99 9 '9

9

9 9 9

9 99 (XXIV)>

a compound of formula XXV

H

1 / S (XXV);

or with a compound of formula XXVI

(XXVI);

or with a compound of formula XXVII

O

(XXVII);

or with a compound of formula XXVIII

R = NH- (CH

2'8

R

AND

N ( ^CH 2 V (XXVIII) wherein n is 0 or 1 or 2 etc., and

R is hydrogen or -C (= NH) NH _2;

• · · # # # # # # # # # # # # # # t t t t t t t t t t t

899 9 9 · · · 4 8 9 9 9 9 8 8 9

8899 98 89 898 99 89 is particularly effective in fighting or crops. These combinations show vita.

prevention of fungal diseases by a synergistic fungicidal acti. If an expanded spectrum of controlled diseases is desired, the combinations of the present invention may also comprise more than one active ingredient (b). 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 preferred member of a group of compounds of formula I.

The following specific kinds of compounds of the formula I are known from WO 97/33890:

Compound No. Ri r ₂ ^R 3 1.01 Cl n-propyl n-propyl 1.02 Br n-propyl n-propyl 1.03 Cl n-propyl n-butyl I. 04 / Br n-propyl . n-butyl 1.05 Cl n-butyl n-propyl I .06 Br n-butyl n-propyl I. 07 / Cl i-butyl n-propyl 1.08 Br i-butyl n-propyl 1.09 Cl n-propyl i-butyl I. 10 Br n-propyl i-butyl

A preferred embodiment of the present invention is represented by those combinations which comprise as component a) a compound of formula I wherein R ₁ is chlorine or bromine and R ₂ is n-propyl, n-butyl, i-butyl and R ₃ is n-propyl, n-butyl, i-butyl.

Among the compositions of the present invention, most preferred are mixtures of the compounds of formula 1.01, 1.02, 1.03, 1.04, 1.05, 1.06,

1.07 or 1.08 with compounds of component b), particularly commercially

• ♦

9 9 9

9 9

9 9

Available products belonging to the given range, ie. commercially available products mentioned herein.

Salts of azole, amine and morpholine active ingredients are prepared by reaction with acids, for example, hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid or sulfuric acid, phosphoric acid or nitric acid, or with organic acids such as acetic acid , trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphthalenedisulfonic acid.

The active ingredient combinations are active against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Sclerotinia, Mycosphaerella, Uncinula); Basidiomycetes (for example, the genus Hemileia, Rhizoctonia, Tilletia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella herpotrichoides); Oomycetes (e.g., Phytofthora, Peronospora, Bremia, Pythium, Plasmopara).

Target crops for areas of indication according to the invention include, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, sorghum and similar cereals); beet (sugar beet and fodder beet); puffs, drupes and soft fruits (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes (beans, lentils, peas, soybeans); oil plants (rapeseed, mustard, poppy, olives, sunflowers, coconuts, castor oil plants) _φ φφφ φ φ φ φ φ γ ♦ 13 ··· ·· ·· ·· · · · * ♦ cocoa beans, groundnuts); cucumber plants (gourd, cucumbers, melons); fibrous plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); laurel plants (avocado, cinnamon, camphor); or plants, such as. is corn, tobacco, nuts, coffee, sugarcane, tea, wine, hops, grass, bananas and natural rubber plants, as well as ornamental plants (flowers, shrubs, broadleaf trees and evergreen trees such as conifers) and their seeds. This list does not limit the scope of the present invention.

The composition of the present invention can also be used in the field of protecting technical materials against fungal attack. Technical areas include wood, paper; skins, buildings, cooling and heating systems, ventilation and air conditioning systems and the like. The composition of the present invention can prevent preventive effects such as rotting, discoloration or mold. .

The composition of the present invention is particularly effective against powdery mildew and gangrene, pyrenophora, rhynchosporium and leptosfaeria, in particular against pathogens of monocotyledons such as cereals, including wheat and barley. They are also effective against downy mildew species, especially against plasmopara on wine.

The amount of the composition of the present invention to be used will depend on various factors, such as the compound used, the article to be treated (plant, soil, seeds), the type of treatment (e.g. spraying, dusting, seed dressing), purpose of treatment (prophylactic or therapeutic) , the type of fungus to be treated and the time of application.

Particularly preferred mixed partners of the compounds of formula II are those wherein R ₄ is methyl or cyclopro 14 ft · ftft ftft ftftft · ftft ftft ft ftft ft ft ftft ft ftft ft · ft · ft ftftftft · ftft Ftft ftftftft ftft ftft ftft ftft ftft ftft ftft These compounds are commonly known as pyrimethanil and cyprodinil.

Particularly preferred mixed partners of the compounds of formula III is a compound wherein _R is chloro, _R and R ₇ are hydrogen, R _a is CH _and and _Rg is cyclopropyl and A is a group (i) (commonly known such as cyproconazole); a compound wherein _R and R ₆ are chlorine, R ₇ and R _a is hydrogen, _R9 is propyl and A is a group (i) (commonly known as hexaconazole); Compounds wherein R ₅ is 4-chlorophenoxy, _R is chlorine, R @ _{7, R} 'and _R9 are hydrogen and A is a group (ii) (commonly known as difenoconazole); a compound wherein R _s . and _R are chlorine, _R7 and R are hydrogen _and R ₉ is ethyl and A is a group (ii) (commonly known as etaconazole); a compound wherein R ₅ and _R are Cl, _R7 and _A are both hydrogen, R ₉ · is propyl and A is a group (ii) (commonly known as propiconazole); Compounds wherein R ₅ is chloro, _R is hydrogen, R _{7, and} R and R ₉ are CH ₃ and A is a group (iii) (commonly known as tebuconazole); a compound wherein _R is chloro, _R6 is hydrogen and A is the moiety (iv) (commonly known as triticonazole); Compounds wherein R ₅ is hydrogen, _R is fluorine, Rio is 4 - fluorophenyl enyl and A is a group (v) (commonly known as flutriafol); a compound wherein _R is hydrogen, _R is Cl, _R10 is 4-fluoro-enyl and A is a group (vi) (commonly known as epoxiconazole); a compound wherein R is chloro, _R is hydrogen, R _u is f enyl and A is a group (vii) (commonly known as fenbuconazole); a compound wherein R ₅ and _R are Cl, and A is the moiety (viii) (commonly known as bromuconazole); a compound wherein R ₅ and _R are Cl, _R12 is propyl and A is the moiety (ix) (commonly known as penconazole); a compound wherein R ₅ and _R are chlorine, R _i2 is allyloxy and A is the moiety (ix) (commonly known as imazalil); a compound wherein R ₅ and _R are Cl, R12 is 1,1,2,2-tetrafluorethoxymethylová group and A is a moiety (ix) (commonly known as tetraconazole); a compound wherein _R is

