AU676031B2 - Fungicidal mixture - Google Patents

Abstract

The invention concerns a fungicidal mixture comprising (a) alpha -methoximino-2-[(2-methylphenoxy)methyl]-phenylacetic acid methyl ester represented by formula (I) and (b) 4-(2-methyl-3-[4-tert.-butylphenyl]-propyl)-2,6-dimethylmorpholine (fenpropimorph) represented by formula (II) or the active substance tridemorph or the active substance fenpropidin and (c) the active substance prochloraz or another azol active substance. The invention also concerns a method of controlling fungi using this mixture.

Description

0050/43931 Fungicidal composition The present invention relates to fungicidal compositions having a synergistic fungicidal action and methods of combating fungi with these compositions.

It is known (EP 253 213) to use methyl a-methoximino-2-((2-methylphenoxy)-methyl -phenylacetate

H

3 0- CH 2 C=NOCH3

H

3 COO C as a fungicide. It is also known (DE 26 56 747) to use the active ingredient 4-(2-methyl-3-[4-tert.-butylphenyl] -propyl)-2,6-dimethylmorpholine

CH

3

CH

3

CH

3

CH

3 -C CH- CH CH 2 N O 251

CH

3 CH3 or the active ingredient tridemorph or the active ingredient fenpropidin or salts thereof as fungicides.

It is further known (EP 72 156) to use N-propyl-N-[2,4,6-trichlorophenoxy)-ethyllimidazole-l-carboxamide C~l Pr Cl 0 [CH212-N CtIN 0 Cl as a fungicide.

Furthermore, numerous azole active ingredients are known which have a fungicidal action, namely

RAL

LU

NV

'9N 0pS 0050/ 43931 2 (l,2,4-triazol-1l-ylmethyl)-2-(4-fluorophenyl)-3- (2-chiorophenyl)-oxirane of the formula

SN

l-butyl-l- 4-dichiorophenyl) 4-triazol-1-yl) -ethanol (common name hexaconazole), 1-E (2-chlorophenyl)methyl]-l-(l, 1-dimethyl)-2-(l,2,4--triazol-l-yl-ethanol, 1-(4-fluorophenyl)-l-(2fluorophenyl)-2- (1,2,4-triazol-l-yl)-ethanol (common name flutriafol), (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-l,:2,4-triazol-l-ylmethyl,)-butyronitrile, RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- 4-dichiorophenyl) -tetrahydrofurfuryl] -lH- 1,2,4-triazole, 3-(2,4-dichlorophenyl.)-2-(lH-,2,4-triazol-l-yl) -quinazolin-4 (3H) -one, (RS)-2,2-dimethyl-3-(2-chlorobenv zyl) -4-(lH-l,2,4-triazol-l-yl)-butan-3-ol, bitertanol, triadimeton, triadimenol, cyproconazole, dichlobutrazol, difenoconazole, diniconazole, etaconaz-ole, propiconazole, flusilazole, tebuconazole, imazalil, penconazole, tetraconazole or a salt of such an azole active ingredient.

we have now found that a composition of a) methyl a-methoximino-2- (2-methylphenoxy) -methyl]I -phenylacetate

H

3 0- C11 2 "q

~H

3 CO00< C=NOCH 3 and b) 4- (2-methyl-3- £4-tert.-butylphenyl) -propyl) 6-dimethylmorpholime (fenpropimorph) CH3

CH

3

CH

3 el 3 C CH 2 CH- CH2-N 0 1 0050/43931 3 or the active ingredient tridemorph or the active ingredient fenpropidin and c) an azole active ingredient selected from the group consisting of N-propyl-N- 12,4, 6-trichiorophenoxy) ethyl] imidazole- 1-carboxainide Cl

P

Cl 0- N- O CH]- C-N' 0 Cl (Z)-2-(1,2,4-triazol-1-ylmethyl)-2-(4-fluorophenyl)-3- (2-chlorophenyl)-oxirane of the formula KN- 0

