U.S. patent application number 10/180859 was filed with the patent office on 2003-07-10 for fungicidal combinations comprising thieno[2,3-d]pyrimidin-4-one.
Invention is credited to Hermann, Dietrich, Knauf-Beiter, Gertrude, Muller, Kaspar, Walter, Harald.
Application Number | 20030130290 10/180859 |
Document ID | / |
Family ID | 26312696 |
Filed Date | 2003-07-10 |
United States Patent
Application |
20030130290 |
Kind Code |
A1 |
Muller, Kaspar ; et
al. |
July 10, 2003 |
Fungicidal combinations comprising thieno[2,3-d]pyrimidin-4-one
Abstract
The invention relates to novel fungicidal compositions having a
synergistically increased action, wherein component a) is a
thieno[2,3-d]pyrimidin-4-one of formula I 1 wherein R.sub.1 is
halogen, R.sub.2 is C.sub.1-C.sub.5alkyl, --CH.sub.2-cyclopropyl
and R.sub.3 is C.sub.1-C.sub.5alkyl, --CH.sub.2-cyclopropyl; in
association with b) either an anilinopyrimidine 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
mancozeb,maneb,metiram and zineb, or a copper compound selected
from 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
chlorothalonil, or cymoxanil, or dimethomorph, or famoxadone, or
fenhexamide, or fenarimol, or fluazinam, or fosetyl-aluminium,
orquinoxyfen, or fenpropidine, or spiroxamine, or carbendazime, or
thiabendazole, or ethirimol, or triazoxide, or guazatine.
Inventors: |
Muller, Kaspar;
(Schonenbuch, CH) ; Knauf-Beiter, Gertrude;
(Mullheim, DE) ; Hermann, Dietrich; (Wittlingen,
DE) ; Walter, Harald; (Rodersdorf, DE) |
Correspondence
Address: |
SYNGENTA CROP PROTECTION , INC.
PATENT AND TRADEMARK DEPARTMENT
410 SWING ROAD
GREENSBORO
NC
27409
US
|
Family ID: |
26312696 |
Appl. No.: |
10/180859 |
Filed: |
June 26, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10180859 |
Jun 26, 2002 |
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09555444 |
Sep 15, 2000 |
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6432965 |
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09555444 |
Sep 15, 2000 |
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PCT/EP98/07677 |
Nov 27, 1998 |
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Current U.S.
Class: |
514/260.1 ;
514/275; 514/383 |
Current CPC
Class: |
A01N 43/54 20130101;
A01N 43/54 20130101; A01N 43/54 20130101; A01N 2300/00 20130101;
A01N 37/50 20130101; A01N 43/40 20130101; A01N 43/36 20130101; A01N
43/653 20130101 |
Class at
Publication: |
514/260.1 ;
514/275; 514/383 |
International
Class: |
A01N 043/90; A01N
043/54; A01N 043/64 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 12, 1997 |
GB |
9725445.2 |
Claims
What is claimed is:
1. A method of combating phytopathogenic diseases on crop plants
which comprises applying to the crop plants or the locus thereof
being infested with said phytopathogenic disease an effective
amount of a) a thieno[2.3-d]pyrimidin-4-one derivative of formula I
37wherein R.sub.1 is halogen, R.sub.2 is C.sub.1-C.sub.5alkyl,
--CH.sub.2-cyclopropyl and R.sub.3 is C.sub.1-C.sub.5alkyl,
--CH.sub.2-cyclopropyl; in association with an amount of b) either
an anilinopyrimidine of formula II 38wherein R.sub.4 is methyl,
1-propynyl or cyclopropyl; or an azole of formula III 39wherein A
is selected from 4041whereby the .beta.-carbon attaches to benzene
ring of formula III, and wherein R.sub.5 is H, F, Cl, phenyl,
4-fluorophenoxy or 4-chlorophenoxy; R.sub.6 is H, Cl or F; R.sub.7
and R.sub.8 are independently H or CH.sub.3; R.sub.9 is
C.sub.1-4alkyl or cyclopropyl; R.sub.10 is 4-chlorophenyl or
4-fluorophenyl; R.sub.11 is phenyl, and R.sub.12 is allyloxy,
C.sub.1-4alkyl, or 1,1,2,2-tetrafluoroethoxy-methyl, and the salts
of such azole fungicide; or a morpholine fungicide of formula IV
42wherein R.sub.13 is C.sub.8-15cycloalkyl, C.sub.8-15alkyl, or
C.sub.1-4alkylphenyl-C.sub.1-4a- lkyl, and the salts of such
morpholine fungicide; or a strobilurin compound of formula V
43wherein X is NH or O, Y is CH or N, and R.sub.14 is
2-methylphenoxy-methyl, 2,5-dimethylphenoxy-methyl,
4-(2-cyanophenoxy)-pyrimidin-6-yloxy, or
4-(3-trifluoromethylphenyl)-3-az- a-2-oxa-3-pentenyl; or a pyrrole
compound of the formula VI 44wherein R.sub.15 and R.sub.16 are
indendently halo, or together from a perhalomethylendioxo bridge;
or a phenylamide of the formula VII 45wherein R.sub.17 is benzyl,
methoxymethyl, 2-furanyl, chloromethyl or 46R.sub.18 is
1-methoxycarbonyl-ethyl, or 47Z is CH or N, R.sub.21 is hydrogen or
methyl, R.sub.22 is hydrogen or methyl; or a dithiocarbamate
fungicide selected from mancozeb, maneb, metiram and zineb; or a
copper compound selected from copper hydroxide, copper oxychloride,
copper sulfate and oxine-copper; or sulfur; or a phthalimide
compound of the formula VIII 48wherein R.sub.19 and R.sub.20
together form a 4-membered bridge --CH.sub.2--CH.dbd.CH--CH.sub.2--
or .dbd.CH--CH.dbd.CH--CH.dbd.; or with compound of formula IX 49or
with a compound of formula X 50or with a compound of formula XI
51or with a compound of formula XII 52or with a compound of formula
XIII 53or with a compound of formula XIV 54or with a compound of
formula XV 55or with a compound of formula XVI 56or with a compound
of formula XVII 57or with a compound of formula XVIII 58or with a
compound of formula XIX 59or with a compound of formula XX 60or
with a compound of formula XXI 61or with a compound of formula XXII
62or with a compound of formula XXIII 63or with a compound of
formula XXIV 64or with a compound of formula XXV 65or with a
compound of formula XXVI 66or with a compound of formula XXVII 67or
with a compound of formula XXVIII 68wherein n is 0 or 1 or 2 etc,
and R is hydrogen or --C(.dbd.NH)NH.sub.2; which synergistically
enhances the activity against phytopathogenic diseases.
2. A method according to claim 1 wherein the component a) comprises
a compound of the formula I wherein R.sub.1 is chloro or bromo,
R.sub.2 is n-propyl, n-butyl, i-butyl and R.sub.3 is n-propyl,
n-butyl, i-butyl.
3. A method according to any one of claims 1 to 2 wherein the
component b) is selected from the group comprising 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, mancozeb, maneb,
metiram, zineb, copper hydroxide, copper oxychloride, copper
sulfate, oxine-copper, sulfur, kresoxim-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-pe-
ntenyl]-phenyl}-2-methoxyimino-acetate, fenpiclonil, fludioxonil,
benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, orfurace, oxadixyl,
carboxin, captan, folpet, prochloraz, triflumizole, pyrifenox,
acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph,
famoxadone, fenhexamide, fenarimol, fluazinam, fosetyl-aluminium,
quinoxyfen, fenpropidine, spiroxamine, carbendazime, thiabendazol,
ethirimol, triazoxide and guazatine, preferably selected from a
group comprising cyproconazole, hexaconazole, difenoconazole,
propiconazole, tebuconazole, flutriafol, epoxiconazole,
fenbuconazole, bromuconazole, penconazole, tetraconazole,
flusilazole, metconazole, diniconazole, triadimenol,
fluquinconazole and prochloraz; and especially propiconazole,
difenoconazole, penconazole, tebuconazole, prochloraz,
epoxiconazole and cyproconazole, more specifically selected from a
group comprising cyprodinil, tridemorph, fenpropimorph,
kresoxim-methyl, azoxystrobin, methyl
2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pent-
enyl]-phenyl}-2-methoxyimino-acetate, acibenzolar-S-methyl,
chlorothalonil, famoxadone, quinoxyfen, fenpropidine and
carbendazime; and especially cyprodinil, fenpropimorph,
kresoxim-methyl, azoxystrobin, methyl
2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl]-phenyl}--
2-methoxyimino-acetate, acibenzolar-S-methyl and fenpropidine.
