Patent Application
20240365783
The present invention relates to specific malonamide compounds and compositions comprising the same. The invention also relates to the use of said malonamide compounds or the corresponding compositions for controlling unwanted vegetation. Furthermore, the invention relates to methods of applying the malonamide compounds or the corresponding compositions.
For the purpose of controlling unwanted vegetation, especially in crops, there is an ongoing need for new herbicides that have high activity and selectivity together with a substantial lack of toxicity for humans and animals.
WO 2012/130798, WO 2014/004882, WO 2014/048882, WO 2018/228985, WO 2018/228986, WO 2019/034602, and WO 2019/145245 describe 3-phenylisoxazoline-5-carboxamides and their use as herbicides.
WO 87/05898 describes the use of malonic acid derivatives for retarding plant growth.
Malonic acid derivatives are also described in U.S. Pat. No. 3,072,473 as plant growth regulators.
The prior art compounds often suffer from 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 malonamide 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 malonamide 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 including their agriculturally acceptable salts, stereoisomers and tautomers.
Accordingly, the present invention relates to compounds of formula (I)
wherein the substituents have the following meanings:
including their agriculturally acceptable salts, stereoisomers and tautomers.
The invention also relates to a composition comprising at least one compound of formula (I) and at least one auxiliary, which is customary for formulating crop protection compounds.
The present invention also provides combinations comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C(component C).
The invention relates moreover to the use of a compound of formula (I) or of said compositions for controlling unwanted vegetation, and to a method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one compound of formula (I) or of said compositions to act on plants, their seed and/or their habitat.
Depending on the kind of substituents, the compounds of formula (I) may have one or more centers of chirality, in which case they may be present as mixtures of enantiomers or diastereomers but also in the form of the pure enantiomers or pure 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 formula I also include all possible geometrical stereoisomers (cis/trans isomers) as a specific form of diastereomers and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen doublebond, nitrogen-sulfur double bond, amide group or a cyclic, non-aromatic moiety. The term “stereoisomer(s)” encompasses both optical isomers, such as enantiomers or diastereomers existing due to more than one stereogenic center in the molecule, as well as geometrical isomers (cis/trans isomers). Just by way of example, a stereogenic center is the C atom carrying R10 and R11 in X1 to X6, provided of course that R10 and R11 are different. Another example for a stereogenic center is the C atom carrying R7 and R8, provided, of course, that R7 and R8 are different from each other.
If the above-mentioned herbicidal compounds B and/or the safeners C have one or more centres of chirality they may also be present as enantiomers or diastereomers, and it is possible to use both the pure enantiomers and diastereomers or their mixtures.
If the compounds of formula (I), the herbicidal compounds B and/or the safeners C as described herein have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. Suitable are, in general, the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the activity of the active compounds.
Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl) ammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium (olamine salt), 2-(2-hydroxyeth-1-oxy) eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl) ammonium (diolamine salt), tris(2-hydroxyethyl) ammonium (trolamine salt), tris(2-hydroxypropyl) ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N, N-trimethylethanolammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri (C1-C4-alkyl) sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri (C1-C4-alkyl) sulfoxonium, and finally the salts of polybasic amines such as N, N-bis-(3-aminopropyl)methylamine and diethylenetriamine.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensulfate, methylsulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
The compounds (I) may be present in form of different tautomers. For instance, if ring Z is a lactam, i.e. contains an amide group as ring member (=unsubstituted, secondary nitrogen ring atom neighboured to a carbon ring atom carrying an oxo group), this ring moiety —N(H)—C(═O)— can be in equilibrium with its tautomeric form —N═C(OH)—. The same applies to the two mandatorily present amide groups of the malonamide moiety —N(R1)—C(═O)—C(R7) (R8)—C(═O)—N(R9)— if one or both of R1 and R9 are hydrogen:
The amount in which the one or other tautomeric form is present depends on the complete molecular structure and even stronger on the surrounding conditions (presence or absence of solvent, type of solvent, pH, temperature etc.).
The term “undesired vegetation” (“weeds”) is understood to include any vegetation growing in non-crop-areas or 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 (if any). Weeds, in the broadest sense, are plants considered undesirable in a particular location.
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, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 12 carbon atoms (═C1-C12-alkyl), frequently from 1 to 6 carbon atoms (═C1-C6-alkyl), in particular 1 to 4 carbon atoms (═C1-C4-alkyl) and especially from 1 to 3 carbon atoms (═C1-C3-alkyl) or 1 or 2 carbon atoms (═C1-C2-alkyl). C1-C2-Alkyl is methyl or ethyl. C1-C3-Alkyl is methyl, ethyl, npropyl or iso-propyl. Examples of C1-C4-alkyl are methyl, ethyl, n-propyl, iso-propyl, nbutyl, 2-butyl(=sec-butyl), isobutyl and tert-butyl. Examples for C1-C6-alkyl are, in addition to 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-C8-alkyl are, in addition to 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-methylheptyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl and 2-propylpentyl. Examples for C1-C12-alkyl are, apart those mentioned for C1-C6-alkyl, nonyl, decyl, 2-propylheptyl, 3-propylheptyl, undecyl, dodecyl and positional isomers thereof.
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), which is also expressed as “alkyl which is partially or fully halogenated”, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms (═C1-C6-haloalkyl), more frequently 1 to 3 carbon atoms (═C1-C3-haloalkyl), as defined above, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from C1-C3-haloalkyl, specifically from C1-C2-haloalkyl, in particular from fluorinated C1-C2-alkyl. Examples for C1-C2-haloalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 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-C3-haloalkyl are, in addition to 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, and the like.
The term “hydroxyalkyl” denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms (═C1-C6-hydroxyalkyl), more frequently 1 to 3 carbon atoms (═C1-C3-hydroxyalkyl), as defined above, wherein one hydrogen atom of this group is replaced with a hydroxyl group. Examples are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-2-propyl 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 12 (═C2-C12-alkenyl), preferably 2 to 6 carbon atoms (═C2-C6-alkenyl), e.g. 3 to 6 carbon atoms (═C3-C6-alkenyl), in particular 2 or 3 carbon atoms (═C2-C3-alkenyl), and a double bond in any position, for example C2-C3-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl or 1-methylethenyl; 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-C12-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, the nonenyls, decenyls, undecenyls, dodecenyls and the positional isomers thereof.
Examples for C3-C6-alkenyl are those mentioned above for C2-C6-alkenyl, except for ethenyl.
The term “haloalkenyl” as used herein, which may also be expressed as “alkenyl which is substituted by halogen”, and the haloalkenyl moieties in haloalkenyloxy and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 6 (═C2-C6-haloalkenyl) or 2 to 3 (═C2-C3-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 12 (═C2-C12-alkynyl), frequently 2 to 6 (═C2-C6-alkynyl), preferably 2 to 4 carbon atoms (═C2-C4-alkynyl) or 2 to 3 carbon atoms (═C2-C3-alkynyl) and a triple bond in any position, for example C2-C3-alkynyl, such as ethynyl, 1-propynyl or 2-propynyl; C2-C4-alkynyl, such as ethynyl, 1-propynyl or 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 is substituted by halogen”, refers to unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 6 carbon atoms (═C2-C6-haloalkynyl), preferabyl 2 or 3 carbon atoms (═C2-C3-haloalkynyl), and a triple bond 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 “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, saturated cycloaliphatic radical having usually from 3 to 8 carbon atoms (═C3-C8-cycloalkyl), preferably 3 to 6 carbon atoms (═C3-C6-cycloalkyl), 3 to 5 carbon atoms (═C3-C5-cycloalkyl) or 3 to 4 carbon atoms (═C3-C4-cycloalkyl) as (only) ring members. Examples of monocyclic saturated cycloaliphatic radicals having 3 or 4 carbon atoms comprise cyclopropyl and cyclobutyl. Examples of monocyclic saturated cycloaliphatic radicals having 3 to 5 carbon atoms comprise cyclopropyl, cyclobutyl and cyclopentyl. Examples of monocyclic saturated cycloaliphatic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic saturated cycloaliphatic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. C5-C6-Cycloalkyl is cyclopentyl or cyclohexyl. Examples of bicyclic radicals having 6 to 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) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 8 carbon atoms (“C3-C8-halocycloalkyl”), preferably 3 to 5 carbon atoms (“C3-C5-halocycloalkyl”), 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 “hydroxycycloalkyl” denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 6 carbon atoms (“hydroxy-(C3-C6)-cycloalkyl”), preferably 3 to 5 carbon atoms (“hydroxy-(C3-C5)-cycloalkyl”), wherein at least one, e.g. 1, 2, 3, 4 or 5 of the hydrogen atoms are replaced by a hydroxyl group. Examples are 1-hydroxycyclopropyl, 2-hydroxycyclopropyl, 1,2-dihydroxycyclopropyl, 2,3-dihydroxycyclopropyl, 1-hydroxycyclobutyl, 2-hydroxycyclobutyl, 3-hydroxycyclobutyl, 1,2-dihydroxycyclobutyl, 1,3-dihydroxycyclobutyl, 2,3-dihydroxycyclobutyl, 1-hydroxycyclopentyl, 2-hydroxycyclopentyl, 3-hydroxycyclopentyl, 1,2-dihydroxycyclopentyl, 1,3-dihydroxycyclopentyl, 2,3-dihydroxycyclopentyl and the like.