1.5

4 44 44 4444

4 4 4 4 9 9

4 4 4 4 445 4

444 44 4,444. 4 4 4 4

4444 · 44 4 89 9 fluorine, _R is hydrogen, R ₉ is CH _3, R ₁₀ is 4fluorfenylová group and A is a group (x) (commonly known as flusilazole); Compounds wherein R ₅ is chloro, _R is hydrogen, R ₇ and R _a are methyl and A is the moiety (xi) (commonly known as metconazole); a compound wherein _R and _R are Cl, _R7 and _A are both hydrogen, R ₉ is a t-butyl 'group and A is a group (xii) (commonly known as diniconazole); a compound wherein R ₅ and _R are Cl, and A is a group (xiii) (commonly known as fluquinconazole); a compound wherein R _a is chlorine, R _s , R ₇ and R _a are hydrogen, R ₉ is n-butyl and A is (xiv) (commonly known as myclobutanil); a compound wherein _R is chloro, _R is hydrogen, R _7, R _a and _Rg are methyl and A is the moiety (xv) (commonly known as triadimenol); and a compound wherein R ₅ is phenyl, R _{7, and} R ₉ and R j sou. a methyl group and A is a group (xv) (commonly known as bitertanol).

Particularly preferred mixed partners of compounds of formula IV are those wherein R ₁₃ is a cyclododecyl group (commonly known as dodemorph), or an alkyl group containing 10 to 13 carbon atoms (commonly known as tridemorph), or 3- (4-tert-butylphenyl) -2-methylpropyl (commonly known as fenpropimorph). Preferably, methyl compounds are present in the cis position on the morpholine ring when used in the composition of the present invention when used in the composition of the present invention.

Particularly preferred mixed partners of the compounds of formula V are those wherein X and Y are oxygen, and R ₁₄ is a 2-methylphenoxymethyl group (commonly known as cresoxime-methyl); or. wherein X is NH, Y is N and R ₁₄ is 2,5-dimethylphenoxymethyl; or wherein X is O, Y is CH and R 14 is 4- (2-cyanophenoxy) -pyrimidin-6-yloxy (commonly known as azoxystrobin); or wherein X is O, Y is N and Rh is 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl.

• · • «9 9 9 99 99 9999 9 «99 9 9 9999 99 99 9 9 9 9 16 9 • 999 9 99 99 999 9 99 9 » Especially preferred mixed partners that compounds of formula VI are compounds, where R ₁₅ a Ris are both chlorine atom (generally

known as fenpiclonil); or wherein R and R _{1 S 1 S} together form a bridge -O-CF ₂ -O- (commonly known as fludioxonil).

Particularly preferred mixed partners of the compounds of formula VII are those wherein R ₁₇ is benzyl, R ₂₁ and R ₂₂ . They are methyl, and R _i is 1-methoxycarbonylethyl group (commonly known as benalaxyl); or wherein _R17 is 2-furanyl, R ₂₁ and R ₂₂ are methyl and R _{1 S} is 1-methoxycarbonylethyl group (commonly known as furalaxyl); or wherein R ₁₇ is methoxymethyl, R ₂₁ . and R ₂₂ are methyl and R _{1 S} is 1-methoxycarbonyl-ethyl or-. A (R) -1-methoxycarbonyl-ethyl group (commonly known as metalaxyl and R-metalaxyl); or wherein R ₁₇ is a chloromethyl group, R ₂₁ a

R ₂₂ is methyl and R 18 is

wherein Z is a group

CH (commonly known as orfuration); or wherein R ₁₇ 'is a methoxymethyl group, R ₂₁ and R ₂₂ are methyl and R _1S is

o wherein Z is a group N (commonly known as oxadixyl); or

CH, where R _i7 SEA R _g, R ₂₁ and R ₂₂ are hydrogen (commonly known as carboxin).

Particularly preferred mixed partners of the compounds of formula VIII are those wherein R ₁₉ and R ₂₀ together form a bridge -CH ₂ CH = CH-CH ₂ - (commonly known as captan); or wherein R _{X 9} and R ₂₀ together form the bridge = CH-CH = CH-CH = (commonly known as folpet).

The compound of formula IX is commonly known as prochloraz.

The compound of formula X is commonly known as triflumizole.

♦ 4 ···· · · 9 · ··· · · φ ·

4 4 4 4 * · 4 * 4 · ··· * 4 4 444 4 4 · ♦ · ♦ · 44 ···

444 4 ·· 4 · · 4 · · ·

The compound of formula XI is commonly known as pyrifenox.

The compound of formula XII is commonly known as acibenzolar-methyl.

The compound of formula XIII is commonly known as chlorothalonil.

The compound of formula XIV is commonly known as cymoxanil.

The compound of formula XV is commonly known as dimethomrph.

The compound of formula XVI is commonly known as famoxadone.

The compound of formula XVII is commonly known as fenhexamide:

The compound of formula XVIII is commonly known as fenarimol.

The compound of formula XIX is commonly known as fluazinam,

The compound of formula XX is commonly known as fosetyl-aluminum.

The compound of formula XXI 'is commonly known as quinoxyfen.

The compound of formula XXII is commonly known as fenpropidine.

The compound of formula XXIII is commonly known as spiroxamine.

The compound of formula XXIV is commonly known as carbendazime.

The compound of formula XXV is commonly known as thiabendazole.

The compound of formula XXVI is commonly known as ethirimol.

The compound of formula XXVII is commonly known as the triazoxide.

The compound of formula XXVIII is commonly known as guazatin.

The specific compounds b) mentioned in the preceding paragraphs are commercially available. Other compounds within the different groups of component (b) may be obtained by methods analogous to those known for the preparation of commercially available compounds.

· · · · Φ φ φ • - - · · φ φ φ φ φ - - - - - φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

It has been found that the compounds of the formulas II to XXVIII in combination with the compound of the formula I surprisingly and considerably increase the activity of the compounds of the formula I against fungi and vice versa. Further, the method of the present invention is effective against a broad spectrum of these fungi that can be controlled by the active ingredients of the method when used alone.

