# Patent

## Title
Substituted 1,2,5-oxadiazole compounds and their use as herbicides II

## Abstract

The present invention relates to substituted 1,2,5-oxadiazole compounds of the formula (I) and the N-oxides and salts thereof and to compositions comprising the same. The invention also relates to the use of the 1,2,5-oxadiazole compounds or of the compositions comprising such compounds for controlling unwanted vegetation. Furthermore, the invention relates to methods of applying such compounds.

## Background
This application is a National Stage application of International Application No. PCT/EP2012/072692, filed Nov. 15, 2012, which claims the benefit of U.S. Provisional Application No. 61/560,333, filed Nov. 16, 2011, the entire contents of which are hereby incorporated herein by reference.


The present invention relates to substituted 1,2,5-oxadiazole compounds and the N-oxides and salts thereof and to compositions comprising the same. The invention also relates to the use of the 1,2,5-oxadiazole compounds or of the compositions comprising such compounds for controlling unwanted vegetation. Furthermore, the invention relates to methods of applying such compounds.
For the purposes of controlling unwanted vegetation, especially in crops, there is an ongoing need for new herbicides which have high activities and selectivities together with a substantial lack of toxicity for humans and animals.
EP 0 173 657 A1 describes N-(1,2,5-oxadiazol-3-yl) carboxamides, herbicidal compositions comprising them and the use of such compositions for controlling the growth of weeds.
WO 2011/035874 describes N-(1,2,5-oxadiazol-3-yl)benzamides carrying 3 substituents in the 2-, 3- and 4-positions of the phenyl ring and their use as herbicides.
The N-(1,2,5-oxadiazol-3-yl) carboxamides of the prior art often suffer form insufficient herbicidal activity in particular at low application rates and/or unsatisfactory selectivity resulting in a low compatibility with crop plants.
Accordingly, it is an object of the present invention to provide further 1,2,5-oxadiazole compounds having a strong herbicidal activity, in particular even at low application rates, a sufficiently low toxicity for humans and animals and/or a high compatibility with crop plants. The 1,2,5-oxadiazole compounds should also show a broad activity spectrum against a large number of different unwanted plants.
These and further objectives are achieved by the compounds of formula I defined below and their N-oxides and also their agriculturally suitable salts.
It has been found that the above objectives can be achieved by substituted 1,2,5-oxadiazole compounds of the general formula I, as defined below, including their N-oxides and their salts, in particular their agriculturally suitable salts.
Therefore, in a first aspect the present invention relates to compounds of formula I,




wherein
R is selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, O—Ra, Z—S(O)n—Rb, Z—C(═O)—Rc, Z—C(═O)—ORd, Z—C(═O)—NReRf, Z—NRgRh, Z-phenyl and Z-heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R′, which are identical or different;
CYC indicates a bi- or tricyclic radical of the following formulae Cyc-1 or Cyc-2




