Patent Grant
8288316
1. Field of the Invention
The invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of broad-leaved weeds and grass weeds in crops of useful plants.
2. Description of Related Art
EP 0 173 657 A1 discloses herbicidal mixtures which contain certain N-(1,2,5-oxa-diazol-3-yl)benzamides. That document also describes the compound N-(4-methyl-furazan-3-yl)-2,4-dichlorophenylcarboxamide.
However, the herbicidal activity of the herbicidal mixtures and N-(1,2,5-oxadiazol-3-yl)benzamides which are known from that document is frequently not sufficient. It is therefore an object of the present invention to provide further herbicidally active compounds.
It has now been found that N-(1,2,5-oxadiazol-3-yl)benzamides whose phenyl ring is substituted in the 2-, 3- and 4-position by selected radicals are particularly well suited as herbicides.
A subject matter of the present invention are N-(1,2,5-oxadiazol-3-yl)benzamides of the formula (I) or their salts
in which
R is hydrogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, halo-(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy, (C2-C6)-alkenyl, (C2-C6)-alkenyloxy, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C2-C6)-alkynyloxy, (C2-C6)-haloalkynyl, cyano, nitro, methylsulfenyl, methylsulfinyl, methylsulfonyl, acetylamino, benzoylamino, methoxycarbonyl, ethoxy-carbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, benzoyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, halogen, amino, aminocarbonyl, methyl-aminocarbonyl, dimethylaminocarbonyl, methoxymethyl or heteroaryl, heterocyclyl or phenyl, each of which is substituted by s radicals selected from the group consisting of methyl, ethyl, methoxy, trifluoromethyl and halogen,
X and Z independently of one another are in each case nitro, halogen, cyano, formyl, rhodano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C3-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C3-C6)-halocycloalkyl-(C1-C6)-alkyl, COR1, OR1, OCOR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-COOR1, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, NR1R2, P(O)(OR5)2, or heteroaryl, heterocyclyl or phenyl, each of which is substituted by s radicals selected from the group consisting of methyl, ethyl, methoxy, nitro, trifluoromethyl and halogen,
Y is nitro, halogen, cyano, rhodano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C3-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C3-C6)-halocycloalkyl-(C1-C6)-alkyl, COR1, CO2R1, OR1, OCOR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-heteroaryl, O—(C1-C6)-alkyl-heterocyclyl, O—(C1-C6)-alkyl-heteroaryl, (C1-C6)-alkyl-heterocyclyl, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-COOR1, (C1-C6)-alkyl-CN, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, NR1R2, P(O)(OR5)2, tetrahydrofuranyloxymethyl, tetrahydrofuranylmethoxymethyl, O(CH2)-3,5-dimethyl-1,2-oxazol-4-yl, O(CH2)2—O(3,5-dimethoxypyrimidin-2-yl, O(CH2)-5-pyrrolidin-2-one, P(CH2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, or
heteroaryl or heterocyclyl, each of which is substituted by s radicals selected from the group consisting of methyl, ethyl, methoxy, halogen and cyanomethyl,
R1 is hydrogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-halo-cycloalkyl, (C1-C6)-alkyl-O—(C1-C6)-alkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl or phenyl-(C1-C6)-alkyl, where the 12 last-mentioned radicals are substituted by s radicals selected from the group consisting of cyano, halogen, nitro, rhodano, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, SCOR3, NR3COR3, CO2R3, COSR3, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl,
R2 is (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl or phenyl-(C1-C6)-alkyl, where the seven last-mentioned radicals are substituted by s radicals from the group consisting of cyano, halogen, nitro, thiocyanato, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, SCOR3, NR3COR3, CO2R3, COSR3, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl,
R3 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl,
R4 is (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl,
R5 is methyl or ethyl,
n is 0, 1 or 2,
s is 0, 1, 2 or 3.
In formula (I) and all the formulae below, alkyl radicals having more than two carbon atoms can be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Halogen is fluorine, chlorine, bromine or iodine.
Heterocyclyl is a saturated, partially saturated or fully unsaturated cyclic radical which contains from 3 to 6 ring atoms, of which 1 to 4 are from the group consisting of oxygen, nitrogen and sulfur, and which radical can additionally be fused by a benzo ring. For example, heterocyclyl is piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, 4,5-dihydro-1,2-oxazol-3-yl and oxetanyl.