4. A method according to claim 3 wherein component a) is selected
from the group comprising 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.
5. A fungicidal composition comprising a fungicidally effective
combination of component a) and component b) as defined in claim 1,
wherein the components are present in amounts which synergistically
enhances the activity against phytopathogenic diseases.
6. A composition according to claim 5 wherein the weight ratio of
a) to b) is between 100:1 and 1:400.
7. A composition according to claim 5 wherein the component a)
comprises a compound of the formula I wherein R.sub.1 is chloro or
bromo, R.sub.2 is n-propyl, n-butyl, i-butyl and R.sub.3 is
n-propyl, n-butyl, i-butyl.
8. A composition according to any one of claims 6 or 7 wherein the
component b) is selected from the group comprising 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, mancozeb, maneb,
metiram, zineb, copper hydroxide, copper oxychloride, copper
sulfate, oxine-copper, sulfur, kresoxim-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-pe-
ntenyl]-phenyl}-2-methoxyimino-acetate, fenpiclonil, fludioxonil,
benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, orfurace, oxadixyl,
carboxin, captan, folpet, prochloraz, triflumizole, pyrifenox,
acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph,
famoxadone, fenhexamide, fenarimol, fluazinam, fosetyl-aluminium,
quinoxyfen, fenpropidine, spiroxamine, carbendazime, thiabendazol,
ethirimol, triazoxide and guazatine, preferably selected from a
group comprising cyproconazole, hexaconazole, difenoconazole,
propiconazole, tebuconazole, flutriafol, epoxiconazole,
fenbuconazole, bromuconazole, penconazole, tetraconazole,
flusilazole, metconazole, diniconazole, triadimenol,
fluquinconazole and prochloraz; and especially propiconazole,
difenoconazole, penconazole, tebuconazole, prochloraz,
epoxiconazole and cyproconazole, more specifically selected from a
group comprising cyprodinil, tridemorph, fenpropimorph,
kresoxim-methyl, azoxystrobin, methyl
2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pent-
enyl]-phenyl}-2-methoxyimino-acetate, acibenzolar-S-methyl,
chlorothalonil, famoxadone, quinoxyfen, fenpropidine and
carbendazime; and especially cyprodinil, fenpropimorph,
kresoxim-methyl, azoxystrobin, methyl
2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl]-phenyl}--
2-methoxyimino-acetate, acibenzolar-S-methyl and fenpropidine.
9. A composition according to claim 8 wherein component a) is
selected from the group comprising 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.
10. A method according to claim 1 for treating plant propagation
material, preferably seeds.
Description
[0001] The present invention relates to novel fungicidal
compositions for the treatment of phytopathogenic diseases of crop
plants and against infestation on propagation stock of plants or on
other vegetable material, especially phytopathogenic fungi, and to
a method of combating phytopathogenic diseases on crop plants or
for seed dressing.
[0002] It is known that certain pyrimidin-4-one derivatives have
biological activity against phytopathogenic fungi, e.g. known from
WO 97/33890 where their properties and methods of preparation are
described. On the other hand anilinopyrimidines, azole fungicides,
phthalimides, phenylamides, strobilurines, pyrroles,
dithiocarbamates and morpholines are widely known as plant
fungicides for application in various crops of cultivated plants.
However, crop tolerance and activity against phytopathogenic plant
fungi do not always satisfy the needs of agricultural practice in
many incidents and aspects.
[0003] It has now been found that the use of
[0004] a) a thieno[2.3-d]pyrimidin-4-one of formula I 2
[0005] wherein
[0006] R.sub.1 is halogen,
[0007] R.sub.2 is C.sub.1-C.sub.5alkyl, --CH.sub.2-cyclopropyl
and
[0008] R.sub.3 is C.sub.1-C.sub.5alkyl, --CH.sub.2-cyclopropyl;
[0009] in association with
[0010] b) either an anilinopyrimidine of formula II 3
[0011] wherein
[0012] R.sub.4 is methyl, 1-propynyl or cyclopropyl;
[0013] or an azole of formula III 4
[0014] wherein
[0015] A is selected from 56
[0016] whereby the .beta.-carbon attaches to benzene ring of
formula III, and wherein
[0017] R.sub.5 is H, F, Cl, phenyl, 4-fluorophenoxy or
4-chlorophenoxy;
[0018] R.sub.6 is H, Cl or F;
[0019] R.sub.7 and R.sub.8 are independently H or CH.sub.3;
[0020] R.sub.9 is C.sub.1-4alkyl or cyclopropyl;
[0021] R.sub.10 is 4-chlorophenyl or 4-fluorophenyl;
[0022] R.sub.11 is phenyl, and
[0023] R.sub.12 is allyloxy, C.sub.1-4alkyl, or
1,1,2,2-tetrafluoroethoxy-- methyl, and the salts of such azole
fungicide;
[0024] or a morpholine fungicide of formula IV 7
[0025] wherein
[0026] R.sub.13 is C.sub.8-15cycloalkyl, C.sub.8-15alkyl, or
C.sub.1-4alkylphenyl-C.sub.1-4alkyl, and the salts of such
morpholine fungicide;
[0027] or a strobilurin compound of formula V 8
[0028] wherein
[0029] X is NH or O,
[0030] Y is CH or N, and
[0031] R.sub.14 is 2-methylphenoxy-methyl,
2,5-dimethylphenoxy-methyl, 4-(2-cyanophenoxy)-pyrimidin-6-yloxy,
or 4-(3-trifluoromethylphenyl)-3-az- a-2-oxa-3-pentenyl;
[0032] or a pyrrole compound of the formula VI 9
[0033] wherein
[0034] R.sub.15 and R.sub.16 are indendently halo, or together from
a perhalomethylendioxo bridge;
[0035] or a phenylamide of the formula VII 10
[0036] wherein
[0037] R.sub.17 is benzyl, methoxymethyl, 2-furanyl, chloromethyl
or 11
[0038] R.sub.18 is 1-methoxycarbonyl-ethyl, or 12
[0039] Z is CH or N,
[0040] R.sub.21 is hydrogen or methyl,
[0041] R.sub.22 is hydrogen or methyl;
[0042] or a dithiocarbamate fungicide selected from mancozeb,
maneb, metiram and zineb;
[0043] or a copper compound selected from copper hydroxide, copper
oxychloride, copper sulfate and oxine-copper;
[0044] or sulfur;
[0045] or a phthalimide compound of the formula VIII 13
[0046] wherein
[0047] R.sub.19 and R.sub.20 together form a 4-membered bridge
--CH.sub.2--CH.dbd.CH--CH.sub.2-- or
.dbd.CH--CH.dbd.CH--CH.dbd.;
[0048] or with compound of formula IX 14
[0049] or with a compound of formula X 15
[0050] or with a compound of formula XI 16
[0051] or with a compound of formula XII 17
[0052] or with a compound of formula XIII 18
[0053] or with a compound of formula XIV 19
[0054] or with a compound of formula XV 20
[0055] or with a compound of formula XVI 21
[0056] or with a compound of formula XVII 22
[0057] or with a compound of formula XVIII 23
[0058] or with a compound of formula XIX 24
[0059] or with a compound of formula XX 25
[0060] or with a compound of formula XXI 26
[0061] or with a compound of formula XXII 27
[0062] or with a compound of formula XXIII 28
[0063] or with a compound of formula XXIV 29
[0064] or with a compound of formula XXV 30
[0065] or with a compound of formula XXVI 31
[0066] or with a compound of formula XXVII 32
[0067] or with a compound of formula XXVIII 33
[0068] wherein
[0069] n is 0 or 1 or 2 etc, and
[0070] R is hydrogen or --C(.dbd.NH)NH.sub.2;
[0071] is particularly effective in combating or preventing fungal
diseases of crop plants. These combinations exhibit synergistic
fungicidal activity.
[0072] The combinations according to the invention may also
comprise more than one of the active components b), if broadening
of the spectrum of disease control is desired. For instance, it may
be advantageous in the agricultural practice to combine two or
three components b) with the any of the compounds of formula I, or
with any preferred member of the group of compounds of formula
I.
