TREA

SUBSTITUTED PYRIDINE COMPOUNDS HAVING HERBICIDAL ACTIVITY

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Information

  • Patent Application
  • 20160102103
  • Publication Number
    20160102103
  • Date Filed
    May 14, 2014
    10 years ago
  • Date Published
    April 14, 2016
    8 years ago
Information
Abstract
The present invention provides a substituted pyridine compound of the formula I
Description

The present invention relates to substituted pyridine compounds of the general formula (I) defined below and to their use as herbicides. Moreover, the invention relates to compositions for crop protection and to a method for controlling unwanted vegetation.


WO 2009/063180 and WO 2010/029311 describe certain herbicidal pyridopyrazines.


WO 2010/130970 describes certain 6,6-dioxo-6-thia-1,4-diaza-naphthalene derivatives having herbicidal activity.


WO 2012/084755 and WO 2011/117152 describe certain substituted pyridine derivatives having herbicidal activity.


However, the herbicidal properties of these known compounds with regard to the harmful plants are not always entirely satisfactory.


It is therefore an object of the present invention to provide compounds having improved herbicidal action. To be provided are in particular compounds which have high herbicidal activity, in particular even at low application rates, and which are sufficiently compatible with crop plants for commercial utilization.


These and further objects are achieved by substituted pyridine compounds of formula (I), defined below, and by their agriculturally suitable salts or N-oxides.


Accordingly, the present invention provides substituted pyridine compound of the formula I