The term “alkoxy” as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms (═C1-C6-alkoxy), preferably 1 to 3 carbon atoms (═C1-C3-alkoxy), in particular 1 or 2 carbon atoms (═C1-C2-alkoxy), which is bound to the remainder of the molecule via an oxygen atom. C1-C2-Alkoxy is methoxy or ethoxy. C1-C3-Alkoxy is additionally, for example, n-propoxy or 1-methylethoxy (isopropoxy). C1-C6-Alkoxy is additionally, for example, butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1,1-dimethylethoxy (tertbutoxy), 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.
The term “haloalkoxy” as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 6 carbon atoms (═C1-C6-haloalkoxy), preferably 1 to 3 carbon atoms (═C1-C3-haloalkoxy), in particular 1 or 2 carbon atoms (═C1-C2-haloalkoxy), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms (in this case, the radical is also termed fluorinated alkoxy). 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-C3-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 or 1-(CH2Br)-2-bromoethoxy. C1-C6-Haloalkoxy is additionally, for example, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.
The term “alkenyloxy” denotes an alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-Alkenyloxy is a C2-C6-alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C3-C6-Alkenyloxy is a C3-C6-alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
The term “haloalkenyloxy” denotes a haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-Haloalkenyloxy is a C2-C6-haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C3-C6-Haloalkenyloxy is a C3-C6-haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
The term “alkynyloxy” denotes an alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-Alkynyloxy is a C2-C6-alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C3-C6-Alkynyloxy is a C3-C6-alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
The term “haloalkynyloxy” denotes a haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-Haloalkynyloxy is a C2-C6-haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C3-C6-Haloalkynyloxy is a C3-C6-haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
The term “cycloalkoxy” denotes a cycloalkyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C3-C6-Cycloalkoxy is a C3-C6-cycloalkyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. Examples of C3-C6-cycloalkoxy comprise cyclopropoxy, cyclobutoxy, cyclopentoxy and cyclohexoxy.
The term “alkoxy-alkoxy” as used herein, refers to an alkoxy group, as defined above, where one hydrogen atom is replaced by another alkoxy group, as defined above. The term “C1-C3-alkoxy-C1-C3-alkoxy” as used herein, refers to an alkoxy group having 1 to 3 carbon atoms, as defined above, where one hydrogen atom is replaced by a C1-C3-alkoxy group, as defined above. Examples are methoxymethoxy, ethoxymethoxy, propoxymethoxy, isopropoxymethoxy, 1-methoxyethoxy, 1-ethoxyethoxy, 1-propoxyethoxy, 1-isopropoxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-propoxyethoxy, 2-isopropoxyethoxy, 1-methoxypropoxy, 1-ethoxypropoxy, 1-propoxypropoxy, 1-isopropoxypropoxy, 2-methoxypropoxy, 2-ethoxypropoxy, 2-propoxypropoxy, 2-isopropoxypropoxy, 3-methoxypropoxy, 3-ethoxypropoxy, 3-propoxypropoxy, 3-isopropoxypropoxy, and the like.
The term “alkylthio” (also alkylsulfanyl or “alkyl-S”) as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 6 carbon atoms (═C1-C6-alkylthio), preferably 1 to 3 carbon atoms (═C1-C3-alkylthio), which is attached via a sulfur atom at any position in the alkyl group. C1-C2-Alkylthio is methylthio or ethylthio. C1-C3-Alkylthio is additionally, for example, npropylthio or 1-methylethylthio(isopropylthio). C1-C6-Alkylthio is additionally, for example, butylthio, 1-methylpropylthio(sec-butylthio), 2-methylpropylthio(isobutylthio), 1,1-dimethylethylthio(tert-butylthio), 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.
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 term “alkylsulfinyl” denotes 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-C3-alkylsulfinyl” refers to a C1-C3-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-C3-alkylsulfinyl is additionally, for example, n-propylsulfinyl or 1-methylethylsulfinyl(isopropylsulfinyl). C1-C6-alkylsulfinyl is additionally, for example, butylsulfinyl, 1-methylpropylsulfinyl(sec-butylsulfinyl), 2-methylpropylsulfinyl(isobutylsulfinyl), 1,1-dimethylethylsulfinyl(tert-butylsulfinyl), 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 term “haloalkylsulfinyl” denotes a haloalkyl group, as defined above, attached via a sulfinyl [S(O)] group to the remainder of the molecule. C1-C2-Haloalkylsulfinyl is, for example, S(O)CH2F, S(O)CHF2, S(O)CF3, S(O)CH2Cl, S(O)CHCl2, S(O)CCl3, chlorofluoromethylsulfinyl, dichlorofluoromethylsulfinyl, chlorodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl or S(O) C2F5. C1-C3-Haloalkylsulfinyl is additionally, for example, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2,3-dichloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloropropylsulfinyl, S(O)CH2-C2F5, S(O)CF2-C2F5, 1-(CH2F)-2-fluoroethylsulfinyl, 1-(CH2Cl)-2-chloroethylsulfinylor 1-(CH2Br)-2-bromoethylsulfinyl. C1-C4-Haloalkylsulfinyl is additionally, for example, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl or nonafluorobutylsulfinyl. C1-C6-Haloalkylsulfinyl is additionally, for example, 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-brompentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl.
The term “alkylsulfonyl” denotes 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-C3-alkylsulfonyl” refers to a C1-C3-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-C3-alkylsulfonyl is additionally, for example, n-propylsulfonyl or 1-methylethylsulfonyl(isopropylsulfonyl). C1-C6-alkylsulfonyl is additionally, for example, butylsulfonyl, 1-methylpropylsulfonyl(sec-butylsulfonyl), 2-methylpropylsulfonyl(isobutylsulfonyl), 1,1-dimethylethylsulfonyl (tert-butylsulfonyl), 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 “haloalkylsulfonyl” denotes a haloalkyl group, as defined above, attached via a sulfonyl [S(O)2] group to the remainder of the molecule. C1-C2-Haloalkylsulfonyl is, for example, S(O)2CH2F, S(O)2CHF2, S(O)2CF3, S(O)2CH2Cl, S(O)2CHCl2, S(O)2CCl3, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl or S(O)2C2F5. C1-C3-Haloalkylsulfonyl is additionally, for example, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, S(O)2CH2-C2F5, S(O)2CF2-C2F5, 1-(CH2F)-2-fluoroethylsulfonyl, 1-(CH2Cl)-2-chloroethylsulfonylor 1-(CH2Br)-2-bromoethylsulfonyl. C1-C4-Haloalkylsulfonyl is additionally, for example, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl. C1-C6-Haloalkylsulfonyl is additionally, for example, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-brompentylsulfonyl, 5-iodopentylsulfonyl, undecafluoropentylsulfonyl, 6-fluorohexylsulfonyl, 6-chlorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl or dodecafluorohexylsulfonyl.
The substituent “oxo” replaces a CH2 group by a C(═O) group.
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 “alkoxycarbonyl” denotes an alkoxy group, as defined above, attached via a carbonyl [C(═O)] group to the remainder of the molecule. C1-C3-Alkoxycarbonyl is a C1-C3-alkoxy group, as defined above, attached via a carbonyl [C(═O)] group to the remainder of the molecule. Examples for C1-C3-alkoxycarbonyl are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoxycarbonyl. C1-C6-Alkoxycarbonyl is a C1-C6-alkoxy group, as defined above, attached via a carbonyl [C(═O)] group to the remainder of the molecule. Examples for C1-C6-alkoxycarbonyl are, in addition to those listed for C1-C3-alkoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl and hexoxycarbonyl.
The term “haloalkoxycarbonyl” denotes a haloalkoxy group, as defined above, attached via a carbonyl [C(═O)] group to the remainder of the molecule. C1-C3-Halolkoxycarbonyl is a C1-C3-haloalkoxy group, as defined above, attached via a carbonyl [C(═O)] group to the remainder of the molecule. Examples for C1-C3-haloalkoxycarbonyl are —C(O)OCH2F, —C(O)OCHF2, —C(O)OCF3, —C(O)OCH2Cl, C(O) OCHCl2, —C(O) OCCl3, chlorofluoromethoxycarbonyl, dichlorofluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl, 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-iodoethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2-chloro-2-fluoroethoxycarbonyl, 2-chloro-2,2-difluoroethoxycarbonyl, 2,2-dichloro-2-fluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, —C(O) OC2F5, 2-fluoropropoxycarbonyl, 3-fluoropropoxycarbonyl, 2,2-difluoropropoxycarbonyl, 2,3-difluoropropoxycarbonyl, 2-chloropropoxycarbonyl, 3-chloropropoxycarbonyl, 2,3-dichloropropoxycarbonyl, 2-bromopropoxycarbonyl, 3-bromopropoxycarbonyl, 3,3,3-trifluoropropoxycarbonyl, 3,3,3-trichloropropoxycarbonyl, —C(O)OCH2-C2F5, —C(O)OCF2-C2F5, 1-(CH2F)-2-fluoroethoxycarbonyl, 1-(CH2Cl)-2-chloroethoxycarbonyl or 1-(CH2Br)-2-bromoethoxycarbonyl.
