Haloalkyl carboxamides
View Patent ↗New haloalkyl carboxamides of formula (I) in which R, R 1 , R 2 , R 3 , R 4 , M and A have the meanings specified in the description, several processes for synthesizing these materials and their use in combating undesirable microorganisms, as well as new intermediate products and their synthesis.
1. A haloalkyl carboxamide of the formula (I)
in which
R stands for hydrogen or halogen,
R 1 stands for hydrogen or methyl,
R 2 stands for methyl, ethyl or C 1 -C 4 haloalkyl with 1 to 9 fluorine, chlorine and/or bromine atoms,
R 3 stands for halogen or C 1 -C 4 haloalkyl with 1 to 9 fluorine, chlorine and/or bromine atoms,
R 4 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, C 1 -C 4 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 and/or bromine atoms 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 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 and/or bromine atoms in each case; or —C(═O)C(═O)R 5 , —CONR 6 R 7 or —CH 2 NR 8 R 9 ,
R 5 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 -alkoxyl-C 1 -C 4 -alkyl, C 3 -C 8 halocycloalkyl with 1 to 9 fluorine, chlorine and/or bromine atoms in each case,
R 6 and R 7 stand independently of one another in each case for hydrogen, C 1 -C 8 alkyl, C 1 -C 4 alkoxyl C 1 -C 4 allyl, 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 and/or bromine atoms in each case, or
R 6 and R 7 , together with the nitrogen atom to which they are bound, form a substituted, saturated heterocycle with 5 to 8 ring atoms, with single or multiple, the same or different substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle optionally contains 1 or 2 additional, non-adjacent hetero atoms constituted of oxygen, sulfur or NR 10 ,
R 8 and R 9 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 and/or bromine atoms in each case, or
R 8 and R 9 , together with the nitrogen atom to which they are bound, form a substituted, saturated heterocycle with 5 to 8 ring atoms, with single or multiple, the same or different substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle optionally contains 1 or 2 additional, non-adjacent hetero atoms constituted of oxygen, sulfur or NR 10 ,
R 10 stands for hydrogen or C 1 -C 6 alkyl,
M stands in each case for a phenyl ring with a single substitution by R 11 ,
R 11 stands for hydrogen, fluorine, chlorine, methyl, isopropyl, methylthio or trifluoromethyl,
A stands for the group of the 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, 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, and
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 haloalkyl carboxamide of the formula (I) according to claim 1 , in which
R stands for hydrogen, fluorine, chlorine or bromine,
R 1 stands for hydrogen or methyl,
R 2 stands for methyl, ethyl or in each case for methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl with single or multiple, the same or different, substitution by fluorine, chlorine or bromine,
R 3 stands for fluorine, chlorine, bromine, iodine or in each case for methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl with single or multiple, the same or different, substitution by fluorine, chlorine or bromine,
R 4 stands for hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 6 cycloalkyl; C 1 -C 4 haloalkyl, C 1 -C 4 haloalkylthio, C 1 -C 4 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 and/or bromine atoms 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 in each case; (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 and/or bromine atoms in each case; or —C(═O)C(═O)R 5 , —CONR 6 R 7 or —CH 2 NR 8 R 9 ,
R 5 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 and/or bromine atoms in each case,
R 6 and R 7 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; C 1 -C 4 haloalkyl, halo-C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 6 halocycloalkyl with 1 to 9 fluorine, chlorine and/or bromine atoms in each case, or
R 6 and R 7 , together with the nitrogen atom to which they are bound, form a substituted, saturated heterocycle with 5 to 8 ring atoms, with single or multiple, the same or different substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle optionally contains 1 or 2 additional, non-adjacent hetero atoms constituted of oxygen, sulfur or NR 10 ,
R 8 and R 9 stand independently of one another for hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl; —C 4 haloalkyl, C 3 -C 6 halocycloalkyl with 1 to 9 fluorine, chlorine and/or bromine atoms in each case, or
R 8 and R 9 , together with the nitrogen atom to which they are bound, form a substituted, saturated heterocycle with 5 to 8 ring atoms, with single or multiple, the same or different substitution by halogen or C 1 -C 4 alkyl, whereby the heterocycle optionally contains 1 or 2 additional, non-adjacent hetero atoms constituted of oxygen, sulfur or NR 10 ,
R 10 stands for hydrogen or C 1 -C 4 alkyl,
M stands for the following cyclic
whereby the bond marked with an asterisk (“*”) is a link with the amide, and the bond marked with “#” is a link with the haloalkyl group,
R 11 stands for hydrogen, fluorine, chlorine, methyl or trifluoromethyl,
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 and/or bromine atoms, trifluoromethylthio, difluoromethylthio, aminocarbonyl, aminocarbonylmethyl or aminocarbonylethyl,
R 13 stands for hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio, and
R 14 stands for hydrogen, methyl, ethyl, n-propyl, isopropyl, C 1 -C 2 haloalkyl with 1 to 5 fluorine, chlorine and/or bromine atoms, hydroxymethyl, hydroxyethyl, cyclopropyl, cyclopentyl, cyclohexyl or phenyl.
3. A process for synthesizing a haloalkyl carboxamide of the formula (I) according to claim 1 , comprising
a) reacting a carboxylic acid derivative of the formula (II)
in which
A has the meaning as defined above in claim 1 and
X 1 stands for halogen or hydroxy,
with an aniline derivative of the formula (III)
in which
R, R 1 , R 2 , R 3 , R 4 and M have the meanings as defined above in claim 1 ,
optionally in the presence of a catalyst, optionally in the presence of a condensation agent, optionally in the presence of an acid binder and optionally in the presence of a diluent,
or
b) reacting a haloalkylcarboxanilide of the formula (I-a)
in which
R, R 1 , R 2 , R 3 , M and A have the meanings as defined above in claim 1 , with a halide of the formula (IV)
R 4-A —X 2 (IV)
in which
X 2 stands for chlorine, bromine or iodine,
R 4-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, haloalkylthio, C 1 -C 4 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 and/or bromine atoms 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 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 and/or bromine atoms in each case; or —C(═O)C(═O)R 5 , —CONR 6 R 7 or —CH 2 NR 8 R 9 , whereby R 5 , R 6 , R 7 , R 8 and R 9 have the meanings as defined above in claim 1 ,
in the presence of a base and a dilution medium.
4. A composition for combating undesirable microorganisms, comprising at least one haloalkyl carboxamide of the formula (I) according to claim 1 together with extenders and/or surface-active materials.
5. A method for combating undesired microorganisms, comprising applying at least one haloalkyl carboxamide of the formula (I) according to claim 1 to the microorganisms and/or their environment.
6. A method for preparing a composition to combat undesired microorganisms, comprising mixing at least one haloalkyl carboxamide of the formula (I) according to claim 1 with extenders and/or surface-active materials.