where
# indicates the point of attachment of the bicyclic radical to the carbonyl group,
Q, Q′ independently of each other indicate a fused 5-, 6-, 7-, 8-, 9- or 10-membered carbocycle or a fused 5-, 6-, 7-, 8-, 9- or 10-membered heterocycle, where the fused heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members, where the fused carbocycle and the fused heterocycle are monocyclic or bicyclic and where the fused carbocycle and the fused heterocycle are unsubstituted or carry 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 radicals R2;
R1 in formula Cyc-1 is selected from the group consisting of Z1-cyano, halogen, nitro, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, Z1—C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylthio-C1-C4-alkyl, Z1—C1-C4-alkylthio-C1-C4-alkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkyl, Z1—C1-C4-haloalkoxy-C1-C4-alkoxy, Z1—S(O)k—R1b, Z1-phenoxy and Z1-heterocyclyloxy, where heterocyclyloxy is an oxygen bound 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1, 2, 3 or 4 groups R11, which are identical or different;
R2 is selected from the group consisting of halogen, Z2—OH, Z2—NO2, Z2-cyano, oxo (═O), ═N—R22, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Z2—C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, Z2—C1-C4-haloalkoxy, Z2—C3-C10-cycloalkyl, O—Z2—C3-C10-cycloalkyl, Z2-(tri-C1-C4-alkyl)silyl, Z2—S(O)k—R2b, Z2—C(═O)—R2c, Z2—NR2gR2h and Z2-phenyl, where phenyl in Z2-phenyl is unsubstituted or substituted by 1, 2, 3 or 4 groups R21, which are identical or different;
R3 in formula Cyc-2 is selected from the group consisting of hydrogen, halogen, Z3—OH, Z3—NO2, Z3-cyano, C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, Z3—C3-C10-cycloalkyl, Z3—C3-C10-cycloalkoxy, where the C3-C10-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C8-haloalkyl, Z3—C1-C8-alkoxy, Z3—C1-C8-haloalkoxy, Z3—C1-C4-alkoxy-C1-C4-alkoxy, Z3—C1-C4-alkylthio-C1-C4-alkylthio, Z3—C2-C8-alkenyloxy, Z3—C2-C8-alkynyloxy, Z3—C1-C8-haloalkoxy, Z3—C1-C4-haloalkoxy-C1-C4-alkoxy, Z3-(tri-C1-C4-alkyl)silyl, Z3—S(O)k—R3b, Z3—C(═O)—R3c, Z3—C(═O)—OR3d, Z3—C(═O)—NR3eR3f, Z3—NR3gR3h, Z3a-phenyl and Z3a-heterocyclyl, where heterocyclyl is a 3-, 4-, 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in Z3a-phenyl and Z3a-heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R31, which are identical or different;
R4 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C4-alkyl and C1-C4-haloalkyl;
R5 is selected from the group consisting of hydrogen, halogen, C1-C4-alkyl and C1-C4-haloalkyl;
n is 0, 1 or 2;
k is 0, 1 or 2;
R′, R11, R21, R31 independently of each other are selected from the group consisting of halogen, NO2, CN, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C7-cycloalkoxy and C1-C6-haloalkyloxy;
R22 is selected from the group consisting of C1-C4-alkoxy, C1-C4-haloalkoxy and C3-C7-cycloalkoxy, which is unsubstituted or partially or completely halogenated;
Z, Z1, Z2, Z3 independently of each other are selected from the group consisting of a covalent bond and C1-C4-alkanediyl;
Z3a is selected from the group consisting of a covalent bond, C1-C4-alkanediyl, O—C1-C4-alkanediyl, C1-C4-alkanediyl-O and C1-C4-alkanediyl-O—C1-C4-alkanediyl;
Ra is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rb, R1b, R2b, R3b independently of each other are selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and phenyl, where phenyl is unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rc, R2c, R3c independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rd, R3d independently of each other are selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Re, Rf independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, or
Re, Rf together with the nitrogen atom, to which they are bound may form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
R3e, R3f independently of each other have the meanings given for Re, Rf;
Rg is from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rh is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, a radical C(═O)—Rk, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, or
Rg, Rh together with the nitrogen atom, to which they are bound may form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of ═O, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
R2g, R2h independently of each other have the meanings given for Rg, Rh;
R3g, R3h independently of each other have the meanings given for Rg, Rh;
Rk has the meanings given for Rc;
or an N-oxide or an agriculturally suitable salt thereof.
The compounds of the present invention, i.e. the compounds of formula I, their N-oxides, or their salts are particularly useful for controlling unwanted vegetation. Therefore, the invention also relates to the use of a compound of the present invention, an N-oxide or a salt thereof for combating or controlling unwanted vegetation.
The invention also relates to a composition comprising at least one compound according to the invention, including an N-oxide or a salt thereof, and at least one auxiliary. In particular, the invention relates to an agricultural composition comprising at least one compound according to the invention including an N-oxide or an agriculturally suitable salt thereof, and at least one auxiliary customary for crop protection formulations.
The present invention also relates to the use of a composition comprising at least one compound of the invention, an N-oxide or an agriculturally suitable salt thereof, for combating or controlling unwanted vegetation.
The present invention also relates to a method for combating or controlling unwanted vegetation, which method comprises allowing a herbicidally effective amount of at least one compound according to the invention, including an N-oxide or a salt thereof, to act on unwanted plants, their seed and/or their habitat.
Depending on the substitution pattern, the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or pure diastereomers of the compounds of formula I, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula I or its mixtures. Suitable compounds of the formula I also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group. The term “stereoisomer(s)” encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
Depending on the substitution pattern, the compounds of the formula I may be present in the form of their tautomers. Hence the invention also relates to the tautomers of the formula I and the stereoisomers, salts and N-oxides of said tautomers.
The term “N-oxide” includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides in compounds I can in particular be prepared by oxidizing the ring nitrogen atom(s) of the oxadiazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides, or the ring nitrogen atom(s) of a heterocyclic substituent R, R1, R2 or R3.
The present invention moreover relates to compounds as defined herein, wherein one or more of the atoms depicted in formula I have been replaced by its stable, preferably non-radioactive isotope (e.g., hydrogen by deuterium, 12C by 13C, 14N by 15N, 16O by 18O) and in particular wherein at least one hydrogen atom has been replaced by a deuterium atom. Of course, the compounds according to the invention contain more of the respective isotope than this naturally occurs and thus is anyway present in the compounds I.
The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of formula I, their enantiomers or diastereomers, mixtures of different crystalline states of the respective compound of formula I, its enantiomers or diastereomers, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the present invention are preferably agriculturally suitable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
Useful agriculturally suitable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the herbicidal action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4+) and substituted ammonium in which one to four of the hydrogen atoms are replaced by C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of the present invention with an acid of the corresponding anion, preferably with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The term “undesired vegetation” is understood to include any vegetation growing at a crop plant site or locus of seeded and otherwise desired crop, where the vegetation is any plant species, including their germinant seeds, emerging seedlings and established vegetation, other than the seeded or desired crop.
The organic moieties mentioned in the above definitions of the variables are—like the term halogen—collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term “halogen” denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
The term “partially or completely halogenated” will be taken to mean that 1 or more, e.g. 1, 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine. A partially or completely halogenated radical is termed below also “halo-radical”. For example, partially or completely halogenated alkyl is also termed haloalkyl.
The term “alkyl” as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of C1-C4-alkyl are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl(sec-butyl), isobutyl and tert-butyl. Examples for C1-C6-alkyl are, apart those mentioned for C1-C4-alkyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. Examples for C1-C10-alkyl are, apart those mentioned for C1-C6-alkyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.
The term “alkylene” (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
The term “haloalkyl” as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 8 carbon atoms (“C1-C8-haloalkyl”), frequently from 1 to 6 carbon atoms (“C1-C6-haloalkyl”), more frequently 1 to 4 carbon atoms (“C1-C4-haloalkyl”), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from C1-C4-haloalkyl, more preferably from C1-C2-haloalkyl, more preferably from halomethyl, in particular from C1-C2-fluoroalkyl. Halomethyl is methyl in which 1, 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like. Examples for C1-C2-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. Examples for C1-C2-haloalkyl are, apart those mentioned for C1-C2-fluoroalkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 2-chloroethyl, 2,2,-dichloroethyl, 2,2,2-trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 1-bromoethyl, and the like. Examples for C1-C4-haloalkyl are, apart those mentioned for C1-C2-haloalkyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1,1,1-trifluoroprop-2-yl, 3-chloropropyl, 4-chlorobutyl and the like.
The term “cycloalkyl” as used herein (and in the cycloalkyl moieties of other groups comprising a cycloalkyl group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms (“C3-C10-cycloalkyl”), preferably 3 to 7 carbon atoms (“C3-C7-cycloalkyl”) or in particular 3 to 6 carbon atoms (“C3-C6-cycloalkyl”). Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals having 3 to 7 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Examples of bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
The term “halocycloalkyl” as used herein (and in the halocycloalkyl moieties of other groups comprising an halocycloalkyl group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms, preferably 3 to 7 carbon atoms or in particular 3 to 6 carbon atoms, wherein at least one, e.g. 1, 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine. Examples are 1- and 2-fluorocyclopropyl, 1,2-, 2,2- and 2,3-difluorocyclopropyl, 1,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1- and 2-chlorocyclopropyl, 1,2-, 2,2- and 2,3-dichlorocyclopropyl, 1,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1-, 2- and 3-fluorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1-, 2- and 3-chlorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlorocyclopentyl and the like.
The term “cycloalkyl-alkyl” used herein denotes a cycloalkyl group, as defined above, which is bound to the remainder of the molecule via an alkylene group. The term “C3-C7-cycloalkyl-C1-C4-alkyl” refers to a C3-C7-cycloalkyl group as defined above which is bound to the remainder of the molecule via a C1-C4-alkyl group, as defined above. Examples are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, and the like.
The term “alkenyl” as used herein denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 8 (“C2-C8-alkenyl”), preferably 2 to 6 carbon atoms (“C2-C6-alkenyl”), in particular 2 to 4 carbon atoms (“C2-C4-alkenyl”), and a double bond in any position, for example C2-C4-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl or 2-methyl-2-propenyl; C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl and the like, or C2-C8-alkenyl, such as the radicals mentioned for C2-C6-alkenyl and additionally 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl and the positional isomers thereof.
The term “haloalkenyl” as used herein, which may also be expressed as “alkenyl which may be substituted by halogen”, and the haloalkenyl moieties in haloalkenyloxy and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 8 (“C2-C8-haloalkenyl”) or 2 to 6 (“C2-C6-haloalkenyl”) or 2 to 4 (“C2-C4-haloalkenyl”) carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
The term “alkynyl” as used herein denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 8 (“C2-C8-alkynyl”), frequently 2 to 6 (“C2-C6-alkynyl”), preferably 2 to 4 carbon atoms (“C2-C4-alkynyl”) and one or two triple bonds in any position, for example C2-C4-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl and the like, C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and the like.
The term “haloalkynyl” as used herein, which is also expressed as “alkynyl which may be substituted by halogen”, refers to unsaturated straight-chain or branched hydrocarbon radicals having usually 3 to 8 carbon atoms (“C2-C8-haloalkynyl”), frequently 2 to 6 (“C2-C6-haloalkynyl”), preferably 2 to 4 carbon atoms (“C2-C4-haloalkynyl”), and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
The term “alkoxy” as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 8 carbon atoms (“C1-C8-alkoxy”), frequently from 1 to 6 carbon atoms (“C1-C6-alkoxy”), preferably 1 to 4 carbon atoms (“C1-C4-alkoxy”), which is bound to the remainder of the molecule via an oxygen atom. C1-C2-Alkoxy is methoxy or ethoxy. C1-C4-Alkoxy is additionally, for example, n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1,1-dimethylethoxy (tert-butoxy). C1-C6-Alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy. C1-C8-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof.
The term “haloalkoxy” as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 8 carbon atoms (“C1-C8-haloalkoxy”), frequently from 1 to 6 carbon atoms (“C1-C6-haloalkoxy”), preferably 1 to 4 carbon atoms (“C1-C4-haloalkoxy”), more preferably 1 to 3 carbon atoms (“C1-C3-haloalkoxy”), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. C1-C2-Haloalkoxy is, for example, OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5. C1-C4-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2Cl)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. C1-C6-Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.
The term “alkoxyalkyl” as used herein denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 8, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. “C1-C6-Alkoxy-C1-C6-alkyl” is a C1-C6-alkyl group, as defined above, in which one hydrogen atom is replaced by a C1-C6-alkoxy group, as defined above. Examples are CH2OCH3, CH2—OC2H5, n-propoxymethyl, CH2—OCH(CH3)2, n-butoxymethyl, (1-methylpropoxy)-methyl, (2-methylpropoxy)methyl, CH2—OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2-(1-methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl, 2-(1,1-dimethylethoxy)-ethyl, 2-(methoxy)-propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1-methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1-methylpropoxy)-propyl, 2-(2-methylpropoxy)-propyl, 2-(1,1-dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)-propyl, 3-(1-methylethoxy)-propyl, 3-(n-butoxy)-propyl, 3-(1-methylpropoxy)-propyl, 3-(2-methylpropoxy)-propyl, 3-(1,1-dimethylethoxy)-propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n-propoxy)-butyl, 2-(1-methylethoxy)-butyl, 2-(n-butoxy)-butyl, 2-(1-methylpropoxy)-butyl, 2-(2-methyl-propoxy)-butyl, 2-(1,1-dimethylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n-propoxy)-butyl, 3-(1-methylethoxy)-butyl, 3-(n-butoxy)-butyl, 3-(1-methylpropoxy)-butyl, 3-(2-methylpropoxy)-butyl, 3-(1,1-dimethylethoxy)-butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl, 4-(n-propoxy)-butyl, 4-(1-methylethoxy)-butyl, 4-(n-butoxy)-butyl, 4-(1-methylpropoxy)-butyl, 4-(2-methylpropoxy)-butyl, 4-(1,1-dimethylethoxy)-butyl and the like.
The term “haloalkoxy-alkyl” as used herein denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an haloalkoxy radical as defined above, usually comprising 1 to 8, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 1-fluoroethoxymethyl, 2-fluoroethoxymethyl, 1,1-difluoroethoxymethyl, 1,2-difluoroethoxymethyl, 2,2-difluoroethoxymethyl, 1,1,2-trifluoroethoxymethyl, 1,2,2-trifluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl, pentafluoroethoxymethyl, 1-fluoroethoxy-1-ethyl, 2-fluoroethoxy-1-ethyl, 1,1-difluoroethoxy-1-ethyl, 1,2-difluoroethoxy-1-ethyl, 2,2-difluoroethoxy-1-ethyl, 1,1,2-trifluoroethoxy-1-ethyl, 1,2,2-trifluoroethoxy-1-ethyl, 2,2,2-trifluoroethoxy-1-ethyl, pentafluoroethoxy-1-ethyl, 1-fluoroethoxy-2-ethyl, 2-fluoroethoxy-2-ethyl, 1,1-difluoroethoxy-2-ethyl, 1,2-difluoroethoxy-2-ethyl, 2,2-difluoroethoxy-2-ethyl, 1,1,2-trifluoroethoxy-2-ethyl, 1,2,2-trifluoroethoxy-2-ethyl, 2,2,2-trifluoroethoxy-2-ethyl, pentafluoroethoxy-2-ethyl, and the like.
The term “alkylthio” (also alkylsulfanyl or S-alkyl)” as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 8 carbon atoms (“C1-C8-alkylthio”), frequently comprising 1 to 6 carbon atoms (“C1-C6-alkylthio”), preferably 1 to 4 carbon atoms (“C1-C4-alkylthio”), which is attached via a sulfur atom at any position in the alkyl group. C1-C2-Alkylthio is methyl-thio or ethylthio. C1-C4-Alkylthio is additionally, for example, n-propylthio, 1-methylethylthio(isopropylthio), butylthio, 1-methylpropylthio(sec-butylthio), 2-methylpropylthio(isobutylthio) or 1,1-dimethylethylthio(tert-butylthio). C1-C6-Alkylthio is additionally, for example, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio. C1-C8-Alkylthio is additionally, for example, heptylthio, octylthio, 2-ethylhexylthio and positional isomers thereof.
The term “haloalkylthio” as used herein refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or completely substituted by fluorine, chlorine, bromine and/or iodine. C1-C2-Haloalkylthio is, for example, SCH2F, SCHF2, SCF3, SCH2Cl, SCHCl2, SCCl3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio or SC2F5. C1-C4-Haloalkylthio is additionally, for example, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCH2—C2F5, SCF2—C2F5, 1-(CH2F)-2-fluoroethylthio, 1-(CH2Cl)-2-chloroethylthio, 1-(CH2Br)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or nonafluorobutylthio. C1-C6- Haloalkylthio is additionally, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio.
The terms “alkylsulfinyl” and “S(O)n-alkyl” (wherein n is 1) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group. For example, the term “C1-C2-alkylsulfinyl” refers to a C1-C2-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term “C1-C4-alkylsulfinyl” refers to a C1-C4-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term “C1-C6-alkylsulfinyl” refers to a C1-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. C1-C2-alkylsulfinyl is methylsulfinyl or ethylsulfinyl. C1-C4-alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1-methylethylsulfinyl(isopropylsulfinyl), butylsulfinyl, 1-methylpropylsulfinyl(sec-butylsulfinyl), 2-methylpropylsulfinyl(isobutyl-sulfinyl) or 1,1-dimethylethylsulfinyl(tert-butylsulfinyl). C1-C6-alkylsulfinyl is additionally, for example, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl or 1-ethyl-2-methylpropylsulfinyl.
The terms “alkylsulfonyl” and “S(O)n-alkyl” (wherein n is 2) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(O)2] group. The term “C1-C2-alkylsulfonyl” refers to a C1-C2-alkyl group, as defined above, attached via a sulfonyl [S(O)2] group. The term “C1-C4-alkylsulfonyl” refers to a C1-C4-alkyl group, as defined above, attached via a sulfonyl [S(O)2] group. The term “C1-C6-alkylsulfonyl” refers to a C1-C6-alkyl group, as defined above, attached via a sulfonyl [S(O)2] group. C1-C2-alkylsulfonyl is methylsulfonyl or ethylsulfonyl. C1-C4-alkylsulfonyl is additionally, for example, n-propylsulfonyl, 1-methylethylsulfonyl(isopropylsulfonyl), butylsulfonyl, 1-methylpropylsulfonyl(sec-butylsulfonyl), 2-methylpropylsulfonyl(isobutylsulfonyl) or 1,1-dimethylethylsulfonyl(tert-butylsulfonyl). C1-C6-alkylsulfonyl is additionally, for example, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl or 1-ethyl-2-methylpropylsulfonyl.
The term “alkylamino” as used herein denotes in each case a group —NHR*, wherein R* is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms (“C1-C6-alkylamino”), preferably 1 to 4 carbon atoms (“C1-C4-alkylamino”). Examples of C1-C6-alkylamino are methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso-butylamino, tert-butylamino, and the like.
The term “dialkylamino” as used herein denotes in each case a group-NR*Ro, wherein R* and Ro, independently of each other, are a straight-chain or branched alkyl group each usually having from 1 to 6 carbon atoms (“di-(C1-C6-alkyl)-amino”), preferably 1 to 4 carbon atoms (“di-(C1-C4-alkyl)-amino”). Examples of a di-(C1-C6-alkyl)-amino group are dimethylamino, diethylamino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl-propyl-amino, methyl-isopropylamino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl-amino, ethyl-isopropylamino, ethyl-butyl-amino, ethyl-isobutyl-amino, and the like.
The suffix “-carbonyl” in a group denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C═O group. This is the case e.g. in alkylcarbonyl, haloalkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl.
The term “aryl” as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl.
The term “het(ero)aryl” as used herein refers to a mono-, bi- or tricyclic heteroaromatic hydrocarbon radical, preferably to a monocyclic heteroaromatic radical, such as pyridyl, pyrimidyl and the like.
The term “5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms as ring members selected from the groups consisting of N, O and S” as used herein denotes monocyclic or bicyclic heterocyclic radicals, the monocyclic or bicyclic heterocyclic radicals being saturated, unsaturated or aromatic. An unsaturated heterocyclic radical contains at least one C—C and/or C—N and/or N—N double bond(s). A partially unsaturated heterocyclic radical contains less conjugated C—C and/or C—N and/or N—N double bonds than maximally allowed by the size(s) of the ring(s). A fully unsaturated heterocyclic radical contains as many conjugated C—C and/or C—N and/or N—N double bonds as allowed by the size(s) of the ring(s). An aromatic monocyclic heterocyclic radical is a fully unsaturated 5- or 6-membered monocyclic heterocyclic radical. An aromatic bicyclic heterocyclic radical is an 8-, 9- or 10-membered bicyclic heterocyclic radical consisting of a 5- or 6-membered heteroaromatic ring which is fused to a phenyl ring or to another 5- or 6-membered heteroaromatic ring. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. As a matter of course, the heterocyclic ring contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.
Examples of a 3-, 4-, 5- or 6-membered monocyclic saturated heterocycle include: oxirane-2-yl, aziridine-1-yl, aziridine-2-yl, oxetan-2-yl, azetidine-1-yl, azetidine-2-yl, azetidine-3-yl, thietane-1-yl, thietan-2-yl, thietane-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, pyrazolidin-1-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-3-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxazolidin-2-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-3-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-1-yl, 1,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, 1,3,5-hexahydrotriazin-1-yl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl, thiomorpholin-4-yl, 1-oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1-oxothiomorpholin-4-yl, 1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl, 1,1-dioxothiomorpholin-4-yl and the like.
Examples of a 5- or 6-membered monocyclic partially unsaturated heterocycle include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydro-pyrazinyl, 1,3,5-di- or tetrahydrotriazin-2-yl and 1,2,4-di- or tetrahydrotriazin-3-yl.
A 5- or 6-membered monocyclic fully unsaturated (including aromatic) heterocyclic ring is e.g. a 5- or 6-membered monocyclic fully unsaturated (including aromatic) heterocyclic ring. Examples are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazol-1-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-oxopyridin-2-yl, 1-oxopyridin-3-yl, 1-oxopyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like.
If two radicals bound on the same nitrogen atom (for example Re and Rf or R2e and R2f or Rg and Rh or R2g and R2h) together with the nitrogen atom, to which they are bound, form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N, this is for example pyrrolidine-1-yl, pyrazolidin-1-yl, imidazolidin-1-yl, oxazolidin-3-yl, thiazolidin-3-yl, isoxazolidin-2-yl, isothiazolin-2-yl, [1,2,3]-triazolidin-1-yl, [1,2,3]-triazolidin-2-yl, [1,2,4]-triazolidin-1-yl, [1,2,4]-triazolidin-4-yl, [1,2,3]-oxadiazolidin-2-yl, [1,2,3]-oxadiazolidin-3-yl, [1,2,5]-oxadiazolidin-2-yl, [1,2,4]-oxadiazolidin-2-yl, [1,2,4]-oxadiazolidin-4-yl, [1,3,4]-oxadiazolidin-3-yl, [1,2,3]-thiadiazolidin-2-yl, [1,2,3]-thiadiazolidin-3-yl, [1,2,5]-thiadiazolidin-2-yl, [1,2,4]-thiadiazolidin-2-yl, [1,2,4]-thiadiazolidin-4-yl, [1,3,4]-thiadiazolidin-3-yl, piperidin-1-yl, piperazine-1-yl, morpholin-1-yl, thiomorpholin-1-yl, 1-oxothiomorpholin-1-yl, 1,1-dioxothiomorpholin-1-yl, azepan-1-yl, 1,4-diazepan-1-yl, pyrrolin-1-yl, pyrazolin-1-yl, imidazolin-1-yl, oxazolin-3-yl, isoxazolin-2-yl, thiazolin-3-yl, isothiazolin-1-yl, 1,2-dihydropyridin-1-yl, 1,2,3,4-tetrahydropyridin-1-yl, 1,2,5,6-tetrahydropyridin-1-yl, 1,2-dihydropyridazin, 1,6-dihydropyridazin, 1,2,3,4-tetrahydropyridazin-1-yl, 1,2,5,6-tetrahydropyridazin-1-yl, 1,2-dihydropyrimidin, 1,6-dihydropyrimidin, 1,2,3,4-tetrahydropyrimidin-1-yl, 1,2,5,6-tetrahydropyrimidin-1-yl, 1,2-dihydropyrazin-1-yl, 1,2,3,4-tetrahydropyrazin-1-yl, 1,2,5,6-tetrahydropyrazin-1-yl, pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, [1,2,3]-1H-triazol-1-yl, [1,2,3]-2H-triazol-2-yl, [1,2,4]-1H-triazol-1-yl and [1,2,4]-4H-triazol-4-yl.
The term “fused 5-, 6-, 7-, 8-, 9- and 10-membered carbocycle or 5-, 6-, 7-, 8-, 9- and 10-membered heterocycle” refers to a carbo- or heterocycle that is adjoined at two consecutive positions with the phenyl group of the radical Cyc-1 or Cyc-1 in such a way that both rings share the ring atoms at said two positions. The fused carbo- and heterocycles may be saturated, partially unsaturated or fully unsaturated and in addition may be mono-, bi- or tricyclic, where each one of the two or three rings of the bi- and tricyclic fused carbo- and heterocycles is either fused to one or two of the other rings, i.e. two rings share two ring atoms, or spiro-linked, i.e. two rings share 1 ring atom. Examples of 5-, 6-, 7-, 8-, 9- and 10-membered fused carbocycles are cyclopentane, cyclohexane, cycloheptane, cyclo[3.3.0]octane, cyclo[4.3.0]nonane, cyclo[4.4.0]decane cyclopentene, cyclohexene and benzene. Examples of 5-, 6-, 7-, 8-, 9- and 10-membered fused carbocycles are pyrrolidine, tetrahydrofuran, tetrahydrothiophen, dihydrofuran, dihydrothiophen, pyrrole, furan, thiopene, thiazole, thiazine, piperidine, tetrahydropyran, tetrahydrothiopyrane, dioxane, piperazine, morpholine, pyridine, azepane, oxepane, thiepane, azepine, oxepine, thiepine, pyrazole, pyrazoline, imidazole, benzimidazole, imidazoline, indole, indoline, chinoline, isochinoline, pyrimidine, oxazole, isoxazole, oxazoline, isoxazoline and the like.
The remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formula I are valid on their own as well as preferably in combination with each other, as well as in combination with the stereoisomers, salts, tautomers or N-oxides thereof.
The remarks made below concerning preferred embodiments of the variables further are valid on their own as well as preferably in combination with each other concerning the compounds of formulae I, where applicable, as well as concerning the uses and methods according to the invention and the composition according to the invention.
Preferred compounds according to the invention are compounds of formula I or a stereoisomer, salt or N-oxide thereof, wherein the salt is an agriculturally suitable salt. Further preferred compounds according to the invention are compounds of formula I or an N-oxide or salt thereof, especially an agriculturally suitable salt. Particularly preferred compounds according to the invention are compounds of formula I or a salt thereof, especially an agriculturally suitable salt thereof.
According to a preferred embodiment of the invention the variable R in the compounds of formula I is selected from the group consisting of halogen, cyano, nitro, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C7-cycloalkyl, C1-C6-haloalkyl, C(═O)—Rc, C(═O)—ORd, C(═O)—NReRf, NH—C(═O)Rk and NRgRh, where Rc, Rd, Re, Rf, Rk, Rg and Rh are as defined above and which preferably have on their own or in particular in combination the following meanings:
Rc is hydrogen, C1-C6-alkyl C3-C7-cycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C1-C6-haloalkyl or phenyl, in particular C1-C4-alkyl or C1-C4-haloalkyl;
Rd is C1-C6-alkyl or C1-C6-haloalkyl, in particular C1-C4-alkyl;
Re, Rf are independently of each other selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl and benzyl, and in particular from the group consisting of hydrogen and C1-C4-alkyl; or
Re, Rf together with the nitrogen atom, to which they are bound form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-haloalkyl, and in particular Re, Rf together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 methyl groups;
Rg, Rh are independently of each other selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl and benzyl, and in particular from the group consisting of hydrogen and C1-C4-alkyl, or
Rg, Rh together with the nitrogen atom, to which they are bound form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-haloalkyl, and in particular Rg, Rh together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 methyl groups; and
Rk is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or phenyl, in particular C1-C4-alkyl.
According to a more preferred embodiment the variable R of the compounds of the formula I is selected from the group consisting of halogen, cyano, nitro, NH2, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C7-cycloalkyl, C1-C4-haloalkyl, C(═O)—Rc, C(═O)—ORd, C(═O)—NReRf and NH—C(═O)Rk, where Rc, Rd, Re, Rf and Rk are as defined above and which preferably have on their own or in particular in combination the following meanings:
Rc is C1-C4-alkyl or C1-C4-haloalkyl,
Rd is C1-C4-alkyl,
Re is hydrogen or C1-C4-alkyl,
Rf is hydrogen or C1-C4-alkyl, or
Re, Rf together with the nitrogen atom, to which they are bound may form a 5-, 6 or 7-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 methyl groups, and
Rk is C1-C4-alkyl.
According to a particular preferred embodiment of the invention the variable R in the compounds of formula I is selected from halogen, cyano, nitro, C1-C4-alkyl, C3-C7-cycloalkyl, C1-C4-haloalkyl, acetylamino, methoxycarbonyl, ethoxycarbonyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, amino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl and methoxymethyl, in particular from Cl, Br, F, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, CF3, CHF2, CClF2, CH2CF3, CF2CF3, CH2Cl, CHCl2, cyano, nitro, acetylamino, methoxycarbonyl, ethoxycarbonyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, amino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl and methoxymethyl.
According to a further preferred embodiment of the invention the variable R in the compounds of formula I is a radical ORa, where Ra is as defined above and in particular selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, preferably from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, and in particular from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C6-cycloalkyl. In this context Ra specifically is hydrogen, CH3, CH2H3, CH(CH3)2, CH2CH2CH3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, CH2Cl, C(CH3)3, CHF2, CF3, CH2CH═CH2, CH2C≡CH, CH2OCH3, CH2CH2OCH3 and CH2CH2OCH2CH3.
According to another preferred embodiment of the invention the variable R in the compounds of formula I is phenyl or heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R′ which are as defined above and which are independently from one another preferably selected from the group consisting of halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl and C1-C6-haloalkyloxy, more preferably from halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl and C1-C4-alkoxy, in particular from halogen, methyl, ethyl, methoxy and trifluoromethyl, and specifically from Cl, F, Br, methyl, methoxy and trifluoromethyl.
According to a more preferred embodiment of the invention the variable R in the compounds of formula I is phenyl or heterocyclyl, where heterocyclyl is a partially unsaturated or aromatic 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the bicyclic heterocycle consists of a 5- or 6-membered heteroaromatic ring which is fused to a phenyl ring, and where phenyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R′ which independently from one another have the aforementioned preferred meanings.
According to particular preferred embodiments the variable R in the compounds of the formula I is phenyl or heterocyclyl selected from pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, benzisoxazole-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, isoxazol-4-yl, isoxazol-5-yl, oxazol-2-yl, oxazol-3-yl, oxazol-4-yl, oxazol-5-yl, pyrrol-2-yl, pyrrol-3-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-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, where phenyl and heterocyclyl are unsubstituted or carry 1, 2, or 3 groups R′ which independently from one another have the aforementioned preferred meanings.
According to a preferred embodiment of the invention the variable R in the compounds of formula I is S(O)n—Rb, where Rb is as defined above and in particular selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1, 2 or 3 groups, which are identical or different and preferably selected from the group consisting of halogen, C1-C4-alkyl, C1-C2-haloalkyl and C1-C2-alkoxy.
According to a more preferred embodiment of the invention the variable R in the compounds of formula I is S(O)n—Rb, where Rb is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C7-cycloalkyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S.
According to an even more preferred embodiment of the invention the variable R in the compounds of formula I is S(O)n—Rb, where Rb is selected from C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, phenyl and heterocyclyl, where heterocyclyl is a 6-membered aromatic heterocyclic radical having 1 or 2 nitrogen atoms as ring members.
According to a particularly preferred embodiment of the invention the variable R in the compounds of formula I is S(O)2—Rb, where Rb is CH3, CH2H3, CH(CH3)2, CH2CH2CH3, CH2CH═CH2, CH2C≡CH or phenyl.
According to specifically preferred embodiments of the invention the variable R in the compounds of formula I is selected from the group consisting of Cl, Br, F, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, CF3, CHF2, CClF2, CH2CF3, CF2CF3, CH2Cl, CHF2, CHCl2, cyano, nitro, acetylamino, benzoylamino, methoxycarbonyl, ethoxycarbonyl, benzoyl, methylcarbonyl, piperidinylcarbonyl, trifluoromethylcarbonyl, amino, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxymethyl, OH, OCH3, OCH2H3, OCH(CH3)2, OCH2CH2CH3, O-cyclopropyl, O-cyclobutyl, O-cyclopentyl, O-cyclohexyl, O—CH2Cl, O—C(CH3)3, O—CHF2, O—CF3, O—CH2CH═CH2, O—CH2C≡CH, O—CH2OCH3, O—CH2CH2OCH3, O—CH2CH2OCH2CH3, S(O)2—CH3, S(O)2—CH2H3, S(O)2—CH(CH3)2, S(O)2—CH2CH2CH3, S(O)2—CH2CH═CH2, S(O)2—CH2C≡CH and S(O)2-phenyl, and in particular from methyl, ethyl and methoxy.
Preferred compounds according to the invention are compounds of formula I, wherein R2, if present, is selected from the group consisting of halogen, NO2, cyano, oxo (═O), ═N—R22, where R22 is as defined above and in particular is C1-C4-alkoxy or C1-C4-haloalkoxy, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkoxy, C3-C10-cycloalkyl, O—C3-C10-cycloalkyl, C1-C4-alkylsulfonyl, C1-C4-alkylcarbonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino and Z2-phenyl, where Z2 is as defined herein, and where phenyl is unsubstituted or carries 1, 2 or 3 radicals R21 which are as defined above and preferably are independently of one another selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl and C1-C4-alkoxy-C1-C4-alkoxy, and more preferably from halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl and C1-C2-alkoxy-C1-C2-alkoxy.
More preferably R2, if present, is selected from halogen, NO2, cyano, oxo, ═N—R22, where R22 is C1-C4-alkoxy or C1-C4-haloalkoxy, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkoxy, C3-C10-cycloalkyl, C1-C4-alkylsulfonyl, C1-C4-alkylcarbonyl, phenyl and benzyl, where phenyl in the last two mentioned radicals is unsubstituted or carries 1, 2 or 3 radicals R21 which are as defined above and in particular are independently of one another selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-alkoxy-C1-C4-alkoxy.
Even more preferably R2, if present, is selected from halogen, oxo, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkoxy, C1-C4-alkylsulfonyl, ═N—R22, where R22 is C1-C4-alkoxy, and phenyl, where phenyl is unsubstituted or carries 1, 2 or 3 radicals R21 which are identical or different and are selected from halogen, C1-C4-alkyl and C1-C4-alkoxy.
Particularly preferred R2, if present, is selected from halogen, oxo, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C3-C4-alkenyl, C3-C4-alkynyl and ═N—R22, where R22 is C1-C4-alkoxy.
In particular, R2, if present, is selected from halogen, oxo, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-haloalkoxy, C3-C4-alkenyl and ═N—R22, where R22 is C1-C4-alkoxy.
Specifically, R2, if present, is halogen, oxo, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-alkenyl or ═N—R22, where R22 is C1-C4-alkoxy, and more specifically F, Cl, ═O, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, CH2CH═CH2, OCF3, OCHF2, OCH2F, OCH2Cl, OCH2CH2F, OCF2CF3, OCH3, OCH2CH3, ═N—OCH3 or ═N—OCH2CH3.
Preferred compounds according to the invention are compounds of formula I, wherein R4 is selected from the group consisting of hydrogen, cyano, halogen, nitro, C1-C2-alkyl and C1-C2-haloalkyl, in particular from the group consisting of hydrogen, CHF2, CF3, CN, NO2, CH3 and halogen, which is preferably from Cl, Br and F. Specifically R4 is hydrogen.
Preferred compounds according to the invention are compounds of formula I, wherein R5 is selected from the group consisting of hydrogen, halogen, C1-C2-alkyl and C1-C2-haloalkyl, and in particular from the group consisting of hydrogen, CHF2, CF3 and halogen.
According to a particular embodiment of the invention R4 and R5 are both hydrogen.
According to a preferred embodiment of the invention the variable CYC in the compound of formula I is a radical Cyc-1, as defined above.
According to a more preferred embodiment of the invention the variable Q of the radical Cyc-1 indicates a fused 5- or 6-membered monocyclic heterocycle or a fused 7-, 8-, 9- or 10-membered spiro-bicyclic heterocycle, where the fused monocyclic heterocycle has 1 or 2 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7 or 8 radicals R2, where the fused spiro-bicyclic heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 radicals R2, where R2 has the herein defined meanings and in particular those mentioned as preferred.
According to an even more preferred embodiment of the invention the variable Q of the radical Cyc-1 indicates a fused 5- or 6-membered monocyclic heterocycle or a fused 8-, 9- or 10-membered spiro-bicyclic heterocycle which are both either saturated or partially unsaturated, where the fused monocyclic heterocycle has 1 or 2 and the fused spiro-bicyclic heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members, where S as ring member is unsubstituted or is part of a S(O)2 group or a S(O) group, and where one carbon atom that is a ring member of the fused mono-cyclic or spiro-bicyclic heterocycle may be part of a carbonyl group. In addition, according to this embodiment the fused monocyclic heterocycle carries 0, 1, 2, 3, 4 or 5 and the fused spiro-bicyclic heterocycle carries 0, 1, 2, 3, 4, 5, 6 or 7 radicals R2, which have the herein defined meanings and in particular are independently of one another selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-alkenyl and ═N—R22, where R22 is C1-C4-alkoxy.
According to a particularly preferred embodiment of the invention the variable Q of the radical Cyc-1 indicates a fused 5- or 6-membered monocyclic heterocycle or a fused 8- or 9-membered spiro-bicyclic heterocycle which are both either saturated or partially unsaturated, where the fused monocyclic heterocycle has 1 or 2 and the fused spiro-bicyclic heterocycle has 1, 2 or 3 heteroatoms selected from O, S and N as ring members, where S as ring member is unsubstituted or is part of a S(O)2 group and where one carbon atom that is a ring member of the fused monocyclic or spiro-bicyclic heterocycle may be part of a carbonyl group, where said heterocycle includes one or two S(O)2 groups and/or one carbonyl group. In addition, according to this embodiment the fused monocyclic heterocycle carries 0, 1, 2 or 3 and the fused spiro-bicyclic heterocycle carries 0, 1, 2, 3 or 4 radicals R2, which have the herein defined meanings and in particular are independently of one another are selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-alkenyl and ═N—R22, where R22 is C1-C4-alkoxy.
According to a particular embodiment of the invention the radical CYC of the 1,2,5-oxadiazole compound of the formula I is a radical Cyc-1 that is selected from the following groups Cyc-1a to Cyc-1h:




where # indicates the point of attachment of the bi- or tricyclic radical to the carbonyl group of the compound of formula I, R1, R2, R4 and R5 have the herein defined meanings, in particular those mentioned as preferred, R5 is in particular hydrogen or halogen, especially hydrogen, F, Cl or Br, and R23 and R24 are hydrogen or have one of the meanings given for R2 in particular those mentioned as preferred.
According to a specific embodiment of the invention the radical Cyc-1 is selected from the following groups Cyc-1a′ to Cyc-1h′ and Cyc-1f′′:







where
# indicates the point of attachment of the bi- or tricyclic radical to the carbonyl group of the compound of formula I;
R1 has the herein defined meanings, in particular those mentioned herein below as preferred;
R2p, R2q are independently of each other hydrogen, C1-C4-alkyl or C1-C4-alkoxy, preferably R2p is hydrogen, CH3, CH2CH3 or CH2(CH3)2 and R2q is hydrogen, CH3, CH2CH3, CH2(CH3)2, OCH3 or OCH2CH3, and in particular R2p is hydrogen or CH3 and R2q is hydrogen, CH3 or OCH3;
R2r, R2s are independently of each other hydrogen, halogen or C1-C4-alkyl, preferably hydrogen or halogen, and in particular hydrogen, fluorine or chlorine;
R2t is C1-C4-alkoxy or C1-C4-haloalkoxy, preferably C1-C4-haloalkoxy, and in particular OCH2CH2F;
R2u is C1-C4-alkoxy or C1-C4-haloalkoxy, preferably C1-C4-alkoxy, and in particular OCH3 or OCH2CH3;
R2v is C1-C4-alkyl or C3-C4-alkenyl, preferably C1-C3-alkyl or C3-C4-alkenyl, and in particular CH3, CH2CH3, CH2CH2CH3, CH(CH3)2 or CH2CH═CH2.
According to an even more specific embodiment of the invention the radical Cyc-1 is selected from the following groups Cyc-1a′-1 to Cyc-1a′-6, Cyc-1b′, Cyc-1c′, Cyc-1d′-1 to Cyc-1d′-9, Cyc-1e′, Cyc-1f′, Cyc-1f′′-1 and Cyc-1f′′-2, Cyc-1fg′, and Cyc-1h′-1 to Cyc-1h′-5:













where # indicates the point of attachment of the bi- or tricyclic radical to the carbonyl group of the compound of formula I and R1 has the herein defined meanings, in particular those mentioned herein below as preferred.
Among the compounds of formula I wherein CYC is Cyc-1, preference is given to those compounds, wherein R1 is selected from the group consisting of CN, halogen, nitro, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, Z1—C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylthio-C1-C4-alkyl, Z1—C1-C4-alkylthio-C1-C4-alkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy and S(O)kR1b, where k and Z1 are as defined herein and where R1b is as defined above and in particular selected from the group consisting of C1-C4-alkyl and C1-C4-haloalkyl. In this context Z1 is in particular a covalent bond.
More preferably, R1 is selected from halogen, CN, nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy, S(O)k—C1-C4-alkyl and S(O)k—C1-C4-haloalkyl, where k is 0 or 2.
In particular, R1 is selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio and C1-C4-alkylsufonyl, specifically R1 is F, Cl, Br, CH3, CF3, OCH3, OCF3, SCF3, SO2CH3 or CH2OCH2CH2OCH3, and more specifically R1 is Cl, CH3, CF3 or SO2CH3.
According to a preferred embodiment of the invention the variable CYC in the compound of formula I is a radical Cyc-2, as defined above.
According to a more preferred embodiment of the invention the variable Q′ of the radical Cyc-1 indicates a fused 5- or 6-membered monocyclic heterocycle or a fused 7-, 8-, 9- or 10-membered bicyclic heterocycle, where the fused monocyclic heterocycle has 1 or 2 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7 or 8 radicals R2, where the fused bicyclic heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 radicals R2, where R2 has the herein defined meanings in particular those mentioned as preferred.
According to an even more preferred embodiment of the invention the variable Q′ of the radical Cyc-2 indicates a fused 5- or 6-membered monocyclic heterocycle or a fused 8-, 9- or 10-membered bicyclic heterocycle which are both either partially unsaturated or fully unsaturated, where the fused monocyclic heterocycle has 1 or 2 and the fused bicyclic heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members, and where the fused monocyclic heterocycle is unsubstituted or carries 1, 2, 3, 4, 5 or 6 and the fused bicyclic heterocycle is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7 or 8 radicals R2, which are as defined herein and in particular are independently of one another selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-alkenyl and ═N—R22, where R22 is C1-C4-alkoxy.
According to a particularly preferred embodiment of the invention the variable Q′ of the radical Cyc-2 indicates a fused aromatic 5- or 6-membered monocyclic heterocycle or a fused aromatic 8-, 9- or 10-membered bicyclic heterocycle, where the fused monocyclic heterocycle has 1 or 2 and the fused bicyclic heterocycle has 1, 2 or 3 heteroatoms selected from O and N as ring members, and where the fused monocyclic heterocycle is unsubstituted or carries 1, 2, 3 or 4 and the fused bicyclic heterocycle is unsubstituted or carries 1, 2, 3, 4, 5 or 6 radicals R2, which are as defined herein and in particular are independently of one another selected from halogen, C1-C4-alkyl, C1-C4-alkoxy and C1-C4-haloalkyl.
According to a particular embodiment of the invention the radical CYC of the 1,2,5-oxadiazole compound of the formula I is a radical Cyc-2 that is selected from the following groups Cyc-2a to Cyc-2d:




where # indicates the point of attachment of the bicyclic radical to the carbonyl group of the compound of formula I, R2, R3 and R4 have the herein defined meanings, in particular those mentioned as preferred, and p is 0, 1, 2 or 3, preferably is 0 or 1 and in particular is 0.
According to a specific embodiment of the invention the radical Cyc-1 is selected from the following groups Cyc-2a′ to Cyc-2d′:




where # indicates the point of attachment of the bicyclic radical to the carbonyl group of the compound of formula I and R3 has the herein defined meanings, in particular those mentioned herein below as preferred.
Among the compounds of formula I wherein CYC is Cyc-2, preference is given to those compounds, wherein R3 is selected from the group consisting of hydrogen, cyano, halogen, nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-alkenyloxy, C2-C4-alkynyloxy and S(O)kR2b, where the variables k and R2b have one of the herein defined meanings.
More preferably, R3 is selected from the group consisting of hydrogen, halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, S(O)2—C1-C4-alkyl and S(O)2—C1-C4-haloalkyl.
In particular, R3 is selected from the group consisting of hydrogen, halogen, CN, NO2, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy, C1-C2-alkylthio, C1-C2-haloalkylthio, S(O)2—C1-C2-alkyl and S(O)2—C1-C2-haloalkyl, specifically from hydrogen, Cl, F, CN, NO2, CH3, CF3, CHF2, OCH3, OCF3, OCHF2, SCH3, SCF3, SCHF2, S(O)2CH3 and S(O)2CH2CH3, and more specifically from Cl, F, CN, CF3 and S(O)2CH3.
The variables R′, R11, R21, R31, Z, Z1, Z2, Z3, Z3a, Ra, Rb, R1b, R2b, R3b, Rc, R2c, R3c, Rd, R3d, Re, Rf, R3e, R3f, Rg, Rh, R2g, R2h, R3g, R3h, Rk, n and k, independently of each other, preferably have one of the following meanings:
R′, R11, R21, R31 independently of each other are selected from halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl and C1-C6-haloalkyloxy, more preferably from halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl and C1-C4-alkoxy.
More preferably R′, R11, R21, R31 independently of each other are selected from the group consisting of halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-alkoxy-C1-C4-alkyl; in particular selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-alkoxy-C1-C4-alkyl; and specifically from Cl, F, Br, methyl, ethyl, methoxy and trifluoromethyl.
R22 is selected from C1-C4-alkoxy, C1-C4-haloalkoxy and C3-C7-cycloalkoxy; more preferably from C1-C4-alkoxy and C1-C4-haloalkoxy, particularly from C1-C4-alkoxy, and specifically is OCH3 or OCH2CH3.
Z, Z1, Z2, Z3 independently of each other are selected from a covalent bond, methanediyl and ethanediyl, and in particular are a covalent bond.
Z3a is selected from a covalent bond, C1-C2-alkanediyl, O—C1-C2-alkanediyl, C1-C2-alkanediyl-O and C1-C2-alkanediyl-O—C1-C2-alkanediyl; more preferably from a covalent bond, methanediyl, ethanediyl, O-methanediyl, O-ethanediyl, methanediyl-O, and ethanediyl-O; and in particular from a covalent bond, methanediyl and ethanediyl.
Ra is selected from hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl.
More preferably Ra is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, and in particular selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C6-cycloalkyl.
Rb, R1b, R2b, R3b independently of each other are selected from C1-C6-alkyl, C3-C7-cycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and phenyl, where phenyl is unsubstituted or substituted by 1, 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C2-haloalkyl and C1-C2-alkoxy.
More preferably Rb, R1b, R2b, R3b independently of each other are selected from the group consisting of C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl and phenyl.
In particular, Rb, R1b, R2b, R3b independently of each other are selected from C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl and phenyl.
Rc, R2c, R3c, Rk independently of each other are selected from hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1, 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl and C1-C4-alkoxy.
More preferably Rc, R2c, R3c, Rk independently of each other are selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C-alkenyl, C2-C-haloalkenyl, C2-C-alkynyl, C3-C6-cycloalkyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S.
In particular, Rc, R2c, R3c, Rk independently of each other are selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C3-C6-cycloalkyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered aromatic heterocyclic radical having 1 or 2 nitrogen atoms as ring members.
Rd, R3d independently of each other are selected from C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl.
More preferably Rd, R3d independently of each other are selected from C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, and in particular selected from C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C3-C6-cycloalkyl.
Re, Rf, R3e, R3f independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl and C1-C4-alkoxy, or Re and Rf or R3e and R3f together with the nitrogen atom, to which they are bound may form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl and C1-C4-alkoxy.
More preferably Re, Rf, R3e, R3f independently of each other are selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl and benzyl, or Re and Rf or R3e and R3f together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-haloalkyl.
In particular, Re, Rf, R3e, R3f independently of each other are selected from hydrogen and C1-C4-alkyl, or Re and Rf or R3e and R3f together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2 or 3 methyl groups.
Rg, R2g, R3g independently of each other are selected from hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl.
More preferably Rg, R2g, R3g independently of each other are selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, benzyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, and in particular selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, benzyl and C3-C6-cycloalkyl.
Rh, R2h, R3h independently of each other are selected from hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl, benzyl and a radical C(═O)—Rk, where Rk is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or phenyl.
More preferably Rh, R2h, R3h independently of each other are selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, benzyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated, and in particular selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, benzyl and C3-C6-cycloalkyl; or
Rg and Rh or R2g and R2h or R3g and R3h together with the nitrogen atom, to which they are bound may form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of ═O, halogen, C1-C4-alkyl and C1-C4-haloalkyl and C1-C4-alkoxy;
more preferably Rg and Rh or R2g and R2h or R3g and R3h together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-haloalkyl;
and in particular, Rg and Rh or R2g and R2h or R3g and R3h together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2 or 3 methyl groups.
n and k independently of each other are 0 or 2, and in particular 2.
Examples of preferred compounds are the individual compounds compiled in the Tables 1 to 3 below. Moreover, the meanings mentioned below for the individual variables in the Tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 1 Compounds of the formula I in which R is methyl and the combination of R1, if present, CYC and R3, if present, for a compound corresponds in each case to one row of Table A;
Table 2 Compounds of the formula I in which R is ethyl and the combination of R1, if present, CYC and R3, if present, for a compound corresponds in each case to one row of Table A;
Table 3 Compounds of the formula I in which R is methoxy and the combination of R1, if present, CYC and R3, if present, for a compound corresponds in each case to one row of Table A.











TABLE A







R1
CYC
R3





















A-1
Cl
Cyc-1a′-1
—



A-2
Cl
Cyc-1a′-2
—



A-3
Cl
Cyc-1a′-3
—



A-4
Cl
Cyc-1a′-4
—



A-5
Cl
Cyc-1a′-5
—



A-6
Cl
Cyc-1a′-6
—



A-7
Cl
Cyc-1b′
—



A-8
Cl
Cyc-1c′
—



A-9
Cl
Cyc-1d′-1
—



A-10
Cl
Cyc-1d′-2
—



A-11
Cl
Cyc-1d′-3
—



A-12
Cl
Cyc-1d′-4
—



A-13
Cl
Cyc-1d′-5
—



A-14
Cl
Cyc-1d′-6
—



A-15
Cl
Cyc-1d′-7
—



A-16
Cl
Cyc-1d′-8
—



A-17
Cl
Cyc-1d′-9
—



A-18
Cl
Cyc-1e′
—



A-19
Cl
Cyc-1f′
—



A-20
Cl
Cyc-1f′′-1
—



A-21
Cl
Cyc-1f′′-2
—



A-22
Cl
Cyc-1g′
—



A-23
Cl
Cyc-1h′-1
—



A-24
Cl
Cyc-1h′-2
—



A-25
Cl
Cyc-1h′-3
—



A-26
Cl
Cyc-1h′-4
—



A-27
Cl
Cyc-1h′-5
—



A-28
CH3
Cyc-1a′-1
—



A-29
CH3
Cyc-1a′-2
—



A-30
CH3
Cyc-1a′-3
—



A-31
CH3
Cyc-1a′-4
—



A-32
CH3
Cyc-1a′-5
—



A-33
CH3
Cyc-1a′-6
—



A-34
CH3
Cyc-1b′
—



A-35
CH3
Cyc-1c′
—



A-36
CH3
Cyc-1d′-1
—



A-37
CH3
Cyc-1d′-2
—



A-38
CH3
Cyc-1d′-3
—



A-39
CH3
Cyc-1d′-4
—



A-40
CH3
Cyc-1d′-5
—



A-41
CH3
Cyc-1d′-6
—



A-42
CH3
Cyc-1d′-7
—



A-43
CH3
Cyc-1d′-8
—



A-44
CH3
Cyc-1d′-9
—



A-45
CH3
Cyc-1e′
—



A-46
CH3
Cyc-1f′
—



A-47
CH3
Cyc-1f′′-1
—



A-48
CH3
Cyc-1f′′-2
—



A-49
CH3
Cyc-1g′
—



A-50
CH3
Cyc-1h′-1
—



A-51
CH3
Cyc-1h′-2
—



A-52
CH3
Cyc-1h′-3
—



A-53
CH3
Cyc-1h′-4
—



A-54
CH3
Cyc-1h′-5
—



A-55
CF3
Cyc-1a′-1
—



A-56
CF3
Cyc-1a′-2
—



A-57
CF3
Cyc-1a′-3
—



A-58
CF3
Cyc-1a′-4
—



A-59
CF3
Cyc-1a′-5
—



A-60
CF3
Cyc-1a′-6
—



A-61
CF3
Cyc-1b′
—



A-62
CF3
Cyc-1c′
—



A-63
CF3
Cyc-1d′-1
—



A-64
CF3
Cyc-1d′-2
—



A-65
CF3
Cyc-1d′-3
—



A-66
CF3
Cyc-1d′-4
—



A-67
CF3
Cyc-1d′-5
—



A-68
CF3
Cyc-1d′-6
—



A-69
CF3
Cyc-1d′-7
—



A-70
CF3
Cyc-1d′-8
—



A-71
CF3
Cyc-1d′-9
—



A-72
CF3
Cyc-1e′
—



A-73
CF3
Cyc-1f′
—



A-74
CF3
Cyc-1f′′-1
—



A-75
CF3
Cyc-1f′′-2
—



A-76
CF3
Cyc-1g′
—



A-77
CF3
Cyc-1h′-1
—



A-78
CF3
Cyc-1h′-2
—



A-79
CF3
Cyc-1h′-3
—



A-80
CF3
Cyc-1h′-4
—



A-81
CF3
Cyc-1h′-5
—



A-82
SO2CH3
Cyc-1a′-1
—



A-83
SO2CH3
Cyc-1a′-2
—



A-84
SO2CH3
Cyc-1a′-3
—



A-85
SO2CH3
Cyc-1a′-4
—



A-86
SO2CH3
Cyc-1a′-5
—



A-87
SO2CH3
Cyc-1a′-6
—



A-88
SO2CH3
Cyc-1b′
—



A-89
SO2CH3
Cyc-1c′
—



A-90
SO2CH3
Cyc-1d′-1
—



A-91
SO2CH3
Cyc-1d′-2
—



A-92
SO2CH3
Cyc-1d′-3
—



A-93
SO2CH3
Cyc-1d′-4
—



A-94
SO2CH3
Cyc-1d′-5
—



A-95
SO2CH3
Cyc-1d′-6
—



A-96
SO2CH3
Cyc-1d′-7
—



A-97
SO2CH3
Cyc-1d′-8
—



A-98
SO2CH3
Cyc-1d′-9
—



A-99
SO2CH3
Cyc-1e′
—



A-100
SO2CH3
Cyc-1f′
—



A-101
SO2CH3
Cyc-1f′′-1
—



A-102
SO2CH3
Cyc-1f′′-2
—



A-103
SO2CH3
Cyc-1g′
—



A-104
SO2CH3
Cyc-1h′-1
—



A-105
SO2CH3
Cyc-1h′-2
—



A-106
SO2CH3
Cyc-1h′-3
—



A-107
SO2CH3
Cyc-1h′-4
—



A-108
SO2CH3
Cyc-1h′-5
—



A-109
—
Cyc-2a′
F



A-110
—
Cyc-2b′
F



A-111
—
Cyc-2c′
F



A-112
—
Cyc-2d′
F



A-113
—
Cyc-2a′
Cl



A-114
—
Cyc-2b′
Cl



A-115
—
Cyc-2c′
Cl



A-116
—
Cyc-2d′
Cl



A-117
—
Cyc-2a′
Br



A-118
—
Cyc-2b′
Br



A-119
—
Cyc-2c′
Br



A-120
—
Cyc-2d′
Br



A-121
—
Cyc-2a′
CH3



A-122
—
Cyc-2b′
CH3



A-123
—
Cyc-2c′
CH3



A-124
—
Cyc-2d′
CH3



A-125
—
Cyc-2a′
CF3



A-126
—
Cyc-2b′
CF3



A-127
—
Cyc-2c′
CF3



A-128
—
Cyc-2d′
CF3



A-129
—
Cyc-2a′
OCH3



A-130
—
Cyc-2b′
OCH3



A-131
—
Cyc-2c′
OCH3



A-132
—
Cyc-2d′
OCH3










The compounds of the formula I can be prepared by standard methods of organic chemistry, e.g. by the methods described hereinafter in schemes 1 to 5. The substituents, variables and indices in schemes 1 to 5 are as defined above for formula I, if not otherwise specified.
The compounds of formula I can be prepared for instance as shown in the Scheme 1 below.




