Title of Invention

FUNGICIDAL MIXTURES

Abstract Fungicidal mixtures, comprising as active components 1) carbamate oxime ethers of the formula I, in which X is N or CH, and 2) at least one active compound II selected from the group of the azoles, stro- bilurins, carboxamides, heterocyclic compounds, carbamates, guanidines, antibiotics, nitrophenyl derivatives, sulfur-containing heterocyclyl com- pounds, organometallic compounds, organophosphorus compounds, or- ganochlorine compounds, inorganic active compounds, cyflufenamid, cy- moxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine, in a synergistically effective amount, methods for controlling harmful fungi using mix- tures of the compound I with active compounds II, the use of the compound I with ac- tive compounds II for preparing such mixtures and compositions comprising these mix- tures.
Full Text PF 56210
1
Fungicidal mixtures
Description
The present invention relates to fungicidal mixtures comprising, as active components,
1) carbamate oxime ethers of the formula I,

in which X is N or CH,
and
2) at least one active compound II selected from the following groups:
A) azoles, such as bitertanol, bromuconazole, cyproconazole, difenoconazole,
diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole,
flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,
metconazole, myclobutanil, penconazole, propiconazole, prothioconazole,
simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole,
triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid,
benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam,
etridiazole, hymexazole,
B) strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxa-
strobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin, trifloxystrobin;
C) carboxamides, such as carboxin, benalaxyl, boscalid, fenhexamid,
flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl,
oxycarboxin, penthiopyrad, thifluzamide, tiadinil,
3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide, dimethomorph,
flumorph,
flumetover, fluopicolide (picobenzamid), zoxamide,
carpropamid, diclocymet, mandipropamid,
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-
methanesulfonylamino-3-methylbutyramide,
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-
ethanesulfonylamino-3-methylbutyramide,
amides of the formula III,

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in which the variables and the index are as defined below:
R1 and R2 independently of one another are hydrogen, halogen, C1-C6-alkyl
or C1-C6 haloalkyl, cyano, nitro, methoxy or trifluoromethoxy, with the
proviso that R1 and R2 are not simultaneously hydrogen,
and R3 is CF3 or CHF2;
D) heterocyclic compounds, such as fluazinam, pyrifenox,
bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol,
pyrimethanil,
triforine,
fenpiclonil, fludioxonil,
aldimorph, dodemorph, fenpropimorph, tridemorph,
fenpropidin,
iprodione, procymidone, vinclozolin,
famoxadone, fenamidone, octhilinone, probenazole,
5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri-
azolo[1,5-a]pyrimidine,
anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole,
2-butoxy-6-iodo-3-propylchromen-4-one
acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quin-
oxyfen, or
N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]triazole-
1-sulfonamide;
E) carbamates, such as mancozeb, maneb, metam, metiram, ferbam,
propineb, thiram, zineb, ziram,
diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb,
methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl-butyryl-
amino)propanoate,

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and
F) other fungicides, selected from the group consisting of
guanidines: dodine, iminoctadine, guazatine,
antibiotics: kasugamycin, streptomycin, polyoxine, validamycin A,
nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane,
organometallic compounds: fentin salts, such as fentin acetate,
organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetyl
aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl,
organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide,
hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-
methyl, tolylfluanid,
inorganic active compounds: Bordeaux mixture, copper acetate, copper
hydroxide, copper oxychloride, basic copper sulfate, sulfur,
others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl,
metrafenone and spiroxamine,
in a synergistically effective amount.
In addition, the invention relates to a method for controlling harmful fungi using
mixtures of the compound I with active compounds II, to the use of the compound I with
active compounds II for preparing such mixtures and to compositions comprising these
mixtures.
The oxime ethers, referred to above as component 1, of the formula I, their preparation
and their action against harmful fungi are known from the literature (EP-A 12 01 648).
The active compounds II, mentioned above as component 2, their preparation and their
action against harmful fungi are generally known (cf.:
http://www.hclrss.demon.co.uk/index.html); they are commercially available.
Bitertanol, P-([1,1 '-biphenyl]-4-yloxy)-a-(1,1 -dimethylethy!)-1 H-1,2,4-triazole-1 -ethanol
(DE 23 24 020),
bromuconazole, 1-[[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furanyl]methyl]-1H-
1,2,4-triazole (Proc. 1990 Br. Crop. Prot. Conf. -Pests Dis. Vol. 1, p. 459),
cyproconazole, 2-(4-chlorophenyl)-3-cyclopropyl-1 -[1,2,4]triazol-1 -ylbutan-2-ol
(US 4 664 696);
difenoconazole, 1-{2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-[1,3]dioxolan-2-
ylmethyl}-1H-[1,2,4]triazole (GB-A 2 098 607);
diniconazole, (bE)-p-[(2,4-dichlorophenyl)methylene]-a-(1,1-dimethylethyl)-1H-1,2,4-
triazole-1 -ethanol (Noyaku Kagaku, 1983, Vol. 8, p. 575),

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enilconazole (imazalil), 1 -[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)ethyl]-1 H-imidazole
(Fruits, 1973, Vol. 28, p. 545),
epoxiconazole, (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-
1H-1,2,4-triazole (EP-A 196 038);
fluquiconazole, 3-(2,4-dichlorophenyl)-6-fluoro-2-[1,2,4]-triazol-1-yl-3H-quinazolin-4-
one (Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992));
fenbuconazole, a-[2-(4-chlorophenyl)ethyl]-a-phenyl-1H-1,2,4-triazole-1-propannitrile
(Proc. 1988 Br. Crop Prot. Conf. - Pests Dis. Vol. 1, p. 33),
flusilazole, 1-{[bis-(4-fluorophenyl)methylsilanyl]methyl}-1H-[1,2,4]triazole (Proc. Br.
Crop Prot. Conf.-Pests Dis., 1, 413 (1984));
flutriafol, a-(2-fluorophenyl)-a-(4-fluorophenyl)-1H-1,2,4-triazole-1-ethanol (EP 15 756),
hexaconazole, 2-(2,4-dichlorophenyl)-1-[1,2,4]triazo!-1-ylhexan-2-ol (CAS RN
[79983-71-4]);
imibenconazole, (4-chlorophenyl)methyl N-(2,4-dichlorophenyl)-1 H-1,2,4-triazole-1 -
ethaneimidothioate ((Proc. 1988 Br. Crop Prot. Conf. - Pests Dis. Vol. 2, p. 519),
ipconazole, 2-[(4-chlorophenyl)methyl]-5-(1-methylethyl)-1-(1H-1,2,4-triazol-1-yl-
methyl)cydopentanol (EP 267 778),
metconazole, 5-(4-chlorobenzyl)-2,2-dimethyl-1 -[1,2,4]triazol-1 -ylmethylcyclopentanol
(GB 857 383);
myclobutanil, 2-(4-chlorophenyl)-2-[1,2,4]triazol-1-ylmethylpentanenitrile (CAS RN
[88671-89-0]);
penconazole, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-[1,2,4]triazole (Pesticide Manual,
12th Ed. (2000), page 712);
propiconazole, 1 -[[2-(2,4-dichlorphenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1 H-1,2,4-
triazole (BE 835 579),
prothioconazole, 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-
dihydro[1,2,4]triazol-3-thione (WO 96/16048);
simeconazole, a-(4-fluorophenyl)-a-[(trimethylsilyl)methyl]-1 H-1,2,4-triazole-1 -ethanol
[CAS RN 149508-90-7],
triadimefon, 1 -(4-chlorophenoxy)-3,3-dimethyl-1 -(1 H-1,2,4-triazol-1 -yl)-2-butanone;
triadimenol, b-(4-chlorophenoxy)-a-(1,1-dimethylethyl)-1 H-1,2,4-triazole-1-ethanol;
tebuconazole, 1 -(4-chlorophenyl)-4,4-dimethyl-3-[1,2,4]triazol-1 -ylmethylpentan-3-o!
(EP-A 40 345);
tetraconazole, 1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]-1H-1,2,4-
triazole (EP 234 242),
triticonazole, (5E)-5-[(4-chlorophenyl)methylene]-2,2-dimethyl-1 -(1 H-1,2,4-triazol-1 -
ylmethyl)cyclopentanol (FR 26 41 277),
prochloraz, N-{propyl-[2-(2,4,6-trichlorophenoxy)ethyl]}imidazole-1-carboxamide (US 3
991 071);

