EP1761498A1

EP1761498A1 - 1-methyl-3-difluoromethyl-pyrazol-4-carbonic acid-(ortho-phenyl)-anilides, and use thereof as a fungicide

Info

Publication number: EP1761498A1
Application number: EP05750478A
Authority: EP
Inventors: Markus Gewehr; Bernd Müller; Thomas Grote; Wassilios Grammenos; Anja Schwögler; Joachim Rheinheimer; Carsten Blettner; Peter Schäfer; Frank Schieweck; Oliver Wagner; Frank Werner; Jan Rether; Siegfried Strathmann; Reinhard Stierl; Maria Scherer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-06-18
Filing date: 2005-06-16
Publication date: 2007-03-14
Also published as: TW200615264A; BRPI0512118A; IL179448A0; JP2008502636A; UY28967A1; US20080108686A1; WO2005123690A1; CN1968934A; AR049524A1; PE20060096A1

Abstract

The invention relates to 1-methyl-3-difluoromethyl-pyrazol-4-carbonic acid-(ortho-phenyl)-anilides of formula (I), wherein the substituents have the following meaning: R1 and R2 independently represent halogen, C1-C6 alkyl, C1-C6 alkyl halide, cyano, nitro, methoxy, trifluoromethoxy, or difluoromethoxy.

Description

1-Methyl-3-difluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl) -anilides and their use as fungicide

description

The present invention relates to 1-methyl-3-difluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl) -anilides of the formula I.

in which the substituents have the following meaning:

R ¹ and R ² are independently halogen, Cι-C ₆ -alkyl, C ₆ halogen-alkyl, cyano, nitro, methoxy, trifluoromethoxy or difluoromethoxy.

In addition, the invention relates to a method for controlling harmful fungi with the compounds I and the use of the compounds I for the preparation of fungicidal compositions.

1-Methyl-3-difluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl) -anilides are known from EP-A 0589301, in which also a process for their preparation and a list of possible mixing partners from the series of fungicides, bactericides , Acaricides, nematicides or insecticides.

WO 01/42223 likewise discloses 1-methyl-3-difluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl) -anilides, which are monosubstituted on the phenyl ring.

However, the described 1-methyl-3-difluoromethyl-pyrazole-4-carboxylic acid anilides can not be fully satisfied, in particular at low application rates.

The object of the present invention was to provide new 1-methyl-3-difluoromethyl-pyrazole-4-carboxylic acid anilides which have an improved fungicidal action, in particular even at low application rates.

Accordingly, the compounds of formula I defined above were found. Preference is given to 1-methyl-3-difluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl) -anilides of the formula I.

in which the substituents have the following meaning:

R ¹ and R ² independently of one another are fluorine, chlorine, cyano, methyl, methoxy or trifluoromethyl.

Furthermore, compounds of the formula I are preferred in which R ¹ and R ^{2 are} independently fluorine, chlorine, cyano or methoxy.

Particular preference is given to compounds of the formula I in which R ¹ and R ² independently of one another are fluorine or chlorine.

Very particular preference is given to compounds of the formula I in which R ¹ and R ^{2 are} in the 3- and 4-position of the phenyl ring.

Of the compounds I according to the invention compounds of the formulas Ia to If are preferred, which are listed in the following tables.

Table A

Table 1 :

Connection 1.1 - 1.11

Compounds of the formula Ia in which R ^{1 is} fluorine and R ^{2 is} in each case one of the meanings of Table A.

Table 2:

Connection 2.1 - 2.11

Compounds of the formula Ia in which R ^{1 is} chlorine and R ^{2 is} in each case one of the meanings of Table A.

Table 3:

Connection 3.1 - 3.11

Compounds of the formula Ia in which R ^{1 is} bromine and R ^{2 is} in each case one of the meanings of Table A.

Table 4:

Connection 4.1 - 4.11

Compounds of the formula Ia in which R ^{1 is} iodine and R ^{2 is} in each case one of the meanings of Table A.

Table 5:

Connection 5.1 - 5.11

Compounds of the formula Ia in which R ^{1 is} methyl and R ^{2 is} each one of the meanings of Table A.

Table 6:

Connection 6.1 - 6.11

Compounds of the formula Ia in which R ^{1 is} methoxy and R ^{2 is} each one of the meanings of Table A.

Table 7:

Connection 7.1 - 7.11

Compounds of the formula Ia in which R ^{1 is} trifluoromethyl and R ^{2 is} in each case one of the meanings of Table A.