The term “alkoxycarbonyl-alkyl” denotes an alkyl group, as defined above, in which one hydrogen atom is replaced by an alkoxycarbonyl group, as defined above. C1-C6-Alkoxycarbonyl-C1-C6-alkyl is a C1-C6-alkyl group, as defined above, in which one hydrogen atom is replaced by a C1-C6-alkoxycarbonyl group, as defined above.
Phenyl-(C1-C3-alkyl) is a C1-C3-alkyl group, as defined above, in which one hydrogen atom is replaced by a phenyl ring (i.e. the attachment to the remainder of the molecule is via the alkyl group). Examples are benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl or 2-phenyl-2-propyl.
Furanyl-(C1-C3-alkyl) is a C1-C3-alkyl group, as defined above, in which one hydrogen atom is replaced by a 2- or 3-furanyl ring (i.e. the attachment to the remainder of the molecule is via the alkyl group). Examples are furan-2-yl-methyl, furan-3-yl-methyl, 1-(furan-2-yl)-ethyl, 1-(furan-3-yl)-ethyl, 2-(furan-2-yl)-ethyl, 2-(furan-3-yl)-ethyl and the like.
Phenylthio is a phenyl ring attached via an S atom to the remainder of the molecule.
Phenylsulfinyl is a phenyl ring attached via a S(O) group to the remainder of the molecule.
Phenylsulfonyl is a phenyl ring attached via a S(O)2 group to the remainder of the molecule.
Z is a three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic ring, except phenyl, which is formed from r carbon atoms, n nitrogen atoms, n sulfur atoms and n oxygen atoms. The ring can thus be carbocyclic (i.e. containing only carbon atoms as ring members; r being here 3 to 6 and n being 0) or heterocyclic (i.e. containing also at least one N, O and/or S atom as ring member(s); r being here thus from 1 to 5 and at least one of the n's being 1).
An unsaturated carbocycle contains at least one C═C double bond(s). An unsaturated heterocycle contains at least one C—C and/or C—N and/or N—N double bond(s). Partially unsaturated carbocyclic rings contain less than the maximum number of C═C double bond(s) allowed by the ring size. Partially unsaturated heterocyclic rings contain less than the maximum number of C—C and/or C—N and/or N—N double bond(s) allowed by the ring size. A fully (or maximally) unsaturated carbocyclic ring contains as many conjugated C═C double bonds as allowed by the size(s) of the ring(s). Not encompassed in the definition of Z is however phenyl. A fully (or maximally) unsaturated heterocycle 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). Maximally unsaturated 5- or 6-membered heteromonocyclic rings are generally aromatic. Exceptions are maximally unsaturated 6-membered rings containing O, S, SO and/or SO2 as ring members, such as pyran and thiopyran, which are not aromatic.
Examples for three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic carbocyclic rings Z are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloprop-1-enyl, cycloprop-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl, cyclobutadienyl, cyclopent-1-enyl, cyclopent-2-enyl, cyclopent-3-enyl, cyclopenta-1,3-dienyl, cyclopenta-1,4-dienyl, cyclopenta-2,4-dienyl, cyclohex-1-enyl, cyclohex-2-enyl, cyclohex-3-enyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, cyclohexa-1,5-dienyl, cyclohexa-2,4-dienyl, cyclohexa-2,5-dienyl, and the like.
Examples for three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic heterocyclic rings Z are:
3-, 4-, 5- or 6-membered monocyclic saturated heterocycle: e.g. oxiran-2-yl, thiiran-2-yl, aziridin-1-yl, aziridin-2-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, 1-oxothietan-2-yl, 1-oxothietan-3-yl, 1,1-dioxothietan-2-yl, 1,1-dioxothietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-oxotetrahydrothien-2-yl, 1,1-dioxotetrahydrothien-2-yl, 1-oxotetrahydrothien-3-yl, 1,1-dioxotetrahydrothien-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-ditholan-2-yl, 1,3-ditholan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-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, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-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;
5- or 6-membered monocyclic partially unsaturated heterocycles: e.g. 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,5-dihydrothien-2-yl, 2,5-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, 3,6-dihydro-2H-pyran-2-, -3-, -4-, -5- or 6-yl, 3,4-dihydro-2H-pyran-2-, -3-, -4-, -5- or 6-yl, 3,6-dihydro-2H-thiopyran-2-, -3-, -4-, -5- or 6-yl, 3,4-dihydro-2H-thiopyran-2-, -3-, -4-, -5- or 6-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 tetrahydropyrazinyl;
5- or 6-membered monocyclic fully unsaturated (including aromatic) heterocyclic ring: e.g. 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, 5-imidazolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
Specifically, Z is a five- or six-membered partly unsaturated carbocyclic ring. Examples therefor are cyclopent-1-en-1-yl, cyclopent-2-en-1-yl, cyclopent-3-en-1-yl, cyclopenta-1,3-dien-1-yl, cyclopenta-1,4-dien-1-yl, cyclopenta-2,4-dien-1-yl, cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl, cyclohexa-1,3-dien-1-yl, cyclohexa-1,4-dien-1-yl, cyclohexa-1,5-dien-1-yl, cyclohexa-2,4-dien-1-yl and cyclohexa-2,5-dien-1-yl.
If two radicals bound on the same nitrogen atom (for example Rb2 and Rb3), together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered, saturated N-bound heterocyclic ring which may contain as a ring member a further heteroatom or heteroatom group selected from the group consisting of N, O, S, S(O) and S(O)2, this is for example aziridn-1-yl, azetidin-1-yl, pyrrolidin-1-yl, pyrazolidin-1-yl, imidazolidin-1-yl, oxazolidin-3-yl, thiazolidin-3-yl, isoxazolidin-2-yl, isothiazolin-2-yl, piperdin-1-yl, piperazin-1-yl, morpholin-1-yl, thiomorpholin-1-yl, 1-oxothiomorpholin-1-yl, 1,1-dioxothiomorpholin-1-yl, azepan-1-yl or 1,4-diazepan-1-yl.
If two radicals bound on the same nitrogen atom (for example Rb2 and Rb3), together with the nitrogen atom to which they are bound, form a 5- or 6-membered, saturated N-bound heterocyclic ring, this is pyrrolidin-1-yl or piperidin-1-yl.
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 or salts 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.
Preferably, R1 is hydrogen or (C1-C3)-alkyl, and is more preferably hydrogen.
Preferably, R9 is hydrogen or (C1-C3)-alkyl, and is more preferably hydrogen.
Preferably, R1 and R9 are both hydrogen.
Preferably, R2 is hydrogen, halogen or (C1-C3)-alkyl. More preferably, R2 is hydrogen or halogen. In particular, R2 is hydrogen.
Preferably, R6 is hydrogen, halogen or (C1-C3)-alkyl. More preferably, R6 is hydrogen.
Preferably, R2 and R6, independently of each other, are hydrogen, halogen or (C1-C3)alkyl. More preferably, R2 is hydrogen or halogen and R6 is hydrogen. In particular, R2 is hydrogen and R6 is hydrogen.
Preferably, R3 is hydrogen, halogen, (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy or
(C1-C3)-haloalkoxy. More preferably, R3 is hydrogen, halogen, (C1-C2)-alkyl, (C1-C2)-haloalkyl, (C1-C2)-alkoxy or (C1-C2)-haloalkoxy. Even more preferably, R3 is halogen, (C1-C2)-alkyl, (C1-C2)-haloalkyl, (C1-C2)-alkoxy or (C1-C2)-haloalkoxy. In particular, R3 is halogen, (C1-C2)-alkyl or (C1-C2)-haloalkoxy. Specifically, R3 is hydrogen or halogen.
Preferably, R5 is hydrogen, halogen, (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy or (C1-C3)-haloalkoxy. More preferably, R5 is hydrogen, halogen or (C1-C2)-alkyl. Specifically, R5 is hydrogen or halogen.
Preferably R3 and R5, independently of each other, are hydrogen, halogen, (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy or (C1-C3)-haloalkoxy. More preferably, R3 is hydrogen, halogen, (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy or (C1-C3)-haloalkoxy and R5 is hydrogen, halogen or (C1-C2)-alkyl. Even more preferably, R3 is halogen, (C1-C3)-alkyl or (C1-C3)-haloalkoxy and R5 is hydrogen or halogen. In particular, R3 and R5, independently of each other, are hydrogen or halogen.
Preferably, R4 is hydrogen or halogen. In particular, R4 is hydrogen.
Preferably, R7 and R8, independently of each other, are (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl, each substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl and cyano. Preferably, m is 0, 1 or 2, more preferably, 0 or 1 and specifically 0. Thus, more preferably, R7 and R8, independently of each other, are (in each case unsubstituted) (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl. Even more preferably, R7 and R8, independently of each other, are (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C2-C6)-alkenyl. In particular, R7 and R8, independently of each other, are (C1-C6)-alkyl or (C2-C6)-alkenyl; more particularly (C1-C6)-alkyl; even more particularly (C1-C4)-alkyl, specifically methyl or ethyl, and are very specifically both methyl.
In the divalent radicals (X1) to (X6), the orientation within the molecule is as depicted, the left arrow representing the bond to the adjacent nitrogen atom and the right arrow representing the bond to Y.