Heteroaryl is an aromatic cyclic radical which contains 3 to 6 ring atoms, of which 1 to 4 are from the group consisting of oxygen, nitrogen and sulfur, and which radical can additionally be fused by a benzo ring. For example, heteroaryl is benzimidazol-2-yl, furanyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridinyl, benzisoxazolyl, thiazolyl, pyrrolyl, pyrazolyl, thiophenyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl, 1,2,4-triazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, 2H-1,2,3,4-tetrazolyl, 1H-1,2,3,4-tetrazolyl, 1,2,3,4-oxatriazolyl, 1,2,3,5-oxatriazolyl, 1,2,3,4-thiatriazolyl and 1,2,3,5-thiatriazolyl.
Where a group is substituted by a plurality of radicals, this means that this group is substituted by one or more identical or different representatives of the radicals mentioned.
Depending on the nature and the attachment of the substituents, the compounds of the formula (I) may be present as stereoisomers. If, for example, one or more asymmetric carbon atoms are present, there may be enantiomers and diastereomers. There may also be stereoisomers if n is 1 (sulfoxides). Stereoisomers may be obtained from the mixtures resulting from the preparation using customary separation methods, for example by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively by using stereoselective reactions employing optically active starting materials and/or auxiliaries. The invention also relates to all stereoisomers and mixtures thereof embraced by the general formula (I) but not specifically defined.
Preferred compounds of the general formula (I) are those in which
R is hydrogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, halo-(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy, cyano, nitro, methylsulfenyl, methylsulfinyl, methylsulfonyl, acetylamino, benzoylamino, methoxycarbonyl, ethoxycarbonyl, benzoyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, halogen, amino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxymethyl,
a heterocycle selected from the group consisting of pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, benzisoxazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-triazol-3-yl, 1-ethylbenzimidazol-2-yl, 4-methylthiazol-2-yl, thiophen-2-yl, furan-2-yl, furan-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, isoxazol-2-yl, isoxazol-3-yl, oxazol-2-yl, oxazol-3-yl, pyrrol-2-yl, pyrrol-3-yl, imidazol-2-yl, imidazol-5-yl, imidazol-4-yl, pyrazol-3-yl, pyrazol-5-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, 1,2,5-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,5-thiadiazol-3-yl, 2H-1,2,3,4-tetrazol-5-yl, 1H-1,2,3,4-tetrazol-1-yl, 1,2,3,4-oxatriazol-5-yl, 1,2,3,5-oxatriazol-4-yl, 1,2,3,4-thiatriazol-5-yl, 1,2,3,5-thiatriazol-4-yl, pyrazin-2-yl, pyrazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-3-yl and pyridazin-4-yl,
which heterocycle is substituted by s radicals selected from the group consisting of methyl, methoxy, trifluoromethyl and halogen, or
phenyl which is substituted by s radicals selected from the group consisting of methyl, methoxy, trifluoromethyl and halogen,
X and Z independently of each other are in each case nitro, halogen, cyano, rhodano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C3-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C3-C6)-halocycloalkyl-(C1-C6)-alkyl, COR1, OR1, OCOR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C5)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-COOR1, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, benzoxazol-2-yl, 1-ethylbenzimidazol-2-yl, piperidin-1-yl or 1,2,4-triazol-1-yl,
Y is nitro, halogen, cyano, rhodano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C3-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C3-C6)-halocycloalkyl-(C1-C6)-alkyl, COR1, OR1, COR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-COOR1, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, tetrahydrofuranyloxymethyl, tetrahydrofuranylmethoxymethyl, O(CH2)-3,5-dimethyl-1,2-oxazol-4-yl, O(CH2)2—O(3,5-dimethoxypyrimidin-2-yl, O(CH2)-5-pyrrolidin-2-one or O(CH2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one,
R1 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl or phenyl-(C1-C6)-alkyl, where the seven last-mentioned radicals are substituted by s radicals selected from the group consisting of cyano, halogen, nitro, thiocyanato, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, SCOR3, NR3COR3, CO2R3, COSR3, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl,
R2 is (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl or phenyl-(C1-C6)-alkyl, where the seven last-mentioned radicals are substituted by s radicals selected from the group consisting of cyano, halogen, nitro, thiocyanato, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, SCOR3, NR3COR3, CO2R3, COSR3, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl,
R3 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl,
R4 is (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl,
n is 0, 1 or 2,
s is 0, 1, 2 or 3.