Table 8:

Connection 8.1 - 8.11

Compounds of the formula Ia in which R ^{1 is} trifluoromethoxy and R ^{2 is} each one of the meanings of Table A. Table 9:

Connection 9.1 - 9.11

Compounds of the formula Ia in which R ^{1 is} cyano and R ^{2 is} each one of the meanings of Table A.

Table 10:

Connection 10.1 - 10.11

Compounds of the formula Ia in which R ^{1 is} nitro and R ^{2 is} each one of the meanings of Table A.

Table n:

Connection 11.1 - 11.11

Compounds of the formula Ib in which R ^{1 is} difluoromethoxy and R ^{2 is} in each case one of the meanings of Table A.

Table 12:

Connection 12.1 - 12.11

Compounds of the formula Ib in which R ^{1 is} fluorine and R ^{2 is} each one of the meanings of Table A.

Table 13:

Connection 13.1 - 13.11

Compounds of the formula Ib in which R ^{1 is} chlorine and R ^{2 is} each one of the meanings of Table A.

Table 14:

Connection 14.1 - 14.11

Compounds of the formula Ib in which R ^{1 is} bromine and R ^{2 is} each one of the meanings of Table A.

Table 15:

Connection 15.1 - 15.11

Compounds of the formula Ib in which R ^{1 is} iodine and R ^{2 is} each one of the meanings of Table A.

Table 16:

Connection 16.1 - 16.11

Compounds of the formula Ib in which R ^{1 is} methyl and R ^{2 is} each one of the meanings of Table A.

Table 17: Connection 17.1 - 17.11 Compounds of the formula Ib, in which R ^{1 is} methoxy and R ^{2 is} in each case one of the meaning of Table A.

Table 18: Compound 18.1 - 18.11

Compounds of the formula Ib in which R ^{1 is} trifluoromethyl and R ^{2 is} each one of the meanings of Table A.

Table 19: Compound 19.1 - 19.11

Compounds of the formula Ib in which R ^{1 is} trifluoromethoxy and R ^{2 is} each one of the meanings of Table A.

Table 20: Compound 20.1 - 20.11

Compounds of the formula Ib in which R ^{1 is} cyano and R ^{2 is} each one of the meanings of Table A.

Table 21: Connection 21.1 - 21.11

Compounds of the formula Ib in which R ^{1 is} nitro and R ^{2 is} each one of the meanings of Table A.

Table 22: Connection 22.1 - 22.11

Table 23: Connection 23.1 - 23.11

Compounds of the formula Ic in which R ^{1 is} fluorine and R ^{2 is} each one of the meanings of Table A.

Table 24: Connection 24.1 - 24.11

Compounds of the formula Ic in which R ^{1 is} chloro and R ^{2 is} in each case one of the meanings of Table A.

Table 25: Compound 25.1 - 25.11

Compounds of the formula Ic in which R ^{1 is} bromine and R ^{2 is} each one of the meanings of Table A. Table 26:

Connection 26.1 - 26.11

Compounds of the formula Ic in which R ^{1 is} iodine and R ^{2 is} in each case one of the meanings of Table A.

Table 27:

Connection 27.1 - 27.11

Compounds of the formula Ic in which R ^{1 is} methyl and R ^{2 is} each one of the meanings of Table A.

Table 28:

Connection 28.1 - 28.11

Compounds of the formula Ic in which R ^{1 is} methoxy and R ^{2 is} each a meaning of Table A.

Table 29:

Compound 29.1 - 29.11

Compounds of the formula Ic in which R ^{1 is} trifluoromethyl and R ^{z is} each a meaning of Table A.

Table 30:

Connection 30.1 - 30.11

Compounds of the formula Ic in which R ^{1 is} trifluoromethoxy and R ^{2 is} each a meaning of Table A.

Table 31:

Connection 31.1 - 31.11

Compounds of the formula Ic in which R ^{1 is} cyano and R ^{2 is} in each case one of the meanings of Table A.

Table 32:

Connection 32.1 - 32.11

Compounds of the formula Ic in which R ^{1 is} nitro and R ^{2 is} each one of the meanings of Table A.

Table 33:

Compound 33.1 - 33.11

Compounds of the formula Ic in which R ^{1 is} difluoromethoxy and R ^{2 is} each one of the meanings of Table A. Table 34:

Connection 34.1 - 34.11

Compounds of the formula Id, in which R ^{1 is} fluorine and R ^{2 is} each one of the meanings of Table A.