When X is a bond (“X0”), the compound (I) can also be depicted as follows:
When X is a divalent radical of the formula (X1), the compound (I) can also be depicted as follows:
When X is a divalent radical of the formula (X2), the compound (I) can also be depicted as follows:
When X is a divalent radical of the formula (X3), the compound (I) can also be depicted as follows:
When X is a divalent radical of the formula (X4), the compound (I) can also be depicted as follows:
When X is a divalent radical of the formula (X5), the compound (I) can also be depicted as follows:
When X is a divalent radical of the formula (X6), the compound (I) can also be depicted as follows:
In the divalent radicals (X1) to (X6), R10-R15, independently of each other and independently of each occurrence, are preferably selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, CO2Re, CONRbRd; (C1-C6)-alkyl, (C3-C5)-cycloalkyl, (C2-C6)-alkenyl, where the three last-mentioned aliphatic and cycloaliphatic radicals are each independently substituted by m fluorine atoms; (C1-C6)-alkoxy, (C3-C6)-cycloalkoxy, (C2-C6)-alkenyloxy, (C2-C6)-alkynyloxy, (C1-C3)-alkylsulfinyl, (C1-C3)-alkylsulfonyl and (C1-C3)-alkylthio, where the aliphatic and cycloaliphatic moieties in the 7 last-mentioned radicals are each independently substituted by m fluorine atoms.
More preferably, R10-R15, independently of each other and independently of each occurrence, are selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, CO2Re, CONRbRd; (C1-C6)-alkyl, (C3-C5)-cycloalkyl, (C2-C6)-alkenyl, where the three last-mentioned aliphatic and cycloaliphatic radicals are each independently substituted by m fluorine atoms; (C1-C6)-alkoxy, (C3-C6)-cycloalkoxy, (C2-C6)-alkenyloxy or (C2-C6)-alkynyloxy, where the aliphatic and cycloaliphatic moieties in the four last-mentioned radicals are each independently substituted by m fluorine atoms.
In particular, R10-R15, independently of each other and independently of each occurrence, are selected from the group consisting of hydrogen, fluorine, chlorine, CO2Re, CONRbRd, (C1-C6)-alkyl substituted by m fluorine atoms, or (C1-C6)-alkoxy substituted by m fluorine atoms.
In particular, R10-R15, independently of each other and independently of each occurrence, are selected from the group consisting of hydrogen, halogen, (C1-C6)-alkyl, (C1-C3)-alkoxy, and CO2Re. More particularly, R10-R15, independently of each other and independently of each occurrence, are hydrogen or (C1-C6)-alkyl and specifically hydrogen or methyl.
Non-exhaustive examples for suitable divalent radicals (X1) to (X6) are CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH(CH2CH3), CH(CH3) CH2, C(CH3) 2, C(CH3) 2CH2, C(iPr)CH3, CH(CH2iPr) CH2, CH2CH═CH, C(CH3) 2C═C, CH(CF3) CH2, CH(CH3) CH2O, CH2CH2O, CH(cPr) CH2O, CH(CH2OCH3), CH(CH2CH2SCH3), CH(COOH), CH(COOCH3), CH(COOH) CH2, CH(COOCH3) CH2, CH2C(OH) (CF3), CH(CONHCH3), CH(CONHCH3) CH2 and CH2CH2CONHCH2, cPr is cyclopropyl; iPr is isopropyl.
In a preferred embodiment, X is a bond or the divalent unit (X1). In the latter, preferably, R10 and R11, independently of each other, are hydrogen or (C1-C6)-alkyl, and more preferably hydrogen or methyl. In particular, one of R10 and R11 is hydrogen and the other is methyl, X1 thus being in particular CH(CH3).
In a preferred embodiment, Y is Z.
Z is preferably a three-, four-, five- or six-membered saturated, partly unsaturated or fully unsaturated carbocyclic ring, except phenyl, which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, S(O), Ra, SO2NRbRd, SO2NRbCORe, CORD, CONReS(O)Ra, CONReSO2Ra, CONRb1SO2NRb2Rb3, NRbRe, NRbCORe, NRbCONReRe, NRbCO2Re, NRbSO2Re, NRb1SO2NRb2Re, OCONRbRe, OCSNRbRe, PORfRf and C(Rb)═NORe, and more preferably by p radicals selected from the group consisting of CO2Re, CONRbRh and CONReS(O)Ra; and where the carbon ring atoms bear n oxo groups. p is in this context preferably 1 or 2, more preferably 1. n is in this context preferably 0 or 1, in particular 0. More preferably, Z is a five- or sixmembered saturated or partly unsaturated carbocyclic ring which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh and CONReS(O)Ra. In particular, Z is a five- or six-membered saturated or partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re. Re is in this context preferably hydrogen, (C1 -C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, and p is in this context preferably 1 or 2, more preferably 1. Thus, more particularly, Z is a five- or sixmembered saturated or partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, more specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is 1 or 2, preferably 1. Even more particularly, Z is a five- or six-membered partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, more specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is 1 or 2, preferably 1. Specifically, Z is a five-membered partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, more specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is 1 or 2, preferably 1.
Examples for five- or six-membered saturated or partly unsaturated carbocyclic rings are listed above. Among these, preference is given to cyclopentyl, cyclopent-1-en-1-yl, cyclopent-2-en-1-yl, cyclopent-3-en-1-yl and cyclohexyl. A specific example is cyclopent-2-en-1-yl. In the latter ring, if p is 1, the mandatory substituent (CO2Re etc.) is preferably bound in the 4-position.
In an alternatively preferred embodiment, Z is a three-, four-, five- or six-membered saturated, partly unsaturated or fully unsaturated heterocyclic ring containing one or two oxygen atoms as ring members, where the ring is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, S(O), Ra, SO2NRbRd, SO2NRbCORe, CORD, CONReS(O)Ra, CONReSO2Ra, CONRb1SO2NRb2Rb3, NRbRe, NRbCORe, NRb- CONReRe, NRbCO2Re, NRbSO2Re, NRb1SO2NRb2Re, OCONRbRe, OCSNRbRe, PORIRf and C(Rb)═NORe, and where the carbon ring atoms bear n oxo groups. p is in this context preferably 1 or 2, more preferably 1. n is in this context preferably 0 or 1, in particular 0. More preferably, Z is a saturated or partly unsaturated five- or six-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by p radicals CO2Re. Re is in this context preferably hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, and p is in this context preferably 1 or 2, more preferably 1. Thus, more particularly, Z is a saturated or partly unsaturated five- or six-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, and p is 1 or 2, preferably 1. Even more particularly, Z is a saturated or partly unsaturated five-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C6)-alkyl. and p is in this context preferably 1 or 2, more preferably 1. Specifically, Z is a saturated or partly unsaturated five-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by one radical CO2Re, where Re is hydrogen or (C1-C6)-alkyl.
Examples for three-, four-, five- or six-membered saturated, partly unsaturated or fully unsaturated heterocyclic rings containing one or two oxygen atoms as ring members are oxiran-2-yl, oxetan-2-yl, oxetan-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 3,6-dihydro-2H-pyran-2-yl, 3,6-dihydro-2H-pyran-3-yl, 3,6-dihydro-2H-pyran-4-yl, 3,6-dihydro-2H-pyran-5-yl, 3,6-dihydro-2H-pyran-6-yl, 3,4-dihydro-2H-pyran-2-yl, 3,4-dihydro-2H-pyran-3-yl, 3,4-dihydro-2H-pyran-4-yl, 3,4-dihydro-2H-pyran-5-yl or 3,4-dihydro-2H-pyran-6-yl.
Examples for saturated or partly unsaturated five- or six-membered heterocyclic rings containing one oxygen atom as ring member are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 3,6-dihydro-2Hpyran-2-yl, 3,6-dihydro-2H-pyran-3-yl, 3,6-dihydro-2H-pyran-4-yl, 3,6-dihydro-2Hpyran-5-yl, 3,6-dihydro-2H-pyran-6-yl, 3,4-dihydro-2H-pyran-2-yl, 3,4-dihydro-2Hpyran-3-yl, 3,4-dihydro-2H-pyran-4-yl, 3,4-dihydro-2H-pyran-5-yl or 3,4-dihydro-2Hpyran-6-yl.
Examples for saturated or partly unsaturated five-membered heterocyclic rings containing one oxygen atom as ring member are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,5-dihydrofuran-2-yl, or 2,5-dihydrofuran-3-yl.
Preferably, however, ring Z is carbocyclic.
In another preferred embodiment, Y is (C1-C8)-alkyl which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, S(O), Ra, SO2NRbRd, SO2NRbCORe, CORD, CONReS(O)Ra, CONReSO2Ra, CONRb1SO2NRb2Rb3, NRbRe, NRbCORe, NRbCONReRe, NRbCO2Re, NRbSO2Re, NRb1SO2NRb2Re, OCONRbRe, OCSNRbRe, PORfRf and C(Rb)═NORe. p is in this context preferably 1 or 2, more preferably 1.
More preferably, Y is (C1-C4)-alkyl which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, CONReS(O)Ra, CONReSO2Ra and
CONRb1SO2NRb2Rb3, where Ra, Rb, Rb1, Rb2, Rb3, Re and Rh are as defined above, where however in particular:
In a preferred embodiment, X is a bond and Y is Z, where Z has one of the above general or preferred meanings.
