WO2008053044A2 - Hetaryl carbon acid-n-(biphen-2-yl)amide compounds - Google Patents

Abstract

The present invention relates to hetaryl carbon acid-N-(biphen-2-yl) compounds, the use thereof for controlling harmful fungi, fungicidal substances comprising said compounds, and method for controlling harmful fungi, wherein m stands for 0, 1, 2, 3 or 4, n for 0, 1 or 2, R for C1-C4-alkyl or C1-C4-halogen alkyl or n = 2 can also stand for NH2; Hal for halogen, particularly for fluoride or chlorine, and A for a heteroaromatic remainder, chosen from the remainders of the common formula A.1, A.2, and A.3, wherein R1 stands for methyl or halogen methyl, R2 for carbon, fluoride or chlorine, R3 for carbon, chlorine, methyl or trifluormethyl, R4 for carbon, fluoride, chlorine, methyl or trifluormethyl; and R5 for fluoride, chlorine, methyl, difluourmethyl, trifluormethyl or methoxy; and the salts thereof, except compounds, wherein the group S(O)n-R stands for a thio-C1-C4-alkyl group, that is bound in the 4'-position of the biphenyl unit, when A stands for a remainder A.2 or a remainder A.3.

Description

 Hetarylcarbonsäure-N- (biphen-2-yl) amide compounds

description

The present invention relates to hetarylcarboxylic acid N- (biphen-2-yl) amide

Compounds, their use for controlling harmful fungi, fungicidal compositions containing such compounds, and methods for controlling harmful fungi.

In the case of crop protection agents, it is generally desirable to increase the specific action of an active substance and the safety of action. In particular, it is desirable that the crop protection agent have good crop tolerance and high long-term action under field conditions.

EP 545099 describes anilides of heteroaromatic carboxylic acids having a fungicidal action, for example nicotinic anilides, and anilides of 2-methyl-4-trifluoromethylthiazol-5-ylcarboxylic acid or of 5-chloro-1,3-dimethylpyraizol-4-ylcarboxylic acid, the compounds being described in the 2-position of the phenyl ring of the Ani lidgruppe carry an optionally substituted phenyl ring. Similar compounds are known from DE 19531813 A1 and JP 2001-302605.

EP 589301 A1 likewise describes anilides of heteroaromatic carboxylic acids having a fungicidal action, for example anilides of 1,3-dimethylpyrazol-4-ylcarboxylic acid or of 1-methyl-S-trifluoromethylpyrazol-6-ylcarboxylic acid.

DE 19840322 A1 describes 5-fluoro-1, 3-dimethylyrazol-4-ylcarboxanilide with fungicidal activity, which have in the 2-position of the anilide an optionally substituted phenyl ring.

WO 03/066610 describes 4-difluoromethyl-2-methylthiazol-4-ylcarboxamides of substituted biphenyl-2-ylamines. Similar compounds are known from WO 2006/024389.

The earlier patent application WO 2007/003603 describes 1-methylpyrazol-4-ylcarboxamides of substituted biphenyl-2-ylamines which are substituted in the 3'-position of the biphenylamine moiety.

The earlier patent application WO 2007/006806 describes 1-methylpyrazol-4-ylcarboxamides of substituted biphenyl-2-ylamines which are substituted in the 2'-position of the biphenylamino moiety.

The hetarylcarboxylic acid N- (biphen-2-yl) amide compounds known from the prior art are in some cases unsatisfactory with regard to their fungicidal action. lend, especially at low application rates, or have other undesirable properties, such as a low crop compatibility or rapid decay of efficacy under field conditions.

The present invention is therefore based on the object to provide new compounds with better fungicidal activity and / or better crop compatibility.

This object is achieved by Hetarylcarbonsäure N- (biphen-2-yl) amide compounds of general formula I.

wherein m is 0, 1, 2, 3 or 4; n is O, 1 or 2;

R is Ci-C4-alkyl or Ci-C4-haloalkyl or for n = 2 also Nhb can stand;

Hal is halogen, in particular fluorine or chlorine; and

A is a heteroaromatic radical which is selected from radicals of the general formulas A.1, A.2 and A.3

A.1 A.2 A.3 wherein

R ^{1 is} methyl or halomethyl;

R ^{2 is} hydrogen, fluorine or chlorine;

R ^{3 is} hydrogen, chloro, methyl or trifluoromethyl;

R ^{4 is} hydrogen, chloro, methyl or trifluoromethyl; and

R ^{5 is} fluoro, chloro, methyl, difluoromethyl, trifluoromethyl or methoxy; and their salts, except compounds in which the group S (O) _n -R is a thio-C 1 -C 4 -alkyl group which is bonded in the 4'-position of the biphenyl unit, when A is a radical A.2 or a residue A.3 is.

In the embodiment of the invention in which A is a radical A.1, those compounds of the formula I and their salts are preferably excluded in which the group S (O) _n -R is a thio-C 1 -C 4 -alkyl group (S--). (Ci-C4-alkyl) which is bonded in the 4'-position of the biphenyl moiety and the variable m has a meaning other than O.

In the embodiment of the invention wherein A is a radical A.1, those compounds of the formula I and their salts are preferably excluded, wherein the group S (O) _n -R is methylthio (CH ₃ -S), difluoromethylthio (CHF ₂ -S) or trifluoromethylthio (CF ₃ -S), which are bonded in the 3'-position of the biphenyl moiety, and wherein the variable m is O.

In the embodiment of the invention in which A is a radical A.1, those compounds of the formula I and their salts are preferably excluded in which the group S (O) _n -R is a thio-C 1 -C 4 -alkyl group (S--). (Ci-C4-alkyl) which is bonded in the 2'-position of the biphenyl moiety and the variable m is O.

The present invention thus relates to the hetarylcarboxylic acid N- (biphen-2-yl) amides of the general formula I and salts thereof.

The present invention furthermore relates to the use of the hetarylcarboxylic acid N- (biphen-2-yl) amides of the general formula I and their salts for controlling phytopathogenic fungi (= harmful fungi) and to a method for controlling phytopathogenic fungi characterized in that the fungi, their habitat or the plants to be protected against fungal attack, the soil, seeds, areas, materials or spaces treated with an effective amount of at least one compound of general formula I and / or with a salt of I.

The present invention furthermore relates to an agent for controlling phytopathogenic fungi (= harmful fungi), comprising at least one compound of the general formula I and / or a salt thereof and at least one inert additive, e.g. a liquid or solid carrier.

The invention also relates, in particular, to fungicidal compositions which comprise at least one compound of the general formula I and at least one further active ingredient, in particular a fungicidal active ingredient. The present invention further seed with at least one compound of general formula I and / or a salt thereof in an amount of 1 g to 1000 g per 100 kg of seed.

Depending on the substitution pattern, the compounds of the formula I can have one or more chiral centers and are then present as pure enantiomers or pure diastereomers or as mixtures of enantiomers or diastereomers. The invention relates to both the pure enantiomers or diastereomers and mixtures thereof. The compounds of the formula I can be present in amorphous form as well as in various crystal modifications or as solvates which may differ in their biological activity. The subject matter is all forms, including the solvates of the compounds I.

The compounds of formula I are suitable both in their neutral form and in charged form, i. as a salt, for controlling phytopathogenic fungi. For this purpose, in particular those salts are suitable which are agriculturally compatible. Suitable agriculturally useful or compatible salts are, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the fungicidal activity of the compounds I. In the case of a heterocyclic radical A.3, the compounds may be present in particular as acid addition salts. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 alkanoic acids, preferably formate, acetate , Propionate and butyrate. They may be formed by reaction of I with an acid of the corresponding anion, preferably hydrochloric, hydrobromic, sulfuric, phosphoric or nitric acid.

The definitions of variables given in the above formulas use collective terms that are generally representative of the respective substituents. The meaning C _n -C m indicates the particular possible number of carbon atoms in the respective substituent or substituent part:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 carbon atoms, e.g. Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl.

Halo (gen) alkyl: straight-chain or branched alkyl groups having 1 to 4, in particular having 1 or 2 carbon atoms and especially having one carbon atom as above mentioned, in which groups the hydrogen atoms may be partially or completely replaced by fluorine, chlorine, bromine and / or iodine, for. For example, CH 2 F, difluoromethyl, trifluoromethyl, CH 2 Cl, dichloromethyl, trichloromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 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, C ₂ F ₅ , 2-fluoropropyl, 3-fluoropropyl , 2,2-Difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl , 2,2,3,3,3-Pentafluoropropyl, hepafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl , 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl.