Specific preferred compositions of the present invention are understood to mean the combination of the active ingredients of formula I or any subgroup of compounds of formula I or specifically mentioned subgroup members with a second fungicide selected from the group consisting of pyrimethanil, cyprodinil, cyproconazole, hexaconazole, difenoconazole, etaconazole, propiconazole, tebuconazole, triticonazole , flutriafol, epoxiconazole, fenbuconazole, bromuconazole, penconazole, imazalil, tetraconazole, flusilazole, metconazole, diniconazole, fluquinconazole, myclobutanil, triadimenol, bitertanol, dodemorph, tridemorph, fenpropimorph, methane, mancozeb, mecozeb, mecozeb, copper, oxine-copper, sulfur, cresoxime-methyl, azoxystrobin, N-methylamide. 2- [2- (2,5-dimethylphenoxymethyl) phenyl] -2-methoximinoacetic acid, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl] phenyl} - 2-methoxyiminoacetate, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, orfuration, oxadixyl, carboxin, captan, folpete, prochloraz, triflumizole, pyrifenox, acibenzolar-S-methyl, chlorothalonil, dimethonanilone, cyethxanone, cyethxanil, fenhexamide, fenarimol, fluazinam, fosetyl-aluminum, quinoxyfen, fenpropidine, spiroxamine, carbendazime, thiabendazole, ethirimol, triazoxide and guazatin. ·

Within this group, a subgroup b1 which includes combinations with cyproconazole, hexaconazole, diphenoconazole, propiconazole, tebuconazole, flutriafol, epoxiconazole, fenbuconazole, is preferred. bromuconazole, pencoriazole, tetraconazole,

4444

4

4 4 4 4

4

4 4

4 4 4 4

4444 44

· 4 4

4 4 4

4 4 4

4 4 4

4 4 lus.ilazole, metconazole, diniconazole, triadimenol, fluquinconazole and prochloraz.

Of this, combinations with propiconazole, diphenoconazole, penconazole, tebuconazole, prochloraz, epoxiconazole and cyproconazole, which are designated as subgroup bia, are particularly preferred.

Another preferred subgroup of b2 comprises combinations with cyprodinil, tridmorph, fenpropimorph, kresoxim-methyl, azoxystrobin, methyl-2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3pentenyl] -phenyl} -2 methoxyiminoacetate, acibenzolar-S-methyl, chlorthalonil, famoxadone, quinoxyfen, fenpropidine and carbendazim.

Of this group of combinations, combinations of cyprodinil, fenpropimorph, cresoxime-methyl, azoxystrobin, methyl 2- {2- [4- (3-trifluoromethylphenyl) -3-aza-2-oxa-4-pentenyl] - phenyl} -2-methoxyiminoacetate, acbenzolar-5-methyl and fenpropidine, which are designated as subgroup b2a.

Other preferred combinations are as follows:. '

compound with any 1.01 with any member a member of the b1a and b2a groups; groups bl and b2, or compound 1.02 with any member groups bl and b2, or with any a member of groups b1a and b2a; compound 1.03 with any member groups bl and b2, or with any a member of groups b1a and b2a; compound 1.04 with any member groups bl and b2, or with anybody member of groups bia and b2a. compound 1.05 with any member groups bl and b2, or with any a member of groups b1a and b2a;

• ·· ·· • ♦ · • · · • ··· · • · ·· ···· • · · • · · · · · · • ·. * • ·  · · • · • · • · • · • · • · • · compound 20 ...... Z.06 with any group member • β · · · bl a • · b2, • 9 or with any a member of groups b1a and b2a; * compound 1.07 with any member groups bl a b2, or with any a member of groups b1a and b2a; compound 1.08 with any member groups bl a b2, or with any member of groups bia and b2a. Weight the ratio (a): (b) is chosen so that: to achieve syner-

gic fungicidal action. In general, the weight ratio of a): b) is 100: 1 to 1: 400.

If it is. component b) anilinopyrimidine of formula II, the weight ratio a): b) is, for example, 1: 2 to 1:36, in particular 1: 2 to 1:18, and more preferably 1: 3 to 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, and 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, and more preferably 1: 3 to 1:10.

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

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

1: 6, and more preferably 2: 1 to 1: 3.

9 9 9 99 9999 9 9 4 4 9 9 99 9 9 999 9 9 9 9 9 9

9,999,999 9

999999 999999999

If it is component b). The dithiocarbamate fungicide is a weight ratio of a): b) of, for example, 1: 3 to 1: 120, in particular 1: 4 to 1:60, and more preferably 1: 7 to 1:25.

When component b) is a copper-based fungicidal compound, the weight ratio of a): b) is, for example, 1: 1.5 to 1: 100, especially 1: 2 to 1:50, and 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, and 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, and more preferably 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, and preferably 1: 5 to 1: 8.

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

When component b) is a compound of formula XI, the weight ratio a): b) is, for example, 8: 1 to 1: 4, especially 2.5: 1 to 1: 2, and 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, and 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, and more preferably 1: 5 to 1:10.

· · * »98 89 98

8 9 8 9 9 9 9 8 8 9

9 · 9 9 989 9 9 8 · · «4 4 · · · · 8.

8989 99 88 999 98 98

For example, when component b) a): b) is 3: 2 to 1: 2.

a compound of formula 1 to 1: 8, in particular

XIV, the weight ratio is 2.5: 1 to 1: 4, and preferably if component b) is a compound of formula XV, the weight ratio a): b) is for example 1.5: 1 to 1:12, especially 1: 1 to 1: 6, and 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, and more preferably 1: 1 to 1: 3.

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

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

When component b) is a compound of formula XX, the weight ratio a): b) is for example 1: 3 to 1:80, especially 1: 4 to 1:40 and 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, and 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, especially 1: 3 to 1:15, and more preferably 1: 3 to 1:10.

* «Λ» · «• 9

998 9 9

9 9 «

9 9 9 9 9 • • ···

When 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, and 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, and 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, and preferably 10: 1 to 1: 2.

When component b) is a compound of formula XXVI, the weight ratio of a): b) is, for example, 1: 1 to 1:10, in particular 1: 1 to 1: 5, and 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, especially 5: 1 to 50: 1, and 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, and preferably 2: 1 to 1: 1.

The method of the present invention comprises applying a fungicidally effective total amount of a compound of formula I and a compound of component, b) to the plants to be treated or to their locus in a mixture or separately.