Especially preferred compounds of the general formula (I) are those in which
R is hydrogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, halo-(C1-C6)-alkyl, (C1-C5)-alkoxy, halogen-(C1-C6)-alkoxy, cyano, nitro, methylsulfenyl, methylsulfinyl, methylsulfonyl, acetylamino, benzoylamino, methoxycarbonyl, ethoxycarbonyl, benzoyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, halogen, amino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxymethyl,
X and Z independently of one another are in each case nitro, halogen, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, OR1, S(O)nR2, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2 or 1,2,4-triazol-1-yl,
Y is nitro, halogen, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, OR1, S(O)nR2, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, tetrahydrofuranyloxymethyl, tetrahydrofuranylmethoxymethyl, O(CH2)-3,5-dimethyl-1,2-oxazol-4-yl, O(CH2)2—O(3,5-dimethoxypyrimidin-2-yl, O(CH2)-5-pyrrolidin-2-one or O(CH2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one,
R1 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl or phenyl-(C1-C6)-alkyl, where the seven last-mentioned radicals are substituted by s radicals selected from the group consisting of halogen and OR3,
R2 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, where the three last-mentioned radicals are substituted by s radicals selected from the group consisting of halogen and OR3,
R3 is hydrogen or (C1-C6)-alkyl,
n is 0, 1 or 2,
s is 0, 1, 2 or 3.
Especially preferred compounds of the general formula (I) are also those in which
R is hydrogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, halo-(C1-C6)-alkyl, (C1-C6)-alkoxy, halogen-(C1-C6)-alkoxy, cyano, nitro, methylsulfenyl, methylsulfinyl, methylsulfonyl, acetylamino, benzoylamino, methoxycarbonyl, ethoxycarbonyl, benzoyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, halogen, amino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxymethyl,
X and Z independently of one another are in each case nitro, halogen, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, OR1, S(O)nR2, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2 or 1,2,4-triazol-1-yl,
Y is S(O)nR2, 4,5-dihydro-1,2-oxazol-3-yl, 5-cyanomethyl-4,5-dihydro-1,2-oxazol-3-yl or 5-methoxymethyl-4,5-dihydro-1,2-oxazol-3-yl,
R1 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl or phenyl-(C1-C6)-alkyl, where the seven last-mentioned radicals are substituted by s radicals selected from the group consisting of halogen and OR3,
R2 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, where the three last-mentioned radicals are substituted by s radicals selected from the group consisting of halogen and OR3,
R3 is hydrogen or (C1-C6)-alkyl,
n is 0, 1 or 2,
s is 0, 1, 2 or 3.
In all of the formulae below, the substituents and symbols have the same definition as described under formula (I), unless otherwise defined.
Compounds according to the invention can be prepared for example by the method specified in scheme 1 by reacting, with base catalysis, a benzoyl chloride (II) with a 4-amino-1,2,5-oxadiazole (III):
The benzoyl chlorides of the formula (II), or the benzoic acids on which they are based, are known in principle and can be prepared for example according to the methods described in U.S. Pat. No. 6,376,429 B1, EP 1 585 742 A1 and EP 1 202 978 A1.
Compounds according to the invention can also be prepared by the method specified in scheme 2 by reacting a benzoic acid of the formula (IV) with a 4-amino-1,2,5-oxadiazole (III):
Dehydrating reagents which are conventionally used for amidation reactions, such as, for example, 1,1′-carbonyldiimidazole (CDI), dicyclohexylcarbodiimide (DCC), 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (T3P) and the like may be employed for the activation.
