[(1,4,5-TRISUBSTITUTED-1H-PYRAZOL-3-YL)SULFANYL]ACETIC ACID DERIVATIVES, SALTS THEREOF, AND USE THEREOF AS ACTIVE HERBICIDAL INGREDIENTS
20230126893 · 2023-04-27
Inventors
- Thomas MUELLER (Frankfurt, DE)
- Michael Gerhard HOFFMANN (Konstanz, DE)
- Estella Buscato Arsequell (Frankfurt am Main, DE)
- Harald JAKOBI (Leverkusen, DE)
- Dirk Schmutzler (Hattersheim, DE)
- Christopher Hugh ROSINGER (Hofheim am Taunus, DE)
- Anu Bheemaiah MACHETTIRA (Frankfurt, DE)
- Elisabeth Asmus (Hösbach, DE)
Cpc classification
A01N43/80
HUMAN NECESSITIES
C07D403/04
CHEMISTRY; METALLURGY
C07D401/04
CHEMISTRY; METALLURGY
C07D409/04
CHEMISTRY; METALLURGY
C07D417/04
CHEMISTRY; METALLURGY
International classification
C07D401/04
CHEMISTRY; METALLURGY
C07D403/04
CHEMISTRY; METALLURGY
C07D409/04
CHEMISTRY; METALLURGY
Abstract
The present invention relates to the technical field of crop protection products, especially that of herbicides for control of broad-leaved weeds and weed grasses in crops of useful plants.
Specifically, this invention relates to novel substituted [(1,4,5-trisubstituted 1H-pyrazol yl)sulfanyl]acetic acid derivatives of the formula (I) or an agrochemically acceptable salt thereof, to processes for preparation thereof and to the use thereof as herbicides.
Claims
1. [(1,4,5-Trisubstituted 1H-pyrazol-3-yl)sulfanyl]acetic acid derivatives of the general formula (I) or an agrochemically acceptable salt thereof, ##STR00079## in which Q.sup.1 is phenyl and hetaryl, where the phenyl and the hetaryl are unsubstituted or each independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, isocyano, nitro, hydroxy, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl and NH.sub.2 (amino), Q.sup.2 is phenyl, which is unsubstituted or in each case independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, isocyano, NO.sub.2, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl and NH.sub.2 (amino), Z is the groups ##STR00080## Y is halogen, cyano, isocyano, NO.sub.2, NH.sub.2 (amino), (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.1-C.sub.6)-hydroxyalkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4-alkyloxycarbonyl, (C.sub.1-C.sub.6)-alkylcarbonyl, CHO, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.2-C.sub.6)-alkenyl and (C.sub.2-C.sub.6)-haloalkenyl, W is oxygen or sulfur, R.sup.1 is hydrogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.2-C.sub.6)-alkenyl and (C.sub.2-C.sub.6)-haloalkenyl, R.sup.2 is hydrogen, (C.sub.1-C.sub.10)-alkyl and (C.sub.3-C.sub.10)-cycloalkyl, where the alkyl and cycloalkyl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, cyano, isocyano, nitro, NH.sub.2 (amino), (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl, heterocyclyl-(C.sub.1-C.sub.4)-alkyl, heteroaryl-(C.sub.1-C.sub.4)-alkyl and aryl-(C.sub.1-C.sub.4)-alkyl, where the aryl, heterocyclyl and heteroaryl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, R.sup.3 is hydrogen and (C.sub.1-C.sub.12)-alkyl, R.sup.4 is hydrogen, cyano, nitro, (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.10)-haloalkyl, (C.sub.2-C.sub.10)-alkenyl, (C.sub.3-C.sub.10)-alkynyl, (C.sub.1-C.sub.10)-alkoxy-(C.sub.1-C.sub.10) -alkyl, (C.sub.1-C.sub.10)-haloalkoxy-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.10)-cycloalkyl, (C.sub.3-C.sub.10)-halocycloalkyl, hydroxy-(C.sub.1-C.sub.10)-alkylcarbonyl, amino-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-alkoxycarbonyl-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-cyanoalkyl, S(O).sub.nR.sup.5, OR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, COR.sup.6, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8, aryl, heteroaryl and heterocyclyl, which is unsubstituted or each independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, nitro, OR.sup.5, S(O).sub.nR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, CONR.sup.6R.sup.8, COR.sup.E, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CONR.sup.8R.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8, NR.sup.6SO.sub.2NR.sup.6R.sup.8, C(R.sup.6)═NOR.sup.8; Or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are bonded form a fully saturated or partly saturated 3- to 10-membered monocyclic or bicyclic ring optionally interrupted by heteroatoms and optionally having further substitution, R.sup.5 is hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.8)-haloalkyl and aryl, R.sup.6 is hydrogen and R.sup.5, R.sup.7 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl, (C.sub.3-C.sub.4)-alkynyl and (C.sub.1-C.sub.10)-alkylcarbonyl-(C.sub.1-C.sub.6)-alkyl, R.sup.8 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl, and (C.sub.3-C.sub.4)-alkynyl, m is 0, 1 or 2, and n is 0, 1 or 2, excluding the compounds ethyl {[4-nitro-1-phenyl-5-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl]sulfanyl}acetate CAS [1360702-86-8] and methyl {[5-(5-methyl-1,3,4-oxadiazol-2-yl)-4-nitro-1-phenyl-1H-pyrazol-3-yl]sulfanyl}acetate CAS [1360690-60-3].
2. Compounds of the formula (I) according to claim 1 or an agrochemically acceptable salt thereof, in which Q.sup.1 is the groups Q.sup.1-1.1 to Q.sup.1-6.5 ##STR00081## ##STR00082## ##STR00083## Q.sup.2 is phenyl, which is unsubstituted or in each case independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, isocyano, NO.sub.2, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl and NH.sub.2 (amino), Z is the groups ##STR00084## Y is halogen, cyano, isocyano, NO.sub.2, NH.sub.2 (amino), (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.1-C.sub.6)-hydroxyalkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-alkyloxycarbonyl, (C.sub.1-C.sub.6)-alkylcarbonyl, CHO, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.2-C.sub.6)-alkenyl and (C.sub.2-C.sub.6)-haloalkenyl, W is oxygen or sulfur, R.sup.1 is hydrogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.2-C.sub.6)-alkenyl and (C.sub.2-C.sub.6)-haloalkenyl, R.sup.2 is hydrogen, (C.sub.1-C.sub.10)-alkyl and (C.sub.3-C.sub.10)-cycloalkyl, where the alkyl and cycloalkyl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, cyano, isocyano, nitro, NH.sub.2 (amino), (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl, heterocyclyl-(C.sub.1-C.sub.6)-alkyl, heteroaryl-(C.sub.1-C.sub.4)-alkyl and aryl-(C.sub.1-C.sub.4)-alkyl, where the aryl, heterocyclyl and heteroaryl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, (C.sub.1-C.sub.6)-alkyl and (C.sub.1-C.sub.6)-haloalkyl, R.sup.3 is hydrogen and (C.sub.1-C.sub.10)-alkyl, R.sup.4 is hydrogen, cyano, nitro, (C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-haloalkyl, (C.sub.2-C.sub.10)-alkenyl, (C.sub.3-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-alkoxy-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-haloalkoxy-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.10)-cycloalkyl, (C.sub.3-C.sub.10)-halocycloalkyl, hydroxy-(C.sub.1-C.sub.10)-alkylcarbonyl, amino-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-alkoxycarbonyl-(C.sub.1-C.sub.10)-alkyl, (C.sub.1-C.sub.10)-cyanoalkyl, S(O).sub.nR.sup.5, OR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, COR.sup.8, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8; aryl, heteroaryl and heterocyclyl, which are unsubstituted or each independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, nitro, OR.sup.5, S(O).sub.nR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, CONR.sup.6R.sup.8, COR.sup.E, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CONR.sup.8R.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8, NR.sup.6SO.sub.2NR.sup.6R.sup.8, C(R.sup.6)═NOR.sup.8; or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are bonded form a fully saturated or partly saturated 3- to 10-membered monocyclic or bicyclic ring optionally interrupted by heteroatoms and optionally having further substitution, R.sup.5 is hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.8)-haloalkyl and aryl, R.sup.6 is hydrogen and R.sup.5, R.sup.7 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl, (C.sub.3-C.sub.4)-alkynyl and (C.sub.1-C.sub.6)-alkylcarbonyl-(C.sub.1-C.sub.4)-alkyl, R.sup.8 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl and (C.sub.3-C.sub.4)-alkynyl, R.sup.9 is hydrogen, halogen, cyano, isocyano, nitro, hydroxy, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl and NH.sub.2 (amino), m is 0,1, and 2, n is 0, 1 and 2.
3. Compounds of the formula (I) according to claim 1 or an agrochemically acceptable salt thereof, in which Q.sup.1 is the groups Q.sup.1-1.1 to Q.sup.1-6.3, ##STR00085## ##STR00086## ##STR00087## Q.sup.2 is phenyl, which is unsubstituted or in each case independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n and (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, Z is the groups ##STR00088## Y is halogen, cyano, isocyano, NO.sub.2, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.4)-alkyloxycarbonyl, (C.sub.1-C.sub.6)-alkylcarbonyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.2-C.sub.6)-alkenyl and (C.sub.2-C.sub.6)-haloalkenyl, W is oxygen, R.sup.1 is hydrogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.2-C.sub.6)-alkenyl and (C.sub.2-C.sub.6)-haloalkenyl, R.sup.2 is hydrogen, (C.sub.1-C.sub.6)-alkyl and (C.sub.3-C.sub.6)-cycloalkyl, where the alkyl and cycloalkyl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, cyano, nitro, NH.sub.2 (amino), (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl, heterocyclyl-(C.sub.1-C.sub.4)-alkyl, heteroaryl-(C.sub.1-C.sub.4)-alkyl and aryl-(C.sub.1-C.sub.4)-alkyl, where the aryl, heterocyclyl and heteroaryl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, (C.sub.1-C.sub.6)-alkyl and (C.sub.1-C.sub.6)-haloalkyl, R.sup.3 is hydrogen and (C.sub.1-C.sub.6)-alkyl, R.sup.4 is hydrogen, cyano, nitro, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.3-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl and (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, hydroxy-(C.sub.1-C.sub.6)-alkylcarbonyl, amino-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.1-C.sub.6)-alkyl, S(O).sub.11R.sup.5, OR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, COR.sup.6, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8; aryl, heteroaryl and heterocyclyl, which are unsubstituted or each independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, nitro, OR.sup.5, S(O).sub.nR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, CONR.sup.6R.sup.8, COR.sup.E, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CONR.sup.8R.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8, NR.sup.6SO.sub.2NR.sup.6R.sup.8, C(R.sup.6)═NOR.sup.8; or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are bonded form a fully saturated or partly saturated 3- to 10-membered monocyclic or bicyclic ring optionally interrupted by heteroatoms and optionally having further substitution, R.sup.5 is hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.8)-haloalkyl and aryl, R.sup.6 is hydrogen and R.sup.5, R.sup.7 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl, and (C.sub.3-C.sub.4)-alkynyl, R.sup.8 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl, (C.sub.3-C.sub.4)-alkynyl and (C.sub.1-C.sub.10)-alkylcarbonyl-(C.sub.1-C.sub.6)-alkyl, R.sup.9 is hydrogen, halogen, cyano, isocyano, nitro, hydroxy, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl and NH.sub.2 (amino), m is 0, 1 and 2, n is 0, 1 and 2.
4. Compounds of the formula (I) according to claim 1 or an agrochemically acceptable salt thereof, in which Q.sup.1 is the groups Q.sup.1-1.1 to Q.sup.1-6.3, ##STR00089## ##STR00090## ##STR00091## Q.sup.2 is phenyl, which is unsubstituted or in each case independently substituted by m radicals selected from the group consisting of hydrogen, fluorine, chlorine and bromine, Z is the groups ##STR00092## Y is fluorine, chlorine, bromine, cyano, NO.sub.2, (C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-haloalkyl, (C.sub.1-C.sub.2)-alkylcarbonyl, (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.2)-haloalkoxy, (C.sub.1-C.sub.2)-alkyl-S(O).sub.n, and (C.sub.1-C.sub.2)-haloalkyl-S(O).sub.n, W is oxygen, R.sup.1 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl and (C.sub.1-C.sub.6)-alkoxy, R.sup.2 is hydrogen, (C.sub.1-C.sub.6)-alkyl and (C.sub.3-C.sub.6)-cycloalkyl, where the alkyl and cycloalkyl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, cyano, nitro, NH.sub.2 (amino), (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl, heterocyclyl-(C.sub.1-C.sub.4)-alkyl, heteroaryl-(C.sub.1-C.sub.4)-alkyl and aryl-(C.sub.1-C.sub.4)-alkyl, where the aryl, heterocyclyl and heteroaryl are unsubstituted or each independently substituted by m radicals selected from the group consisting of halogen, (C.sub.1-C.sub.6)-alkyl and (C.sub.1-C.sub.6)-haloalkyl, R.sup.3 is hydrogen and (C.sub.1-C.sub.6)-alkyl, R.sup.4 is hydrogen, cyano, nitro, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.3-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl and (C.sub.1-C.sub.4)-haloalkyl-S(O).sub.n—(C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-halocycloalkyl, hydroxy-(C.sub.1-C.sub.6)-alkylcarbonyl, amino-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.1-C.sub.6)-alkyl, S(O).sub.nR.sup.5, OR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, COR.sup.6, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8; aryl, heteroaryl and heterocyclyl, which are unsubstituted or each independently substituted by m radicals selected from the group consisting of hydrogen, halogen, cyano, nitro, OR.sup.5, S(O).sub.nR.sup.5, SO.sub.2NR.sup.6R.sup.8, CO.sub.2R.sup.8, CONR.sup.6R.sup.8, COR.sup.E, NR.sup.6R.sup.8, NR.sup.6COR.sup.8, NR.sup.6CONR.sup.8R.sup.8, NR.sup.6CO.sub.2R.sup.8, NR.sup.6SO.sub.2R.sup.8, NR.sup.6SO.sub.2NR.sup.6R.sup.8, C(R.sup.6)═NOR.sup.8; or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are bonded form a fully saturated or partly saturated 3- to 10-membered monocyclic or bicyclic ring optionally interrupted by heteroatoms and optionally having further substitution, R.sup.5 is hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.8)-haloalkyl and aryl, R.sup.6 is hydrogen and R.sup.5, R.sup.7 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl, (C.sub.3-C.sub.4)-alkynyl and (C.sub.1-C.sub.10)-alkylcarbonyl-(C.sub.1-C.sub.6)-alkyl, R.sup.8 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.4)-alkenyl and (C.sub.3-C.sub.4)-alkynyl, R.sup.9 is hydrogen, halogen, cyano, isocyano, nitro, hydroxy, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.4)-alkyl-S(O).sub.n, CHO, (C.sub.1-C.sub.4)-alkyloxycarbonyl and NH.sub.2 (amino), m is 0, 1 and 2, n is 0, 1 and 2.
