The present invention relates to (hetero)cyclic carboxanilides having an oxime ether function and their use for controlling harmful fungi.
WO 02/08197 describes fungicidally active hetarylcarboxanilides having a phenyl group in the 2-position on the phenyl ring, which phenyl group carries an oxime ether group. 1,3-Dimethyl-5-fluoropyrazole-4-carboxanilides of a similar structure are known from WO 02/08197.
WO 98/03500 describes hetarylcarboxanilides which may, inter alia, have a phenoxy group on the phenyl ring.
WO 95/01339 discloses 4-pyridinecarboxanilides which carry a phenoxy substituent in the 2-position of the anilide ring.
However, the (heteroaryl)carboxanilides described in the prior art are, in particular at low application rates, not entirely satisfactory.
Accordingly, it is an object of the present invention to provide fungicidally active compounds which overcome the disadvantages of the compounds known from the prior art and, in particular, have improved action at low application rates. Moreover, these compounds should have good compatibility with useful plants and, if possible, cause little, if any, harm to useful animals.
This object is achieved by the (hetero)cyclyl(thio)carboxanilides of the formula I described below and by their agriculturally acceptable salts.
Accordingly, the present invention relates to (hetero)cyclyl(thio)carboxanilides of the formula I,
in which the variables are as defined below:
Moreover, the present invention relates to the use of the (hetero)cyclyl(thio)carbox-anilides of the formula I and their agriculturally acceptable salts as fungicides, and to crop protection compositions comprising these compounds.
Furthermore, the present invention relates to a method for controlling phytopathogenic fungi (harmful fungi), which method comprises treating the harmful fungi, their habitat or the plants, areas, materials or spaces to be kept free from them with a fungicidally effective amount of a (hetero)cyclylcarboxamide of the formula I and/or an agriculturally useful salt of I.
Depending on the substitution pattern, the compounds of the formula I may have one or more centers of chirality, in which case they are present as enantiomer or diastereomer mixtures. The invention provides both the pure enantiomers or diastereomers and also their mixtures. Suitable compounds of the formula I also include all possible stereoisomers (cis/trans isomers) and mixtures thereof.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
In the definitions of the variables given in the formulae above, collective terms are used which are generally representative of the substituents in question. The term Cn-Cm denotes the number of carbon atoms possible in each case in the respective substituent or substituent moiety. All carbon chains, i.e. all alkyl, haloalkyl, phenylalkyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl and phenylalkynyl moieties may be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms. The term “halogen” denotes in each case fluorine, chlorine, bromine or iodine.
Examples of other meanings are:
With a view to the fungicidal activity of the compounds I according to the invention, preference is given to those compounds of the formula I in which A is a cyclic radical A-1 to A-6:
in which * denotes the point of attachment to C(═Y) and the variables are as defined below:
In the radicals of the formulae A-1, A-2, A-3, A-4, A-5 and A-6, the variables Ra1, Ra2 and Ra3 have in particular the following meanings:
In the formula A-2, W is preferably a group N—Ra4 in which Ra4 has the meanings given above and in particular the meanings given as being preferred.
If X in the formulae A-1, A-2, A-3 or A-4 is a group C—Rc, Rc is preferably hydrogen.
X in the formulae A-2, A-3 and A-4 is in particular N. In formula A-1, X is in particular CH.
In the formula A-1, X1 is in particular N. In a preferred embodiment, A is A-6 in which X1 is N. In a further preferred embodiment, A is A-6 in which X1 is C—Rc and in particular C—H.
Examples of radicals A-1 are in particular:
in which *, Ra1, Ra2 and Rc have the meanings given above and in particular the preferred meanings.
Examples of radicals A-2 are in particular:
in which *, Ra1, Ra3, Ra4 and Rc have the meanings given above and in particular the preferred meanings.
Examples of radicals A-3 are in particular:
in which *, Ra1, Ra3 and Rc have the meanings given above and in particular the preferred meanings.