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pefurazoate,4-pentenyl2-[(2-furanylmethyl)(1H-imidazol-1-ylcarbonyl)amino]butanoate
[CAS RN 101903-30-4],
triflumizole, (4-chloro-2-trifluoromethylphenyl)-(2-propoxy-1-[1,2,4]triazol-1-ylethyli-
dene)amine (JP-A 79/119 462)
cyazofamid, 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1 H-imidazole-1 -sulfon-
amide (CAS RN 120116-88-3],
benomyl, N-butyl-2-acetylaminobenzoimidazole-1-carboxamide (US 3 631 176);
carbendazim, methyl (1H-benzoimidazol-2-yl)-carbamate (US 3 657 443);
thiabendazole, 2-(1,3-thiazol-4-yl)benzimidazole (US 3 017 415),
fuberidazole, 2-(2-furanyl)-1H-benzimidazole (DE 12 09 799),
ethaboxam, N-(cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide
(EP-A 639 574),
etridiazole,
hymexazole, 5-methyl-1,2-oxazol-3-ol (JP 518249, JP 532202),
azoxystrobin, methyl 2-{2-[6-(2-cyano-1-vinylpenta-1,3-dienyloxy)pyrimidin-4-
yloxy]phenyl}-3-methoxyacrylate (EP-A 382 375),
dimoxystrobin, (E)-2-(methoxyimino)-N-methyl-2-[a-(2,5-xylyloxy)-o-tolyl]acetamide
(EP-A 477 631);
fluoxastrobin, (E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6-
dihydro-1,4,2-dioxazin-3-yl)methanone O-methyloxime (WO 97/27189);
kresoxim-methyl, methyl (E)-methoxyimino[a-(o-tolyloxy)-o-tolyl]acetate (EP-A 253
213);
metominostrobin, (E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (EP-
A 398 692);
orysastrobin, (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-
2,8-dioxa-3,7-diazanona-3,6-dien-1 -yl]phenyl}-N-methylacetamide (WO 97/15552);
picoxystrobin, methyl 3-methoxy-2-[2-(6-trifluoromethylpyridin-2-yloxymethyl)phenyl]-
acrylate (EP-A 278 595);
pyraclostrobin, methyl N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(N-
methoxy)carbamate (WO-A 96/01256);
trifloxystrobin, methyl (E)-methoxyimino-{(E)-a-[1-(a,a,a-trifluoro-m-tolyl)ethylidene-
aminooxy]-o-tolyl}acetate (EP-A 460 575);
carboxin, 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (US 3 249 499),
benalaxyl, methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninate (DE 29 03 612),
boscalid, 2-chloro-N-(4'-chlorbiphenyl-2-yl)nicotinamide (EP-A 545 099);
fenhexamid, N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide
(Proc. Br. Crop Prot. Conf. - Pests Dis., 1998, Vol. 2, p. 327);
flutolanil, a,a,a-trifluoro-3'-isopropoxy-o-toluanilide (JP 1104514),
furametpyr, 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-1 H-
pyrazole-4-carboxamide [CAS RN 123572-88-3],

PF 56210
6
mepronil, 3'-isopropoxy-o-toluanilide (US 3 937 840),
metalaxyl, methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (GB 15 00 581);
mefenoxam, methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate;
ofurace, (RS)-a-(2-chloro-N-2,6-xylylacetamido)-Y-butyrolactone [CAS RN 58810-48-3];
oxadixyl; N-(2,6-dimethylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide (GB
20 58 059),
oxycarboxin, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (US
3 399 214),
penthiopyrad, N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-
pyrazole-4-carboxamide (JP 10130268),
thifluzamide,
tiadinil, 3'-chloro-4,4'-dimethyl-1,2,3-thiadiazole-5-carboxanilide [CAS RN 223580-51-
6],
dimethomorph, 3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylpropenone
(EP-A120 321);
flumorph, 3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-1 -morpholin-4-ylpropenone (EP-
A 860 438);
flumetover, 2-(3,4-dimethoxyphenyl)-N-ethyl-a,a,a-trifluoro-N-methyl-p-toluamide
[AGROW No. 243, 22 (1995)],
fluopicolide (picobenzamid), 2,6-dichloro-N-(3-chloro-5-trifluoromethylpyridin-2-
ylmethyl)benzamide (WO 99/42447);
zoxamide, (RS)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-p-toluamide
[CAS RN 156052-68-5];
carpropamid, 2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropane-
carboxamide [CAS RN 104030-54-8],
diclocymet, 2-cyano-N-[(1R)-1-(2,4-dichlorophenyl)ethyl]-3,3-dimethylbutanamide;
mandipropamid, (RS)-2-(4-chlorophenyl)-N-[3-methoxy-4-(prop-2-ynyloxy)phenethyl]-2-
(prop-2-ynyloxy)acetamide [CAS RN 374726-62-2];
fluazinam, 3-chloro-N-[3-chloro-2,6-dinitro-4-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-
2-pyridinamine (The Pesticide Manual, publ. The British Crop Protection Council, 10th
ed. (1995), p. 474);
pyrifenox, 1-(2,4-dichlorophenyl)-2-(3-pyridinyl)ethanone O-methyloxime (EP-A 49
854);
bupirimate,
cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl)phenylamine (EP-A 310 550);
fenarimol, (4-chlorophenyl)-(2-chlorophenyl)pyrimidin-5-ylmethanol (GB 12 18 623);
ferimzone, (Z)-2'-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone;
mepanipyrim, (4-methyl-6-prop-1-ynylpyrimidin-2-yl)phenylamine (EP-A224 339);
nuarimol, a-(2-chlorophenyl)-a-(4-fluorophenyl)-5-pyrimidinemethanol (GB 12 18 623);
pyrimethanil, 4,6-dimethylpyrimidin-2-ylphenylamine (DD-A 151 404);

