The invention relates to novel carboxamides of formula (I), in which M represents a phenyl ring, pyridine ring or pyrimidine, pyridazine or pyrazine ring, respectively monosubstituted by R 8 , or represents a thiazole ring substituted by R 8-A ; R 8 represents hydrogen, fluorine, chlorine, methyl, isopropyl, methylthio or trifluoromethyl; R 8 can also represent methoxy; R 8-A represents hydrogen, methyl, methylthio or trifluoromethyl; L 1 represents C 1 -C 10 alkene (alkanediyl); Q represents O, S, SO, SO 2 or NR 9 ; L 2 represents a direct bond, SiR 10 R 11 or CO; R represents hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 4 alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 alkylthio-C 1 -C 4 -alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 haloalkynyl or C 3 -C 6 cycloalkyl; A represents the group of formula (AI); the remaining substituents are defined in claim 1 . The inventive substances have a powerful microbicidal action and can be used to control undesirable micro-organisms such as fungi and bacteria in the phyto-protection and material protection fields.
1. A carboxamide of formula (I)
in which
R 1 stands for hydrogen, C 1 -C 8 alkyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 cycloalkyl; C 1 -C 6 haloalkyl, C 1 -C 4 haloalkylthio, haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case; or formyl, formyl-C 1 -C 3 -alkyl, (C 1 -C 3 -alkyl)carbonyl-C 1 -C 3 -alkyl, (C 1 -C 3 -alkoxy)carbonyl-C 1 -C 3 -alkyl; halo-(C 1 -C 3 -alkyl)carbonyl-C 1 -C 3 -alkyl, halo-(C 1 -C 3 -alkoxy)carbonyl-C 1 -C 3 -alkyl with 1 to 13 fluorine, chlorine, and/or bromine atoms, or combinations thereof in each case; or
(C 1 -C 8 -alkyl)carbonyl, (C 1 -C 8 -alkoxy)carbonyl, (C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl)carbonyl, (C 3 -C 8 -cycloalkyl)carbonyl; (C 1 -C 6 -haloalkyl)carbonyl, (C 1 -C 6 -haloalkoxy)carbonyl, (halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl)carbonyl, (C 3 -C 8 -halocycloalkyl)carbonyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case; or —C(═O)C(═O)R 2 , —CONR 3 R 4 or —CH 2 NR 5 R 6 ,
R 2 stands for hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 cycloalkyl; C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, halo-C 1 -C 4 -alkoxy 1 -C 4 -alkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorin, bromine atoms, or combinations thereof in each case,
R 3 and R 4 stand independently of one another in each case for hydrogen, C 1 -C 8 alkyl, C 1 -C 4 -alkoxy 1 -C 4 -alkyl, C 3 -C 8 cycloalkyl; C 1 -C 8 haloalkyl, halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case, or
R 3 and R 4 form a substituted, saturated heterocycle with 5 to 8 ring atoms together with the nitrogen atom to which they are bound, with single or multiple, the same or various substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle can contain 1 or 2 additional, non-adjacent hetero atoms constituted by oxygen, sulfur or NR 7 ,
R 5 and R 6 stand independently of one another for hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 cycloalkyl; C 1 -C 8 haloalkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case, or
R 5 and R 6 form a substituted, saturated heterocycle with 5 to 8 ring atoms together with the nitrogen atom to which they are bound, with single or multiple, the same or various substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle can contain 1 or 2 additional, non-adjacent hetero atoms constituted by oxygen, sulfur or NR 7 ,
R 7 stands for hydrogen or C 1 -C 6 alkyl,
M is a phenyl ring with a single substitution by R 8 ,
R 8 stands for hydrogen, fluorine, chlorine, methyl, isopropyl, methylthio or trifluoromethyl, or
R 8 stands for methoxy,
L 1 stands for C 1 -C 10 alkylene (alkanediyl),
Q stands for O, S, SO, SO 2 or NR 9 ,
L 2 stands for a direct link, SiR 10 R 11 or CO,
R stands for hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl or C 3 -C 6 cycloalkyl,
R 9 stands for hydrogen, C 1 -C 8 alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl or C 3 -C 6 cycloalkyl,
R 10 and R 11 stand independently of one another for hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl or C 1 -C 6 haloalkyl,
A is a group of formula (A1)
in which
R 12 stands for hydrogen, cyano, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy or C 1 -C 4 haloalkylthio, in each case with 1 to 5 halogen atoms, aminocarbonyl or aminocarbonyl-C 1 -C 4 -alkyl,
R 13 stands for hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio,
R 14 stands for hydrogen, C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 cycloalkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl in each case with 1 to 5 halogen atoms, or phenyl.