Table 35:

Compound 35.1 -35.11

Compounds of the formula Id, in which R ^{1 is} chlorine and R ^{2 is} in each case one of the meaning of Table A.

Table 36:

Compound 36.1 - 36.11

Compounds of the formula Id, in which R ^{1 is} bromine and R ^{2 is} in each case one of the meaning of Table A.

Table 37:

Compound 37.1 - 37.11

Compounds of the formula Id in which R ^{1 is} iodine and R ^{2 is} each one of the meanings of Table A.

Table 38:

Compound 38.1 - 38.11

Compounds of the formula Id in which R ^{1 is} methyl and R ^{2 is} each one of the meanings of Table A.

Table 39:

Compound 39.1 - 39.11

Compounds of the formula Id, in which R ^{1 is} methoxy and R ^{2 is} in each case one

Meaning of Table A stands.

Table 40:

Connection 40.1 - 40.11

Compounds of the formula Id, in which R ^{1 is} trifluoromethyl and R ^{2 is} each one of the meanings of Table A.

Table 41:

Connection 41.1 - 41.11

Compounds of the formula Id, in which R ^{1 is} trifluoromethoxy and R ^{2 is} in each case one of the meaning of Table A.

Table 42

Compound 42.1 - 42.11 Compounds of formula Id in which R ^{1 is} cyano and R ^{2 is} in each case one of the meaning of Table A.

Table 43: Compound 43.1 - 43.11

Compounds of the formula Id, in which R ^{1 is} nitro and R ^{2 is} each one of the meanings of Table A.

Table 44: Compound 44.1 - 44.11

Compounds of the formula Id, in which R ^{1 is} difluoromethoxy and R ^{2 is} in each case one of the meaning of Table A.

Table 45: Compound 45.1 - 45.11

Compounds of the formula Ie in which R ^{1 is} fluorine and R ^{2 is} in each case one of the meanings of Table A.

Table 46: Compound 46.1 - 46.11

Compounds of the formula Ie in which R ^{1 is} chlorine and R ^{2 is} in each case one of the meanings of Table A.

Table 47: Compound 47.1 -47.11

Compounds of the formula Ie in which R ^{1 is} bromine and R ^{2 is} in each case one of the meanings of Table A.

Table 48: Compound 48.1 - 48.11

Compounds of the formula Ie in which R ^{1 is} iodine and R ^{2 is} in each case one of the meanings of Table A.

Table 49: Compound 49.1 - 49.11

Compounds of the formula Ie in which R ^{1 is} methyl and R ^{2 is} in each case one of the meanings of Table A.

Table 50: Compound 50.1 - 50.11

Compounds of the formula Ie in which R ^{1 is} methoxy and R ^{2 is} in each case one of the meanings of Table A. Table 51:

Connection 51.1 - 51.11

Compounds of the formula Ie in which R ^{1 is} trifluoromethyl and R ^{2 is} in each case one of the meanings of Table A.

Table 52:

Connection 52.1 - 52.11

Compounds of the formula Ie in which R ^{1 is} trifluoromethoxy and R ^{2 is} in each case one of the meanings of Table A.

Table 53:

Compound 53.1 - 53.11

Compounds of the formula Ie in which R ^{1 is} cyano and R ^{2 is} in each case one of the meanings of Table A.

Table 54:

Connection 54.1 - 54.11

Compounds of the formula Ie in which R ^{1 is} nitro and R ^{2 is} in each case one of the meanings of Table A.

Table 55:

Connection 55.1 - 55.11

Compounds of the formula Ie in which R ^{1 is} difluoromethoxy and R ^{2 is} in each case one of the meanings of Table A.

Table 56:

Compound 56.1 - 56.11

Compounds of the formula If in which R ^{1 is} fluorine and R ^{2 is} in each case one of the meanings of Table A.

Table 57:

Connection 57.1 - 57.11

Compounds of the formula If in which R ^{1 is} chlorine and R ^{2 is} in each case one of the meanings of Table A.

Table 58:

Compound 58.1 - 58.11

Compounds of the formula If in which R ^{1 is} bromine and R ^{2 is} in each case one of the meanings of Table A. Table 59:

Compound 59.1 - 59.11

Compounds of the formula If, in which R ^{1 is} iodine and R ^{2 is} each a meaning of Table A.