NJ

N. Cl l-butyl-l- 4-dichlorophenyl) 2, 4-triazol-l-yl) -ethanol (common name hexaconazole), 1-1(2-chlorophenyl)methyll-l- l-dimethyl)-2- 4-triazol-l-yl-ethanol, 1-(4-fluorophenyl)-l-(2.-fluorophenyl)-2-(1,2,4-triazol-l-yl)-ethanol (common name flutriafol), (4-chlorophenyl) -2-phenyl-2- 2, 4-triazol-l-ylmethyl) -butyronitrile, 1-11(2 RS, 4 RS; 2 RS, 4 SR)-4-bromo-2-(2,4-dichlorophenyl)-tetrahydrofurfuryl]-lH-l,2,4-triazole, 3-(2,4-dichlorophenyl) (1H-l,2, 4-triazol-1-yl) -quinazolin-4 (3H) -one, (RS) -2 ,2-dimethyl-3- (2-chlorobenzyl) 2 ,4-triazol-l-yl) -butan-3-ol, bitertanol, triadimef on, triadimenol, cyproconazole, dichlobutrazol, difenoconazole, diniconazole, etaconazole, propiconazole, flusilazole, tebuconazole, imazalii, penconazole, tetraconazole or a salt of such an azole active ingredient, has a synergistic fungicidal action. The weight ratio of compounds b) and c) is selected in such a way as to give a synergistic fungicidal action, for example from 0050/43931 4 to 1:10 to 1:10 to 1, for instance 5 to 1:5 to 1:5 to 1, especially 3 to 1:3 to 1:3 to 1, and preferably 2 to 1:2 to 1:2 to 1. The ratio of may for example be 10:1:1 to 1:10:1 to 1:1:10. The synergistic action of the composition is apparent from the fact that the fungicidal action of the composition of a) b) c) is greater than the sum of the fungicidal actions of of b) and of c).

With regardd to the -C=N double bond, component a) may be present in two stereoisomeric forms. The isomer is preferred.

The invention embraces compositions containing the pure isomers of compound especially the isomer, and compositions containing mixtures of the isomers.

The component fenpropimorph may be present in two stereoisomeric forms (morpholine ring), the cis isomer being preferred.

The invention embraces compositions containing the pure isomers of the compound fenpropimorph, especially the cis isomer, and compositions containing mixtures of the isomers.

Compositions containing component a) predominantly as (E) isomer and at the same time component b) predominantly as cis isomer are preferred.

CH

3

I

H 0- CH 2

OCH

3

C=N

H

3

COOC

CH

3

CH

3 CH3 CH3-C CH 2 CH- CH-- N 0

CH

3 CH3 a, isomer b, cis isomer The the the active ingredient fenpropimorph b) may also be present in form of its salts. These compositions too are embraced by invention.

0050/43931 Salts are produced by reaction with acids, hydrohalo acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, or sulfuric acid, phosphoric acid, nitric acid, or organic acids such as acetic acid, trifluoracetic acid, trichloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-tolueiesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid or 1,2-naphthalenedisulfonic acid.

In practice, the pure active ingredients b) and c) are advantageously used, to which further active ingredients such as insecticides, acaricides, nematicides, herbicides, other fungicides, growth regulatores and/or fertilizers may be added.

The fungicidal compositions according to the invention may be applied for instance in the form of directly sprayable solutions.

powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

Normally, the plants are sprayed or dusted with the compositions or the seeds of the plants are treated with the compositions.

The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics xylene), chlorinated aromatics chlorobenzenes), paraffins crude oil fractions), alcohols methanol, butanol), ketones cyclohexanone), amines ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals kaolins, aluminas, talc and chalk) and ground synthetic minerals highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.

L III 0050/43931 6 Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers.

Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The compositions are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and may be used as foliar and soil fungicides.

The fungicidal compositions are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals i,n horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

I

b~ 0050/43931 7 The compounds are applied by treating the seeds, plants, materials or soil to be protected against fungus attack with a fungicidally effective amount of the active ingredients.

The compounds may be applied before or after infection of the materials, plants or seeds by the fungi.

