Silylated carboxamides
View Patent ↗Novel silylated carboxamides of the formula (I) in which R, L, R 1 , R 3 , R 3 , R 4 and A are as defined in the description, a plurality of processes for preparing these compounds and their use for controlling unwanted microorganisms.
1. Silylated carboxamides of the formula (I)
in which
R is hydrogen, fluorine, chlorine, methyl, isopropyl, methylthio or trifluoro-methyl,
L is a direct bond or is in each case optionally substituted straight-chain or branched alkylene (alkanediyl), alkenylene (alkenediyl) or alkynylene (alkyndiyl),
R 1 and R 2 independently of one another are 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,
R 3 is 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 -halo-alkenyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, or is in each case optionally substituted phenyl or phenylalkyl,
R 4 is hydrogen, C 1 -C 8 -alkyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, 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 -haloalkylsulphinyl, C 1 -C 4 -haloalkylsulphonyl, halo -C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms; 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 having in each case 1 to 13 fluorine, chlorine and/or bromine atoms; (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 -halo-alkoxy)carbonyl, (halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl)carbonyl, (C 3 -C 8 -halocyclo-alkyl)carbonyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms; or —C(═O)C(═O)R 5 , —CONR 6 R 7 or —CH 2 NR 8 R 9 ,
R 5 is 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-C 1 -C 4 -alkyl, C 3 -C 8 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,
R 6 and R 7 independently of one another each are hydrogen, C 1 -C 8 -alkyl, C 1 -C 4 -alkoxy-C 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 having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,
R 6 and R 7 furthermore together with the nitrogen atom to which they are attached form a saturated heterocycle having 5 to 8 ring atoms which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C 1 -C 4 -alkyl, where the heterocycle may contain 1 or 2 further nonadjacent heteroatoms from the group consisting of oxygen, sulphur and NR 10 ,
R 8 and R 9 independently of one another, are hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl; C 1 -C 8 -haloalkyl, C 3 -C 8 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,
R 8 and R 9 furthermore together with the nitrogen atom to which they are attached form a saturated heterocycle having 5 to 8 ring atoms which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C 1 -C 4 -alkyl, where the heterocycle may contain 1 or 2 further nonadjacent heteroatoms from the group consisting of oxygen, sulphur and NR 10 ,
R 10 is hydrogen or C- 1 -C 6 -alkyl,
A is the radical of the formula (A2)
R 12 is chlorine or iodine.
2. A silylated caboxamide of the formula (I) of claim 1 , wherein
R is hydrogen, fluorine, chlorine, methyl or trifluoromethyl,
L is a direct bond or is in each case optionally halogen-substituted straight-chain or branched C 1 -C 6 -alkylene, C 2 -C 6 -alkenylene or C 2 -C 6 -alkynylene,
R 1 and R 2 independently of one another are 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,
R 3 is 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, C 3 -C 6 -cycloalkyl, phenyl or benzyl,
R 4 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -alkylsulphinyl, C 1 -C 4 -alkylsulphonyl, 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, C 1 -C 4 -haloalkylsulphinyl, C 1 -C 4 -haloalkylsulphonyl, halo -C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl, C 3 -C 8 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms; 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 having in each case 1 to 13 fluorine, chlorine and/or bromine atoms; (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 -halo-alkoxy)carbonyl, (halo-C 1 -C 3 -alkoxy-C 1 -C 3 -alkyl)carbonyl, (C 3 -C 6 -halo-cycloalkyl)carbonyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms, or —C(═O)C(═O)R 5 , —CONR 6 R 7 or —CH 2 NR 8 R 9 ,
R 5 is 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 having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,
R 6 and R 7 independently of one another each are 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 having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,
R 6 and R 7 furthermore together with the nitrogen atom to which they are attached form a saturated heterocycle having 5 or 6 ring atoms which is optionally mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen and C 1 -C 4 -alkyl, where the heterocycle may contain 1 or 2 further non-adjacent heteroatoms from the group consisting of oxygen, sulphur and NR 10 ,
R 8 and R 9 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl; C 1 -C 4 -haloalkyl, C 3 -C 6 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,
R 8 and R 9 furthermore together with the nitrogen atom to which they are attached form a saturated heterocycle having 5 or 6 ring atoms which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C 1 -C 4 -alkyl, where the heterocycle may contain 1 or 2 further non-adjacent heteroatoms from the group consisting of oxygen, sulphur and NR 10 ,
R 10 is hydrogen or C 1 -C 4 -alkyl,
A is the radical of the formula (A2)
R 12 is chlorine or iodine.