Table 60:

Connection 60.1 - 60.11

Compounds of the formula If in which R ^{1 is} methyl and R ^{2 is} in each case one of the meaning of Table A.

Table 61:

Connection 61.1 - 61.11

Compounds of the formula If, in which R ^{1 is} methoxy and R ^{2 is} each a meaning of Table A.

Table 62:

Compound 62.1 - 62.11

Compounds of the formula If in which R ^{1 is} trifluoromethyl and R ^{2 is} in each case one

Meaning of Table A stands.

Table 63:

Compound 63.1 - 63.11

Compounds of the formula If, in which R ^{1 is} trifluoromethoxy and R ^{2 is} in each case one of the meanings of Table A.

Table 64:

Connection 64.1 - 64.11

Compounds of the formula If in which R ^{1 is} cyano and R ^{2 is} in each case one of the meanings of Table A.

Table 65:

Compound 65.1 - 65.11

Compounds of the formula If in which R ^{1 is} nitro and R ^{2 is} in each case one of the meanings of Table A.

Table 66:

Connection 66.1 - 66.11

Compounds of the formula If in which R ^{1 is} difluoromethoxy and R ^{2 is} in each case one of the meanings of Table A. In the context of the present invention, halogen is fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine.

The term "alkyl" includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C ₆ -alkyl groups. Examples of alkyl groups are alkyl, in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl.

Haloalkyl is an alkyl group as defined above, which is partially or completely halogenated with one or more halogen atoms, in particular fluorine and chlorine. Preferably, 1 to 3 halogen atoms are present, with the difluoromethane / - or the trifluoromethyl group being particularly preferred.

Process for the preparation of the compounds of general formula F are known from EP-A 0 589 301.

For example, the 1-methyl-3-difluoromethyl-pyrazolecarboxylic acid halide of the formula II is reacted with an aniline of the formula III to give the compounds of the formula I:

The radical shark in the formula II represents a halogen atom, such as chlorine, bromine and iodine, in particular chlorine or bromine.

This reaction is usually carried out at temperatures from -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C.

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene. ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and

Tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol and also dimethyl sulfoxide and dimethylformamide, particularly preferably toluene and tetrahydrofuran.

It is also possible to use mixtures of the solvents mentioned.

Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and Calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, and organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium also organic bases, eg tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.

Triethylamine and pyridine are particularly preferably used.

The bases are generally used in equimolar amounts based on the compound II. But they can also be used in an excess of 5 mol% to 30 mol%, preferably 5 mol% to 10 mol%, or - in the case of using tertiary amines - optionally as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use II in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, based on III.

The compounds I according to the invention can also be present in the application form as fungicides together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity. The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate, tetramethylthiuram disulfides, ammonia complex of zihk- (N, N-ethylene-bis-dithiocarbamate) , Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis (thiocarbamoyl) disulfide;

Nitro derivatives, such as dinitro (1-methylheptyl) -phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropylcarbonate, 5-nitro- isophthalate di-isopropyl;

Heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1-bis [... (dimethylamino) -phosphinyl] -3-phenyl-1, 2,4-triazole, 2,3-dicyano-1, 4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1 (Butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylaminobenzimidazole, 2- (furyl- (2)) benzimidazole, 2- (thiazolyl- (4)) benzimidazole, N- (1,1, 2, 2-tetrachloroethylthio) -tetrahydrophthalimide, N-trichloromethylthiothetrahydrophthalimide, N-trichloromethylthio-phthalimide,

N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanemethylthiobenzothiazole, 1, 4-dichloro-2,5 -dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl -1, 4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid -anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide , N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxylic acid amide, 2-methylbenzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2 trichloroethyl acetal, piperazine-1,4-diylbis-1- (2,2,2-trichloroethyl) -formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2.6 -Dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl- N-cyclododecyl-morpholine or its salts, N- [3- (p-tert.-butylphenyI) -2-methylpropyl] -cis-2,6-dimethyl-morpholine, N- [3- (p-tert. Butylphenyl) - 2-methylpropyl] -piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole , 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl ) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1, 2,4-triazole -1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) - oxiran-2-ylmethyl] -1H-1, 2,4-triazole, a- (2-chlorophenyl) -a- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4 hydroxy-6-methyl-pyrimidine, bis (p-chlorophenyl) -3-pyridinemethanol, 1, 2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2 thioureido) benzene, strobilurins such as methyl-E-methoxyimino [a- (o-tolyloxy) -o-tolyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy) -pyrimidine 4-yloxy] -phenyl} -3-methoxyacrylate, methyl-E-methoxyimino [a- (2-phenoxyphenyl)] - acetamide, methyl-E-methoxyimino [a- (2,5-dimethylphenoxy) -o-tolylj acetamide, • anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) -aniline, N- [4-methyl-6- (1-propynyl) -pyrimidin-2-yl] -aniline, N- [4 methyl-6-cyclopropyl-pyrimidin-2-yl] aniline,