[0073] From WO 97/33890 the following specific species of formula I
are known:
1 Compound No. R.sub.1 R.sub.2 R.sub.3 1.01 Cl n-propyl n-propyl
1.02 Br n-propyl n-propyl 1.03 Cl n-propyl n-butyl 1.04 Br n-propyl
n-butyl 1.05 Cl n-butyl n-propyl 1.06 Br n-butyl n-propyl 1.07 Cl
i-butyl n-propyl 1.08 Br i-butyl n-propyl 1.09 Cl n-propyl i-butyl
1.10 Br n-propyl i-butyl
[0074] A preferred embodiment of the present invention is
represented by those combinations which comprise as component a) a
compound of the formula I wherein R.sub.1 is chloro or bromo and
R.sub.2 is n-propyl, n-butyl, i-butyl and R.sub.3 is n-propyl,
n-butyl, i-butyl.
[0075] Among the mixtures of present invention most preference is
given to the mixture of compounds I.01, I.02, I.03, I.04, I.05,
I.06, I.07 or I.08 with the compounds of component b), especially
the commercially available products falling within the given
ranges, i.e. the commercial products mentioned throughout this
document.
[0076] Salts of the azole, amine and morpholine active ingredients
are prepared by reaction with acids, e.g., hydrohalo acids such as
hydrofluoric acid, hydrochloric acid, hydrobromic acid and
hydroiodic acid, or sulfuric acid, phosphoric acid or nitric acid,
or 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, benzensulfonic acid, p-toluenesulfonic acid,
methanesulfonic acid, salicylic acid, p-aminosalicylic acid and
1,2-naphtalenedisulfonic acid.
[0077] The active ingredient combinations are effective against
phytopathogenic fungi belonging to the following classes:
Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia,
Sclerotinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the
genus Hemileia, Rhizoctonia, Tilletia, Puccinia); Fungi imperfecti
(e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium,
Septoria, Cercospora, Alternaria, Pyricularia and
Pseudocercosporella herpotrichoides); Oomycetes (e.g. Phytophthora,
Peronospora, Bremia, Pythium, Plasmopara).
[0078] Target crops for the areas of indication disclosed herein
comprise within the scope of this invention e.g. the following
species of plants: cereals (wheat, barley, rye, oats, rice, sorghum
and related crops); beet (sugar beet and fodder beet); pomes, stone
fruit and soft fruit (apples, pears, plums, peaches, almonds,
cherries, strawberries, raspberries and black-berries); leguminous
plants (beans, lentils, peas, soybeans); oil plants (rape, mustard,
poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans,
groundnuts); cucumber plants (marrows, cucumbers, melons); fibre
plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons,
grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,
cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae
(avocados, cinnamon, camphor); or plants such as maize, tobacco,
nuts, coffee, sugar cane, tea, vines, hops, turf, bananas and
natural rubber plants, as well as ornamentals (flowers, shrubs,
broad-leaved trees and evergreens, such as conifers) and their
seeds. This list does not represent any limitation.
[0079] The combinations of the present invention may also be used
in the area of protecting technical material against attack of
fungi. Technical areas include wood, paper, leather, constructions,
cooling and heating systems, ventilation and air conditioning
systems, and the like. The combinations according the present
invention can prevent the disadvantageous effects such as decay,
discoloration or mold.
[0080] The combinations according to the present invention are
particularly effective against powdery mildews and rusts,
pyrenophora, rhynchosporium and leptosphaeria fungi, in particular
against pathogens of monocotyledonous plants such as cereals,
including wheat and barley. They are furthermore particularly
effective aginst downy mildew species, especially against
plasmopara in vine.
[0081] The amount of combination of the invention to be applied,
will depend on various factors such as the compound employed, the
subject of the treatment (plant, soil, seed), the type of treatment
(e.g. spraying, dusting, seed dressing), the purpose of the
treatment (prophylactic or therapeutic), the type of fungi to be
treated and the application time.
[0082] Particularly preferred mixing partners of the compounds of
formula II are those in which R.sub.4 is methyl or cyclopropyl.
These compounds are commonly known as pyrimethanil and
cyprodinil.
[0083] Particularly preferred mixing partners of the compounds of
formula III are those in which R.sub.5 is Cl, R.sub.6 and R.sub.7
are H, R.sub.8 is CH.sub.3 and R.sub.9 is cyclopropyl and A is the
moiety (i) (commonly known as cyproconazole); those wherein R.sub.5
and R.sub.6 are Cl, R.sub.7 and R.sub.8 are H, R.sub.9 is propyl
and A is the moiety (i) (commonly known as hexaconazole); those in
which R.sub.5 is 4-chlorophenoxy, R.sub.6 is Cl, R.sub.7, R.sub.8
and R.sub.9 are H and A is the moiety (ii) (commonly known as
difenoconazole); those in which R.sub.5 and R.sub.6 are Cl, R.sub.7
and R.sub.8 are H, R.sub.9 is ethyl and A is the moiety (ii)
(commonly known as etaconazole); those in which R.sub.5 and R.sub.6
are Cl, R.sub.7 and R.sub.8 are H, R.sub.9 is propyl and A is the
moiety (ii) (commonly known as propiconazole); those in which
R.sub.5 is Cl, R.sub.6 is H, R.sub.7, R.sub.8 and R.sub.9 are
CH.sub.3 and A is the moiety (iii) (commonly known as
tebuconazole); those in which R.sub.5 is Cl, R.sub.6 is H and A is
the moiety (iv) (commonly known as triticonazole); those in which
R.sub.5 is H, R.sub.6 is F, R.sub.10 is 4-fluorophenyl and A is the
moiety (v) (commonly known as flutriafol); those in which R.sub.5
is H, R.sub.6 is Cl, R.sub.10 is 4-fluorophenyl and A is the moiety
(vi) (commonly known as epoxiconazole); those in which R.sub.5 is
Cl, R.sub.6 is H, R.sub.11 is phenyl and A is the moiety (vii)
(commonly known as fenbuconazole); those in which R.sub.5 and
R.sub.6 are Cl, and A is the moiety (viii) (commonly known as
bromuconazole); those in which R.sub.5 and R.sub.6 are Cl, R.sub.12
is propyl and A is the moiety (ix) (commonly known as penconazole);
those in which R.sub.5 and R.sub.6 are Cl, R.sub.12 is allyloxy and
A is the moiety (ix) (commonly known as imazalil); those in which
R.sub.5 and R.sub.6 are Cl, R.sub.12 is
1,1,2,2-tetrafluoroethoxyme- thyl and A is the moiety (ix)
(commonly known as tetraconazole); those wherein R.sub.5 is F,
R.sub.6 is H, R.sub.9 is CH.sub.3, R.sub.10 is 4-fluorophenyl, and
A is the moiety (x) (commonly known as flusilazole); those in which
R.sub.5 is chloro, R.sub.6 is hydrogen, R.sub.7 and R.sub.8 are
methyl and A is the moiety (xi) (commonly known as metconazole);
those wherein R.sub.5 and R.sub.6 are chloro, R.sub.7 and R.sub.8
are H, R.sub.9 is t-butyl and A is the moiety (xii) (commonly known
as diniconazole); those wherein R.sub.5 and R.sub.6 are chloro and
A is the moiety (xiii) (commonly known as fluquinconazole); those
wherein R.sub.5 is chloro, R.sub.6, R.sub.7 and R.sub.8 are H,
R.sub.9 is n-butyl and A is the moiety (xiv) (commonly known as
myclobutanil); those wherein R.sub.5 is chloro, R.sub.6 is H,
R.sub.7, R.sub.8 and R.sub.9 are methyl and A is the moiety (xv)
(commonly known as triadimenol); and those wherein R.sub.5 is
phenyl, R.sub.7,R.sub.8 and R.sub.9 are methyl and A is the moiety
(xv) (commonly known as bitertanol).
[0084] Particularly preferred mixing partners of the compounds of
formula IV are those wherein R.sub.13 is cyclododecyl (commonly
known as dodemorph), or C.sub.10-13alkyl (commonly known as
tridemorph), or 3-(4-tert-butylphenyl)-2-methylpropyl (commonly
known as fenpropimorph). Predominantly, the cis-positioning of the
methyl groups at the morpholine ring is present in the compounds of
formula IV when used in the combinations of the invention.