5. Compounds of the formula (I) according to claim 1 or an agrochemically acceptable salt thereof, in which Q.sup.1 is the groups Q.sup.1-1.1 to Q.sup.1-5.7 ##STR00093## ##STR00094## Q.sup.2 is phenyl, which is unsubstituted or in each case independently substituted by m radicals selected from the group consisting of hydrogen, fluorine, chlorine and bromine, Z is the groups ##STR00095## Y is fluorine, chlorine, bromine, cyano, NO.sub.2, methyl, CF.sub.3 and OCF.sub.3, W is oxygen, R.sup.1 is hydrogen, methyl and ethyl, R.sup.2 is hydrogen, methyl, ethyl, allyl, propargyl and PhCH.sub.2, R.sup.3 is hydrogen, R.sup.4 is (C.sub.1-C.sub.6)-alkyl, S(O).sub.11R.sup.5, OR.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, COR.sup.6, which are unsubstituted or in each case independently of one another substituted by m radicals selected from the group consisting of hydrogen, OR.sup.5, S(O).sub.11R.sup.5, SO.sub.2NR.sup.6R.sup.7, CO.sub.2R.sup.8, COR.sup.E, NR.sup.6CO.sub.2R.sup.8, R.sup.5 is methyl, ethyl, CF.sub.3, CH.sub.2CF.sub.3, R.sup.6 is hydrogen and R.sup.5, R.sup.7 is hydrogen, methyl, ethyl, and ethyl-2-ethanoyl, R.sup.8 is methyl and ethyl, R.sup.9 is hydrogen, fluorine, chlorine, bromine, cyano, hydroxy, methyl, ethyl, OCH.sub.3, CF.sub.3, and OCF.sub.3, m is 0, 1 and 2, n is 0, 1 and 2.
6. Process for preparing compounds of the general formula (Ia) or an agrochemically acceptable salt thereof according to claim 1 by converting compounds of the general formulae (II) and (III) to compounds of the general formula (Ia) ##STR00096## in which Q.sup.1, Q.sup.2, Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the definitions given above.
7. Agrochemical composition comprising a) at least one compound of the formula (I) or an agrochemically acceptable salt thereof as defined in claim 1, and b) auxiliaries and additives customary in crop protection.
8. Agrochemical composition comprising a) at least one compound of the formula (I) or an agrochemically acceptable salt thereof as defined in claim 1, b) one or more active agrochemical ingredients other than component a), and optionally c) auxiliaries and additives customary in crop protection.
9. Method of controlling unwanted plants or for regulating the growth of plants, wherein an effective amount of at least one compound of the formula (I) or an agrochemically acceptable salt thereof, as defined in claim 1, is applied to the plants, the seed or the area in which the plants grow.
10. Use of compounds of the formula (I) or an agrochemically acceptable salt thereof, as defined in claim 1, as herbicides or plant growth regulators.
11. Use according to claim 10, wherein the compounds of the formula (I) or an agrochemically acceptable salt thereof are used for controlling harmful plants or for regulating growth in plant crops.
12. Use according to claim 11, wherein the crop plants are transgenic or nontransgenic crop plants.
Description
SYNTHESIS EXAMPLES
Synthesis Example No. 1-005
[0174] Synthesis stage 1: Ethyl(3Z)-4-(3,4-difluorophenyl)-4-hydroxy-2-oxobut-3-enoate
##STR00044##
[0175] A 1 M lithium trimethyl-N-(trimethylsilyl)silanaminide solution in THF (33.63 ml, 33.63 mmol, 1.05 equiv) was dissolved in diethyl ether (80 ml) under nitrogen atmosphere and cooled to −78° C. with a dry ice bath. Added dropwise to the solution within 10 min was a solution of 1-(3,4-difluorophenyl)ethanone (5.0 g, 35.02 mmol, 1.0 equiv.) in diethyl ether (20 ml). The resulting reaction mixture was stirred at −78° C. for 3 h and then at room temperature overnight. Subsequently, the suspension was cooled down to 0 to 4° C. with an ice bath, 1 M hydrochloric acid was added thereto and the mixture was stirred at room temperature for 30 min. The reaction mixture was extracted three times with 100 ml each time of ethyl acetate. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. The desired ethyl(3Z)-4-(3,4-difluorophenyl)-4-hydroxy-2-oxobut enoate product was isolated in the form of a white solid (8.00 g, 97% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 15.05 (bs, 1H), 7.87-7.77 (m, 2H), 7.33-7.29 (m, 1H), 7.00 (s, 1H), 4.41 (q, 2H), 1.42 (t, 3H).
[0176] Synthesis stage 2: Ethyl 5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylate
##STR00045##
Ethyl(3Z)-4-(3,4-difluorophenyl)-4-hydroxy-2-oxobut-3-enoate (2.0 g, 7.81 mmol, 1.0 equiv) and (2-fluorophenyl)hydrazine hydrochloride (1:1) (1.90 g, 11.71 mmol, 1.5 equiv) were suspended in 1.25 M hydrogen chloride in ethanol (30 ml) and heated to boiling for 4 h. The reaction mixture was neutralized with a saturated sodium hydrogencarbonate solution and then extracted three times with 50 ml each time of dichloromethane. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), ethyl 5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylate was isolated in the form of a yellow oil (3.02 g, 98% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3 δ, ppm) 7.57-7.53 (m, 1H), 7.47-7.41 (m, 1H), 7.29-7.25 (m, 1H), 7.13-7.01 (m, 4H), 6.97-6.93 (m, 1H), 4.46 (q, 2H), 1.43 (t, 3H).
[0177] Synthesis stage 3: Ethyl 4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylate
##STR00046##
Ethyl 5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylate (2.38 g, 6.87 mmol, 1.0 equiv) was dissolved in acetic acid (20 ml), and bromine (1.10 g, 6.87 mmol, 1.0 equiv) was added at room temperature. The resulting reaction mixture was stirred at room temperature for 2 h, and then more bromine (0.55 g, 3.43 mmol, 0.5 equiv) was added. The reaction was stirred at room temperature overnight and then ice-water (150 ml) was added, which resulted in a precipitate. The precipitate was dissolved in dichloromethane (100 ml) and extracted with saturated sodium thiosulfate solution. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), ethyl 4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylate was isolated in the form of a white solid (2.4 g, 78% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.51-7.45 (m, 1H), 7.44-7.39 (m, 1H), 7.27-7.22 (m, 1H), 7.17-6.98 (m, 4H), 4.49 (q, 2H), 1.44 (t, 3H).
[0178] Synthesis stage 4:4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylic acid
##STR00047##
Ethyl 4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylate (2.08 g, 4.88 mmol, 1.0 equiv) and lithium hydroxide (350.6 mg, 14.64 mmol, 3.0 equiv) were dissolved in a mixture of THF and water (18 ml, THF:water=7:2) and heated to boiling for 6 h. After cooling, the solution was acidified with 2 M hydrochloric acid and extracted twice with ethyl acetate (50 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. 4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylic acid was isolated in the form of a white solid (1.51 g, 77% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.52-7.42 (m, 1H), 7.29-7.26 (m, 1H), 7.48 (m, 1H), 7.19-7.08 (m, 3H), 7.03-7.00 (m, 1H).
[0179] Synthesis stage 5: tert-Butyl[4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]carbamate
##STR00048##
[0180] 4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-carboxylic acid (1.02 g, 2.57 mmol, 1.0 equiv) and triethylamine (0.90 ml, 6.42 mmol, 2.5 equiv) were dissolved in tert-butanol (15 ml), and diphenylphosphorus azide (0.55 ml, 2.57 mmol, 1.0 equiv) was added at room temperature. The reaction was stirred at 60° C. for 4 h, in the course of which evolution of gas occurred. After cooling to room temperature, a saturated sodium hydrogencarbonate solution (10 ml) was added to the reaction solution, and the mixture was extracted twice with ethyl acetate (50 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), tert-butyl[4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]carbamate was isolated in the form of a white solid (625 mg, 51% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.52-7.48 (m, 1H), 7.38-7.32 (m, 1H), 7.21 (dt, 1H), 7.15-7.09 (m, 2H), 7.05-6.97 (m, 2H), 6.48 (bs, 1H), 1.56 (s, 9H).
[0181] Synthesis stage 6:4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-amine
##STR00049##
tert-Butyl[4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]carbamate (625 mg, 1.34 mmol, 1.0 equiv) and trifluoroacetic acid (0.21 ml, 2.67 mmol, 2.0 equiv) were dissolved in dichloromethane (20 ml) and heated to boiling for 2 h. After cooling, the reaction mixture was diluted with saturated sodium hydrogencarbonate solution (10 ml), and then extracted twice with DCM (50 ml). 4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-amine was isolated in the form of a white solid (480 mg, 99% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.96 (bs, 2H), 7.46-7.36 (m, 2H), 7.26-7.23 (m, 1H), 7.18-7.10 (m, 3H), 7.08-7.00 (m, 1H).
[0182] Synthesis stage 7: Ethyl {[4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]sulfanyl}acetate (Example No. 1-002)
##STR00050##
4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazole-3-amine (223 mg, 0.61 mmol, 1.0 equiv), diethyl 2,2′-disulfanediyldiacetate (0.22 ml, 1.21 mmol, 2 equiv) and copper powder (7.70 mg, 0.12 mmol, 0.2 equiv) were suspended in 1,2-dichloroethane (10 ml) and heated to 60° C. for 15 min. Subsequently, tert-butyl nitrite (0.22 ml, 1.21 mmol, 2.0 equiv) was added dropwise and the reaction mixture was heated to 80° C. for 4 h. After cooling, the reaction mixture was diluted with water (10 ml) and dichloromethane (30 ml), and then extracted twice with DCM (50 ml). The phases were separated with a phase separator. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), ethyl {[4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]sulfanyl}acetate was isolated in the form of a white solid (129 mg, 44% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.44-7.34 (m, 2H), 7.26-7.20 (m, 1H), 7.13-7.02 (m, 3H), 6.99-6.96 (m, 1H), 4.22 (q, 2H), 3.89 (s, 2H), 1.24 (t, 3H).
[0183] Synthesis stage 8: {[4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]sulfanyl}acetic acid (Example No. 1-005)
##STR00051##
[0184] Ethyl {[4-bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]sulfanyl}acetate (83 mg, 0.18 mmol, 1.0 equiv) and lithium hydroxide (12.6 mg, 0.53 mmol, 3.0 equiv) were dissolved in a mixture of THF and water (9 ml, THF:water=7:2) and heated to boiling for 6 h. After cooling, the solution was acidified with 2 M hydrochloric acid and extracted twice with ethyl acetate (50 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. {[4-Bromo-5-(3,4-difluorophenyl)-1-(2-fluorophenyl)-1H-pyrazol-3-yl]sulfanyll acetic acid was isolated in the form of a white solid (56 mg, 68% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.45-7.35 (m, 2H), 7.27-7.22 (m, 1H), 7.18-7.09 (m, 3H), 7.01-6.97 (m, 3H), 3.86 (s, 2H).
Synthesis Example No. 1-008
[0185] Synthesis stage 1: Ethyl {[4-bromo-1-(2,3-difluorophenyl)-5-phenyl-1H-pyrazol-3-yl]sulfonyl}acetate
##STR00052##
[0186] Ethyl {[4-bromo-1-(2,3-difluorophenyl)-5-phenyl-1H-pyrazol-3-yl]sulfanyl}acetate (115 mg, 0.25 mmol, 1.0 equiv) was dissolved in dichloromethane (5 ml). 3-Chloroperoxybenzoic acid (114 mg, 0.51 mmol, 2.0 equiv, 77% pure) was added to the solution. The resulting reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with dichloromethane (30 ml) and extracted with a saturated sodium hydrogencarbonate solution. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), ethyl {[4-bromo (2,3-difluorophenyl)-5-phenyl-1H-pyrazol-3-yl]sulfonyllacetate was isolated in the form of a colourless solid (90 mg, 55% of theory, 80% pure). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.71-7.63 (m, 2H), 7.58-7.32 (m, 6H), 4.76 (s, 2H), 4.12 (q, 2H), 1.13 (t, 3H).
Synthesis Example No. II-001
[0187] Synthesis stage 1:1H-Pyrazol-3-ol
##STR00053##
Methyl (2E)-3-methoxyacrylate (20.00 g, 172.24 mmol, 1.0 equiv) was dissolved in methanol (15 ml), and hydrazine hydrate (1:1) (8.38 ml, 172.24 mmol, 1 equiv) was added dropwise, in the course of which the reaction mixture heated up to boiling. Subsequently, the reaction mixture was heated to boiling for 2 h and then concentrated under reduced pressure. The crude product was used in the next synthesis stage without further purification. 1H-Pyrazol-3-ol was isolated in the form of a yellow oil (15.30 g, 95% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 9.85 (bs, 1H), 7.35 (d, 1H), 5.43 (d, 1H).
[0188] Synthesis stage 2:1-(3-Hydroxy-1H-pyrazol-1-yl)ethanone
##STR00054##
1H-Pyrazol-3-ol (15.30 g, 181.97 mmol, 1.0 equiv) was dissolved in pyridine (100 ml). Added dropwise to the solution within 30 min was a mixture of acetic anhydride (19.00 ml, 201.37 mmol) and pyridine (10 ml). The resulting reaction mixture was heated to a temperature of 100° C. for 2 h. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was stirred with diethyl ether (50 ml), in the course of which it crystallized. 1-(3-Hydroxy-1H-pyrazol-1-yl)ethanone was isolated in the form of a pale yellow solid (18.00 g, 78% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 10.98 (bs, 1H), 8.12 (d, 1H), 6.01 (d, 2H), 2.47 (s, 3H).
[0189] Synthesis stage 3:3-(Benzyloxy)-1H-pyrazole
##STR00055##
1-(3-Hydroxy-1H-pyrazol-1-yl)ethanone (18.00 g, 142.73 mmol, 1.0 equiv), (bromomethyl)benzene (16.98 ml, 142.73 mmol, 1.0 equiv) and potassium carbonate (19.73 g, 142.73 mmol, 1.0 equiv) were suspended in butan-2-one (200 ml) and heated to boiling for 3 h. After cooling, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The residue was dissolved in THF (150 ml) and methanol (150 ml), and a 6 M sodium hydroxide solution (24 ml) was added. The reaction mixture was stirred at room temperature for 1 h and then the solvent was concentrated under reduced pressure. The residue was dissolved in dichloromethane (150 ml) and washed twice with water (50 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. The crude product was used in the next synthesis stage without further purification. 3-(Benzyloxy)-1H-pyrazole was isolated in the form of a yellow oil (19.82 g, 75% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 10.55 (bs, 1H), 7.43-7.23 (m, 6H), 5.74 (d, 1H), 5.20 (s, 2H).