The 4-amino-1,2,5-oxadiazoles of the formula (III) are either commercially available or known or can be prepared analogously to methods known from the literature. For example, 3-alkyl-4-amino-1,2,5-oxadiazoles can be prepared from β-keto esters following the method described in Russian Chemical Bulletin, Int. Ed., Vol. 54, No. 4, p. 1032-1037 (2005):
In the abovementioned formula, R is, for example, an alkyl or phenyl radical. 3-Aryl-4-amino-1,2,5-oxadiazoles can be synthesized for example as described in Russian Chemical Bulletin, 54(4), 1057-1059, (2005) or Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 26B(7), 690-2, (1987):
3-Amino-4-halo-1,2,5-oxadiazoles can be prepared from 3,4-diamino-1,2,5-oxadiazole, which is commercially available, for example by the method described in Heteroatom Chemistry 15(3), 199-207 (2004):
Nucleophilic radicals R can be introduced by substitution of the leaving group L in 3-amino-1,2,5-oxadiazoles of the general formula V as described in Journal of Chemical Research, Synopses, (6), 190, 1985 or in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, (9), 2086-8, 1986 or in Russian Chemical Bulletin (Translation of lzvestiya Akademii Nauk, Seriya Khimicheskaya), 53(3), 596-614, 2004:
Collections of compounds of the formula (I) and/or salts thereof which can be synthesized by the aforementioned reactions can also be prepared in a parallel manner, it being possible for this to take place in a manual, partly automated or completely automated manner. In this connection, it is, for example, possible to automate the reaction procedure, the work-up or the purification of the products and/or intermediates. Overall, this is understood as meaning a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Gunther Jung), Verlag Wiley 1999, on pages 1 to 34.
For the parallel reaction procedure and work-up, it is possible to use a series of commercially available instruments, for example Calpyso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MuItiPROBE Automated Workstations from Perkin Elmer, Waltham, Mass. 02451, USA. For the parallel purification of compounds of the formula (I) and salts thereof or of intermediates produced during the preparation, there are available, inter alia, chromatography apparatuses, for example from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.
The apparatuses listed lead to a modular procedure in which the individual process steps are automated, but between the process steps manual operations have to be carried out. This can be circumvented by using partly or completely integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be acquired, for example, from Caliper, Hopkinton, Mass. 01748, USA.
The implementation of single or several synthesis steps can be supported through the use of polymer-supported reagents/scavenger resins. The specialist literature describes a series of experimental protocols, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).
Besides the methods described here, the preparation of compounds of the formula (I) and salts thereof can take place completely or partially by solid-phase supported methods. For this purpose, individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bonded to a synthesis resin. Solid-phase supported synthesis methods are sufficiently described in the specialist literature, e.g. Barry A. Bunin in “The Combinatorial Index”, Verlag Academic Press, 1998 and Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Günther Jung), Verlag Wiley, 1999. The use of solid-phase supported synthesis methods permits a series of protocols known in the literature, which again can be carried out manually or in an automated manner. The reactions can be carried out, for example, by means of IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, Calif. 92064, USA.
Both on a solid phase and in liquid phase can the procedure of individual or several synthesis steps be supported through the use of microwave technology. The specialist literature describes a series of experimental protocols, for example in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and A. Stadler), Verlag Wiley, 2005.
The preparation according to the process described here produces compounds of the formula (I) and their salts in the form of substance collections which are called libraries. The present invention also provides libraries which comprise at least two compounds of the formula (I) and their salts.
The compounds of the formula (I) according to the invention (and/or their salts), hereinbelow also referred to together as “compounds according to the invention”, have excellent herbicidal efficacy against a broad spectrum of economically important monocotyledonous and dicotyledonous annual harmful plants. The active compounds act efficiently even on perennial weeds which produce shoots from rhizomes, rootstocks and other perennial organs and which are difficult to control.
The present invention therefore also relates to a method for controlling unwanted plants or for regulating the growth of plants, preferably in crops of plants, where one or more compound(s) according to the invention is/are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), to the seed (for example grains, seeds or vegetative propagules such as tubers or shoot parts with buds) or to the area on which the plants grow (for example the area under cultivation). In this context, the compounds according to the invention can be applied for example pre-planting (if appropriate also by incorporation into the soil), pre-emergence or post-emergence. Specific examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the invention, without the enumeration being restricted to certain species.
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, lschaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Dicotyledonous weeds 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.
If the compounds according to the invention are applied to the soil surface before germination, the weed seedlings are either prevented completely from emerging or else the weeds grow until they have reached the cotyledon stage, but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
If the active compounds 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 of the point of 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.