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -acrylic acid morpholide, as well as various fungicides such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2- hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate, DL-N- (2,6-dimethyl-phenyl) -N- (2 '-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl ] -1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxylic acid imide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] -acetamide, 1 - [2- (2,4-dichlorophenyl) -pentyl] -1H-1, 2,4-triazole, 2,4-difluoro -a- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl- 3-chloro-2-aminopyridine, 1 - ((bis (4-fluorophenyl) methylsilyl) methyl) -1H-1, 2,4-triazole.

The compounds of the formula I are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. You are currently systemically effective and can therefore also be used as foliar and soil fungicides. They can also be used for seed treatment.

Of particular importance for the control of a variety of fungi on various crops such as cotton, vegetables (eg cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye, soybean , Wine, wheat, ornamentals, sugar cane and a variety of seeds. In particular, they are suitable for controlling the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Podosphaera leucotricha on apples, Unin cinula necator on vines, Puccinia species on cereals, Rhizoctonia species Cotton, rice and turf, Ustilago species on cereals and sugarcane, Venturia inaequalis on apples, Helminthosporium on cereals, Septoria nodorum on wheat, Botrytis cinera on gray strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruits, Mycosphaerella species in bananas, and Fusarium and Verticillium species, Phakopsora pachyrhizi and P. meibomiae on soya.

The application rates of the compounds of formula I according to the invention, especially in agricultural crops, depending on the nature of the desired effect at 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.1 to 3.0 kg / ha.

In particular, the application rates for compound I are 0.01 to 1 kg / ha, preferably 0.05 to 0.5 kg / ha, in particular 0.05 to 0.3 kg / ha.

In the seed treatment, application rates of mixture of 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg are generally used.

If pathogenic harmful fungi are to be controlled for plants, compound I is applied by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants.

The fungicidal compounds I according to the invention can be prepared, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-percentage aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules and by spraying, atomizing, dusting , Scattering or pouring are applied. The application form depends on the intended use; It should in any case ensure the finest possible and uniform distribution of the mixture according to the invention.

The formulations are prepared in a manner known per se, for example by adding solvents and / or carriers, if desired using Emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

Water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (Glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used, - carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.

As surfactants, the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols or Fet- talkoholglycolethern, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol, fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, Polyoxyethylene alkyl or polyoxypropylene, Laurylalkoholpolyglycoletheracetat, sorbitol esters, lignin-Sulphatablaugen or methylcellulose into consideration.

Powder scattering and dusting agents can be prepared by mixing or co-grinding Compound I with a solid carrier.

Granules (e.g., coated, impregnated or homogeneous granules) are usually prepared by binding the active ingredient or agents to a solid carrier.

As fillers or solid carriers are, for example, mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cornmeal, tree bark, wood and nutshell meal, cellulose powder or other solid carriers. The formulations generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the compound I.

The active compounds are used in a purity of 90% to 100%, preferably 95% to 100% (by NMR or HPLC spectrum).

Examples of formulations are: 1. Products for dilution in water

A) Water-soluble concentrates (SL) 10 parts by weight of the active compounds are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves.

B) Dispersible Concentrates (DC) 20 parts by weight of the active compounds are dissolved in cyclohexanone with the addition of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.

C) Emulsifiable Concentrates (EC) 15 parts by weight of the active compounds are dissolved in xylene with addition of calcium

Dodecylbenzoisulfonate and castor oil ethoxylate (each 5%) dissolved. Dilution in water results in an emulsion.

D) Emulsions (EW, EO) 40 parts by weight of the active compounds are dissolved in xylene with addition of calcium

Dodecylbenzenesulfonate and castor oil ethoxylate (5% each). This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E) suspensions (SC, OD)

20 parts by weight of the active ingredients are comminuted with the addition of dispersing and wetting agents and water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.