[0190] Synthesis stage 4:3-(Benzyloxy)-1-(2-fluorophenyl)-1H-pyrazole
##STR00056##
3-(Benzyloxy)-1H-pyrazole (2.74 g, 15.73 mmol, 1.0 equiv), 1-fluoro-2-iodobenzene (1.83 ml, 15.73 mmol, 1 equiv), copper(I) iodide (299 mg, 1.57 mmol, 0.10 equiv), potassium carbonate (5.43 g, 39.31 mmol, 2.50 equiv) and N,N′-dimethylethane-1,2-diamine (0.87 ml, 7.88 mmol, 0.10 equiv) were suspended in toluene (25 ml) and heated to 115° C. for 5 h. The solvent was removed under reduced pressure, and the residue was extracted with dichloromethane (50 ml) and water (20 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), 3-(benzyloxy)-1-(2-fluorophenyl)-1H-pyrazole was isolated in the form of a yellow solid (2.09 g, 49% of theory, 80% pure). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.91-7.85 (m, 2H), 7.51-7.49 (m, 2H), 7.42-7.32 (m, 3H), 7.25-7.16 (m, 3H), 5.95 (d, 1H), 5.32 (s, 2H).
[0191] Synthesis stage 5:3-(Benzyloxy)-1-(2-fluorophenyl)-5-iodo-1H-pyrazole
##STR00057##
3-(Benzyloxy)-1-(2-fluorophenyl)-1H-pyrazole (4.81 g, 17.92 mmol, 1.0 equiv) was dissolved in THF (140 ml) and cooled to −78° C. with a cold bath (dry ice/acetone). Added dropwise to this cooled solution within 10 min was a 2 M lithium diisopropylamide solution in THF, and the mixture was stirred at this temperature for a further 30 min. This was followed by dropwise addition of iodine (4.55 g, 17.92 mmol, 1 equiv) dissolved in THF (10 ml) within 10 min. Thereafter, the reaction mixture was warmed to room temperature overnight and extracted with water (300 ml) and ethyl acetate (250 ml). The organic phase was washed with a saturated sodium thiosulfate solution (75 ml). Subsequently, the organic phase was dried over magnesium sulfate, and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), 3-(benzyloxy)-1-(2-fluorophenyl)-5-iodo-1H-pyrazole was isolated in the form of a brown oil (5.20 g, 73% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 7.90-7.84 (m, 2H), 7.52-7.47 (m, 2H), 7.41-7.31 (m, 2H), 7.25-7.15 (m, 3H), 5.94 (s, 1H), 5.31 (s, 2H).
[0192] Synthesis stage 6:5-[3-(Benzyloxy)-1-(2-fluorophenyl)-1H-pyrazol-5-yl]-2-fluoropyridine
##STR00058##
3-(Benzyloxy)-1-(2-fluorophenyl)-5-iodo-1H-pyrazole (2.20 g, 5.58 mmol, 1.0 equiv), (6-fluoropyridin-3-yl)boronic acid (1.18 mg, 8.37 mmol, 1.5 equiv) and caesium carbonate (7.27 mg, 22.32 mmol, 4 equiv) were suspended in a solvent mixture consisting of toluene (56 ml), ethanol (16 ml) and water (8 ml), and degassed and flooded with argon three times in succession. Bis(di-tert-butyl(4-dimethylaminophenyl)phosphino)palladium(II) chloride was added to the suspension. Then the reaction mixture was heated to boiling for 2 h. The solvent was removed under reduced pressure, and the residue was extracted with dichloromethane (750 ml) and water (30 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), 5-[3-(benzyloxy) (2-fluorophenyl)-1H-pyrazol-5-yl]-2-fluoropyridine was isolated in the form of a yellow solid (1.01 g, 45% of theory). .sup.1H-NMR (400 MHz, DMSO-d.sup.6δ, ppm) 8.15 (d, 1H), 7.81-7.77 (m, 1H), 7.63-7.59 (m, 1H), 7.54-7.48 (m, 3H), 7.43-7.30 (m, 5H), 7.22-7.19 (m, 1H), 6.44 (s, 1H), 5.24 (s, 2H).
[0193] Synthesis stage 7:5-[3-(Benzyloxy)-4-bromo-1-(2-fluorophenyl)-1H-pyrazol-5-yl]-2-fluoropyridine
##STR00059##
5-[3-(Benzyloxy)-1-(2-fluorophenyl)-1H-pyrazol-5-yl]-2-fluoropyridine (870 mg, 1.92 mmol, 1.0 equiv, 80% pure) was dissolved in DMF (10 ml), and 1-bromopyrrolidine-2,5-dione (0.51 g, 2.87 mmol, 1.5 equiv) was added at room temperature. The resulting reaction mixture was stirred at room temperature overnight and then admixed with ice-water (50 ml), which resulted in a precipitate. The precipitate was dissolved in dichloromethane (100 ml) and extracted with saturated sodium thiosulfate solution. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), 5-[3-(benzyloxy)-4-bromo-1-(2-fluorophenyl)-1H-pyrazol-5-yl]-2-fluoropyridine was isolated in the form of a white solid (847 mg, 99% of theory). .sup.1H-NMR (400 MHz, DMSO-d.sup.6δ, ppm) 8.20 (d, 1H), 7.96-7.91 (m, 1H), 7.61 (dt, 1H), 7.52-7.27 (m, 9H), 5.33 (s, 2H).
[0194] Synthesis stage 8:4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-ol
##STR00060##
5-[3-(Benzyloxy)-4-bromo-1-(2-fluorophenyl)-1H-pyrazol-5-yl]-2-fluoropyridine (811 mg, 1.83 mmol, 1.0 equiv) was dissolved in dichloromethane (25 ml), and trifluoromethanesulfonic acid (0.33 ml, 3.67 mmol, 2.0 equiv) was added at room temperature. The resulting reaction mixture was stirred at room temperature for 2 h and then extracted with a saturated sodium hydrogencarbonate solution (20 ml). The aqueous phase was extracted twice with dichloromethane (25 ml). The combined organic phase was dried over magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was used in the next synthesis stage without further purification. 4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-ol was isolated in the form of a white solid (700 mg, 92% of theory, 90% pure). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 9.51 (bs, 1H), 8.12 (d, 1H), 7.76 (dt, 1H), 7.48-7.43 (m, 1H), 7.41-7.38 (m, 1H), 7.27-7.24 (m, 1H), 7.08-7.06 (m, 1H), 6.96-6.94 (m, 1H).
[0195] Synthesis stage 8:4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazole-3-thiol
##STR00061##
4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-ol (930 mg, 2.64 mmol, 1.0 equiv) was suspended in toluene (20 ml), and phosphorus pentasulfide (2.35 g, 5.28 mmol, 2.0 equiv) was added at room temperature. The resulting reaction mixture was heated to boiling for 6 h (evolution of gas). After cooling to room temperature, the precipitate was filtered off, and this was extracted by stirring with toluene (50 ml). The toluene phases were combined, and the solvent was removed under reduced pressure. The crude product was used in the next synthesis stage without further purification. 4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazole-3-thiol was isolated in the form of a yellow solid (515 mg, 52% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm)
[0196] Synthesis stage 9: Ethyl {[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol-3-yl]sulfanyl}acetate (Example No. II-001)
##STR00062##
4-Bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazole-3-thiol (515 mg, 1.40 mmol, 1.0 equiv) and sodium acetate (172 mg, 2.10 mmol, 1.5 equiv) was suspended in ethanol (10 ml), and then ethyl bromoacetate (0.17 ml, 1.54 mmol, 1.1 equiv) was added. The resulting reaction mixture was heated to boiling for 3 h. After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was extracted with dichloromethane (50 ml) and water (10 ml), then stirred with toluene (50 ml). The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. By final purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), ethyl {[4-bromo-1-(2-fluorophenyl)-5-(6-fluoropyridin-3-yl)-1H-pyrazol yl]sulfanyl}acetate was isolated in the form of a white solid (21 mg, 3% of theory). .sup.1H-NMR (400 MHz, CDCl.sub.3δ, ppm) 8.10 (d, 1H), 7.72 (dt, 1H), 7.48-7.42 (m, 1H), 7.41-7.37 (m, 1H), 7.27-7.23 (m, 1H), 7.07-7.03 (m, 1H), 6.97-6.92 (m, 1H), 4.22 (q, 2H), 3.90 (s, 2H), 1.25 (t, 3H).
[0197] In analogy to the preparation examples cited above and recited at the appropriate point, and taking account of the general details relating to the preparation of substituted pyrazoles, the compounds cited below are obtained:
TABLE-US-00001 TABLE I
TABLE-US-00002 TABLE II
TABLE-US-00003 TABLE III
TABLE-US-00004 TABLE IV
TABLE-US-00005 TABLE V
TABLE-US-00006 TABLE VI
TABLE-US-00007 TABLE VII
TABLE-US-00008 TABLE VIII
[0198] Spectroscopic data of selected table examples:
[0199] Selected detailed synthesis examples for the inventive compounds of the general formula (I) are adduced below. The .sup.1H NMR, .sup.13C-NMR and .sup.19F-NMR spectroscopy data reported for the chemical examples described in the sections which follow (400 MHz for .sup.1H NMR and 150 MHz for .sup.13C-NMR and 375 MHz for .sup.19F-NMR, solvent CDCl.sub.3, CD.sub.3OD or d.sub.6-DMSO, internal standard: tetramethylsilane δ=0.00 ppm) were obtained on a Bruker instrument, and the signals listed have the meanings given below: br=broad; s=singlet, d=doublet, t=triplet, dd=doublet of doublets, ddd=doublet of a doublet of doublets, m=multiplet, q=quartet, quint=quintet, sext=sextet, sept=septet, dq=doublet of quartets, dt=doublet of triplets. In the case of diastereomer mixtures, either the significant signals for each of the two diastereomers are reported or the characteristic signal of the main diastereomer is reported. The abbreviations used for chemical groups have, for example, the following meanings: Me=CH.sub.3, Et=CH.sub.2CH.sub.3, t-Hex=C(CH.sub.3).sub.2CH(CH.sub.3).sub.2, t-Bu=C(CH.sub.3).sub.3, n-Bu=unbranched butyl, n-Pr=unbranched propyl, i-Pr=branched propyl, c-Pr=cyclopropyl, c-Hex=cyclohexyl.
[0200] The spectroscopic data listed hereinafter for selected table examples were evaluated via conventional .sup.1H NMR interpretation or via NMR peak list methods.
[0201] Conventional .sup.1H NMR Interpretation
Synthesis Example No. I-001
[0202] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.42 (m, 2H), 7.25 (m, 1H), 7.12 (m, 2H), 7.07 (m, 1H), 4.20 (q, 2H), 3.87 (s, 2H), 1.24 (t, 3H).
Synthesis Example No. 1-003
[0203] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.46 (d, 1H), 8.27 (d, 1H), 7.47 (m, 1H), 7.39 (m, 2H), 7.26 (m, 1H), 7.05 (m, 1H), 4.22 (q, 2H), 3.90 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. 1-004
[0204] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.35 (m, 3H), 7.26 (m, 2H), 7.12 (m, 3H), 4.22 (q, 2H), 3.90 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. 1-006
[0205] .sup.1H-NMR (400 MHz, DMSO-d.sup.6, 6, ppm) 7.57 (m, 1H), 7.45-7.28 (m, 7H), 3.96 (s, 2H).
Synthesis Example No. 1-007
[0206] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.44 (m, 2H), 7.26 (m, 1H), 7.12 (m, 3H), 6.99 (m, 1H), 4.40 (s, 2H), 4.26 (q, 2H), 1.27 (t, 3H).
Synthesis Example No. 1-009
[0207] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 10.80 (br s, 1H), 7.42 (m, 2H), 7.25 (m, 1H), 7.11 (m, 3H), 3.87 (s, 2H).
Synthesis Example No. I-010
[0208] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.64 (m, 1H), 7.47 (m, 4H), 7.33 (m, 3H), 4.55 (q, 2H), 4.15 (m, 2H), 1.16 (t, 3H).
Synthesis Example No. 11-002
[0209] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.45 (d, 1H), 8.27 (d, 1H), 7.46 (m, 1H), 7.42-7.36 (m, 2H), 7.27 (m, 1H), 7.05 (m, 1H), 4.22 (q, 2H), 3.90 (s, 2H), 1.25 (t, 3H).
Synthesis Example No. 111-002
[0210] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 9.23 (s, 1H), 8.67 (s, 2H), 7.40 (m, 3H), 7.18 (m, 2H), 3.90 (s, 2H).
Synthesis Example No. 111-003
[0211] .sup.1H-NMR (400 MHz, DMSO-d.sup.6, 6, ppm) 9.23 (s, 1H), 8.77 (s, 2H), 7.43 (m, 3H), 7.29 (m, 2H), 4.13 (q, 2H), 4.09 (s, 2H), 1.16 (t, 3H).
Synthesis Example No. IV-001
[0212] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.44 (m, 2H), 7.26 (m, 1H), 7.16 (m, 1H), 6.86 (d, 1H), 6.81 (d, 1H), 4.19 (q, 2H), 3.86 (s, 2H), 1.23 (t, 3H).
Synthesis Example No. V-001
[0213] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.43 (m, 1H), 7.31 (m, 1H), 7.29 (m, 1H), 7.18 (m, 1H), 7.10 (s, 1H), 4.20 (q, 2H), 3.87 (s, 2H), 2.25 (s, 3H), 1.24 (t, 3H).
Synthesis Example No. V-002
[0214] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.53 (m, 1H), 7.43 (m, 1H), 7.32 (m, 1H), 7.21 (m, 1H), 7.13 (s, 1H), 3.86 (s, 2H), 2.46 (s, 3H).
Synthesis Example No. 11-003
[0215] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.50 (d, 1H), 8.28 (s, 1H), 7.53-7.39 (m, 3H), 7.28 (m, 1H), 7.09 (m, 1H), 4.41 (s, 2H), 4.24 (m, 2H), 1.27 (t, 3H).
Synthesis Example No. 11-004
[0216] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 11.09 (br s, 1H), 8.25 (s, 1H), 7.57-7.51 (m, 2H), 7.46-7.42 (m, 1H), 7.38 (dd, 1H), 7.31-7.25 (m, 2H), 4.07 (q, 2H), 4.01 (s, 2H), 1.10 (t, 3H).
Synthesis Example No. I-011
[0217] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.80 (d, 2H), 7.57-7.48 (m, 2H), 7.34-7.28 (m, 2H), 7.05 (d, 2H), 4.09 (q, 2H), 3.97 (s, 2H), 1.11 (t, 3H).
Synthesis Example No. 11-005
[0218] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.50 (d, 1H), 8.29 (d, 1H), 7.47-7.39 (m, 3H), 7.27 (m, 1H), 7.10-7.05 (m, 1H), 3.91 (s, 2H).