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wherein

    • R is hydroxy or O—RA, where RA is C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, aryl-C1-C4-alkyl, C1-C8-alkylcarbonyl, C1-C8-alkoxycarbonyl, C1-C8-alkylthiocarbonyl, C1-C8-alkylsulfonyl, —C(O)—NRiRii or —CH2OC(O)—C1-C8-alkyl, where the aryl moiety is unsubstituted or substituted by one to five Ra and each Ra is independently halogen, cyano, nitro, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy or C1-C8-haloalkoxy;
    • R1 is cyano, halogen, nitro, C1-C6-alkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, O—Z—C3-C10-cycloalkyl, C1-C6-alkyl-C3-C10-cycloalkyl, C1-C6-alkyl-C3-C10-halocycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C6-haloalkynyl, Z—C1-C6-alkoxy, Z—C1-C4-alkoxy-C1-C4-alkoxy, Z—C1-C4-alkylthio, Z—C1-C4-haloalkylthio, Z—C1-C4-alkylthio-C1-C4-alkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy, S(O)nRb, Z-phenoxy, Z-heterocyclyl or Z-heterocyclyloxy, where heterocyclyl is a 4-, 5- or 6-membered monocyclic or 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, where the cyclic groups are unsubstituted or partially or fully substituted by Rc;
      • Z is independently a covalent bond or C1-C4-alkylene;
      • n is independently 0, 1 or 2;
      • Rb is independently C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C2-C6-haloalkenyl, C3-C6-haloalkynyl, C1-C6-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C10-cycloalkyl, C1-C6-alkyl-C3-C10-cycloalkyl, heterocyclyl, C1-C6-alkyl-heterocyclyl, C1-C6-alkyloxyheterocyclyl or NRiRii, where heterocyclyl is a 4-, 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, where the cyclic groups are unsubstituted or partially or fully substituted by Rc;
      • Rc is independently Z—CN, Z—OH, Z—NO2, Z-halogen, oxo (═O), ═N—Rd, C1-C8-alkyl, C1-C4-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, Z—C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, Z—C1-C8-haloalkoxy, Z—C3-C10-cycloalkyl, O—Z—C3-C10-cycloalkyl, Z—C(═O)—Rd, NRiRii, Z-(tri-C1-C4-alkyl)silyl, Z-phenyl or S(O)nRb; or two groups Rc may together form a ring which has 3 to 6 ring members and, in addition to carbon atoms, may contain heteroatoms selected from the group consisting of O, N and S and may be unsubstituted or substituted by further groups Rc;
        • Rd is independently hydrogen, OH, C1-C8-alkyl, C1-C4-haloalkyl, Z—C3-C6-cycloalkyl, C2-C8-alkenyl, Z—C5-C6-cycloalkenyl, C2-C8-alkynyl, Z—C1-C6-alkoxy, Z—C1-C4-haloalkoxy, Z—C3-C8-alkenyloxy, Z—C3-C8-alkynyloxy, NRiRii, C1-C6-alkylsulfonyl, Z-(tri-C1-C4-alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino or a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, where the cyclic groups are unsubstituted or substituted by 1, 2, 3 or 4 groups Rc;
        • Ri, Rii independently of one another are hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, Z—C3-C6-cycloalkyl, Z—C1-C8-alkoxy, Z—C1-C8-haloalkoxy, Z—C(═O)—Rd, Z-phenyl, a 3- to 7-membered monocyclic or 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S and which is attached via Z;
        • Ri and Rii together with the atom or atoms to which they are attached may also form a 3-, 4-, 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S;
    • R2, R3 independently of one another are hydrogen, Z-halogen, Z—CN, Z—OH, Z—NO2, C1-C8-alkyl, C1-C4-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C2-C8-haloalkenyl, C2-C8-haloalkynyl, Z—C1-C8-alkoxy, Z—C1-C8-haloalkoxy, Z—C1-C4-alkoxy-C1-C4-alkoxy, Z—C1-C4-alkythio, Z—C1-C4-alkylthio-C1-C4-alkylthio, Z—C1-C6-haloalkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C2-C6-haloalkenyloxy, C2-C6-haloalkynyloxy, C1-C4-haloalkoxy-C1-C4-alkoxy, Z—C3-C10-cycloalkyl, O—Z—C3-C10-cycloalkyl, C1-C6-alkyl-C3-C10-cycloalkyl, Z1—C3-C10-cycloalkyl, Z1—C(O)NRiRii, Z1—SO2NRiRii, Z1—RCORii, Z1—NRiSO2Rii, Z—C(═O)—Rd, NRiRii, Z-(tri-C1-C4-alkyl)silyl, S(O)nRb, NRiSO2Rii, NRiCO2Rii, NRiCORii, NRiCONRiRii, Z—S(O)nNRiRii, Z—NRiCORii, Z—NRiSO2Rii, Z-phenyl, Z1-phenyl, Z-heterocyclyl or Z1-heterocyclyl, where heterocyclyl is a 4-, 5- or 6-membered monocyclic or 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, where cyclic groups are unsubstituted or partially or fully substituted by Rc;
      • R2 together with the group attached to the adjacent carbon atom may also form a 5- to 10-membered saturated or partially or fully unsaturated mono- or bicyclic ring which, in addition to carbon atoms, may contain 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S and may be substituted by further groups Rc;
      • Z1 is independently a covalent bond, C1-C4-alkyleneoxy, C1-C4-oxyalkylene or C1-C4-alkyleneoxy-C1-C4-alkylene;
    • R4, R5, R6, R7 independently of one another are hydrogen, halogen, C1-C4-alkyl or C3-C10-cycloalkyl;
    • Rx, Ry independently of one another are hydrogen, C1-C5-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C8-haloalkyl, C1-C2-alkoxy-C1-C2-alkyl or halogen; or Rx and Ry are together a C2-C5-alkylene or C2-C5-alkenylene chain and form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or fully unsaturated monocyclic ring together with the carbon atom they are bonded to, wherein 1 or 2 of any of the CH2 or CH groups in the C2-C5-alkylene or C2-C5-alkenylene chain may be replaced by 1 or 2 heteroatoms independently selected from O or S;
    • where in the groups R1, R2 and R3 and their subsubstituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by groups Rc,


      or an agriculturally suitable salt or N-oxide thereof.


The present invention also provides agrochemical compositions comprising at least one substituted pyridine compound of formula (I) and auxiliaries customary for formulating crop protection agents.


The present invention also provides herbicidal compositions comprising at least one substituted pyridine 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 present invention also provides the use of the substituted pyridine compound of formula (I) as herbicides, i.e. for controlling harmful plants.


The present invention furthermore provides a method for controlling unwanted vegetation where a herbicidal effective amount of at least one substituted pyridine compound of the formula (I) is allowed to act on plants, their seeds and/or their habitat. Application can be done before, during and/or after, preferably during and/or after, the emergence of the undesirable plants.


Moreover, the invention relates to processes and intermediates for preparing the substituted pyridine compound of formula (I).


As used herein, the terms “controlling” and “combating” are synonyms.


As used herein, the terms “undesirable vegetation” and “harmful plants” are synonyms.


If the compounds of formula (I), the herbicidal compounds B and/or the safeners C as described herein are capable of forming geometrical isomers, for example E/Z isomers, it is possible to use both, the pure isomers and mixtures thereof, in the compositions according to the invention.


If the compounds of formula (I), the herbicidal compounds B and/or the safeners C as described herein have one or more centres of chirality and, as a consequence, are present as enantiomers or diastereomers, it is possible to use both, the pure enantiomers and diastereomers and their mixtures, in the compositions according to the invention.