4-Amino-1,2,5-oxadiazole compounds of formula III can be reacted with benzoyl derivatives of formula II to afford compounds of the formula I. Z is a leaving group, such as halogen, in particular Cl, an anhydride residue or an active ester residue. Especially in case of Z being halogen the reaction is suitably carried out in the presence of a base. Suitable bases are for example carbonates, such as lithium, sodium or potassium carbonates, amines, such as trimethylamine or triethylamine, and basic N-heterocycles, such as pyridine, 2,6-dimethylpyridine or 2,4,6-trimethylpyridine. Suitable solvents are in particular aprotic solvents such as pentane, hexane, heptane, octane, cyclohexane, dichloromethane, chloroform, 1,2-dichlorethane, benzene, chlorobenzene, toluene, the xylenes, dichlorobenzene, trimethylbenzene, pyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, acetonitrile, diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, methyl tert-butylether, 1,4-dioxane, N,N-dimethyl formamide, N-methyl pyrrolidinone or mixtures thereof. The starting materials are generally reacted with one another in equimolar or nearly equimolar amounts at a reaction temperature usually in the range of −20° C. to 100° C. and preferably in the range of −5° C. to 50° C.
Alternatively, compounds of formula I can also be prepared as shown in Scheme 2. Reaction of a 4-amino-1,2,5-oxadiazole compound III with a benzoic acid derivative of formula IV yields compound I. The reaction is preferably carried in the presence of a suitable activating agent which converts the acid group of compound IV into an activated ester or amide. For this purpose activating agents known in the art, such as 1,1′,carbonyldiimidazole (CDI), dicyclohexyl carbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) can be employed. The activated ester or amide can be formed, depending in particular on the specific activating agent used, either in situ by contacting compound IV with the activating agent in the presence of compound III, or in a separate step prior to the reaction with compound III. It may be advantageous, especially in cases where DCC or EDC are used as activating agent, to include further additives in the activating reaction, such as hydroxybenzotriazole (HOBt), nitrophenol, pentafluorophenol, 2,4,5-trichlorophenol or N-hydroxysuccinimide. It may further be advantageous to prepare the activated ester or amide in the presence of a base, for example a tertiary amine. The activated ester or amide is either in situ or subsequently reacted with the amine of formula III to afford the amide of formula I. The reaction normally takes place in anhydrous inert solvents, such as chlorinated hydrocarbons, e.g. dichloromethane or dichloroethane, ethers, e.g. tetrahydrofuran or 1,4-dioxane or carboxamides, e.g. N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone. The reaction is ordinarily carried out at temperatures in the range from −20° C. to +25° C.




The compounds of formula II and their respective benzoic acid precursors of formula IV can be obtained by purchase or can be prepared by processes known in the art or disclosed in the literature, e.g. in WO 2000/020408, WO 2001/040176, WO 96/30368, WO 97/30986, DE 4428000, WO 2002/048121 and WO 98/12192.
The 4-amino-1,2,5-oxadiazole compounds of the formula III are either commercially available or are obtainable according to methods known from the literature. For example, 3-alkyl-4-amino-1,2,5-oxadiazoles can be prepared from β-ketoesters pursuant to a procedure described in Russian Chemical Bulletin, Int. Ed., 54(4), 1032-1037 (2005), as depicted in Scheme 3.




As shown in Scheme 4, the compounds of the formula III, where R is halogen, can be prepared from commercially available 3,4-diamino-1,2,5-oxadiazole according to procedures described in the literature, e.g. by the Sandmeyer-type reaction disclosed in Heteroatom Chemistry, 15(3), 199-207 (2004).




As shown in Scheme 5, the compounds of the formula III, where R is a nucleophilic residue, can be prepared by introducing the nucleophilic residue via the substitution of a leaving group L, e.g. halogene, in the 4-position of the 1,2,5-oxadiazoles compounds of formula V in accordance to precedures disclosed, for example in Journal of Chemical Research, Synopses (6), 190 (1985), in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (9), 2086-8 (1986) or in Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya), 53(3), 596-614 (2004).




As a rule, the compounds of formula I including their stereoisomers, salts, tautomers and N-oxides, and their precursors in the synthesis process, can be prepared by the methods described above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds I or the respective precursor or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of formula I by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or trituration.
The compounds I and their agriculturally suitable salts are useful as herbicides. They are useful as such or as an appropriately formulated composition. The herbicidal compositions comprising the compound I, in particular the preferred aspects thereof, control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and weed grasses in crops such as wheat, rice, corn, soybeans and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
Depending on the application method in question, the compounds I, in particular the preferred aspects thereof, or compositions comprising them can additionally be employed in a further number of crop plants for eliminating unwanted plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays. 
The term “crop plants” also includes plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mutations or natural recombination (i.e. reassembly of the genetic information). Here, in general, one or more genes are integrated into the genetic material of the plant to improve the properties of the plant.
Accordingly, the term “crop plants” also includes plants which, by breeding and genetic engineering, have acquired tolerance to certain classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as, for example, sulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659) or imidazolinones (see, for example, U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors, such as, for example, glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors, such as, for example, glufosinate (see, for example, EP-A-0242236, EP-A-242246), or oxynil herbicides (see, for example, U.S. Pat. No. 5,559,024).
Numerous crop plants, for example Clearfield® oilseed rape, tolerant to imidazolinones, for example imazamox, have been generated with the aid of classic breeding methods (mutagenesis). Crop plants such as soybeans, cotton, corn, beet and oilseed rape, resistant to glyphosate or glufosinate, which are available under the tradenames RoundupReady® (glyphosate) and Liberty Link® (glufosinate) have been generated with the aid of genetic engineering methods.
Accordingly, the term “crop plants” also includes plants which, with the aid of genetic engineering, produce one or more toxins, for example those of the bacterial strain Bacillus ssp. Toxins which are produced by such genetically modified plants include, for example, insecticidal proteins of Bacillus spp., in particular B. thuringiensis, such as the endotoxins Cry1Ab, Cry1Ac, Cry1F, CrylFa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs), for example VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins of nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp.; toxins of animal organisms, for example wasp, spider or scorpion toxins; fungal toxins, for example from Streptomycetes; plant lectins, for example from peas or barley; agglutinins; proteinase inhibitors, for example trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors, ribosome-inactivating proteins (RIPs), for example ricin, corn-RIP, abrin, luffin, saporin or bryodin; steroid-metabolizing enzymes, for example 3-hydroxysteroid oxidase, ecdysteroid-IDP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase; ion channel blockers, for example inhibitors of sodium channels or calcium channels; juvenile hormone esterase; receptors of the diuretic hormone (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the plants, these toxins may also be produced as pretoxins, hybrid proteins or truncated or otherwise modified proteins. Hybrid proteins are characterized by a novel combination of different protein domains (see, for example, WO 2002/015701). Further examples of such toxins or genetically modified plants which produce these toxins are disclosed in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 and WO 03/052073. The methods for producing these genetically modified plants are known to the person skilled in the art and disclosed, for example, in the publications mentioned above. Numerous of the toxins mentioned above bestow, upon the plants by which they are produced, tolerance to pests from all taxonomic classes of arthropods, in particular to beetles (Coeleropta), dipterans (Diptera) and butterflies (Lepidoptera) and to nematodes (Nematoda).
Genetically modified plants which produce one or more genes coding for insecticidal toxins are described, for example, in the publications mentioned above, and some of them are commercially available, such as, for example, YieldGard® (corn varieties producing the toxin Cry1Ab), YieldGard® Plus (corn varieties which produce the toxins Cry1Ab and Cry3Bb1), Starlink® (corn varieties which produce the toxin Cry9c), Herculex® RW (corn varieties which produce the toxins Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton varieties which produce the toxin Cry1Ac), Bollgard® I (cotton varieties which produce the toxin Cry1Ac), Bollgard® II (cotton varieties which produce the toxins Cry1Ac and Cry2Ab2); VIPCOT® (cotton varieties which produce a VIP toxin); NewLeaf® (potato varieties which produce the toxin Cry3A); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (for example Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France (corn varieties which produce the toxin Cry1Ab and the PAT enzyme), MIR604 from Syngenta Seeds SAS, France (corn varieties which produce a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn varieties which produce the toxin Cry3Bb1), IPC 531 from Monsanto Europe S.A., Belgium (cotton varieties which produce a modified version of the toxin Cry1Ac) and 1507 from Pioneer Overseas Corporation, Belgium (corn varieties which produce the toxin Cry1F and the PAT enzyme).
Accordingly, the term “crop plants” also includes plants which, with the aid of genetic engineering, produce one or more proteins which are more robust or have increased resistance to bacterial, viral or fungal pathogens, such as, for example, pathogenesis-related proteins (PR proteins, see EP-A 0 392 225), resistance proteins (for example potato varieties producing two resistance genes against Phytophthora infestans from the wild Mexican potato Solanum bulbocastanum) or T4 lysozyme (for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora).
Accordingly, the term “crop plants” also includes plants whose productivity has been improved with the aid of genetic engineering methods, for example by enhancing the potential yield (for example biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.
The term “crop plants” also includes plants whose ingredients have been modified with the aid of genetic engineering methods in particular for improving human or animal diet, for example by oil plants producing health-promoting long-chain omega 3 fatty acids or monounsaturated omega 9 fatty acids (for example Nexera® oilseed rape).
The term “crop plants” also includes plants which have been modified with the aid of genetic engineering methods for improving the production of raw materials, for example by increasing the amylopectin content of potatoes (Amflora® potato).
Furthermore, it has been found that the compounds of the formula I are also suitable for the defoliation and/or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable. In this regard, there have been found compositions for the desiccation and/or defoliation of plants, processes for preparing these compositions and methods for desiccating and/or defoliating plants using the compounds of the formula I.
As desiccants, the compounds of the formula I are particularly suitable for desiccating the above-ground parts of crop plants such as potato, oilseed rape, sunflower and soybean, but also cereals. This makes possible the fully mechanical harvesting of these important crop plants.
Also of economic interest is to facilitate harvesting, which is made possible by concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives and other species and varieties of pomaceous fruit, stone fruit and nuts. The same mechanism, i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the readily controllable defoliation of useful plants, in particular cotton.
Moreover, a shortening of the time interval in which the individual cotton plants mature leads to an increased fiber quality after harvesting.
The compounds I, or the herbicidal compositions comprising the compounds I, can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading, watering or treatment of the seed or mixing with the seed. The use forms depend on the intended purpose; in each case, they should ensure the finest possible distribution of the active ingredients according to the invention.
The herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I, and auxiliaries which are customary for the formulation of crop protection agents.
Examples of auxiliaries customary for the formulation of crop protection agents are inert auxiliaries, solid carriers, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, if appropriate colorants and, for seed formulations, adhesives.
Examples of thickeners (i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion) are polysaccharides, such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), and also organic and inorganic sheet minerals, such as Attaclay® (from Engelhardt).
Examples of antifoams are silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
Bactericides can be added for stabilizing the aqueous herbicidal formulation. Examples of bactericides are bactericides based on diclorophen and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas), and also isothiazolinone derivates, such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS from Thor Chemie).
Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
Examples of colorants are both sparingly water-soluble pigments and water-soluble dyes. Examples which may be mentioned are the dyes known under the names Rhodamin B, C.I. Pigment Red 112 and C.I. Solvent Red 1, and also pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
Suitable inert auxiliaries are, for example, the following:
mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone, and water.
Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants and also emulsifiers) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids (e.g. Borrespers-types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, Lupamine types), polyethyleneimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.
Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the compounds of the formula I or Ia, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is also possible to prepare concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
The concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The formulations or ready-to-use preparations may also comprise acids, bases or buffer systems, suitable examples being phosphoric acid or sulfuric acid, or urea or ammonia.
The compounds I of the invention can for example be formulated as follows:
1. Products for Dilution with Water
A Water-Soluble Concentrates
10 parts by weight of active compound are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other adjuvants are added. The active compound dissolves upon dilution with water. This gives a formulation with an active compound content of 10% by weight.
B Dispersible Concentrates
20 parts by weight of active compound are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.
C Emulsifiable Concentrates
15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The formulation has an active compound content of 15% by weight.
D Emulsions
25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.
E Suspensions
In an agitated ball mill, 20 parts by weight of active compound are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.
F Water-Dispersible Granules and Water-Soluble Granules
50 parts by weight of active compound are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.
G Water-Dispersible Powders and Water-Soluble Powders
75 parts by weight of active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.
H Gel Formulations
In a ball mill, 20 parts by weight of active compound, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or of an organic solvent are ground to give a fine suspension. Dilution with water gives a stable suspension with active compound content of 20% by weight.
2. Products to be Applied Undiluted
I Dusts
5 parts by weight of active compound are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dusting powder with an active compound content of 5% by weight.
J Granules (GR, FG, GG, MG)
0.5 parts by weight of active compound are ground finely and associated with 99.5 parts by weight of carriers. Current methods here are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted with an active compound content of 0.5% by weight.
K ULV Solutions (UL)
10 parts by weight of active compound are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted with an active compound content of 10% by weight.
The compounds I or the herbicidal compositions comprising them can be applied pre- or post-emergence, or together with the seed of a crop plant. It is also possible to apply the herbicidal compositions or active compounds by applying seed, pretreated with the herbicidal compositions or active compounds, of a crop plant. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
In a further embodiment, the compounds of the formula I or the herbicidal compositions can be applied by treating seed.
The treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of the formula I according to the invention or the compositions prepared therefrom. Here, the herbicidal compositions can be applied diluted or undiluted.
The term seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, cuttings and similar forms. Here, preferably, the term seed describes corns and seeds.
The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
The rates of application of active compound are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage. To treat the seed, the compounds I are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
It may also be advantageous to use the compounds of the formula I in combination with safeners. Safeners are chemical compounds which prevent or reduce damage to useful plants without substantially affecting the herbicidal action of the compounds of the formula I on unwanted plants. They can be used both before sowing (for example in the treatment of seed, or on cuttings or seedlings) and before or after the emergence of the useful plant. The safeners and the compounds of the formula I can be used simultaneously or in succession. Suitable safeners are, for example, (quinolin-8-oxy)acetic acids, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acids, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamides, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazolecarboxylic acids, phosphorothiolates and O-phenyl N-alkylcarbamates and their agriculturally useful salts and, provided that they have an acid function, their agriculturally useful derivatives, such as amides, esters and thioesters.
To broaden the activity spectrum and to obtain synergistic effects, the compounds of the formula I can be mixed and jointly applied with numerous representatives of other herbicidal or growth-regulating groups of active compounds or with safeners. Suitable mixing partners are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/heteroaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivates, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenyl-propionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils and also phenylpyrazolines and isoxazolines and their derivatives.
Moreover, it may be useful to apply the compounds I alone or in combination with other herbicides or else also mixed with further crop protection agents, jointly, for example with compositions for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for alleviating nutritional and trace element deficiencies. Other additives such as nonphytotoxic oils and oil concentrates may also be added.
Examples of herbicides which can be used in combination with the pyridine compounds of the formula I according to the present invention are:
b1) from the group of the lipid biosynthesis inhibitors:
alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
b2) from the group of the ALS inhibitors:
amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;
b3) from the group of the photosynthesis inhibitors:
ametryn, amicarbazone, atrazine, bentazone, bentazone-sodium, bromacil, bromofenoxim, bromoxynil and its salts and esters, chlorobromuron, chloridazone, chlorotoluron, chloroxuron, cyanazine, desmedipham, desmetryn, dimefuron, dimethametryn, diquat, diquat-dibromide, diuron, fluometuron, hexazinone, ioxynil and its salts and esters, isoproturon, isouron, karbutilate, lenacil, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, metribuzin, monolinuron, neburon, paraquat, paraquat-dichloride, paraquat-dimetilsulfate, pentanochlor, phenmedipham, phenmedipham-ethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thidiazuron and trietazine;
b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:
acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, 2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluoro-N-[(isopropyl)-methylsulfamoyl]benzamide (H-1; CAS 372137-35-4), ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (H-2; CAS 353292-31-6), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (H-3; CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (H-4; CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (H-5; CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (H-6; CAS 45100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione, 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione, 2-(2,2,7-Trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione and 1-Methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione;
b5) from the group of the bleacher herbicides:
aclonifen, amitrol, beflubutamid, benzobicyclon, benzofenap, clomazone, diflufenican, fluridone, flurochloridone, flurtamone, isoxaflutole, mesotrione, norflurazon, picolinafen, pyrasulfutole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one (H-7; CAS 352010-68-5) and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (H-8; CAS 180608-33-7);
b6) from the group of the EPSP synthase inhibitors:
glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate);
b7) from the group of the glutamine synthase inhibitors:
bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium;
b8) from the group of the DHP synthase inhibitors:
asulam;
b9) from the group of the mitose inhibitors:
amiprophos, amiprophos-methyl, benfluralin, butamiphos, butralin, carbetamide, chlorpropham, chlorthal, chlorthal-dimethyl, dinitramine, dithiopyr, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, propham, propyzamide, tebutam, thiazopyr and trifluralin;
b10) from the group of the VLCFA inhibitors:
acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethanamid, dimethenamid-P, diphenamid, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, metolachlor-S, naproanilide, napropamide, pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone (KIH-485) and thenylchlor;
Compounds of the formula 2:




in which the variables have the following meanings:

    Y is phenyl or 5- or 6-membered heteroaryl as defined at the outset, which radicals may be substituted by one to three groups Raa; R21, R22, R23, R24 are hydrogen, halogen or C1-C4-alkyl; X is O or NH; N is 0 or 1.