Synthesis Example No. 11-006
[0219] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 11.09 (br s, 1H), 8.29 (d, 1H), 7.56-7.53 (m, 2H), 7.50-7.44 (m, 2H), 7.36-7.27 (m, 2H), 3.96 (s, 2H).
Synthesis Example No. 11-007
[0220] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.54 (s, 1H), 8.31 (s, 1H), 7.66 (s, 1H), 711H)111117.49-7.36 (m, 2H), 7.27-7.23 (m, 1H), 7.08-7.03 (m, 1H), 4.21 (q, 2H), 3.90 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. 1-012
[0221] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 711H)111117.48-7.43 (m, 2H), 7.27-7.26 (m, 1H), 7.20-7.07 (m, 4H), 4.21 (q, 2H), 3.93 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. 11-008
[0222] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.54 (s, 1H), 8.31 (s, 1H), 7.66 (s, 1H), 711H)111117.49-7.36 (m, 2H), 7.27-7.23 (m, 1H), 7.08-7.03 (m, 1H), 3.92 (s, 2H).
Synthesis Example No. 11-009
[0223] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 11.26 (s, 1H), 8.71 (m, 2H), 8.09 (s, 1H), 7.66-7.59 (m, 1H), 711H)111117.50-7.43 (m, 1H), 7.37-7.24 (m, 2H), 7.08-7.03 (m, 1H), 4.77 (s, 2H), 3.95 (q, 2H), 0.95 (t, 3H).
Synthesis Example No. II-010
[0224] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 11.26 (s, 1H), 8.59 (d, 1H), 8.01 (d, 1H), 7.91 (d, 1H), 7.61-7.56 (m, 1H), 711H)111117.48-7.43 (m, 1H), 7.32-7.24 (m, 2H), 4.25-4.22 (d, 1H), 4.03-3.96 (m, 3H), 1.04 (t, 3H).
Synthesis Example No. 1-013
[0225] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.46-7.35 (m, 2H), 711H)111117.27-7.18 (m, 1H), 7.17-7.02 (m, 2H), 6.97-6.92 (m, 1H), 4.22 (q, 2H), 3.89 (s, 2H), 1.24 (t, 3H).
Synthesis Example No. II-011
[0226] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.51 (s, 1H), 8.28 (s, 1H), 711H)111117.53-7.38 (m, 3H), 7.32-7.26 (m, 1H), 7.12-7.07 (m, 1H), 4.40 (d, 2H), 4.25 (q, 2H), 1.27 (t, 3H).
Synthesis Example No. 11-014
[0227] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.80 (d, 2H), 7.57-7.48 (m, 2H), 7.34-7.28 (m, 2H), 7.05 (d, 2H), 3.97 (s, 2H).
Synthesis Example No. 111-004
[0228] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 9.22 (s, 1H), 8.67 (s, 2H), 7.25-7.22 (m, 3H), 4.22 (q, 2H), 3.91 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. 1-015
[0229] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.42-7.36 (m, 2H), 7.22 (m, 1H), 7.16-6.95 (m, 4H), 4.21-4.13 (m, 3H), 1.62 (d, 3H), 1.22 (t, 3H).
Synthesis Example No. VI-001
[0230] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.94 (s, 1H), 8.68 (m, 1H), 8.59 (m, 1H), 7.55-7.46 (m, 2H), 7.34-7.27 (m, 2H), 4.10 (q, 2H), 4.01 (s, 2H), 1.12 (t, 3H).
Synthesis Example No. 11-012
[0231] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.24 (m, 1H), 7.60 (dd, 1H), 7.46 (dt, 1H), 7.37 (m, 1H), 7.33 (m, 1H), 7.23 (m, 1H), 7.05 (dt, 1H), 4.21 (q, 2H), 3.89 (s, 2H), 1.25 (t, 3H).
Synthesis Example No. 1-016
[0232] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.43 (m, 1H), 7.25-6.95 (m, 3H), 6.84 (m, 1H), 4.38 (s, 2H), 4.25 (q, 2H), 1.27 (t, 3H).
Synthesis Example No. 11-013
[0233] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.59 (m, 1H), 8.32 (m, 1H), 7.66 (m, 1H), 7.53-7.44 (m, 2H), 7.30 (m, 1H), 7.10 (m, 1H), 4.40 (s, 2H), 4.25 (q, 2H), 1.27 (t, 3H).
Synthesis Example No. 1-019
[0234] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.25-7.22 (m, 2H), 7.17-7.13 (m, 2H), 7.10-7.05 (m, 2H), 7.01-6.97 (m, 2H), 4.22 (q, 2H), 3.89 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. 1-017
[0235] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 12.81 (bs, 1H), 7.78 (d, 2H), 7.59-7.48 (m, 2H), 7.33-7.29 (m, 2H), 7.07 (d, 2H), 3.92 (s, 2H).
Synthesis Example No. 1-020
[0236] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.25-7.23 (m, 2H), 7.20-7.16 (m, 1H), 7.07-6.95 (m, 4H), 4.22 (q, 2H), 3.89 (s, 2H), 1.26 (t, 3H).
Synthesis Example No. I-021
[0237] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.41 (m, 1H), 7.27 (m, 1H), 7.24-7.20 (m, 2H), 7.04-7.00 (m, 2H), 4.20 (q, 2H), 3.88 (s, 2H), 1.25 (t, 3H).
Synthesis Example No. 1-022
[0238] .sup.1H-NMR (400 MHz, d.sup.6-DMSO, δ, ppm) 7.71-7.12 (m, 7H), 4.15 (m, 1H), 1.52 (d, 3H).
Synthesis Example No. 1-023
[0239] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.39-7.30 (m, 2H), 7.24-7.20 (m, 2H), 7.02-6.95 (m, 3H), 6.79 (d, 1H), 4.20 (q, 2H), 3.87 (s, 2H), 3.43 (s, 3H), 1.25 (t, 3H).
Synthesis Example No. 1-024
[0240] .sup.1H-NMR (400 MHz, d.sup.6-DMSO, δ, ppm) 12.85 (bs, 1H), 7.75 (m, 1H), 7.64 (m, 1H), 7.58-7.45 (m, 2H), 7.37-7.28 (m, 3H), 4.02 (s, 2H).
Synthesis Example No. 11-015
[0241] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.22 (m, 1H), 7.49-7.38 (m, 4H), 7.26 (m, 1H, 7.05 (dt, 1H), 4.20 (q, 2H), 3.89 (s, 2H), 1.24 (t, 3H).
Synthesis Example No. 1-016
[0242] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 8.26 (m, 1H), 7.60 (dd, 1H), 7.45-7.40 (m, 2H), 7.35 (d, 1H), 7.26 (m, 1H), 7.10 (m, 1H), 3.89 (s, 2H).
Synthesis Example No. 1-025
[0243] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.38 (m, 1H), 7.31-7.21 (m, 3H), 6.90 (m, 1H), 6.80 (m, 1H), 4.20 (q, 2H), 3.88 (s, 2H), 1.24 (t, 3H).
Synthesis Example No. 1-026
[0244] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.42 (m, 1H), 7.32-7.26 (m, 2H), 7.15-7.08 (m, 2H) 6.96-6.93 (m, 1H), 4.19 (q, 2H), 3.87 (s, 2H), 1.24 (t, 3H).
Synthesis Example No. 1-027
[0245] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.39 (m, 1H), 7.17-7.08 (m, 2H), 6.98-6.93 (m, 2H), 6.81 (m, 1H), 4.20 (q, 2H), 3.88 (s, 2H), 1.25 (t, 3H).
Synthesis Example No. VII-001
[0246] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.55 (bs, 1H), 7.47-7.39 (m, 2H), 7.25 (m, 1H), 7.17-7.06 (m, 3H), 6.99 (m, 1H), 4.05 (d, 2H), 3.81 (s, 2H), 3.71 (s, 3H).
Synthesis Example No. 1-014
[0247] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.46-7.39 (m, 2H), 7.25 (m, 1H), 7.14-7.10 (m, 3H), 6.97 (m, 1H), 3.86 (s, 2H).
Synthesis Example No. VII-002
[0248] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.47-7.36 (m, 2H), 7.25 (m, 1H), 7.15-7.04 (m, 3H), 6.97 (m, 1H), 4.16 (s, 2H), 4,10 (s, 2H), 3.73 (s, 3H), 3.18 (s, 3H).
Synthesis Example No. VIII-001
[0249] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.53-7.42 (m, 2H), 7.28 (m, 1H), 6.85 (d, 1H), 4.20 (q, 2H), 3.80 (s, 2H), 1.25 (t, 3H).
Synthesis Example No. VII-003
[0250] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.52 (bt, 1H), 7.47-7.36 (m, 2H), 7.23 (m, 1H), 7.18-7.04 (m, 3H), 7.00 (m, 1H), 4.17 (q, 2H), 4.03 (d, 2H), 3.82 (s, 2H), 1.25 (t, 3H).
Synthesis Example No. VII-004
[0251] .sup.1H-NMR (400 MHz, CDCl.sub.3, δ, ppm) 7.47-7.41 (m, 2H), 7.25-7.02 (m, 6H), 4.05 (d, 2H), 3.89 (s, 2H), 3.72 (s, 3H).
[0252] NMR Peak List Method
[0253] The 1H NMR data of selected examples are noted in the form of 1H NMR peak lists. For each signal peak, first the 6 value in ppm and then the signal intensity in round brackets are listed. The 6 value/signal intensity number pairs for different signal peaks are listed with separation from one another by semicolons.
[0254] The peak list for one example therefore takes the form of:
δ.sub.1(intensity.sub.1);δ.sub.2(intensity.sub.2); . . . ;δ.sub.i;(intensity.sub.i); . . . ;δ.sub.n(intensity.sub.n)
[0255] The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and the relative intensity thereof may be shown in comparison to the most intense signal in the spectrum.
[0256] For calibration of the chemical shift of 1H NMR spectra we use tetramethylsilane and/or the chemical shift of the solvent, particularly in the case of spectra measured in DMSO. Therefore, the tetramethylsilane peak may but need not occur in NMR peak lists.
[0257] The lists of the 1H NMR peaks are similar to the conventional 1H NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.
[0258] In addition, like conventional 1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds, which likewise form part of the subject matter of the invention, and/or peaks of impurities.
[0259] In the reporting of compound signals in the delta range of solvents and/or water, our lists of 1H NMR peaks show the usual solvent peaks, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water, which usually have a high intensity on average.
[0260] The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for example with a purity of >90%).
[0261] Such stereoisomers and/or impurities may be typical of the particular preparation process. Their peaks can thus help in identifying reproduction of our preparation process with reference to “by-product fingerprints”.
[0262] An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can, if required, isolate the peaks of the target compounds, optionally using additional intensity filters. This isolation would be similar to the relevant peak picking in conventional 1H NMR interpretation.
[0263] Further details of 1H NMR peak lists can be found in the Research Disclosure Database Number 564025.