[0085] Particularly preferred mixing partners of the compounds of
formula V are those wherein X and Y are O, and R.sub.14 is
2-methylphenoxy-methyl (commonly known as kresoxim-methyl); or
wherein X is NH, Y is N and R.sub.14 is 2,5-dimethylphenoxy-methyl;
or wherein X is O, Y is CH and R.sub.14 is
4-(2-cyanophenoxy)-pyrimidin-6-yloxy (commonly known as
azoxystrobin); or wherein X is O, Y is N and R.sub.14 is
4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl.
[0086] Particularly preferred mixing partners of the compounds of
formula VI are those wherein R.sub.15 and R.sub.16 are both chloro
(commonly known as fenpiclonil); or wherein R.sub.15 and R.sub.16
together form a bridge --O--CF.sub.2--O-- (commonly known as
fludioxonil).
[0087] Particularly preferred mixing partners of the compounds of
formula VII are those wherein R.sub.17 is benzyl, R.sub.21 and
R.sub.22 are methyl and R.sub.18 is 1-methoxycarbonyl-ethyl
(commonly known as benalaxyl); or wherein R.sub.17 is 2-furanyl,
R.sub.21 and R.sub.22 are methyl and R.sub.18 is
1-methoxycarbonyl-ethyl (commonly known as furalaxyl); or wherein
R.sub.17 is methoxymethyl, R.sub.21 and R.sub.22 are methyl and
R.sub.18 is 1-methoxycarbonyl-ethyl or is
(R)-1-methoxycarbonyl-ethyl (commonly known as metalaxyl and
R-metalaxyl); or wherein R.sub.17 is chloromethyl, R.sub.21 and
R.sub.22 are methyl and R.sub.18 is 34
[0088] whereby Z is CH (commonly known as orfurace); or
[0089] wherein R.sub.17 is methoxymethyl, R.sub.21 and R.sub.22 are
methyl and R.sub.18 is 35
[0090] whereby Z is N
[0091] (commonly known as oxadixyl); or wherein R.sub.17 is 36
[0092] and R.sub.18, R.sub.21 and R.sub.22 is hydrogen (commonly
known as carboxin).
[0093] Particularly preferred mixing partners of the compounds of
formula VIII are those wherein R.sub.19 and R.sub.20 together form
the bridge --CH.sub.2--CH.dbd.CH--CH.sub.2-- (commonly known as
captan); or wherein R.sub.19 and R.sub.20 together form the bridge
.dbd.CH--CH.dbd.CH--CH.dbd- . (commonly known as folpet).
[0094] The compound of formula IX is commonly known as
prochloraz.
[0095] The compound of formula X is commonly known as
triflumizole.
[0096] The compound of formula XI is commonly known as
pyrifenox.
[0097] The compound of formula XII is commonly known as
acibenzolar-S-methyl.
[0098] The compound of formula XIII is commonly known as
chlorothalonil.
[0099] The compound of formula XIV is commonly known as
cymoxanil.
[0100] The compound of formula XV is commonly known as
dimethomorph.
[0101] The compound of formula XVI is commonly known as
famoxadone.
[0102] The compound of formula XVII is commonly known as
fenhexamide.
[0103] The compound of formula XVIII is commonly known as
fenarimol.
[0104] The compound of formula XIX is commonly known as
fluazinam.
[0105] The compound of formula XX is commonly known as
fosetyl-aluminium.
[0106] The compound of formula XXI is commonly known as
quinoxyfen.
[0107] The compound of formula XXII is commonly known as
fenpropidine.
[0108] The compound of formula XXIII is commonly known as
spiroxamine.
[0109] The compound of formula XXIV is commonly known as
carbendazime.
[0110] The compound of formula XXV is commonly known as
thiabendazole.
[0111] The compound of formula XXVI is commonly known as
ethirimol.
[0112] The compound of formula XXVII is commonly known as
triazoxide.
[0113] The compound of formula XXVIII is commonly known as
guazatine.
[0114] The specific compounds b) mentioned in the preceding
paragraphs are commercially available. Other compounds falling
under the scope of the various groups of component b) are
obtainable according to procedures analogous to those known for
preparing the commercially available compounds.
[0115] It has been found that the use of compounds of formulae II
to XXVIII in combination with the compound of formula I
surprisingly and substantially enhance the effectiveness of the
latter against fungi, and vice versa. Additionally, the method of
the invention is effective against a wider spectrum of such fungi
that can be combated with the active ingredients of this method,
when used solely.
[0116] Specific preferred mixtures according to the present
invention are understood to be represented by the combinations of
active ingredients of formula I, or any of the subgroups of formula
I, or specifically mentioned members of the subgroups with a second
fungicide selected from the group comprising 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, mancozeb, maneb,
metiram, zineb, copper hydroxide, copper oxychloride, copper
sulfate, oxine-copper, sulfur, kresoxim-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-metho-
xyimino-acetate, fenpiclonil, fludioxonil, benalaxyl, furalaxyl,
metalaxyl, R-metalaxyl, orfurace, oxadixyl, carboxin, captan,
folpet, prochloraz, triflumizole, pyrifenox, acibenzolar-S-methyl,
chlorothalonil, cymoxanil, dimethomorph, famoxadone, fenhexamide,
fenarimol, fluazinam, fosetyl-aluminium, quinoxyfen, fenpropidine,
spiroxamine, carbendazime, thiabendazol, ethirimol, triazoxide and
guazatine.
[0117] From this group a subgroup b1 is preferred comprising
combinations with cyproconazole, hexaconazole, difenoconazole,
propiconazole, tebuconazole, flutriafol, epoxiconazole,
fenbuconazole, bromuconazole, penconazole, tetraconazole,
flusilazole, metconazole, diniconazole, triadimenol,
fluquinconazole and prochloraz.
[0118] From this group combinations with propiconazole,
difenoconazole, penconazole, tebuconazole, prochloraz,
epoxiconazole and cyproconazole are of particular interest as
preferred embodiments of this invention as subgroup b1a.
[0119] A further preferred subgroup b2 comprises combinations with
cyprodinil, tridemorph, lenpropimorph, kresoxim-methyl,
azoxystrobin, methyl
2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl]-phenyl}--
2-methoxyimino-acetate, acibenzolar-S-methyl, chlorothalonil,
famoxadone, quinoxyfen, fenpropidine and carbendazime.
[0120] From this group combinations with cyprodinil, fenpropimorph,
kresoxim-methyl, azoxystrobin, methyl
2-{2-[4-(3-trifluoromethylphenyl)-3-
-aza-2-oxa-4-pentenyl]-phenyl}-2-methoxyimino-acetate,
acibenzolar-S-methyl and fenpropidine are of particular interest as
preferred embodiments of this invention as subgroup b2a.
[0121] Further combinations of interest are the following:
[0122] compound I.01 with any member of groups b1 and b2, or with
any member of groups b1a and b2a;
[0123] compound I.02 with any member of groups b1 and b2, or with
any member of groups b1a and b2a;
[0124] compound I.03 with any member of groups b1 and b2, or with
any member of groups b1a and b2a;
[0125] compound I.04 with any member of groups b1 and b2, or with
any member of groups b1a and b2a.
[0126] compound I.05 with any member of groups b1 and b2, or with
any member of groups b1a and b2a;
[0127] compound I.06 with any member of groups b1 and b2, or with
any member of groups b1a and b2a;
[0128] compound I.07 with any member of groups b1 and b2, or with
any member of groups b1a and b2a;
[0129] compound I.08 with any member of groups b1 and b2, or with
any member of groups b1a and b2a.
[0130] The weight ratio of a):b) is so selected as to give a
synergistic fungicidal action. In general the weight ratio of a):
b) is between 100:1 and 1:400. The synergistic action of the
composition is apparent from the fact that the fungicidal action of
the composition of a)+b) is greater than the sum of the fungicidal
actions of a) and b).
[0131] Where the component b) is an anilinopyrimidine of formula II
the weight ratio of a):b) is for example between 1:2 and 1:36,
especially 1:2 and 1:18, and more preferably 1:3 and 1:8.
[0132] Where the component b) is an azole fungicide of formula III
the weight ratio of a):b) is for example between 10:1 and 1:20,
especially 5:1 and 1:10, and more preferably 2:1 and 1:4.