PF 56210
7
triforine, N,N'-{piperazine-1,4-diylbis[(trichloromethyl)methylene]}diformamide (DE
19 01 421);
fenpiclonil, 4-(2,3-dichlorophenyl)-1H-pyrrole-3-carbonitrile (Proc. 1988 Br. Crop Prot.
Conf. - Pests Dis., Vol. 1, p. 65);
fludioxonil, 4-(2,2-difIuorobenzo[1,3]dioxol-4-yl)-1H-pyrrole-3-carbonitrile (The Pesticide
Manual, publ. The British Crop Protection Council, 10th ed. (1995), p. 482);
aldimorph, 4-alkyl-2,5(or 2,6)-dimethylmorpholine, comprising 65-75% of 2,6-dimethyl-
morpholine and 25-35% of 2,5-dimethylmorpholine, comprising more than 85% of 4-
dodecyl-2,5(or 2,6)-dimethylmorpholine, where "alkyl" may also include octyl, decyl,
tetradecyl and hexadecyl and where the cis/trans ratio is 1:1;
dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE 1198125);
fenpropimorph, (RS)-cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethyl-
morpholine (DE 27 52 096);
tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE 11 64 152);
fenpropidin, (RS)-1-[3-(4-ferf-butylphenyl)-2-methylpropyl]piperidine (DE 27 52 096);
iprodione, N-isopropyl-3-(3,5-dichlorophenyl)-2,4-dioxoimidazoNdine-1-carboxamide
(GB 13 12 536);
procymidone, A/-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide (US
3 903 090);
vinclozolin, 3-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione (DE-OS
22 07 576);
famoxadone, (RS)-3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione;
fenamidone, (S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one;
octhilinone,
probenazole, 3-allyloxy-1,2-benzothiazole 1,1-dioxide [CAS RN 27605-76-1];
anilazine, 4,6-dichloro-A/-(2-chlorophenyl)-1,3,5-triazine-2-amine (US 2 720 480);
diclomezine, 6-(3,5-dichlorophenyl-p-tolyl)pyridazin-3(2H)-one;
pyroquilone, 1,2,5,6-tetrahydropyrrolo[3,2,1-ij]quinolin-4-one (GB 13 94 373);
proquinazid, 6-iodo-2-propoxy-3-propylquinazolin-4(3H)-one (WO 97/48684);
tricyclazole, 5-methyl-1,2,4-triazolo[3,4-jb]benzothiazole (GB 14 19 121);
acibenzolar-S-methyl, methyl benzo[1,2,3]thiadiazole-7-carbothionate;
captafol, N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboximide;
captan, 2-trichloromethylsulfanyl-3a,4,7,7a-tetrahydroisoindole-1,3-dione (US 2 553
770);
dazomet, 3,5-dimethyl-1,3,5-thiadiazinane-2-thione;
folpet, 2-trichloromethylsulfanylisoindole-1,3-dione (US 2 553 770);
fenoxanil, N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propanamide (EP-A
262 393);
quinoxyfen, 5,7-dichloro-4-(4-fluorophenoxy)quinoline (US 5 240 940);

PF 56210
8
mancozeb, manganese-ethylenebis(dithiocarbamate) zinc complex (US 3 379 610);
maneb, manganese ethylenebis(dithiocarbamate) (US 2 504 404);
metam, methyldithiocarbaminic acid (US 2 791 605);
metiram, zinc ammoniate ethylenebis(dithiocarbamate) (US 3 248 400);
propineb, zinc propylenebis(dithiocarbamate) polymer (BE 611 960);
ferbam, iron(3+) dimethyldithiocarbamate (US 1 972 961);
thiram, bis(dimethylthiocarbamoyl) disulfide (DE 642 532);
ziram, dimethyldithiocarbamate [CAS RN 137-30-4];
zineb, zinc ethylenebis(dithiocarbamate) (US 2 457 674);
diethofencarb, isopropyl 3,4-diethoxycarbanilate;
iprovalicarb, isopropyl [(1S)-2-methyl-1-(1-p-tolylethylcarbamoyl)propyl]carbamate
(EP-A 472 996);
flubenthiavalicarb (benthiavalicarb), isopropyl {(S)-1 -[(1 R)-1 -(6-fluorobenzothiazol-2-yl)-
ethylcarbamoyl]-2-methylpropyl}carbamate (JP-A 09/323 984);
propamocarb, propyl 3-(dimethylamino)propylcarbamate (DE 16 43 040);
dodine, (2,4-dichlorophenoxy)acetic acid (US 2 867 562);
guazatine, mixture comprising iminoctadine, bis(8-guanidinooctyl)amine (GB 11 14
155);
kasugamycin, 1L-1,3,4/2,5,6-1 -deoxy-2,3,4,5,6-pentahydroxycyclohexyl-2-amino-
2,3,4,6-tetradeoxy-4-(a-iminoglycino)-a-D-arabino-hexopyranoside;
streptomycin, 0-2-deoxy-2-methylamino-a-L-glucopyranosyl-(1→2)-0-5-deoxy-3-C-
formyl-a-L-lyxofuranosyl-(1 →4)-N1,N3-diamidino-D-streptamine;
polyoxins, 5-(2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1 -(5-carboxy-1,2,3,4-
tetrahydro-2,4-dioxopyrimidin-1-yl)-1,5-dideoxy-b-D-allofuranuronicacid and the salts
thereof;
validamycin A,
binapacryl, (RS)-2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate;
dinocap, the mixture of 2,6-dinitro-4-octy!phenyl crotonate and 2,4-dinitro-6-octylphenyl
crotonate, wherein "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-
propylpentyl (US 2 526 660);
dinobuton, (RS)-2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;
dithianon, 5,10-dioxo-5,10-dihydronaphtho[2,3-b][1,4]dithiin-2,3-dicarbonitrile (GB
857 383);
isoprothiolane, indol-3-ylacetic acid [CAS RN 50512-35-1];
fentin acetate, triphenyl tin acetate;
edifenphos, O-ethyl S,S-diphenylphosphorodithioate;
iprobenfos,
fosetyl, fosetyl aluminum, ethylphosphonate, aluminum salt (FR 22 54 276);
pyrazophos,

PF 56210
9
tolclofos-methyl, 0-2,6-dichloro-p-tolyl O,O-dimethyl phosphorothioate (GB 14 67 561);
chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3 290 353);
dichlofluanid, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (DE
11 93 498);
flusulfamide,
hexachlorobenzene,
phthalide,
pencycuron, 1-(4-chloroben2yl)-1-cyclopentyl-3-phenylurea (DE 27 32 257);
quintozene, pentachloronitrobenzene (DE 682 048);
thiophanate-methyl, 1,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-
OS 19 30 540);
tolylfluanid, N-dichlorofluoromethylthio-N,N'-dimethyl-N-p-tolylsulfamide (DE
11 93 498);
cyflufenamid, (Z)-N-[a-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoromethyl)ben-
zyl]-2-phenylacetamide (WO 96/19442);
cymoxanil, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (US 3 957 847);
dimethirimol,
ethirimol,
furalaxyl,
metrafenone, 3'-bromo-2,3,4,6'-tetramethoxy-2',6-dimethylbenzophenone (US 5 945
567);
spiroxamine, (8-tert-butyl-1,4-dioxaspiro[4.5]dec-2-yl)diethylamine (EP-A281 842).
The compounds named according to IUPAC, their preparation and their fungicidal
action are likewise known:
5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyri-
midine (WO 98/46608),

R methyl (Il-A) or ethyl (Il-B);
amides of the formula III (WO 03/066609),
2-butoxy-6-iodo-3-propylchromen-4-one of the formula IV (WO 03/14103),
3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide (WO 99/24413),
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonyl-
amino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-
methoxyphenyl}ethyl)-2-ethanesuifonylamino-3-methylbutyramide (WO 04/049804),



PF 56210
10
N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]tria2ole-1-
sulfonamide of the formula V (WO 03/053145),
methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)-
propanoate of the formula VI (EP-A 1028125).