Examples of radicals A-4 are in particular:
in which *, Ra1, Ra3 and Rc have the meanings given above and in particular the preferred meanings.
Examples of A-5 are in particular:
in which * and Ra1 have the meanings given above and in particular the preferred meanings.
Examples of A-6 are in particular:
in which *, Ra1, Ra2 and Rc have the meanings given above and in particular the preferred meanings.
Examples of radicals A are: 2-chlorophenyl, 2-trifluoromethylphenyl, 2-difluoromethylphenyl, 2-methylphenyl, 2-chloropyridin-3-yl, 2-trifluoromethylpyridin-3-yl, 2-difluoromethylpyridin-3-yl, 2-methylpyridin-3-yl, 4-methylpyrimidin-5-yl, 4-trifluoromethylpyrimidin-5-yl, 4-difluoromethylpyrimidin-5-yl, 1-methyl-3-trifluoromethylpyrazol-4-yl, 1-methyl-3-difluoromethylpyrazol-4-yl, 1,3-dimethylpyrazol-4-yl, 1-methyl-3-trifluoromethyl-5-fluoropyrazol-4-yl, 1-methyl-3-difluoromethyl-5-fluoropyrazol-4-yl, 1-methyl-3-trifluoromethyl-5-chloropyrazol-4-yl, 1-methyl-3-trifluoromethylpyrrol-4-yl, 1-methyl-3-difluoromethylpyrrol-4-yl, 2-methyl-4-trifluoromethylthiazol-5-yl, 2-methyl-4-difluoromethylthiazol-5-yl, 2,4-dimethylthiazol-5-yl, 2-methyl-5-trifluoromethylthiazol-4-yl, 2-methyl-5-difluoromethylthiazol-4-yl, 2,5-dimethylthiazol-4-yl, 2-methyl-4-trifluoromethyloxazol-5-yl, 2-methyl-4-difluoromethyloxazol-5-yl, 2,4-dimethyloxazol-5-yl, 2-trifluoromethylthiophen-3-yl, 5-methyl-2-trifluoromethylthiophen-3-yl, 2-methylthiophen-3-yl, 2,5-dimethylthiophen-3-yl, 3-trifluoromethylthiophen-2-yl, 3-methylthiophen-2-yl, 3,5-dimethylthiophen-2-yl, 5-methyl-3-trifluoromethylthiophen-2-yl, 2-trifluoromethylfuran-3-yl, 5-methyl-2-trifluoromethylfuran-3-yl, 2-methylfuran-3-yl, 2,5-dimethylfuran-3-yl, 2-methyl-5,6-dihydro-[1,4]oxathiin-3-yl, 2-methyl-5,6-dihydro-4H-thiopyran-3-yl.
With particular preference, A is a radical A-1a, A-2a or A-3a,
in which *, Ra1, Ra2, Ra3 and Ra4 have the meanings given above and in particular the preferred meanings.
Preference is given to radicals A-1a where Ra1 is hydrogen, halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-fluoroalkoxy or C1-C2-fluoroalkyl; in particular hydrogen, chlorine, bromine, fluorine, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy or difluoromethoxy, very particularly preferably fluorine, bromine, chlorine, methyl or trifluoromethyl, and especially chlorine; where Ra2 is hydrogen, halogen, nitro, CN, C1-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, where the 5 lastmentioned groups may be substituted by halogen, especially hydrogen.