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, diisopropylammonium, trimethylammonium, 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.


Compounds of formula (I), herbicidal compounds B and/or safeners C as described herein having a carboxyl group can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative, for example as amides, such as mono- and di-C1-C6-alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, C1-C10-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters and also as thioesters, for example as C1-C10-alkylthio esters. Preferred mono- and di-C1-C6-alkylamides are the methyl and the dimethylamides. Preferred arylamides are, for example, the anilides and the 2-chloroanilides. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl or isooctyl (2-ethylhexyl) esters. Preferred C1-C4-alkoxy-C1-C4-alkyl esters are the straight-chain or branched C1-C4-alkoxy ethyl esters, for example the 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester. An example of a straight-chain or branched C1-C10-alkylthio ester is the ethylthio ester.


Further embodiments of the present invention are evident from the claims, the description and the examples. It is to be understood that the features mentioned above and still to be illustrated below of the subject matter of the invention can be applied not only in the combination given in each particular case but also in other combinations, without leaving the scope of the invention.


The organic moieties mentioned in the definition of the variables R, R1, R2, R3, R4, R5, R6, R7, Rx, Ry, RA, Ra Rb, Rc, Rd, Ri, Rii, Z and Z1, are—like the term halogen—collective terms for individual enumerations of the individual group members. The term halogen denotes in each case fluorine, chlorine, bromine or iodine. All hydrocarbon chains, e.g. alkyl, alkenyl or alkynyl chains, can be straight-chain or branched, the prefix Cn-Cm denoting in each case the possible number of carbon atoms in the group.


Examples of such meanings are:

    • C1-C2-alkyl and also the C1-C2-alkyl moieties of C1-C2-alkoxy-C1-C2-alkyl include CH3 and C2H5;
    • C1-C4-alkyl and also the C1-C4-alkyl moieties of Z-(tri-C1-C4-alkyl)silyl, aryl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, N—(C1-C4-alkyl)amino-N-sulfonyl-C1-C4-alkyl and C3-C6-cycloalkyl-C1-C4-alkyl: C1-C2-alkyl as mentioned above, and also, for example, n-propyl, CH(CH3)2, n-butyl, CH(CH3)—C2H5, CH2—CH(CH3)2 and C(CH3)3;
    • C1-C5-alkyl: C1-C4-alkyl as mentioned above, and also, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 1-ethylpropyl;
    • C1-C6-alkyl and also the C1-C6-alkyl moieties of C1-C6-alkylsulfonyl, C1-C6-alkyl-C3-C10-cycloalkyl, C1-C6-alkyl-C3-C10-halocycloalkyl, C1-C6-alkyl-heterocyclyl, C1-C6-alkyloxyheterocyclyl and C1-C6-alkyoxy-C1-C6-alkyl: C1-C5-alkyl as mentioned above, and also, for example, n-hexyl, 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 or 1-ethyl-2-methylpropyl, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1,1-dimethylethyl, n-pentyl or n-hexyl;
    • C1-C8-alkyl and also the C1-C8-alkyl moieties of C1-C8-alkylcarbonyl, C1-C8-alkylthiocarbonyl, —SO2—C1-C8-alkyl, —CH2OC(O)—C1-C8-alkyl and C1-C8-alkylsulfonyl: C1-C6-alkyl as mentioned above, and also, for example, n-heptyl, n-octyl or 2-ethylhexyl;
    • C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 1,1,2,2,-tetrafluoroethyl and 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl;
    • C1-C8-haloalkyl: C1-C4-haloalkyl as mentioned above, and also, for example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl and undecafluoropentyl;
    • C1-C6-haloalkyl: C1-C8-haloalkyl as mentioned above, and also, for example, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;
    • C1-C8-haloalkyl and also the C1-C8-haloalkyl moieties of S(O)2—C1-C8-haloalkyl: C1-C6-haloalkyl as mentioned above, and also, for example, chloroheptyl, bromoheptyl, fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4-dichloromethylheptyl, chlorooctyl, bromooctyl, iodooctyl, 2,4-dichoromethylhexyl, and 2,4-dichlorooctyl;
    • C3-C4-cycloalkyl: monocyclic saturated hydrocarbons having 3 to 4 ring members, such as cyclopropyl and cyclobutyl;
    • C3-C6-cycloalkyl and also the C3-C6-cycloalkyl moieties of Z—C3-C6-cycloalkyl and C3-C6-cycloalkyl-C1-C4-alkyl: C3-C4-cycloalkyl as mentioned above, and also, for example cyclopentyl and cyclohexyl;
    • C3-C10-cycloalkyl and also the C3-C10-cycloalkyl moieties of Z—C3-C10-cycloalkyl, Z—C3-C10-cycloalkyl, O—Z—C3-C10-cycloalkyl and C1-C6-alkyl-C3-C10-cycloalkyl: C3-C6-cycloalkyl as mentioned above, and also, for example, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;
    • C2-C5-alkenyl: for example 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 and 1-ethyl-2-propenyl;
    • C2-C6-alkenyl and also the alkenyl moieties of C2-C6-alkenyloxy: C2-C5-alkenyl as mentioned above, and also, for example, 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 and 1-ethyl-2-methyl-2-propenyl;
    • C3-C6-alkenyl and also the C3-C6-alkenyl moieties of C3-C6-alkenyloxy: C2-C6-alkenyl as mentioned above, with the exception of ethenyl;
    • C2-C8-alkenyl: C2-C6-alkenyl as mentioned above, and also, for example 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl and 4-octenyl;
    • C3-C8-alkenyl and also the C3-C8-alkenyl moieties of Z—C3-C8-alkenyloxy: C2-C8-alkenyl as mentioned above, with the exception of ethenyl;
    • C3-C6-cycloalkenyl and also the C3-C6-cycloalkenyl moieties of Z—C3-C6-cycloalkenyl: for example cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl;
    • C2-C6-cycloalkenyl and also the C5-C6-cycloalkenyl moieties of Z—C5-C6-cycloalkenyl: for example cyclopentenyl and cyclohexenyl;
    • C2-C6-haloalkenyl: a C2-C6-alkenyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 2-dibromoethenyl, 2-fluoro-2-bromoethenyl, 2-chloroprop-2-en-1-yl, 3-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-en-1-yl, 2,3,3-trichloro-2-en-1-yl, 2,3-dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2,3-dibromoprop-2-en-1-yl, 3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromo-2-en-1-yl or 2,3-dibromobut-2-en-1-yl;
    • C3-C6-haloalkenyl and also the C3-C6-haloalkenyl moieties of C3-C6-haloalkenyloxy: C2-C6-haloalkenyl as mentioned above with the exception of C2-haloalkenyl radicals;
    • C2-C8-haloalkenyl: C2-C6-haloalkenyl as mentioned above, and also, for example, 3-fluoro-n-heptenyl-1,1,3,3,-trichloro-n-heptenyl-5 and 1,3,5-trichloro-n-octenyl-6;
    • C2-C5-alkynyl: for example 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 and 1-ethyl-2-propynyl;
    • C2-C6-alkynyl and also the C2-C6-alkynyl moieties of C2-C6-alkynyloxy: C2-C5-alkynyl as mentioned above, and also, for example, 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 and 1-ethyl-1-methyl-2-propynyl;
    • C3-C6-alkynyl and also the C3-C6-alkynyl moieties of C3-C6-alkynyloxy: C2-C6-alkynyl as mentioned above, with the exception of ethynyl;
    • C2-C8-alkynyl: C2-C6-alkynyl as mentioned above, and also, for example, 1-heptynyl, 2-heptynyl, 1-octynyl and 2-octynyl;
    • C3-C8-alkynyl and also the C3-C8-alkynyl moieties of Z—C3-C8-alkynyloxy: a C2-C8-alkynyl radical as mentioned above with the exception of C2-alkynyl radicals;
    • C2-C6-haloalkynyl: a C2-C6-alkynyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 1,1-difluoroprop-2-yn-1-yl, 3-chloroprop-2-yn-1-yl, 3-bromoprop-2-yn-1-yl, 3-iodoprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl;
    • C3-C6-haloalkynyl and also the haloalkynyl moieties of C3-C6-haloalkynyloxy: a C2-C6-haloalkynyl as mentioned above with the exception of C2-haloalkynyl radicals;
    • C2-C8-haloalkynyl: C2-C6-haloalkynyl as mentioned above, and also, for example, 1-chloro-2-heptynyl and 1-chloro-2-octynyl;
    • C1-C2-alkoxy and also the C1-C2-alkoxy moieties of C1-C2-alkoxy-C1-C2-alkyl: for example methoxy and ethoxy;
    • C1-C4-alkoxy and also the C1-C4-alkoxy moieties of Z—C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, hydroxycarbonyl-C1-C4-alkoxy and C1-C6-alkoxycarbonyl-C1-C4-alkoxy: C1-C2-alkoxy as mentioned above, and also, for example, propoxy, 1-methylethoxy butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;
    • C2-C4-alkoxy: C1-C4-alkoxy as mentioned above, with the exception of methoxy;