Compounds of the formula 2 have in particular the following meanings:
Y is




where # denotes the bond to the skeleton of the molecule; and
R21, R22, R23, R24 are hydrogen, Cl, F or CH3; R25 is halogen, C1-C4-alkyl or C1-C4-haloalkyl; R26 is C1-C4-alkyl; R27 is halogen, C1-C4-alkoxy or C1-C4-haloalkoxy; R28 is hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-haloalkoxy; M is 0, 1, 2 or 3; X is oxygen; N is 0 or 1.
Preferred compounds of the formula 2 have the following meanings:
Y is




R21 is H; R22, R23 are F; R24 is hydrogen or F; X is oxygen; N is 0 or 1.
Particularly preferred compounds of the formula 2 are:
3-[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethane-sulfonyl]-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-1); 3-{[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]fluoromethanesulfonyl}-5,5-dimethyl-4,5-dihydroisoxazole (2-2); 4-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonylmethyl)-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-3); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)fluoromethyl]-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-4); 4-(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonylmethyl)-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-5); 3-{[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]difluoromethanesulfonyl}-5,5-dimethyl-4,5-dihydroisoxazole (2-6); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)difluoromethyl]-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-7); 3-{[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]difluoromethanesulfonyl}-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-8); 4-[difluoro-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)methyl]-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-9);
b11) from the group of the cellulose biosynthesis inhibitors:
chlorthiamid, dichlobenil, flupoxam and isoxaben;
b12) from the group of the decoupler herbicides:
dinoseb, dinoterb and DNOC and its salts;
b13) from the group of the auxin herbicides:
2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, and 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (H-9; CAS 858956-08-8) and its salts and esters;
b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;
b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (H-10; CAS 499223-49-3) and its salts and esters.
Examples of preferred safeners C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (H-11; MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (H-12; R-29148, CAS 52836-31-4).
The active compounds of groups b1) to b15) and the safeners C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart, 1995. Further herbicidally active compounds are known from WO 96/26202, WO 97/41116, WO 97/41117, WO 97/41118, WO 01/83459 and WO 2008/074991 and from W. Kramer et al. (ed.) “Modern Crop Protection Compounds”, Vol. 1, Wiley VCH, 2007 and the literature quoted therein.
The invention also relates to compositions in the form of a crop protection composition formulated as a 1-component composition comprising an active compound combination comprising at least one pyridine compound of the formula I and at least one further active compound, preferably selected from the active compounds of groups b1 to b15, and at least one solid or liquid carrier and/or one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions. The invention also relates to compositions in the form of a crop protection composition formulated as a 2-component composition comprising a first component comprising at least one pyridine compound of the formula I, a solid or liquid carrier and/or one or more surfactants and a second component comprising at least one further active compound selected from the active compounds of groups b1 to b15, a solid or liquid carrier and/or one or more surfactants, where additionally both components may also comprise further auxiliaries customary for crop protection compositions.
In binary compositions comprising at least one compound of the formula I as component A and at least one herbicide B, the weight ratio of the active compounds A:B is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.
In binary compositions comprising at least one compound of the formula I as component A and at least one safener C, the weight ratio of the active compounds A:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.
In ternary compositions comprising both at least one compound of the formula I as component A, at least one herbicide B and at least one safener C, the relative parts by weight of the components A:B are generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1; the weight ratio of the components A:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1; and the weight ratio of the components B:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1. Preferably, the weight ratio of the components A+B to the component C is in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.
Examples of particularly preferred compositions according to the invention comprising in each case one individualized compound of the formula I and one mixing partner or a mixing partner combination are given in Table B below.
A further aspect of the invention relates to the compositions B-1 to B-1236 listed in Table B below, where in each case one row of Table B corresponds to a herbicidal composition comprising one of the compounds of the formula I individualized in the above description (component 1) and the further active compound from groups b1) to b15) and/or safener C stated in each case in the row in question (component 2). The active compounds in the compositions described are in each case preferably present in synergistically effective amounts.