A thio-C 1 -C ₄ -alkyl group is a radical of the formula S-C 1 -C ₄ -alkyl, ie a C 1 -C ₄ -alkyl group, as mentioned above, which is bonded via a sulfur atom.

With regard to the use as fungicides, preference is given to those compounds of the formula I and salts thereof in which the variables A and R, Hal and the indices n and m, independently of one another and in particular in combination, have the following meanings.

R is preferably C 1 -C 4 -haloalkyl, in particular C 1 -C 2 -haloalkyl, especially C 1 -C 2 -fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. Also preferred are compounds of formula I wherein R is NH 2 when n = 2.

The variable n is in particular 0 or 2. According to a first embodiment of the invention, n is 0. R then preferably represents C 1 -C 2 -haloalkyl, especially C 1 -C 2 -fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. According to a second embodiment of the invention, n is 2. R then preferably represents C 1 -C 2 -haloalkyl, especially C 1 -C 2 -fluoroalkyl, and more preferably difluoromethyl or trifluoromethyl. Also preferred are compounds of the formula I in which n = 2 and R is NH 2 or C 1 -C 2 -alkyl and especially methyl.

The variable m is preferably 0 or 1 and in particular 0.

Hal, if present, is in particular fluorine or chlorine.

According to a specific embodiment, the group S (O) _n R is located in the 4'-position of the biphenyl moiety, ie in para to the binding site of the adjacent phenyl ring, the variable n is 0 and R is Ci-C2-fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. In this particular embodiment, the variable m is preferably 0. According to another specific embodiment, the group S (O) _n R is located in the 3'-position of the biphenyl unit, ie in meta to the binding site of the adjacent phenyl ring, the variable n is 0 and R is Ci-C2- Fluoroalkyl, and more preferably difluoromethyl or trifluoromethyl. In this particular embodiment, the variable m is preferably 0 or 1 and especially 0.

A preferred embodiment of the present invention relates to compounds of general formula I, wherein m is 0, and their salts. These compounds are also referred to below as compounds La. In the compounds of the formula Ia, A, R and n have the abovementioned meanings and in particular the meanings mentioned as being preferred.

Examples of preferred compounds of the formula Ia are the compounds I.a-1 to Ia-369 indicated in the following Table A.

Table A:

A further preferred embodiment of the present invention relates to compounds of the general formula I in which m is 1 and salts thereof. Among these, preferred are those compounds and salts wherein Hal is chlorine bonded in the 3-position of the biphenyl ring. These compounds are also referred to below as compounds 1b. Among these are still such compounds and salts wherein Hal is fluoro linked in the 3-position of the biphenyl ring. These compounds are also referred to below as compounds lc. Among these, further preferred are those compounds and salts wherein Hal is chlorine bonded in the 4-position of the biphenyl ring. These compounds are also referred to below as compounds ld. Among these, further preferred are those compounds and salts wherein Hal is fluorine bonded at the 4-position of the biphenyl ring. These compounds are also referred to below as compounds le. Among these, further preferred are those compounds and salts wherein Hal is chlorine bonded in the 5-position of the biphenyl ring. These compounds are also referred to below as compounds lf. Among these, further preferred are those compounds and salts wherein Hal is fluorine bonded in the 5-position of the biphenyl ring. These compounds are also referred to below as compounds lg. Among these, further preferred are those compounds and salts wherein Hal is chlorine bonded in the 6-position of the biphenyl ring. These compounds are also referred to below as compounds lh. Among these, further preferred are those compounds and salts wherein Hal is fluorine bonded at the 6-position of the biphenyl ring. These compounds are also referred to below as compounds li.

lb: Hal = 3-chloro lc: Hal = 3-fluoro ld: Hal = 4-chloro le: Hal = 4-fluoro lf: Hal = 5-chloro lg: HaI = 5-fluoro lh: Hal = 6-chloro

li: Hal = 6-fluorine

In the formulas 1b, 1c, 1d, 1e, 1f, 1g, 1h and 1i, A, R and n have the abovementioned meanings and in particular the meanings mentioned as being preferred. Examples of preferred compounds of the formula Ib are the compounds Ib-1 to Ib-369, in which A and SO _n -R in each case in each case have the meanings given in one row of Table A.

Examples of preferred compounds of the formula Ic are the compounds Ic-1 to Ic-369, in which A and SO _n -R in each case have the meanings given in a row of Table A together.

Examples of preferred compounds of the formula Ic are the compounds Ic-1 to Ic-369, in which A and SO _n -R in each case have the meanings given in one row of Table A. Examples of preferred compounds of the formula Id are the compounds ld-1 to ld-369, in which A and SO _n -R in each case have the meanings given in one row of Table A.

Examples of preferred compounds of the formula Ie are the compounds Ie-1 to Ie-369, in which A and SO _n -R in each case have, together, the meanings indicated in one row of Table A.

Examples of preferred compounds of the formula If are the compounds IF-1 to IF-369, wherein A and SO _n -R in each case together have the meanings given in a row of Table A. Examples of preferred compounds of formula Ig are the compounds Ig-1 to Ig-369, wherein A and SO _n -R in each case together have the meanings given in a row of Table A.

Examples of preferred compounds of the formula Ih are the compounds Ih-1 to Ih-369, in which A and SO _n -R in each case have the meanings given in a row of Table A together.

Examples of preferred compounds of the formula Ii are the compounds I-1 to Ii-369, in which A and SO _n -R in each case in each case have the meanings given in one row of Table A.

A first embodiment of the invention relates to compounds of the formula I and their salts, in which A is a radical A.1. Among the compounds of the formula I in which A is A.1, preference is given to those compounds in which R, m and n have the meanings mentioned as being preferred. With regard to the fungicidal action, particular preference is given to those compounds of the formula I and salts thereof in which R ^{1 is} CH 3, CHF 2 or CF 3, with particular preference being given to CHF 2 and CF 3. R ² is in particular hydrogen. In this first embodiment, m is in particular O. In this first embodiment, the group S (O) _n R is in particular in the 4'-position of the biphenyl unit, ie in para to the binding site of the adjacent phenyl ring. The variable n is in particular O and R is in particular C 1 -C 2 -fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. In this first embodiment, m is in particular O. In this first embodiment, compounds are likewise preferred in which the group S (O) _n R is arranged in the 4'-position of the biphenyl unit, ie in para to the binding site of the adjacent phenyl ring is m = 1 and R is Ci-C2-fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. The variable n then stands in particular for O.

In this first embodiment, particular preference is given to compounds of the formula I in which the group S (O) _n R is located in the 4'-position of the biphenyl unit, ie in para to the binding site of the adjacent phenyl ring and in which the variables n, m, R, R ¹ and R ^{2 have} the following meanings: n O; m is O or 1; R is Ci-C2-fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl;

R ^{1 is} CH ₃ , CHF ₂ or CF ₃ ;

R ^{2 is} hydrogen, fluorine or chlorine, in particular hydrogen.

Examples of particularly preferred compounds I, in which A is a radical A.1, are the compounds Ia-1 to Ia-189, Ib-1 to Ib-189, Ic-1 to Ic-189, Id-1 to Id 189, le-1 to le-189, lf-1 to lf-189, lg-1 to lg-189, lh-1 to lh-189, li-1 to li-189. Of these, particular preference is given to the following compounds and their salts: 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (2'-methylthiobiphenyl-2-yl) -amide (1a-1), 1-methyl- 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (3 '- (trifluoromethylthio) -biphenyl-2-yl) -amide (1a-8), 1-methyl-3-trifluoromethyl-1H-pyrazole-4 carboxylic acid (3'-sulfamoyl-biphenyl-2-yl) -amide (la-11), 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4 '- (trifluoromethylthio) biphenyl-2 -yl) -amide (Ia-16), 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methylthiobiphenyl-2-yl) -amide (Ia-17), 1-methyl- 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-sulfamoyl-biphenyl-2-yl) -amide (la-18), 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide (la-19), 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (3 '- (trifluoromethylthio) biphenyl-2-yl) -amide (Ia-31), 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (4 '- (trifluoromethylthio) biphenyl-2-yl) -amide (la -37), 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (3 '- (trifluoromethylthio) biphenyl-2-yl) -amide (Ia-31), and 1-methyl-3-difluoromethyl -1 H-pyrazole-4-carboxylic acid (4'-methylthiobiphenyl-2-yl) -amide (la-38).