C1-C6-alkoxy and also the C1-C6-alkoxy moieties of Z—C1-C6-alkoxy and C1-C6-alkoxycarbonyl-C1-C4-alkoxy: C1-C4-alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 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 and 1-ethyl-2-methylpropoxy;


C1-C8-alkoxy and also the C1-C8-alkoxy moieties of Z—C1-C8-alkoxy and C1-C8-alkoxycarbonyl: C1-C6-alkoxy as mentioned above, and also, for example, heptoxy, octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy;

    • C1-C4-haloalkoxy and also the C1-C4-haloalkoxy moieties of Z—C1-C4-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkyl and C1-C4-haloalkoxy-C1-C4-alkoxy: for example OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5. C1-C4-haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2Cl)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy;
    • C2-C4-haloalkoxy: C1-C4-haloalkoxy as mentioned above with the exception of C1-haloalkoxy radicals;
    • C1-C6-haloalkoxy: C1-C4-haloalkoxy as mentioned above, and also, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
    • C1-C8-haloalkoxy and also the C1-C8-haloalkoxy moieties of Z—C1-C8-haloalkoxy: C1-C6-haloalkoxy as mentioned above, and also, for example, 7-fluoroheptoxy, 7-chloroheptoxy, 7-bromoheptoxy, 7-iodoheptoxy, perfluoroheptoxy, 8-fluorooctoxy, 8-chlorooctoxy, 8-bromooctoxy, 8-iodooctoxy and octadecafluorooctoxy;
    • C1-C4-alkylthio also the C1-C4-alkylthio moieties of Z—C1-C4-alkylthio, Z—C1-C4-alkylthio-C1-C4-alkylthio and C1-C4-alkylthio-C1-C4-alkyl: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;
    • C1-C4-haloalkylthio: for example SCH2F, SCHF2, SCF3, SCH2Cl, SCHC2, 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 and also the C1-C6-alkylthio moieties of Z—C1-C6-haloalkylthio: C1-C4-haloalkylthio as mentioned above, and also, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio;
    • C1-C4-alkylene and also the C1-C4-alkylene moieties in C1-C4-alkyleneoxy, C1-C4-oxyalkylene and C1-C4-alkyleneoxy-C1-C4-alkylene: a straight carbon chain having from 1 to 4 carbon atoms and having only carbon-carbon single bonds, for example methylene (CH2), ethylene (CH2CH2), n-propylene (CH2CH2CH2) and n-butylene (CH2CH2CH2CH2);
    • C2-C5-alkylene: C1-C4-alkylene as mentioned above, and also n-pentylene (CH2CH2CH2CH2CH2);
    • C2-C5-alkenylene chain: a straight carbon chain having from 2 to 5 carbon atoms and at least one carbon-carbon double bond and no carbon-carbon triple bond, for example, CH═CH, CH═CH—CH2, CH═CH—CH2CH2, CH═CH—CH═CH2 and CH═CH—CH2CH2CH2;
    • a 3- to 7-membered monocyclic or 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S means, for example, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, pyrollidin-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl; [2H]-tetrazol-5-yl, 2-tetrahydrofuryl, 3-tetrahydrofuryl, 2-oxetanyl, 3-oxetanyl and azetidin-1-yl;
    • a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S means, for example: pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, pyrollidin-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thiazol-5-yl, pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl and [2H]-tetrazol-5-yl, 2-tetrahydrofuryl and 3-tetrahydrofuryl;
    • a 5- to 10-membered saturated or partially or fully unsaturated mono- or bicyclic ring which, in addition to carbon atoms, may contain 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S means, for example: pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, pyrollidin-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thiazol-5-yl, pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl and [2H]-tetrazol-5-yl, cyclopentyl, cyclohexyl, 2-tetrahydrofuryl and 3-tetrahydrofuryl.
    • a 4-, 5- or 6-membered monocyclic or 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S means, for example: azetin-1-yl, oxetanyl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, pyrollidin-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thiazol-5-yl, pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl, [2H]-tetrazol-5-yl, 2-tetrahydrofuryl and 3-tetrahydrofuryl;
    • a 3-, 4-, 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S means, for example: azetin-1-yl, oxetanyl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, pyrollidin-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thiazol-5-yl, pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl, [2H]-tetrazol-5-yl, 2-tetrahydrofuryl and 3-tetrahydrofuryl;
    • a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S means, for example: pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, piperidin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, pyrollidin-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thiazol-5-yl, pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl, [2H]-tetrazol-5-yl, 2-tetrahydrofuryl and 3-tetrahydrofuryl;
    • the term “aryl” refers to an unsaturated aromatic carbocyclic group of from 6 to 20 carbon atoms having a single ring (e.g., phenyl) or multiple condensed (fused) rings, wherein at least one ring is aromatic (e.g. naphthalenyl or dihydrophenanthrenyl). Examples of aryls include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.