It is an object of the present invention, with a view to reducing the application rates and
broadening the activity spectrum of the known compounds, to provide mixtures which,
at a reduced total amount of active compounds applied, have improved activity against
harmful fungi, in particular for certain indications.
We have found that this object is achieved by the mixtures defined at the outset. In
addition, we have found that simultaneous, that is joint or separate, application of the
compound I and an active compound II or successive application of the compound I
and an active compound II allows better control of harmful fungi than is possible with
the individual compounds (synergistic mixtures). The compound I can be used as a
synergist for a large number of different active compounds. The simultaneous, that is
joint or separate, application of the compound I with an active compound II increases
the fungicidal activity in a superadditive manner.
The mixtures of the compound I and an active compound II or the simultaneous, that is
joint or separate, use of the compound I and an active compound II are distinguished
by being highly active against a wide range of phytopathogenic fungi, in particular from
the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes.
Some of them act systemically and can be used in crop protection as foliar- and soil-
acting fungicides.

PF 56210
11
They are particularly important for controlling a multitude of fungi on various crop
plants, such as bananas, cotton, vegetable species (for example cucumbers, beans
and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit species, rice, rye,
soybeans, tomatoes, grapevines, wheat, ornamental plants, sugar cane and on a large
number of seeds.
They are advantageously suitable for the control of the following phytopathogenic fungi:
Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and
Sphaerotheca fuliginea on cucurbits, Podosphaera leucotricha on apples, Uncinula
necatoron grapevines, Puccinia species on cereals, Rhizoctonia species on cotton,
rice and lawns, Ustilago species on cereals and sugar cane, Venturia inaequalis on
apples, Bipolaris and Drechslera species on cereals, rice and lawns, Septoria species
on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and
grapevines, Mycosphaerella species on bananas, peanuts and cereals,
Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora species on
cucurbits and hops, Plasmopara viticola on grapevines, Alternaria species on fruit and
vegetables and also Fusarium and Verticillium species.
The mixtures of the compound I and an active compound II are especially suitable for
controlling Botrytis species.
The compound I and active compounds II can be applied simultaneously, that is jointly
or separately, or in succession, the sequence, in the case of separate application,
generally not having any effect on the result of the control measures.
In the definitions of the symbols given for formula III, collective terms were used which
denote the following substituents:
halogen: fluorine, chlorine, bromine and iodine;
alkyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 6 carbon
atoms, for example C1-C4alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl,
1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl;
haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, where
some or all of the hydrogen atoms in these groups may be replaced by halogen atoms
as mentioned above: in particular C1-C2-haloalkyl, such as chloromethyl, bromomethyl,
dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,
chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-

PF 56210
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bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-
2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl
or pentafluoroethyl.
The formula I denotes compounds in which X is N (I-A) or CH (I-B).
One embodiment of the invention relates to mixtures of the compound I-A with an
active compound II.
Another embodiment of the invention relates to mixtures of the compound I-B with an
active compound II.
With a view to the use of the amides of the formula III in the mixtures according to the
invention, the following compounds of the formulae IlIa to Illf are particularly suitable:


PF 56210
13

Among these, particular preference is given to the compounds of the formula IIId.
Especially preferred are the compounds compiled in the tables below:
Table 1
Compound 1.1-1.22: compounds of the formula IlIa in which R1 is fluorine and the
combination of R2 and R3 is in each case one row of table A
Table 2
Compound 2.1 - 2.22: compounds of the formula IlIa in which R1 is chlorine and the
combination of R2 and R3 is in each case one row of table A
Table 3
Compound 3.1 - 3.22: compounds of the formula IlIa in which R1 is bromine and the
combination of R2 and R3 is in each case one row of table A
Table 4
Compound 4.1 - 4.22: compounds of the formula IlIa in which R1 is iodine and the
combination of R2 and R3 is in each case one row of table A
Table 5
Compound 5.1 -5.22: compounds of the formula IlIa in which R1 is methyl and the
combination of R2 and R3 is in each case one row of table A
Table 6
Compound 6.1 - 6.22: compounds of the formula Ilia in which R1 is methoxy and the
combination of R2 and R3 is in each case one row of table A

PF 56210
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Table 7
Compound 7.1 - 7.22: compounds of the formula IlIa in which R1 is trifluoromethyl and
the combination of R2 and R3 is in each case one row of table A
Table 8
Compound 8.1 - 8.22: compounds of the formula IlIa in which R1 is trifluoromethoxy
and the combination of R2 and R3 is in each case one row of table A
Table 9
Compound 9.1 - 9.22: compounds of the formula IlIa in which R1 is cyano and the
combination of R2 and R3 is in each case one row of table A
Table 10
Compound 10.1 - 10.22: compounds of the formula IlIa in which R1 is nitro and R2 is in
each case one row of table A
Table 11
Compound 11.1 - 11.20: compounds of the formula IlIa in which R1 is hydrogen and
the combination of R2 and R3 is in each case one of rows 2 to 21 of table A
Table 12
Compound 12.1 - 12.22: compounds of the formula Illb in which R1 is fluorine and the
combination of R2 and R3 is in each case one row of table A
Table 13
Compound 13.1 - 13.22: compounds of the formula Illb in which R1 is chlorine and the
combination of R2 and R3 is in each case one row of table A
Table 14
Compound 14.1 - 14.22: compounds of the formula Illb in which R1 is bromine and the
combination of R2 and R3 is in each case one row of table A
Table 15
Compound 15.1 - 15.22: compounds of the formula Illb in which R1 is iodine and the
combination of R2 and R3 is in each case one row of table A
Table 16
Compound 16.1 - 16.22: compounds of the formula Illb in which R1 is methyl and the
combination of R2 and R3 is in each case one row of table A

PF 56210
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Table 17
Compound 17.1 - 17.22: compounds of the formula Illb in which R1 is methoxy and the
combination of R2 and R3 is in each case one row of table A
Table 18
Compound 18.1 - 18.22: compounds of the formula Illb in which R1 is trifluoromethyl
and the combination of R2 and R3 is in each case one row of table A
Table 19
Compound 19.1 - 19.22: compounds of the formula Illb in which R1 is trifluoromethoxy
and the combination of R2 and R3 is in each case one row of table A
Table 20
Compound 20.1 -20.22: compounds of the formula Illb in which R1 is cyano and the
combination of R2 and R3 is in each case one row of table A
Table 21
Compound 21.1 -21.22: compounds of the formula Illb in which R1 is nitro and the
combination of R2 and R3 is in each case one row of table A
Table 22
Compound 22.1 - 22.20: compounds of the formula Illb in which R1 is hydrogen and
the combination of R2 and R3 is in each case one of rows 2 to 21 of table A
Table 23
Compound 23.1 - 23.22: compounds of the formula Illc in which R1 is fluorine and the
combination of R2 and R3 is in each case one row of table A
Table 24
Compound 24.1 - 24.22: compounds of the formula Illc in which R1 is chlorine and the
combination of R2 and R3 is in each case one row of table A
Table 25
Compound 25.1 - 25.22: compounds of the formula Illc in which R1 is bromine and the
combination of R2 and R3 is in each case one row of table A
Table 26
Compound 26.1 -26.22: compounds of the formula Illc in which R1 is iodine and the
combination of R2 and R3 is in each case one row of table A