Preferably, Z is a three-, four-, five- or six-membered saturated, partly unsaturated or fully unsaturated carbocyclic ring, except phenyl, which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, S(O), Ra, SO2NRbRd, SO2NRbCORe, CORD, CONReS(O)Ra, CONReSO2Ra, CONRb1SO2NRb2Rb3, NRbRe, NRbCORe, NRbCONReRe, NRbCO2Re, NRbSO2Re, NRb1SO2NRb2Re, OCONRbRe, OCSNRbRe, PORfRf and C(Rb)═NORe, and where the carbon ring atoms bear n oxo groups. p is in this context preferably 1 or 2, more preferably 1. n is in this context preferably 0 or 1, in particular 0.
More preferably, Z is a five- or six-membered saturated or partly unsaturated carbocyclic ring which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh and CONReS(O)Ra. In particular, Z is a five- or six-membered saturated or partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re. Re is in this context preferably hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, more specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is in this context preferably 1 or 2, more preferably 1. Thus, particularly, Z is a five- or six-membered saturated or partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, more specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is 1 or 2, preferably 1. More particularly, Z is a five- or six-membered partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, more specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is 1 or 2, preferably 1. Specifically, Z is a five-membered partly unsaturated carbocyclic ring which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C6)-alkyl, specifically hydrogen or (C1-C4)-alkyl, very specifically hydrogen or methyl, and p is 1 or 2, preferably 1.
In an alternatively preferred embodiment, Z is a three-, four-, five- or six-membered saturated, partly unsaturated or fully unsaturated heterocyclic ring containing one or two oxygen atoms as ring members, where the ring is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, S(O),Ra, SO2NRbRd, SO2NRbCORe, CORD, CONReS(O)Ra, CONReSO2Ra, CONRb1SO2NRb2Rb3, NRbRe, NRbCORe, NRb- CONReRe, NRbCO2Re, NRbSO2Re, NRb1SO2NRb2Re, OCONRbRe, OCSNRbRe, PORfRf and C(Rb)═NORe, and where the carbon ring atoms bear n oxo groups. p is in this context preferably 1 or 2, more preferably 1. n is in this context preferably 0 or 1, in particular 0.
More preferably, Z is a saturated or partly unsaturated five- or six-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by p radicals CO2Re. Re is in this context preferably hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, and p is in this context preferably 1 or 2, more preferably 1. Thus, particularly, Z is a saturated or partly unsaturated five- or six-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by p radicals CO2Re, where Re is hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; specifically hydrogen or (C1-C6)-alkyl, and p is 1 or 2, preferably 1. More particularly, Z is a saturated or partly unsaturated five-membered heterocyclic ring containing one oxygen atom as ring member, where the ring is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C6)-alkyl and p is 1 or 2, preferably 1.
Preferably, however, ring Z is carbocyclic.
In another preferred embodiment,
In an alternative preferred embodiment,
More preferably,
In this context, Y is preferably (C1-C4)-alkyl which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C4)-alkyl, e.g. hydrogen or methyl; specifically (C1-C4)-alkyl, e.g. methyl.
In an alternative more preferred embodiment,
In this latter alternative more preferred embodiment, (C1-C6)-alkyl in Y is preferably a group-C(R101) (R111)—C1-C4-alkyl which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, CONReS(O)Ra, CONReSO2Ra and CONRb1SO2NRb2Rb3, where Ra, Rb, Rb1, Rb2, Rb3, Re and Rh have one of the above general or preferred meanings and R101 and R111 are independently hydrogen or methyl, where however preferably one of R101 and R111 is hydrogen and the other is methyl.
In this context, Y is preferably a group-C(R101) (R111)—C1-C4-alkyl which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C4)-alkyl, e.g. hydrogen or methyl, specifically (C1-C4)-alkyl, e.g. methyl, and R101 and R111 are independently hydrogen or methyl, where however preferably one of R101 and R111 is hydrogen and the other is methyl.
Even more preferably,
In this context, Y is preferably (C1-C4)-alkyl which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C4)-alkyl (e.g. hydrogen or methyl), in particular (C1-C4)-alkyl (e.g. methyl).
In an alternative even more preferred embodiment,
In this latter alternative even more preferred embodiment, (C1-C6)-alkyl in Y is preferably a group-C(R101) (R111)—C1-C4-alkyl which is substituted by p radicals selected from the group consisting of CO2Re, CONRbRh, CONReS(O)Ra, CONReSO2Ra and CONRb1SO2NRb2Rb3, where Ra, Rb, Rb1, Rb2, Rb3, Re and Rh have one of the above general or preferred meanings and R101 and R111 are independently hydrogen or methyl, where however preferably one of R101 and R111 is hydrogen and the other is methyl.
In this context, Y is preferably a group-C(R101) (R111)—C1-C4-alkyl which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C4)-alkyl, specifically hydrogen or methyl, and R101 and R111 are independently hydrogen or methyl, where however preferably one of R101 and R111 is hydrogen and the other is methyl.
Specifically,
In this context, Y is preferably (C1-C4)-alkyl which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C4)-alkyl; specifically hydrogen or methyl.
In an alternative specific embodiment,
In this context, Y is preferably CH(CH3)—(C1-C4)-alkyl which is substituted by p radicals CO2Re, where Re is hydrogen or (C1-C4)-alkyl.
In an alternatively preferred embodiment, -X-Y form together a group of the formula (XY1) or (XY2)
where
Re in groups (XY1) and (XY2) is preferably hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; more preferably hydrogen or (C1-C6)-alkyl, and is specifically (C1-C6)-alkyl.
More preferably,
in group of the formula (XY2)
In an alternatively preferred embodiment, -X-Y form together a group of the formula (XY1) or (XY2)
where
Re in this context is preferably hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl; more preferably hydrogen or (C1-C6)-alkyl, and is specifically (C1-C6)-alkyl.
More preferably,
In a particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
In a more particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
Rb2 and Rb3, together with the nitrogen atom they are bound to, form a saturated 5- or 6-membered N-bound heterocyclic ring; and
In an even more particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
In a specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
In a more specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
In a very specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
In an alternative particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
In an alternative more particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
In an even more particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
In a specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
In an alternative more specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
In a very specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
In the above particular and specific embodiments, the five-membered partly unsaturated carbocyclic ring Z is preferably a ring Z9 (depicted below), wherein # denotes the attachment point to the remainder of the molecule and Rx is CO2Re.
In another particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
where
In another more particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
in group of the formula (XY2)
In another specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
in group of the formula (XY1)
in group of the formula (XY2)
In another more specific embodiment, in the compounds of formula (I), the substituents have the following meanings:
in group of the formula (XY1)
in group of the formula (XY2)
In yet another particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
where
In yet another more particular embodiment, in the compounds of formula (I), the substituents have the following meanings:
Compounds (I), wherein R1, R6 and R9 are hydrogen and R2, R3, R4, R5, R7 and R8 have the meanings as defined in each line of table A below are particularly preferred.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—H.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CH2CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH(CH3) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—C(CH3) 3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CN.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CHF2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CH2F.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CF3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2CH═CH2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2C═CH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O—CH2C6H5 (CH2C6H5=benzyl).
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O-cyclopropyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O-cyclobutyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O-cyclopentyl.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O)O-cyclohexyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—H.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH(CH3) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—C(CH3) 3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CN.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CHF2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CH2F.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CF3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2CH═CH2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2C═CH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O—CH2C6H5 (CH2C6H5=benzyl).
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O-cyclopropyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O-cyclobutyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O-cyclopentyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2CH2—C(═O)O-cyclohexyl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—OCH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—OCH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)—CF3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)—CH2CH2F.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)—CH2CHF2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)—CH2CF3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH(CH3) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—C(CH3) 3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CF3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CHF2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CH2F.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—CH2CF3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH2CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH(CH3) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) CH2CH(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(H) C(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) CH2CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) CH(CH3) 2.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) CH2CH2CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) CH(CH3) CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) CH2CH(CH3) 2.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2—N(CH3) C(CH3) 2.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2-piperdin-1-yl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2-piperazin-1-yl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2-morpholin-4-yl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for —CH(CH3)—CH2—C(═O) NH—S(O)2-thiomorpholin-4-yl.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z1), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z1), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z1), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z2), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z2), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z2), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z3), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z3), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z3), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z4), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z4), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z4), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z5), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z5), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z5), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z6), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z6), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z6), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z7), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z7), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z7), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z8), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z8), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z8), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z9), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z9), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z9), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z10), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z10), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z10), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z11), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z11), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z11), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z12), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z12), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z12), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z13), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z13), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z13), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z14), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z14), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z14), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z15), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z15), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z15), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z16), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z16), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z16), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z17), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z17), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z17), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z18), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z18), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z18), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z19), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z19), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z19), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z20), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z20), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z20), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z21), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z21), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z21), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z22), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z22), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z22), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z23), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z23), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z23), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z24), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z24), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z24), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z25), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z25), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z25), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z26), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z26), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z26), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z27), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z27), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z27), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z28), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z28), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z28), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z29), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z29), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z29), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z30), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z30), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z30), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z31), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z31), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z31), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z32), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z32), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z32), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z33), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z33), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z33), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z34), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z34), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (1) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z34), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z35), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z35), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z35), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH2CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z36), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O) OH.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R5, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z36), wherein # denotes the attachment point to the remainder of the molecule and Rx is-C(═O)O—CH3.