A second embodiment of the invention relates to compounds of the formula I in which A is a radical A.2. Among the compounds of the formula I in which A is A.2, preference is given to those compounds in which R, m and n have the meanings mentioned as being preferred. With regard to the fungicidal action, those compounds of the formula I and salts thereof are particularly preferred in which R ^{3 is} CH ₃ or CF ₃ , with particular preference for CF ₃ . R ⁴ is in particular CH ₃ . In this second embodiment, the group S (O) _n R is in particular in the 4'-position of the biphenyl unit, ie in para to the binding site of the adjacent phenyl ring arranged. The variable n is in particular 0 and R is in particular C1-C2-fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. The variable m stands in particular for 0 or 1 and especially for 0.

Examples of particularly preferred compounds I in which A is a radical A.2 are the compounds Ia-190 to Ia-249, Ib-190 to Ib-249, Ic-190 to Ic-249, Id-190 to Id 249, le-190 to le-249, lf-190 to lf-249, lg-190 to lg-249, lh-190 to lh-249, li-190 to li-249. Of these, particularly preferred are the following compounds and their salts: 2-methyl-4-trifluoromethyl-thiazole-5-carboxylic acid (4'-sulfamoyl-biphenyl-2-yl) -amide

(la-226), 2-methyl-4-trifluoromethylthiazole-5-carboxylic acid (3'-sulfamoyl-biphenyl-2-yl) -amide (la-220), 2-methyl-4-trifluoromethyl-thiazole-5-carboxylic acid (4 '-methansulfonyl- biphenyl-2-yl) amide (la-227), 2-methyl-4-trifluoromethylthiazole-5-carboxylic acid (3'- (trifluoromethylthio) biphenyl-2-yl) -amide (la-219), 2-methyl 4-trifluoromethylthiazole-5-carboxylic acid (4 '- (trifluoromethylthio) biphenyl-2-yl) -amide (la-225), 2-methyl-4-trifluoromethylthiazole-5-carboxylic acid (2'-methylthiobiphenyl-2-yl) yl) amide (la-210), 2-methyl-4-trifluoromethylthiazole-5-carboxylic acid (3'-methylthiobiphenyl-2-yl) -amide (I -a- 217), 2-methyl-4-difluoromethylthiazole 5-Carboxylic acid (4'-sulfamoyl-biphenyl-2-yl) -amide (Ia-246), 2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid- (3'-sulfamoyl-biphenyl-2-yl) -amide (Ia-240 ), 2-methyl-4-difluoromethyl-thiazole-5-carboxylic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide (Ia-247), 2-methyl-4-difluoromethyl-thiazole-5-carboxylic acid (3'-methyl) (trifluoromethylthio) biphenyl-2-yl) amide (la-239), 2-methyl-4-difluoromethylthiazole-5-carboxylic acid (4 '- (trifluoromethylthio) biphenyl-2-yl) -amide (la-245), 2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (2'-methylthiobiphenyl-2-yl) -amide (la-230) and 2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (3'-methylthiobiphenyl-2-yl) -amide (Ia-237).

A third embodiment of the invention relates to compounds of the formula I in which A is a radical A.3. Among the compounds of the formula I in which A is A.3, preference is given to those compounds in which R, m and n have the meanings mentioned as being preferred. With regard to the fungicidal action, those compounds of the formula I and salts thereof are particularly preferred in which R ^{5 is} CF 3 or in particular fluorine or chlorine. In this third embodiment, the group S (O) _n R is located in particular in the 4'-position of the biphenyl unit, ie in para to the binding site of the adjacent phenyl ring. The variable n is in particular 0 and R is in particular C 1 -C 2 -fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl. The variable m stands in particular for 0 or 1 and especially for 0.

Examples of particularly preferred compounds I, wherein A is a radical A.3, are the compounds la-250 to la-369, lb-250 to lb-369 and lc-250 to lc-369, ld-250 to ld 369, le-250 to le-369 and lf-250 to lf-369, lg-250 to lg-369, lh-250 to lh-369 and li-250 to li-369. Of these, particularly preferred are the following compounds and their salts:

2-Chloronicotinic acid (3'-sulfamoyl-biphenyl-2-yl) -amide (Ia-260), 2-chloronicotinic acid (4'-sulfamoyl-biphenyl-2-yl) -amide (Ia-266), 2-chloronicotinic acid (4 '-methanesulfonyl-biphenyl-2-yl) -amide (la-267), 2-chloronicotinic acid (3' - (trifluoromethylthio) biphenyl-2-yl) -amide (la-92), 2-chloronicotinic acid (4 '- ( trifluoromethylthio) biphenyl-2-yl) amide (la-265),

2-chloronicotinic acid (2'-methylthiobiphenyl-2-yl) -amide (Ia-250), 2-chloronicotinic acid (3'-methylthiobiphenyl-2-yl) -amide (Ia-257);

Among the compounds of the formula Ia, the following compounds are very particularly preferred: la-16, la-17, la-37 and la-38. The compounds of the formula I according to the invention can be prepared analogously to known methods of the prior art for the preparation of carboxamides, and advantageously according to the syntheses described in the following schemes and in the experimental section.

Scheme 1:

(H)

C ") (I)

In Scheme 1, A, R, Hal, m and n have the meanings given above, Hal 'is halogen, in particular chlorine.

In accordance with the process illustrated in Scheme 1, a carboxylic acid halide II is reacted with a biphenylamine III in a manner known per se [cf. J. March, Advanced Organic Chemistry, 2nd ed., 382f, McGraw-Hill, 1977].

The reaction is usually carried out in the presence of a base. As 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 carbonates such as lithium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate and alkali metal and alkaline earth metal such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, and also organic bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, di-isopropyl-ethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Especially preferred are tertiary amines, e.g. Triethylamine or pyridine.

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. This reaction is usually carried out at temperatures of (-2O) ⁰ C to 100 ⁰ C, preferably 0 ° C to 50 ⁰ C.

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.

In general, the reaction is carried out in an inert solvent. 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 methylene chloride, dimethyl sulfoxide and Dimethylformamide, more preferably toluene, methylene chloride and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.

According to the method illustrated in Scheme 2, carboxylic acids of the formula IV are reacted in a manner known per se with an aniline of the formula III in the presence of dehydrating agents and, if desired, an organic base.

Scheme 2:

(IV)

C ") (I)

In Scheme 2, A, R, Hal, m and n have the meanings given above.

Examples of suitable dehydrating agents are 1, 1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride, carbodiimides such as N, N'-dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide, phosphonium salts such as (benzotriazole). 1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate, bromotripyrrolidinophosphonium hexafluorophosphate, bromotris (dimethylamino) phosphonium hexafluorophosphate, chlorotripyrrolidinophosphonium hexafluorophosphate, uronium and thiuronium salts such as O- (benzotriazol-1-yl) -N, N, N ', N' tetramethyluronium hexafluorophosphate, O- (7-azabenzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, S- (1-oxido- 2-pyridyl) -N, N, N ', N'-tetramethylthiuronium tetrafluoroborate, O- (2-oxo-1 (2H) pyridyl) -N, N, N', N'-tetramethyluronium tetrafluoroborate, O - [(ethoxycarbonyl) cyanomethylene - amino] -N, N, N ', N'-tetramethyluronium tetrafluoroborate, carbenium salts such as (benzotriazole-1-ynyloxy) dipyrrolidinocarbenium hexafluorophosphate, (benzotriazole-1-ynyloxy) dipiperidino-carbenium hexafluorophosphate, O- (3,4-dihydro-4-oxo -1, 2,3-benzotriazin-3-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, chloro-N'-N'-bis (tetramethylene) formamidinium tetrafluoroborate, chlorodipyrrolidinocarbenium hexafluorophosphate, chloro-N, N, N ', N'-bis (pentamethylene) formamidinium tetrafluoroborate, imidazolium salts such as 2-chloro-1,3-dimethylimidazolidinium tetrafluoroborate, preferably 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride, N, N'-dicyclohexyl carbodiimide and N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide.

Suitable organic bases are, for example, tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and also bicyclic amines. Triethylamine and pyridine are particularly preferably used. The bases are generally used in excess of from 10 mol% to 200 mol%, preferably from 50 mol% to 150 mol%, based on the compound IV.