The preferred embodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another.


According to a preferred embodiment of the invention preference is also given to those compounds of formula I, wherein the variables, either independently of one another or in combination with one another, have the following meanings:


Preferably, R is hydroxy or O—RA, where RA is C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, aryl-C1-C4-alkyl, C1-C8-alkylcarbonyl, C1-C8-alkoxycarbonyl, C1-C8-alkylthiocarbonyl, C1-C8-alkylsulfonyl or —CH2OC(O)—C1-C8-alkyl, where the aryl moiety is unsubstituted.


More preferably, R is hydroxy or O—RA, where RA is C1-C8-alkylcarbonyl.


In one embodiment, R is hydroxy.


In one embodiment, R is O—RA, where RA is C1-C8-alkylcarbonyl, in particular 2-methyl-prop-2-ylcarbonyloxy.


In another embodiment, R is selected from the group consisting of hydroxy, methoxy, allyloxy, propargyloxy, cyclopropylcarbonyloxy, benzyloxy, prop-2-ylcarbonyloxy, 2-methyl-prop-2-ylcarbonyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, methylthiocarbonyloxy, ethylthiocarbonyloxy and methylsulfonyloxy.


In one embodiment, R is selected from the group consisting of hydroxy, methoxy, prop-2-ylcarbonyloxy, cyclopropylcarbonyloxy, 2-methyl-prop-2-ylcarbonyloxy and methoxycarbonyloxy.


Preferably, R is selected from the group consisting of hydroxy, cyclopropylcarbonyloxy, and 2-methyl-prop-2-ylcarbonyloxy.


In particular, R is hydroxy or 2-methyl-prop-2-ylcarbonyloxy.


Ri and Rii are preferably C1-C8-alkyl, C1-C4-haloalkyl, Z—C3-C6-cycloalkyl, Z—C1-C8-alkoxy, Z—C1-C8-haloalkoxy, Z-phenyl, Z—C(═O)—Rd or Z-hetaryl. Preference is given here to CH3, C2H5, n-propyl, CH(CH3)2, butyl, 2-chloroethyl, cyclopentyl, cyclohexyl, 2-ethoxymethyl, 2-chloroethoxy, phenyl, pyrimidines or triazines, which rings are unsubstituted or substituted. Preferred substituents are C1-C4-alkylcarbonyl or C1-C4-haloalkylcarbonyl, in particular C(═O)—CH3, C(═O)—C2H5, C(═O)—C3H7, C(═O)—CH(CH3)2, butylcarbonyl and C(═O)—CH2Cl. Particularly preferred aspects of group NRiRii are N(di-C1-C4-alkyl), in particular N(CH3)—C1-C4-alkyl, such as N(CH3)2, N(CH3)CH2CH3, N(CH3)C3H7 and N(CH3)CH(CH3)2.


Further particularly preferred aspects of NRiRii are NH-aryl, where aryl is preferably phenyl which is substituted—in particular in the 2- and 6-position—by one to three identical or different groups selected from the group consisting of halogen, CH3, halo-C1-C2-alkyl, halo-C1-C2-alkoxy and carboxyl, such as 2-Cl, 6-COOH—C6H3, 2,6-Cl2—CO6H3, 2,6-F2—C6H3, 2,6-Cl2 3-C6H2, 2-CF3, 6-CH2CHF2—O6H3, 2-CF3, 6-OCF3—O6H3 and 2-CF3, 6-CH2CHF2—O6H3.


For the compounds of the formula I, the groups Rc are preferably selected from the group consisting of halogen, oxo (═O), ═N—Rd, C1-C4-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Z—C1-C4-haloalkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkylthio-C1-C4-alkyl, Z—C(═O)—Rd and S(O)nRb, where Rb is preferably C1-C4-alkyl or C1-C4-haloalkyl and n is 0, 1 or 2.