Although the compounds according to the invention display an outstanding 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, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, in particular Zea and Triticum, are damaged only to an insignificant extent, or not at all, depending on the structure of the respective compound according to the invention and its application rate. This is why the present compounds are highly suitable for the selective control of unwanted plant growth in plant stands such as stands of agriculturally useful plants or ornamentals.
Moreover, the compounds according to the invention (depending on their respective structure and the application rate applied) have outstanding growth-regulatory properties in crop plants. They engage in the plants' metabolism in a regulatory fashion and can therefore be employed for the influencing, in a targeted manner, of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since for example lodging can be reduced, or prevented completely, hereby.
By virtue of their herbicidal and plant-growth-regulatory properties, the active compounds can also be employed for controlling harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis. In general, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or causative organisms 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. Thus, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition.
It is preferred, with respect to transgenic crops, to use the compounds according to the invention in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, sorghum/millet, rice and maize or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables. It is preferred to employ the compounds according to 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.
It is preferred to use the compounds according to the invention or their salts in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, sorghum/millet, rice, cassaya and maize or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables. It is preferred to employ the compounds according to 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.
Conventional methods of generating novel plants which have modified properties in comparison to plants occurring to date consist, for example, in traditional breeding methods and the generation of mutants. Alternatively, novel plants with altered properties can be generated with the aid of recombinant methods (see, for example, EP-A-0221044, EP-A-0131624). For example, the following have been described in several cases:
A large number of molecular-biology techniques which allow the generation of novel transgenic plants with modified properties are known in principle, see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, “Trends in Plant Science” 1 (1996) 423-431).
To carry out such recombinant manipulations, nucleic acid molecules which allow mutagenesis or sequence changes by recombination of DNA sequences can be introduced into plasmids. For example, base substitutions can be carried out, partial sequences can be removed, or natural or synthetic sequences may be added with the aid of standard methods. To link the DNA fragments to each other, adapters or linkers may be added to the fragments, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., or Winnacker “Gene and Klone”, VCH Weinheim, 2nd Edition 1996.
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 above-mentioned gene product. To this end, it is 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, it being necessary for these portions to be long enough to have an antisense effect in the cells. The use of DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them, is also possible.
When expressing nucleic acid molecules in plants, the protein synthesized can be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to link the coding region with DNA sequences which ensure localization in a particular compartment. A person skilled in the art is familiar with such sequences (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850, Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acid molecules may also be expressed in the organelles of the plant cells.
The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants can be plants of any desired plant species, i.e. not only monocotyledonous, but also dicotyledonous, plants.
Thus, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or the expression of heterologous (=foreign) genes or gene sequences.
It is preferred to employ the compounds according to the invention 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, glyphosate, glufosinate or benzoylisoxazoles and analogous active compounds.
When the active compounds according to the invention are used in transgenic crops, effects are frequently observed—in addition to the effects on harmful plants which can be observed in other crops—which are specific for the application in the transgenic crop in question, for example a modified or specifically widened spectrum of weeds which can be controlled, modified application rates which may be employed for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.
The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dustable powders or granules in the customary formulations. The invention therefore also provides herbicidal and plant growth-regulating compositions which comprise the compounds according to the invention.
The compounds according to the invention 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), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dustable powders (DP), seed-dressing products, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
These individual types of formulations are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973, K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries required, such as inert materials, surfactants, solvents and further additives, are likewise known 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, Schonfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.
Based on these formulations, it is also possible to produce combinations with other pesticidally active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a readymix or as a tank mix. Suitable safeners are, for example, mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and dichlormid.
Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, 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, alkane-sulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthyl-methane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurinate. To prepare the wettable powders, the herbicidally active compounds are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation assistants.
Emulsifiable concentrates are prepared by dissolving the active compound 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 surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: calcium alkylarylsulfonate salts such as 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.
Dustable powders are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants, as have, for example, already been listed above for the other formulation types.
Granules can be prepared either by spraying the active compound onto adsorptive granular inert material or by applying active compound 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 mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules—if desired as a mixture with fertilizers.
Water-dispersible granules are prepared 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.
To prepare plate granules, fluidized-bed granules, extruder granules and spray granules, see, for example, methods 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.
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.