2. A carboxamide of the formula (I) according to claim 1 ,
in which when L 2 is a direct link, R is hydrogen, C 1 -C 8 alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl or C 3 -C 6 cycloalkyl.
3. A carboxamide of formula (I) according to claim 1 or 2 , in which
R 1 stands for hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkylsulfinyl, alkylsulfonyl, C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 6 cycloalkyl; C 1 -C 4 haloalkyl, C 1 -C 4 haloalkylthio, haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, halo-C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case; or formyl, formyl-C 1 -C 3 -alkyl, (C 1 -C 3 -alkyl)carbonyl-C 1 -C 3 -alkyl, (C 1 -C 3 -alkoxy)carbonyl-C 1 -C 3 -alkyl; halo-(C 1 -C 3 -alkyl)carbonyl-C 1 -C 3 -alkyl, halo-(C 1 -C 3 -alkoxy)carbonyl-C 1 -C 3 -alkyl with 1 to 13 fluorine, chlorine, bromine atoms, or combinations thereof in each case; or
(C 1 -C 6 alkyl)carbonyl, (C 1 -C 4 alkoxy)carbonyl, (C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl)carbonyl, (C 3 -C 6 cycloalkyl)carbonyl; (C 1 -C 4 haloalkyl)carbonyl, (C 1 -C 4 haloalkoxy)carbonyl, (halo-C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl)carbonyl, (C 3 -C 6 halocycloalkyl)carbonyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case; or —C(═O)C(═O)R 2 , —CONR 3 R 4 or —CH 2 NR 5 R 6 ,
R 2 stands for hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 6 cycloalkyl; C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halo-C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 6 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case,
R 3 and R 4 stand independently of one another in each case for hydrogen, C 1 -C 6 alkyl, C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 6 cycloalkyl; haloalkyl, halo-C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 6 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case, or
R 3 and R 4 form a substituted, saturated heterocycle with 5 to 8 ring atoms together with the nitrogen atom to which they are bound, with single or multiple, the same or various substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle can contain 1 or 2 additional, non-adjacent hetero atoms constituted by oxygen, sulfur or NR 7 ,
R 5 and R 6 stand independently of one another for hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl; C 1 -C 4 haloalkyl, C 3 -C 6 halocycloalkyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case, or
R 5 and R 6 form a substituted, saturated heterocycle with 5 to 8 ring atoms together with the nitrogen atom to which they are bound, with single or multiple, the same or various substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle can contain 1 or 2 additional, non-adjacent hetero atoms constituted by oxygen, sulfur or NR 7 ,
R 7 stands for hydrogen or C 1 -C 4 alkyl,
M stands for
whereby the bond marked with an asterisk is linked to the amide,
R 8 stands for hydrogen, fluorine, chlorine, methyl, isopropyl, methylthio or trifluoromethyl, or
R 8 stands for methoxy,
L 1 stands for C 1 -C 10 alkylene (alkanediyl),
Q stands for O, S, SO, SO 2 or NR 9 ,
L 2 stands for a direct link, SiR 10 R 11 or CO,
R stands for hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 1 -C 3 -alkylthio-C 1 -C 3 -alkyl or C 1 -C 4 haloalkyl or C 3 -C 6 cycloalkyl,
R 9 stands for hydrogen, C 1 -C 6 alkyl, C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 1 -C 3 -alkylthio-C 1 -C 3 -alkyl or C 3 -C 6 cycloalkyl,
R 10 and R 11 stand independently of one another preferably for C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl or C 1 -C 3 -alkylthio-C 1 -C 3 -alkyl,
A stands for the group of the formula (A1)
in which
R 12 stands for hydrogen, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, C 1 -C 2 haloalkyl, C 1 -C 2 haloalkoxy in each case with 1 to 5 fluorine, chlorine, bromine atoms, or combinations thereof, trifluoromethylthio, difluoromethylthio, aminocarbonyl, aminocarbonylmethyl or aminocarbonylethyl,
R 13 stands for hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio,
R 14 stands for hydrogen, methyl, ethyl, n-propyl, isopropyl, C 1 -C 2 haloalkyl with 1 to 5 fluorine, chlorine, bromine atoms, or combinations thereof, hydroxymethyl, hydroxyethyl, cyclopropyl, cyclopentyl, cyclohexyl or phenyl.