The term locus according to the present invention includes fields in which the crop to be treated is cultivated or where the planting of the crop plants is planted or the place where the planting is planted in the soil. The term planting includes plant propagation material such as cuttings, seedlings, seeds, sprouted or soaked seeds. The new combinations are extremely effective on a wide range of phytopathogenic fungi, especially from the Ascomycetes and Basi classes. φ φ φ φ om di di di di di di di di di di Some of them act systemically and can be used as foliar or soil fungicides.

The fungicidal combinations are particularly suitable for controlling a large number of fungi on various crops or their seeds, in particular on wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, cane, fruit and ornamental plants in horticulture and viticulture and vegetables such as cucumbers, beans and pumpkins.

The combinations are applied by treating fungi or seeding, plants or materials threatened by fungal attack or soil with a fungicidally effective amount of the active ingredients.

The agents may be applied before or after attack of materials, plants or fungal planting.

The novel combinations are particularly suitable for controlling the following plant diseases:

Erysiphe graminis on cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkins, Podosphaera leucotricha on apples,.

Uncinula necator on wine,

Puccinia species on cereals,

Rhizoctonia species on cotton, rice and grass,

Ustilago species on cereals and sugar cane,

Venturia inaequalis (scab) on apples,

Helminthosporium species on cereals,

Septoria nodorum on wheat,.

Septoria tritici on wheat,

Rhynchosporium secalis barley,

Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice,

Phytophthora infestans on potatoes and tomatoes,

Fusarium and Verticillium species on different plants,

Plasmopara viticola on grapevines, 4

4 4

4 4 4 4

Alternaria species on fruits and vegetables

When applied to plants, the compound of formula I is used in a ratio of 25 to 150 g / ha, in particular 50 to 125 g / ha, for example 75, 100, or 125 g / ha. in conjunction with 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, such as sulfur up to 10000 g / ha of the compound of component b), depending on the class of the chemical used as component b).

If component b) is anilinopyrimidine of formula II, for example 300 to 900 g ai / ha is used in conjunction with a compound of formula I. If component b) is an azole fungicide of formula III, for example 20 to 350 g ai / ha is used in conjunction with a compound If component b) is morpholine of formula IV, for example 300 to 750 g ai / ha in conjunction with a compound of formula I is used. If component b) is strobilurin of formula V, for example 75 to 250 g ai / ha in conjunction with If the component b) is a pyrrole of the formula VI, for example 200 to 750 g ai / ha are used in conjunction with the compound of the formula I. If the component b) is a phenylamide of formula VII, for example 50 to 300 g ai / ha in conjunction with a compound of formula I. If component b) is a dithiocarbamate, for example, 500 to 3000 g ai / ha are used in conjunction with a compound of formula I. If component b) is a copper compound, for example 250 to 2500 g ai in conjunction with the compound of formula I. If component b) is sulfur, for example 1000 to 10,000 g, a.i. in conjunction with a compound of formula I. When component b) is a phthalimide of formula

VIII, for example 500 to 2000 g a.i./ha in conjunction with a compound of formula I. If component b) is a compound of formula

IX, for example 400 to 600 g a.i./ha in conjunction with a compound of formula I. If component b) is a compound of formula X, for example 50 to 400 g a.i./ha in conjunction with

I · · 9

9 9

9 9 9 9

9999 98 • 9 ··

9 • 9

9

26 compound if Yippee ingredient (b) XI for example, 20 to 100 g a . and compound if Yippee ingredient (b) XII for example, 20 to 40 g a . and compound if. Yippee ingredient (b) XIII, for example 500 to 500 are used 1000 g and. compound if Yippee ingredient (b)

XIV, for example 50 to 200 g a.i./ha are used in conjunction with a compound of formula I. If component b) is a compound of formula

XV, for example, 100 to 300 g ai / ha are used in conjunction with a compound of formula I. If it is _; component b) a compound of the formula

XVI, for example 125 to 250 g a.i./ha are used in conjunction with a compound of formula I. When component b) is a compound of formula

XVII, for example, 100 to 750 g a.i./ha are used in conjunction with a compound of formula I. When component b) is a compound of formula

XVIII, for example 20-100 g a.i./ha are used in conjunction with a compound of formula I. When component b) is a compound of formula

XIX, for example, 100 to 100 are used. 300 g a.i./ha in conjunction with

XXI,

formulas I.. If Yippee ingredient (b) compound of formula for example, 500 to 2 0 00 g a. i ./ha in conjunction with if Yippee ingredient ' (b) compound of formula for example, 75 to 125 g. a. i. / ha in conjunction with of formula I, if Yippee ingredient (b) compound of formula

XXII, for example 300 to 750 g a.i .. / ha are used in conjunction with a compound of formula I. If component b) is a compound of formula

XXIII, for example 375 to 750 g a.i./ha are used in conjunction with a compound of formula I. When component b) is a compound of formula

XXIV, shall apply. for example 125 to 250 g a.i./ha in conjunction with a compound of formula I. When component b) is a compound of formula

XXV, for example 5 to 200 g is used in the seed dressing

ai / 100kg in conjunction with a compound of formula I. If component (b) is a compound of formula XXVI, for example, 200 g is used in the seed dressing and i / 100kg in conjunction with a compound of formula I. »« * 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 For example, 2 g ai / 100kg in conjunction with a compound of formula I is used in the seed dresser, if component b) is a compound of formula XXVIII, for example, 40 to 80 g ai / 100kg in conjunction with a compound of formula I.

In agricultural practice, the application rates of the combinations depend on the type of effect desired and range from 0.02 to 4 kg active ingredient per hectare.

When the active ingredient is used for seed treatment, ratios of 0.001 to 50 g a.i. per kg, and preferably 0.01 to 10g per kg of seed.

The present invention also encompasses a fungicidal composition comprising a compound of formula I and compounds of component b).

The compositions of the present invention can be used in any conventional form, for example in the form of a double pack, instant granulate, flowable _; or a wettable powder, in combination with agriculturally acceptable ingredients. These .components. the compositions may be prepared by any conventional method, for example by mixing the active ingredients with suitable additives (diluents or solvents and optionally other formulating agents such as surfactants); .