TABLE-US-00009 VI-002: .sup.1H-NMR (400.6 MHz, d.sub.6-DMSO): δ = 12.8357 (0.6); 8.9379 (3.3); 8.9343 (3.4); 8.6831 (3.2); 8.6772 (3.8); 8.6002 (2.7); 8.5963 (2.8); 8.5939 (2.5); 8.5901 (2.4); 7.5822 (0.6); 7.5779 (0.7); 7.5628 (1.3); 7.5584 (1.5); 7.5434 (0.8); 7.5390 (0.8); 7.5006 (0.6); 7.4958 (0.6); 7.4879 (0.6); 7.4835 (0.6); 7.4756 (0.5); 7.4673 (0.5); 7.3431 (0.8); 7.3406 (1.0); 7.3242 (1.2); 7.3210 (1.6); 7.3107 (1.0); 7.3078 (0.8); 7.3018 (0.8); 7.2900 (0.8); 7.2842 (1.0); 7.2811 (0.8); 7.2633 (0.7); 7.2602 (0.6); 5.7568 (16.0); 3.9748 (10.0); 3.3213 (18.7); 2.6744 (0.8); 2.6698 (1.1); 2.6652 (0.8); 2.5404 (1.1); 2.5236 (3.3); 2.5189 (4.3); 2.5101 (60.8); 2.5056 (133.6); 2.5010 (187.3); 2.4964 (129.6); 2.4918 (58.7); 2.4642 (0.8); 2.3327 (0.8); 2.3280 (1.1); 2.3235 (0.8); 1.9885 (0.7); 1.1689 (0.5); 0.0103 (0.6); 0.0080 (4.4); 0.0064 (1.2); 0.0056 (1.3); 0.0047 (1.7); 0.0039 (2.4); −0.0002 (151.4); −0.0050 (2.1); −0.0058 (1.8); −0.0067 (1.6); −0.0085 (4.4); −0.0106 (0.8); −0.0114 (0.7); −0.0122 (0.6) VII-005: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 7.3896 (0.6); 7.3866 (0.7); 7.3797 (0.6); 7.3768 (1.0); 7.3724 (3.8); 7.3699 (1.4); 7.3674 (1.8); 7.3623 (0.5); 7.3578 (0.9); 7.3539 (2.2); 7.3391 (0.8); 7.3315 (0.6); 7.2773 (2.3); 7.2735 (2.3); 7.2604 (19.9); 7.2533 (1.5); 7.2015 (0.7); 7.1830 (0.6); 7.1592 (0.5); 7.1453 (0.7); 7.1416 (0.8); 7.1306 (0.7); 7.1287 (0.8); 7.1223 (1.1); 7.1115 (0.6); 7.1079 (0.6); 7.0999 (0.6); 7.0874 (0.6); 5.2998 (6.8); 4.0637 (3.9); 4.0505 (3.9); 3.8259 (8.2); 3.7125 (16.0); 2.0453 (0.6); 1.5502 (4.2); 1.2595 (0.5); 0.0079 (0.8); −0.0002 (29.7); −0.0085 (0.9) II-017: .sup.1H-NMR (400.6 MHz, d.sub.6-DMSO): δ = 12.8229 (0.9); 8.5977 (3.0); 8.5936 (3.3); 8.5856 (3.3); 8.5815 (3.2); 8.4763 (3.0); 8.4742 (3.3); 8.4706 (3.4); 8.4685 (3.2); 7.7351 (1.6); 7.7309 (1.9); 7.7296 (1.8); 7.7252 (1.6); 7.7153 (1.9); 7.7111 (2.1); 7.7097 (2.3); 7.7054 (1.8); 7.6479 (1.0); 7.6437 (1.2); 7.6285 (2.0); 7.6242 (2.2); 7.6092 (1.2); 7.6048 (1.3); 7.5378 (0.6); 7.5334 (0.6); 7.5251 (0.7); 7.5189 (1.0); 7.5145 (0.9); 7.5061 (1.0); 7.5018 (1.0); 7.4983 (1.0); 7.4938 (0.8); 7.4855 (0.8); 7.4810 (0.8); 7.4662 (2.1); 7.4640 (2.1); 7.4541 (2.0); 7.4519 (2.0); 7.4464 (1.8); 7.4442 (1.9); 7.4343 (1.9); 7.4320 (1.9); 7.3629 (1.2); 7.3602 (1.5); 7.3440 (2.0); 7.3409 (2.4); 7.3209 (2.2); 7.3175 (1.3); 7.2997 (1.2); 7.2946 (1.6); 7.2913 (1.3); 7.2736 (1.1); 7.2705 (1.0); 4.0377 (1.0); 4.0199 (1.0); 3.9568 (16.0); 3.3233 (77.7); 2.6745 (1.0); 2.6699 (1.4); 2.6653 (1.0); 2.5405 (5.3); 2.5237 (4.0); 2.5190 (5.7); 2.5103 (72.3); 2.5057 (159.3); 2.5011 (224.2); 2.4965 (157.2); 2.4919 (71.2); 2.4698 (0.7); 2.3328 (0.9); 2.3282 (1.3); 2.3236 (0.9); 1.9885 (4.8); 1.9083 (1.1); 1.6520 (1.7); 1.3550 (3.2); 1.2353 (0.6); 1.1921 (1.5); 1.1744 (3.0); 1.1566 (1.4); 0.1458 (0.5); 0.0103 (0.6); 0.0080 (5.0); 0.0064 (1.2); 0.0056 (1.2); 0.0048 (1.5); 0.0039 (2.0); 0.0023 (6.3); −0.0002 (174.8); −0.0050 (3.1); −0.0058 (2.6); −0.0067 (2.1); −0.0085 (5.3); −0.0106 (1.1); −0.0114 (1.0); −0.0122 (0.9); −0.0138 (0.5); −0.0146 (0.5); −0.1493 (0.5) III-005: .sup.1H-NMR (400.6 MHz, d.sub.6-DMSO): δ = 12.8568 (0.7); 9.2554 (7.2); 8.8381 (16.0); 7.6143 (0.7); 7.5956 (0.6); 7.4214 (0.7); 7.4175 (1.0); 7.4023 (0.8); 7.3846 (0.5); 7.3806 (0.6); 7.3719 (0.5); 7.3643 (0.6); 7.3599 (0.7); 7.3511 (0.6); 7.3467 (0.6); 6.8702 (0.6); 5.7567 (1.4); 3.9818 (9.2); 3.3199 (73.7); 2.6790 (0.6); 2.6745 (1.3); 2.6698 (1.8); 2.6651 (1.3); 2.6605 (0.6); 2.5404 (6.8); 2.5326 (1.4); 2.5280 (1.6); 2.5236 (5.4); 2.5189 (6.6); 2.5101 (98.2); 2.5056 (220.8); 2.5010 (313.5); 2.4964 (221.6); 2.4918 (101.7); 2.4713 (0.6); 2.4663 (0.7); 2.4614 (0.8); 2.4567 (0.8); 2.3373 (0.6); 2.3326 (1.4); 2.3280 (1.9); 2.3234 (1.4); 2.3188 (0.7); 2.1826 (1.0); 1.9885 (1.5); 1.9081 (0.8); 1.3549 (8.7); 1.2352 (1.9); 1.1744 (1.0); 0.1457 (0.7); 0.0317 (0.5); 0.0080 (6.1); 0.0063 (1.2); 0.0055 (1.3); 0.0046 (1.6); −0.0002 (226.6); −0.0051 (4.1); −0.0059 (3.4); −0.0068 (3.0); −0.0085 (7.2); −0.0139 (0.8); −0.0179 (0.5); −0.1494 (0.7) VII-006: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 8.6037 (1.0); 8.5996 (1.0); 8.5916 (1.0); 8.5875 (1.0); 8.5004 (1.3); 8.4964 (1.3); 7.6568 (0.7); 7.6523 (0.9); 7.6469 (0.7); 7.6370 (0.8); 7.6324 (1.0); 7.6271 (0.7); 7.4838 (0.5); 7.4795 (0.6); 7.4645 (1.1); 7.4604 (1.2); 7.4457 (0.9); 7.4414 (0.9); 7.3832 (0.5); 7.3208 (0.8); 7.3189 (0.8); 7.3086 (0.8); 7.3067 (0.8); 7.3010 (0.7); 7.2991 (0.7); 7.2888 (0.7); 7.2868 (0.7); 7.2613 (18.0); 7.2550 (0.7); 7.2518 (0.7); 7.2333 (1.0); 7.0887 (0.6); 7.0855 (0.6); 7.0678 (0.6); 7.0641 (1.0); 7.0604 (0.7); 7.0428 (0.6); 7.0396 (0.6); 5.3002 (6.6); 4.1309 (0.7); 4.1131 (0.7); 3.7656 (8.2); 3.5734 (16.0); 3.5581 (0.9); 3.5427 (2.4); 3.5273 (2.5); 3.5117 (1.0); 2.5239 (1.8); 2.5085 (3.1); 2.4931 (1.7); 2.0454 (3.1); 1.5705 (1.0); 1.2774 (0.9); 1.2596 (1.8); 1.2417 (0.8); 0.0080 (0.7); −0.0002 (27.4); −0.0085 (0.8) VII-007: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 8.6051 (0.9); 8.6010 (1.0); 8.5929 (1.0); 8.5888 (1.0); 8.4964 (1.2); 8.4926 (1.2); 7.6601 (0.6); 7.6556 (0.8); 7.6503 (0.6); 7.6403 (0.7); 7.6350 (0.9); 7.6304 (0.7); 7.4842 (0.5); 7.4799 (0.6); 7.4649 (0.9); 7.4607 (1.0); 7.4461 (0.6); 7.4418 (0.7); 7.3235 (0.7); 7.3214 (0.7); 7.3113 (0.7); 7.3093 (0.7); 7.3037 (0.6); 7.3017 (0.6); 7.2916 (0.6); 7.2605 (49.9); 7.2372 (0.6); 7.2186 (1.0); 7.0829 (0.6); 7.0797 (0.6); 7.0621 (0.6); 7.0582 (1.0); 7.0544 (0.6); 7.0370 (0.6); 7.0337 (0.5); 5.3001 (4.9); 4.0637 (3.8); 4.0504 (3.8); 3.8357 (8.0); 3.7110 (16.0); 2.0454 (2.1); 1.5474 (2.9); 1.2775 (0.6); 1.2597 (1.2); 1.2418 (0.6); 0.0080 (2.3); −0.0002 (75.2); −0.0085 (2.1) VII-008: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 8.5875 (0.8); 8.5839 (0.8); 8.5754 (0.9); 8.5718 (0.8); 8.4805 (1.0); 8.4761 (1.3); 7.6535 (0.6); 7.6480 (0.9); 7.6436 (0.8); 7.6337 (0.7); 7.6282 (1.0); 7.6238 (0.8); 7.4739 (0.8); 7.4697 (0.8); 7.4553 (0.6); 7.4508 (0.6); 7.3633 (0.5); 7.3089 (0.8); 7.2968 (0.8); 7.2951 (0.8); 7.2892 (0.8); 7.2769 (0.7); 7.2753 (0.7); 7.2622 (12.6); 7.2449 (0.7); 7.2432 (0.8); 7.2237 (1.1); 7.0597 (0.6); 7.0566 (0.6); 7.0389 (0.6); 7.0352 (0.9); 7.0315 (0.6); 5.3002 (10.6); 4.2356 (1.6); 4.1673 (6.1); 4.1351 (8.0); 4.1309 (1.8); 4.1129 (1.2); 3.9867 (1.8); 3.7333 (16.0); 3.1909 (12.9); 3.0185 (2.9); 2.0451 (6.0); 1.2773 (1.6); 1.2595 (3.4); 1.2417 (1.6); −0.0002 (18.5); −0.0085 (0.6) VII-009: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 8.4704 (2.1); 8.4635 (2.1); 8.2948 (1.1); 8.2910 (2.0); 8.2873 (1.1); 7.5201 (0.6); 7.5161 (0.6); 7.5010 (1.0); 7.4968 (1.2); 7.4822 (1.0); 7.4780 (1.0); 7.4207 (1.0); 7.4164 (1.2); 7.4139 (1.2); 7.4095 (0.9); 7.4058 (0.6); 7.3989 (1.1); 7.3943 (1.0); 7.3921 (1.0); 7.3875 (0.8); 7.3851 (0.5); 7.2690 (0.7); 7.2610 (26.4); 7.2494 (1.0); 7.1008 (0.7); 7.0976 (0.6); 7.0799 (0.6); 7.0761 (1.0); 7.0724 (0.7); 7.0548 (0.6); 7.0516 (0.6); 5.3002 (5.6); 4.0627 (3.9); 4.0495 (3.9); 3.8378 (8.0); 3.7142 (16.0); 2.0454 (1.2); 1.5671 (2.7); 1.2774 (0.6); 1.2597 (1.4); 0.8989 (0.6); 0.8820 (2.0); 0.8642 (0.8); 0.0080 (1.1); −0.0002 (39.8); −0.0085 (1.1) VII-010: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 8.4700 (1.9); 8.4631 (2.0); 8.2975 (1.0); 8.2937 (1.8); 8.2901 (1.0); 7.5105 (0.5); 7.4955 (0.8); 7.4913 (0.9); 7.4768 (0.6); 7.4724 (0.6); 7.4215 (1.2); 7.4170 (1.3); 7.4147 (1.1); 7.4103 (1.3); 7.4064 (0.7); 7.4045 (0.7); 7.4023 (0.8); 7.3995 (1.2); 7.3951 (1.2); 7.3926 (1.1); 7.3899 (0.8); 7.3882 (1.0); 7.3857 (0.6); 7.2859 (0.5); 7.2843 (0.6); 7.2827 (0.6); 7.2813 (0.5); 7.2620 (14.8); 7.1077 (0.6); 7.1045 (0.6); 7.0869 (0.6); 7.0831 (1.0); 7.0794 (0.6); 7.0618 (0.5); 7.0586 (0.5); 5.3004 (4.8); 4.1309 (0.8); 4.1131 (0.8); 3.7682 (7.8); 3.5761 (16.0); 3.5562 (0.9); 3.5409 (2.2); 3.5256 (2.2); 3.5101 (0.9); 2.5218 (1.7); 2.5063 (2.7); 2.4911 (1.6); 2.0454 (3.8); 1.2774 (1.1); 1.2596 (2.3); 1.2418 (1.1); 0.0080 (0.6); −0.0002 (22.3); −0.0085 (0.6) VII-011: .sup.1H-NMR (400.6 MHz, CDCl3): δ = 7.4393 (0.7); 7.4351 (0.8); 7.4207 (0.6); 7.4162 (0.6); 7.4025 (0.5); 7.3879 (0.6); 7.3835 (0.5); 7.2620 (8.0); 7.2447 (0.7); 7.2255 (1.1); 7.1314 (0.6); 7.1259 (1.0); 7.1220 (0.6); 7.1185 (0.5); 7.1127 (0.6); 7.1103 (0.7); 7.1050 (1.3); 7.1015 (1.0); 7.0914 (0.6); 7.0858 (0.6); 7.0801 (1.1); 7.0619 (0.5); 7.0581 (0.8); 7.0546 (0.5); 6.9874 (0.6); 6.9830 (0.5); 5.3003 (4.2); 4.2298 (1.5); 4.1623 (5.6); 4.1181 (7.0); 3.9701 (1.7); 3.7315 (16.0); 3.1842 (11.4); 3.0133 (2.7); 1.5743 (12.3); 1.2593 (0.7); 1.2563 (0.7); −0.0002 (10.7)
[0264] The present invention further provides for the use of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I.001) to (VII.002) and/or salts thereof, in each case as defined above,
as herbicide and/or plant growth regulator, preferably in crops of useful plants and/or ornamental plants.
[0265] The present invention further provides a method of controlling harmful plants and/or for regulating the growth of plants, characterized in that an effective amount [0266] of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I.001) to (VII.002) and/or salts thereof, in each case as defined above, or [0267] of a composition of the invention, as defined below,
is applied to the (harmful) plants, seeds of (harmful) plants, the soil in which or on which the (harmful) plants grow or the area under cultivation.
[0268] The present invention also provides a method for controlling unwanted plants, preferably in crops of useful plants, characterized in that an effective amount [0269] of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I.001) to (VII.002) and/or salts thereof, in each case as defined above, or [0270] of a composition of the invention, as defined below,
is applied to unwanted plants (for example harmful plants such as mono- or dicotyledonous weeds or unwanted crop plants), the seed of the unwanted plants (i.e. plant seeds, for example grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds), the soil in which or on which the unwanted plants grow (for example the soil of crop land or non-crop land) or the area under cultivation (i.e. the area on which the unwanted plants will grow).
[0271] The present invention also further provides methods for controlling for regulating the growth of plants, preferably of useful plants, characterized in that an effective amount [0272] of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the general formulae (I.001) to (VII.002) and/or salts thereof, in each case as defined above, or [0273] of a composition of the invention, as defined below,
is applied to the plant, the seed of the plant (i.e. plant seed, for example grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds), the soil in which or on which the plants grow (for example the soil of crop land or non-crop land) or the area under cultivation (i.e. the area on which the plants will grow).
[0274] In this context, the compounds of the invention or the compositions of the invention can be deployed, for example, by pre-sowing (if appropriate also by incorporation into the soil), pre-emergence and/or post-emergence methods. Specific examples of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds of the invention are as follows, though there is no intention to restrict the enumeration to particular species.
[0275] In a method of the invention for controlling harmful plants or for regulating the growth of plants, preference is given to using one or more compounds of the general formula (I) and/or salts thereof for control of harmful plants or for regulation of growth in crops of useful plants or ornamental plants, where the useful plants or ornamental plants in a preferred configuration are transgenic plants.
[0276] The inventive compounds of the general formula (I) and/or their salts are suitable for controlling the following genera of monocotyledonous and dicotyledonous harmful plants:
[0277] Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
[0278] Dicotyledonous harmful plants of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
[0279] When the compounds of the invention are applied to the soil surface before germination of the harmful plants (weed grasses and/or broad-leaved weeds) (pre-emergence method), either the seedlings of the weed grasses or broad-leaved weeds are prevented completely from emerging or they grow until they have reached the cotyledon stage, but then stop growing and eventually, after three to four weeks have elapsed, die completely.
[0280] If the active ingredients are applied post-emergence to the green parts of the plants, growth stops after the treatment, and the harmful plants remain at the growth stage at the time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.
[0281] Although the compounds of the invention display excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, are damaged only to an insignificant extent, or not at all, depending on the structure of the respective compound of the invention and its application rate. For these reasons, the present compounds are very suitable for selective control of unwanted plant growth in plant crops such as agriculturally useful plants or ornamental plants.