3. A process for preparing silylated carboxamides of the formula (I) according to claim 1 , comprising reacting
a) carboxylic acid derivatives of the formula (II)
in which
X 1 is halogen or hydroxyl and
A is as defined in claim 1 are reacted with amines of the formula (III)
in which R, L, R 1 , R 2 , R 3 and R 4 are as defined in claim 1 , optionally in the presence of a catalyst, optionally in the presence of a condensing agent, optionally in the presence of an acid binder and optionally in the presence of a diluent,
or
b) silylated carboxamides of the formula (I-1)
in which R, L, R 1 , R 2 , R 3 and A are as defined in claim 1 , are reacted with halides of the formula (VIII)
R 4a —X 2 (VIII)
in which
X 2 is chlorine, bromine or iodine,
R 4a is C 1 -C 8 -alkyl, C 1 -C 6 -alkylsulphinyl, C 1 -C 6 -alkylsulphonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyl; C 1 -C 6 -haloalkyl, C 1 -C 4 -haloalkyl-thio, C 1 -C 4 -haloalkylsulphinyl, C 1 -C 4 -haloalkylsulphonyl, halo-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms; 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 having in each case 1 to 13 fluorine, chlorine and/or bromine atoms;
(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 having in each case 1 to 9 fluorine, chlorine and/or bromine atoms; or —C(═O)C(═O)R 5 , —CONR 6 R 7 or —CH 2 NR 8 R 9 , where R 5 , R 6 , R 7, R 8 and R 9 are as defined in claim 1 ,
in the presence of a base and in the presence of a diluent.
4. A composition, comprising at least one silylated carboxamide of the formula (I) according to claim 1 , in addition to extenders and/or surfactants.
5. A method of controlling fungi in the protection of crops or industrial materials comprising applying the composition of claim 4 to said fungi or their habitat, or both.
6. A method for controlling fungi in the protection of crops or industrial materials, comprising applying the silylated carboxamides of the formula (I) according to claim 1 to said fungi, their habitats, or both.
7. A process for preparing a composition comprising mixing the silylated carboxamides of the formula (I) according to claim 1 with extenders, surfactants, or both.
8. The method of claim 5 wherein said fungi is selected from the group consisting of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes , and Deuteromycetes.
9. The method of claim 5 wherein said fungi is selected from the group consisting of Basidiomycetes, Altemaria, Aspergillus, Chaetomium, Coniophora, Lentinus, Penicillium, Polyporus, Aureobasidium, Scierophoma , and Trichoderma.
10. The method of claim 5 wherein said fungi is selected from the group consisting of Puccinia, Sphaerotheca and Venturia.
11. The method of claim 5 wherein said fungi is selected from the group consisting of Puccinia recondita, Sphaerotheca fuliginia and Venturia inaequalis.
12. The method of claim 6 wherein said fungi is selected from the group consisting of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes , and Deuteromycetes.
13. The method of claim 6 wherein said fungi is selected from the group consisting of Basidiomycetes, Alternaria, Aspergillus , Chaetomium, Coniophora, Lentinus, Penicillium, Polyporus, Aureobasidium, Sclerophoma, and Trichoderma.
14. The method of claim 6 wherein said fungi is selected from the group consisting of Puccinia, Sphaerotheca and Venturia.
15. The method of claim 6 wherein said fungi is selected from the group consisting of Puccinia recondita, Sphaerotheca fuliginia and Venturia inaequalis.