[0133] Where component b) is a morpholine fungicide of formula IV,
the weight ratio of a):b) is for example between 1:2 and 1:30,
especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
[0134] Where component b) is a strobilurin fungicide of formula V,
the weight ratio of a):b) is for example between 2:1 and 1:10,
especially 1:1 and 1:8, and more preferably 1:2 and 1:5.
[0135] Where component b) is a pyrrole fungicide of formula VI, the
weight ratio of a): b) is for example between 1:3 and 1:30,
especially 1:1.5 and 1:7, and more preferably 1:2 and 1:5.
[0136] Where component b) is a phenylamide fungicide of formula
VII, the weight ratio of a):b) is for example between 3:1 and 1:12,
especially 2.5:1 and 1:6, and more preferably 2:1 to 1:3.
[0137] Where component b) is a dithiocarbamate fungicide, the
weight ratio of a):b) is for example between 1:3 and 1:120,
especially 1:4 and 1:60, and more preferably 1:7 and 1:25.
[0138] Where component b) is a copper compound fungicide, the
weight ratio of a):b) is for example between 1:1.5 and 1:100,
especially 1:2 and 1:50, and more preferably 1:5 and 1:30.
[0139] Where component b) is a sulfur fungicide, the weight ratio
of a):b) is for example between 1:6 and 1:400, especially 1:8 and
1:200, and more preferably 1:10 and 1:100.
[0140] Where component b) is a phthalimide fungicide of formula
VIII, the weight ratio of a):b) is for example between 1:3 and
1:80, especially 1:4 and 1:40, and more preferably 1:8 and
1:20.
[0141] Where component b) is the compound of formula IX, the weight
ratio of a):b) is for example between 1:2 and 1:25, especially 1:4
and 1:12, and more preferably 1:5 and 1:8.
[0142] Where component b) is the compound of formula X, the weight
ratio of a):b) is for example between 3:1 and 1:16, especially
2.5:1 and 1:8, and more preferably 1:1 and 1:4.
[0143] Where component b) is the compound of formula XI, the weight
ratio of a):b) is for example between 8:1 and 1:4, especially 2.5:1
and 1:2, and more preferably 2:1 and 1:1.
[0144] Where component b) is the compound of formula XII, the
weight ratio of a):b) is for example between 6:1 and 1:2,
especially 6:1 and 2:1, and more preferably 5:1 and 2:1. Where
component b) is the compound of formula XIII, the weight ratio of
a):b) is for example between 1:3 and 1:40, especially 1:4 and 1:20,
and more preferably 1:5 and 1:10.
[0145] Where component b) is the compound of formula XIV, the
weight ratio of a): b) is for example between 3:1 and 1:8,
especially 2.5:1 and 1:4, and more preferably 2:1 and 1:2.
[0146] Where component b) is the compound of formula XV, the weight
ratio of a):b) is for example between 1.5:1 and 1:12, especially
1:1 and 1:6, and more preferably 1:1 and 1:4.
[0147] Where component b) is the compound of formula XVI, the
weight ratio of a):b) is for example between 1.5:1 and 1:10,
especially 1:1 and 1:5, and more preferably 1:1 and 1:3.
[0148] Where component b) is the compound of formula XVII, the
weight ratio of a):b) is for example between 2:1 and 1:30,
especially 1.5:1 and 1:15, and more preferably 1:1 and 1:5.
[0149] Where component b) is the compound of formula XVIII, the
weight ratio of a):b) is for example between 8:1 and 1:4,
especially 2.5:1 and 1:2, and more preferably 2:1 and 1:1.
[0150] Where component b) is the compound of formula XIX, the
weight ratio of a):b) is for example between 1.5:1 and 1:12,
especially 1:1 and 1:6, and more preferably 1:1 and 1:4.
[0151] Where component b) is the compound of formula XX, the weight
ratio of a):b) is for example between 1:3 and 1:80, especially 1:4
and 1:40 and more preferably 1:1 and 1:25.
[0152] Where component b) is the compound of formula XXI, the
weight ratio of a):b) is for example between 2:1 and 1:5,
especially 1.5:1 and 1:2.5, and more preferably 1:1 and 1:2.
[0153] Where component b) is the compound of formula XXII, the
weight ratio of a):b) is for example between 1:2 and 1:30,
especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
[0154] Where component b) is the compound of formula XXIII, the
weight ratio of a):b) is for example between 1:2.5 and 1:30,
especially 1:3 and 1:15, and more preferably 1:3 and 1:10. Where
component b) is the compound of formula XXIV, the weight ratio of
a):b) is for example between 1.5:1 and 1:10, especially 1:1 and
1:5, and more preferably 1:2 and 1:4.
[0155] Where component b) is the compound of formula XXV, the
weight ratio of a):b) is for example between 40:1 and 1:10,
especially 20:1 and 1:5, and more preferably 10:1 and 1:2.
[0156] Where component b) is the compound of formula XXVI, the
weight ratio of a): b) is for example between 1:1 and 1:10,
especially 1:1 and 1:5, and more preferably 1:1 and 1:2.
[0157] Where component b) is the compound of formula XXVII, the
weight ratio of a):b) is for example between 10:1 and 100:1,
especially 5:1 and 50:1, and more preferably 2:1 and 20:1.
[0158] Where component b) is the compound of formula XXVIII, the
weight ratio of a):b) is for example between 5:1 and 1:4,
especially 3:1 and 1:2, and more preferably 2:1 and 1:1.
[0159] The method of the invention comprises applying to the plants
to be treated or the locus thereof in admixture or separately, a
fungicidally effective aggregate amount of a compound of formula I
and a compound of component b).
[0160] The term locus as used herein is intended to embrace the
fields on which the treated crop plants are growing, or where the
seeds of cultivated plants are sown, or the place where the seed
will be placed into the soil. The term seed is intended to embrace
plant propagating material such as cuttings, seedlings, seeds,
germinated or soaked seeds. The novel combinations are extremely
effective on a broad spectrum of phytopathogenic fungi, in
particular from the Ascomycetes and Basidiomycetes classes. Some of
them have a systemic action and can be used as foliar and soil
fungicides.
[0161] The fungicidal combinations are of particular interest for
controlling a large number of fungi in various crops or their
seeds, especially wheat, rye, barley, oats, rice, maize, lawns,
cotton, soybeans, coffee, sugarcane, fruit and ornamentals in
horticulture and viticulture, and in vegetables such as cucumbers,
beans and cucurbits. The combinations are applied by treating the
fungi or the seeds, plants or materials threatened by fungus
attack, or the soil with a fungicidally effective amount of the
active ingredients.
[0162] The agents may be applied before or after infection of the
materials, plants or seeds by the fungi.
[0163] The novel combinations are particularly useful for
controlling the following plant diseases:
[0164] Erysiphe graminis in cereals,
[0165] Erysiphe cichoracearum and Sphaerotheca fuliginea in
cucurbits,
[0166] Podosphaera leucotricha in apples,
[0167] Uncinula necator in vines,
[0168] Puccinia species in cereals,
[0169] Rhizoctonia species in cotton, rice and lawns,
[0170] Ustilago species in cereals and sugarcane,
[0171] Venturia inaequalis (scab) in apples,
[0172] Helminthosporium species in cereals,
[0173] Septoria nodorum in wheat,
[0174] Septoria tritici in wheat wheat,
[0175] Rhynchosporium secalis on barley,
[0176] Pseudocercosporella herpotrichoides in wheat and barley,
[0177] Pyricularia oryzae in rice,
[0178] Phytophthora infestans in potatoes and tomatoes,
[0179] Fusarium and Verticillium species in various plants,
[0180] Plasmopara viticola in grapes,
[0181] Alternaria species in fruit and vegetables.
[0182] When applied to the plants the compound of formula I is
applied at a rate of 25 to 150 g/ha, particularly 50 to 125 g/ha,
e.g. 75, 100, or 125 g/ha, in association with 20 to 3000 g/ha,
particularly 20 to 2000 g/ha, e.g. 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 like sulfur up to 10000 g/ha of a compound of
component b), depending on the class of chemical employed as
component b). Where the component b) is an anilinopyrimidine of
formula II for example 300 to 900 g a.i./ha is applied in
association with the compound of formula I. Where the component b)
is an azole fungicide of formula III for example 20 to 350 g
a.i./ha is applied in association with the compound of formula I.