F) Water-dispersible and water-soluble granules (WG, SG)

50 parts by weight of the active ingredients are finely ground with the addition of dispersants and wetting agents and prepared by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. G) Water-dispersible and water-soluble powders (WP, SP) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.

2. Products for direct application

H) dusts (DP)

5 parts by weight of the active ingredients are finely ground and mixed intimately with 95% finely divided kaolin. This gives you a dust.

I) Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 95.5% excipients. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.

J) ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in an organic solvent, e.g. Xylene dissolved. This gives you a product for direct application.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare from effective substance wetting, adhesion, dispersing or emulsifying agents and any solvents or oil concentrates which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the inventive compositions in a weight ratio of 1:10 to 10: 1.

The application of the compound I or the corresponding formulations is carried out by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free of them with a fungicidally effective amount of compound I.

The application can be made before or after the attack by the harmful fungi.

Preparation Examples

example 1

1.) Synthesis of 4,4-difluoro-3-oxo-butyric acid ethyl ester 1

In 300 ml of absolute tetrahydrofuran was added 13.9 g of sodium hydride. At 35 ° -40 ° C., a solution of 62 g of ethyl difluoroacetate in 44 g of ethyl acetate was added. After 7 h at 40 ° C was stirred, the reaction mixture was stirred into 1 l of ice water, adjusted with 10% sulfuric acid to pH = 3 and extracted twice with 300 ml of methyl tert-butyl ether. The combined organic phase was washed twice with NaCl solution, dried over sodium sulfate and concentrated in vacuo. The residue was distilled. This gave 59.1 g of the product as a colorless oil Kp (100mb) = 90-94 ° C.

2.) Synthesis of 2-ethoxymethylene-4,4-difluoro-3-oxo-butyric acid ethyl ester 2

A mixture of 30 g of 4,4-difluoro-3-oxo-ButtersäureethyIester 1, 44 g of ortho-formic triethyl ether and 55 g of acetic anhydride was stirred under reflux for 4 h. It was then distilled. 35 g of the product were obtained as a colorless oil. Bp = 85-87 ° C.

3.) Synthesis of 3-Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid ethyl ester 3

In 250 ml absol. Ethanol were dissolved at -40 ° C 33.5 g of 2-ethoxymethylene-4,4-difluoro-3-oxobutyrate 2. 7 g of methylhydrazine were added, stirred at -40 ° C. for 1 h and at room temperature for 15 h. The reaction mixture was concentrated in vacuo. The residue was recrystallized from pentane. This gave 29.6 g of the product. Mp = 50-51 ° C.

4.) Synthesis of 3-Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid 4

In a mixture of 80 ml of ethanol and 40 ml of water were dissolved 19.3 g of ethyl 3-difluoromethyl-1-methyl-pyrazole-4-carboxylate 3 and 5.7 g of sodium hydroxide. The mixture was stirred at 60 ° C. for 2 h. The mixture was then concentrated in vacuo and the residue taken up in 500 ml of ice water and adjusted to pH = 3 with 10% hydrochloric acid. It was extracted twice with a mixture of 300 ml of THF and methyl tert-butyl ether (2: 3). The combined organic phase was washed three times with dilute sodium chloride solution, dried over sodium sulfate and concentrated in vacuo. 14.5 g of the product were obtained as a light yellow powder. Mp = 192-193 ° C.

5.) Synthesis of ortho- (3,4-dichlorophenyl) -aniline 5

To a solution of 20.47 g of 2-bromoaniline, 24.98 g of 3,4-dichlorophenylboronic acid and 25.23 g of sodium carbonate in a mixture of 150 ml of water and 450 ml of ethylene glycol dimethyl ether were added 0.14 g of tetrakistriphenylphosphine palladium (O) given. you stirred for 48 hrs. under reflux. The reaction was concentrated in vacuo. The residue was taken up in methyl tert-butyl ether, washed once with sodium bicarbonate solution and four times with water, dried over sodium sulfate and concentrated in vacuo. After chromatographic purification with a mixture of toluene and cyclohexane (1: 2) gave 15.5 g of the product as a light yellow powder.