PF 56210
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Table 27
Compound 25.1 - 25.22: compounds of the formula Illc in which R1 is methyl and the
combination of R2 and R3 is in each case one row of table A
Table 28
Compound 28.1 -28.22: compounds of the formula Illc in which R1 is methoxy and the
combination of R2 and R3 is in each case one row of table A
Table 29
Compound 29.1 - 29.22: compounds of the formula Illc in which R1 is trifluoromethyl
and the combination of R2 and R3 is in each case one row of table A
Table 30
Compound 30.1 - 30.22: compounds of the formula Illc in which R1 is trifluoromethoxy
and the combination of R2 and R3 is in each case one row of table A
Table 31
Compound 31.1 -31.22: compounds of the formula Illc in which R1 is cyano and the
combination of R2 and R3 is in each case one row of table A
Table 32
Compound 32.1 - 32.22: compounds of the formula Illc in which R1 is nitro and the
combination of R2 and R3 is in each case one row of table A
Table 34
Compound 34.1 - 34.22: compounds of the formula IIId in which R1 is fluorine and the
combination of R2 and R3 is in each case one row of table A
Table 35
Compound 35.1 -35.22: compounds of the formula IIId in which R1 is chlorine and the
combination of R2 and R3 is in each case one row of table A
Table 36
Compound 36.1 - 36.22: compounds of the formula IIId in which R1 is bromine and the
combination of R2 and R3 is in each case one row of table A
Table 37
Compound 37.1 -37.22: compounds of the formula IIId in which R1 is iodine and the
combination of R2 and R3 is in each case one row of table A

PF 56210
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Table 38
Compound 38.1 -38.22: compounds of the formula IIId in which R1 is methyl and the
combination of R2 and R3 is in each case one row of table A
Table 39
Compound 39.1 - 39.22: compounds of the formula IIId in which R1 is methoxy and the
combination of R2 and R3 is in each case one row of table A
Table 40
Compound 40.1 -40.22: compounds of the formula IIId in which R1 is trifluoromethyl
and the combination of R2 and R3 is in each case one row of table A
Table 41
Compound 41.1 -41.22: compounds of the formula IIId in which R1 is trifluoromethoxy
and the combination of R2 and R3 is in each case one row of table A
Table 42
Compound 42.1 -42.22: compounds of the formula IIId in which R1 is cyano and the
combination of R2 and R3 is in each case one row of table A
Table 43
Compound 43.1 -43.22: compounds of the formula IIId in which R1 is nitro and the
combination of R2 and R3 is in each case one row of table A
Table 44
Compound 44.1 -44.20: compounds of the formula IIId in which R1 is hydrogen and
the combination of R2 and R3 is in each case one of rows 2 to 21 of table A
Table 45
Compound 45.1 -45.22: compounds of the formula Ille in which R1 is fluorine and the
combination of R2 and R3 is in each case one row of table A
Table 46
Compound 46.1 -46.22: compounds of the formula Ille in which R1 is chlorine and the
combination of R2 and R3 is in each case one row of table A
Table 47
Compound 47.1 -47.22: compounds of the formula Ille in which R1 is bromine and the
combination of R2 and R3 is in each case one row of table A

PF 56210
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Table 48
Compound 48.1 -48.22: compounds of the formula Ille in which R1 is iodine and the
combination of R2 and R3 is in each case one row of table A
Table 49
Compound 49.1 -49.22: compounds of the formula Ille in which R1 is methyl and the
combination of R2 and R3 is in each case one row of table A
Table 50
Compound 50.1 - 50.22: compounds of the formula Ille in which R1 is methoxy and the
combination of R2 and R3 is in each case one row of table A
Table 51
Compound 51.1 - 51.22: compounds of the formula Ille in which R1 is trifluoromethyl
and the combination of R2 and R3 is in each case one row of table A
Table 52
Compound 52.1 - 52.22: compounds of the formula Ille in which R1 is trifluoromethoxy
and the combination of R2 and R3 is in each case one row of table A
Table 53
Compound 53.1 - 53.22: compounds of the formula Ille in which R1 is cyano and the
combination of R2 and R3 is in each case one row of table A
Table 54
Compound 54.1 - 54.22: compounds of the formula Ille in which R1 is nitro and the
combination of R2 and R3 is in each case one row of table A
Table 56
Compound 56.1 -56.22: compounds of the formula Illf in which R1 is fluorine and the
combination of R2 and R3 is in each case one row of table A
Table 57
Compound 57.1 -57.22: compounds of the formula Illf in which R1 is chlorine and the
combination of R2 and R3 is in each case one row of table A
Table 58
Compound 58.1 - 58.22: compounds of the formula Illf in which R1 is bromine and the
combination of R2 and R3 is in each case one row of table A

PF 56210
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Table 59
Compound 59.1 -59.22: compounds of the formula Illf in which R1 is iodine and the
combination of R2 and R3 is in each case one row of table A
Table 60
Compound 60.1 - 60.22: compounds of the formula Illf in which R1 is methyl and the
combination of R2 and R3 is in each case one row of table A
Table 61
Compound 61.1 -61.22: compounds of the formula Illf in which R1 is methoxy and the
combination of R2 and R3 is in each case one row of table A
Table 62
Compound 62.1 - 62.22: compounds of the formula Illf in which R1 is trifluoromethyl
and the combination of R2 and R3 is in each case one row of table A
Table 63
Compound 63.1 - 63.22: compounds of the formula Illf in which R1 is trifluoromethoxy
and the combination of R2 and R3 is in each case one row of table A
Table 64
Compound 64.1 - 64.22: compounds of the formula Illf in which R1 is cyano and the
combination of R2 and R3 is in each case one row of table A
Table 65
Compound 65.1 -65.22: compounds of the formula Illf in which R1 is nitro and the
combination of R2 and R3 is in each case one row of table A
Table 66
Compound 66.1 - 66.20: compounds of the formula Illf in which R1 is hydrogen and the
combination of R2 and R3 is in each case one of rows 2 to 21 of table A

Table A
No. R2 R3
1 H CF3
2 F CF3
3 Cl CF3
4 Br CF3
5 I CF3
6 CH3 CF3

PF 56210
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7 OCH3 CF3
8 CF3 CF3
9 OCF3 CF3
10 CN CF3
11 NO2 CF3
12 F CHF2
13 Cl CHF2
14 Br CHF2
15 I CHF2
16 CH3 CHF2
17 OCH3 CHF2
18 CF3 CHF2
19 OCF3 CHF2
20 CN CHF2
21 NO2 CHF2
22 H CHF2
A preferred embodiment of the mixtures according to the invention relates to the
combination of the compound of the formula I and an active compound from the
following groups:
dithiocarbamates, in particular mancozeb, propineb, thiram,
benzimidazole, in particular benomyl, thiophanate, carbendazim,
dicarboximides, in particular iprodione, procymidone, vinclozolin, chlozolinate,
phthalimides, in particular captan, chlorothalonil, folpet,
anilinopyrimidines, in particular cyprodinil, pyrimethanil, mepanipyrim,
triazoles, in particular tebuconazole, difenoconazole, cyproconazole, myclobutanil,
carboxanilides, in particular fenhexamid, benalaxyl, boscalid, penthiopyrad,
an anilide of the formula III, the compound of the formula IV,
organochlorine compounds, in particular dichlofluanid, chlorothalonil, tolyfluanid,
carbamate, in particular diethofencarb,
nitrogen-containing heterocyclyl compounds, in particular fludioxonil, fluazinam,
strobilurins, in particular kresoxim-methyl, pyraclostrobin, azoxystrobin, trifloxystrobin,
enestroburin, picoxystrobin, fluoxastrobin,
organotin compounds, in particular fentin acetyl, and, in particular
5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyri-
midine.
When preparing the mixtures, it is preferred to employ the pure active compounds, to
which further active compounds against harmful fungi or against other pests, such as