The starting materials are generally reacted with each other in approximately equimolar amounts. It may be advantageous for the yield to use one of the compounds in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%. The dehydrating agents are generally used in excess of from 5 mol% to 100 mol%, preferably from 5 mol% to 60 mol%, based on the acid IV.

The reaction is usually carried out in a solvent. 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, and dimethyl sulfoxide and dimethylformamide, particularly preferably methylene chloride, toluene and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.

The starting materials of the formula II required for the preparation of the compounds I are known (for example from EP-A-545 099, EP-A-589 301, WO 2003/066610, WO2005 / 034628 or WO 2006/024389) or can be prepared analogously to known ones Connections are made. The starting materials of the formula IV required for the preparation of the compounds I are known or can be synthesized analogously to the known compounds.

The biphenylamines III are generally known or obtainable in a manner known per se (cf., for example, Tetrahedron Letters 28, page 5093 to page 5096, 1987). The preparation of biphenylamines III succeeds, for example, according to the synthesis routes shown in Schemes 3 and 3a.

Scheme 3:

Scheme 3a:

In Schemes 3 and 3a, R, Hal, n and m have the meanings given above, Hal ^* represents chlorine, bromine or iodine, in particular chlorine or bromine and R ¹ and RJ independently of one another represent hydrogen or C 1 -C ₄ -alkyl or R ¹ and RJ together are 1, 2-ethanediyl, 1, 3-propanediyl, where the hydrogens in ethanediyl and propanediyl may be wholly or partially replaced by methyl. Cat. Stands for catalyst.

According to Scheme 3, the halobenzene of the formula V is reacted with an aniline boronic acid derivative of the general formula VI under the conditions of a Suzuki coupling, ie in the presence of a palladium catalyst under known reaction conditions, as described for example in Acc. Chem. Res. 15, p. 178-184 (1982), Chem. Rev. 95, pp. 2457-2483 (1995), and the literature cited therein, as well as from J. Org. Chem. 68, p. 9412 (2003). Particularly suitable catalysts are tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride, bis (acetonitrile) palladium (II) chloride, [1, 1'-bis (diphenylphosphino) ferrocene] - palladium (II) chloride-dichloromethane complex, bis [1,2-bis (diphenylphosphine) ethane] palladium (0) and [1,4-bis (diphenylphosphine) butane] palladium (II) chloride. The amount of catalyst is usually 0.1 to 10 mol%, based on the compound V. The molar ratio of compound V to the Anilinlboronsäurederivat VI is typically in the range of 1: 2 to 2: 1.

The reaction is usually carried out in the presence of a base. Suitable bases are alkali metal carbonates and alkali metal bicarbonates, such as sodium carbonate, potassium carbonate, cesium carbonate or sodium bicarbonate, alkaline earth metal carbonates and alkaline earth metal hydrogencarbonates, such as magnesium carbonate or magnesium hydrogencarbonate, or tertiary amines, such as triethylamine, trimethylamine, triisopropylamine or N-ethyl-N-diisopropylamine , preferably sodium carbonate.

Usually, the coupling of the compound V with the compound VI takes place in a solvent. As solvents are organic solvents such as ethers, z. B. 1, 2-dimethoxyethane, cyclic ethers such as tetrahydrofuran or 1, 4-dioxane, polyalkylene glycols such as diethylene glycol, ethylene glycol dimethyl ether, carbonitriles such as acetonitrile or propionitrile and carboxylic acid amides such as dimethylformamide or dimethylacetamide suitable. In the Suzuki coupling, the aforementioned solvents can also be used in admixture with water, for. For example, the ratio of organic solvent to water may range from 5: 1 to 1: 5.

The halobenzene compounds of formula V are known or can be prepared by known methods.

The aniline boronic acid derivatives of formula VI are known or can be prepared by known methods.

The first step of the synthesis shown in Scheme 3a is analogous to the synthesis shown in Scheme 3. The resulting nitrobiphenyl IIIa may then be purified in a conventional manner, e.g. by catalytic reduction with hydrogen, are converted to the corresponding 2-aminobiphenyl.

Another synthetic approach to the compounds of the formula I according to the invention is shown in Schemes 4 and 4a:

Scheme 4:

(VII) (V)

Scheme 4a:

(VIIa) (Va)

In Schemes 4 and 4a, A, R, Hal, n and m are as defined above, Hal represents bromine or iodine, especially bromine, and R ¹ and RJ independently represent hydrogen or Ci-C ₄ -AlkVl or R ¹ and RJ together are 1, 2-ethanediyl, 1, 3-propanediyl, wherein the hydrogens in ethanediyl and propanediyl may be wholly or partially replaced by methyl. Cat. Stands for catalyst. The reactions shown can be carried out analogously to the reaction carried out in Scheme 3.

The reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products. The intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.

If individual compounds I are not accessible in the ways described above, they can be prepared by derivatization of other compounds I, for example by reduction of a group SO 2 -R to a group S-R.

The compounds I are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Basidiomycetes and Peronospo- romyceten (syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are of particular importance for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants.

In particular, they are suitable for controlling the following plant diseases:

Alternaria species on vegetables, oilseed rape, sugar beets and fruits and rice, such as A.solani or A. alternata on potatoes and tomatoes,

• Aphanomyces species of sugar beets and vegetables,

• Ascochyta species on cereals and vegetables, • Bipolaris and Drechslera species on maize, cereals, rice and turf, e.g. D.maydis on corn,

• Blumeria graminis (powdery mildew) on cereals,

• Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,

• Bremia lactucae on lettuce, • Cercospora species on corn, soybeans, rice and sugar beet,

Cochliobolus species on corn, cereals, rice, e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice,

• Colletotricum species on soybeans and cotton,

• Drechslera species, Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to wheat,

Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus),

• Elsinoe ampelina on grapevine,

• Exserohilum species on maize, • Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on various plants, e.g. F. graminea rum or F. culmorum on cereal or F. oxysporum on a variety of plants such as e.g. Tomatoes,

Gaeumanomyces graminis on cereals, Gibberella species on cereals and rice (e.g., Gibberella fujikuroi on rice),

Glomerella cingulata on grapevine and other plants

• Grainstaining complex on rice,

• Guignardia budwelli on grapevine,

• Helminthosporium species on maize and rice, • Isariopsis clavispora on grapevine,

Michrodochium nivale on cereals, Mycosphaerella species on cereals, bananas and peanuts, such as M. graminicola on wheat or M.fijiensis on bananas,

Peronospora species on cabbage and onion plants, such as P. brassicae on cabbage or P. destructor on onion, • Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,

• Phomopsis species on soybeans and sunflowers, P. viticola on grapevine,

• Phytophthora infestans on potatoes and tomatoes,

Phytophthora species on various plants, e.g. P.capsici on paprika,

• Plasmopara viticola on vines, • Podosphaera leucotricha on vines,

Pseudocercosporella herpotrichoides on cereals,

Pseudoperonospora on various plants, e.g. P. cubensis on cucumber or P. humili on hops,

• pseudo-pedicel tracheiphilai on grapevine, • Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus,

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entenoma oryzae, on rice,

• Pyricularia grisea on lawn and cereals, • Pythium spp. on turf, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as e.g. P.ultiumum on different plants, P. aphanidermatum on grass,

• Rhizoctonia species on cotton, rice, potatoes, turf, corn, canola, potatoes, sugar beets, vegetables and on various plants such as e.g. R.solani on turnips and various plants,

• Rhynchosporium secalis on barley, rye and triticale,

• Sclerotinia species on oilseed rape and sunflowers,

• Septoria tritici and Stagonospora nodorum on wheat,

• Erysiphe (syn. Uncinula) necator on grapevine, • Setospaeria species on maize and turf,

• Sphacelotheca reilinia on corn,

Thievaliopsis species on soybeans and cotton,

• Tilletia species of cereals,

• Ustilago species on cereals, maize and sugar cane, e.g. U. maydis on corn, • Venturia species (scab) on apples and pears like. e.g. V. inaequalis to apple.

The compounds I are also suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sciophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleu- rotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.

In the seed treatment, in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.

The compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.

The compounds I can be formulated as agents which, in addition to the compounds of the formula I, contain at least one inert additive. Inert additives in the context of the invention are those chemical substances which themselves have no or no appreciable fungicidal action, for example solid or liquid carriers or other auxiliaries, such as are commonly used in the formulation of fungicidal active ingredients.