Particularly preferably, Rc is a group selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C3—O4-alkenyl, C3-C4-alkynyl and ═N—C1-C4-alkoxy.


Two groups Rc together may form a ring which preferably has three to seven ring members and, in addition to carbon atoms, may also contain heteroatoms from the group consisting of O, N and S and which may be unsubstituted or substituted by further groups Rc. These substituents Rc are preferably selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy and C1-C4-haloalkyl.


Groups Rd preferred for the compounds of the formula I are selected from the group consisting of OH, C1-C8-alkyl, C1-C4-haloalkyl, C3-C8-alkenyl, C3-C8-alkynyl, Z—C1-C6-alkoxy, Z—C1-C4-haloalkoxy, Z—C3-C8-alkenyloxy, Z—C3-C8-alkynyloxy and NRiRii.


Groups Rc and Rd are selected independently of one another if a plurality of such groups is present.


In a preferred embodiment of the compounds of the formula I, R1 is cyano, halogen, nitro, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C10-cycloalkyl, O—Z—C3-C10-cycloalkyl, Z—C1-C6-alkoxy, Z—Cl_C4-alkoxy-C1-C4-alkoxy, Z—C1-C4-alkythio, Z—C1-C4-alkylthio-C1-C4-alkylthio, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy, S(O)nRb, Z-phenoxy, or Z-heterocyclyloxy, where heterocyclyl is a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, cyclic groups being unsubstituted or partially or fully substituted by Rc.


In a particularly preferred embodiment of the compounds of the formula I, R1 is halogen, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, O—Z—C3-C6-cycloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy, S(O)n—C1-C4-alkyl, S(O)n—C1-C4-alkoxy-C1-C4-alkyl and S(O)n—C1-C4-haloalkyl. Particularly preferably, R1 is selected from the group consisting of F, Cl, Br, NO2, CH3, CH2CH3, CH2CH2CH3, iso-propyl, cyclopropyl, CHF2, CF3, OCH3, OCHF2, OCH2CH3, OCH2CHF2, OCH2CF3, O-(cyclopropyl), O-(iso-propyl), OCF3, SCH3, SCH2CH3, SCF3, S(O)CF3, SO2CF3, S(O)CH3, S(O)CH2CH3, SO2CH3, SO2CH2CH3, SCH2OCH3, SO2CH2OCH3, CH2OCH3, CH2SCH3, OCH2-(cyclopropyl), OCH2CH2OCH3, OCH2CH2CF3, CH2OCH2CH2OCH3 and CH2OCH2CF3. Particularly preferably, R1 is selected from the group consisting of F, Cl, Br, NO2, CH3, CF3, OCH3, OCHF2, OCF3, SCF3, SO2CH3, SCH2CH3, OCH2CH2OCH3, CH2OCH2CH2OCH3, CH2OCH2CF3, OCH2CHF2, OCH2CH3 and OCH2CF3.


In another particularly preferred embodiment, R1 is halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy. Particularly preferably, R1 is selected from the group consisting of F, Cl, Br, CH3, CH2CH3, iso-propyl, cyclopropyl, OCH3 and OCHF2.


In a preferred embodiment of the compounds of the formula I, R2 is hydrogen, halogen, Z—C1-C8-alkoxy, Z—C1-C8-haloalkoxy, Z—C1-C4-alkoxy-C1-C4-alkoxy, Z—C1-C4-alkythio, O—Z—C3-C10-cycloalkyl, Z1—C(O)NRiRii, Z1—NRiCORii, Z1—NRiSO2Rii, S(O)nRb, NRiSO2Rii, NRiCORii, Z-heterocyclyl or Z1-heterocyclyl, where heterocyclyl is a 4-, 5- or 6-membered monocyclic or 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, where cyclic groups are unsubstituted or partially or fully substituted by Rc.


More preferably, R2 is halogen, Z—C1-C4-alkoxy, Z—C1-C4-haloalkoxy, Z—C1-C4-alkoxy-C1-C4-alkoxy, Z—C1-C4-alkythio, O—Z—C3-C6-cycloalkyl, O—C1-C3-alkyl-C(O)NRiRii, O—(C1-C3)-alkyl-NRiCORii, O—(C1-C3)-alkyl-NRiSO2Rii, S(O)n—C1-C4-alkyl, NRiSO2Rii or NRiCORii.