[0282] In addition, the compounds of the invention (depending on their particular structure and the application rate deployed) have outstanding growth-regulating properties in crop plants. They intervene in the plants' own metabolism with regulatory effect, and can thus be used for the controlled influencing of plant constituents and to facilitate harvesting, for example by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth without killing the plants in the process. Inhibition of vegetative growth plays a major role for many mono- and dicotyledonous crops since, for example, this can reduce or completely prevent lodging.
[0283] By virtue of their herbicidal and plant growth regulatory properties, the active ingredients can also be used to control harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis. In general, the transgenic plants are characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
[0284] Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. For instance, there are known transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested material.
[0285] It is preferred with a view to transgenic crops to use the compounds of the invention and/or their salts in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, millet, rice and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
[0286] It is also preferred to employ the compounds of the invention as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.
[0287] By virtue of their herbicidal and plant growth regulatory properties, the active ingredients can also be used to control harmful plants in crops of genetically modified plants which are known or are yet to be developed. In general, the transgenic plants are characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. For instance, there are known transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested material. Further special properties may be tolerance or resistance to abiotic stressors, for example heat, cold, drought, salinity and ultraviolet radiation.
[0288] Preference is given to the use of the inventive compounds of the general formula (I) or salts thereof in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, triticale, millet, rice, cassava and corn, or else crops of sugar beet, cotton, soybean, oilseed rape, potatoes, tomatoes, peas and other vegetables.
[0289] It is preferable to employ the compounds of the general formula (I) as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.
[0290] Conventional ways of producing novel plants which have modified properties in comparison to existing plants consist, for example, in traditional cultivation methods and the generation of mutants. Alternatively, novel plants with altered properties can be generated with the aid of recombinant methods.
[0291] A large number of molecular-biological techniques by means of which novel transgenic plants with modified properties can be generated are known to the person skilled in the art. For such genetic manipulations, nucleic acid molecules which allow mutagenesis or sequence alteration by recombination of DNA sequences can be introduced into plasmids. With the aid of standard methods, it is possible, for example, to undertake base exchanges, remove part sequences or add natural or synthetic sequences. To connect the DNA fragments to each other, adapters or linkers may be added to the fragments.
[0292] For example, the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect, or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.
[0293] To this end, it is firstly possible to use DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, and also DNA molecules which only encompass portions of the coding sequence, in which case it is necessary for these portions to be long enough to have an antisense effect in the cells. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them.
[0294] When expressing nucleic acid molecules in plants, the protein synthesized may be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to join the coding region to DNA sequences which ensure localization in a particular compartment. Sequences of this kind are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227). The nucleic acid molecules can also be expressed in the organelles of the plant cells.
[0295] The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants may be plants of any desired plant species, i.e. not only monocotyledonous but also dicotyledonous plants.
[0296] Obtainable in this way are transgenic plants having properties altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or expression of heterologous (=foreign) genes or gene sequences.
[0297] It is preferable to employ the inventive compounds (I) in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogous active ingredients.
[0298] When the active ingredients of the invention are employed in transgenic crops, not only do the effects towards harmful plants observed in other crops occur, but frequently also effects which are specific to the application in the particular transgenic crop, for example an altered or specifically widened spectrum of weeds which can be controlled, altered application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing of growth and yield of the transgenic crop plants.
[0299] The invention therefore also relates to the use of the inventive compounds of the general formula (I) and/or their salts as herbicides for controlling harmful plants in crops of useful plants or ornamentals, optionally in transgenic crop plants.
[0300] Preference is given to the use in cereals, here preferably corn, wheat, barley, rye, oats, millet or rice, by the pre- or post-emergence method.
[0301] Preference is also given to the use in soybeans by the pre- or post-emergence method.
[0302] The inventive use for control of harmful plants or for regulation of plant growth also includes the case in which the active ingredient of the general formula (I) or its salt is not formed from a precursor substance (“prodrug”) until after application on the plant, in the plant or in the soil.
[0303] The invention also provides for the use of one or more compounds of the general formula (I) or salts thereof or of a composition of the invention (as defined below) (in a method) for controlling harmful plants or for regulating the growth of plants which comprises applying an effective amount of one or more compounds of the general formula (I) or salts thereof onto the plants (harmful plants, if appropriate together with the useful plants), plant seeds, the soil in which or on which the plants grow or the area under cultivation.
[0304] The invention also provides a herbicidal and/or plant growth-regulating composition, characterized in that the composition comprises
[0305] (a) one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I.001) to (VII.002) and/or salts thereof, in each case as defined above,
and
[0306] (b) one or more further substances selected from groups (i) and/or (ii):
[0307] (i) one or more further agrochemically active substances, preferably selected from the group consisting of insecticides, acaricides, nematicides, further herbicides (i.e. those not conforming to the general formula (I) defined above), fungicides, safeners, fertilizers and/or further growth regulators,
[0308] (ii) one or more formulation auxiliaries customary in crop protection.
[0309] The further agrochemically active substances of component (i) of a composition of the invention are preferably selected from the group of substances mentioned in “The Pesticide Manual”, 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012.
[0310] A herbicidal or plant growth-regulating composition of the invention comprises preferably one, two, three or more formulation auxiliaries (ii) customary in crop protection selected from the group consisting of surfactants, emulsifiers, dispersants, film formers, thickeners, inorganic salts, dusting agents, carriers that are solid at 25° C. and 1013 mbar, preferably adsorptive granulated inert materials, wetting agents, antioxidants, stabilizers, buffer substances, antifoam agents, water, organic solvents, preferably organic solvents miscible with water in any ratio at 25° C. and 1013 mbar.
[0311] The inventive compounds of the general formula (I) can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the customary formulations. The invention therefore also provides herbicidal and plant growth-regulating compositions which comprise compounds of the general formula (I) and/or salts thereof.
[0312] The compounds of the general formula (I) and/or salts thereof can be formulated in various ways according to which biological and/or physicochemical parameters are required. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), dressings, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, absorption and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
[0313] These individual formulation types and the formulation auxiliaries, such as inert materials, surfactants, solvents and further additives, are known to the person skilled in the art and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd ed., Darland Books, Caldwell N.J., H. v. Olphen, “Introduction to Clay Colloid Chemistry”, 2nd ed., J. Wiley & Sons, N.Y., C. Marsden, “Solvents Guide”, 2nd ed., Interscience, N.Y. 1963, McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J., Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964, Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Interface-active Ethylene Oxide Adducts], Wiss. Verlagsgesellschaft, Stuttgart 1976, Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.
[0314] Wettable powders are preparations which can be dispersed uniformly in water and, in addition to the active ingredient, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurate. To produce the wettable powders, the active herbicidal ingredients are finely ground, for example in customary apparatuses such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.
[0315] Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with addition of one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are: calcium alkylarylsulfonate salts, for example calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
[0316] Dusting products are obtained by grinding the active ingredient with finely distributed solids, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
[0317] Suspension concentrates may be water- or oil-based. They may be produced, for example, by wet-grinding by means of commercial bead mills and optional addition of surfactants as already listed above, for example, for the other formulation types.
[0318] Emulsions, for example oil-in-water emulsions (EW), can be produced, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants as already listed above, for example, for the other formulation types.
[0319] Granules can be produced either by spraying the active ingredient onto granular inert material capable of adsorption or by applying active ingredient concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules—if desired as a mixture with fertilizers.
[0320] Water-dispersible granules are produced generally by the customary processes such as spray-drying, fluidized-bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.
[0321] For the production of pan granules, fluidized bed granules, extruder granules and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff.; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
[0322] For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
[0323] The agrochemical preparations, preferably herbicidal or plant growth-regulating compositions, of the present invention preferably comprise a total amount of 0.1 to 99% by weight, preferably 0.5 to 95% by weight, more preferably 1 to 90% by weight, especially preferably 2 to 80% by weight, of active ingredients of the general formula (I) and their salts.
[0324] In wettable powders, the active ingredient concentration is, for example, about 10% to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In emulsifiable concentrates, the active ingredient concentration may be about 1% to 90% and preferably 5% to 80% by weight. Formulations in the form of dusts comprise 1% to 30% by weight of active ingredient, preferably usually 5% to 20% by weight of active ingredient; sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends partly on whether the active compound is present in liquid or solid form and on which granulation auxiliaries, fillers, and so forth are used. In the water-dispersible granules, the content of active ingredient is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.
[0325] In addition, the active ingredient formulations mentioned optionally comprise the respective customary stickers, wetters, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.
[0326] Examples of formulation auxiliaries are described, inter alia, in “Chemistry and Technology of Agrochemical Formulations”, ed. D. A. Knowles, Kluwer Academic Publishers (1998).
[0327] The compounds of the general formula (I) or salts thereof can be used as such or in the form of their preparations (formulations) in a combination with other pesticidally active substances, for example insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or of a tank mix. The combination formulations can be produced on the basis of the abovementioned formulations, taking account of the physical properties and stabilities of the active ingredients to be combined.
[0328] Combination partners usable for the inventive compounds of the general formula (I) in mixed formulations or in a tankmix are, for example, known active ingredients based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or “The Pesticide Manual”, 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012, and the literature cited therein.
[0329] Of particular interest is the selective control of harmful plants in crops of useful plants and ornamentals. Although the inventive compounds of the general formula (I) have already demonstrated very good to adequate selectivity in a large number of crops, in principle, in some crops and in particular also in the case of mixtures with other, less selective herbicides, phytotoxicities on the crop plants may occur. In this connection, combinations of inventive compounds (I) that are of particular interest are those which comprise the compounds of the general formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which are used in an antidotically effective amount, reduce the phytotoxic side effects of the herbicides/pesticides employed, for example in economically important crops, such as cereals (wheat, barley, rye, corn, rice, millet), sugarbeet, sugarcane, oilseed rape, cotton and soybeans, preferably cereals.
[0330] The weight ratios of herbicide (mixture) to safener depend generally on the herbicide application rate and the efficacy of the safener in question and may vary within wide limits, for example in the range from 200:1 to 1:200, preferably 100:1 to 1:100, in particular 20:1 to 1:20. Analogously to the compounds of the general formula (I) or mixtures thereof, the safeners can be formulated with further herbicides/pesticides and be provided and employed as a finished formulation or tank mix with the herbicides.
[0331] For application, the herbicide formulations or herbicide-safener formulations in the commercial form are diluted if appropriate in a customary manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in dust form, granules for soil application or granules for scattering and sprayable solutions are not normally diluted further with other inert substances prior to application.
[0332] The application rate of the compounds of the general formula (I) and/or their salts is affected to a certain extent by external conditions such as temperature, humidity, etc. The application rate may vary within wide limits. For the application as a herbicide for controlling harmful plants, the total amount of compounds of the general formula (I) and their salts is preferably in the range from 0.001 to 10.0 kg/ha, with preference in the range from 0.005 to 5 kg/ha, more preferably in the range from 0.01 to 1.5 kg/ha, particularly preferably in the range from 0.05 to 1 kg/ha. This applies both to pre-emergence and to post-emergence application.
[0333] When compounds of the general formula (I) and/or their salts are used as plant growth regulator, for example as culm stabilizer for crop plants like those mentioned above, preferably cereal plants, such as wheat, barley, rye, triticale, millet, rice or corn, the total application rate is preferably in the range of from 0.001 to 2 kg/ha, preferably in the range of from 0.005 to 1 kg/ha, in particular in the range of from 10 to 500 g/ha, very particularly preferably in the range from 20 to 250 g/ha. This applies both to pre-emergence and to post-emergence application.
[0334] The application as culm stabilizer may take place at various stages of the growth of the plants. Preferred is, for example, the application after the tillering phase, at the beginning of the longitudinal growth.
[0335] As an alternative, application as plant growth regulator is also possible by treating the seed, which includes various techniques for dressing and coating seed. The application rate depends on the particular techniques and can be determined in preliminary tests.
[0336] Combination partners usable for the inventive compounds of the general formula (I) in compositions of the invention (e.g. mixed formulations or in a tankmix) are, for example, known active ingredients based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II or protoporphyrinogen oxidase, as described, for example, from Weed Research 26 (1986) 441-445 or “The Pesticide Manual”, 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012, and literature cited therein. Known herbicides or plant growth regulators which can be combined with the compounds of the invention are, for example, the following, where said active ingredients are referred to either by their “common name” in accordance with the International Organization for Standardization (ISO) or by the chemical name or by the code number. They always encompass all the use forms, for example acids, salts, esters and also all isomeric forms such as stereoisomers and optical isomers, even if they are not mentioned explicitly.
Examples of Such Herbicidal Mixing Partners are
[0337] acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammoniumsulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate and -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, 2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, isooctyl, -potassium and -sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-9600, F-5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]-phenyl]ethanesulfonamide, F-7967, i.e. 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium and -trimesium, H-9201, i.e. 0-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphoramidothioate, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e. 1-(dimethoxyphosphoryl)ethyl(2,4-dichlorophenoxy)acetate, imazamethabenz, Imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, -potassium and sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, i.e. 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e. 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trifluoroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e. 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline, and the following compounds:
##STR00071##
[0338] Examples of plant growth regulators as possible mixing partners are:
acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, brassinolide, catechol, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, -disodium, and mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid methyl ester, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, 4-oxo-4[(2-phenylethyl)amino]butyric acid, paclobutrazole, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.
[0339] Useful combination partners for the inventive compounds of the general formula (I) also include, for example, the following safeners:
[0340] S1) Compounds from the group of heterocyclic carboxylic acid derivatives:
[0341] S1.sup.a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (S P), preferably compounds such as
1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) (“mefenpyr-diethyl”), and related compounds as described in WO-A-91/07874;
[0342] S1.sup.b) Derivatives of dichlorophenylpyrazolecarboxylic acid (S1.sup.b), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl) isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole carboxylate (S1-4) and related compounds as described in EP-A-333131 and EP-A-269806;
[0343] S1.sup.c) Derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1.sup.c), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related compounds as described, for example, in EP-A-268554;
[0344] S1.sup.d) Compounds of the triazolecarboxylic acid type (S1.sup.d), preferably compounds such as fenchlorazole(-ethyl ester), i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (S1-7), and related compounds, as described in EP-A-174562 and EP-A-346620;
[0345] S1.sup.e) Compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type (S1.sup.e), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (51-9) and related compounds as described in WO-A-91/08202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-11) (“isoxadifen-ethyl”) or n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13) as described in patent application WO-A-95/07897.