The term diluent according to the present invention means any liquid or solid agriculturally acceptable material comprising carriers that can be added to the active ingredients to obtain an easier or better applicable form, of appropriate or desired potency. Suitable solvents are: aromatic hydrocarbons, preferably C8-C12 fractions, for example mixtures of xylenes or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols a)

their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as

9 99 99

9 9 9 9 9 9

9 9 · ····

999 9 9 9 9 9 9 9 9 9

9 9 9 9 9

- Lohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as vegetable oils or epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water. The solid carriers used, for example, for powders and dispersible powders, are conventional natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers to improve physical properties. Suitable granulated adsorptive carriers are of the porous type, for example pumice, crushed bricks, sepiolite or bentonite, and suitable non-absorbent carriers are, for example, calcite and sand. Furthermore, a large number of materials of an inorganic or organic nature can be used, for example in particular dolomite or ground plant residues. Depending on the nature of the compound of formula I and component b) ^which: to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactant" also refers to mixtures of surfactants. Especially preferred additives promoting applicability. are natural or synthetic phospholipids from the group of cephalin and lecithin, for example. phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol and lysolcithine.

Particular formulations which are applied in the form of a spray, such as water-dispersible concentrates or wettable powders, may contain surfactants as wetting and dispersing agents, for example the condensation product of formaldehyde with naphthalene sulfonate. alkylarylsulfonate, ligninsulfonate, fatty alkyl sulfate, ethoxylated alkylphenol and ethoxylated fatty alcohol.

The seed dressing compositions are applied in a conventional manner to the seeds using the combination of the present invention and 9. 99 • 9 9 9 9 9 9 9 9

9999 «· · 9 9 · ·» · 9 9 9 ··· '··

9999 9 9 99 9 · 9 99 99 diluents suitable for seed dressings, for example in the form of an aqueous suspension or in the form of a dry powder having good seed adhesion. Such seed dressing compositions are known to those skilled in the art. The seed dressing compositions may comprise a single active ingredient or a combination of the active ingredients in an encapsulated. in the form of capsules or slow release microcapsules.

Generally, the compositions comprise 0.01 to 90%. 0 to 20% of an agriculturally acceptable surfactant; and 10 to 99.99% of a solid or liquid additive, wherein the active agent comprises at least a compound of formula I together with a pharmaceutically acceptable surfactant. a compound of component b) and optionally other active agents, in particular microbides or preservatives and the like. Concentrated forms of compositions generally contain 2 to 80%, preferably 5 to 70% by weight of the active ingredient. For example, the dosage forms of the compositions may contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of the active agent.

The examples which follow serve to illustrate the present invention, "active ingredient" means a mixture of a compound of formula I and a compound of component b) in a specific weight ratio.

The compositions may be prepared in an analogous manner to that described, for example, in WO -97/33890.

IN

EXAMPLES OF THE INVENTION »

A slow release capsule suspension of parts of the combination of the compound of formula I and the compound of component b) or each of these compounds separately is mixed with 2 parts of an aromatic solvent and 7 parts of a diisocyanate / polymethylene polyphenylisocyanate (8: 1) mixture. This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of antifoam agent 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 β · β β β β β φ β β β β β β β β β dílu β · · * ««

Φ ··

2Q ···················· · · ·

1,6-diaminohexane ν 5.3 parts water. The mixture is shaken until the polymerization reaction is complete.

The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension composition contains 28% active ingredients. The mean capsule diameter is 8 to 15 microns. The composition obtained is applied to the seeds as an aqueous suspension by means of a device suitable for this purpose.

Means for dressing seeds

25 parts of a combination of 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 a dye and 0.5 parts of xanthan gum are ground and ground on a counterplex mill at about 10,000 rpm to a mean particle size of less than 20 microns. The composition obtained is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.

While commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.

Examples of biological testing

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

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

ftft ftftft ftft ftft ftftft ftft ftftftftft ftftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ppm = milligrams of active ingredient

i.) per liter of spray

X =% folders action active . component I for use Y =% folders action active component II for use According to Colby's expected (additive) action

I + II using p + q ppm active ingredients p ppm active q ppm active active ingredients

100 ALIGN!

E = X + Y. there is a synergistic effect.

Alternatively, the synergistic effect can also be determined from the dose response curve according to the so-called WADLEY method. In this method, the efficacy ai is determined. by comparing the degree of fungal infestation on the treated plants with the untreated infestation, similar to inoculated and incubated as the reference plants. Each ai is tested at 4-5 concentrations. Dose response curves are used for the determined EC90 (i.e., concentration ai providing 90% disease control) of the individual compounds as well as the combination (EC 90 _pO ). Thus, the experimentally obtained values for mixtures at a given weight ratio are compared to would be found only by the complementary action of the components present (EC 90 (A + B) expected) EC 90 (A + B) expected is calculated according to Wadley (Levi et al., EPPO Bulletin 16, 1986, 651-657). ): a + b ^λ '

EC 90 (A + B) expected ⁼ “a. b

- ₊ -EC90 (A) observed EC90 (B) observed /

Φ φ φ · · · φ φ φ φ · · kde • • • • • • • • • • • φ φ φ φ φ φ kde kde kde kde kde kde kde A and B in the mixture and the indexes (A), (Β), (A + B) denote the EC 90 values of compounds A, B or a given combination thereof A + B. The ratio EC90 '(A + _B), has unexpectedly / EC90 (A + B) P ₀ of _0rovan s expresses the factor of interaction (F). In the case of synergistic action, F> 1.

Example B-1

Action against Erysiphe graminis f.sp. tritici on wheat

Wheat plants c.v. Arina, about 10 days old, is sprayed with a suspension of the active ingredients or mixtures thereof. One day later, plants are inoculated by dusting with spores of Erysiphe graminis. The test may also be performed with curative application, i. application 1 to 3 days after artificial inoculation of plants. The plants are incubated in a greenhouse or in air-conditioned chambers at 20 ° C and 70% relative humidity. 7-10 days after inoculation, fungal infestation on primary leaves is evaluated.

Results:

• 4

4 «4,444 · -« 4,444

444 · 4 4 · 4 * 4

444 4 4 444 4 4 5 »

44444 4 4 »4 4 4 4 • 4 '4 4 ..