Examples of formulation types are solutions, emulsions, suspensions, dusts, powders, pastes and granules. The formulations can be used as such or after dilution with water. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention. The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired using surface-active substances such as emulsifiers and dispersants. Suitable solvents / carriers 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 can also be used, - carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate. fat, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

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

A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC) 20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient 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 in water results in an emulsion. The formulation has 15% by weight active ingredient content.

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 water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of 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. The active ingredient content in the formulation is 20% by weight. F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial 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. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations (GF)

In a ball mill, 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight of water or an organic solvent are ground to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.

2. Products for direct application

I dusts (DP, DS)

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

J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV Solutions (UL) 10 parts by weight of the active ingredients are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations are usually used (GF) used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

If the formulations are used for seed treatment, they may contain other common ingredients as used in seed treatment, e.g. used in pickling or coating. In addition to the aforementioned constituents, these include in particular colorants, adhesives, fillers and plasticizers.

Suitable colorants are all the dyes and pigments customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned are those under the designations Rhodamine B, CI Pigment Red 1 12 and CI Solvent Red 1, Pigment blue 15: 4, Pigment blue 15: 3, Pigment blue 15: 2, Pigment blue 15: 1, Pigment blue 80, Pigment yellow 1, Pigment yellow 13, Pigment red 48: 2, Pigment red 48: 1, Pigment red 57: 1, Pigment red 53: 1, Pigment orange 43, Pigment orange 34, Pigment orange 5, Pigment green 36, Pigment green 7, Pigment white 6, Pigment brown 25, Basic violet 10, Basic violet 49, Acid red 51, Acid red 52, Acid red 14, Acid blue 9, Acid yellow 23, Basic red 10, Basic red 108 well-known dyes and pigments. The amount of colorant will usually be no more than 20% by weight of the formulation and is preferably in the range of 0.1 to 15% by weight, based on the total weight of the formulation.

Suitable adhesives are all customary binders which can be used in pickling agents. Examples of suitable binders include thermoplastic polymers such as polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose furthermore polyacrylates, polymethacrylates, polybutenes, polyisobutenes, polystyrene, polyethyleneamines, polyethylene amides, the abovementioned protective colloids, polyesters, polyether esters, polyanhydrides, polyester urethanes, polyesteramides, thermoplastic polysaccharides, eg Cellulose derivatives such as cellulose esters, cellulose ethers, cellulose ether esters including methylcellulose, ethylcellulose, hydroxymethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and starch derivatives and modified starches, dextrins, maltodextrins, alginates and chitosans, furthermore fats, oils, proteins including casein, gelatin and zein, rubbers Arabic, shellac. Preferably, the adhesives are plant compatible, i. they have no or no appreciable phytotoxic effects. Preferably, the adhesives are biodegradable. Preferably, the adhesive is selected to act as a matrix for the active ingredients of the formulation. The amount of adhesive will usually not constitute more than 40% by weight of the formulation and is preferably in the range of from 1 to 40% by weight, and more preferably in the range of from 5 to 30% by weight, based on the total weight of the formulation.

In addition to the adhesive, the formulation for seed treatment may also contain inert fillers. Examples include the aforementioned solid support materials, in particular special finely divided inorganic materials such as clays, chalk, bentonite, kaolin, talc, perlite, mica, silica gel, diatomaceous earth, quartz powder, montmorillonite, but also finely divided organic materials such as wood flour, cereal flour, activated carbon and the like. The amount of filler is preferably selected so that the total amount of filler does not exceed 75% by weight, based on the total weight of all non-volatile constituents of the formulation. Often, the amount of filler ranges from 1 to 50 weight percent, based on the total weight of all nonvolatile components of the formulation.

In addition, the formulation for seed treatment may still contain a plasticizer which increases the flexibility of the coating. Examples of plasticizers are oligomeric polyalkylene glycols, glycerol, dialkyl phthalates, alkylbenzyl phthalates, glycol benzoates and comparable compounds. The amount of plasticizer in the coating is often in the range of 0.1 to 20% by weight, based on the total weight of all non-volatiles of the formulation.

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, litter, 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 (wettable 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 wetting agents, tackifiers, dispersants or emulsifiers. But it can also be effective substance wetting, adhesion, dispersing or emulsifying agents and possibly

Solvent or oil concentrates are prepared, 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, possibly also just immediately before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

Suitable adjuvants in this sense are in particular: organically modified polysiloxanes, for example Break Thru S ^240® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluronic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e.g. B. Leophen RA ^®.

The agents according to the invention, in the form of application as fungicides, may also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers. When mixing the compounds (I) or the agents containing them with one or more further active compounds, in particular fungicides, for example, in many cases, the activity spectrum can be broadened or development of resistance can be prevented. In many cases, synergistic effects are obtained.

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.

Azoles (Group A), for example:

Triazoles: bitertanol, bromonuconazoles, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimol, Triadicon, triticonazole;

Imidazoles: cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole; Benzimidazoles: Benomyl, Carbendazim, Fuberidazole, Thiabendazole; Other: Ethaboxam, Etridiazole, Hymexazole;

Strobilurins (group B), for example:

Azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-Chloro-5- [1- (6-methyl-pyridin-2-ylmethoxyimino) -ethyl] -benzyl) -carbamic acid methyl ester or 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3- methoxy-methyl acrylate;

Carboxylic acid amides (group C), for example: Carboxylic acid anilides: benalaxyl, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamide, flutolanil, furametpyr, metalaxyl, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid- (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl- 2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4' dichloro-4-fluoro-biphenyl-2-yl) -amide, 3,4-dichloro-isothiazole-5-carboxylic acid (2-cyano-phenyl) -amide;

Carboxylic acid morpholides: Dimethomorph, Flumorph; Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide;

Other carboxylic acid amides: carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl-propyl) -sinyloxy-S-methoxy-phenyl-ethyl-1-methanesulfonylamino-S-methyl-butyramide , N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethanesulfonylamino-3-methyl-butyramide and compounds of the formula XI:

in which R ^{4 is} methyl or ethyl.

Nitrogen-containing heterocyclyl compounds (group D), for example:

Pyridines: fluazinam, pyrifenox, 3- [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine;

Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol,

pyrimethanil;

Piperazines: triforins ¹

Pyrroles: fludioxonil, fenpiclonil; Morpholine: aldimorph, dodemorph, fenpropimorph, tridemorph;

Dicarboximides: iprodione, procymidone, vinclozolin; other: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomezine,

Fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole,

Proquinazide, pyroquilon, quinoxyfen, tricyclazole, 2-butoxy-6-iodo-3-propyl-chromen-4-one or 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1 , 2,4] triazole-1-sulfonic acid dimethylamide;

Carbamates and dithiocarbamates (Group E), for example:

Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Flubenthiavalicarb, Iprovalicarb, Propamocarb,

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate, N- (1- (1 - (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4- fluorophenyl) ester and the compound of formula X-II

Z is N or CH;

[1, 2,4] triazolo [1,5-a] pyrimidines (group F) which carry the following radicals in the 5-, 6- and 7- positions: in the 6-position, a phenyl ring, which is substituted by 1, 2 or 3 halogen atoms, in the 5-position a halogen atom, CN or a methyl group and in the 7-position a radical which is branched C3-C8-alkyl, C 1 -C 8 -alkylamino, C 1 -C ₄ -Alkyl-C 1 -C ₈ -alkylamino, C 1 -C ₄ -haloalkyl-C 1 -C ₈ -alkylamino and N-bonded, saturated C 1 -C 2 -cyclocyclic, which may also have a methyl group, for example 5-chloro-7 (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine;

Other fungicides (group G), for example:

Guanidines: guanidine, dodine, iminoctadine, guazatine;

- Antibiotics: Kasugamycin, Polyoxins, Streptomycin, Validamycin A;

Organometallic compounds: fentin salts;

Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone; Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;

Organochlorine compounds: thiophanates methyl, chlorothalonil, dichlofluanid, toluylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;

Nitrophenyl derivatives: binapacryl, dinocap, dinobuton; - Inorganic active substances: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur;

- Other: Spiroxamine, Cyflufenamid, Cymoxanil, Metrafenone.