Where the component b) is an morpholine of formula IV for example
300 to 750 g a.i./ha is applied in association with the compound of
formula I. Where the component b) is a strobilurin of formula V for
example 75 to 250 g a.i./ha is applied in association with the
compound of formula I. Where the component b) is a pyrrole of
formula VI for example 200 to 750 g a.i./ha is applied in
association with the compound of formula I.
[0183] Where the component b) is a phenylamide of formula VII for
example 50 to 300 g a.i./ha is applied in association with the
compound of formula I. Where the component b) is a dithiocarbamate
for example 500 to 3000 g a.i./ha is applied in association with
the compound of formula I. Where the component b) is a copper
compound for example 250 to 2500 g a.i. is applied in association
with the compound of formula I. Where the component b) is sulfur
for example 1000 to 10000 g a.i. is applied in association with the
compound of formula I. Where the component b) is a phthalimide of
formula VIII for example 500 to 2000 g a.i./ha is applied in
association with the compound of formula I. Where the component b)
is the compound of formula IX for example 400 to 600 g a.i./ha is
applied in association with the compound of formula I. Where the
component b) is the compound of formula X for example 50 to 400 g
a.i./ha is applied in association with the compound of formula I.
Where the component b) is the compound of formula XI for example 20
to 100 g a.i./ha is applied in association with the compound of
formula I. Where the component b) is the compound of formula XII
for example 20 to 40 g a.i./ha is applied in association with the
compound of formula I. Where the component b) is the compound of
formula XIII for example 500 to 1000 g a.i./ha is applied in
association with the compound of formula I. Where the component b)
is the compound of formula XIV for example 50 to 200 g a.i./ha is
applied in association with the compound of formula I. Where the
component b) is the compound of formula XV for example 100 to 300 g
a.i./ha is applied in association with the compound of formula I.
Where the component b) is the compound of formula XVI for example
125 to 250 g a.i./ha is applied in association with the compound of
formula I. Where the component b) is the compound of formula XVII
for example 100 to 750 g a.i./ha is applied in association with the
compound of formula I. Where the component b) is the compound of
formula XVIII for example 20 to 100 g a.i./ha is applied in
association with the compound of formula I. Where the component b)
is the compound of formula XIX for example 100 to 300 g a.i./ha is
applied in association with the compound of formula I. Where the
component b) is the compound of formula XX for example 500 to 2000
g a.i./ha is applied in association with the compound of formula I.
Where the component b) is the compound of formula XXI for example
75 to 125 g a.i./ha is applied in association with the compound of
formula I. Where the component b) is the compound of formula XXII
for example 300 to 750 g a.i./ha is applied in association with the
compound of formula I. Where the component b) is the compound of
formula XXIII for example 375 to 750 g a.i./ha is applied in
association with the compound of formula I. Where the component b)
is the compound of formula XXIV for example 125 to 250 g a.i./ha is
applied in association with the compound of formula I. Where the
component b) is the compound of formula XXV for example 5 to 200 g
a.i./100 kg is applied for seed dressing in association with the
compound of formula I. Where the component b) is the compound of
formula XXVI for example 200 g a.i./100 kg is applied for seed
dressing in association with the compound of formula I. Where the
component b) is the compound of formula XXVII for example 2 g
a.i./100 kg is applied for seed dressing in association with the
compound of formula I. Where the component b) is the compound of
formula XXVIII for example 40 to 80 g a.i./100 kg is applied for
seed dressing in association with the compound of formula I.
[0184] In agricultural practice the application rates of the
combination depend on the type of effect desired, and range from
0.02 to 4 kg of active ingredient per hectare.
[0185] When the active ingredients are used for treating seed,
rates of 0.001 to 50 g a.i. per kg, and preferably from 0.01 to 10
g per kg of seed are generally sufficient.
[0186] The invention also provides fungicidal compositions
comprising a compound of formula I and a compound of component
b).
[0187] The composition of the invention may be employed in any
conventional form, for example in the form of a twin pack, an
instant granulate, a flowable or a wettable powder in combination
with agriculturally acceptable adjuvants. Such compositions may be
produced in conventional manner, e.g. by mixing the active
ingredients with appropriate adjuvants (diluents or solvents and
optionally other formulating ingredients such as surfactants).
[0188] The term diluent as used herein means any liquid or solid
agriculturally acceptable material including carriers which may be
added to the active constituents to bring them in an easier or
improved applicable form, respectively, to a usable or desirable
strength of activity. Suitable solvents are: aromatic hydrocarbons,
preferably the fractions containing 8 to 12 carbon atoms, e.g.
xylene mixtures or substituted naphthalenes, phthalates, such as
dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons,
such as cyclohexane or paraffins, alcohols and glycols and their
ethers and esters, such as ethanol, ethylene glycol, ethylene
glycol monomethyl or monoethyl ether, ketones, such as
cyclohexanone, strongly polar solvents, such as
N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as
well as vegetable oils or epoxidised vegetable oils, such as
epoxidised coconut oil or soybean oil; or water. The solid carriers
used, e.g. for dusts and dispersible powders, are normally natural
mineral fillers, such as calcite, talcum, kaolin, montmorillonite
or attapulgite. In order to improve the physical properties it is
also possible to add highly dispersed silicic acid or highly
dispersed absorbent polymers. Suitable granulated adsorptive
carriers are porous types, for example pumice, broken brick,
sepiolite or bentonite, and suitable non-absorbent carriers are,
for example, calcite or sand. In addition, a great number of
materials of inorganic or organic nature can be used, e.g.
especially dolomite or pulverised plant residues. Depending upon
the nature of the compounds of formula I and component b) to be
formulated, suitable surface-active compounds are non-ionic,
cationic and/or anionic surfactants having good emulsifying,
dispersing and wetting properties. The term "surfactants" will also
be understood as comprising mixtures of surfactants. Particularly
advantageous application-promoting adjuvants are also natural or
synthetic phospholipids of the cephalin and lecithin series, e.g.
phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol
and lysolecithin.
[0189] Particularly formulations to be applied in spraying forms
such as water dispersible concentrates or wettable powders may
contain surfactants such as wetting and dispersing agents, e.g. the
condensation product of formaldehyde with naphthalene sulphonate,
an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl
sulphate, and ethoxylated alkylphenol and an ethoxylated fatty
alcohol.
[0190] A seed dressing formulation is applied in a manner known per
se to the seeds employing the combination of the invention and a
diluent in suitable seed dressing formulation form, e.g. as an
aqueous suspension or in a dry powder form having good adherence to
the seeds. Such seed dressing formulations are known in the art.
Seed dressing formulations may contain the single active
ingredients or the combination of active ingredients in
encapsulated form, e.g. as slow release capsules or
microcapsules.
[0191] In general, the formulations include from 0.01 to 90% by
weight of active agent, from 0 to 20% agriculturally acceptable
surfactant and 10 to 99.99% solid or liquid adjuvant(s), the active
agent consisting of at least the compound of formula I together
with a compound of component b), and optionally other active
agents, particularly microbides or conservatives or the like.
[0192] Concentrate forms of compositions generally contain in
between about 2 and 80%, preferably between about 5 and 70% by
weight of active agent. Application forms of formulation may for
example contain from 0.01 to 20% by weight, preferably from 0.01 to
5% by weight of active agent.
[0193] The Examples which follow serve to illustrate the invention,
"active ingredient" denoting a mixture of compound I and a compound
of component b) in a specific mixing ratio.
[0194] Formulations may be prepared analogously to those described
in, for example, WO 97/33890.
[0195] Slow Release Capsule Suspension
[0196] 28 parts of a combination of the compound of formula I and a
compound of component b), or of each of these compounds separately,
are mixed with 2 parts of an aromatic solvent and 7 parts of
toluene diisocyanatete/polymethylene-polyphenylisocyanate-mixture
(8:1). This mixture is emulsified in a mixture of 1.2 parts of
polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water
until the desired particle size is achieved. To this emulsion a
mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is
added. The mixture is agitated until the polymerisation reaction is
completed.
[0197] The obtained capsule suspension is stabilized by adding 0.25
parts of a thickener and 3 parts of a dispersing agent. The capsule
suspension formulation contains 28% of the active ingredients. The
medium capsule diameter is 8-15 microns. The resulting formulation
is applied to seeds as an aqueous suspension in an apparatus
suitable for that purpose.