4444 44 «4444 44 44

Table 1: Mixture 1.01 + fludioxonil (compound VI, where R ₁₅ and R _1S together form a bridge -OCF ₂ -O-)

Merge. Fludioxonil Ratio % activity % activity Colby's 1.01 ppm observed expected factor ppm _ - - 10 0 25 0 50 12 100 ALIGN! 26 250 34 500 66 ' 10 .2 25 0 50 6 100 ALIGN! 14 250 19 Dec 500 27 Mar: 10 10 1 - 1 21 2 13.7 10 25 1: 2.5 27 Mar: 0 - ¹⁰ 50 1: 5 ii 6 1,8 10 100 ALIGN! 1: 10 30 14 2.2 10 250 1:25 19 Dec 19 Dec 1.0 25 25 1 - 1 13 0 - 25 50 1: 2 31 6 4.9 25 100 ALIGN! 1: 4 50 14 3.6 25 250 1:10 23 19 Dec 1,2 25 500 1:20 4 6 27 Mar: 1.7 > 50 ⁵⁰ 1 - 1 39 17 2.3 50 100 ALIGN! 1: 2 56 24 2.3 50 2 50 1: 5 39 29 1.4 50 500 1:10 72 36 2,0

4 • 4 4

44

4 4 »

4 4 • • 4 4 4 4 4 4 4 4

44 • 4 4 ·

4 4

4 44 ·

4444 44

44

4 4 4 4

9 4 4 · 4

444

100 ALIGN! 100 ALIGN! 1 - 1 62 36 1.7 100 ALIGN! 250 1: 2.5 70 41 1.7 100 ALIGN! 500 1: 5 63 46 1.4 250 250 1 ·: 1 75 47 1.6 250 500 1: 2 81 52 1.6 500 500 1 - 1 93 73 1.3

Table 2:. A mixture of 1.01 + cyproconazole (compound III where R ₅ is Cl, _R and _R7 are H, _R8 is _{CH3, R9} is cyclopropyl and A is the group (i))

Merge. cyproconazole Ratio % activity % activity Colby's 1.01 ppm ppm observed expected factor - - 0 (control) 0.5 0 1 0 225 0 5 8 10. 8 1 8 2.5 49 5 100 ALIGN! 10 100 ALIGN! 0.5 1 1: 2 18 8 2.4. 0.5 2.5 1: 5 69 49 1.4 0.5 5 1:10 100 ALIGN! 100 ALIGN! 1.0 1 1 1 - 1 23 8 3.0 1 2.5 1: 2.5 92 49 1.9 1 5 1: 5 100 ALIGN! 100 ALIGN! 1.0 2.5 1 2.5: 1 38 8 5.0 2.5 2.5 1 - 1 74 49 1.5

99 99 999 94 94 9 9 44 444 «* 9 * 99

9 9 9999

99999 9,999,999

9 9 9 9 9

9999 99 99 49

2.5 5 1: 2 100 ALIGN! 100 ALIGN! 1.0 5 1 It was 5 - 1 at the break 43 15 Dec 2.9 5 2.5 2 ^{- 1} 92 53 1.7 5 5 1 - 1 100 ALIGN! 100 ALIGN! 1.0 10 2.5 4 - 1 98 53 1.9

Table 3: Mixture 1.01 + propiconazole (compound III · where R ₅ and R ₆ are Cl, R ₇ and R ₃ are H, R ₉ is propyl and A is group (ii))

Merge. propiconazole Ratio % activity % activity Colby's 1.01 ppm ppm observed expected factor - - 0 (control) 0.5 2 1 .0 2.5 14 5 8 10 4 0.1 0 0.25 0 0.5 6 1 8 2.5 72 0.5 0.1 It was 5 - 1 at the break 18 2 7.7 0.5 0.25 2 - 1 19 ' 2 8.2 0.5 0.5 1: 23 8 2.8 0.5 1 1: 2 51 11 4.8 0.5 2.5 1: 5 90 73 1,2 1 0.5 2 - 1 25 6 4.2 1 1 1 - 1 42 8 5.0 1 2.5 2.5 87 72 1,2 1 5 1: 5 ⁹⁹ 99 1.0

·· 44 · 44 444 44 44 44 4 4 4 4 4 44 4 4 4 ·

4 4 4 4 «45 · 4 4 ·

444445 444445 4

4 4 4 4 4

4444 44 44 444 44 44

2.5 0.5 It was 5 - 1 at the break 42 ^{19 Dec} 2.2 2.5 1 2.5: 1 57 .22 2.6 2.5 2.5 1 - 1 94 76 1,2 5. 1 It was 5 - 1 at the break 61 16 3.8 5 2.5 2 - 1 90 75 1,2 5 5 1 - 1 99 99 1, 0 10 2.5 That made the score 4 - 1 92 73 1,2

Table 4 ': Mixture 1.01 + fenpropidine (compound XXII)

Merge. 1.01 ppm fenpropidine. ppm Ratio % activity observed % activity expected Colby's factor - - - 0 (control) 0.25 0 0.5 O 1 0 2.5 0 2.5 35 5 51 10 63 0.25 5 1:20 ' 63 51 1,2 0.5 5 1: 10 ⁵⁹ 51 1,2 0.5 10 1:20 88 63 1.4 1. 5 1: 4 59 51 1,2 2.5 10 1: 4 80 63 1.3

·· ·· ·· ···· 99 99 • 9 9 9 9 9 9 999

9 9 9 9 99

99999 999999 9

9 9 9 9 9 9 9 9 • 999 99 99 999 99 99

Example Β-2

Action against Erysiphe graminis f.sp. hordei barley

(a) Protective or curative activity

Barley plants, cv., Golden Promise, are used. Testing is carried out in the same manner as described in Example B-1.

b) Systemic activity

Aqueous spray mixtures of the active ingredients or mixtures thereof are poured next to barley plants about 8 cm high. The treatment is carried out so that the mixture does not come into contact with the aerial parts of the plants. After 48 hours, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22 ° C. Disease infestation on the leaves is evaluated 12 days after infection.

Example B-3

Action against Podosphaera leucotricha on apple trees

Apple seedlings with fresh shoots of approximately 10 cm in length are sprayed with an aqueous spray mixture of the active ingredients or mixtures thereof. After 24 hours, the treated plants are infected with the equine suspension of the fungus and then placed in a controlled environmental chamber at a relative air humidity of 70% and a temperature of 20 ° C. The test may also be performed with curative application 2 days after infection. The fungal infestation is evaluated 12-14 days after infection.

Example B-4

Action against Uncinula necator on vines

Vine plants grown from seeds (c. 'Gutedel'), at the 4 to 4 leaf stage, are sprayed with an aqueous spray mixture.

*

Φ · Φ • Φ Φ ΦΦ

Φ · ·

Φ · Φ Φ Φ

Φ ΦΦ ♦ ♦ Φ Φ

Φ Φ Φ «

Φ Φ Φ «

Φ Φ Φ 9

The active ingredients or mixtures thereof. After one day, the treated plants are infected with the sputtering of a spicicula necator spore and then incubated in a growth chamber at a temperature of +24 ° C and 70% relative humidity. Test. can also. performed using curative application 2 days after infection. Disease infestation is assessed 14 days after infection.