PF 56210
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insects, arachnids or nematodes, or else herbicidal or growth-regulating active
compounds or fertilizers can be added according to need as further active components.
What is usually used are mixtures of the compound I with one active compound II.
However, in certain cases, mixtures of the compound I with two or, if appropriate, a
plurality of active components may be advantageous.
Suitable further active components in the above sense are in particular the active
compounds II mentioned at the outset and especially the preferred active compounds
mentioned above.
The compound I and the active compound II are usually applied in a weight ratio of
from 100:1 to 1:100, preferably from 20:1 to 1:20, in particular from 10:1 to 1:10.
The further active components are, if desired, added in a ratio of from 20:1 to 1:20 to
the compound I.
Depending on the type of compound and the desired effect, the application rates of the
mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to
900 g/ha, in particular from 50 to 750 g/ha.
Correspondingly, the application rates for the compound I are generally from 1 to
1000 g/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.
Correspondingly, the application rates for the active compound II are generally from 1
to 2000 g/ha, preferably from 10 to 900 g/ha, in particular from 40 to 500 g/ha.
In the treatment of seed, application rates of mixture are generally from 1 to
1000 g/100 kg of seed, preferably from 1 to 750 g/100 kg, in particular from 5 to
500g/100kg.
The method for controlling harmful fungi is carried out by the separate or joint
application of the compound I and the active compound II or of the mixtures of the
compound I and the active compound II by spraying or dusting the seeds, the plants or
the soil before or after sowing of the plants or before or after emergence of the plants.
The mixtures according to the invention, or the compound I and the active compound II,
can be converted into the customary formulations, for example solutions, emulsions,
suspensions, dusts, powders, pastes and granules. The use form depends on the

PF 56210
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particular intended purpose; in each case, it should ensure a fine and even distribution
of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active
compound with solvents and/or carriers, if desired using emulsifiers and dispersants.
Solvents/auxiliaries suitable for this purpose are essentially:
water, aromatic solvents (for example Solvesso products, xylene), paraffins (for
example mineral oil fractions), alcohols (for example methanol, butanol, pentanol,
benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone),
pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid
dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures
may also be used,
carriers such as ground natural minerals (for example kaolins, clays, talc, chalk)
and ground synthetic minerals (for example highly disperse silicic acid, silicates);
emulsifiers such as nonionogenic and anionic emulsifiers (for example
polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and
dispersants such as lignosulfite waste liquors and methylcellulose.
Suitable for use as surfactants are alkali metal, alkaline earth metal and ammonium
salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid,
dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty
alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore
condensates of sulfonated naphthalene and naphthalene derivatives with
formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol
and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,
tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol
ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,
ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions,
emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling
point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or
animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene,
paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol,
ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar
solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or

PF 56210
23
concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous
granules, can be prepared by binding the active compounds to solid carriers. Examples
of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,
magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as,
for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and
products of vegetable origin, such as cereal meal, tree bark meal, wood meal and
nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1
to 90% by weight, of the active compounds. The active compounds are employed in a
purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
For the treatment of seed, the formulations in question give, after two- to ten-fold
dilution, active compound concentrations of from 0.01 to 60% by weight, preferably
from 0.1 to 40% by weight, in the ready-to-use preparations.
The following are examples of formulations of the invention:
1. Products for dilution with water
A Water-soluble concentrates (SL, LS)
10 parts by weight of the active compounds are dissolved with 90 parts by weight of
water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are
added. The active compound dissolves upon dilution with water. In this way, a
formulation having an active compound content of 10% by weight is obtained.
B Dispersible concentrates (DC)
20 parts by weight of the active compounds are dissolved in 70 parts by weight of
cyclohexanone with addition of 10 parts by weight of a dispersant, for example
polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound
content is 20% by weight.
C Emulsifiable concentrates (EC)
15 parts by weight of the active compounds are dissolved in 75 parts by weight of
xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in
each case 5 parts by weight). Dilution with water gives an emulsion. The formulation
has an active compound content of 15% by weight.

PF 56210
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D Emulsions (EW, EO, ES)
25 parts by weight of the active compounds are dissolved in 35 parts by weight of
xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in
each case 5 parts by weight). This mixture is added to 30 parts by weight of water by
means of an emulsifying machine (for example Ultraturrax) and made into a
homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an
active compound content of 25% by weight.
E Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compounds are comminuted
with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of
water or an organic solvent to give a fine active compound suspension. Dilution with
water gives a stable suspension of the active compound. The active compound content
in the formulation is 20% by weight.
F Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compounds are ground finely with addition of 50 parts
by weight of dispersants and wetters and prepared as water-dispersible or water-
soluble granules by means of technical appliances (for example extrusion, spray tower,
fluidized bed). Dilution with water gives a stable dispersion or solution of the active
compound. The formulation has an active compound content of 50% by weight.
G Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compounds are ground in a rotor-stator mill with
addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water
gives a stable dispersion or solution of the active compound. The active compound
content of the formulation is 75% by weight.
H Gel formulations
In a bead mill, 20 parts by weight of the active compounds, 10 parts by weight of
dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an
organic solvent are ground to give a fine suspension. Dilution with water gives a stable
suspension having an active compound content of 20% by weight.
2. Products to be applied undiluted
I Dusts (DP, DS)
5 parts by weight of the active compounds are ground finely and mixed intimately with
95 parts by weight of finely divided kaolin. This gives a dustable product having an
active compound content of 5% by weight.

PF 56210
25
J Granules (GR, FG, GG, MG)
0.5 part by weight of the active compounds is ground finely and associated with 99.5
parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized
bed. This gives granules to be applied undiluted having an active compound content of
0.5% by weight.
K ULV solutions (UL)
10 parts by weight of the active compounds are dissolved in 90 parts by weight of an
organic solvent, for example xylene. This gives a product to be applied undiluted
having an active compound content of 10% by weight.
For seed treatment, it is customary to employ water-soluble concentrates (LS),
suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS),
emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF). These
formulations can be applied to the seed undiluted or, preferably, diluted. Application
can be prior to sowing.
Preference is given to using FS formulations for seed treatment. Usually, such
formulations comprise from 1 to 800 g of active compound/I, from 1 to 200 g of
surfactants/I, from 0 to 200 g of antifreeze agents/I, from 0 to 400 g of binders/I, from 0
to 200 g of colorants/I and solvents, preferably water.
The active compounds can be used as such, in the form of their formulations or the use
forms prepared therefrom, for example in the form of directly sprayable solutions,
powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable
products, materials for spreading, or granules, by means of spraying, atomizing,
dusting, spreading or pouring. The use forms depend entirely on the intended
purposes; they are intended to ensure in each case the finest possible distribution of
the active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable
powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions,
pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can
be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
However, it is also possible to prepare concentrates composed of active substance,
wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, with these
concentrates being suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied

PF 56210
26
within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from
0.01 to 1%.
The active compounds may also be used successfully in the ultra-low-volume process
(ULV), it being possible to apply formulations comprising over 95% by weight of active
compound, or even to apply the active compound without additives.
Oils of various types, wetters, adjuvants, herbicides, fungicides, other pesticides, or
bactericides may be added to the active compounds even, if appropriate, not until
immediately prior to use (tank mix). These agents can be admixed with the
compositions according to the invention in a weight ratio of from 1:100 to 100:1,
preferably from 1:10 to 10:1.
Suitable adjuvants in this context are in particular: organic modified polysiloxanes, for
example Break Thru S 240®; alcohol alkoxylates, for example Atplus 245®, Atplus MBA
1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, for example
Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates, for example
Lutensol XP 80®; and sodium dioctylsulfosuccinate, for example Leophen RA®.
The compounds I and II or the mixtures or the corresponding formulations are applied
by treating the harmful fungi, and the plants, seeds, soils, areas, materials or spaces to
be kept free from them, with a fungicidally effective amount of the mixture or, in the
case of separate application, of the compounds I and II. Application can be carried out
before or after infection by the harmful fungi.
The fungicidal effect of the compound and the mixtures can be demonstrated by the
following tests:
The active compounds were separately or jointly prepared as a stock solution
comprising 25 mg of active compound which was made up to 10 ml using a mixture of
acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having
emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio
of soivent/emulsifier of 99 to 1. The mixture was then made up with water to 100 ml.
This stock solution was diluted with the solvent/emulsifier/water mixture described to
the concentration of active compounds stated below.
The visually determined percentages of infected leaf areas were converted into
efficacies in % of the untreated control:
The efficacy (E) is calculated as follows using Abbot's formula:

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27
E = (1 -a/b) • 100
a corresponds to the fungal infection of the treated plants in % and
P corresponds to the fungal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that
of the untreated control plants; an efficacy of 100 means that the treated plants were
not infected.
The expected efficacies of combinations of active compounds were determined using
Colby's formula (Colby, S.R. "Calculating synergistic and antagonistic responses of
herbicide combinations", Weeds, 15, 20-22, 1967) and compared with the observed
efficacies.
Colby's formula:
E = x + y-x-y/100
E expected efficacy, expressed in % of the untreated control, when using the
mixture of the active compounds A and B at the concentrations a and b
x efficacy, expressed in % of the untreated control, when using the active
compound A at the concentration a
y efficacy, expressed in % of the untreated control, when using the active
compound B at the concentration b
Greenhouse experiments
Use example 1 - activity against Botrytis cinerea on bell peppers
Bell pepper seedlings of the cultivar "Neusiedler Ideal Elite" were, after 2-3 leaves
were well developed, sprayed to runoff point with an aqueous suspension in the active
compound concentration stated below. The next day, the treated plants were
inoculated with a spore suspension of Botrytis cinerea which comprised 1.7 x 106
spores/ml in a 2% strength biomalt solution. The test plants were then placed in a dark
climatized chamber at 22 to 24°C and high atmospheric humidity. After 5 days, the
extent of the fungal infection on the leaves could be determined visually in %.

PF 56210
28

No. Activecompound Cone,[ppm] Ratio Observedactivity (%) Activity calculatedaccording to Colby (%)
1 - (control) - 0(100%infection)
2 I-B 6316 2010
3 dithianon (F11) 63 10
4 I-B + F11 63 + 63 1 :1 60 28
5 I-B + F11 16 + 63 1 :4 50 19
Use example 2 - curative activity against brown rust of wheat caused by Puccinia
recondita
Leaves of wheat seedlings of the cultivar "Kanzler" cultivated in pots were inoculated with
a spore suspension of brown rust (Puccinia recondita). The pots were then placed in a
chamber with high atmospheric humidity (90 to 95%) and at 20 to 22°C for 24 hours.
During this time, the spores germinated and the germ tubes penetrated into leaf tissue.
The next day, the infected plants were sprayed to runoff point with the solution of active
compound described above having the active compound concentration stated below.
After the spray coating had dried on, the test plants were cultivated in a greenhouse at
temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for
7 days. The extent of the rust fungus development on the leaves was then determined.

No. Activecompound Cone,[ppm] Ratio Observedactivity (%) Activity calculatedaccording to Colby(%)
6 - (control) - 0 (85%infection)
7 I-B 16 6
8 kresoxim-methyl (B5) 634 180
9 boscalid (C3) 16 0
10 metalaxyl (C8) 16 0
11 dimethomorph(C17) 82 00
12 I-B + B5 16 + 63 1 :4 99 22
13 I-B + C3 16 + 16 1 : 1 82 6
14 I-B + C8 16 + 16 1 : 1 94 6
15 I-B + C17 16 + 8 2: 1 92 6
16 I-B + C17 16+2 8 : 1 76 6

PF 56210
29
Microtiter tests
The active compounds were formulated separately in DMSO as a stock solution having a
concentration of 10 000 ppm. Fluazinam and epoxiconazole were used as commercial
formulations and diluted with water to give a 10 000 ppm stock solution.
The measured parameters were compared to the growth of the active compound-free
control variant and the fungus- and active compound-free blank value to determine the
relative growth in % of the pathogens in the individual active compounds.
Use example 3 - activity against the late blight pathogen Phytophthora infestans in the
microtiter test
The stock solution is pipetted into a microtiter piate (MTP) and diluted with a pea juice-
based aqueous fungus nutrient medium to the stated active compound concentration.
An aqueous zoospore suspension of Phytophthora infestans was then added. The
plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using
an absorption photometer, the MTPs were measured at 405 nm on day 7 after the
inoculation.

No. Activecompound Cone,[ppm] Ratio Observedactivity (%) Activity calculatedaccording to Colby(%)
17 I-B 12532840.25 57352754
18 epoxiconazole(A7) 12532 319
19 prothioconazole(A19) 328 460
20 kresoxim-methyl (B5) 1 36
21 fluazinam (D1) 1 0
22 I-B + A7 125 + 32 4: 1 73 61
23 I-B + A7 32 + 125 1 :4 88 55
24 I-B + A19 32 + 8 4: 1 47 35
25 I-B + A19 8 + 32 1 :4 77 60
26 I-B + B5 4 + 1 4:1 65 39

PF 56210
30

No. Activecompound Cone.[PPm] Ratio Observedactivity (%) Activity calculatedaccording to Colby(%)
27 I-B + B5 0.25 + 1 1 :4 53 38
28 I-B + D1 4 + 1 4:1 92 5
29 I-B + D1 0.25 + 1 1 :4 41 5
Use example 4 - activity against the gray mold pathogen Botrytis cinerea in the microtiter
test
The stock solution was pipetted into a microtiter plate (MTP) and diluted with a malt-
based aqueous fungus nutrient medium to the stated active compound concentration.
An aqueous spore suspension of Botrytis cinerea was then added. The plates were
placed in a water vapor-saturated chamber at temperatures of 18°C. Using an
absorption photometer, the MTPs were measured at 405 nm on day 7 after the
inoculation.

No. Activecompound Cone,[ppm] Ratio Observedactivity (%) Activity calculatedaccording to Colby(%)
30 I-B 410.25 67402
31 epoxiconazole(A7) 1 2
32 cyazofamid(A30) 1 00
33 pyraclostrobin(B8) 0.25 20
34 mancozeb (E1) 4 9
35 I-B + A7 1 + 1 1 :1 67 41
36 I-B + A30 1 + 0.25 4:1 58 40
37 I-B + A30 1 +4 1 :4 100 40
38 I-B + B8 0.25 + 0.25 1 :1 55 22
39 I-B + E1 4 + 4 1 :1 97 70
The test results show that, by virtue of the synergism, the mixtures according to the
invention are considerably more active than had been predicted using Colby's formula.

PF 56210
31
We claim:
1. A fungicidal mixture for controlling phytopathogenic harmful fungi, which mixture
comprises two active components:
1) carbamate oxime ethers of the formula I.