TABLE B







Herbicide(s) B
Safener C


















B-1
clodinafop-propargyl
—


B-2
cycloxydim
—


B-3
cyhalofop-butyl
—


B-4
fenoxaprop-P-ethyl
—


B-5
pinoxaden
—


B-6
profoxydim
—


B-7
tepraloxydim
—


B-8
tralkoxydim
—


B-9
esprocarb
—


B-10
prosulfocarb
—


B-11
thiobencarb
—


B-12
triallate
—


B-13
bensulfuron-methyl
—


B-14
bispyribac-sodium
—


B-15
cyclosulfamuron
—


B-16
flumetsulam
—


B-17
flupyrsulfuron-methyl-sodium
—


B-18
foramsulfuron
—


B-19
imazamox
—


B-20
imazapic
—


B-21
imazapyr
—


B-22
imazaquin
—


B-23
imazethapyr
—


B-24
imazosulfuron
—


B-25
iodosulfuron-methyl-sodium
—


B-26
mesosulfuron
—


B-27
nicosulfuron
—


B-28
penoxsulam
—


B-29
propoxycarbazone-sodium
—


B-30
pyrazosulfuron-ethyl
—


B-31
pyroxsulam
—


B-32
rimsulfuron
—


B-33
sulfosulfuron
—


B-34
thiencarbazone-methyl
—


B-35
tritosulfuron
—


B-36
2,4-D and its salts and esters
—


B-37
aminopyralid and its salts and esters
—


B-38
clopyralid and its salts and esters
—


B-39
dicamba and its salts and esters
—


B-40
fluroxypyr-meptyl
—


B-41
quinclorac
—


B-42
quinmerac
—


B-43
H-9
—


B-44
diflufenzopyr
—


B-45
diflufenzopyr-sodium
—


B-46
clomazone
—


B-47
diflufenican
—


B-48
fluorochloridone
—


B-49
isoxaflutol
—


B-50
mesotrione
—


B-51
picolinafen
—


B-52
sulcotrione
—


B-53
tefuryltrione
—


B-54
tembotrione
—


B-55
topramezone
—


B-56
H-7
—


B-57
atrazine
—


B-58
diuron
—


B-59
fluometuron
—


B-60
hexazinone
—


B-61
isoproturon
—


B-62
metribuzin
—


B-63
propanil
—


B-64
terbuthylazine
—


B-65
paraquat dichloride
—


B-66
flumioxazin
—


B-67
oxyfluorfen
—


B-68
saflufenacil
—


B-69
sulfentrazone
—


B-70
H-1
—


B-71
H-2
—


B-72
glyphosate
—


B-73
glyphosate-isopropylammonium
—


B-74
glyphosate-trimesium (sulfosate)
—


B-75
glufosinate
—


B-76
glufosinate-ammonium
—


B-77
pendimethalin
—


B-78
trifluralin
—


B-79
acetochlor
—


B-80
cafenstrole
—


B-81
dimethenamid-P
—


B-82
fentrazamide
—


B-83
flufenacet
—


B-84
mefenacet
—


B-85
metazachlor
—


B-86
metolachlor-S
—


B-87
pyroxasulfone
—


B-88
isoxaben
—


B-89
dymron
—


B-90
indanofan
—


B-91
oxaziclomefone
—


B-92
triaziflam
—


B-93
chlorotoluron
—


B-94
atrazine + H-1
—


B-95
atrazine + glyphosate
—


B-96
atrazine + mesotrione
—


B-97
atrazine + nicosulfuron
—


B-98
atrazine + tembotrione
—


B-99
atrazine + topramezone
—


B-100
clomazone + glyphosate
—


B-101
diflufenican + clodinafop-propargyl
—


B-102
diflufenican + fenoxaprop-P-ethyl
—


B-103
diflufenican + flupyrsulfuron-methyl-sodium
—


B-104
diflufenican + glyphosate
—


B-105
diflufenican + mesosulfuron-methyl
—


B-106
diflufenican + pinoxaden
—


B-107
diflufenican + pyroxsulam
—


B-108
flumetsulam + glyphosate
—


B-109
flumioxazin + glyphosate
—


B-110
imazapic + glyphosate
—


B-111
imazethapyr + glyphosate
—


B-112
isoxaflutol + H-1
—


B-113
isoxaflutol + glyphosate
—


B-114
metazachlor + H-1
—


B-115
metazachlor + glyphosate
—


B-116
metazachlor + mesotrione
—


B-117
metazachlor + nicosulfuron
—


B-118
metazachlor + terbuthylazine
—


B-119
metazachlor + topramezone
—


B-120
metribuzin + glyphosate
—


B-121
pendimethalin + H-1
—


B-122
pendimethalin + clodinafop-propargyl
—


B-123
pendimethalin + fenoxaprop-P-ethyl
—


B-124
pendimethalin + flupyrsulfuron-methyl-sodium
—


B-125
pendimethalin + glyphosate
—


B-126
pendimethalin + mesosulfuron-methyl
—


B-127
pendimethalin + mesotrione
—


B-128
pendimethalin + nicosulfuron
—


B-129
pendimethalin + pinoxaden
—


B-130
pendimethalin + pyroxsulam
—


B-131
pendimethalin + tembotrione
—


B-132
pendimethalin + topramezone
—


B-133
pyroxasulfone + tembotrione
—


B-134
pyroxasulfone + topramezone
—


B-135
sulfentrazone + glyphosate
—


B-136
terbuthylazine + H-1
—


B-137
terbuthylazine + foramsulfuron
—


B-138
terbuthylazine + glyphosate
—


B-139
terbuthylazine + mesotrione
—


B-140
terbuthylazine + nicosulfuron
—


B-141
terbuthylazine + tembotrione
—


B-142
terbuthylazine + topramezone
—


B-143
trifluralin + glyphosate
—


B-144
—
benoxacor


B-145
—
cloquintocet


B-146
—
cyprosulfamide


B-147
—
dichlormid


B-148
—
fenchlorazole


B-149
—
isoxadifen


B-150
—
mefenpyr


B-151
—
H-11


B-152
—
H-12


B-153
clodinafop-propargyl
benoxacor


B-154
cycloxydim
benoxacor


B-155
cyhalofop-butyl
benoxacor


B-156
fenoxaprop-P-ethyl
benoxacor


B-157
pinoxaden
benoxacor


B-158
profoxydim
benoxacor


B-159
tepraloxydim
benoxacor


B-160
tralkoxydim
benoxacor


B-161
esprocarb
benoxacor


B-162
prosulfocarb
benoxacor


B-163
thiobencarb
benoxacor


B-164
triallate
benoxacor


B-165
bensulfuron-methyl
benoxacor


B-166
bispyribac-sodium
benoxacor


B-167
cyclosulfamuron
benoxacor


B-168
flumetsulam
benoxacor


B-169
flupyrsulfuron-methyl-sodium
benoxacor


B-170
foramsulfuron
benoxacor


B-171
imazamox
benoxacor


B-172
imazapic
benoxacor


B-173
imazapyr
benoxacor


B-174
imazaquin
benoxacor


B-175
imazethapyr
benoxacor


B-176
imazosulfuron
benoxacor


B-177
iodosulfuron-methyl-sodium
benoxacor


B-178
mesosulfuron
benoxacor


B-179
nicosulfuron
benoxacor


B-180
penoxsulam
benoxacor


B-181
propoxycarbazone-sodium
benoxacor


B-182
pyrazosulfuron-ethyl
benoxacor


B-183
pyroxsulam
benoxacor


B-184
rimsulfuron
benoxacor


B-185
sulfosulfuron
benoxacor


B-186
thiencarbazone-methyl
benoxacor


B-187
tritosulfuron
benoxacor


B-188
2,4-D and its salts and esters
benoxacor


B-189
aminopyralid and its salts and esters
benoxacor


B-190
clopyralid and its salts and esters
benoxacor


B-191
dicamba and its salts and esters
benoxacor


B-192
fluroxypyr-meptyl
benoxacor


B-193
quinclorac
benoxacor


B-194
quinmerac
benoxacor


B-195
H-9
benoxacor


B-196
diflufenzopyr
benoxacor


B-197
diflufenzopyr-sodium
benoxacor


B-198
clomazone
benoxacor


B-199
diflufenican
benoxacor


B-200
fluorochloridone
benoxacor


B-201
isoxaflutol
benoxacor


B-202
mesotrione
benoxacor


B-203
picolinafen
benoxacor


B-204
sulcotrione
benoxacor


B-205
tefuryltrione
benoxacor


B-206
tembotrione
benoxacor


B-207
topramezone
benoxacor


B-208
H-7
benoxacor


B-209
atrazine
benoxacor


B-210
diuron
benoxacor


B-211
fluometuron
benoxacor


B-212
hexazinone
benoxacor


B-213
isoproturon
benoxacor


B-214
metribuzin
benoxacor


B-215
propanil
benoxacor


B-216
terbuthylazine
benoxacor


B-217
paraquat dichloride
benoxacor


B-218
flumioxazin
benoxacor


B-219
oxyfluorfen
benoxacor


B-220
saflufenacil
benoxacor


B-221
sulfentrazone
benoxacor


B-222
H-1
benoxacor


B-223
H-2
benoxacor


B-224
glyphosate
benoxacor


B-225
glyphosate-isopropylammonium
benoxacor


B-226
glyphosate-trimesium (sulfosate)
benoxacor


B-227
glufosinate
benoxacor


B-228
glufosinate-ammonium
benoxacor


B-229
pendimethalin
benoxacor


B-230
trifluralin
benoxacor


B-231
acetochlor
benoxacor


B-232
cafenstrole
benoxacor


B-233
dimethenamid-P
benoxacor


B-234
fentrazamide
benoxacor


B-235
flufenacet
benoxacor


B-236
mefenacet
benoxacor


B-237
metazachlor
benoxacor


B-238
metolachlor-S
benoxacor


B-239
pyroxasulfone
benoxacor


B-240
isoxaben
benoxacor


B-241
dymron
benoxacor


B-242
indanofan
benoxacor


B-243
oxaziclomefone
benoxacor


B-244
triaziflam
benoxacor


B-245
atrazine + H-1
benoxacor


B-246
atrazine + glyphosate
benoxacor


B-247
atrazine + mesotrione
benoxacor


B-248
atrazine + nicosulfuron
benoxacor


B-249
atrazine + tembotrione
benoxacor


B-250
atrazine + topramezone
benoxacor


B-251
clomazone + glyphosate
benoxacor


B-252
diflufenican + clodinafop-propargyl
benoxacor


B-253
diflufenican + fenoxaprop-P-ethyl
benoxacor


B-254
diflufenican + flupyrsulfuron-methyl-sodium
benoxacor


B-255
diflufenican + glyphosate
benoxacor


B-256
diflufenican + mesosulfuron-methyl
benoxacor


B-257
diflufenican + pinoxaden
benoxacor


B-258
diflufenican + pyroxsulam
benoxacor


B-259
flumetsulam + glyphosate
benoxacor


B-260
flumioxazin + glyphosate
benoxacor


B-261
imazapic + glyphosate
benoxacor


B-262
imazethapyr + glyphosate
benoxacor


B-263
isoxaflutol + H-1
benoxacor


B-264
isoxaflutol + glyphosate
benoxacor


B-265
metazachlor + H-1
benoxacor


B-266
metazachlor + glyphosate
benoxacor


B-267
metazachlor + mesotrione
benoxacor


B-268
metazachlor + nicosulfuron
benoxacor


B-269
metazachlor + terbuthylazine
benoxacor


B-270
metazachlor + topramezone
benoxacor


B-271
metribuzin + glyphosate
benoxacor


B-272
pendimethalin + H-1
benoxacor


B-273
pendimethalin + clodinafop-propargyl
benoxacor


B-274
pendimethalin + fenoxaprop-P-ethyl
benoxacor


B-275
pendimethalin + flupyrsulfuron-methyl-sodium
benoxacor


B-276
pendimethalin + glyphosate
benoxacor


B-277
pendimethalin + mesosulfuron-methyl
benoxacor


B-278
pendimethalin + mesotrione
benoxacor


B-279
pendimethalin + nicosulfuron
benoxacor


B-280
pendimethalin + pinoxaden
benoxacor


B-281
pendimethalin + pyroxsulam
benoxacor


B-282
pendimethalin + tembotrione
benoxacor


B-283
pendimethalin + topramezone
benoxacor


B-284
pyroxasulfone + tembotrione
benoxacor


B-285
pyroxasulfone + topramezone
benoxacor


B-286
sulfentrazone + glyphosate
benoxacor


B-287
terbuthylazine + H-1
benoxacor


B-288
terbuthylazine + foramsulfuron
benoxacor


B-289
terbuthylazine + glyphosate
benoxacor


B-290
terbuthylazine + mesotrione
benoxacor


B-291
terbuthylazine + nicosulfuron
benoxacor


B-292
terbuthylazine + tembotrione
benoxacor


B-293
terbuthylazine + topramezone
benoxacor


B-294
trifluralin + glyphosate
benoxacor


B-295
clodinafop-propargyl
cloquintocet


B-296
cycloxydim
cloquintocet


B-297
cyhalofop-butyl
cloquintocet


B-298
fenoxaprop-P-ethyl
cloquintocet


B-299
pinoxaden
cloquintocet


B-300
profoxydim
cloquintocet


B-301
tepraloxydim
cloquintocet


B-302
tralkoxydim
cloquintocet


B-303
esprocarb
cloquintocet


B-304
prosulfocarb
cloquintocet


B-305
thiobencarb
cloquintocet


B-306
triallate
cloquintocet


B-307
bensulfuron-methyl
cloquintocet


B-308
bispyribac-sodium
cloquintocet


B-309
cyclosulfamuron
cloquintocet


B-310
flumetsulam
cloquintocet


B-311
flupyrsulfuron-methyl-sodium
cloquintocet


B-312
foramsulfuron
cloquintocet


B-313
imazamox
cloquintocet


B-314
imazapic
cloquintocet


B-315
imazapyr
cloquintocet


B-316
imazaquin
cloquintocet


B-317
imazethapyr
cloquintocet


B-318
imazosulfuron
cloquintocet


B-319
iodosulfuron-methyl-sodium
cloquintocet


B-320
mesosulfuron
cloquintocet


B-321
nicosulfuron
cloquintocet


B-322
penoxsulam
cloquintocet


B-323
propoxycarbazone-sodium
cloquintocet


B-324
pyrazosulfuron-ethyl
cloquintocet


B-325
pyroxsulam
cloquintocet


B-326
rimsulfuron
cloquintocet


B-327
sulfosulfuron
cloquintocet


B-328
thiencarbazone-methyl
cloquintocet


B-329
tritosulfuron
cloquintocet


B-330
2,4-D and its salts and esters
cloquintocet


B-331
aminopyralid and its salts and esters
cloquintocet


B-332
clopyralid and its salts and esters
cloquintocet


B-333
dicamba and its salts and esters
cloquintocet


B-334
fluroxypyr-meptyl
cloquintocet


B-335
quinclorac
cloquintocet


B-336
quinmerac
cloquintocet


B-337
H-9
cloquintocet


B-338
diflufenzopyr
cloquintocet


B-339
diflufenzopyr-sodium
cloquintocet


B-340
clomazone
cloquintocet


B-341
diflufenican
cloquintocet


B-342
fluorochloridone
cloquintocet


B-343
isoxaflutol
cloquintocet


B-344
mesotrione
cloquintocet


B-345
picolinafen
cloquintocet


B-346
sulcotrione
cloquintocet


B-347
tefuryltrione
cloquintocet


B-348
tembotrione
cloquintocet


B-349
topramezone
cloquintocet


B-350
H-7
cloquintocet


B-351
atrazine
cloquintocet


B-352
diuron
cloquintocet


B-353
fluometuron
cloquintocet


B-354
hexazinone
cloquintocet


B-355
isoproturon
cloquintocet


B-356
metribuzin
cloquintocet


B-357
propanil
cloquintocet


B-358
terbuthylazine
cloquintocet


B-359
paraquat dichloride
cloquintocet


B-360
flumioxazin
cloquintocet


B-361
oxyfluorfen
cloquintocet


B-362
saflufenacil
cloquintocet


B-363
sulfentrazone
cloquintocet


B-364
H-1
cloquintocet


B-365
H-2
cloquintocet


B-366
glyphosate
cloquintocet


B-367
glyphosate-isopropylammonium
cloquintocet


B-368
glyphosate-trimesium (sulfosate)
cloquintocet


B-369
glufosinate
cloquintocet


B-370
glufosinate-ammonium
cloquintocet


B-371
pendimethalin
cloquintocet


B-372
trifluralin
cloquintocet


B-373
acetochlor
cloquintocet


B-374
cafenstrole
cloquintocet


B-375
dimethenamid-P
cloquintocet


B-376
fentrazamide
cloquintocet


B-377
flufenacet
cloquintocet


B-378
mefenacet
cloquintocet


B-379
metazachlor
cloquintocet


B-380
metolachlor-S
cloquintocet


B-381
pyroxasulfone
cloquintocet


B-382
isoxaben
cloquintocet


B-383
dymron
cloquintocet


B-384
indanofan
cloquintocet


B-385
oxaziclomefone
cloquintocet


B-386
triaziflam
cloquintocet


B-387
atrazine + H-1
cloquintocet


B-388
atrazine + glyphosate
cloquintocet


B-389
atrazine + mesotrione
cloquintocet


B-390
atrazine + nicosulfuron
cloquintocet


B-391
atrazine + tembotrione
cloquintocet


B-392
atrazine + topramezone
cloquintocet


B-393
clomazone + glyphosate
cloquintocet


B-394
diflufenican + clodinafop-propargyl
cloquintocet


B-395
diflufenican + fenoxaprop-p-ethyl
cloquintocet


B-396
diflufenican + flupyrsulfuron-methyl-sodium
cloquintocet


B-397
diflufenican + glyphosate
cloquintocet


B-398
diflufenican + mesosulfuron-methyl
cloquintocet


B-399
diflufenican + pinoxaden
cloquintocet


B-400
diflufenican + pyroxsulam
cloquintocet


B-401
flumetsulam + glyphosate
cloquintocet


B-402
flumioxazin + glyphosate
cloquintocet


B-403
imazapic + glyphosate
cloquintocet


B-404
imazethapyr + glyphosate
cloquintocet


B-405
isoxaflutol + H-1
cloquintocet


B-406
isoxaflutol + glyphosate
cloquintocet


B-407
metazachlor + H-1
cloquintocet


B-408
metazachlor + glyphosate
cloquintocet


B-409
metazachlor + mesotrione
cloquintocet


B-410
metazachlor + nicosulfuron
cloquintocet


B-411
metazachlor + terbuthylazine
cloquintocet


B-412
metazachlor + topramezone
cloquintocet


B-413
metribuzin + glyphosate
cloquintocet


B-414
pendimethalin + H-1
cloquintocet


B-415
pendimethalin + clodinafop-propargyl
cloquintocet


B-416
pendimethalin + fenoxaprop-P-ethyl
cloquintocet


B-417
pendimethalin + flupyrsulfuron-methyl-sodium
cloquintocet


B-418
pendimethalin + glyphosate
cloquintocet


B-419
pendimethalin + mesosulfuron-methyl
cloquintocet


B-420
pendimethalin + mesotrione
cloquintocet


B-421
pendimethalin + nicosulfuron
cloquintocet


B-422
pendimethalin + pinoxaden
cloquintocet


B-423
pendimethalin + pyroxsulam
cloquintocet


B-424
pendimethalin + tembotrione
cloquintocet


B-425
pendimethalin + topramezone
cloquintocet


B-426
pyroxasulfone + tembotrione
cloquintocet


B-427
pyroxasulfone + topramezone
cloquintocet


B-428
sulfentrazone + glyphosate
cloquintocet


B-429
terbuthylazine + H-1
cloquintocet


B-430
terbuthylazine + foramsulfuron
cloquintocet


B-431
terbuthylazine + glyphosate
cloquintocet


B-432
terbuthylazine + mesotrione
cloquintocet


B-433
terbuthylazine + nicosulfuron
cloquintocet


B-434
terbuthylazine + tembotrione
cloquintocet


B-435
terbuthylazine + topramezone
cloquintocet


B-436
trifluralin + glyphosate
cloquintocet


B-437
clodinafop-propargyl
dichlormid


B-438
cycloxydim
dichlormid


B-439
cyhalofop-butyl
dichlormid


B-440
fenoxaprop-P-ethyl
dichlormid


B-441
pinoxaden
dichlormid


B-442
profoxydim
dichlormid


B-443
tepraloxydim
dichlormid


B-444
tralkoxydim
dichlormid


B-445
esprocarb
dichlormid


B-446
prosulfocarb
dichlormid


B-447
thiobencarb
dichlormid


B-448
triallate
dichlormid


B-449
bensulfuron-methyl
dichlormid


B-450
bispyribac-sodium
dichlormid


B-451
cyclosulfamuron
dichlormid


B-452
flumetsulam
dichlormid


B-453
flupyrsulfuron-methyl-sodium
dichlormid


B-454
foramsulfuron
dichlormid


B-455
imazamox
dichlormid


B-456
imazapic
dichlormid


B-457
imazapyr
dichlormid


B-458
imazaquin
dichlormid


B-459
imazethapyr
dichlormid


B-460
imazosulfuron
dichlormid


B-461
iodosulfuron-methyl-sodium
dichlormid


B-462
mesosulfuron
dichlormid


B-463
nicosulfuron
dichlormid


B-464
penoxsulam
dichlormid


B-465
propoxycarbazone-sodium
dichlormid


B-466
pyrazosulfuron-ethyl
dichlormid


B-467
pyroxsulam
dichlormid


B-468
rimsulfuron
dichlormid


B-469
sulfosulfuron
dichlormid


B-470
thiencarbazone-methyl
dichlormid


B-471
tritosulfuron
dichlormid


B-472
2,4-D and its salts and esters
dichlormid


B-473
aminopyralid and its salts and esters
dichlormid


B-474
clopyralid and its salts and esters
dichlormid


B-475
dicamba and its salts and esters
dichlormid


B-476
fluroxypyr-meptyl
dichlormid


B-477
quinclorac
dichlormid


B-478
quinmerac
dichlormid


B-479
H-9
dichlormid


B-480
diflufenzopyr
dichlormid


B-481
diflufenzopyr-sodium
dichlormid


B-482
clomazone
dichlormid


B-483
diflufenican
dichlormid


B-484
fluorochloridone
dichlormid


B-485
isoxaflutol
dichlormid


B-486
mesotrione
dichlormid


B-487
picolinafen
dichlormid


B-488
sulcotrione
dichlormid


B-489
tefuryltrione
dichlormid


B-490
tembotrione
dichlormid


B-491
topramezone
dichlormid


B-492
H-7
dichlormid


B-493
atrazine
dichlormid


B-494
diuron
dichlormid


B-495
fluometuron
dichlormid


B-496
hexazinone
dichlormid


B-497
isoproturon
dichlormid


B-498
metribuzin
dichlormid


B-499
propanil
dichlormid


B-500
terbuthylazine
dichlormid


B-501
paraquat dichloride
dichlormid


B-502
flumioxazin
dichlormid


B-503
oxyfluorfen
dichlormid


B-504
saflufenacil
dichlormid


B-505
sulfentrazone
dichlormid


B-506
H-1
dichlormid


B-507
H-2
dichlormid


B-508
glyphosate
dichlormid


B-509
glyphosate-isopropylammonium
dichlormid


B-510
glyphosate-trimesium (sulfosate)
dichlormid


B-511
glufosinate
dichlormid


B-512
glufosinate-ammonium
dichlormid


B-513
pendimethalin
dichlormid


B-514
trifluralin
dichlormid


B-515
acetochlor
dichlormid


B-516
cafenstrole
dichlormid


B-517
dimethenamid-P
dichlormid


B-518
fentrazamide
dichlormid


B-519
flufenacet
dichlormid


B-520
mefenacet
dichlormid


B-521
metazachlor
dichlormid


B-522
metolachlor-S
dichlormid


B-523
pyroxasulfone
dichlormid


B-524
isoxaben
dichlormid


B-525
dymron
dichlormid


B-526
indanofan
dichlormid


B-527
oxaziclomefone
dichlormid


B-528
triaziflam
dichlormid


B-529
atrazine + H-1
dichlormid


B-530
atrazine + glyphosate
dichlormid


B-531
atrazine + mesotrione
dichlormid


B-532
atrazine + nicosulfuron
dichlormid


B-533
atrazine + tembotrione
dichlormid


B-534
atrazine + topramezone
dichlormid


B-535
clomazone + glyphosate
dichlormid


B-536
diflufenican + clodinafop-propargyl
dichlormid


B-537
diflufenican + fenoxaprop-p-ethyl
dichlormid


B-538
diflufenican + flupyrsulfuron-methyl-sodium
dichlormid


B-539
diflufenican + glyphosate
dichlormid


B-540
diflufenican + mesosulfuron-methyl
dichlormid


B-541
diflufenican + pinoxaden
dichlormid


B-542
diflufenican + pyroxsulam
dichlormid


B-543
flumetsulam + glyphosate
dichlormid


B-544
flumioxazin + glyphosate
dichlormid


B-545
imazapic + glyphosate
dichlormid


B-546
imazethapyr + glyphosate
dichlormid


B-547
isoxaflutol + H-1
dichlormid


B-548
isoxaflutol + glyphosate
dichlormid


B-549
metazachlor + H-1
dichlormid


B-550
metazachlor + glyphosate
dichlormid


B-551
metazachlor + mesotrione
dichlormid


B-552
metazachlor + nicosulfuron
dichlormid


B-553
metazachlor + terbuthylazine
dichlormid


B-554
metazachlor + topramezone
dichlormid


B-555
metribuzin + glyphosate
dichlormid


B-556
pendimethalin + H-1
dichlormid


B-557
pendimethalin + clodinafop-propargyl
dichlormid


B-558
pendimethalin + fenoxaprop-P-ethyl
dichlormid


B-559
pendimethalin + flupyrsulfuron-methyl-sodium
dichlormid


B-560
pendimethalin + glyphosate
dichlormid


B-561
pendimethalin + mesosulfuron-methyl
dichlormid


B-562
pendimethalin + mesotrione
dichlormid


B-563
pendimethalin + nicosulfuron
dichlormid


B-564
pendimethalin + pinoxaden
dichlormid


B-565
pendimethalin + pyroxsulam
dichlormid


B-566
pendimethalin + tembotrione
dichlormid


B-567
pendimethalin + topramezone
dichlormid


B-568
pyroxasulfone + tembotrione
dichlormid


B-569
pyroxasulfone + topramezone
dichlormid


B-570
sulfentrazone + glyphosate
dichlormid


B-571
terbuthylazine + H-1
dichlormid


B-572
terbuthylazine + foramsulfuron
dichlormid


B-573
terbuthylazine + glyphosate
dichlormid


B-574
terbuthylazine + mesotrione
dichlormid


B-575
terbuthylazine + nicosulfuron
dichlormid


B-576
terbuthylazine + tembotrione
dichlormid


B-577
terbuthylazine + topramezone
dichlormid


B-578