4. A process for synthesizing a carboxamide of the formula (I) according to claim 1 , comprising
(a) reacting a carboxylic acid derivative of formula (II)
in which
A is as defined in claim 1 and
X 1 stands for halogen or hydroxy,
with an aniline derivative of formula (III)
in which
R 1 , M, Q, L 2 and R are as defined in claim 1 and
L 3 stands for hydrogen or C 1 -C 9 alkyl,
optionally in the presence of a catalyst, optionally in the presence a condensation agent, optionally in the presence of an acid binder and optionally in the presence of a diluent,
or
(b) reacting a carboxamide of formula (IV)
in which M, L 1 , Q and A are as defined in claim 1
with a compound of formula (V),
in which
L 2 and R are as defined in claim 1 and
Y stands for halogen, triflate (trifluoromethylsulfonyl), mesylate (methylsulfonyl) or tosylate (4-methylphenylsulfonyl),
in the presence of a base and in the presence of a dilution medium,
or
(c) reacting a carboxamide of formula (I-a)
in which M, L 1 , Q, L 2 , R and A are ad defined in claim 1 ,
with a halide of formula (VI)
R 1-A —X 2 (VI)
in which
X 2 stands for chlorine, bromine or iodine,
R 1-A stands for C 1 -C 8 alkyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 cycloalkyl; C 1 -C 6 haloalkyl, C 1 -C 4 haloalkylthio, haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorin; bromine atoms, or combinations thereof in each case; formyl, formyl-C 1 -C 3 -alkyl, (C 1 -C 3 -alkyl)carbonyl-C 1 -C 3 -alkyl, (C 1 -C 3 -alkoxy)carbonyl-C 1 -C 3 -alkyl; halo-(C 1 -C 3 alkyl)carbonyl-C 1 -C 3 -alkyl, halo-(C 1 -C 3 alkoxy)carbonyl-C 1 -C 3 -alkyl with 1 to 13 fluorine, chlorine, and/or bromine atoms, or combinations thereof in each case;
(C 1 -C 8 alkyl)carbonyl, (C 1 -C 8 alkoxy)carbonyl, (C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl)carbonyl, (C 3 -C 8 cycloalkyl)carbonyl; (C 1 -C 6 haloalkyl)carbonyl, (C 1 -C 6 haloalkoxy)carbonyl, (halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl)carbonyl, (C 3 -C 8 halocycloalkyl)carbonyl with 1 to 9 fluorine, chlorine, bromine atoms, or combinations thereof in each case; or —C(═O)C(═O)R 2 , —CONR 3 R 4 or —CH 2 NR 5 R 6 ,
whereby R 2 , R 3 , R 4 , R 5 and R 6 are as defined in claim 1 ,
in the presence of a base and in the presence of a dilution medium.
5. A composition comprising at least one carboxamide of the formula (I) according to claim 1 and one or more extenders, surface active materials, or combinations thereof.
6. A process for combating undesired microorganisms, comprising applying a carboxamide of the formula (I) according to claim 1 to microorganisms, their environment, or a combination thereof.
7. A process for preparing a composition to combat undesired microorganisms, comprising mixing a carboxamide of the formula (I) according to claim 1 with one or more extenders, surface active materials, or combinations thereof.