2) at least one active compound II selected from the following groups:
A) azoles, such as bitertanol, bromuconazole, cyproconazole,
difenoconazole, diniconazole, enilconazol, epoxiconazole,
fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole,
imibenconazole, ipconazole, metconazole, myclobutanil,
penconazole, propiconazole, prothioconazole, simeconazoie, triadi-
mefon, triadimenol, tebuconazole, tetraconazole, triticonazole,
prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl,
carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole,
hymexazole,
B) strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin,
fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,
picoxystrobin, pyraclostrobin, trifloxystrobin;
C) carboxamides, such as carboxin, benalaxyl, boscalid, fenhexamid,
flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace,
oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil,
3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide,
dimethomorph, flumorph,
flumetover, fluopicolide (picobenzamid), zoxamide,
carpropamid, diclocymet, mandipropamid,
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-
methanesulfonylamino-3-methylbutyramide,
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-
ethanesulfonylamino-3-methylbutyramide,


PF 56210
32
amides of the formula III,
in which the variables and the index are as defined below:
R1 and R2 independently of one another are hydrogen, halogen, d-
C6-alkyl or d-C6 haloalkyl, cyano, nitro, methoxy or trifluoromethoxy,
with the proviso that R1 and R2 are not simultaneously hydrogen, and
R3 is CF3 or CHF2;
D) heterocyclic compounds, such as fluazinam, pyrifenox,
bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol,
pyrimethanil,
triforine,
fenpiclonil, fludioxonil,
aldimorph, dodemorph, fenpropimorph, tridemorph,
fenpropidin,
iprodione, procymidone, vinclozolin,
famoxadone, fenamidone, octhilinone, probenazole,
5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri-
azolo[1,5-a]pyrimidine,
anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole,
2-butoxy-6-iodo-3-propylchromen-4-one
acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil,
quinoxyfen, or
N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-
[1,2,4]triazole-1-sulfonamide;
E) carbamates, such as mancozeb, maneb, metam, metiram, ferbam,
propineb, thiram, zineb, ziram,
diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb,
methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl-
butyrylamino)propanoate,
F) other fungicides, selected from the group consisting of
guanidines: dodine, iminoctadine, guazatine,

PF 56210
33
antibiotics: kasugamycin, streptomycin, polyoxine, validamycin A,
nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane,
organometallic compounds: fentin salts, such as fentin acetate,
organophosphorus compounds: edifenphos, iprobenfos, fosetyl,
fosetyl aluminum, phosphorous acid and its salts, pyrazophos,
tolclofos-methyl,
organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide,
hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-
methyl, tolylfluanid,
inorganic active compounds: Bordeaux mixture, copper acetate,
copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl,
metrafenone and spiroxamine,
in a synergistically effective amount.
The fungicidal mixture according to claim 1, which comprises, as carbamate
oxime ether of the formula I, the compound I-B

2. The fungicidal mixture according to claim 1, which comprises, as carbamate
oxime ether of the formula I, the compound I-A

4. The fungicidal mixture according to any of claims 1 to 3 which comprises the
compound of the formula I and the compound of the formula II in a weight ratio of
from 100:1 to 1:100.
5. A composition comprising a liquid or solid carrier and a mixture according to any
of claims 1 to 4.
6. A method for controlling phytopathogenic harmful fungi which comprises treating
the fungi, their habitat or the seed, the soil or the plants to be protected against

PF 56210
34
fungal attack with an effective amount of the compound I and the compound II
according to claim 1.
7. The method according to claim 6, wherein the compounds I and II according to
claim 1 are applied simultaneously, that is jointly or separately, or in succession.
8. The method according to claim 6 or 7, wherein the compounds I and II according
to claim 1 or the mixture according to any of claims 1 to 3 are/is applied in an
amount of from 5 g/ha to 2000 g/ha.
9. The method according to claim 6 or 7, wherein the compounds I and II according
to claim 1 or the mixture according to any of claims 1 to 4 are/is applied in an
amount of from 1 to 1000 g/100 kg of seed.
10. Seed comprising the mixture according to any of claims 1 to 4 in an amount of
from 1 to 1000 g/100 kg.
11. The use of the compounds I and II according to claim 1 for preparing a
composition suitable for controlling harmful fungi.

Fungicidal mixtures, comprising as active components
1) carbamate oxime ethers of the formula I,

in which X is N or CH,
and
2) at least one active compound II selected from the group of the azoles, stro-
bilurins, carboxamides, heterocyclic compounds, carbamates, guanidines,
antibiotics, nitrophenyl derivatives, sulfur-containing heterocyclyl com-
pounds, organometallic compounds, organophosphorus compounds, or-
ganochlorine compounds, inorganic active compounds, cyflufenamid, cy-
moxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine,
in a synergistically effective amount, methods for controlling harmful fungi using mix-
tures of the compound I with active compounds II, the use of the compound I with ac-
tive compounds II for preparing such mixtures and compositions comprising these mix-
tures.

Documents:

02040-kolnp-2007-abstract.pdf

02040-kolnp-2007-claims.pdf

02040-kolnp-2007-correspondence others 1.1.pdf

02040-kolnp-2007-correspondence others 1.2.pdf

02040-kolnp-2007-correspondence others.pdf

02040-kolnp-2007-description complete.pdf

02040-kolnp-2007-form 1.pdf

02040-kolnp-2007-form 18.pdf

02040-kolnp-2007-form 3 1.1.pdf

02040-kolnp-2007-form 3.pdf

02040-kolnp-2007-form 5 1.1.pdf

02040-kolnp-2007-form 5.pdf

02040-kolnp-2007-pct request form.pdf

02040-kolnp-2007-priority document.pdf

2040-KOLNP-2007-ABSTRACT.pdf

2040-KOLNP-2007-AMANDED CLAIMS.pdf

2040-KOLNP-2007-CANCELLED PAGES.pdf

2040-KOLNP-2007-CORRESPONDENCE OTHERS 1.3.pdf

2040-KOLNP-2007-DESCRIPTION (COMPLETE).pdf

2040-KOLNP-2007-FORM 13.pdf

2040-KOLNP-2007-FORM 2.pdf

2040-KOLNP-2007-FORM 3-1.2.pdf

2040-KOLNP-2007-FORM 5-1.2.pdf

2040-KOLNP-2007-PA.pdf

2040-KOLNP-2007-PCT IPER.pdf

2040-KOLNP-2007-PETITION UNDER RULE 137.pdf

2040-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

abstract-02040-kolnp-2007.jpg


Patent Number 242543
Indian Patent Application Number 2040/KOLNP/2007
PG Journal Number 36/2010
Publication Date 03-Sep-2010
Grant Date 31-Aug-2010
Date of Filing 05-Jun-2007
Name of Patentee BASF AKTIENGESELLSCHAFT
Applicant Address 67056 LUDWIGSHAFEN
Inventors:
# Inventor's Name Inventor's Address
1 GEWEHR MARKUS GOETHESTR. 21, 56288 KASTELLAUN
2 NIEDENBRUCK, MATTHIAS ALBERT-EINSTEIN-ALLEE 3, 67117 LIMBURGERHOF
3 STIERL, REINHARD JAHNSTR. 8, 67251 FRIENSHEIM
PCT International Classification Number A01N 47/12
PCT International Application Number PCT/EP2005/013816
PCT International Filing date 2005-12-21
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10 2004 063 382.7 2004-12-23 Germany