The compositions are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctcnia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Rhynchosporium in cereals, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.

The novel compositions may also be used for protecting materials (timber), for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient.

The application rates depend on the type of effect desired, but are generally from 0.01 to 3 kg of active ingredient composition per hectare.

When the compositions are used for treating seed, application rates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are generally required.

M

0050/43931 8 Biological experiments Example 1 Eradicative action on wheat mildew Wheat plants of the "Kanzler" variety were inoculated at the 3-leaf stage with triazole-resistant wheat mildew (Erysiphe graminis var. tritici) and treated at a degree of fungus attack of about 30% with aqueous active ingredient formulations in the concentrations given. The amount of water corresponded to 200 1/h.

The plants were cultivated in the greenhouse for 20 days at 10 to 220C. The experiment was then evaluated by determining the leaf area under attack in percent. These figures were converted into degrees of action. The expected degrees of action of the active ingredient composition were determined by the Colby formula (Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, S. 20-22, 1967) and compared with the degrees of action observed.

The values for the fungicidal action varied between the various experiments because the plants exhibited varying degrees of attack, which meant that the figures for the fungicidal action vary too. For this reason, Only the results within the same experiment can be compared with one another.

Colby formula E y x-y/100 E expected degree of action, expressed in of the untreated control, when active ingredients A and B are used in concentrations of m and n x degree of action, expressed in of the untreated control, when active ingredient A is used in a concentration of m y degree of action, expressed in of the untreated control, when active ingredient B is used in a concentration of n Ilr ilr 0050/43931.

Active ingredient methyl a -methoxirnino- 2- (2 -me thylphenoxy) -met hy 1J -pheny- H3 0- CH 2 N.H3COO<CNOH (Ct) -cis-4-[3- (4-tert-butylphenyl) -2-methylpropyl] 6-di- ".ylmorpholine (fenpropimorph) C3

CH

3 CH 3

ICIH

3 C143c- CH 2 CH -CH 2 N 0 III. 2-(1,2,4-triazol-1-ylmethyl)-2-(4-fluorophenyl)-3- (2-chlorophenyl) -oxirane (epoxiconazol) rN NN- 0 N.

N

C C H Cl 1- (N-propyl-N-2- 6-trichlorophenoxy)ethylcarbamoyl) imidazole (prochloraz) 0

,,,CH

2

-CH

2 0 6 a--u I

C

3 H7 Active ingredient combination Active ingredient I fenpropimorph 105 :210 0050/43931 Active ingredient combination Active ingredient I epoxiconazol 1 1 Active ingredient combination Active ingredient I prochloraz 1 1

VII.

VIII. Active ingredient fenpropimorph prochloraz 281 200 combination Active ingredient combination fenpropimorph epoxiconazol 3:1 Table 1 Erysiphe graminis test (wheat) eradicative Triazole-resistant Erysiphe graminis Active ingredient Active ingredient con- Degree of action centration in the spray in of the unliquor in treated control Control (untreated) 0 I. prior art a.i. 0.05 EP 253 213 II. p-ior art a.i. 0.05 47 fenpropimorph, DE 2 656 747 III. prior art a.i. 0.05 26 epoxiconazol IV. prior art a.i. 0.05 24 prochloraz, EP 72 156 V. prior art a.i. combina- 0.05 tion a.i. I fenpropimorph EP 524 496 VI. prior art a.i. combina- 0.05 52 tion a.i. I epoxiconazol EP 531 837 VII. prior art a.i. combina- 0.05 52 tion a.i. I prochloraz EP 531 837 0050/43931 Active ingredient Active ingredient con- Degree of action centration in the spray in of the unliquor in treated control VIII. prior art a.i. combi- 0.05 48 nation fenpropimorph prcchloraz IX. prior art a.i. combina- 0.05 tion fenpropimorph epoxiconazol EP 425 857 Compositions according to the invention I. VIII. ratio 1:3 0.01 0.03 58 I. IX. ratio 1:3 0.01 0.03 62 II. VI. ratio 1:3 0.01 0.03 61 II. VII. ratio 1:3 0.01 0.03 59 III. V. ratio 1:3 0.01 0.03 71 IV. V. ratio 1:3 0.01 0.03 69 The results show that 0.04% (0.01 0.03) of the compositions containing three active ingredients has a better fungicidal action than 0.05% of the individual active ingredients and the twocomponent active ingredient composition.