[0346] S2) Compounds from the group of the 8-quinolinoxy derivatives (S2):
[0347] S2.sup.a) Compounds of the 8-quinolinoxyacetic acid type (S2.sup.a), preferably 1-methylhexyl(5-chloro-8-quinolinoxy)acetate (“cloquintocet-mexyl”) (S2-1), 1,3-dimethylbut-1-yl(5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl(5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxyprop-2-yl(5-chloro-8-quinolinoxy)acetate (S2-4), ethyl(5-chloro-8-quinolinoxy)acetate (S2-5),
[0348] methyl (5-chloro-8-quinolinoxy)acetate (S2-6),
allyl(5-chloro-8-quinolinoxy)acetate (S2-7), 2-(2-propylideneiminoxy)-1-ethyl(5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxoprop-1-yl(5-chloro-8-quinolinoxy)acetate (S2-9) and related compounds, as described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0 492 366, and also (5-chloro-8-quinolinoxy)acetic acid (S2-10), hydrates and salts thereof, for example the lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts thereof, as described in WO-A-2002/34048;
[0349] S2.sup.b) Compounds of the (5-chloro-8-quinolinoxy)malonic acid type (S2.sup.b), preferably compounds such as diethyl(5-chloro-8-quinolinoxy)malonate, diallyl(5-chloro-8-quinolinoxy)malonate, methyl ethyl(5-chloro-8-quinolinoxy)malonate and related compounds, as described in EP-A-0 582 198.
[0350] S3) Active ingredients of the dichloroacetamide type (S3), which are frequently used as pre-emergence safeners (soil-acting safeners), for example
[0351] “dichlormid” (N,N-diallyl-2,2-dichloroacetamide) (S3-1),
[0352] “R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2),
[0353] “R-28725” (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3),
[0354] “benoxacor” (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),
[0355] “PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl]methylldichloroacetamide) from PPG Industries (S3-5),
[0356] “DKA-24” (N-allyl-N-Rallylaminocarbonyl)methyl]dichloroacetamide) from Sagro-Chem (S3-6),
[0357] “AD-67” or “MON 4660” (3-dichloroacetyl-1-oxa-3-azaspiro[4.5]decane) from Nitrokemia or Monsanto (S3-7),
[0358] “TI-35” (1-dichloroacetylazepane) from TRI-Chemical RT (S3-8), “diclonon” (dicyclonon) or “BAS145138” or “LAB145138” (S3-9)
[0359] ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) from BASF,
[0360] “furilazole” or “MON 13900” ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), and the (R) isomer thereof (S3-11).
[0361] S4) Compounds from the class of the acylsulfonamides (S4):
[0362] S4.sup.a)N-Acylsulfonamides of the formula (S4.sup.a) and salts thereof, as described in WO-A-97/45016,
##STR00072##
in which
[0363] R.sub.A.sup.1 is (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, where the 2 latter radicals are substituted by v.sub.A substituents from the group of halogen, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy and (C.sub.1-C.sub.4)-alkylthio and, in the case of cyclic radicals, also by (C.sub.1-C.sub.4)-alkyl and (C.sub.1-C.sub.4)-haloalkyl;
[0364] R.sub.A.sup.2 is halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, CF.sub.3;
[0365] m.sub.A is 1 or 2;
[0366] V.sub.A is 0, 1, 2 or 3;
S4.sup.b) Compounds of the 4-(benzoylsulfamoyl)benzamide type of the formula (S4.sup.b) and salts thereof, as described in WO-A-99/16744,
##STR00073##
in which
[0367] R.sub.B.sup.1, R.sub.B.sup.2 are independently hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-alkenyl, (C.sub.3-C.sub.6)-alkynyl,
[0368] R.sub.B.sup.3 is halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl or (C.sub.1-C.sub.4)-alkoxy and
[0369] m.sub.B is 1 or 2,
[0370] e.g. those in which
[0371] R.sub.B.sup.1=cyclopropyl, R.sub.B.sup.2=hydrogen and (R.sub.B.sup.3)=2-OMe (“cyprosulfamide”, S4-1),
[0372] R.sub.B.sup.1=cyclopropyl, R.sub.B.sup.2=hydrogen and (R.sub.B.sup.3)=5-C.sub.1-2-OMe (S4-2),
[0373] R.sub.B.sup.1=ethyl, R.sub.B.sup.2=hydrogen and (R.sub.B.sup.3)=2-OMe (S4-3),
[0374] R.sub.B.sup.1=isopropyl, R.sub.B.sup.2=hydrogen and (R.sub.B.sup.3)=5-C.sub.1-2-OMe (S4-4) and
[0375] R.sub.B.sup.1=isopropyl, R.sub.B.sup.2=hydrogen and (R.sub.B.sup.3)=2-OMe (S4-5);
[0376] S4c) Compounds from the class of the benzoylsulfamoylphenylureas of the formula (S4.sup.c), as described in EP-A-365484,
##STR00074##
in which
[0377] R.sub.c.sup.1, R.sub.c.sup.2 are independently hydrogen, (C.sub.3-C.sub.8)-alkyl, (C.sub.3-C.sub.8)-cycloalkyl, (C.sub.3-C.sub.6)-alkenyl, (C.sub.3-C.sub.6)-alkynyl,
[0378] R.sub.c.sup.3 is halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, CF.sub.3 and
[0379] mc is 1 or 2;
[0380] for example
[0381] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,
[0382] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
[0383] 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea;
[0384] S4.sup.d) Compounds of the N-phenylsulfonylterephthalamide type of the formula (S4.sup.d) and salts thereof, which are known, for example, from CN 101838227,
##STR00075##
in which
[0385] R.sub.D.sup.4 is halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, CF.sub.3;
[0386] m.sub.D is 1 or 2;
[0387] R.sub.D.sup.5 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.5-C.sub.6)-cycloalkenyl.
[0388] S5) Active ingredients from the class of the hydroxyaromatics and the aromatic-aliphatic carboxylic acid derivatives (S5), for example
[0389] ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
[0390] S6) Active ingredients from the class of the 1,2-dihydroquinoxalin-2-ones (S6), for example
[0391] 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
[0392] S7) Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), e.g. methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in WO-A-98/38856.
[0393] S8) Compounds of the formula (S8), as described in WO-A-98/27049,
##STR00076##
[0394] in which the symbols and indices are defined as follows:
[0395] R.sub.D.sup.1 is halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy,
[0396] R.sub.D.sup.2 is hydrogen or (C.sub.1-C.sub.4)-alkyl,
[0397] R.sub.D.sup.3 is hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-alkynyl or aryl, where each of the aforementioned carbon-containing radicals is unsubstituted or substituted by one or more, preferably up to three, identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof,
[0398] n.sub.D is an integer from 0 to 2.
[0399] S9) Active ingredients from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example
[0400] 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.: 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 95855-00-8), as described in WO-A-1999/000020.
[0401] S10) Compounds of the formulae (S10a) or (S10.sup.b) [0402] as described in WO-A-2007/023719 and WO-A-2007/023764
in which
##STR00077##
[0403] R.sub.E.sup.1 is halogen, (C.sub.1-C.sub.4)-alkyl, methoxy, nitro, cyano, CF.sub.3, OCF.sub.3,
[0404] Y.sub.E, Z.sub.E are independently O or S,
[0405] n.sub.E is an integer from 0 to 4,
[0406] R.sub.E.sup.2 is (C.sub.1-C.sub.16)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.3-C.sub.6)-cycloalkyl, aryl; benzyl, halobenzyl,
[0407] R.sub.E.sup.3 is hydrogen or (C.sub.1-C.sub.6)-alkyl.
[0408] S11) Active ingredients of the oxyimino compounds type (S11), which are known as seed-dressing agents, for example
[0409] “oxabetrinil” ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage,
[0410] “fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage, and
[0411] “cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage.
[0412] S12) Active ingredients from the class of the isothiochromanones (S12), for example methyl[(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (512-1) and related compounds from WO-A-1998/13361.
[0413] S13) One or more compounds from group (S13):
[0414] “naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed-dressing safener for corn against thiocarbamate herbicide damage,
[0415] “fenclorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as a safener for pretilachlor in sown rice,
[0416] “flurazole” (benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (513-3), which is known as a seed-dressing safener for millet/sorghum against alachlor and metolachlor damage,
[0417] “CL 304415” (CAS Reg. No. 31541-57-8)
[0418] (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (513-4) from American Cyanamid, which is known as a safener for corn against damage by imidazolinones,
[0419] “MG 191” (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (513-5) from Nitrokemia, which is known as a safener for corn,
[0420] “MG 838” (CAS Reg. No. 133993-74-5)
[0421] (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) from Nitrokemia
[0422] “disulfoton” (0,0-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7),
[0423] “dietholate” (0,0-diethyl 0-phenyl phosphorothioate) (S13-8),
[0424] “mephenate” (4-chlorophenyl methylcarbamate) (513-9).
[0425] S14) Active ingredients which, in addition to herbicidal action against harmful plants, also have safener action on crop plants such as rice, for example
[0426] “dimepiperate” or “MY-93” (S-1-methyl 1-phenylethylpiperidine-1-carbothioate), which is known as a safener for rice against damage by the herbicide molinate,
[0427] “daimuron” or “SK 23” (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as a safener for rice against damage by the herbicide imazosulfuron,
[0428] “cumyluron”=“JC-940” (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087270), which is known as a safener for rice against damage by some herbicides,
[0429] “methoxyphenone” or “NK 049” (3,3′-dimethyl-4-methoxybenzophenone), which is known as a safener for rice against damage by some herbicides,
[0430] “CSB” (1-bromo-4-(chloromethylsulfonyl)benzene) from Kumiai, (CAS Reg. No. 54091-06-4), which is known as a safener against damage by some herbicides in rice.
[0431] S15) Compounds of the formula (S15) or tautomers thereof
##STR00078##
as described in WO-A-2008/131861 and WO-A-2008/131860 [0432] in which
[0433] R.sub.H.sup.1 is a (C.sub.1-C.sub.6)-haloalkyl radical and
[0434] R.sub.H.sup.2 is hydrogen or halogen and
[0435] R.sub.H.sup.3, R.sub.H.sup.4 are independently hydrogen, (C.sub.1-C.sub.16)-alkyl, (C.sub.2-C.sub.16)-alkenyl or (C.sub.2-C.sub.16)-alkynyl,
[0436] where each of the 3 latter radicals is unsubstituted or substituted by one or more radicals from the group of halogen, hydroxyl, cyano, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-alkylamino, di[(C.sub.1-C.sub.4)-alkyl]amino, [(C.sub.1-C.sub.4)-alkoxy]carbonyl, [(C.sub.1-C.sub.4)-haloalkoxy]carbonyl, (C.sub.3-C.sub.6)-cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted,
[0437] or (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.4-C.sub.6)-cycloalkenyl, (C.sub.3-C.sub.6)-cycloalkyl fused on one side of the ring to a 4 to 6-membered saturated or unsaturated carbocyclic ring, or (C.sub.4-C.sub.6)-cycloalkenyl fused on one side of the ring to a 4 to 6-membered saturated or unsaturated carbocyclic ring,
[0438] where each of the 4 latter radicals is unsubstituted or substituted by one or more radicals from the group of halogen, hydroxyl, cyano, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-alkylamino, di[(C.sub.1-C.sub.4)-alkyl]amino, [(C.sub.1-C.sub.4)-alkoxy]carbonyl, [(C.sub.1-C.sub.4) -haloalkoxy]carbonyl, (C.sub.3-C.sub.6)-cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted,
or
[0439] R.sub.H.sup.3 is (C.sub.1-C.sub.4)-alkoxy, (C.sub.2-C.sub.4)-alkenyloxy, (C.sub.2-C.sub.6)-alkynyloxy or (C.sub.2-C.sub.4)-haloalkoxy and
[0440] R.sub.H.sup.4 is hydrogen or (C.sub.1-C.sub.4)-alkyl or
[0441] R.sub.H.sup.3 and R.sub.H.sup.4 together with the directly attached nitrogen atom represent a four- to eight-membered heterocyclic ring which, as well as the nitrogen atom, may also contain further ring heteroatoms, preferably up to two further ring heteroatoms from the group of N, O and S, and which is unsubstituted or substituted by one or more radicals from the group of halogen, cyano, nitro, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy and (C.sub.1-C.sub.4)-alkylthio.
[0442] S16) Active ingredients which are used primarily as herbicides but also have safener action on crop plants, for example
[0443] (2,4-dichlorophenoxy)acetic acid (2,4-D),
[0444] (4-chlorophenoxy)acetic acid,
[0445] (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
[0446] 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
[0447] (4-chloro-o-tolyloxy)acetic acid (MCPA),
[0448] 4-(4-chloro-o-tolyloxy)butyric acid,
[0449] 4-(4-chlorophenoxy)butyric acid,
[0450] 3,6-dichloro-2-methoxybenzoic acid (dicamba),
[0451] 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloro-ethyl).
[0452] Preferred safeners in combination with the compounds of the formula (I) according to the invention and/or salts thereof, in particular with the compounds of the formulae (I.1) to (1.182) and/or salts thereof, are: cloquintocet-mexyl, cyprosulfamide, fenchlorazole ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumyluron, S4-1 and S4-5, and particularly preferred safeners are: cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.
Biological Examples
[0453] 1. Pre-emergence herbicidal effect and crop plant compatibility
[0454] Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are laid out in sandy loam soil in wood-fibre pots and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil as aqueous suspension or emulsion at a water application rate equating to 600 to 800 L/ha with addition of 0.2% wetting agent.
[0455] After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the trial plants. The damage to the test plants is scored visually after a test period of 3 weeks by comparison with untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants).
[0456] Undesired Plants/Weeds:
TABLE-US-00010 ALOMY: Alopecurus myosuroides SETVI: Setaria viridis AMARE: Amaranthus retroflexus KCHSC: Bassia scoparia CYPES: Cyperus esculentus ECHCG: Echinochloa crus-galli LOLRI: Lolium rigidum STEME: Stellaria media VERPE: Veronica persica MATIN: Tripleurospermum inodorum POAAN: Poa annua ABUTH: Abutylon threophrasti DIGSA: Digitaria sanguinalis
[0457] 1. Pre-Emergence Effectiveness
[0458] As shown by the results from Tables 1.1 to 1.10, compounds of the invention have good herbicidal pre-emergence efficacy against a broad spectrum of weed grasses and broad-leaved weeds.