[0198] Seed Dressing Formulation
[0199] 25 parts of a combination of compounds of formulae I and 11,
15 parts of dialkylphenoxypoly(ethylenoxy)ethanol, 15 parts of fine
silica, 44 parts of fine kaolin, 0.5 parts of Rhodamine B as a
colirant and 0.5 parts of Xanthan Gum are mixed and ground in a
contraplex mill at approx. 10000 rpm to an average particle size of
below 20 microns. The resulting formulation is applied to the seeds
as an aqueous suspension in an apparatus suitable for that
purpose.
[0200] Whereas commercial products will preferably be formulated as
concentrates, the end user will normally employ dilute
formulations.
[0201] Biological Examples
[0202] A synergistic effect exists whenever the action of an active
ingredient combination is greater than the sum of the actions of
the individual components.
[0203] The action to be expected E for a given active ingredient
combination obeys the so-called COLBY formula and can be calculated
as follows (COLBY, S. R. "Calculating synergistic and antagonistic
responses of herbicide combination". Weeds, Vol. 15, pages 20-22;
1967):
[0204] ppm=milligrams of active ingredient (=a.i.) per litre of
spray mixture
[0205] X=% action by active ingredient I using p ppm of active
ingredient
[0206] Y=% action by active ingredient II using q ppm of active
ingredient.
[0207] According to Colby, the expected (additive) action of active
ingredients I+II using p+q ppm of active ingredient is 1 E = X + Y
- X Y 100
[0208] If the action actually observed (O) is greater than the
expected action (E), then the action of the combination is
superadditive, i.e. there is a synergistic effect. Alternatively
the synergistic action may also be determined from the dose
response curves according to the so-called WADLEY method. With this
method the efficacy of the a.i. is determined by comparing the
degree of fungal attack on treated plants with that on untreated,
similarly inoculated and incubated check plants. Each a.i. is
tested at 4 to 5 concentrations. The dose response curves are used
to establish the EC90 (i.e. concentration of a.i. providing 90%
disease control) of the single compounds as well as of the
combinations (EC 90.sub.observed). The thus experimentally found
values of the mixtures at a given weight ratio are compared with
the values that would have been found were only a complementary
efficacy of the components was present (EC 90 (A+B).sub.expected).
The EC90 (A+B).sub.expected is calculated according to Wadley (Levi
et al., EPPO- Bulletin 16, 1986, 651-657): 2 EC 90 ( A + B )
expected = a + b a EC 90 ( A ) observed + b EC 90 ( B )
observed
[0209] wherein a and b are the weight ratios of the compounds A and
B in the mixture and the indexes (A), (B), (A+B) refer to the
observed EC 90 values of the compounds A, B or the given
combination A+B thereof. The ratio EC90 (A+B).sub.expected/EC90
(A+B).sub.observed expresses the factor of interaction (F). In case
of synergism, F is>1.
EXAMPLE B-1
Efficacy Against Erysiphe graminis f.sp. tritici on Wheat
[0210] Wheat plants c.v. "Arina", about 10 days old, are sprayed
with aqueous suspensions of the active ingredients or mixtures
thereof. One day later, the plants are inoculated by dusting with
spores of Erysiphe graminis. The tests may also be carried out with
curative applications, i.e. application 1-3 days after artificial
inoculation of the plants. The plants are incubated in the
greenhouse or in climate chambers at 20.degree. C., 70% relative
humidity. 7 to 10 days after inoculation, fungal attack on primary
leaves is assessed.
2TABLE 1 Mixture I.01 + fludioxonil (compound VI wherein R.sub.15
and R.sub.16 together form a bridge --OCF.sub.2--O--) cmpd I.01
Fludioxonil % activity % activity Colby's ppm ppm Ratio observed
expected factor -- -- -- 10 0 25 0 50 12 100 26 250 34 500 66 10 2
25 0 50 6 100 14 250 19 500 27 10 10 1:1 21 2 13.7 10 25 1:2.5 27 0
-- 10 50 1:5 11 6 1.8 10 100 1:10 30 14 2.2 10 250 1:25 19 19 1.0
25 25 1:1 13 0 -- 25 50 1:2 31 6 4.9 25 100 1:4 50 14 3.6 25 250
1:10 23 19 1.2 25 500 1:20 46 27 1.7 50 50 1:1 39 17 2.3 50 100 1:2
56 24 2.3 50 250 1:5 39 29 1.4 50 500 1:10 72 36 2.0 100 100 1:1 62
36 1.7 100 250 1:2.5 70 41 1.7 100 500 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
[0211]
3TABLE 2 Mixture I.01 + cyproconazole (compound III wherein R.sub.5
is Cl, R.sub.6 and R.sub.7 are H, R.sub.8 is CH.sub.3, R.sub.9 is
cyclopropyl and A is moiety (i)) cmpd. I.01 cyproconazole %
activity % activity Colby's ppm ppm Ratio observed expected factor
-- -- 0(control) o.5 0 1 0 2.5 0 5 8 10 8 1 8 2.5 49 5 100 10 100
0.5 1 1:2 18 8 2.4 0.5 2.5 1:5 69 49 1.4 0.5 5 1:10 100 100 1.0 1 1
1:1 23 8 3.0 1 2.5 1:2.5 92 49 1.9 1 5 1:5 100 100 1.0 2.5 1 2.5:1
38 8 5.0 2.5 2.5 1:1 74 49 1.5 2.5 5 1:2 100 100 1.0 5 1 5:1 43 15
2.9 5 2.5 2:1 92 53 1.7 5 5 1:1 100 100 1.0 10 2.5 4:1 98 53
1.9
[0212]
4TABLE 3 Mixture I.01 + propiconazole (compound III wherein R.sub.5
and R.sub.6 are Cl, R.sub.7 and R.sub.8 are H, R.sub.9 is propyl
and A is the moiety(ii)) cmpd. I.01 propiconazole % activity %
activity Colby's ppm ppm Ratio 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 5:1 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 1:2.5 87 72 1.2 1 5 1:5 99 99 1.0 2.5 0.5 5:1 42 19 2.2
2.5 1 2.5:1 57 22 2.6 2.5 2.5 1:1 94 76 1.2 5 1 5:1 61 16 3.8 5 2.5
2:1 90 75 1.2 5 5 1:1 99 99 1.0 10 2.5 4:1 92 73 1.2
[0213]
5TABLE 4 Mixture I.01 + fenpropidine (compound XXII) cmpd. I.o1
fenpropidine % activity % activity Colby's ppm ppm Ratio observed
expected factor -- -- 0(control) 0.25 0 0.5 0 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
EXAMPLE B-2
Efficacy Against Erysiphe graminis f.sp. hordei on Barley
[0214] a) Protective or Curative Activity
[0215] Barley plants c.v. "Golden Promise" are used. The testing
procedure is the same as described in Example B-1.
[0216] b) Systemic Activity
[0217] Aqueous spray mixtures of the active ingredients or mixtures
thereof are poured next to barley plants approximately 8 cm high.
Care is taken that the spray mixture does not come into contact
with the aerial parts of the plants. 48 hours later, the plants are
dusted with conidia of the fungus. The infected plants are placed
in a greenhouse at 22.degree. C. The disease attack on the foliage
is assessed 12 days after the infection.
EXAMPLE B-3
Activity Against Podosphaera leucotricha on Apples
[0218] Apple seedlings with about 10 cm long fresh shoots are
sprayed with aqueous spray mixtures of the active ingredients or
the mixtures thereof. The treated plants are inoculated 24 hours
later with a conidia suspension of the fungus and placed in a
climatic chamber at 70% relative humidity and 20.degree. C. The
test may also be carried out with curative application 2 days after
inoculation. Disease attack is evaluated 12-14 days after
inoculation.
EXAMPLE B-4
Activity Against Uncinula necator on Grapes
[0219] Grape plants grown from seeds (c.v. "Gutedel"), at the 4-5
leaves stage, are sprayed with aqueous spray mixtures of the active
ingredients or the mixtures thereof. One day later, the treated
plants are inoculated with a spore suspension of Uncinula necator
and then incubated in the growth chamber at +24.degree. C. and 70%
relative humidity. The test may also be carried out using curative
application 2 days after inoculation. Disease attack is evaluated
14 days after inoculation.