The same experiment, carried out with triazole-sensitive Erysiphe graminis, confirmed the results given in Table 1.

Table 2 Erysiphe graminis test (wheat) eradicative Triazole-resistant Erysiphe graminis Active ingredient Active ingredient con- Degree of action centration in the spray in of the unliquor in treated control Control (untreated) 0 I. prior art a.i. 0.1 0.01 29 II. prior art a.i. 0.1 52 fenpropimorph 0.01 III. prior art a.i. 0.1 36 epoxiconazol 0.01 IV. prior art a.i. 0.1 29 prochloraz 0.01 V. prior art a.i. 0.1 83 Sa.i. I fenpropimorph 0.01 0050/43931t Active ingredient Active ingredient con- Degree of action cent ion in the spray in of the unliquor in treated control VI. prior art a.i. combina- 0.1 67 tion 0.01 38 a.i. I epoxiconazol VII. prior art a.i. combina- 0.1 tion 0.01 34 a.i. I prochloram VIII. prior art a.i. combi- 0.1 nation 0.01 38 fenpropimorph prochloraz IX. prior art a.i. composi- 0.1 tion 0.01 42 fenpropimorph epoxiconazol Compositions according to the invention degree of ac- degree of action observed tion calcula ted*) I. VIII. 0.01 0.01 69 55.98 ratio 1:1 I. VIII. 0.1 0.1 93 79.75 ratio 1:1 I. VIII. 0.01 81 72.10 ratio 10:1 I. VIII. 0.01 0.1 73 60.05 ratio 1:10 I. IX. 0.01 0.01 71 58.85 ratio 1:1 I. IX. 0.1 0.1 100 82.00 ratio 1:1 I. IX. 0.1 0.01 88 73.90 ratio 10:1 I. IX. 0.01 0.1 83 71.60 ratio 1:10 I. VI. 0.01 0.01 64 53.50 ratio 1:1 I. VI. 0.1 0.1 100 84.16 ratio 1:1 I. VI. 0.1 0.01 86 70..24 ratio 10:1 I. VI. 0.01 0.1 88 75.25 ratio 1:10 I. VII. 0.01 0.01 62 50.50 ratio 1:1 calculated by the Colby formula 0050/43931 degree of ac- degree of action observed tion calculated*) I. VII. 0.1 0.1 100 83.20 ratio 1:1 I. VII. 0.1 0.01 83 68.32 ratio 10:1 I. VII. 0.01 0.1 86 73.75 ratio 1:10 III. V. 0.01 0.01 71 59.50 ratio 1:1 III. V. 0.1 0.1 100 89.12 ratio 1:1 III. V. 0.1 0.01 100 84.70 ratio 10:1 III. V. 0.01 0.1 86 71.20 ratio 1:10 IV. V. 0.01 0.01 69 57.25 ratio 1:1 IV. V. 0.1 0.1 100 87.93 ratio 1:1 IV. V. 0.1 0.01 83 68.05 ratio 10:1 IV. V. 0.01 0.1 98 83.85 ratio 1:10 In these results for various three-component active ingredient compositions, the observed degrees of action were always greater than the degrees of action calculated by the Colby formula.

The same experiment, carried out with triazole-resistant Erysiphe graminis, confirmed the results given in Table 2.