Particularly preferred are moreover compounds (I) in which for a single compound R1, R6 and R9 are hydrogen, R2, R3, R4, R6, R7 and R8 have one of the meanings as defined in a single line of table A and X-Y in combination stand for a ring of the formula (Z3%), wherein # denotes the attachment point to the remainder of the molecule and Rx is —C(═O)O—CH2CH3.
Among rings Z1 to Z36, particular preference is given to rings Z9.
The compounds of formula (I) according to the invention can be prepared by standard processes of organic chemistry, for example by the following processes:
The compounds of formula (I) can be prepared according to methods or in analogy to methods that are described in the prior art. The synthesis takes advantage of starting materials that are commercially available or may be prepared according to conventional procedures starting from readily available compounds.
Compounds of the formula (I) can be prepared from the carboxylic acids (III) and commercially available amines (II) using an organic base and a coupling reagent. Thus, compounds of formula (I) can be synthesized from the corresponding carboxylic acids (1 eq.) using a coupling reagent (1-2 eq.), for example T3P (propane phosphonic acid anhydride) or HATU (O-(7-azabenzotriazole-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluorophosphate), an organic base (1-3 eq.) and the amines (II) (1-3 eq.). The reaction is typically carried out in an organic solvent. Preferably an aprotic organic solvent is used. Most preferably tetrahydrofuran (THF), N,N-dimethylformamide (DMF) or acetonitrile (ACN) are used. The reaction is carried out at temperatures between 0° C. and reflux. Preferably the reaction is carried out at room temperature. Preferably the organic base is triethylamine or N,N-diisopropylethylamine.
The carboxylic acids (III) are commercially available or can be prepared from the corresponding esters (IV) (wherein RP is alkyl or benzyl). If RP is alkyl, esters (IV) may be cleaved using aqueous alkali metal hydroxides. Preferably lithium hydroxide, sodium hydroxide or potassium hydroxide (1-2 eq.) are employed. The reaction is typically carried out in mixtures of water and an organic solvent. Preferably the organic solvent is THF, methanol or acetonitrile. The reaction is carried out at temperatures between 0° C. and 100° C. Preferably the reaction is carried at room temperature. If RP is benzyl in (IV), then the ester may be cleaved using palladium on charcoal (0.001-1 eq.) as catalyst and hydrogen gas at temperatures between 0° C. and reflux. Preferably the reaction is carried out at room temperature. Typically, an organic solvent is employed. Preferably THF, methanol or ethanol are employed.
Compounds of the formula (IV) are commercially available or can be prepared by known methods. For example, the esters (IV) can be prepared according to methods described in Organometallics 2001, 20 (22), 4675-4682. For example, they can be prepared from the carboxylic acids (VI) and commercially available amines (V) using a base and a coupling reagent.
Thus, compounds of formula (IV) can be synthesized from the corresponding carboxylic acids (1 eq.) using a coupling reagent (1-2 eq.), for example T3P (propanephosphonic acid anhydride) or HATU (O-(7-azabenzotriazole-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluorphosphate), an organic base (1-3 eq.) and the amines (V) (1-3 eq.). The reaction is typically carried out in an organic solvent. Preferably an aprotic organic solvent is used. Most preferably tetrahydrofuran (THF), N,Ndimethylformamide (DMF) or acetonitrile (ACN) are used. The reaction is carried out at temperatures between 0° C. to refluxing temperatures. Preferably the reaction is carried out at room temperature. Preferably the organic base is triethylamine or N,N-diisopropylethylamine.
Carboxylic acid (VI) may be prepared from the corresponding diester by selective cleavage of one ester group. If Ra is an alkyl ester, selective ester cleavage may be achieved using an aqueous base. Preferably an alkali metal hydroxide is used. Most preferably lithium hydroxide, sodium hydroxide or potassium hydroxide are used. The reaction is typically carried out in mixtures of water and an organic solvent. Preferably THF, methanol or acetonitrile are employed. The reaction is carried out at temperatures between 0° C. and 100° C., preferably at room temperature.
Alternatively, trimethyltin hydroxide (e.g. 1 eq.) in 1,2-dichlorethane at room temperature to reflux may be used (as described in Angew. Chem. Int. Ed, 2005, 44:1378-1382), preferably at reflux. If Ra is benzyl in (VII), then the ester may be cleaved using palladium on charcoal (0.001-1 eq.) as catalyst and hydrogen gas at temperatures between 0° C. and reflux. Preferably the reaction is carried out at room temperature. Typically, an organic solvent is employed. Preferably THF, methanol or ethanol are employed.
The diesters (VII) are either commercially available or can be prepared by standard methods of organic chemistry.
Amines of the formula (XIII) can be prepared from the lactames (XIV), which are either commercially available or may be prepared by alkylation as described in Org. Process Res. Dev. 2018, 22, 337-343, and commercially available alcohols (XV) using thionyl chloride (2 eq.) as described in Tetrahedron Lett. 2001, 42, 1347-1350. The reaction is typically carried out in the coupling alcohols (XV) as the solvent. The reaction is carried out at temperatures between 0° C. to refluxing temperatures. Preferably the reaction is carried out at room temperature.
To widen the spectrum of action, the compounds of formula (I) may be mixed with many representatives of other herbicidal or growth-regulating active ingredient groups and then applied concomitantly. Suitable components for combinations are, for example, herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.
It may furthermore be beneficial to apply the compounds of formula (I) alone or in combination with other herbicides, or else in the form of a mixture with other crop protection agents, for example together with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Other additives such as non-phytotoxic oils and oil concentrates may also be added.
In one embodiment of the present invention the combinations according to the present invention comprise at least one compound of formula (I) (compound A or component A) and at least one further active compound selected from herbicides B (compound B), preferably herbicides B of class b1) to b15), and safeners C(compound C).
In another embodiment of the present invention the combinations according to the present invention comprise at least one compound of formula (I) and at least one further active compound B (herbicide B).
Examples of herbicides B which can be used in combination with the compounds A of formula (I) according to the present invention are:
b1) from the group of the lipid biosynthesis inhibitors:
ACC-herbicides such as 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, 4-(4′-Chloro-4-cyclopropyl-2′-fluoro [1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3 (6H)-one (CAS 1312337-72-6); 4-(2′,4′-Dichloro-4-cyclopropyl [1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3 (6H)-one (CAS 1312337-45-3); 4-(4′-Chloro-4-ethyl-2′-fluoro [1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3 (6H)-one (CAS 1033757-93-5); 4-(2′,4′-Dichloro-4-ethyl [1,1′-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2Hpyran-3,5 (4H,6H)-dione (CAS 1312340-84-3); 5-(Acetyloxy)-4-(4′-chloro-4-cyclopropyl-2′-fluoro [1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5-(Acetyloxy)-4-(2′,4′-dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5-(Acetyloxy)-4-(4′-chloro-4-ethyl-2′-fluoro [1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312340-82-1); 5-(Acetyloxy)-4-(2′,4′-dichloro-4-ethyl [1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4′-Chloro-4-cyclopropyl-2′-fluoro [1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312337-51-1); 4-(2′,4′-Dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester; 4-(4′-Chloro-4-ethyl-2′-fluoro [1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312340-83-2); 4-(2′,4′-Dichloro-4-ethyl [1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1033760-58-5); and non ACC herbicides such as 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:
sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methylsodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron, imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, triazolopyrimidine herbicides and sulfonanilides such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam, pyrimidinylbenzoates such as bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, 4-[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1-methylethyl ester (CAS 420138-41-6), 4-[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138 Jan. 8), sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazonesodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl; and triafamone;
among these, a preferred embodiment of the invention relates to those compositions comprising at least one imidazolinone herbicide;
b3) from the group of the photosynthesis inhibitors:
amicarbazone, inhibitors of the photosystem II, e.g. 1-(6-tert-butylpyrimidin-4-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one (CAS 1654744-66-7), 1-(5-tertbutylisoxazol-3-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one (CAS 1637455 Dec. 9), 1-(5-tert-butylisoxazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one (CAS 1637453-94-1), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2Hpyrrol-5-one (CAS 1654057-29-0), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-3-chloro-2-hydroxy-4-methyl-2H-pyrrol-5-one (CAS 1654747-80-4), 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; (CAS 2023785-78-4), 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 2023785-79-5), 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 1701416-69-4), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 1708087-22-2), 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl) pyrazol-3-yl]imidazolidin-2-one (CAS 2023785-80-8), 1-(5-tertbutylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one (CAS 1844836-64-1), triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-dimetilsulfate. Among these, a preferred embodiment of the invention relates to those compositions comprising at least one aryl urea herbicide. Among these, likewise a preferred embodiment of the invention relates to those compositions comprising at least one triazine herbicide. Among these, likewise a preferred embodiment of the invention relates to those compositions comprising at least one nitrile herbicide;
b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:
acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumicloracpentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, 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 (CAS 353292-31-6; S-3100), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452099 May 7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452100 Mar. 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 (CAS 451484-50-7), 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 (CAS 1300118-96-0), 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 (CAS 1304113-05-0), methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1 H-methyl-pyrazol-3-yl]-4-fluorophenoxy]-3-methoxy-but-2-enoate (CAS 948893-00-3), and 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (CAS 212754 Feb. 4), 2-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-fluorophenoxy]-2-methoxy-acetic acid methyl ester (CAS 1970221-16-9), 2-[2-[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-acetic acid methyl ester (CAS 2158274-96-3), 2-[2-[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]acetic acid ethyl ester (CAS 158274-50-9), methyl 2-[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2 -pyridyl]oxy]acetate (CAS 2271389-22-9), ethyl 2-[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2230679-62-4), 2-[3-[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-acetic acid methyl ester (CAS 2158275-73-9), 2-[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]acetic acid ethyl ester (CAS 2158274-56-5), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-N-(methylsulfonyl)-acetamide (CAS 2158274-53-2), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-N-(methylsulfonyl)-acetamide (CAS 2158276-22-1);
b5) from the group of the bleacher herbicides:
PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)-pyrimidine (CAS 180608-33-7), HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione (CAS 1486617-21-3), pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bleacher, unknown target: aclonifen, amitrole flumeturon 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethyl) benzamide (CAS 1361139-71-0), bixlozone and 2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS 81778-66-7);
b6) from the group of the EPSP synthase inhibitors:
glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosatetrimesium (sulfosate);
b7) from the group of the glutamine synthase inhibitors:
bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinateammonium;
b8) from the group of the DHP synthase inhibitors:
asulam;
b9) from the group of the mitosis inhibitors:
compounds of group K1: dinitroanilines such as benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin, phosphoramidates such as amiprophos, amiprophos-methyl, and butamiphos, benzoic acid herbicides such as chlorthal, chlorthal-dimethyl, pyridines such as dithiopyr and thiazopyr, benzamides such as propyzamide and tebutam; compounds of group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flampropM-isopropyl, flamprop-M-methyl and propham; among these, compounds of group K1, in particular dinitroanilines are preferred;
b10) from the group of the VLCFA inhibitors:
chloroacetamides such as acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor, oxyacetanilides such as flufenacet and mefenacet, acetanilides such as diphenamid, naproanilide, napropamide and napropamide-M, tetrazolinones such fentrazamide, and other herbicides such as anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone and isoxazoline compounds of the formulae II.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8 and II.9
b11) from the group of the cellulose biosynthesis inhibitors:
chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam and 1-cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine (CAS 175899 Jan. 1);
b12) from the group of the decoupler herbicides:
dinoseb, dinoterb and DNOC and its salts;
b13) from the group of the auxinic herbicides:
2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, 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, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters (CAS 943832-60-8); 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, florpyrauxifen, florpyrauxifen-benzyl (CAS 1390661-72-9) and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) picolinic acid (CAS 1629965-65-6);
b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyrsodium, naptalam and naptalam-sodium;
b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenolmethyl, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine tetflupyrolimet, and tridiphane.
Moreover, it may be useful to apply the compounds of formula (I) in combination with safeners. Safeners are chemical compounds which prevent or reduce damage on useful plants without having a major impact on the herbicidal action of the compounds of the formula (I) towards undesired vegetation. They can be applied either before sowings (e.g. on seed treatments, shoots or seedlings) or in the pre-emergence application or post-emergence application of the useful plant. The safeners and the compounds of formula (I) and optionally the herbicides B can be applied simultaneously or in succession.
In another embodiment of the present invention the combinations according to the present invention comprise at least one compound of formula (I) and at least one safener C(component C).
Examples of safeners are e.g. (quinolin-8-oxy) acetic acids, 1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acids, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.
Examples of safener compounds C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526 Jul. 3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4), metcamifen and BPCMS (CAS 54091 Jun. 4).
The active compounds B of groups b1) to b15) and the active compounds C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); Farm Chemicals Handbook 2000 volume 86, Meister Publishing Company, 2000; B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart 1995; W. H. Ahrens, Herbicide Handbook, 7th edition, Weed Science Society of America, 1994; and K. K. Hatzios, Herbicide Handbook, Supplement for the 7th edition, Weed Science Society of America, 1998. 2,2,5-Trimethyl-3-(dichloroacetyl)-1,3-oxazolidine [CAS No. 52836-31-4] is also referred to as R-29148. 4-(Dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane [CAS No. 71526 Jul. 3] is also referred to as AD-67 and MON 4660.
The assignment of the active compounds to the respective mechanisms of action is based on current knowledge. If several mechanisms of action apply to one active compound, this substance was only assigned to one mechanism of action.
The invention also relates to formulations comprising at least an auxiliary and at least one compound of formula (I) according to the invention.
A formulation comprises a pesticidally effective amount of a compound of formula (I). The term “effective amount” denotes an amount of the combination or of the compound of formula (I), which is sufficient for controlling undesired vegetation, especially for controlling undesired vegetation in crops (i.e. cultivated plants) and which does not result in a substantial damage to the treated crop plants. Such an amount can vary in a broad range and is dependent on various factors, such as the undesired vegetation to be controlled, the treated crop plants or material, the climatic conditions and the specific compound of formula (I) used.
The compounds of formula (I), their salts, amides, esters or thioesters can be converted into customary types of formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further formulation types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2,6th Ed. May 2008, CropLife International.
The formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in Mccutcheon's, Vol. 1: Emulsifiers & Detergents, Mccutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyland tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for formulation types and their preparation are:
In an agitated ball mill, 20-60 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are comminuted with addition of 2-10 wt % dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt % thickener (e.g. xanthan gum) and water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type formulation up to 40 wt % binder (e.g. polyvinylalcohol) is added.
In an agitated ball mill, 5-25 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are comminuted with addition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose) and water ad 100 wt % to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
5-20 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C(component C) according to the invention are added to 5-30 wt % organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
An oil phase comprising 5-50 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt % of a compound of formula (I) according to the invention, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt %. The wt % relate to the total CS formulation.
1-10 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C(component C) according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt %.
0.5-30 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C(component C) according to the invention is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt %. Granulation is achieved by extrusion, spray-drying or the fluidized bed.
1-50 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C(component C) according to the invention are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %.
The formulation types i) to xi) may optionally comprise further auxiliaries, such as 0,1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0,1-1 wt % anti-foaming agents, and 0,1-1 wt % colorants.
The formulations and/or combinations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of the compounds of formula (I).
The compounds of formula (I) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The formulations in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. (nach unten verschoben)
Methods for applying compounds of formula (I), formulations and/or combinations thereof, on to plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compounds of formula (I), formulations and/or combinations thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
Various types of oils, wetting agents, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the compounds of formula (I), the formulations and/or the combinations comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the formulations according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
The user applies the compounds of formula (I) according to the invention, the formulations and/or the combinations comprising them usually from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the formulation is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the formulation according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, either individual components of the formulation according to the invention or partially premixed components, e.g. components comprising compounds of formula (I) and optionally active substances from the groups B and/or C), may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, individual components of the formulation according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the formulation according to the invention or partially premixed components, e.g. components comprising compounds of formula (I) and optionally active substances from the groups B and/or C), can be applied jointly (e.g. after tank mix) or consecutively.
The compounds of formula (I), are suitable as herbicides. They are suitable as such, as an appropriate formulation or in combination with at least one further compound selected from the herbicidal active compounds B (component B) and safeners C(component C).
The compounds of formula (I), or the formulations and/or combinations comprising the compounds of formula (I), control undesired vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
The compounds of the invention are useful for controlling for example following weeds: Abutilon theophrasti (ABUTH), Alopercurus myosuroides (ALOMY), Amaranthus retro-flexus (AMARE), Apera spica-venti (APESV), Avena fatua (AVEFA), Digitaria sanguinalis (DIGSA), Echinocloa crus-galli (ECHCG), Lolium multiflorum (LOLMU) Setaria faberi (SETFA), Setaria viridis (SETVI), to name just a few representative examples.
The compounds of formula (I), or the formulations and/or the combinations comprising them, are applied to the plants mainly by spraying the leaves. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 100 to 1000 l/ha (for example from 300 to 400 l/ha). The compounds of formula (I), or the formulations and/or the combinations comprising them, may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.
Application of the compounds of formula (I), or the formulations and/or the combinations comprising them, can be done before, during and/or after, preferably during and/or after, the emergence of the undesired vegetation.
Application of the compounds of formula (I), or the formulations and/or the combinations can be carried out before or during sowing.
The compounds of formula (I), or the formulations and/or the combinations comprising them, can be applied pre-, post-emergence or pre-plant, or together with the seed of a crop plant. It is also possible to apply the compounds of formula (I), or the formulations and/or the combinations comprising them, by applying seed, pretreated with the compounds of formula (1), or the formulations and/or the combinations comprising them, of a crop plant. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the combinations 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 ingredients reach the leaves of undesired vegetation growing underneath, or the bare soil surface (postdirected, lay-by).
In a further embodiment, the compounds of formula (I), or the formulations and/or the combinations comprising them, can be applied by treating seed. The treatment of seeds 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 formula (I), or the formulations and/or the combinations prepared therefrom. Here, the combinations can be applied diluted or undiluted.
The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the crop plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
When employed in plant protection, the amounts of active substances applied, i.e. the compounds of formula (I), component B and, if appropriate, component C without formulation auxiliaries, are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha and in particular from 0.1 to 0.75 kg per ha.