Preference is given to radicals A-2a where Ra1 is hydrogen, halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-fluoroalkoxy or C1-C2-fluoroalkyl, in particular hydrogen, chlorine, bromine, fluorine, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy or difluoromethoxy, very particularly preferably fluorine, bromine, chlorine, methyl or trifluoromethyl, especially trifluoromethyl; Ra3 is hydrogen, halogen, nitro, CN, C1-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, where the 5 lastmentioned groups may be substituted by halogen, preferably hydrogen, halogen and C1-C4-alkyl, in particular halogen, hydrogen; and especially hydrogen; and Ra4 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkyl or phenyl which may be unsubstituted or may carry 1, 2 or 3 radicals Rb, preferably hydrogen, C1-C4-alkyl or C1-C4-haloalkyl, especially methyl;
Preference is given to radicals A-3a where Ra1 is hydrogen, halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-fluoroalkoxy or C1-C2-fluoroalkyl, in particular hydrogen, chlorine, bromine, fluorine, methyl, ethyl, methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy or difluoromethoxy, very particularly preferably fluorine, bromine, chlorine, methyl or trifluoromethyl, especially trifluoromethyl; Ra3 is hydrogen, halogen, nitro, CN, C1-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, where the 5 lastmentioned groups may be substituted by halogen, preferably hydrogen, halogen or C1-C4-alkyl, in particular hydrogen, methyl and especially methyl.
With particular preference, A is selected from the group consisting of: A-1a where Ra1=halogen, especially chlorine, and Ra2=hydrogen; A-2a where Ra1═C1-C2-fluoroalkyl, especially trifluoromethyl, Ra3=hydrogen and Ra4═C1-C4-alkyl, especially methyl; and A-3a where Ra1═C1-C2-fluoroalkyl, especially trifluoromethyl, and Ra3═C1-C4-alkyl, especially methyl.
Among the (hetero)cyclylcarboxamides according to the invention, preference is given to those compounds of the formula I in which the group O—B is attached in the ortho-position to the group N—R1, i.e. compounds of the formula I′ given below
where the variables n, m, A, Y, R1, R2, R3, R4 and R5 have the meanings given above and in particular the meanings given here and below as being preferred or particularly preferred.
Among the (hetero)cyclylcarboxamides according to the invention, preference is furthermore given to those compounds of the formula I in which the group —C(R5)═N—OR4 is attached in the meta- or in the para-position to the oxygen of the group O—B and among these in particular to the compounds of the formulae I-A and I-B
where the variables n, m, A, Y, R1, R2, R3, R4 and R5 have the meanings given above and in particular the meanings given here and below as being preferred or particularly preferred.
With a view to their fungicidal activity, preference is given to (hetero)cyclylcarbox-amides of the formula I (or I′, I-A or I-B) in which the variables Y, R1, R2, R3, R4, R5, n and m independently of one another and preferably in combination have the following meanings:
Preferred radicals R6 are those in which R7 and R8 independently of one another have the following meanings:
Otherwise, Rb is in particular halogen, nitro, CN, C1-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-haloalkyl, C2-C4-haloalkenyl or C1-C4-haloalkoxy.
Particular preference is furthermore given to the (heterocyclyl)carboxamides of the formula I (or I′, I-A or I-B) in which R1, R2, R3, R4, R5, n and m have the meanings given above and in particular the preferred meanings, Y is oxygen and A is selected from the group consisting of:
A-1, where X and X, are each nitrogen, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, trifluoromethyl, chlorine, bromine or fluorine; Ra2 has the meanings given above and is especially hydrogen;
A-2, where X is N, W is S, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl; Ra3 has the meanings given above, in particular the preferred meanings and is especially hydrogen;
A-2, where X is CH, W is N—Ra4, where Ra4 is C1-C4-alkyl, especially methyl, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl; Ra3 has the meanings given above, in particular the preferred meanings and is especially hydrogen;
A-3, where U is O, X is N, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl; Ra3 has the meanings given above, in particular the preferred meanings and is especially hydrogen or methyl;
A-3, where U is S, X is CH, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl; Ra3 has the meanings given above, in particular the preferred meanings and is especially hydrogen or methyl;
A-4, where U is O, X is CH or N, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl; Ra3 has the meanings given above, in particular the preferred meanings and is especially hydrogen or methyl;
A-4, where U is S, X is CH or N, Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl; Ra3 has the meanings given above, in particular the preferred meanings and is especially hydrogen or methyl;
A-5, where U is oxygen, Z is CH2, S, S(═O) or S(═O)2 and Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl;
A-6, where X, is nitrogen, Ra2 has the meanings given above and is especially hydrogen; Ra1 has the meanings given above, in particular the preferred meanings and is especially methyl, fluorine, chlorine, bromine or trifluoromethyl.