trifluralin + glyphosate
dichlormid


B-579
clodinafop-propargyl
fenchlorazole


B-580
cycloxydim
fenchlorazole


B-581
cyhalofop-butyl
fenchlorazole


B-582
fenoxaprop-P-ethyl
fenchlorazole


B-583
pinoxaden
fenchlorazole


B-584
profoxydim
fenchlorazole


B-585
tepraloxydim
fenchlorazole


B-586
tralkoxydim
fenchlorazole


B-587
esprocarb
fenchlorazole


B-588
prosulfocarb
fenchlorazole


B-589
thiobencarb
fenchlorazole


B-590
triallate
fenchlorazole


B-591
bensulfuron-methyl
fenchlorazole


B-592
bispyribac-sodium
fenchlorazole


B-593
cyclosulfamuron
fenchlorazole


B-594
flumetsulam
fenchlorazole


B-595
flupyrsulfuron-methyl-sodium
fenchlorazole


B-596
foramsulfuron
fenchlorazole


B-597
imazamox
fenchlorazole


B-598
imazapic
fenchlorazole


B-599
imazapyr
fenchlorazole


B-600
imazaquin
fenchlorazole


B-601
imazethapyr
fenchlorazole


B-602
imazosulfuron
fenchlorazole


B-603
iodosulfuron-methyl-sodium
fenchlorazole


B-604
mesosulfuron
fenchlorazole


B-605
nicosulfuron
fenchlorazole


B-606
penoxsulam
fenchlorazole


B-607
propoxycarbazone-sodium
fenchlorazole


B-608
pyrazosulfuron-ethyl
fenchlorazole


B-609
pyroxsulam
fenchlorazole


B-610
rimsulfuron
fenchlorazole


B-611
sulfosulfuron
fenchlorazole


B-612
thiencarbazone-methyl
fenchlorazole


B-613
tritosulfuron
fenchlorazole


B-614
2,4-D and its salts and esters
fenchlorazole


B-615
aminopyralid and its salts and esters
fenchlorazole


B-616
clopyralid and its salts and esters
fenchlorazole


B-617
dicamba and its salts and esters
fenchlorazole


B-618
fluroxypyr-meptyl
fenchlorazole


B-619
quinclorac
fenchlorazole


B-620
quinmerac
fenchlorazole


B-621
H-9
fenchlorazole


B-622
diflufenzopyr
fenchlorazole


B-623
diflufenzopyr-sodium
fenchlorazole


B-624
clomazone
fenchlorazole


B-625
diflufenican
fenchlorazole


B-626
fluorochloridone
fenchlorazole


B-627
isoxaflutol
fenchlorazole


B-628
mesotrione
fenchlorazole


B-629
picolinafen
fenchlorazole


B-630
sulcotrione
fenchlorazole


B-631
tefuryltrione
fenchlorazole


B-632
tembotrione
fenchlorazole


B-633
topramezone
fenchlorazole


B-634
H-7
fenchlorazole


B-635
atrazine
fenchlorazole


B-636
diuron
fenchlorazole


B-637
fluometuron
fenchlorazole


B-638
hexazinone
fenchlorazole


B-639
isoproturon
fenchlorazole


B-640
metribuzin
fenchlorazole


B-641
propanil
fenchlorazole


B-642
terbuthylazine
fenchlorazole


B-643
paraquat dichloride
fenchlorazole


B-644
flumioxazin
fenchlorazole


B-645
oxyfluorfen
fenchlorazole


B-646
saflufenacil
fenchlorazole


B-647
sulfentrazone
fenchlorazole


B-648
H-1
fenchlorazole


B-649
H-2
fenchlorazole


B-650
glyphosate
fenchlorazole


B-651
glyphosate-isopropylammonium
fenchlorazole


B-652
glyphosate-trimesium (sulfosate)
fenchlorazole


B-653
glufosinate
fenchlorazole


B-654
glufosinate-ammonium
fenchlorazole


B-655
pendimethalin
fenchlorazole


B-656
trifluralin
fenchlorazole


B-657
acetochlor
fenchlorazole


B-658
cafenstrole
fenchlorazole


B-659
dimethenamid-P
fenchlorazole


B-660
fentrazamide
fenchlorazole


B-661
flufenacet
fenchlorazole


B-662
mefenacet
fenchlorazole


B-663
metazachlor
fenchlorazole


B-664
metolachlor-S
fenchlorazole


B-665
pyroxasulfone
fenchlorazole


B-666
isoxaben
fenchlorazole


B-667
dymron
fenchlorazole


B-668
indanofan
fenchlorazole


B-669
oxaziclomefone
fenchlorazole


B-670
triaziflam
fenchlorazole


B-671
atrazine + H-1
fenchlorazole


B-672
atrazine + glyphosate
fenchlorazole


B-673
atrazine + mesotrione
fenchlorazole


B-674
atrazine + nicosulfuron
fenchlorazole


B-675
atrazine + tembotrione
fenchlorazole


B-676
atrazine + topramezone
fenchlorazole


B-677
clomazone + glyphosate
fenchlorazole


B-678
diflufenican + clodinafop-propargyl
fenchlorazole


B-679
diflufenican + fenoxaprop-P-ethyl
fenchlorazole


B-680
diflufenican + flupyrsulfuron-methyl-sodium
fenchlorazole


B-681
diflufenican + glyphosate
fenchlorazole


B-682
diflufenican + mesosulfuron-methyl
fenchlorazole


B-683
diflufenican + pinoxaden
fenchlorazole


B-684
diflufenican + pyroxsulam
fenchlorazole


B-685
flumetsulam + glyphosate
fenchlorazole


B-686
flumioxazin + glyphosate
fenchlorazole


B-687
imazapic + glyphosate
fenchlorazole


B-688
imazethapyr + glyphosate
fenchlorazole


B-689
isoxaflutol + H-1
fenchlorazole


B-690
isoxaflutol + glyphosate
fenchlorazole


B-691
metazachlor + H-1
fenchlorazole


B-692
metazachlor + glyphosate
fenchlorazole


B-693
metazachlor + mesotrione
fenchlorazole


B-694
metazachlor + nicosulfuron
fenchlorazole


B-695
metazachlor + terbuthylazine
fenchlorazole


B-696
metazachlor + topramezone
fenchlorazole


B-697
metribuzin + glyphosate
fenchlorazole


B-698
pendimethalin + H-1
fenchlorazole


B-699
pendimethalin + clodinafop-propargyl
fenchlorazole


B-700
pendimethalin + fenoxaprop-P-ethyl
fenchlorazole


B-701
pendimethalin + flupyrsulfuron-methyl-sodium
fenchlorazole


B-702
pendimethalin + glyphosate
fenchlorazole


B-703
pendimethalin + mesosulfuron-methyl
fenchlorazole


B-704
pendimethalin + mesotrione
fenchlorazole


B-705
pendimethalin + nicosulfuron
fenchlorazole


B-706
pendimethalin + pinoxaden
fenchlorazole


B-707
pendimethalin + pyroxsulam
fenchlorazole


B-708
pendimethalin + tembotrione
fenchlorazole


B-709
pendimethalin + topramezone
fenchlorazole


B-710
pyroxasulfone + tembotrione
fenchlorazole


B-711
pyroxasulfone + topramezone
fenchlorazole


B-712
sulfentrazone + glyphosate
fenchlorazole


B-713
terbuthylazine + H-1
fenchlorazole


B-714
terbuthylazine + foramsulfuron
fenchlorazole


B-715
terbuthylazine + glyphosate
fenchlorazole


B-716
terbuthylazine + mesotrione
fenchlorazole


B-717
terbuthylazine + nicosulfuron
fenchlorazole


B-718
terbuthylazine + tembotrione
fenchlorazole


B-719
terbuthylazine + topramezone
fenchlorazole


B-720
trifluralin + glyphosate
fenchlorazole


B-721
clodinafop-propargyl
isoxadifen


B-722
cycloxydim
isoxadifen


B-723
cyhalofop-butyl
isoxadifen


B-724
fenoxaprop-P-ethyl
isoxadifen


B-725
pinoxaden
isoxadifen


B-726
profoxydim
isoxadifen


B-727
tepraloxydim
isoxadifen


B-728
tralkoxydim
isoxadifen


B-729
esprocarb
isoxadifen


B-730
prosulfocarb
isoxadifen


B-731
thiobencarb
isoxadifen


B-732
triallate
isoxadifen


B-733
bensulfuron-methyl
isoxadifen


B-734
bispyribac-sodium
isoxadifen


B-735
cyclosulfamuron
isoxadifen


B-736
flumetsulam
isoxadifen


B-737
flupyrsulfuron-methyl-sodium
isoxadifen


B-738
foramsulfuron
isoxadifen


B-739
imazamox
isoxadifen


B-740
imazapic
isoxadifen


B-741
imazapyr
isoxadifen


B-742
imazaquin
isoxadifen


B-743
imazethapyr
isoxadifen


B-744
imazosulfuron
isoxadifen


B-745
iodosulfuron-methyl-sodium
isoxadifen


B-746
mesosulfuron
isoxadifen


B-747
nicosulfuron
isoxadifen


B-748
penoxsulam
isoxadifen


B-749
propoxycarbazone-sodium
isoxadifen


B-750
pyrazosulfuron-ethyl
isoxadifen


B-751
pyroxsulam
isoxadifen


B-752
rimsulfuron
isoxadifen


B-753
sulfosulfuron
isoxadifen


B-754
thiencarbazone-methyl
isoxadifen


B-755
tritosulfuron
isoxadifen


B-756
2,4-D and its salts and esters
isoxadifen


B-757
aminopyralid and its salts and esters
isoxadifen


B-758
clopyralid and its salts and esters
isoxadifen


B-759
dicamba and its salts and esters
isoxadifen


B-760
fluroxypyr-meptyl
isoxadifen


B-761
quinclorac
isoxadifen


B-762
quinmerac
isoxadifen


B-763
H-9
isoxadifen


B-764
diflufenzopyr
isoxadifen


B-765
diflufenzopyr-sodium
isoxadifen


B-766
clomazone
isoxadifen


B-767
diflufenican
isoxadifen


B-768
fluorochloridone
isoxadifen


B-769
isoxaflutol
isoxadifen


B-770
mesotrione
isoxadifen


B-771
picolinafen
isoxadifen


B-772
sulcotrione
isoxadifen


B-773
tefuryltrione
isoxadifen


B-774
tembotrione
isoxadifen


B-775
topramezone
isoxadifen


B-776
H-7
isoxadifen


B-777
atrazine
isoxadifen


B-778
diuron
isoxadifen


B-779
fluometuron
isoxadifen


B-780
hexazinone
isoxadifen


B-781
isoproturon
isoxadifen


B-782
metribuzin
isoxadifen


B-783
propanil
isoxadifen


B-784
terbuthylazine
isoxadifen


B-785
paraquat dichloride
isoxadifen


B-786
flumioxazin
isoxadifen


B-787
oxyfluorfen
isoxadifen


B-788
saflufenacil
isoxadifen


B-789
sulfentrazone
isoxadifen


B-790
H-1
isoxadifen


B-791
H-2
isoxadifen


B-792
glyphosate
isoxadifen


B-793
glyphosate-isopropylammonium
isoxadifen


B-794
glyphosate-trimesium (sulfosate)
isoxadifen


B-795
glufosinate
isoxadifen


B-796
glufosinate-ammonium
isoxadifen


B-797
pendimethalin
isoxadifen


B-798
trifluralin
isoxadifen


B-799
acetochlor
isoxadifen


B-800
cafenstrole
isoxadifen


B-801
dimethenamid-P
isoxadifen


B-802
fentrazamide
isoxadifen


B-803
flufenacet
isoxadifen


B-804
mefenacet
isoxadifen


B-805
metazachlor
isoxadifen


B-806
metolachlor-S
isoxadifen


B-807
pyroxasulfone
isoxadifen


B-808
isoxaben
isoxadifen


B-809
dymron
isoxadifen


B-810
indanofan
isoxadifen


B-811
oxaziclomefone
isoxadifen


B-812
triaziflam
isoxadifen


B-813
atrazine + H-1
isoxadifen


B-814
atrazine + glyphosate
isoxadifen


B-815
atrazine + mesotrione
isoxadifen


B-816
atrazine + nicosulfuron
isoxadifen


B-817
atrazine + tembotrione
isoxadifen


B-818
atrazine + topramezone
isoxadifen


B-819
clomazone + glyphosate
isoxadifen


B-820
diflufenican + clodinafop-propargyl
isoxadifen


B-821
diflufenican + fenoxaprop-P-ethyl
isoxadifen


B-822
diflufenican + flupyrsulfuron-methyl-sodium
isoxadifen


B-823
diflufenican + glyphosate
isoxadifen


B-824
diflufenican + mesosulfuron-methyl
isoxadifen


B-825
diflufenican + pinoxaden
isoxadifen


B-826
diflufenican + pyroxsulam
isoxadifen


B-827
flumetsulam + glyphosate
isoxadifen


B-828
flumioxazin + glyphosate
isoxadifen


B-829
imazapic + glyphosate
isoxadifen


B-830
imazethapyr + glyphosate
isoxadifen


B-831
isoxaflutol + H-1
isoxadifen


B-832
isoxaflutol + glyphosate
isoxadifen


B-833
metazachlor + H-1
isoxadifen


B-834
metazachlor + glyphosate
isoxadifen


B-835
metazachlor + mesotrione
isoxadifen


B-836
metazachlor + nicosulfuron
isoxadifen


B-837
metazachlor + terbuthylazine
isoxadifen


B-838
metazachlor + topramezone
isoxadifen


B-839
metribuzin + glyphosate
isoxadifen


B-840
pendimethalin + H-1
isoxadifen


B-841
pendimethalin + clodinafop-propargyl
isoxadifen


B-842
pendimethalin + fenoxaprop-P-ethyl
isoxadifen


B-843
pendimethalin + flupyrsulfuron-methyl-sodium
isoxadifen


B-844
pendimethalin + glyphosate
isoxadifen


B-845
pendimethalin + mesosulfuron-methyl
isoxadifen


B-846
pendimethalin + mesotrione
isoxadifen


B-847
pendimethalin + nicosulfuron
isoxadifen


B-848
pendimethalin + pinoxaden
isoxadifen


B-849
pendimethalin + pyroxsulam
isoxadifen


B-850
pendimethalin + tembotrione
isoxadifen


B-851
pendimethalin + topramezone
isoxadifen


B-852
pyroxasulfone + tembotrione
isoxadifen


B-853
pyroxasulfone + topramezone
isoxadifen


B-854
sulfentrazone + glyphosate
isoxadifen


B-855
terbuthylazine + H-1
isoxadifen


B-856
terbuthylazine + foramsulfuron
isoxadifen


B-857
terbuthylazine + glyphosate
isoxadifen


B-858
terbuthylazine + mesotrione
isoxadifen


B-859
terbuthylazine + nicosulfuron
isoxadifen


B-860
terbuthylazine + tembotrione
isoxadifen


B-861
terbuthylazine + topramezone
isoxadifen


B-862
trifluralin + glyphosate
isoxadifen


B-863
clodinafop-propargyl
mefenpyr


B-864
cycloxydim
mefenpyr


B-865
cyhalofop-butyl
mefenpyr


B-866
fenoxaprop-P-ethyl
mefenpyr


B-867
pinoxaden
mefenpyr


B-868
profoxydim
mefenpyr


B-869
tepraloxydim
mefenpyr


B-870
tralkoxydim
mefenpyr


B-871
esprocarb
mefenpyr


B-872
prosulfocarb
mefenpyr


B-873
thiobencarb
mefenpyr


B-874
triallate
mefenpyr


B-875
bensulfuron-methyl
mefenpyr


B-876
bispyribac-sodium
mefenpyr


B-877
cyclosulfamuron
mefenpyr


B-878
flumetsulam
mefenpyr


B-879
flupyrsulfuron-methyl-sodium
mefenpyr


B-880
foramsulfuron
mefenpyr


B-881
imazamox
mefenpyr


B-882
imazapic
mefenpyr


B-883
imazapyr
mefenpyr


B-884
imazaquin
mefenpyr


B-885
imazethapyr
mefenpyr


B-886
imazosulfuron
mefenpyr


B-887
iodosulfuron-methyl-sodium
mefenpyr


B-888
mesosulfuron
mefenpyr


B-889
nicosulfuron
mefenpyr


B-890
penoxsulam
mefenpyr


B-891
propoxycarbazone-sodium
mefenpyr


B-892
pyrazosulfuron-ethyl
mefenpyr


B-893
pyroxsulam
mefenpyr


B-894
rimsulfuron
mefenpyr


B-895
sulfosulfuron
mefenpyr


B-896
thiencarbazone-methyl
mefenpyr


B-897
tritosulfuron
mefenpyr


B-898
2,4-D and its salts and esters
mefenpyr


B-899
aminopyralid and its salts and esters
mefenpyr


B-900
clopyralid and its salts and esters
mefenpyr


B-901
dicamba and its salts and esters
mefenpyr


B-902
fluroxypyr-meptyl
mefenpyr


B-903
quinclorac
mefenpyr


B-904
quinmerac
mefenpyr


B-905
H-9
mefenpyr


B-906
diflufenzopyr
mefenpyr


B-907
diflufenzopyr-sodium
mefenpyr


B-908
clomazone
mefenpyr


B-909
diflufenican
mefenpyr


B-910
fluorochloridone
mefenpyr


B-911
isoxaflutol
mefenpyr


B-912
mesotrione
mefenpyr


B-913
picolinafen
mefenpyr


B-914
sulcotrione
mefenpyr


B-915
tefuryltrione
mefenpyr


B-916
tembotrione
mefenpyr


B-917
topramezone
mefenpyr


B-918
H-7
mefenpyr


B-919
atrazine
mefenpyr


B-920
diuron
mefenpyr


B-921
fluometuron
mefenpyr


B-922
hexazinone
mefenpyr


B-923
isoproturon
mefenpyr


B-924
metribuzin
mefenpyr


B-925
propanil
mefenpyr


B-926
terbuthylazine
mefenpyr


B-927
paraquat dichloride
mefenpyr


B-928
flumioxazin
mefenpyr


B-929
oxyfluorfen
mefenpyr


B-930
saflufenacil
mefenpyr


B-931
sulfentrazone
mefenpyr


B-932
H-1
mefenpyr


B-933
H-2
mefenpyr


B-934
glyphosate
mefenpyr


B-935
glyphosate-isopropylammonium
mefenpyr


B-936
glyphosate-trimesium (sulfosate)
mefenpyr


B-937
glufosinate
mefenpyr


B-938
glufosinate-ammonium
mefenpyr


B-939
pendimethalin
mefenpyr


B-940
trifluralin
mefenpyr


B-941
acetochlor
mefenpyr


B-942
cafenstrole
mefenpyr


B-943
dimethenamid-P
mefenpyr


B-944
fentrazamide
mefenpyr


B-945
flufenacet
mefenpyr


B-946
mefenacet
mefenpyr


B-947
metazachlor
mefenpyr


B-948
metolachlor-S
mefenpyr


B-949
pyroxasulfone
mefenpyr


B-950
isoxaben
mefenpyr


B-951
dymron
mefenpyr


B-952
indanofan
mefenpyr


B-953
oxaziclomefone
mefenpyr


B-954
triaziflam
mefenpyr


B-955
atrazine + H-1
mefenpyr


B-956
atrazine + glyphosate
mefenpyr


B-957
atrazine + mesotrione
mefenpyr


B-958
atrazine + nicosulfuron
mefenpyr


B-959
atrazine + tembotrione
mefenpyr


B-960
atrazine + topramezone
mefenpyr


B-961
clomazone + glyphosate
mefenpyr


B-962
diflufenican + clodinafop-propargyl
mefenpyr


B-963
diflufenican + fenoxaprop-P-ethyl
mefenpyr


B-964
diflufenican + flupyrsulfuron-methyl-sodium
mefenpyr


B-965
diflufenican + glyphosate
mefenpyr


B-966
diflufenican + mesosulfuron-methyl
mefenpyr


B-967
diflufenican + pinoxaden
mefenpyr


B-968
diflufenican + pyroxsulam
mefenpyr


B-969
flumetsulam + glyphosate
mefenpyr


B-970
flumioxazin + glyphosate
mefenpyr


B-971
imazapic + glyphosate
mefenpyr


B-972
imazethapyr + glyphosate
mefenpyr


B-973
isoxaflutol + H-1
mefenpyr


B-974
isoxaflutol + glyphosate
mefenpyr


B-975
metazachlor + H-1
mefenpyr


B-976
metazachlor + glyphosate
mefenpyr


B-977
metazachlor + mesotrione
mefenpyr


B-978
metazachlor + nicosulfuron
mefenpyr


B-979
metazachlor + terbuthylazine
mefenpyr


B-980
metazachlor + topramezone
mefenpyr


B-981
metribuzin + glyphosate
mefenpyr


B-982
pendimethalin + H-1
mefenpyr


B-983
pendimethalin + clodinafop-propargyl
mefenpyr


B-984
pendimethalin + fenoxaprop-P-ethyl
mefenpyr


B-985
pendimethalin + flupyrsulfuron-methyl-sodium
mefenpyr


B-986
pendimethalin + glyphosate
mefenpyr


B-987
pendimethalin + mesosulfuron-methyl
mefenpyr


B-988
pendimethalin + mesotrione
mefenpyr


B-989
pendimethalin + nicosulfuron
mefenpyr


B-990
pendimethalin + pinoxaden
mefenpyr


B-991
pendimethalin + pyroxsulam
mefenpyr


B-992
pendimethalin + tembotrione
mefenpyr


B-993
pendimethalin + topramezone
mefenpyr


B-994
pyroxasulfone + tembotrione
mefenpyr


B-995
pyroxasulfone + topramezone
mefenpyr


B-996
sulfentrazone + glyphosate
mefenpyr


B-997
terbuthylazine + H-1
mefenpyr


B-998
terbuthylazine + foramsulfuron
mefenpyr


B-999
terbuthylazine + glyphosate
mefenpyr


B-1000
terbuthylazine + mesotrione
mefenpyr


B-1001
terbuthylazine + nicosulfuron
mefenpyr


B-1002
terbuthylazine + tembotrione
mefenpyr


B-1003
terbuthylazine + topramezone
mefenpyr


B-1004
trifluralin + glyphosate
mefenpyr


B-1005
clodinafop-propargyl
H-12


B-1006
cycloxydim
H-12


B-1007
cyhalofop-butyl
H-12


B-1008
fenoxaprop-P-ethyl
H-12


B-1009
pinoxaden
H-12


B-1010
profoxydim
H-12


B-1011
tepraloxydim
H-12


B-1012
tralkoxydim
H-12


B-1013
esprocarb
H-12


B-1014
prosulfocarb
H-12


B-1015
thiobencarb
H-12


B-1016
triallate
H-12


B-1017
bensulfuron-methyl
H-12


B-1018
bispyribac-sodium
H-12


B-1019
cyclosulfamuron
H-12


B-1020
flumetsulam
H-12


B-1021
flupyrsulfuron-methyl-sodium
H-12


B-1022
foramsulfuron
H-12


B-1023
imazamox
H-12


B-1024
imazapic
H-12


B-1025
imazapyr
H-12


B-1026
imazaquin
H-12


B-1027
imazethapyr
H-12


B-1028
imazosulfuron
H-12


B-1029
iodosulfuron-methyl-sodium
H-12


B-1030
mesosulfuron
H-12


B-1031
nicosulfuron
H-12


B-1032
penoxsulam
H-12


B-1033
propoxycarbazone-sodium
H-12


B-1034
pyrazosulfuron-ethyl
H-12


B-1035
pyroxsulam
H-12


B-1036
rimsulfuron
H-12


B-1037
sulfosulfuron
H-12


B-1038
thiencarbazone-methyl
H-12


B-1039
tritosulfuron
H-12


B-1040
2,4-D and its salts and esters
H-12


B-1041
aminopyralid and its salts and esters
H-12


B-1042
clopyralid and its salts and esters
H-12


B-1043
dicamba and its salts and esters
H-12


B-1044
fluroxypyr-meptyl
H-12


B-1045
quinclorac
H-12


B-1046
quinmerac
H-12


B-1047
H-9
H-12


B-1048
diflufenzopyr
H-12


B-1049
diflufenzopyr-sodium
H-12


B-1050
clomazone
H-12


B-1051
diflufenican
H-12


B-1052
fluorochloridone
H-12


B-1053
isoxaflutol
H-12


B-1054
mesotrione
H-12


B-1055
picolinafen
H-12


B-1056
sulcotrione
H-12


B-1057
tefuryltrione
H-12


B-1058
tembotrione
H-12


B-1059
topramezone
H-12


B-1060
H-7
H-12


B-1061
atrazine
H-12


B-1062
diuron
H-12


B-1063
fluometuron
H-12


B-1064
hexazinone
H-12


B-1065
isoproturon
H-12


B-1066
metribuzin
H-12


B-1067
propanil
H-12


B-1068
terbuthylazine
H-12


B-1069
paraquat dichloride
H-12


B-1070
flumioxazin
H-12


B-1071
oxyfluorfen
H-12


B-1072
saflufenacil
H-12


B-1073
sulfentrazone
H-12


B-1074
H-1
H-12


B-1075
H-2
H-12


B-1076
glyphosate
H-12


B-1077
glyphosate-isopropylammonium
H-12


B-1078
glyphosate-trimesium (sulfosate)
H-12


B-1079
glufosinate
H-12


B-1080
glufosinate-ammonium
H-12


B-1081
pendimethalin
H-12


B-1082
trifluralin
H-12


B-1083
acetochlor
H-12


B-1084
cafenstrole
H-12


B-1085
dimethenamid-P
H-12


B-1086
fentrazamide
H-12


B-1087
flufenacet
H-12


B-1088
mefenacet
H-12


B-1089
metazachlor
H-12


B-1090
metolachlor-S
H-12


B-1091
pyroxasulfone
H-12


B-1092
isoxaben
H-12


B-1093
dymron
H-12


B-1094
indanofan
H-12


B-1095
oxaziclomefone
H-12


B-1096
triaziflam
H-12


B-1097
atrazine + H-1
H-12


B-1098
atrazine + glyphosate
H-12


B-1099
atrazine + mesotrione
H-12


B-1100
atrazine + nicosulfuron
H-12


B-1101
atrazine + tembotrione
H-12


B-1102
atrazine + topramezone
H-12


B-1103
clomazone + glyphosate
H-12


B-1104
diflufenican + clodinafop-propargyl
H-12


B-1105
diflufenican + fenoxaprop-P-ethyl
H-12


B-1106
diflufenican + flupyrsulfuron-methyl-sodium
H-12


B-1107
diflufenican + glyphosate
H-12


B-1108
diflufenican + mesosulfuron-methyl
H-12


B-1109
diflufenican + pinoxaden
H-12


B-1110
diflufenican + pyroxsulam
H-12


B-1111
flumetsulam + glyphosate
H-12


B-1112
flumioxazin + glyphosate
H-12


B-1113
imazapic + glyphosate
H-12


B-1114
imazethapyr + glyphosate
H-12


B-1115
isoxaflutol + H-1
H-12


B-1116
isoxaflutol + glyphosate
H-12


B-1117
metazachlor + H-1
H-12


B-1118
metazachlor + glyphosate
H-12


B-1119
metazachlor + mesotrione
H-12


B-1120
metazachlor + nicosulfuron
H-12


B-1121
metazachlor + terbuthylazine
H-12


B-1122
metazachlor + topramezone
H-12


B-1123
metribuzin + glyphosate
H-12


B-1124
pendimethalin + H-1
H-12


B-1125
pendimethalin + clodinafop-propargyl
H-12


B-1126
pendimethalin + fenoxaprop-P-ethyl
H-12


B-1127
pendimethalin + flupyrsulfuron-methyl-sodium
H-12


B-1128
pendimethalin + glyphosate
H-12


B-1129
pendimethalin + mesosulfuron-methyl
H-12


B-1130
pendimethalin + mesotrione
H-12


B-1131
pendimethalin + nicosulfuron
H-12


B-1132
pendimethalin + pinoxaden
H-12


B-1133
pendimethalin + pyroxsulam
H-12


B-1134
pendimethalin + tembotrione
H-12


B-1135
pendimethalin + topramezone