Claims (1)

1. 51. A fungicidal agent containing a fungicidally effective amount of a composition of a) methyl (x -methoximino- 2- E(2 -me thyilphenoxy) -met hyl1J -pheny- lacetate H 3 0-CH C=NOCH3 0C HjLUO and b) 4-(2-methyl-3-4-tert-butylphenyl-propyJ)- 2 1 6-dimethlyl- P morpholime, (fenpropimorph) CH 3 CH 3 CH 3 C 'CH 2 CH -CH2- N 0 or the active ingredient tridemorph-or the active ingredient fenpropidin and c) an azole active ingredient selected from the following group N-propyl-N- 12 ,4'6-trichlorophenoxy) ethyll imidazole- 1-carboxamid Cl Pr Cl [CH 2 2 NC-N 7 4 0 Cl 4 5 9A4 1,2,4-triazol-1 -yI met hyi)-2-(4-f Iluorop hen yl)-3-(2-chlIo rop hen yl oxirane of the formula 1 -butyl-1 -(2,4-dichlorophenyl)-2-(1 ,2,4-triazol-1 -yl)-ethanoI (common name hexaconazole), 1 -(4-fluorophenyl)-1 -(2-fluorophenyl)-2-(1 ,2,4- triazol-1 -yl)-ethanol (common name flutriafol), (RS)-4-(4-chlorophenyl)-2- phenyl-2-(1 H-i ,2,4-triazol-1 -ylmethyl)-butyronitrile, 1 IRS, 4RS, 2 RS, 4 SR)-4-bromo-2-(2,4-dichlorophenyl)-tetrahydrofurfuryl]-1 H-i ,2,4-tria- zole, 3-(2,4-dichlorophenyl)-2-(1 H-i ,2,4-triazol-1 -yl)-quinazolin-4 (3H)- one, (RS)-2,2-di methyl-3-(2-ch lo robe nzyl)-4- (1 H-i 1,2,4-t ri azol1- 1 -yl) butan- 3-ol, bitertanol, triadimefon, triadimenol, cyproconazole, dichiobutrazol, difenoconazole, diniconazole, etaconazole, propiconazole, flusilazole, tebuconazole, imazalil, penconazole, tetraconazole or a salt of such an azole active ingredient, compounds b) and c) being contained in such a weight ratio so as to create a synergistic fungicidal effect. 2. A method of combating fungi, wherein a fungicidally effective amount of a composition of a) methyl a-methoxi mi no-2-[(2-m ethyl ph enoxy)-m ethyll-p henyl acetate CH 3 -C Y and b) _tT 4-(2-methyl-3-[4-tert-butylphenyl]-propyl)-2, 6-dimethylmorpholine (fen- propimorph) 16 C!.a OH 3 0H 3 -C CQr-0 2 H -CH 2 N 0 OH 3 OH 3 or the active ingredient tridemorph or the active ingredient fenpropidin and c) an azole active ingredient selected from the following group N-propyl-N-[2,4,6-trichlorophenoxy)ethyl]imidazole-1 -carboxamid Cl Pr cl 0-[0H 2 2 -N--N2 01 0 ,2,4-triazol-1 -yl met hyl)-2-(4-fluo rophe nyl)-3 -corop hen yl)- oxirane of the formula 1 -butyl-i -(2,4-diohlorophenyl)-2-(1 ,2,4-triazol-i -yI)-ethanol (common name hexaconazole), 1 -(4-,fluorophenyl)-1 -(2-fluorophenyl)-2-(i ,2,4- triazol-i -yl)-ethanol (common name flutriafol), (RS)-4-(4-chlorophenyl)-2- phenyl-2-(1 H-i ,2,4-triazol-1 -ylmethyl)-butyronitrile, 1 RS, 4RS, 2 RS, 4 SR)-4-bromo-2-(2,4-dichlorophenyl)-tetrahydrofurfuryl-1 H-i ,2,4-tria- zole, 3-(2,4-dichlorophenyl)-2-(1 H-i ,2,4-triazol-1 -yI)-quinazolin-4 (3H)- one, (RS)-2,2-di methyl-3-(2-chlo robe nzyl)-4-(1 H-i 1,2,4-triazol-i1 -yl) butan- 3-ol, bitertanol, triadimefon, triadimenol, cyproconazole, dichlobutraz-ol, difenoconazole, diniconazole, etaconazole, propiconazole, flusilazole, tebuconazole, imazalil, penconazole, tetraconazole or a salt of such an azole active ingredient, 17 is allowed to act on the fungi or the materials, areas, plants or seed threatened by fungus attack, said compounds b) and c) being contained in such a weight ratio in the composition so as to create a synergistic fungicidal effect. 