With a view to their use as fungicides, preference is given to compounds of the formula I-A where Y═O, R1═H, n=0 and m=0 and in which the variables A, R4 and R5 have the meanings given above and in particular the meanings given as being preferred or particularly preferred (compounds I-A′). Examples of these are the compounds of the formula I-A′ compiled in tables 1 to 42 below (compounds I-A where R1═H, n=0 and m=0), where R4 and R5 in each case have the meanings given in one row of table A and the variable A has the meaning given in the respective table. In the case of compounds which contain double bonds, both the isomerically pure E isomers, Z isomers and isomer mixtures thereof are included.
With a view to their use as fungicides, preference is given to compounds of the formula I-B where Y═O, R1═H, n=0 and m=0 and in which the variables A, R4 and R5 have the meanings given above and in particular the meanings given as being preferred or particularly preferred (compounds I-B′). Examples of these are the compounds of the formula I—B′ compiled in tables 1 to 42 below (compounds I—B where R1═H, n=0 and m=0), where R4 and R5 in each case have the meanings given in one row of table A and the variable A has the meaning given in the respective table. In the case of compounds which contain double bonds, both the isomerically pure E isomers, Z isomers and isomer mixtures thereof are included.
s-C4H9: —CH(CH3)(C2H5);
i-C4H9: CH2CH(CH3)2;
allyl: —CH2CH═CH2;
propargyl: —CH2C≡CH;
Table 1:
Compounds of the formulae I-A′ and I-B′, where A is 2-chlorophenyl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 2:
Compounds of the formulae I-A′ and I-B′ in which A is 2-trifluoromethylphenyl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 3:
Compounds of the formulae I-A′ and I-B′ in which A is 2-difluoromethylphenyl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 4:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methylphenyl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 5:
Compounds of the formulae I-A′ and I-B′ in which A is 2-chloropyridin-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 6:
Compounds of the formulae I-A′ and I-B′ in which A is 2-trifluoromethylpyridin-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 7:
Compounds of the formulae I-A′ and I-B′ in which A is 2-difluoromethylpyridin-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 8:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methylpyridin-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 9:
Compounds of the formulae I-A′ and I-B′ in which A is 4-methylpyridimidin-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 10:
Compounds of the formulae I-A′ and I-B′ in which A is 4-trifluoromethylpyrimidin-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 11:
Compounds of the formulae I-A′ and I-B′ in which A is 4-difluoromethylpyrimidin-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 12:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-trifluoromethylpyrazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 13:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-difluoromethylpyrazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 14:
Compounds of the formulae I-A′ and I-B′ in which A is 1,3-dimethylpyrazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 15:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-trifluoromethyl-5-fluoropyrazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 16:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-difluoromethyl-5-fluoropyrazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 17:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-trifluoromethyl-5-chloropyrazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 18:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-trifluoromethylpyrol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 19:
Compounds of the formulae I-A′ and I-B′ in which A is 1-methyl-3-difluoromethylpyrol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 20:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-4-trifluoromethylthiazol-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 21:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-4-difluoromethylthiazol-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 22:
Compounds of the formulae I-A′ and I-B′ in which A is 2,4-dimethylthiazol-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 23:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-5-trifluoromethylthiazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 24:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-5-difluoromethylthiazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 25:
Compounds of the formulae I-A′ and I-B′ in which A is 2,5-dimethylthiazol-4-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 26:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-4-trifluoromethyloxazol-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 27:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-4-difluoromethyloxazol-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 28:
Compounds of the formulae I-A′ and I-B′ in which A is 2,4-dimethyloxazol-5-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 29:
Compounds of the formulae I-A′ and I-B′ in which A is 2-trifluoromethylthiophen-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 30:
Compounds of the formulae I-A′ and I-B′ in which A is 5-methyl-2-trifluoromethyl-thiophen-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 31:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methylthiophen-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 32:
Compounds of the formulae I-A′ and I-B′ in which A is 2,5-dimethylthiophen-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 33:
Compounds of the formulae I-A′ and I-B′ in which A is 3-trifluoromethylthiophen-2-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 34:
Compounds of the formulae I-A′ and I-B′ in which A is 3-methylthiophen-2-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 35:
Compounds of the formulae I-A′ and I-B′ in which A is 3,5-dimethylthiophen-2-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 36:
Compounds of the formulae I-A′ and I-B′ in which A is 5-methyl-3-trifluoromethylthiophen-2-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 37:
Compounds of the formulae I-A′ and I-B′ in which A is 2-trifluoromethyfuran-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 38:
Compounds of the formulae I-A′ and I-B′ in which A is 5-methyl-2-trifluoromethylfuran-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 39:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methylfuran-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 40:
Compounds of the formulae I-A′ and I-B′ in which A is 2,5-dimethylfuran-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 41:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-5,6-dihydro-[1,4]oxathiin-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
Table 42:
Compounds of the formulae I-A′ and I-B′ in which A is 2-methyl-5,6-dihydro-4H-thiopyran-3-yl and R4 and R5 for each individual compound correspond in each case to one row of table A.
The compounds of the formula I according to the invention can be prepared by prior art methods known per se, for example according to scheme 1 by reacting activated (heterocyclyl)carboxylic acid derivatives II with an aniline III [Houben-Weyl: “Methoden der organ. Chemie” [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, N.Y. 1985, Volume E5, pp. 941-[1045]. Activated carboxylic acid derivatives II are, for example, halides, activated esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluorophenyl esters, N-hydroxysuccinimides, hydroxybenzotriazol-1-yl esters. In scheme 1, the radicals A, Y, R1, R2, R3, R4, R5, n and m have the meanings mentioned above and in particular the meanings mentioned as being preferred.
The active compounds I can also be prepared, for example, by reacting the acids IV with an aniline III in the presence of a coupling agent according to scheme 2. In scheme 2, the radicals A, Y, R1, R2, R3m, R4m, R5, R6, n and m have the meanings given above and in particular the meanings given as being preferred.
Suitable coupling agents are, for example:
Compounds I where R1=optionally halogen-substituted alkyl or optionally substituted cycloalkyl can also be prepared by alkylating the amides I (in which R1 is hydrogen and which can be obtained according to scheme 1 or 2) using suitable alkylating agents in the presence of bases, see scheme 3.
The (heterocyclyl)carboxylic acids IV can be prepared by methods known from the literature, and from these, the (heterocyclyl)carboxylic acid derivatives II can be prepared by methods known from the literature [for example EP 0589313, EP 915868, U.S. Pat. No. 4,877,441].
The anilines III can be prepared, for example, by the methods shown in scheme 4. In scheme 4, the radicals R1, R2, R3, R4, R5, n and m have the meanings given above and in particular the meanings given as being preferred. The compounds V and X are known from the literature or can be prepared by methods known from the literature.
Scheme 4:
In step 1 in scheme 4, the nitroaromatic compound VI in which L is halogen, for example fluorine, chlorine or bromine, is reacted with an acylphenol IX in the sense of a nucleophilic aromatic substitution, which yields the nitrobiphenyl ether VII. The reaction is carried out analogously to known processes, for example according to Organikum, 21st edition, Wiley-VCH 2001, p. 394ff. S. Raeppel, F. Raeppel, J. Suffert; Synlett [SYNLES] 1998, (7), 794-796. R. Beugelmans, A. Bigot, J. Zhu; Tetrahedron Lett [TELEAY] 1994, 35 (31), 5649-5652. The reaction is usually carried out in the presence of a base. Suitable bases are alkali metal carbonates, alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, alkali metal hydroxides or alkaline earth metal hydroxides, such as sodium hydroxide or potassium hydroxide. In general, the reaction is carried out in an inert organic solvent. Suitable solvents are ethers, such as diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol.