Example B-5

Action against Sphaerotheca fuliginea on cucumbers

Cucumber seedlings c.v. chinsische Schlange, about 2 weeks old (cotyledon stage), are sprayed with an aqueous spray mixture of the active ingredients or mixtures thereof. After one day, the treated plants are infected with a spore suspension of Sphaerotheca fuliginea and then incubated in a growth chamber at +24 ° C and 70% relative humidity. The test can also be performed using curative application 2 days after infection. Disease infestation is evaluated 10 days after infection.

Example B-6

Action against Venturia inaequalis on apple trees

Apple seedlings, with about 10 cm long fresh shoots, are sprayed with an aqueous spray mixture of the active ingredients or mixtures thereof. Treated plants are infected 24 hours later with a conidia suspension of the fungus. The plants are incubated for 2 days at +20 ° C and 95-100% relative humidity, then for an additional 10 days in a greenhouse at 20-24 ° C and 80% relative humidity. Disease infestation is evaluated on the youngest treated leaves.

• · · ·

9 · 9

9

9999 99 ·· ····

9

9 9

9

9 9 • - 9 9

999

9

9

9

Example B-7

Action against Puccinia recondita on wheat

Wheat plants c.v. Arina, about 10 days old, is sprayed with an aqueous suspension of the active ingredients or mixtures thereof. After one day, the plants are infected with a spore suspension of the fungus. The test may also be performed by curative application, i.e., application 1 to 3 days after the artificial infection of the plants. The plants are incubated. in a growth chamber for 2 days at 20 ° C and 95-100% RH, then for an additional 10 days at 20 ° C and 7.0% RH. The fungal infestation on the primary leaves is evaluated.

Table 5: Mixture 1.01 + ' V, wherein X is O, Y is N and R ₁₄ is 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentyl

merge 1.01 ppm merge IN ppm Ratio % activity observed % activity expected Colby's factor - - 0 (control) 0.5 0 1 0 2.5 0 5 0 10 0 25 0 1 17 2.5 32 5 38 10 37 0.5 2.5 1: 5 58 32 1,8 0.5 5 1: 10 45 38 1,2 1 2.5 1: 2.5 53 32 1.6 1 5 1 - 1 52 38 1, 4 1 10 1:10 74 37 2,0 2, 5 1 2.5: 1 43 17 2.6

i ············································· · · · · · · · · · · · · · · · · · · · · · ·

2.5 2.5 1 - 1 .4 6 32 1.4 2.5 5 1: 2. 45 38 1,2 2.5 10 1: 4 70 37 1.9 5 2.5 2 - 1 52 32 1.6 5 5 1 - 1 47 38 1.4 5 10 1: 2 76 37. . 2.1 10. 5 2 - 1 59 38 1.6 10 10 1 - 1 79 37 2.1 25 10 2.5: 1 68 37 1.9

Example B-8

Action against Septoria nodorum on wheat

Wheat plants c.v. Zenith, about 10 days old, is sprayed with an aqueous suspension of the active ingredients or mixtures thereof. After one day, the plants are inoculated with a fungus spore suspension. The test may also be performed at curative timing, i. application 1 to 3 days after artificial infestation of plants. The plants are then incubated in a growth chamber at a relative atmospheric humidity of 95-100%. Disease infestation is evaluated 10 days after inoculation.

Example B-9

Action against Plasmopara viticola on vines

Vine plants grown from seeds (c.v. Gutedel), at the 4-5 leaf stage, se. spray mixtures of active ingredients or mixtures thereof. After one day, the treated plants are inoculated with a fungal spore suspension. The plants are incubated in the growth chamber for 2 days at + 22 ° C and 95-100% RH, then 4 days at 22 ° C and 70% RH, then again for 1 day at high humidity to induce sporulation. Disease infestation is evaluated 7 days after infection.

• ftftft • ft

• ftftftft ft • ftftftft • ft ftft

Example B-10

Action against Phytophthora infestans on tomatoes

Tomato plants cv. Baby, about 4 weeks old, is sprayed with an aqueous spray mixture of the active ingredients or a mixture thereof. After one day, the plants are inoculated with a fungal zoospore suspension. The plants are incubated for 6 days in a humid chamber at 18 ° C and 100% relative humidity. After this time, the disease is evaluated.

The efficacy of the tested combinations and the individual active ingredients in the above tests is determined by comparing the degree of fungal attack with that of untreated, similarly infected plants.

Example B-11

Action against Gerlachia hivalis on wheat

The wheat grains infected with G. nivalis are harvested from the field. This grain is treated with one active ingredient I or b) or a mixture of active ingredients. The active ingredients are first dispersed in water and this dispersion is sprayed onto the grain which is on the rotary disk. This method corresponds to the conditions used in practice. Untreated grains of the same origin are used for comparison purposes.

Sets of 100 grains are sown in sowing dishes (45x35x10 cm) into sterile soil to a depth of 2 cm. The test is started in triplicate. The sowing dishes are kept moist for 21 days at 5 ° C in the absence of light. They are transferred to a controlled environment cabinet with lighting, (day / night: 16/8 hours; 10 ° C), where emergence occurs. Germination does not take place in the case of those grains which are severely infected with G. nivalis. After 10 days, the dishes were covered with a plastic film and kept at 10 ° C without light. Due to the high atmospheric humidity under the covers. mycelium fungi • φ φ φ φφ φφφφ

Φ · • · φ • - φ φ φ φ φ φ φ φ φ φ ·

φ. φ

It appears at the bottom of the stem of those plants that are infected with G. nivalis. About 60 days after sowing, the number of existing plants and the number of infected plants are determined. The sum of the number of non-germinated grains and the number of infected plants constitutes the total infestation rate. The rate is compared to the total infestation rate as compared to untreated seed sieves and expressed as the total percentage infestation rate.

Example B-12

Action against Helminthosporium graminum barley

The barley grains that are infected with H. graminum are harvested from the field. This grain is treated with one active ingredient I or b) or a mixture of active ingredients. The active ingredients are first dispersed in water and this dispersion is sprayed onto the grain that is on the rotary disk. This method corresponds to the conditions used in practice. For comparison purposes, untreated grains of the same origin are used.

Sets of 100 grains are sown in sowing dishes (45x35x10 cm) into sterile soil to a depth of 2 cm. The test is started in triplicate. Sow dishes are kept moist for 28 days at 2 ° C in the dark. They are transferred to a greenhouse (day / night: 16/12 ° C). About 60 days after sowing, the number of existing plants and the number of infected plants are determined. Symptoms appear as typical striped spots on the first leaf. The total infestation rate is compared to the total infestation rate in untreated grain control sowing dishes and expressed as the total percentage infestation rate.