6.) Synthesis of 3-difluoromethyl-1-methyl-N- (ortho- (3,4-dichlorophenyl) phenyl) -pyrazole-4-carboxamide 6

In 20 ml of toluene were added 0.35 g of 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid 4, 0.47 g of ortho- (3,4-dichlorophenyl) aniline 5, 0.3 g of triethylamine and 0.55 g Bis (2-oxo-3-oxazolidinyl) phosphoryl chloride dissolved. After stirring at room temperature for 15 h, 20 ml of methyl tert-butyl ether were added, washed twice with 5% sodium hydroxide solution, twice with 5% hydrochloric acid and once with sodium chloride solution. The organic phase was dried over sodium sulfate and dried in vacuo. After chromatographic purification with a mixture of toluene and methyl tert-butyl ether (5: 1), 0.47 g of the product was obtained as a colorless powder. Mp = 129-130 ° C.

Table 67

example

drug treatment

The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in volume -Dependent solvent emulsifier from 99 to 1 ad 10 ml was made up. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below. Alternatively, the active ingredients were used as a commercial ready-made formulation and with water to the specified Wirkstoffkonz. diluted.

Use Example 1 - Curative activity against wheat brown rust caused by Puccinia recondita

Leaves of potted wheat seedlings of the variety "Chancellor" were inoculated with a spore suspension of the brown rust (Puccinia recondita). Thereafter, the pots were placed in a high humidity chamber (90-95%) and 20-22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were sprayed the next day with an aqueous suspension in the active ingredient concentration below to dripping wetness. The suspension or emulsion was prepared as described above. After the spray coating had dried on, the test plants were cultivated in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity for 7 days. Then the extent of rust fungus development on the leaves was determined.

Application Example 2a) - Activity against the gray mold on pepper leaves caused by Botrytis cinerea in protective application

Paprika seedlings of the cultivar "Neusiedler Ideal Elite" were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below, after 2-3 leaves had developed well. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 ⁶ spores / ml in a 2% aqueous biomalt solution. Subsequently, the test plants were placed in a climatic chamber at 22 to 24 ° C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.

Application Example 2b) - Efficacy against the net blotch of barley caused by Pyrenophora teres at 1 day of protective application

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ° C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

Comparative experiment 1

Curative efficacy against wheat brown rust caused by Puccinia recondita

Compound 35 of EP-A 0589301 was compared with the compounds 67.1-67.14 according to the invention of Table 67. Leaves of potted wheat seedlings of the "Chancellor" variety were inoculated with a spore suspension of the brown rust (Puccinia recondita). Thereafter, the pots were placed in a high humidity chamber (90-95%) and 20-22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were sprayed the next day with an aqueous suspension in the drug concentration given below to dripping wet. The suspension or emulsion was prepared as described above. After the spray coating had dried on, the test plants were cultivated in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity for 7 days. Then the extent of rust fungus development on the leaves was determined.

Comparative experiment 2

Efficacy against leaf spot disease on wheat caused by Leposphaeria nodorum

Comp. 35 of EP-A 0589301 was compared with the compounds 67.1-67.14 according to the invention of Table 67. Pots of wheat plants of the "Chancellor" variety were sprayed to drip point with an aqueous suspension in the concentration of active substance specified below the next day, the pots were inoculated with an aqueous spore suspension of Leptosphaeria nodorum (syn. Stagonospora nodorum, Septoria nodorum) and then placed in a chamber at 20 ° C and maximum humidity. However, infected control plants developed so much that the infestation could be determined visually in%.

Claims

claims

1. 1-Methyl-3-difluoromethyl-pyraΣol-4-carboxylic acid (ortho-phenyl) -anilide of the formula I.

in which the substituents have the following meaning:

R ¹ and R ² are independently halogen, _Cι-C6 alkyl, -C ₆ halogen-alkyl, cyano, nitro, methoxy, trifluoromethoxy or difluoromethoxy.

2. anilides of the formula I according to claim 1, in which R ¹ and R ^{2 are} independently fluorine, chlorine, cyano, methyl, methoxy or trifluoromethyl.

3. Anilides of the formula I according to claim 1 or 2, in which R ¹ and R ² independently of one another represent fluorine, chlorine, cyano or methoxy.

4. anilides of the formula I according to claim 1, in which R ¹ and R ^{2 are} independently fluorine or chlorine.

5. Anilides of the formula I according to any one of claims 1 to 4, containing a compound of formula I, in which the substituents R ¹ and R ^{2 are} in the 3- and 4-position of the phenyl ring.

6. A method for controlling harmful fungi, which comprises treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free of them with an anilide of the formula I according to one of claims 1 to 5.

7. A fungicidal composition containing an anilide of the formula I according to claim 1 and a solid or liquid carrier.