In step 2, the nitrophenyl ether VII is reacted with a hydroxylamine H2N—O—R4 or with an acid addition salt thereof, for example the hydrochloride HCl.H2N—O—R4, which yields the oximated nitrobiphenyl ether VIII. The reaction is generally carried out in a solvent. Suitable solvents are, for example, C1-C4-alcohols or C1-C4-alcohol/water mixtures. The reaction can be carried out in the presence of a base. Suitable bases are aromatic amines, such as pyridine, or alkali metal hydroxides or alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide or calcium hydroxide. The oximation of the keto group in VII can be carried out, for example, analogously to Organikum, 21st edition, Wiley-VCH 2001, p. 467 or D. Dhanak, C. Reese, S. Romana, G. Zappia, J. Chem. Soc. Chem. Comm. 1986 (12), 903-904, DE 3004871 or AU 580091.
In a similar manner, the oximated nitrobiphenyl ether of the formula VIII can be prepared by oximating, in a first step 1′), the acylphenol compound IX analogously to step 2) by reaction with H2N—OR4 and then, in step 2′), reacting the phenol V oximated in this manner with the nitroaromatic compound VI. The reaction conditions in steps 1′) and 2′) correspond essentially to the conditions given for steps 1) and 2), respectively.
In step 3, the nitrobiphenyl ether VIII obtained in step 2) or 2′) is then reduced to the aminobiphenyl ether III. The reduction is carried out by processes customary for reducing organic nitro compounds as described, for example, in Organikum, 21st edition, Wiley-VCH 2001, p. 627ff. The reduction of the nitro group of the nitrobiphenyl ether VIII is preferably carried out as a catalytic reduction over a transition metal catalyst, suitable hydrogen sources including, in addition to hydrogen, hydrazine. Suitable transition metal catalysts are, in particular heterogeneous catalysts with transition metals of group VIII, in particular with palladium, platinum or nickel as active metal, for example palladium-on-carbon or Raney nickel. The reduction is generally carried out in an inert solvent, for example a C1-C4-alcohol, such as methanol or ethanol. The reduction of the nitrobiphenyl ether VIII to the aminobiphenyl ether III can also be effected, for example, by reacting the nitrophenyl ether VIII with a metal compound, such as tin(II) chloride, under acidic reaction conditions such as concentrated hydrochloric acid.
The compounds I are suitable for use as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some are systemically effective and they can be used in plant protection as foliar and soil fungicides.
They are particularly important in the control of a multitude of fungi on various cultivated plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybean, coffee, sugar cane, vines, fruits and ornamental plants, and vegetables, such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
They are especially suitable for controlling the following plant diseases:
The compounds I are also suitable for controlling harmful fungi, such as Paecilomyces variotii, in the protection of materials (e.g. wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
The compounds I are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%, preferably between 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active compound per ha.
In seed treatment, amounts of active compound of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kilogram of seed are generally necessary.
When used in the protection of materials or stored products, the amount of active compound applied depends on the kind of application area and on the effect desired. Amounts customarily applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated material.
The compounds I can be converted to the usual formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective use intended; it should in any case guarantee a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known way, e.g. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, it being possible, when water is the diluent, also to use other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are essentially: solvents, such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers, such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic ores (e.g. highly dispersed silicic acid, silicates); emulsifiers, such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants, such as lignosulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid and dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids, and alkali metal and alkaline earth metal salts thereof, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol and nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Petroleum fractions having medium to high boiling points, such as kerosene or diesel fuel, furthermore coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene or isophorone, or highly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water, are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions.
Powders, combinations for broadcasting and dusts can be prepared by mixing or mutually grinding the active substances with a solid carrier.
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, e.g., mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, and plant products, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
The formulations generally comprise between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active compound. The active compounds are employed therein in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Examples for Formulations are:
The active compounds can be used as such, in the form of their formulations or of the application forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, compositions for broadcasting or granules, by spraying, atomizing, dusting, broadcasting or watering. The application forms depend entirely on the intended uses; they should in any case guarantee the finest possible dispersion of the active compounds according to the invention.
Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances can be homogenized in water, as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers. However, concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil can also be prepared, which concentrates are suitable for dilution with water.
The concentrations of active compound in the ready-for-use preparations can be varied within relatively wide ranges. In general, they are between 0.0001 and 10%. Often even small amounts of active compound I are sufficient in the ready-to use preparation, for example 2 to 200 ppm. Ready-to-use preparations with concentrations of active compound in the range from 0.01 to 1% are also preferred.
The active compounds can also be used with great success in the ultra low volume (ULV) process, it being possible to apply formulations with more than 95% by weight of active compound or even the active compound without additives.
Oils of various types, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if need be also not until immediately before use (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10:1.
The compositions according to the invention can, in the application form as fungicides, also be present together with other active compounds, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. On mixing the compounds I or the compositions comprising them in the application form as fungicides with other fungicides, in many cases an expansion of the fungicidal spectrum of activity is obtained.
The following list of fungicides, with which the compounds according to the invention can be used in conjunction, is intended to illustrate the possible combinations but does not limit them:
The compounds, listed in table B, of the formula I-A or I-B where n=m=0 (Examples 2 to 12) were prepared in an analogous manner.
1) m.p.: melting point
2) s: singlet; t: triplet; q: quartet; m: multiplet; br.s. broad singlet
The active compounds were prepared as a stock solution comprising 0.25% by weight of active compound in acetone or dimethyl sulfoxide (DMSO). 1% by weight of the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution, and the mixture was diluted with water to the desired concentration.
Bell pepper seedlings of the cultivar “Neusiedler Ideal Elite” were, after 2 to 3 leaves were well-developed, sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea in a 2% aqueous biomalt solution having a density of 0.17×106 spores/ml. The test plants were then placed in a climatized chamber at temperatures between 22 and 24° C. and high atmospheric humidity. After 5 days, the extent of the fungal infection of the leaves was determined visually in %.
In this test, the plants which had been treated with 250 ppm of the active compound from example 3, example 4, example 7, example 10 or example 12 of table B showed an infection of at most 5% and the plants which had been treated with 300 ppm of the active compound from example 1, example 2 or example 6 of table B showed an infection of at most 20%, whereas the untreated plants were 90% infected.
Leaves of potted wheat seedlings of the cultivar “Kanzler” were dusted with spores of brown rust (Puccinia recondita). The pots were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-22° C., for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. The suspension or emulsion was prepared as described above. After the spray coating had dried on, the test plants were cultivated in a greenhouse at temperatures of between 20 and 22° C. and at a relative atmospheric humidity of 65 to 70% for 7 days. The extent of the development of the rust fungus on the leaves was then determined.
In this test, the plants which had been treated with 250 ppm of the active compound from example 1, example 2, example 3, example 7, example 8, example 9, example 10, example 11 or example 12 of table 1 showed an infection of at most 10% and the plants which had been treated with 250 ppm of the active compound from example 4 of table B showed an infection of at most 20%, whereas the untreated plants were 70% infected.
Leaves of potted wheat seedlings of the cultivar “Kanzler” were sprayed to runoff point with an aqueous suspension having the concentration of active compounds stated below. The next day, the treated plants were inoculated with a spore suspension of brown rust (Puccinia recondite). The pots were then placed in a chamber with high atmospheric humidity (90 to 95%) and at 20 to 22° C. for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The next day, the plants were returned to the greenhouse and cultivated at temperatures between 20 and 22° C. and at 65 to 70% relative atmospheric humidity for 7 days. The extent of the rust fungus development on the leaves was then determined.
In this test, the plants which had been treated with 250 ppm of the active compound from example 8 or example 11 of table B showed an infection of at most 10%, whereas the untreated plants were 90% infected.
Number | Date | Country | Kind |
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10 2004 043 047.0 | Sep 2004 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP05/09529 | 9/5/2005 | WO | 5/11/2007 |