3. A fungicide as claimed in claim 1, containing compounds b) and c) in a weight ratio of a:b:c of from 10 to 1:10 to 1:10 to 1. DATED this 15th day of November, 1996 BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS S: 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA *o AU6376094.WPC[DOC. 009]LCG/SI:EK INTIDANAfJAONAC WL AR1 U401 1101*1 mrl Apphoitlatin No POT/EP 94/00741 A. CLASSIFICATION OI SUJI!CI' MA' TiT!R IPC 5 A01N37/50 //(A01N37/50,55:00,47:38, ,43:84,43653,43:50,43:40) According to International Patent Classificaton (IPC) or to both natonal classification and IPC B. FIELDS SEARCIIED Minimum documentation searched (classificaUon system followed by classificaion symbols) IPC 5 AO1N Documentauon searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted dunng the international search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category Citaton of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A EP,A,O 524 496 (BASF) 27 January 1993 cited in the application A EP,A,0 531 837 (BASF) 17 March 1993 cited in the application j Further documents are listed in the continuation of box C Patent family members are listed in annex. Specal categories of rated documents Special categories of cted documents later document published after the international filing date Sor prionty date and not in conflict with the application but document defining the general state of the art which is not cited to understand the principle or theoryunderlying the considered to be of particular relevance invention E earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of paraculr r:levance; the claimed invention citation or other special reason (as specified) cannot he considered to involve an inventive step when the document refernng to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the pnority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the intemauonal search report 1 June 1994 1 Name and mailing address of the ISA Authonzed officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rilswijk Tel. 31-70) 340-2040, Tx. 31 651 epo ni, Deorte, Fax: 31-70) 340-3016 Form PCT'ISA.210 (lecond sheet) (July 1992) I NTCANATI %N AL $ICAtCII 101A o pIi~iN in( nii wrion afllyrn~nhr" CT/VP 94/00741 Patent document Publication Patent faumily Publication cited in search rcport date member(s) date EP-A-0524496 27-01-93 OE-A- 4124255 28-01-93 AU-A- 2043592 28-01-193 JP-A- 5194111 03-08-93 US-A- 5286724 15-02-94 US-A- 5242920 07-09-93 EP-A-053 1837 17-03-93 OE-A- 4130298 18-03-93 AU-A- 2353692 18-03-93 CA-A- 2077245 13-03-93 JP-A- 5221811 31-08-93 US-A- 5260326 09-11-93 Frm PCT'IS&210 (patent family annex) (July 1992) INTreRNATIONALER RECOERCIIENB3RICHT I Iwui'kr A~ lw PCT/EP 94/00741 K1.ASSIFIZ/IERUNG DVS* A NM~LI)tINGSGIr~GIANSI'ANDI'S IPK 5 A01N37/50 //(A01N37/50, 55:00,47:38,43:84,43:653,43:50,43:40) Nach der InternnUonalen IPatnticassifikation cider nach dcr nationalcn Kiassifikation und der IPK Rcchcrcliicrtcr Mindestprilfstoff (Klassifikauonystcm und KMassifikalionssyrnbolc) IPK 5 A01N Rcchcrchicrtc abcr micht zumn Mindcstpr-Ufstoff gcha'rcndc Vcroffrndtchungcri, sowelt dicsc untcr dic rcchcrchicrtcn Gebicte fallen Wahrend der intcrnationalcni Recherche