The agrochemical formulations contain generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention. In wettable powders, the active compound concentration is, for example, from about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation components. In the case of emulsifiable concentrates, the active compound concentration can be from about 1 to 90, preferably from 5 to 80, % by weight. Formulations in the form of dusts comprise from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In the case of water-dispersible granules, the active compound content depends partially on whether the active compound is present in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used. In the water-dispersible granules, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
In addition, the active compound formulations mentioned optionally comprise the respective customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.
Based on these formulations, it is also possible to produce combinations with other pesticidally active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a readymix or as a tank mix.
Active compounds which can be employed in combination with the compounds according to the invention in mixed formulations or in the tank mix are, for example, known active compounds which are based on the 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 are described in, for example, Weed Research 26 (1986) 441-445 or “The Pesticide Manual”, 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and the literature cited therein. Known herbicides or plant growth regulators which can be combined with the compounds according to the invention are, for example, the following active compounds (the compounds are either designated by the common name according to the International Organization for Standardization (ISO) or by the chemical name, or by the code number) and always comprise all use forms such as acids, salts, esters and isomers such as stereoisomers and optical isomers. By way of example, one and in some cases a plurality of use forms are mentioned here:
acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminopyralid, amitrole, ammonium sulfamate, ancymidol, anilofos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron-methyl, bentazone, benzfendizone, benzobicyclon, benzofenap, benzofluor, benzoylprop, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromuron, buminafos, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorazifop, chlorazifop-butyl, chlorbromuron, chlorbufam, chlorfenac, chlorfenac-sodium, chlorfenprop, chiorfiurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlormequat-chloride, chlornitrofen, chlorophthalim, chlorthal-dimethyl, chlorotoluron, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop, clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cyclanilide, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine, cyprazole, 2,4-D, 2,4-DB, daimuron/dymron, dalapon, daminozide, dazomet, n-decanol, desmedipham, desmetryn, detosyl-pyrazolate (DTP), di-allate, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethatyl, diethatyl-ethyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dikegulac-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, EPIC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethephon, ethidimuron, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-5331, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]-ethanesulfonamide, fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet (thiafluamide), flufenpyr, flufenpyr-ethyl, flumetralin, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam, flupropacil, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone, fluorochloridone, fluoroxypyr, fluoroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfuron, forchlorfenuron, fosamine, furyloxyfen, gibberellic acid, glufosinate, L-glufosinate, L-glufosinate-ammonium, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, H-9201, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HNPC-9908, HOK-201, HW-02, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, inabenfide, indanofan, indole acetic acid (IAA), 4-indol-3-ylbutyric acid (IBA), iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, isocarbamid, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, IDH-100, KUH-043, KUH-071, karbutilate, ketospiradox, lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet, mefluidide, mepiquat-chloride, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, methazole, methoxyphenone, methyldymron, 1-methylcyclopropen, methyl isothiocyanate, metobenzuron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monocarbamide, monocarbamide dihydrogensulfate, monolinuron, monosulfuron, monuron, MT 128, MT-5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide, NGGC-011, naproanilide, napropamide, naptalam, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrophenolat-sodium (isomer mixture), nitrofluorfen, nonanoic acid, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paclobutrazol, paraquat, paraquat dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden, piperophos, pirifenop, pirifenop-butyl, pretilachlor, primisulfuron, primisulfuron-methyl, probenazole, profluazol, procyazine, prodiamine, prifluraline, profoxydim, prohexadione, prohexadione-calcium, prohydrojasmone, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyzamide, prosulfalin, prosulfocarb, prosulfuron, prynachlor, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalide, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, secbumeton, sethoxydim, siduron, simazine, simetryn, SN-106279, sulcotrione, sulf-allate (CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, TH-547, thenylchlor, thiafluamide, thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, topramezone, tralkoxydim, tri-allate, triasulfuron, triaziflam, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon, trinexapac, trinexapac-ethyl, tritosulfuron, tsitodef, uniconazole, uniconazole-P, vernolate, ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862 and the following compounds
For application, the formulations present in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Preparations in the form of dusts, granules for soil application or granules for broadcasting and sprayable solutions are usually not diluted further with other inert substances prior to application.