In another embodiment of the invention, the application rate of the compounds of formula (I), component B and, if appropriate, component C, is from 0.001 to 3 kg/ha, preferably from 0.005 to 2.5 kg/ha and in particular from 0.01 to 2 kg/ha of active substance (a.s.).
In another preferred embodiment of the invention, the rates of application of the compounds of formula (I) according to the present invention (total amount of compounds of formula (I)) are from 0.1 g/ha to 3000 g/ha, preferably 10 g/ha to 1000 g/ha, depending on the control target, the season, the target plants and the growth stage.
In another preferred embodiment of the invention, the application rates of the compounds of formula (I) are in the range from 0.1 g/ha to 5000 g/ha and preferably in the range from 1 g/ha to 2500 g/ha or from 5 g/ha to 2000 g/ha.
In another preferred embodiment of the invention, the application rate of the compounds of formula (I) is 0.1 to 1000 g/ha, preferablyl to 750 g/ha, more preferably 5 to 500 g/ha.
The required application rates of herbicidal compounds B are generally in the range of from 0.0005 kg/ha to 2.5 kg/ha and preferably in the range of from 0.005 kg/ha to 2 kg/ha or 0.01 kg/ha to 1.5 kg/h of a.s.
The required application rates of safeners C are generally in the range of from 0.0005 kg/ha to 2.5 kg/ha and preferably in the range of from 0.005 kg/ha to 2 kg/ha or 0.01 kg/ha to 1.5 kg/h of a.s.
In treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
In another embodiment of the invention, to treat the seed, the amounts of active substances applied, i.e. the compounds of formula (I), component B and, if appropriate, component C are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect.
Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
In case of combinations according to the present invention it is immaterial whether the compounds of formula (I), and the further component B and/or the component C are formulated and applied jointly or separately.
In the case of separate application, it is of minor importance, in which order the application takes place. It is only necessary, that the compounds of formula (I), and the further component B and/or the component C are applied in a time frame that allows simultaneous action of the active ingredients on the plants, preferably within a time-frame of at most 14 days, in particular at most 7 days.
Depending on the application method in question, the compounds of formula (I), or the formulations and/or combinations comprising them, can additionally be employed in a further number of crop plants for eliminating undesired vegetation. Examples of suitable crops are the following:
Especially preferred crops are crops of cereals, corn, soybeans, rice, oilseed rape, cotton, potatoes, peanuts or permanent crops.
The compounds of formula (I) according to the invention, or the formulations and/or combinations comprising them, can also be used in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
The term “crops” as used herein includes also (crop) plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.
Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
Transgenic corn events comprising herbicide tolerance genes are for example, but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-Ø1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTØH2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN 10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like crylA, crylAb, crylAb-Ac, crylAc, crylA.105, crylF, crylFa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A (a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particular genes coding for protease inhibitors, like CpTI and pinll. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes. An example for such a transgene is dvsnf7.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701, MON87751 and DAS-81419.
Transgenic cotton events comprising genes for insecticidal proteins are for example, but not excluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM CrylA, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321. Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
Crops comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-ØØ410-5.
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-gmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and WO2017/011288.
The use of the compounds of formula (I) or formulations or combinations comprising them according to the invention on crops may result in effects which are specific to a crop comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigor, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of ingredients or new ingredients, specifically to improve raw material production, e.g., potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
Furthermore, it has been found that the compounds of formula (I) according to the invention, or the formulations and/or combinations comprising them, are also suitable for the defoliation and/or desiccation of plant parts of crops such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton. In this regard, formulations and/or combinations for the desiccation and/or defoliation of crops, processes for preparing these formulations and/or combinations and methods for desiccating and/or defoliating plants using the compounds of formula (I) have been found.
As desiccants, the compounds of 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 pernicious 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 controlled 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.
Chemical bonds, drawn as bars in chemical formulae, indicate the relative stereochemistry on the ring system.
1.1 Lithium 3-ethoxy-2,2-dimethyl-3-oxo-propanoate:
Diethyl 2,2-dimethylpropanedioate (20.0 g; 106 mmol) was dissolved in a mixture of THF (50 mL) and water (50 mL). Lithium hydroxide (2.55 g; 106 mmol) was added in portions. The reaction mixture was stirred at room temperature for 60 hours. The solution was concentrated in vacuo and dried in vacuum drying cabinet over night at 50° C. to give the crude product (9.90 g) which was used without further purification for the next step.
1.2 Ethyl 3-(3-chloroanilino)-2,2-dimethyl-3-oxo-propanoate:
A mixture of 3-chloroaniline (1.84 g; 14.5 mmol; 1.2 eq), an aliquot of the crude lithium salt of 3-ethoxy-2,2-dimethyl-3-oxo-propanoate (2.00 g; 12.0 mmol; 1 eq) and triethylamine (3.66 g; 36.1 mmol; 3 eq) in THF (20 mL) was treated with n-propanephosphonic acid anhydride (13.0 g; 20.5 mmol; 1.7 eq; 50% solution in ethyl acetate; T3P; CAS [68957-94-8]) and stirred overnight at room temperature. Water (30 mL) was added, and the reaction mixture extracted with ethyl acetate. The organic solution was washed with aqueous hydrochloric acid solution (1 M) and water, dried over sodium sulfate and concentrated in vacuo to give crude ethyl 3-(3-chloroanilino)-2,2-dimethyl-3-oxopropanoate (3.10 g) which was again used for the next step without further purification.
1.3 3-(3-Chloroanilino)-2,2-dimethyl-3-oxo-propanoic acid:
Crude ethyl 3-(3-chloroanilino)-2,2-dimethyl-3-oxo-propanoate (3.10 g; 11.5 mmol) was dissolved in a mixture of THF (20 mL) and water (20 mL). Lithium hydroxide (0.551 g; 23.0 mmol; 2 eq) was added in portions. The reaction mixture was stirred at room temperature for 3 hours. The THF was evaporated in vacuo and the slurry was treated with methyl tert-butyl ether and the resulting two phases were separated. The aqueous solution was adjusted to ca. pH 1 with concentrated hydrochloric acid solution. The product 3-(3-chloroanilino)-2,2-dimethyl-3-oxo-propanoic acid precipitated overnight and was filtered. (0.80 g; 29% yield).
1H NMR: (400 MHz; DMSO) δ=12.7 (br s, 1H), 9.65 (s, 1H), 7.85 (s, 1H), 7.55 (d, 1H), 7.30 (t, 1H), 7.10 (d, 1H), 1.40 (s, 6H)
1.4 Methyl (3S)-3-[3-(3-chloroanilino)-2,2-dimethyl-3-oxo-propanoyl]amino]butanoate
To a solution of 3-(3-chloroanilino)-2,2-dimethyl-3-oxo-propanoic acid (250 mg, 1.03 mmol) in dimethylformamide (DMF, 5 ml) methyl (3S)-3-aminobutanoate (Shomoalanine) hydrochloride (194 mg, 1.19 mmol) was added. To the resulting solution was added HATU (2-(7-aza-1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate, CAS [148893 Oct. 1]), (452 mg, 1.19 mmol) and then diisopropylethylamine (257 mg, 2.07 mmol)). The resulting reaction mixture was stirred at room temperature for a few hours. Water and ethyl acetate were added. The ethyl acetate phase was washed with saturated sodium chloride solution and the solvent evaporated under reduced pressure. The crude product was purified by reversed phase chromatography using acetonitrile/water as eluent. This gave 190 mg (54%) of the product. 1H NMR: (400 MHZ, CDCl3) d=9.55 (s, 1H), 7.75 (s, 1H), 7.4 (d, 1H), 7.25 (t, 1H), 7.1 (d, 1H), 6.95 (1 H), 4.35 (m, 1H), 3.7 (s, 3H), 2.55 (q, 2H), 1.55 (s, 6H), 1.25 (d, 3H).
In analogy to the examples described above, the following compounds of formula (I), wherein R1, R2, R6 and R9 are hydrogen and R3, R4, R5, R7, R8 and X-Y (depicted together with the nitrogen atom to which-X-Y is bound to show the stereochemistry) are compiled in Table 1, were prepared, starting from commercially available diesters and using commercially available amines:
The herbicidal activity of the compounds of 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 test plants had rooted. This cover caused uniform germination of the test plants, unless this had 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 test plants were kept at 10-25° C. or 20-35° C., respectively.
The test period extended over 2 to 4 weeks. During this time, the test 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 test 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 70 to <90 and a very good herbicidal activity is given at values of 90 to 100.
The test plants used in the greenhouse experiments were of the following species:
Abutilon theophrasti
Alopercurus myosuroides
Amaranthus retroflexus
Apera spica-venti
Avena fatua
Digitaria sanguinalis
Echinocloa crus-galli
Lolium multiflorum
Setaria faberi
Setaria viridis
At an application rate of 0.250 kg/ha, applied by the pre-emergence method:
At an application rate of 0.250 kg/ha, applied by the post-emergence method:
At an application rate of 0.500 kg/ha, applied by the pre-emergence method:
At an application rate of 0.500 kg/ha, applied by the post-emergence method:
| Number | Date | Country | Kind |
|---|---|---|---|
| 21193044.1 | Aug 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/073602 | 8/24/2022 | WO |