konsultierte cektronische 1)steribank (Name dler Datenbank und evii. verwendete Suchbegriffe) C. ALS WEiSENTLICH ANGESEIIENE U NTERLAGEN__________ Katcgone' Bezeichnung der Veroffcntlichung, sowelt erforderlich tinter Angahc der in Betracht kommenden Teile Mer. Anspruch Nr. A EP,A,0 524 496 (BASF) 27. Januar 1993 in der Anmeldung erwahnt A EP,A,0 531 837 (BASF) 17. Mdrz 1993 in der Anmeldung erwdhnt Weitere Vcrolfentlichungen sind der Fortscizung von Feld C zu M71 Sichc Anhang Patentfamile entrnchmcn LA I *Besondere Kategonen von angegebenen Vcroffcntlichungcn 7- SPatecre Verbffentlichung, dic nach dens internationalen Animeidedatum erdffetlicun ie en algeeme Stad dr Tchni ciinirtder dem Pniontatsdatum veroffentlicht worden ist und mit der a Verfenmchung die bodens allgesm and dcer itccnkdlnel Anrocidung nicht kollidicrt, sondem nur z=rVerstindnis des der abernict as bsoncrsbedeisa anu~shen151Erfindting zugrundeliegendien Priaps odier der ihr zugrundeliegenden iijieres Dokumcnt, das ]edoch erst am odcr nach dem intemnationalen Theonc angegeben ist Anmeldedatum veroffenllicht worden ist Wx Ve offentlichurig von besonderer Bedeuwung; dhe beanspruchte Erfindung *L Veroiffeiichung, die geeignet ist, cen Prititsanspruch zweifelhaft Cr- kann allein aufgrund dieser Veroffentlichung nicht als neu oder auf schcinen zu lassen, odcr durch die das Vcrohfentlichungsdatum ciner erfindenscher Tatigkceit beruhend betrachtet werden anderen im Rechcrchenbericifl genanntcn Verolfenllichung belegI wCI-def Verbifentlichung von besonderer iBcdeutung; die bcanspruchtc Erfindunj soil oder die aus ecm anderen besonderen Grund angegeben ist (iei kanin nicht ais auf erfindenschcr Tiigcit beruhend betrachtet ausgefihtn) werden, weon die Vcroffentlichung mit elncr oder mehrrn anderen Veroffenllchung, dic sich auf einc mondliche Offenbaruing, Veroffenilichungen dieser KategBone in Verbindisng gebracht wird und esne Benuizung, cine Ausstellung oder anderc Malinahmen bczicht these Verbindisog ffir cinen Fachxnann nakseltegend iSt Veroffcntlichung, die vor dcm internationalcrn Anmeldedatuns, aber nach ~VrfetihndeMtlc esle aetami S dern beanspruchten l'riontitsdatum veroffentlicht. worden is e1lnlchndeMt5iddrebn5aetaii s Datum des Abschlusses der intemationaicn Recherche Absendedtatsm des mnternationalen Recherchenctchs 1. Juni 1994 15. 05.94 Name und Postanschnft der Internationale Rechcrchcnbehordc BevolimAchtigter hledicnsteter hiuropiischcs Pateniarnt, P.13. 5818 Patentlaant 2 NI. 2280 HV Rijswijk Tel. 31-70) 340-2040, Tx. 31 651 epo riecrt, Fax: 4~ 31-70) 340-3016 Dc re Formblatl PCT WSA 210 (Blatt 2) (Jull 1992) INTERNATIONAIJ~R RECHERCHENBERICI-IT A iiihodn zuvorof[fodichunoon, O zw ir con PaltAirl f gmiorl I PCT/EP 94/00741 Im Recherchenbericlit Datum der Mitglied(cr) der Datum der angefUhrtes PatcntdokUmntn Vcrbrr~cntlichung Patcntfamilic j V crbffentlichung EP-A-0524496 27-01-93 DE-A- 4124255 28-01-93 AU-A- 2043592 28-01-93 JP-A- 5194111 03-08-93 US-A- 5286724 15-02-94 US-A- 5242920 07-09-93 EP-A-0531837 17-03-93 DE-A- 4130298 18-03-93 AU-A- 2353692 18-03-93 CA-A- 2077245 13-03-93 JP-A- 5221811 31-08-93 US-A- 5260326 09-11-93 Formblatt PCT;!ISA 210 fAnhang Patentfamille)(Juli 1992)