The required application rate of the compounds of the formula (I) varies according to the external conditions such as, inter glia, temperature, humidity and the type of herbicide used. It may vary within wide limits, for example between 0.001 and 1.0 kg/ha or more of active substance; however, preferably it is between 0.005 and 750 g/ha.
The examples which follow illustrate the invention.
495 mg (2.02 mmol) of 2-nitro-4-methylsulfonylbenzoic acid and 200 mg (2.02 mmol) of 4-methyl-1,2,5-oxadiazol-3-ylamine are dissolved at room temperature (RT) in 5 ml of CH2Cl2 and treated with 0.28 ml (2.02 mmol) of triethylamine, 49 mg (0.40 mmol) of 4-dimethylaminopyridine (DMAP) and 1.93 g (3.03 mmol) of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (50% solution in THF). The reaction mixture is stirred for 30 h at RT and subsequently washed twice with in each case 5 ml of water. The organic phase is dried over Na2SO4 and evaporated. The residue is purified by column chromatography (silica gel, heptane/ethyl acetate). Yield 350 mg (53%).
200 mg (0.58 mmol) of 2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)-methyl]benzoic acid and 66 mg (0.58 mmol) of 4-methoxy-1,2,5-oxadiazole-3-amine are dissolved in 10 ml of CH2Cl2 at RT and treated with 0.08 ml (0.6 mmol) of triethylamine, 14 mg (0.12 mmol) of DMAP and 511 mg (0.87 mmol) of 2,4,6-tri-propyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (50% solution in THF). The reaction mixture is stirred for 20 h at RT and subsequently washed twice with in each case 5 ml of water. The organic phase is dried over Na2SO4 and evaporated. The residue is purified by column chromatography (silica gel, heptane/ethyl acetate). Yield 90 mg (33%).
Synthesis of 2-chloro-3-[5-(cyanomethyl)-4,5-dihydro-1,2-oxazol-3-yl]-N-(4-cyano-1,2,5-oxadiazol-3-yl)-4-(ethylsulfonyl)benzamide (example No. 8-120 in the table) 200 mg (0.56 mmol) of 2-chloro-3-[5-(cyanomethyl)-4,5-dihydro-1,2-oxazol-3-yl]-4-(ethylsulfonyl)benzoic acid and 62 mg (0.58 mmol) of 4-methoxy-1,2,5-oxadiazol-3-amine are dissolved in 24 ml of CH2Cl2 at RT and treated with 0.08 ml (0.6 mmol) of triethylamine, 14 mg (0.12 mmol) of DMAP and 535 mg (0.84 mmol) of 2,4,6-tri-propyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (50% solution in THF). The reaction mixture is stirred for 20 h at RT and subsequently washed twice with in each case 10 ml of water. The organic phase is dried over Na2SO4 and evaporated. The residue is purified by column chromatography (silica gel, heptane/ethyl acetate). Yield 120 mg (45%).
Synthesis of N-(4-benzoyl-1,2,5-oxadiazol-3-yl)-2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzamide (example No. 11-5 in the tables) 204 mg (0.59 mmol) of 2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]-benzoic acid and 111 mg (0.59 mmol) of (4-amino-1,2,5-oxadiazol-3-yl)(phenyl)-methanone are dissolved in 10 ml of dichloromethane at RT and treated with 59 mg (0.599 mmol) of triethylamine, 14 mg (0.19 mmol) of DMAP and 561 mg (0.882 mmol) of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (50% solution in THF). The reaction mixture is stirred for 30 h at RT and subsequently washed twice with in each case 5 ml of water. The organic phase is dried over Na2SO4 and evaporated. The residue is purified by column chromatography (silica gel, heptane/ethyl acetate). Yield 50 mg (15%).
200 mg (0.85 mmol) of 2-chloro-4-(methylsulfonyl)benzoic acid and 167 mg (0.85 mmol) of 4-(4-chlorophenyl)-1,2,5-oxadiazol-3-ylamine are dissolved in 24 ml of CH2Cl2 at RT and treated with 0.12 ml (0.85 mmol) of triethylamine, 21 mg (0.17 mmol) of DMAP and 1814 mg (1.28 mmol) of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (50% solution in THF). The reaction mixture is stirred for 30 h at RT and subsequently washed twice with in each case 5 ml of water. The organic phase is dried over Na2SO4 and evaporated. The residue is purified by column chromatography (silica gel, heptane/ethyl acetate). Yield 140 mg (36%).