The present invention also relates in particular to fungicidal compositions which comprise at least one compound of the general formula I and at least one further crop protection agent, in particular at least one fungicidal active ingredient, for example one or more, for example 1 or 2, active compounds of the abovementioned groups A to G and optionally one or more several agriculturally suitable carriers included. With regard to a reduction of the application rates, these mixtures are of interest, since many with reduced total amount of active ingredients shown an improved activity against harmful fungi, especially for certain indications show. It has also been found that with simultaneous use of at least one compound I and of at least one fungicidal active compound from groups A to G, harmful fungi can be better controlled than with the individual compounds alone (synergistic). gistic mixtures). The compounds I can be used as synergists for a large number of different fungicidal active compounds, in particular those of groups A to G. By simultaneous joint or separate use of compounds) I with at least one active compound of groups A to G, the fungicidal activity is increased to a superadditive extent.

Common application in the context of this application means that the at least one active ingredient of the formula I and the at least one further active ingredient at the same time at the site of action (ie the fungi to be combated and their habitats such as infested plants, soil, seeds, materials or rooms and the fungal plants, soils, seeds, materials or spaces) are present in an amount sufficient to effectively control fungal growth. This can be achieved by applying the active ingredients together in a common drug preparation or in two separate drug treatments simultaneously or by applying the active ingredients sequentially at the site of action, wherein the time interval of the individual drug applications is chosen so that the first applied drug at the time the application of the other active substance (s) is present in sufficient quantity at the site of action.

Preference is given to those compositions which contain, in addition to at least one active compound from groups A to G, at least one compound of the formula I in which R and n have the meanings given above as preferred, and in particular those compounds of the formula I in which the radical SO _n R is S-CF3 or S-CHF2 and especially those in which the group SO _n R is attached at the 4'-position of the biphenyl moiety. Likewise preferred are those compositions which contain, in addition to at least one active compound from groups A to G, at least one compound of the formula I in which A is a radical A.1 and the radical SO _n R is S-CH 3 or SO 2 -CH 3, and especially those in which the group SO _n R is attached in the 4'-position of the biphenyl unit.

In particular, those compositions are preferred which comprise at least one active ingredient of the formula Ia, for example an active ingredient selected from the active ingredients Ia-1 to Ia-369. Likewise preferred are those compositions which contain at least one active ingredient of the formula Ib, for example an active ingredient selected from the active ingredients Ib-1 to Ib-369. Likewise preferred are those compositions which contain at least one active ingredient of the formula Ic, for example an active ingredient selected from the active ingredients Ic-1 to Ic-369. Likewise preferred are those compositions which contain at least one active ingredient of the formula Ic, for example an active ingredient selected from the active ingredients Ic-1 to Ic-369. Likewise preferred are those compositions which comprise at least one active substance of the formula Id, for example an active substance selected from the active substances ld-1 to ld-369. Likewise preferred are those compositions which comprise at least one active substance of the formula Ie, for example an NEN active ingredient, selected from the active ingredients le-1 to le-369 included. Likewise preferred are those compositions which contain at least one active ingredient of the formula If, for example an active ingredient selected from active ingredients If-1 to If-369. Likewise preferred are those compositions which contain at least one active ingredient of the formula Ig, for example an active ingredient selected from the active ingredients Ig-1 to Ig-369. Likewise preferred are those compositions which contain at least one active ingredient of the formula Ih, for example an active ingredient selected from the active ingredients Ih-1 to Ih-369. Likewise preferred are those compositions which contain at least one active substance of the formula Li, for example an active substance selected from the active ingredients li-1 to li-369.

Particular preference is given to those compositions which comprise at least one active ingredient of the formula I or the formulas La, Lb, Lc, Ld, Le, Lf, Lg, Lh or Lh, in which A has one of the meanings indicated as being preferred, in particular those in which A is a radical A.1, particularly preferably a radical A.1 in which R ¹ and R ^{2 have} the meanings given above as being preferred, and very particularly preferably where A is 1-methyl-3-trifluoromethylpyrazole-4 yl or 1-methyl-3-difluoromethylpyrazol-4-yl.

Very particular preference is given to those compositions in which the compound I is selected from the compounds Ia-16, Ia-17, Ia-37 and Ia-38.

Preference is given to compositions of a compound of the formula I with at least one active compound selected from the group A) of the azoles.

Preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group B) of strobilurins.

Preference is given to compositions of a compound of the formula I with at least one active compound selected from the group C) of the carboxamides.

Also preferred are compositions of a compound of the formula I with at least one active compound selected from the group D) of the heterocyclic compounds.

Also preferred are compositions of a compound of formula I with at least one active ingredient selected from the group E) of the carbamates.

Also preferred are compositions of a compound of the formula I with at least one active compound selected from the group F) of the [1,2,4] triazolo [1,5-a] pyrimidines. Also preferred are compositions of a compound of the formula I with at least one active compound selected from the group G) of the other fungicides.

Also preferred are compositions of a compound of formula I with at least one active ingredient selected from the group A) of azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon , Triadinol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl, carbendazim and ethaboxam.

Particular preference is also given to compositions of a compound of the formula I with at least one active ingredient selected from the group A) of the azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole , Tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl and carbendazim.

Very particular preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group A) of the azoles selected from epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim.

Also preferred are compositions of a compound of the formula I with at least one active ingredient selected from the group B) of strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.

Particular preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group B) of strobilurins selected from kresoxim-methyl, orysastrobin and pyraclostrobin.

Very particular preference is also given to compositions of a compound of the formula I with pyraclostrobin.

Preference is also given to compositions of a compound of the formula I with at least one active substance selected from the group C) of the carboxamides selected from fenhexamide, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolide (picobenzamide), zoxamide, carpropamide and mandipropamide.

Particular preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group C) of the carboxamides, selected from fenhexamide, metalaxyl, mefenoxam, ofurace, dimethomorph, zoxamide and carpropamide.

Preference is also given to compositions of a compound of the formula I having at least one active ingredient selected from the group D) of the heterocyclic compounds selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforin, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione , Vinclozolin, famoxadone, fenamidone, probenazole, proquinazide, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen, in particular fluazinam, cyprodinil, fenranolol, mepanipyrim, pyrimethanil, triforin, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, Iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazide, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen.

Particular preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group D) of the heterocyclic group

Compounds selected from pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozoline and quinoxyfen, especially pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozoline and quinoxyfen.

Preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group E) of the carbamates selected from mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb and propamocarb.

Particular preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group E) of the carbamates selected from mancozeb and metiram.

Preference is also given to compositions of a compound of the formula I having at least one active compound selected from the group F) of the [1,2,4] triazolo [1,5-a] pyrimidines, in particular 5-chloro-7- (4 -methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

Preference is also given to compositions of a compound of the formula I having at least one active ingredient selected from the group G) of the other fungicides selected from dithianone, fentin salts such as fentin acetate, fosetyl, fosetyl-aluminum, phosphorous acid and salts thereof, chlorothalonil , Dichlofluanid, thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine.

Particular preference is also given to compositions of a compound of the formula I with at least one active compound selected from the group G) of the other fungicides. de, selected from phosphorous acid and its salts, chlorothalonil and Metrafe- non.

Preference is also given to compositions which contain a compound of the formula I two further of the abovementioned active compounds A to G.

In the compositions of the invention, the weight ratio of compound I to the total amount of other active agents, e.g. from groups A to G, generally in the range from 1: 100 to 100: 1, often in the range from 1:50 to 50: 1, preferably in the range from 1:20 to 20: 1, in particular in the range from 1:10 to 10: 1.

In so-called dual mixtures, i. Compositions comprising an active ingredient of the formula I and another active ingredient, e.g. a compound from groups A to G, weight ratio of compound I to further active ingredient is usually in the range of 1: 100 to 100: 1, often in the range of 1:50 to 50: 1, preferably in the range of 1: 20 to 20: 1, in particular in the range of 1:10 to 10: 1.

In so-called triple mixtures, i. Compositions comprising an active ingredient of the formula I and a further active ingredient and a second further active ingredient, e.g. contain two different active compounds from groups A to G, the weight ratio of compound I to the first further active ingredient is preferably in the range from 1:50 to 50: 1 and in particular in the range from 1:10 to 10: 1. The weight ratio of compound I to the second further active ingredient is preferably in the range from 1:50 to 50: 1, in particular in the range from 1:10 to 10: 1. The weight ratio of 1. further active ingredient to the second further active ingredient is preferably in the range from 1:50 to 50: 1, in particular in the range from 1:10 to 10: 1.