EXAMPLE B-5
Activity Against Sphaerotheca fuliginea on Cucumbers
[0220] Cucumber seedlings c.v. "chinesische Schlange", about 2
weeks old (cotyledon stage), are sprayed with aqueous spray
mixtures of the active ingredients or the mixtures thereof. One day
later, the treated plants are inoculated with a spore suspension of
Sphaerotheca fuliginea and then incubated in a growth chamber at
+24.degree. C. and 70% relative humidity. The test may also be
carried out using curative application 2 days after inoculation.
Disease attack is evaluated 10 days after inoculation.
EXAMPLE B-6
Activity Against Venturia inaequalis on Apples
[0221] Apple seedlings with about 10 cm long fresh shoots are
sprayed with aqueous spray mixtures of the active ingredients or
the mixtures thereof. The treated plants are inoculated 24 hours
later with a conidia suspension of the fungus. The plants are
incubated for 2 days at +20.degree. C. and 95-100% relative
humidity, then further 10 days in the greenhouse at 20-24.degree.
C. and 80% relative humidity. Disease attack is evaluated on the
youngest treated leaves.
B-7
Activity Against Puccinia recondita in Wheat
[0222] Wheat plants c.v. "Arina", about 10 days old, are sprayed
with aqueous suspensions of the active ingredients or mixtures
thereof. One day later, the plants are inoculated with a spore
suspension of the fungus. The test may also be carried out with
curative applications, i.e. application 1-3 days later after
artificial inoculation of the plants. The plants are incubated in a
growth chamber for 2 days at .degree.20.degree. C. and 95-100%
relative humidity, then further 10 days at 20.degree. C. and 70%
relative humidity. Fungal attack on primary leaves is assessed.
6TABLE 5 Mixture I.01 + cmpd. V wherein X is O, Y is N and R.sub.14
is 4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pen- tyl. cmpd. I.01
cmpd. V % activity % activity Colby's ppm ppm Ratio observed
expected 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 2.5 2.5 1:1 46 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
Activity Against Septoria nodorum in Wheat
[0223] Wheat plants c.v. "Zenith", about 10 days old, are sprayed
with aqueous suspensions of the active ingredients or mixtures
thereof. One day later, the plants are inoculated with a spore
suspension of the fungus. The tests may also be carried out with
curative timings, i.e. application 1-3 days after artificial
inoculation of the plants. The plants are subsequently incubated in
a growth chamber at a relative atmospheric humidity of 95-100%.
Disease attack is assessed 10 days after the inoculation.
EXAMPLE B-9
Activity Against Plasmopara viticola in Grapevines
[0224] Grape plants grown from seeds/c.v. "Gutedel"), at the
4-to-5-leaf stage, are sprayed with aqueous spray mixtures of the
active ingredients or the mixtures thereof. One day later, the
treated plants are inoculated with a spore suspension of the
fungus. The plants are incubated in a growth chamber 2 days at
+22.degree. C. and relative humidity of 95 to 100%, then 4 days at
22.degree. C. and 70% relative humidity, followed again by 1 day at
high humidity to induce sporulation. Disease attack is evaluated 7
days after inoculation.
EXAMPLE B-10
Activity Against Phytophthora infestans in Tomatoes
[0225] Tomato plants cv. "Baby", about 4 weeks old, are sprayed
with aqueous spray mixtures of the active ingredients or the
mixtures thereof. One day later, the treated plants are inoculated
with a zoospore suspension of the fungus. The plants are incubated
for 6 days in moisture chambers at 18.degree. C. and 100% relative
humidity. After this period, disease attack is evaluated.
[0226] The efficacy of the test combinations and the single active
ingredients in the above tests is determined by comparing the
degree of fungal attack with that on untreated, similarly
inoculated check plants.
EXAMPLE B-11
Activity Against Gerlachia nivalis on Wheat
[0227] Wheat seed which is infected with G.nivalis is harvested
from the field. This seed is treated with one of the active
ingredients I or b) or with mixtures of the active ingredients. The
active components are first dispersed in water and this dispersion
is then sprayed onto the seed which is on a rotating disc. This
procedure corresponds to conditions found in practice. Untreated
seeds from the same origin are used for comparison purposes.
Batches of 100 grains are sown in seed trays (45.times.35.times.10
cm) in sterile soil at a depth of 2 cm. Three replicates of the
test are run. The seed trays are kept moist for 21 days at
5.degree. C. with the exclusion of light. They are then transferred
to a control-environment cabinet with illumination (day/night: 16/8
hours; 10.degree. C.) where emergence takes place. Germination does
not take place in the case of those grains which are heavily
infected with G.nivalis. After 10 days, the trays are covered with
a plastic film and maintained at 10.degree. C. without light. Due
to the high atmospheric humidity under the cover, fungal mycelium
becomes apparent on the stem base of those plants which 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 forms the total infection rate. This rate is
compared with the total infection rate in the comparison seed trays
with untreated seeds and expressed as the total percentage
infection rate.
EXAMPLE B-12
Activity Against Helminthosporium gramineum on Barley
[0228] Barley seed which is infected with H.gramineum is harvested
from the field. This seed is treated with one of the active
ingredients I or b) or with mixtures of the active ingredients. The
active components are first dispersed in water and this dispersion
is then sprayed onto the seed which is on a rotating disc. This
procedure corresponds to conditions found in practice. Untreated
seeds from the same origin are used for comparison purposes.
Batches of 100 grains are sown in seed trays (45.times.35.times.10
cm) in sterile soil at a depth of 2 cm. Three replicates of the
test are run. The seed trays are kept moist for 28 days at
2.degree. C. with the exclusion of light. They are then transferred
to a greenhouse (day/night: 18/12.degree. C.). About 60 days after
sowing, the number of existing plants and the number of infected
plants are determined. Symptoms are expressed as typical
stripe-shaped spots on the first leaf. The total infection rate is
compared with the total infection rate in the comparison seed trays
with untreated seeds and expressed as the total percentage
infection rate.
7TABLE 6 Mixture I.01 + triticonazole (compound III wherein R.sub.5
is Cl, R.sub.6 is H and A the moiety (iv)). cmpd. I.01
triticonazole g a.i./100 kg g a.i./100 kg % activity % activity
Colby's seed seed Ratio observed expected factor -- -- 0(control)
20 11 20 12 40 22 20 40 1:2 36 31 1.2 20 20 1:1 29 22 1.3
EXAMPLE B-13
Activity Against Septoria nodorum on Wheat
[0229] Wheat seed which is infected with S.nodorum is harvested
from the field. This seed is treated with one of the active
ingredients I or b) or with mixtures of the active ingredients. The
active components are first dispersed in water and this dispersion
is then sprayed onto the seed which is on a rotating disc. This
procedure corresponds to conditions found in practice. Untreated
seeds from the same origin are used for comparison purposes.
[0230] The testing method used is based on that published by Holmes
and Colhoun (Ann. of appl. Biolg., 1973, 225-232). Batches of 100
grains are sown in seed trays (45.times.35.times.10 cm) in sterile
soil at a depth of 2 cm. Three replicates of the test are run. The
seed trays are kept moist for 14 days at 8-10.degree. C. with the
exclusion of light. They are then transferred to a greenhouse
(20.degree. C.) for a period of another 14 days. After that, the
seedlings are taken out of the soil and washed with water before
infection is assessed. The total infection rate is compared with
the total infection rate in the comparison seed trays with
untreated seeds and expressed as the total percentage infection
rate.
EXAMPLE B-14
Activity Against Erysiphe graminis on Barley or Wheat
[0231] Cereal seed is treated with one of the active ingredients I
or b) or with mixtures of the active ingredients. The active
components are first dispersed in water and this dispersion is then
sprayed onto the seed which is on a rotating disc. This procedure
corresponds to conditions found in practice. Untreated seeds from
the same origin are used for comparison purposes. Batches of 100
grains are sown in seed trays (45.times.35.times.10 cm) in sterile
soil at a depth of 2 cm. Three replicates of the test are run. The
seeds emerge at controlled conditions (day/night: 15/10.degree.
C.). In the stage of 2-3 emerged leaves, the plants are
artificially inoculated by shaking heavily infected plants over the
test trays. The seed trays are then kept at elevated temperatures
(day/night: 22/18.degree. C.). Assessments of the percentage
infected leaf area are done at regular intervals. The total
infection rate is compared with the total infection rate in the
comparison seed trays with untreated seeds and expressed as the
total percentage infection rate.
[0232] The mixtures according to the invention exhibit good
activity in these Examples.
* * * * *