173 mg (0.5 mmol) of 2-chloro-4-(methylsulfonyl)benzoic acid and 191 mg (0.505 mmol) of N-(4-amino-1,2,5-oxadiazol-3-yl)acetamide are dissolved in 5 ml of dichloroethane at RT and treated with 0.071 ml (0.5 mmol) of triethylamine, 31 mg (0.25 mmol) of DMAP and 483 mg (0.76 mmol) of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (50% solution in THF). The reaction mixture is stirred for 24 h at RT and subsequently filtered through a glass frit. The residue is washed twice using in each case 1 ml of CH2Cl2. The filtrate is passed over a silica-gel-filled SPE cartridge and eluted twice using in each case 5 ml of a mixture of ethyl acetate/methyl tert-butyl ester (1:1). The organic phase is dried over Na2SO4 and evaporated. The residue is purified by preparative HPLC using acetonitrile/water. Yield 16 mg (9%).
The examples mentioned in the tables hereinbelow were prepared analogously to the abovementioned methods or can be obtained analogously to the abovementioned methods. The compounds listed in the tables hereinbelow are very specially preferred.
The abbreviations used are:
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H-NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz 9.79 (bs, 1H),
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, MeOD, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CD3OD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H-NMR, CDCl3, 400 MHz
1H NMR, MeOD, 400 MHz
1H NMR, MeOD, 400 MHz
1H NMR, MeOD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, MeOD, 400 MHz
1H NMR, MeOD, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 600 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 600 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H-NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H-NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, CDCl3, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1H NMR, DMSO-d6, 400 MHz
1. Pre-Emergence Herbicidal Action Against Harmful Plants
Seeds of monocotyledonous or dicotyledonous weed plants or crop plants are placed in wood-fiber pots in sandy loam and covered with soil. The compounds according to the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied as aqueous suspension or emulsion at a water application rate of 600 to 800 l/ha (converted) with the addition of 0.2% of wetting agent to the surface of the covering soil. After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. The visual assessment of the damage to the test plants is carried out after a trial period of 3 weeks by comparison with untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants). Here, for example compounds No. 1-119, 1-53, 1-148, 1-54, 1-12, 1-71, 2-56, 9-180 and 9-174 have in each case an activity of at least 80% against Echinochloa crus-galli and Veronica persica at an application rate of 80 g/ha. Compounds No. 1-51, 1-123, 1-148, 1-149, 1-54, 2-119 and 2-71 have in each case an activity of at least 80% against Abutilon theophrasti and Amaranthus retroflexus at an application rate of 80 g/ha. Compounds No. 6-120, 3-120 and 6-3 have an activity of at least 80% against Matricaria inodora and Veronica persica at an application rate of 80 g/ha.
2. Post-Emergence Herbicidal Action Against Harmful Plants
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood-fiber 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 according to the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed as aqueous suspension or emulsion at a water application rate of 600 to 800 l/ha (converted) with the addition of 0.2% of wetting agent onto the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations is rated visually in comparison to untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants). Here, for example compounds No. 1-119, 1-51, 1-53, 1-123, 1-148, 1-54, 2-119, 1-127, 9-180, 9-174, 3-119, 6-120, 4-120, 3-120 and 9-200 have an activity of at least 80% against Amaranthus retroflexus and Viola tricolor at an application rate of 80 g/ha. Compounds No. 1-147, 1-71, 2-71 and 6-3 have an activity of in each case at least 80% against Abutilon theophrasti and Veronica persica at an application rate of 80 g/ha.
| Number | Date | Country | Kind |
|---|---|---|---|
| 09012169 | Sep 2009 | EP | regional |
This application claims priority to European patent application 09012169.0 filed Sep. 25, 2009 and U.S. application 61/246,295 filed Sep. 28, 2009, the entire contents of which are incorporated by reference in their entireties.
| Number | Date | Country |
|---|---|---|
| 0173657 | Mar 1986 | EP |
| 0173657 | Dec 1989 | EP |
| 2006122150 | Nov 2006 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20110152084 A1 | Jun 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61246295 | Sep 2009 | US |