Preferred active substance combinations are listed in the following Tables 1 and 2:

Table 1: Active ingredient composition comprising a compound I and another active compound from groups A to G.

In the mixtures mentioned in Table 1, the weight ratio of compound to further active ingredient is preferably in the range from 1:50 to 50: 1, in particular in the range from 1:10 to 10: 1.

Table 2: Active ingredient composition comprising a compound I and two further active compounds from groups A to G.

In the mixtures mentioned in Table 2, the weight ratio of compound I to the first further active ingredient is preferably in the range from 1:50 to 50: 1, in particular in the range from 1:10 to 10: 1. The weight ratio of compound I to the second further active ingredient is preferably in the range from 1:50 to 50: 1, in particular in the range from 1:10 to 10: 1. The weight ratio of 1 further active ingredient to 2 further active ingredient is preferably in the range from 1:50 to 50: 1, in particular in the range from 1:10 to 10: 1.

The compositions of the invention may be conveniently, e.g. in the manner mentioned for the compounds I, active substances are formulated into agents which contain, in addition to the active substances, at least one inert additive, e.g. an agriculturally acceptable carrier and optionally other ingredients, e.g. contain conventional adjuvants and adjuvants. With regard to the carrier and the other constituents, what has been said above applies analogously.

The active ingredients of the compositions according to the invention may be present together in one formulation, or in one agent, or they may be formulated separately and the agents may be applied together or sequentially. Like the compounds I, the compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi from the class of the Ascomycetes, Deuteromycetes, Basidiomycetes and Peronosporomycetes (syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are of particular importance for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants.

Specifically, they are suitable for controlling the plant diseases mentioned in the compound I.

The compositions according to the invention are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products, in particular against the harmful fungi mentioned in connection with compound I.

The compositions of the invention are applied by treating the fungi or the plants, seeds, materials or soil to be protected against fungal attack with a fungicidally effective amount of the composition. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha (total amount of active ingredient).

In seed treatment, in general, amounts of active ingredient of from 1 to 1000 g / 100 kg, preferably from 5 to 100 g / 100 kg of seed are required (total amount of active substance).

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material (total amount of active substance) in the protection of materials. Example 1: 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide

1.1 4'-methanesulfonyl-biphenyl-2-yl-amide

A mixture of 2.35 g of 1-bromo-4-methanesulfonylbenzene, 2.40 g of 2- (4,4,5,5-tetramethyl- [1,2,2] dioxaborolan-2-yl) -phenylamine), 2 , 12 g of sodium carbonate, 0.08 g of tetrakis (triphenylphosphine) palladium (0) in 38 ml of ethylene glycol dimethyl ether and 13 ml of water was heated to reflux under a nitrogen atmosphere. After 6 h, an additional 0.04 g of tetrakis (triphenylphosphine) palladium (0) was added and heated at reflux for a further 8 h. The reaction mixture was allowed to cool to room temperature, filtered and concentrated under reduced pressure. Thereafter, the residue was taken up in methyl tert-butyl ether, and the organic phase was extracted with water three times. After drying the organic phase and filtering off the drying agent, the organic phase was concentrated under reduced pressure. The residue obtained was recrystallized from diisopropyl ether. This gave 1, 2 g of the title compound as a dark powder.

1.2 1 -methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide

To a solution of 0.31 g of the compound from Example 1.1 and 0.15 g of pyridine in 8.5 ml of tetrahydrofuran was added dropwise at room temperature 0.27 g of 1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbonyl chloride. The mixture was stirred for 16 hours at room temperature and then treated with 300 ml of tetrahydrofuran and 150 ml of methyl tert-butyl ether. The reaction mixture was washed once with 2% hydrochloric acid. The organic phase was then extracted twice with 2% sodium hydroxide solution and once with brine, and then concentrated under reduced pressure. The obtained crude product was washed successively with diisopropyl ether and pentane. 0.40 g of the title compound was obtained as a white powder with a melting point of 253-255 ⁰ C.

In an analogous manner, the compounds of formula I.a indicated in Table I were prepared.

Table I:

M.p .: melting point

Example 25: ¹ H NMR (CDCl ₃ ): d 2.45 (s, 3H), 2.70 (s, 3H), 7.00-7.50 (m, 8H), 7.70 (s, 1H), 8.35 (d, 1H). Example 26: ¹ H NMR (CDCl ₃ ): d 2.40 (s, 3H), 2.70 (s, 3H), 7.00-7.50 (m, 8H), 7.60 (s, 1H), 8.30 (d, 1H).

Examples of the effect against harmful fungi

The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:

Greenhouse experiments (Examples 1 to 6):

The active compounds were prepared 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 on the basis of ethoxylated alkylphenol Ie) in the volume ratio solvent-emulsifier from 99 to 1 ad 10 ml. 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.

Use Example 1 - Efficacy against Tomato Drought on Tomcat caused by Alternaria solani (Alteso P1)

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were inoculated with an aqueous spore suspension of Alternaria solani in 2% biomalt solution. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.

The compounds of Examples 4, 5, 12, 16, 19, 20, 21 and 22 showed an attack of at most 10% at an application rate of 250 ppm, whereas the untreated plants were 90% affected.

Use Example 2 Protective Activity Against Puccinia recondita on Wheat (Wheat Brown Rust) (Puccrt P1)

Leaves of potted wheat seedlings of the variety "Chancellor" were sprayed to drip point with an aqueous suspension in the active ingredient concentration given below. The next day, the treated plants were inoculated with a spore suspension of the wheat brown rust (Puccinia recondita). The plants were then placed in a high humidity chamber (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The following day, the experimental Plants returned to the greenhouse and cultured at temperatures between 20 and 22 ⁰ C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.

The compounds of Examples 5, 23 and 24 showed at an application rate of 250 ppm infestation of less than 20%, whereas the untreated plants were 90% infected.

Use Example 3 - Curative Activity Against Wheat Brown Rust Caused by Puccinia recondita (Puccrt K1) Leaves of potted wheat seedlings were grown with a

Spore suspension of the brown rust (Puccinia recondita) inoculated. 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 the above-described active ingredient solution in the drug concentration indicated below to drip point. 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.

The compounds of Examples 1, 4, 19 and 20 showed at a rate of 250 ppm an infection of not more than 10%, whereas the untreated plants were 90% infected.

Use Example 4 - Action against gray mold on pepper leaves caused by Botrytis cinerea at 1 day of protective application (Botrci P1) Paprika seedlings were sprayed to drip point after 2-3 leaves had developed well with an aqueous suspension in the concentration of active compound stated below. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea in 2% 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%.

The compounds of Examples 11 and 15 showed at an application rate of 250 ppm infestation of less than 20%, whereas the untreated plants were infected to 100%.

Use Example 5 - Efficacy against the net blotchness of barley caused by Pyrenophora teres at 1 day of protective application (Pyrnte P1) 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 ⁰ C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

The compounds of Examples 12 and 26 showed at an application rate of 250 ppm infestation of less than 20%, whereas the untreated plants were 90% infected.

Use Example 6 - Protective Efficacy Against Septoria Leaf Spot Disease of Wheat Caused by Septoria tritici (Septtr P1)

Leaves of potted wheat 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, they were inoculated with an aqueous spore suspension of Septoria tritici. The test plants were then placed in the greenhouse for 3 days at temperatures between 16 and 22 ° C and a relative humidity near 100%, then at a relative humidity of about 70%. After 4 weeks, the extent of disease development was determined visually in% infestation of the total leaf area.

The compounds of Example 23 at an application rate of 250 ppm showed an infection of less than 5%, whereas the untreated plants were 80% infected.

Microtiter experiments (application examples 7 and 8):

The active ingredients were separately formulated as stock solution at a concentration of 10,000 ppm in DMSO.

Use Example 7 Activity Against the Causative Agent of Gray Mold Botrytis cinerea in Microtiter Test (Botrci)

The stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Botrytis cinerea. The plates were placed in a water vapor-saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation. The measured parameters were compared with the growth of the drug-free control variant and the fungus- and drug-free blank to determine the relative growth in% of the pathogens in the individual drugs. The compounds of Examples 4, 13, 14 and 15 showed a relative growth of the pathogen of a maximum of 5% at an active ingredient concentration of 125 ppm. In contrast, compound 3.19 from EP 545099 at the same application rate showed a growth of the pathogen of 9%.