H-12


B-1136
pyroxasulfone + tembotrione
H-12


B-1137
pyroxasulfone + topramezone
H-12


B-1138
sulfentrazone + glyphosate
H-12


B-1139
terbuthylazine + H-1
H-12


B-1140
terbuthylazine + foramsulfuron
H-12


B-1141
terbuthylazine + glyphosate
H-12


B-1142
terbuthylazine + mesotrione
H-12


B-1143
terbuthylazine + nicosulfuron
H-12


B-1144
terbuthylazine + tembotrione
H-12


B-1145
terbuthylazine + topramezone
H-12


B-1146
trifluralin + glyphosate
H-12


B-1147
2-1
—


B-1148
2-2
—


B-1149
2-3
—


B-1150
2-4
—


B-1151
2-5
—


B-1152
2-6
—


B-1153
2-7
—


B-1154
2-8
—


B-1155
2-9
—


B-1156
2-1
benoxacor


B-1157
2-2
benoxacor


B-1158
2-3
benoxacor


B-1159
2-4
benoxacor


B-1160
2-5
benoxacor


B-1161
2-6
benoxacor


B-1162
2-7
benoxacor


B-1163
2-8
benoxacor


B-1164
2-9
benoxacor


B-1165
2-1
cloquintocet


B-1166
2-2
cloquintocet


B-1167
2-3
cloquintocet


B-1168
2-4
cloquintocet


B-1169
2-5
cloquintocet


B-1170
2-6
cloquintocet


B-1171
2-7
cloquintocet


B-1172
2-8
cloquintocet


B-1173
2-9
cloquintocet


B-1174
2-1
cyprosulfamide


B-1175
2-2
cyprosulfamide


B-1176
2-3
cyprosulfamide


B-1177
2-4
cyprosulfamide


B-1178
2-5
cyprosulfamide


B-1179
2-6
cyprosulfamide


B-1180
2-7
cyprosulfamide


B-1181
2-8
cyprosulfamide


B-1182
2-9
cyprosulfamide


B-1183
2-1
dichlormid


B-1184
2-2
dichlormid


B-1185
2-3
dichlormid


B-1186
2-4
dichlormid


B-1187
2-5
dichlormid


B-1188
2-6
dichlormid


B-1189
2-7
dichlormid


B-1190
2-8
dichlormid


B-1191
2-9
dichlormid


B-1192
2-1
fenchlorazole


B-1193
2-2
fenchlorazole


B-1194
2-3
fenchlorazole


B-1195
2-4
fenchlorazole


B-1196
2-5
fenchlorazole


B-1197
2-6
fenchlorazole


B-1198
2-7
fenchlorazole


B-1199
2-8
fenchlorazole


B-1200
2-9
fenchlorazole


B-1201
2-1
isoxadifen


B-1202
2-2
isoxadifen


B-1203
2-3
isoxadifen


B-1204
2-4
isoxadifen


B-1205
2-5
isoxadifen


B-1206
2-6
isoxadifen


B-1207
2-7
isoxadifen


B-1208
2-8
isoxadifen


B-1209
2-9
isoxadifen


B-1210
2-1
mefenpyr


B-1211
2-2
mefenpyr


B-1212
2-3
mefenpyr


B-1213
2-4
mefenpyr


B-1214
2-5
mefenpyr


B-1215
2-6
mefenpyr


B-1216
2-7
mefenpyr


B-1217
2-8
mefenpyr


B-1218
2-9
mefenpyr


B-1219
2-1
H-11


B-1220
2-2
H-11


B-1221
2-3
H-11


B-1222
2-4
H-11


B-1223
2-5
H-11


B-1224
2-6
H-11


B-1225
2-7
H-11


B-1226
2-8
H-11


B-1227
2-9
H-11


B-1228
2-1
H-12


B-1229
2-2
H-12


B-1230
2-3
H-12


B-1231
2-4
H-12


B-1232
2-5
H-12


B-1233
2-6
H-12


B-1234
2-7
H-12


B-1235
2-8
H-12


B-1236
2-9
H-12









The compounds I and the compositions according to the invention may also have a plant-strengthening action. Accordingly, they are suitable for mobilizing the defense system of the plants against attack by unwanted microorganisms, such as harmful fungi, but also viruses and bacteria. Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defense system of treated plants in such a way that, when subsequently inoculated by unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms.
The compounds I can be employed for protecting plants against attack by unwanted microorganisms within a certain period of time after the treatment. The period of time within which their protection is effected generally extends from 1 to 28 days, preferably from 1 to 14 days, after the treatment of the plants with the compounds I, or, after treatment of the seed, for up to 9 months after sowing.
The compounds I and the compositions according to the invention are also suitable for increasing the harvest yield.
Moreover, they have reduced toxicity and are tolerated well by the plants.
The following examples will further illustrate the invention:
With appropriate modification of the starting materials, the procedures given in the synthesis examples below were used to obtain further compounds I. The compounds obtained in this manner are listed in the table that follows, together with physical data. The products shown below were characterized by determination of the melting point, NMR spectroscopy or the masses ([m/z]) determined by HPLC-MS spectrometry.
HPLC-MS=high performance liquid chromatography coupled with mass spectrometry:
HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50*4.6 mm; mobile phase: acetonitrile+0.1% trifluoroacetic acid (TFA)/water+0.1% TFA, using a gradient from 5:95 to 100:0 over 5 minutes at 40° C., flow rate 1.8 ml/min.
MS: quadrupole electrospray ionization, 80 V (positive mode).
DMF: N,N-Dimethyl formamide
DBU: 1,8-Diazabicyclo[5 5.4.0]undec-7-ene
EtOAc: acetic acid ethyl ester
LiHMDS: Lithium bis(trimethylsilyl)amide


EXAMPLE 1
Preparation of 4-chloro-N-(4-methyl-1,2,5-oxadiazol-3-yl)-1,1-dioxo-2,3-dihydrobenzothiophene-5-carboxamide (Corresponds to compound A-1, Table 1)
Step 1)




To a solution of carboxylic acid 1 (3 g, 12.2 mmol), prepared according to WO 2000020408, in CH2Cl2 (50 mL) were added 2 drops of DMF and oxalyl chloride (1.5 mL, 13.4 mmol) at ambient temperature. The reaction mixture was allowed to stir for 18 hours, then concentrated under reduced pressure. The crude product (2) was used without further purification in the subsequent step.
Step 2)




To a solution of 4-methyl-1,2,5-oxadiazol-3-amine 3 (200 mg, 2.0 mmol) in THF (70 mL) was added LiHMDS (1.0 M solution in THF, 2.2 m L, 2.2 mmol) at −78° C. under a nitrogen atmosphere. The mixture was allowed to stir at −78° C. for 1 hour followed by the addition of a solution of acid chloride 2 (535 mg, 2.0 mmol) in THF (10 mL). The reaction was allowed to warm to ambient temperature and stirred for 18 hours. The reaction mixture was quenched by slow addition of saturated aqueous NH4Cl (40 mL) and the aqueous layer was extracted with EtOAc (3×50 mL). The combined organic layers were washed with saturated brine (30 mL), dried (MgSO4) and concentrated. Purification of the obtained residue by preparative HPLC afforded the desired product A-1 of table 1 (120 mg, 18%). 1H NMR (CDCl3 400 MHz): δ 7.97-7.85 (m, 2H), 7.79 (d, 1H), 4.19 (s, 3H), 3.63-3.58 (m, 2H), 3.48-3.42 (m, 2H).
Preparative HPLC Purification:


    Column: Nucleodur C18 Gravity 5 μm (Macherey-Nagel GmbH & Co. KG, Germany); Column diameter: 50*100 mm;
    Mobile phase: acetonitrile+0.05% trifluoroacetic acid (TFA)/water+0.05% TFA, using a gradient from 25:75 to 70:30 over 7.5 minutes at 25° C., flow rate 128 ml/min.


By analogy to the methods described in Example 1 the following compounds of formula I′ of table 4 and of formula I′′ of table 5 were prepared:







TABLE 4







(I′)








 















MS



R1
CYC
R3
(m/z)














I′.A-1
Cl
Cyc-1a′-1
—
328.2


I′.A-8
Cl
Cyc-1c′
—
370.2


I′.A-35
CH3
Cyc-1c′
—
350.2


I′.A-47
CH3
Cyc-1f′-1
—
365.1


I′.A-49
CH3
Cyc-1g′
—
336.1


I′.A-113
—
Cyc-2a′
Cl
289.2


I′.A-117
—
Cyc-2a′
Br
335.0


I′.A-129
—
Cyc-2a′
OCH3
285.3





Cyc-1a′-1





Cyc-1c′ 





Cyc-1f′-1





Cyc-1g′ 





Cyc-2a′ 



















TABLE 5







(I′′)








 















MS



R1
CYC
R3
(m/z)





I′′.A-1 
Cl
Cyc-1a′-1
—
344.2


I′′.A-8 
Cl
Cyc-1c′
—
386.2









II. Use Examples
The herbicidal activity of the compounds of the formula I was demonstrated by the following greenhouse experiments:
The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this has been impaired by the active ingredients.
For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
Depending on the species, the plants were kept at 10-25° C. or 20-35° C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
The plants used in the greenhouse experiments belonged to the following species:















Bayer Code
Scientific name
English name









ABUTH
Abutilon theophrasti
velvetleaf



AMARE
Amaranthus retroflexus
common amaranth



ALOMY
Alopecurus myosuroides
blackgrass



APESV
Apera spica-venti
bentgrass, silky



AVEFA
Avena fatua
wild oat



CHEAL
Chenopodium album
lampsquaters



ECHCG
Echinochloa crus-galli
comon barnyardgrass



POLCO
Polygonum convulvulus
bindweed, black



SETVI
Setaria viridis
green foxtail










At an application rate of 1 kg/ha, the compounds I′.A-35, I.′A-47 and I′.A-49, applied by the post-emergence method, showed very good herbicidal activity against ABUTH.
At an application rate of 1 kg/ha, the compounds I′.A-113, applied by the post-emergence method, showed good herbicidal activity against ABUTH.
At an application rate of 1 kg/ha, the compound I′.A-35, I.′A-47 and I′.A-49, applied by the pre-emergence method, showed very good herbicidal activity against ABUTH.
At an application rate of 0.25 kg/ha, the compounds I.′A-1, I′′.A-1, I′.A-8 and I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against AMARE.
At an application rate of 0.25 kg/ha, the compounds I.′A-1, I′′.A-1, I′.A-8 and I′′.A-8 applied by the pre-emergence method, showed very good herbicidal activity against AMARE.
At an application rate of 0.25 kg/ha, the compounds I′′.A-1 and I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against AVEFA.
At an application rate of 0.25 kg/ha, the compound I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against ALOMY.
At an application rate of 0.25 kg/ha, the compounds I.′A-1, I′′.A-1, I′.A-8 and I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against CHEAL.
At an application rate of 0.25 kg/ha, the compounds I.′A-1, I′′.A-1, I′.A-8 and I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against POLCO.
At an application rate of 0.25 kg/ha, the compounds I′′.A-1, I′.A-8 and I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against SETVI.
At an application rate of 0.25 kg/ha, the compounds I′′.A-1, I′.A-8 and I′′.A-8 applied by the post-emergence method, showed very good herbicidal activity against ECHCG.
At an application rate of 0.25 kg/ha, the compounds I′′.A-1 and I′′.A-8 applied by the pre-emergence method, showed very good herbicidal activity against ECHCG.
At an application rate of 0.25 kg/ha, the compounds I′′.A-1 and I′′.A-8 applied by the pre-emergence method, showed very good herbicidal activity against APESV.

## Claims

1. A compound of formula I,



wherein
R is selected from the group consisting of hydrogen, cyano, nitro, halogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, O—Ra, Z—S(O)n—Rb, Z—C(═O)—Rc, Z—C(═O)—ORd, Z—C(═O)—NReRf, Z—NRgRh, Z-phenyl and Z-heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R′, which are identical or different;
CYC indicates a bi- or tricyclic radical of the following formulae Cyc-1 or Cyc-2




where
# indicates the point of attachment of the bicyclic radical to the carbonyl group,
Q, Q′ independently of each other indicate a fused 5-, 6-, 7-, 8-, 9- or 10-membered heterocycle, where the fused heterocycle has 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, S and N as ring members, where the fused heterocycle is monocyclic or bicyclic and where the fused heterocycle is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 radicals R2;
R1 in formula Cyc-1 is selected from the group consisting of Z1-cyano, halogen, nitro, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, Z1-C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylthio-C1-C4-alkyl, Z1-C1-C4-alkylthio-C1-C4-alkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkyl, Z1-C1-C4-haloalkoxy-C1-C4-alkoxy, Z1—S(O)k—R1b, Z1-phenoxy and Z1-heterocyclyloxy, where heterocyclyloxy is an oxygen bound 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1, 2, 3 or 4 groups R11, which are identical or different;
R2 is selected from the group consisting of halogen, Z2—OH, Z2—NO2, Z2-cyano, oxo (═O), ═N—R22, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Z2-C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, Z2-C1-C4-haloalkoxy, Z2-C3-C10-cycloalkyl,O—Z2-C3-C10-cycloalkyl, Z2-(tri-C1-C4-alkyl)silyl, Z2—S(O)k—R2b, Z2—C(═O)—R2c, Z2—NR2gR2h and Z2-phenyl, where phenyl in Z2-phenyl is unsubstituted or substituted by 1, 2, 3 or 4 groups R21, which are identical or different;
R3 in formula Cyc-2 is selected from the group consisting of hydrogen, halogen, Z3—OH, Z3—NO2, Z3-cyano, C1-C6-alkyl, C2-C8-alkenyl, C2-C8alkynyl, Z3-C3-C10-cycloalkyl, Z3-C3-C10-cycloalkoxy, where the C3-C10-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C8-haloalkyl, Z3-C1-C8-alkoxy, Z3-C1-C8-haloalkoxy, Z3-C1-C4-alkoxy-C1-C4-alkoxy, Z3-C1-C4-alkylthio-C1-C4-alkylthio, Z3-C2-C8-alkenyloxy, Z3-C2-C8-alkynyloxy, Z3-C1-C8-haloalkoxy, Z3-C1-C4-haloalkoxy-C1-C4-alkoxy, Z3-(tri-C1-C4-alkyl)silyl, Z3—S(O)k—R3b, Z3—C(═O)—R3c, Z3—C(═O)—OR3d, Z3—C(═O)—NR3eR3f, Z3—NR3gR3h, Z3a-phenyl and Z3a-heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in Z3a-phenyl and Z3a-heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R31, which are identical or different;
R4 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C4-alkyl and C1-C4-haloalkyl;
R5 is selected from the group consisting of hydrogen, halogen, C1-C4-alkyl and C1-C4-haloalkyl;
n is 0, 1 or 2;
k is 0, 1 or 2;
R′, R11, R21, R31 independently of each other are selected from the group consisting of halogen, NO2, CN, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C7-cycloalkoxy and C1-C6-haloalkyloxy;
R22 is selected from the group consisting of C1-C4-alkoxy, C1-C4-haloalkoxy and C3-C7-cycloalkoxy, which is unsubstituted or partially or completely halogenated;
Z, Z1, Z2, Z3 independently of each other are selected from the group consisting of a covalent bond and C1-C4-alkanediyl;
Z3a is selected from the group consisting of a covalent bond, C1-C4-alkanediyl, O—C1-C4-alkanediyl, C1-C4-alkanediyl-O and C1-C4-alkanediyl-O—C1-C4-alkanediyl;
Ra is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rb, R1b, R2b, R3b independently of each other are selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and phenyl, where phenyl is unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rc, R2c, R3c independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rd, R3d independently of each other are selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl,C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Re, Rf independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, or
Re, Rf together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from the group consisting of O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
R3e, R3f independently of each other have the meanings given for Re, Rf;
Rg is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Rh is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aformentioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, a radical C(═O)—Rk, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, or
Rg, Rh together with the nitrogen atom, to which they are bound may form a 5-, 6 or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 groups, which are identical or different and selected from the group consisting of ═O, halogen,C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
R2g, R2h independently of each other have the meanings given for Rg, Rh;
R3g, R3h independently of each other have the meanings given for Rg, Rh;
Rk has the meanings given for Rc;
an N-oxide or an agriculturally suitable salt thereof.

2. The compound as claimed in claim 1, where R is selected from the group consisting of halogen, cyano, nitro, NH2, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C7-cycloalkyl, C1-C4-haloalkyl, C(═O)—Re, C(═O)—ORd, C(═O)—NReRf and NH—C(═O)Rk, where
Rc is C1-C4-alkyl or C1-C4-haloalkyl,
Rd is C1-C4-alkyl,
Re is hydrogen or C1-C4-alkyl,
Rf is hydrogen or C1-C4-alkyl, or
Re, Rf together with the nitrogen atom, to which they are bound may form a 5-, 6-, or 7-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1, 2, 3 or 4 methyl groups,
Rk is C1-C4-alkyl.

3. The compound as claimed in claim 1, where R is a radical ORa, where Ra is selected from the group consisting of H, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy-C1-C4-alkyl and C3-C7-cycloalkyl, which is unsubstituted or partly or completely halogenated.

4. The compound as claimed in claim 1, where R is phenyl or heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1, 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1, 2, 3 or 4 groups R′, where R′ is selected from the group consisting of halogen, methyl, ethyl, methoxy and trifluoromethyl.

5. The compound as claimed in claim 1, where R is S(O)n—Rb, where Rb is C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, or phenyl.

6. The compound as claimed in claim 1, wherein R2 is selected from the group consisting of oxo, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C3-C4-alkenyl, C3-C4-alkynyl, and ═N—R22, where R22 is C1-C4-alkoxy.

7. The compound as claimed in claim 1, wherein R2 is selected from the group consisting of oxo, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-alkenyl, and ═N—R22, where R22 is C1-C4-alkoxy.

8. The compound as claimed in claim 1, wherein R4 is selected from the group consisting of hydrogen, CN, CHF2, CF3, CH3, NO2 and halogen.

9. The compound as claimed in claim 1, wherein R5 is selected from the group consisting of hydrogen, halogen, CHF2 and CF3.

10. The compound of the formula I according to claim 1, wherein R4 and R5 are hydrogen.

11. The compound as claimed in claim 1, where CYC is a radical Cyc-1.

12. The compound as claimed in claim 11, where Q indicates a fused 5- or 6-membered monocyclic hetorcycle or a fused 7-, 8-, 9- or 10-membered spiro-bicyclic heterocycle, where the fused monocyclic heterocycle has 1 or 2 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7 or 8 radicals R2, where the fused spiro-bicyclic heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 radicals R2.

13. The compound as claimed in claim 11, where R1 in formula Cyc-1 is selected from the group consisting of cyano, halogen, nitro, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, Z1—C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkylthio-C1-C4-alkyl, Z1—C1-C4-alkylthio-C1-C4-alkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, and S(O)kR1b, where
R1b is selected from the group consisting of C1-C4-alkyl and C1-C4-haloalkyl.

14. The compound as claimed in claim 11, where R1 is selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4alkylthio, C1-C4-haloalkylthio and C1-C4-alkylsufonyl.

15. The compound as claimed in claim 11, where Cyc-1 is selected from the following groups Cyc-1a to Cyc-1h:






where R5 is hydrogen or halogen, and where R23 and R24 are hydrogen or have one of the meanings given for R2.

16. The compound as claimed in claim 11, where Cyc-1 is selected from the following groups Cyc-1a′ to Cyc-1h′ and Cyc-1 f′:






where
R2p, R2q are independently of each other hydrogen, C1-C4-alkyl or C1-C4-alkoxy;
R2r, R2s are independently of each other hydrogen or halogen;
R2t is C1-C4-haloalkoxy;
R2u is C1-C4-alkoxy;
R2v is C1-C4-alkyl or C3-C4-alkenyl.

17. The compound as claimed in claim 1, where CYC is a radical Cyc-2.

18. The compound as claimed in claim 17, where Q′ indicates a fused 5- or 6-membered monocyclic heterocycle or a fused 7-, 8-, 9- or 10-membered bicyclic heterocycle, where the fused monocyclic heterocycle has 1 or 2 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7 or 8 radicals R2, where the fused bicyclic heterocycle has 1, 2, 3 or 4 heteroatoms selected from O, S and N as ring members and is unsubstituted or carries 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 radicals R2.

19. The compound as claimed in claim 17, where R3 is selected from the group consisting of hydrogen, cyano, halogen, nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-alkenyloxy, C2-C4-alkynyloxy and S(O)kR3b.

20. The compound as claimed in claim 17, where R3 is selected from the group consisting of hydrogen, halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, S(O)2—C1-C4-alkyl and S(O)2—C1-C4-haloalkyl.

21. The compound as claimed in claim 17, where Cyc-2 is selected from the following groups Cyc-2a to Cyc-2d:



where # p is 0, 1, 2 or 3.

22. The compound as claimed in claim 17, where p is 0 and R4 is hydrogen.

23. The compound as claimed in claim 17, where R3 is selected from the group consisting of hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl and C1-C4-alkoxy.

24. A composition comprising at least one compound as claimed in claim 1 and at least one auxiliary, which is customary for formulating crop protection compounds.

25. A method for controlling unwanted vegetation which comprises treating the unwanted vegetation, their seed or their habitat with a herbicidally effective amount of at least one compound as claimed in claim 1.