• 4,444

44 • 44 4

4 4 4 4444 4 4

44444 4 4444 «4

4 4 4 4 4 4 4 4 β 4 44 44 4 44 444 44 44

Table 6: A mixture of 1.01 + triticonazole (compound III where R ₅ is Cl., _R is H and a group (iv)).

merge 1.01 g a.i./lOOkg grains triticonazole g a.i./lOOkg grains Ratio % activity pozoro- bathtub % activity expected Colby's factor 0 (control) 20 May 11 20 May 12 40 22nd 20 May 40 1: 2 36 31 1,2 20 May 20 May 1 - 1 29 22nd 1.3

Example B-13

Action against Septoria nodorum. on wheat

Grains of wheat that are infested with S.nodorum are harvested from the field. This grain is treated with one active ingredient I or b) or a mixture of active ingredients. The active ingredients are first dispersed in water and this dispersion is sprayed onto the grain which is on the rotary disk. This method corresponds to the conditions which are used in practice. Untreated grains of the same origin are used for comparison purposes.

The test method used is based on the procedure published in Holmes and Colhoun (Ann. Of appl. Biolg., 1973, 225-232). Sets of 100 grains are sown in sowing dishes (45x35X10 cm) into sterile soil to a depth of 2 cm. The test is started in triplicate. The sowing pans are kept moist for 14 days at 8-10 ° C in the dark. They are transferred to a greenhouse (20 ° C) for another 14 days. Then the grains are removed from the soil and washed with water and • 4 ♦♦ ··

44

4 4 4

4 4 4

4 4 4 4

4 4 4

44 • 4 · »4

444 4 • 4 • 44 4 4

4 4

4 4 4 9

4 4

4 4

444 then the assault is evaluated. The overall rate of infection was compared with the total infection rate in the controls aspirator ^CH dishes with untreated grains and expressed as the total percentage infection rate.

Example. B-14

Action against Erysiphe graminis on barley and wheat

The grain grains are treated with one of the active ingredients I or b) or a mixture of active ingredients. The active ingredients are first dispersed in water and this dispersion is sprayed onto the grain which is on the rotary disk. This method corresponds to the following conditions:. which are used in practice. Untreated grains of the same origin are used for comparison purposes.

Doses of 100 grains are sown in sowing dishes (45x35x10 cm) into sterile soil. to a depth of 2 cm. The test is started in triplicate. Seeds germinate under controlled conditions (day / night: 15/10 ° C). At the 2-3 leaf stage, plants are artificially inoculated by shaking heavily infested plants over test dishes. Vacuum pans are then maintained at elevated temperature (day / night: 22/18 ° C). Assessment of the percentage of leaf area infestation is carried out at regular intervals. The total infestation rate is compared to the total infestation rate of the untreated grain control seed pans and expressed as the total percentage infestation rate.

The compositions of the present invention exhibit good activity in these examples.

Claims (4)

P ATITAL CLAIMS CLAIMS 1. A method for combating phytopathogenic diseases in crops comprising administering an effective amount (a) thieno derivative [ 2. 3-d] pyrimidin-4-one of formula I About where R 1 is a halogen atom, R ₂ is C 1 -C 5 alkyl, -CH ₂ cyclopropyl, and R ₃ is C 1 -C 5 alkyl, -CH ₂ cyclopropyl; ' in connection (b) either with anilinopyrimidine of formula II (ID where R ₄ is methyl, 1-propynyl or. a cyclopropyl group; or with an azole of formula III 44 4444 ·· Where 44 Φ * 4 4 4 · 4 444 · 4 · 4 · 4 · 4 · 4 · 4 4 4 · 4 4 4 9 4 4 4 5 4 4 4 4 4 5 44 4 94 44 44 A is selected from (i) OH! c-CH ₂ CR ₇ R _and R ₉ (ii) -C-CH; cr ₇ y ₈ y ₉ OH (iii) ch ₂ —ch ₂ - c —ch ₂ cr ₇ r ₃ r ₉ (V) OH C-CH. (vl) CH • CH, io (villa) CHΟΝΟ— CH ₂ I ' R, < (vili) ~ 7 • CH • Br (ix) CH-CH; (x) Ro • Si · CH; • (xv) -O-CH ¹³ CH-OH i CRyRgRg wherein β-carbon binds to the benzene ring of formula III, and wherein R ₅ is hydrogen, fluoro, chloro, phenyl, 4-fluorophenoxy or 4-chlorophenoxy; R _s is hydrogen, chlorine or fluorine; R ₇ and R 8 are independently hydrogen or CH ₃ ; R ₉ is C 1 -C 4 alkyl or cyclopropyl; R 10 is 4-chlorophenyl or 4-fluorophenyl; R _u is a phenyl group, and R ₁₂ is allyloxy, C 1 -C 4 alkyl or 1,1,2,2-tetrafluoroethoxymethyl, and salts of the azole fungicide; or with a morpholine fungicide of formula (IV). · · · Φ · φφ h ₃ c Ο NR (ν) h ₃ c where R _{13 is} C 8 -C 15 cycloalkyl, C 8 -C 15 alkyl; an alkylphenylalkyl group containing from 1 to 4 carbon atoms in each alkyl moiety, and salts of the morpholine fungicide; or with a strobilurin compound of formula V (V) wherein X is NH or O, Y is CH or Na. R ₁₄ is 2-methylphenoxymethyl, 2,5-dimethylphenoxymethyl, 4- (2-cyanophenoxy) pyrimidin-6-yloxy, or 4- (3-trifluoromethylphenyl) -3-aza-2-oxa-3-pentenyl; or with a pyrrole compound of formula VI. (VI) where · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ··· ·· ·· ··· ·· ·· _R15 and _R1S are each independently a halogen atom or together form a perhalomethylendioxo bridge; or with a phenylamide of formula VII (VII) wherein R ₁₇ is benzyl, methoxymethyl, 2-furanyl, chloromethyl or R ₁₈ is 1-methoxycarbonyl-ethyl or o Z is CH or N, R ₂₁ is a hydrogen atom or a methyl group, R ₂₂ is hydrogen or methyl; or a dithiocarbamate fungicide selected from the group consisting of mancozeb, maneb, metiram and žineb; or with a copper compound selected from the group consisting of copper hydroxide, copper oxychloride, copper sulfate and oxine copper; or with sulfur; or with a phthalimide compound of formula VIII