Use Example 8 - Activity against the causative agent of the Septoria leaf drought Septoria tritici in the microtiter test (Septtr)

The stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Septoria tritici. The plates were placed in a water vapor-saturated chamber at temperatures of 18 ⁰ C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.

The measured parameters were compared with the growth of the drug-free control variant (100%) and the fungus-free and drug-free blank to determine the relative growth in% of the pathogens in the individual drugs.

The compounds of Examples 2, 4, 8, 13, 14, 15 and 21 showed at a drug concentration of 125 ppm, a relative growth of the pathogen of a maximum of 1%.

Claims

claims

1. Hetarylcarboxylic acid N- (biphen-2-yl) amide compounds of the general formula

wherein m is 0, 1, 2, 3 or 4; n is 0, 1 or 2;

R is C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl or, if n = 2, may also be NH 2;

Hal is halogen, in particular fluorine or chlorine; and

A is a heteroaromatic radical which is selected from radicals of the general formulas A.1, A.2 and A.3

A.1 A.2 A.3 wherein

R ^{1 is} methyl or halomethyl;

R ^{2 is} hydrogen, fluorine or chlorine;

R ^{3 is} hydrogen, chloro, methyl or trifluoromethyl;

R ^{4 is} hydrogen, chloro, methyl or trifluoromethyl; and

R ^{5 is} fluoro, chloro, methyl, difluoromethyl, trifluoromethyl or methoxy; and their salts, except compounds in which the group S (O) _n -R is a thio-C 1 -C 4 -alkyl group which is bonded in the 4'-position of the biphenyl unit, when A is a radical A.2 or a residue A.3 is.

2. Compounds of general formula I according to claim 1, wherein R is C1-C2-haloalkyl.

3. Compounds of general formula I according to claim 1 or 2, wherein m = 0.

4. Compounds of general formula I according to any one of the preceding claims, wherein n = 0.

5. Compounds of general formula I according to claim 4, wherein R is CHF 2 or CF ₃ .

6. Compounds of general formula I according to any one of claims 1 to 3, wherein n = 2.

7. Compounds of general formula I according to claim 6, wherein R is CH3, CHF2, NH ₂ or CF ₃ .

8. Compounds of the general formula I according to any one of the preceding claims, wherein the radical R-SO _n is bonded in the 4'-position of the biphenyl unit.

9. Compounds of general formula I according to claim 8, wherein n is 0;

R is C 1 -C 2 -fluoroalkyl and particularly preferably difluoromethyl or trifluoromethyl; and m is 0 or 1.

10. Compounds of general formula I according to any one of the preceding claims, wherein A is a radical of formula A.1.

1 1. Compounds of general formula I according to claim 9, wherein R ^{1 is} CH ₃ , CHF ₂ or CF ₃ .

12. Compounds of general formula I according to claim 9 or 10, wherein R ^{2 is} hydrogen.

13. Compounds of the general formula I according to any one of claims 9 to 12, wherein m is 0 and in which the radical R-SO _n is bonded in the 4'-position of the biphenyl unit.

14. Compounds of general formula I according to any one of claims 9 to 12, wherein m is 1 and wherein the radical R-SO _n is bonded in the 4'-position of the biphenyl unit and wherein R is Ci-C2-fluoroalkyl.

15. Compounds of general formula I according to claim 13, wherein n is O; and

R is Ci-C2-fluoroalkyl and particularly preferably represents difluoromethyl or Triflu- ormethyl.

16. Compounds of general formula I according to any one of claims 9 to 15, selected from:

1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (3'-sulfamoyl-biphenyl-2-yl) -amide,

1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-sulfamoyl-biphenyl-2-yl) -amide,

1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methanesulfonylbiphenyl)

2-yl) -amide,

1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (3 '- (trifluoromethylthio) biphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid - (4 '- (trifluoromethylthio) biphenyl-2-yl) -amide,

1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (3 '- (trifluoromethylthio) biphenyl-2-yl) -amide,

1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (4 '- (trifluoromethylthio) biphenyl-2-yl) -amide,

1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (2'-methylthiobiphenyl-2-yl) -amide,

1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (3'-methylthiobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4 ' -methylthiobiphenyl-2-yl) amide and

1-Methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methylthiobiphenyl-2-yl) -amide, and salts thereof.

17. Compounds of general formula I according to any one of claims 1 to 8, wherein A is a radical of formula A.2.

18. Compounds of general formula I according to claim 17, wherein R ^{3 is} CH ₃ or CF ₃ .

19. Compounds of general formula I according to claim 17 or 18, wherein R ^{4 is} CH ₃ .

20. Compounds of general formula I according to any one of claims 17 to 19, selected from:

2-Methyl-4-trifluoromethylthiazole-5-carboxylic acid (4'-sulfamoyl-biphenyl-2-yl) -amide, 2-methyl-4-trifluoromethyl-thiazole-5-carboxylic acid (3'-sulfamoyl-biphenyl-2-yl) -amide, 2-Methyl-4-trifluoromethyl-thiazole-5-carboxylic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide,

2-Methyl-4-trifluoromethylthiazole-5-carboxylic acid (3 '- (trifluoromethylthio) biphenyl-2-yl) -amide, 2-methyl-4-trifluoromethyl-thiazole-5-carboxylic acid (4' - (trifluoromethylthio) biphenyl-2 yl) amide,

2-methyl-4-trifluoromethylthiazole-5-carboxylic acid (2'-methylthiobiphenyl-2-yl) -amide,

2-methyl-4-trifluoromethylthiazole-5-carboxylic acid (3'-methylthiobiphenyl-2-yl) -amide,

2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (4'-sulfamoyl-biphenyl-2-yl) -amide, 2-methyl-4-difluoromethyl-thiazole-5-carboxylic acid (3'-sulfamoyl-biphenyl-2-yl) -amide,

2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide,

2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (3 '- (trifluoromethylthio) -biphenyl-2-yl) -amide, 2-methyl-4-difluoromethyl-thiazole-5-carboxylic acid (4' - (trifluoromethylthio) biphenyl-2 yl) amide,

2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (2'-methylthiobiphenyl-2-yl) -amide and

2-Methyl-4-difluoromethyl-thiazole-5-carboxylic acid (3'-methylthiobiphenyl-2-yl) -amide and its salts.

21. Compounds of general formula I according to any one of claims 1 to 8, wherein A is a radical of formula A.3.

22. Compounds of general formula I according to claim 21, wherein R ^{5 is} chlorine or CF3.

23. Compounds of general formula I according to one of claims 21 or 22, selected from: 2-chloronicotinic acid (3'-sulfamoyl-biphenyl-2-yl) -amide,

2-chloronicotinic acid (4'-sulfamoyl-biphenyl-2-yl) -amide, 2-chloronicotinic acid (4'-methanesulfonyl-biphenyl-2-yl) -amide, 2-chloronicotinic acid (3 '- (trifluoromethylthio) biphenyl-2-yl ) -amide, 2-chloronicotinic acid- (4 '- (trifluoromethylthio) biphenyl-2-yl) -amide, 2-chloronicotinic acid (2'-methylthiobiphenyl-2-yl) -amide,

2-chloronicotinic acid (3'-methylthiobiphenyl-2-yl) -amide, and its salts.

24. A composition for controlling harmful fungi, comprising at least one compound of the formula I according to any one of claims 1 to 23 and at least one inert additive.

25. A method for controlling harmful fungi, characterized in that the harmful fungi, their habitat and / or the fungal infection to be protected materials, plants, the soil or seeds with a fungicidally effective amount of at least one compound of formula I according to any one of claims 1 treated until 23.

26. Use of the compounds I according to any one of claims 1 to 23 for controlling harmful fungi.

27. Seed containing at least one compound of formula I according to any one of claims 1 to 23 in an amount of 1 to 1000 g per 100 kg of seed.

28. A composition comprising at least one compound of the formula I according to any one of claims 1 to 23 and at least one further fungicidal active substance.

29. A method for controlling harmful fungi, which comprises treating the harmful fungi, their habitat and / or the materials, plants, the soil or seeds to be protected against fungal attack with a fungicidally effective amount of at least one composition according to claim 28.

30. Use of a composition according to claim 28 for controlling harmful fungi.

31. Seed containing at least one compound of formula I according to any one of claims 1 to 23 and at least one further fungicidal active ingredient in a total amount of 1 to 1000 g per 100 kg of seed.