TABLE-US-00011 TABLE 1 Pre-emergence action against ALOMY Example Dosage ALOMY number [g/ha] [%] I-002 1280 90 I-005 1280 90 I-009 1280 90 II-001 1280 100 I-004 1280 90 I-006 1280 90 I-010 1280 100 I-001 1280 100 II-005 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 90 I-018 1280 90 I-016 1280 90 I-020 1280 90 I-019 1280 90 I-023 1280 90 I-024 1280 90 II-012 1280 90 II-016 1280 90 I-014 1280 100 VII-001 1280 90 VII-005 1280 90 II-017 1280 90 VII-011 1280 90 VII-007 1280 90 VII-006 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00012 TABLE 2 Pre-emergence action against DIGSA Example Dosage DIGSA number [g/ha] [%] I-002 1280 90 I-005 1280 100 V-001 1280 90 I-009 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 VI-001 1280 90 I-016 1280 100 I-020 1280 100 I-019 1280 100 I-023 1280 100 I-024 1280 100 II-016 1280 100 I-027 1280 100 I-014 1280 100 VII-001 1280 100
TABLE-US-00013 TABLE 3 Pre-emergence action against ECHCG Example Dosage ECHCG number [g/ha] [%] I-009 1280 90 II-001 1280 100 I-004 1280 90 I-006 1280 90 I-010 1280 100 III-002 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 90 I-018 1280 100 I-016 1280 100 I-019 1280 100 I-024 1280 90 II-012 1280 90 II-016 1280 100 I-014 1280 90 VII-002 1280 100 VII-003 1280 100 VII-005 1280 90 III-005 1280 90 II-017 1280 90 VII-007 1280 100 VII-006 1280 90 VI-002 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00014 TABLE 4 Pre-emergence action against LOLRI Example Dosage LOLRI number [g/ha] [%] I-002 1280 100 I-005 1280 100 IV-001 1280 90 I-009 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 90 I-010 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 90 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 I-016 1280 90 I-020 1280 100 I-024 1280 100 II-012 1280 100 II-016 1280 100 I-027 1280 90 I-014 1280 100 VII-001 1280 100 VII-003 1280 100 VII-005 1280 90 VII-010 1280 100 VII-009 1280 100
TABLE-US-00015 TABLE 5 Pre-emergence action against POAAN Example Dosage POAAN number [g/ha] [%] I-002 1280 100 I-005 1280 100 V-001 1280 90 IV-001 1280 90 I-009 1280 100 V-002 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 90 I-018 1280 100 VI-001 1280 100 I-016 1280 100 I-020 1280 100 I-019 1280 100 I-023 1280 100 I-024 1280 100 II-012 1280 100 II-015 1280 90 II-016 1280 100 I-027 1280 100 I-014 1280 100 VII-001 1280 100 VII-003 1280 100 VII-004 1280 100 VII-005 1280 100 III-005 1280 100 II-017 1280 100 VII-011 1280 100 VII-008 1280 90 VII-007 1280 100 VII-006 1280 100 VI-002 1280 100 VII-010 1280 100 VII-009 1280 100
TABLE-US-00016 TABLE 6 Pre-emergence action against SETVI Example Dosage SETVI number [g/ha] [%] I-002 1280 100 I-005 1280 100 I-009 1280 100 V-002 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 I-016 1280 100 I-020 1280 100 I-019 1280 100 I-023 1280 90 I-024 1280 100 II-012 1280 90 II-016 1280 100 I-027 1280 100 I-014 1280 100 VII-001 1280 100 VII-002 1280 100 VII-003 1280 100 VII-005 1280 90 III-005 1280 90 II-017 1280 90 VII-007 1280 100 VII-006 1280 90 VI-002 1280 90 VII-010 1280 100 VII-009 1280 100
TABLE-US-00017 TABLE 7 Pre-emergence action against ABUTH Example Dosage ABUTH number [g/ha] [%] II-005 1280 90 II-007 1280 90 II-011 1280 90 II-013 1280 90 I-019 1280 90 I-014 1280 100 VII-009 1280 90
TABLE-US-00018 TABLE 8 Pre-emergence action against AMARE Example Dosage AMARE number [g/ha] [%] I-001 1280 100 I-002 1280 100 I-004 1280 100 I-005 1280 100 I-006 1280 100 I-009 1280 100 I-010 1280 100 I-012 1280 100 I-013 1280 100 I-022 1280 90 II-001 1280 100 II-005 1280 100 II-007 1280 100 II-008 1280 100 II-011 1280 100 II-013 1280 100 III-002 1280 100 IV-001 1280 100 V-001 1280 100 V-002 1280 100
TABLE-US-00019 TABLE 9 Pre-emergence action against KCHSC Example Dosage KCHSC number [g/ha] [%] II-005 1280 90 II-007 1280 100 II-011 1280 100 I-013 1280 90 II-013 1280 90 I-015 1280 100 I-016 1280 100 I-019 1280 100 I-014 1280 90 VII-002 1280 90 VII-007 1280 90 VII-010 1280 90
TABLE-US-00020 TABLE 10 Pre-emergence action against MATIN Example Dosage MATIN number [g/ha] [%] I-002 1280 100 I-005 1280 100 V-001 1280 90 IV-001 1280 90 I-009 1280 100 V-002 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 100 I-001 1280 90 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 90 I-018 1280 100 VI-001 1280 90 I-016 1280 100 I-020 1280 100 I-019 1280 100 I-023 1280 100 I-024 1280 100 II-012 1280 100 II-015 1280 100 II-016 1280 100 I-027 1280 100 I-026 1280 100 I-014 1280 100 VII-001 1280 100 VII-003 1280 100 VII-005 1280 100 III-005 1280 90 II-017 1280 90 VII-011 1280 90 VII-007 1280 90 VII-006 1280 90 VI-002 1280 90 VII-010 1280 100 VII-009 1280 100
TABLE-US-00021 TABLE 11 Pre-emergence action against STEME Example Dosage STEME number [g/ha] [%] I-002 1280 100 I-005 1280 100 IV-001 1280 100 I-009 1280 100 II-001 1280 90 I-004 1280 100 I-006 1280 90 I-010 1280 100 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 VI-001 1280 90 I-016 1280 100 I-020 1280 100 I-019 1280 90 I-023 1280 100 I-024 1280 100 II-012 1280 100 II-015 1280 100 II-016 1280 100 I-027 1280 100 I-014 1280 100 VII-001 1280 100 VII-002 1280 100 VII-003 1280 100 VII-004 1280 100 VII-005 1280 100 III-005 1280 90 II-017 1280 90 VII-007 1280 90 VII-006 1280 90 VI-002 1280 90 VII-010 1280 90 VII-009 1280 100
TABLE-US-00022 TABLE 12 Pre-emergence action against VERPE Example Dosage VERPE number [g/ha] [%] I-002 1280 100 I-005 1280 100 IV-001 1280 90 I-009 1280 90 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 I-016 1280 100 I-020 1280 100 I-019 1280 100 I-023 1280 100 I-024 1280 100 II-012 1280 100 II-016 1280 90 I-027 1280 90 I-014 1280 100 VII-001 1280 100 VII-002 1280 90 VII-003 1280 100 VII-005 1280 100 III-005 1280 90 II-017 1280 100 VII-011 1280 90 VII-007 1280 90 VII-006 1280 90 VII-010 1280 100 VII-009 1280 100
[0459] For example, compound nos. 11-005, 11-007, II-011 and 11-013 in tables 1 to 12, at an application rate of 1280 g/ha, each show 90-100% efficacy against Alopecurus myrosoroides, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidu and Setaria viridis.
[0460] The compounds of the invention are therefore suitable for control of unwanted plant growth by the pre-emergence method.
[0461] 2. Post-emergence herbicidal effect and crop plant compatibility
[0462] Seeds of monocotyledonous and dicotyledonous weed and crop plants are laid out in sandy loam soil in wood-fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plants as aqueous suspension or emulsion at a water application rate equating to 600 to 800 l/ha with addition of 0.2% wetting agent. After the test plants have been left to stand in the greenhouse under optimal growth conditions for about 3 weeks, the action of the preparations is assessed visually in comparison to untreated controls (herbicidal action in percent (%): 100% activity=the plants have died, 0% activity=like control plants).
[0463] As shown by the results from Tables 13 to 24, compounds of the invention have good herbicidal post-emergence efficacy against a broad spectrum of weed grasses and broad-leaved weeds.
TABLE-US-00023 TABLE 13 Post-emergence action against ALOMY Example Dosage ALOMY number [g/ha] [%] I-002 1280 100 I-005 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 I-013 1280 100 I-015 1280 100 I-022 1280 100 VI-001 1280 90 I-016 1280 100 I-020 1280 100 I-019 1280 100 I-024 1280 100 II-012 1280 90 II-016 1280 100 I-027 1280 100 I-014 1280 100 VII-001 1280 100 VII-003 1280 100 VII-005 1280 100 II-017 1280 90 VII-011 1280 90 VII-007 1280 90 VII-006 1280 90 VI-002 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00024 TABLE 14 Post-emergence action against DIGSA Example Dosage DIGSA number [g/ha] [%] I-002 1280 100 I-005 1280 100 II-001 1280 100 I-006 1280 100 I-010 1280 90 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 I-013 1280 100 I-022 1280 90 I-018 1280 90 I-016 1280 90 I-020 1280 90 I-019 1280 100 I-024 1280 100 II-016 1280 100 I-027 1280 100 I-014 1280 100 VII-001 1280 100
TABLE-US-00025 TABLE 15 Post-emergence action against ECHCG Example Dosage ECHCG number [g/ha] [%] II-001 1280 100 I-010 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 90 I-016 1280 90 I-020 1280 90 I-024 1280 90 II-012 1280 90 II-016 1280 100 I-014 1280 90 VII-001 1280 100 VII-005 1280 90 III-005 1280 90 II-017 1280 90 VII-007 1280 90 VI-002 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00026 TABLE 16 Post-emergence action against LOLRI Example Dosage LOLRI number [g/ha] [%] II-005 1280 90 I-014 1280 90 VII-010 1280 90
TABLE-US-00027 TABLE 17 Post-emergence action against POAAN Example Dosage POAAN number [g/ha] [%] I-009 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 VI-001 1280 100 I-016 1280 90 I-020 1280 90 I-019 1280 100 I-024 1280 100 II-012 1280 100 II-015 1280 90 II-016 1280 100 I-027 1280 90 I-014 1280 100 VII-001 1280 100 VII-002 1280 100 VII-003 1280 100 VII-005 1280 100 II-017 1280 100 VII-007 1280 90 VII-006 1280 100 VII-010 1280 100 VII-009 1280 100
TABLE-US-00028 TABLE 18 Post-emergence action against SETVI Example Dosage SETVI number [g/ha] [%] I-002 1280 100 II-001 1280 90 I-001 1280 90 II-005 1280 100 I-012 1280 90 II-007 1280 90 II-011 1280 100 II-008 1280 90 II-013 1280 90 I-018 1280 100 I-020 1280 90 I-019 1280 90 I-024 1280 100 II-012 1280 90 I-014 1280 90 VII-001 1280 90 VII-002 1280 90 VII-005 1280 100 II-017 1280 90 VII-007 1280 90 VII-006 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00029 TABLE 19 Post-emergence action against ABUTH Example Dosage ABUTH number [g/ha] [%] I-002 1280 90 I-009 1280 90 II-001 1280 90 I-010 1280 90 I-001 1280 90 II-005 1280 90 II-007 1280 90 II-011 1280 90 II-008 1280 90 I-013 1280 90 II-013 1280 100 I-015 1280 90 I-022 1280 90 I-018 1280 90 VI-001 1280 90 I-019 1280 100 I-024 1280 90 II-015 1280 90 I-014 1280 90 VII-001 1280 90 VII-005 1280 100 III-005 1280 90 VII-008 1280 90 VII-007 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00030 TABLE 20 Post-emergence action against AMARE Example Dosage AMARE number [g/ha] [%] I-001 1280 90 I-002 1280 90 I-004 1280 90 I-005 1280 90 I-006 1280 100 I-009 1280 100 I-010 1280 90 I-012 1280 90 I-013 1280 100 II-001 1280 100 II-005 1280 90 II-007 1280 100 II-008 1280 90 II-011 1280 90 II-013 1280 90 IV-001 1280 90 V-001 1280 100 VI-001 1280 90
TABLE-US-00031 TABLE 21 Post-emergence action against KCHSC Example Dosage KCHSC number [g/ha] [%] I-009 1280 100 I-006 1280 90 I-010 1280 90 I-001 1280 90 II-005 1280 90 I-012 1280 90 II-011 1280 100 I-013 1280 90 II-013 1280 90 I-015 1280 90 I-022 1280 90 I-016 1280 90 I-020 1280 90 I-019 1280 100 I-024 1280 90 I-027 1280 90 I-014 1280 100 VII-001 1280 90 VII-005 1280 100 III-005 1280 90 VII-011 1280 90 VII-008 1280 90 VII-007 1280 90 VII-006 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00032 TABLE 22 Post-emergence action against MATIN Example Dosage MATIN number [g/ha] [%] I-002 1280 100 I-005 1280 100 I-009 1280 100 II-001 1280 100 I-004 1280 100 I-006 1280 100 I-010 1280 100 III-002 1280 90 I-001 1280 100 II-005 1280 100 I-012 1280 90 II-007 1280 100 II-011 1280 90 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-022 1280 100 I-018 1280 90 VI-001 1280 100 I-016 1280 90 I-020 1280 90 I-019 1280 100 I-024 1280 100 II-012 1280 90 II-015 1280 90 II-016 1280 100 I-014 1280 100 VII-001 1280 90 VII-002 1280 90 VII-003 1280 90 VII-005 1280 100 III-005 1280 90 II-017 1280 90 VII-007 1280 90 VII-006 1280 90 VI-002 1280 90 VII-010 1280 90 VII-009 1280 90
TABLE-US-00033 TABLE 23 Post-emergence action against STEME Example Dosage STEME number [g/ha] [%] I-002 1280 100 I-005 1280 100 I-009 1280 100 II-001 1280 90 I-004 1280 90 I-006 1280 100 I-010 1280 90 III-002 1280 90 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 100 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-022 1280 90 I-016 1280 90 I-020 1280 90 I-019 1280 90 II-016 1280 100 I-027 1280 90 I-014 1280 100 VII-001 1280 90 VII-002 1280 90 VII-003 1280 90 VII-005 1280 90 VII-007 1280 90 VII-009 1280 100
TABLE-US-00034 TABLE 24 Post-emergence action against VERPE Example Dosage VERPE number [g/ha] [%] I-002 1280 90 I-005 1280 90 V-001 1280 90 IV-001 1280 90 I-009 1280 90 II-001 1280 90 I-004 1280 90 I-006 1280 90 I-010 1280 90 III-002 1280 100 I-001 1280 100 II-005 1280 100 I-012 1280 100 II-007 1280 100 II-011 1280 90 II-008 1280 100 I-013 1280 100 II-013 1280 100 I-015 1280 100 I-022 1280 100 I-018 1280 100 VI-001 1280 90 I-016 1280 90 I-020 1280 90 I-019 1280 100 I-023 1280 90 I-024 1280 100 II-012 1280 90 II-015 1280 90 II-016 1280 100 I-027 1280 100 I-026 1280 90 I-014 1280 90 VII-001 1280 90 VII-002 1280 90 VII-003 1280 90 VII-005 1280 100 III-005 1280 90 II-017 1280 90 VII-011 1280 90 VII-008 1280 90 VII-007 1280 90 VII-006 1280 90 VI-002 1280 90 VII-010 1280 90 VII-009 1280 90
[0464] For example, all inventive compounds II-001, 11-005, 11-007 and 11-013 in tables 13 and 24, at an application rate of 1280 g/ha, each show 90-100% efficacy against Alopecurus myosuroides, Digitaria sanguinalis, Setaria viridis and Echinochloa crus-galli, and are therefore suitable for control of unwanted plant growth by the post-emergence method.