Particularly preferred are compounds of formula I wherein R2 is F, Cl, Br, OCH3, OCH2CH3, OCH(CH3)2, O-(cyclopropyl), O-(cyclobutyl), O-(cyclopentyl), OCHF2, OCH2CHF2, OCH2CF3, OCH2CH2CF3, OCH2-(cyclopropyl), OCH2CH(CH3)2, O(CH2)2-(cyclopropyl), O(CH2)2-(iso-propyl), OCH2-(cyclobutyl), O(CH2)2-(cyclobutyl), O(CH2)2OCH3, O(CH2)3OCH3, O(CH2)4OCH3, OCH2CON(CH3)2, O(CH2)2CON(CH3)2, O(CH2)-5-pyrrolidin-2-on, O(CH2)-1-pyrrolidin-2-on, O(CH2)-oxetan-3-yl, O-oxetan-3-yl, 1-pyrollidin-2-one, 1-piperidin-2-one, 4-morpholin-3-one, O(CH2)-tetrahydrofuran-2-yl, —CH2O(CH2)-tetrahydrofuran-2-yl, CH2OCH3, CH2OCH2CH3, CH2OCH2CF3, CH2OCH2CHF2, SCH3, S(O)CH3, SO2CH3, SCH2OCH3, S(CH2)2OCH3, SCH2CH3, SO2CH2CH3, SO2CH2OCH3, SO2(CH2)2OCH3, SO2(iso-propyl), SO2(cyclopropyl), NHSO2CH3, N(CH3)SO2CH3 or NHCOCH3.


Especially preferred are compounds of formula I wherein R2 is Cl, Br, OCH3, OCH2CH3, OCH(CH3)2, O(CH2)2OCH3, O(CH2)2-(cyclopropyl), OCH2-(cyclopropyl), OCH2CH(CH3)2, O(CH2)3OCH3, OCH2CHF2, OCHF2, OCH2CON(CH3)2, O(CH2)-1-pyrrolidin-2-on, OCH2CF3, O(CH2)2CF3, O-(cyclopropyl), O-(cyclobutyl), O(CH2)-oxetan-3-yl, O-oxetan-3-yl, SCH3, SO2CH3, SCH2CH3, SO2CH2CH3, SO2(CH2)2OCH3, SO2(iso-propyl), SO2(cyclopropyl), NHSO2CH3, N(CH3)SO2CH3, NHCOCH3, N(CH3)COCH3, 1-pyrollidin-2-one, CH2OCH3, CH2OCH2CH3, CH2OCH2CF3, CH2OCH2CHF2 or O(CH2)-tetrahydrofuran-2-yl.


In another particularly preferred embodiment, R2 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, NRiSO2Rii or NRiCORii wherein Ri and Rii in the groups NRiSO2Rii or NRiCORii are, independently of one another, hydrogen or C1-C4-alkyl (more preferably C1-C4-alkyl, in particular CH3). Particularly preferably, R2 is selected from the group consisting of H, Cl, Br, OCH3, OCH2CH3, OCH2CH2OCH3, N(CH3)SO2CH3 and N(CH3)COCH3.


In a preferred embodiment of the compounds of the formula I, R2 is Z1-heterocyclyl where heterocyclyl is a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic, saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, cyclic groups being unsubstituted or partially or fully substituted by Rc.


More preferably, R2 is a 5- or 6-membered saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, said heterocycle being unsubstituted or partially or fully substituted by Rc.


In particular, R2 is a heterocycle selected from the group consisting of isoxazoline, piperidine, morpholine, thiomorpholine, piperazine, isoxazole, pyrazole, thiazole, oxazole, furyl, pyridine, pyrimidine and pyrazine, said heterocycle being unsubstituted or partially or fully substituted by Rc, where Rc is selected from the group consisting of C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, halogen and oxo.


A preferred aspect of group R2 relates to five- or six-membered saturated or partially unsaturated heterocycles, such as, for example, isoxazoline, piperidine, morpholine, thiomorpholine and piperazine. Particular preference is given to 3-isoxazoline, 5-isoxazoline, and N-morpholine. Especially preferred are: 4,5-dihydroisoxazole-3, unsubstituted or substituted by 5-CH3, 5-CH2F or 5-CHF2; 4,5-dihydroisoxazole-5, unsubstituted or substituted by 3-CH3, 3-OCH3, 3-CH2OCH3, 3-CH2SCH3; and N-morpholine.


A further preferred aspect of group R2 relates to five- or six-membered aromatic heterocycles, such as, for example, isoxazole, pyrazole, thiazole, oxazole, furyl, pyridine, pyrimidine and pyrazine. Particular preference is given to 3-isoxazole, 5-isoxazole, 3-pyrazole, 5-pyrazole, 2-thiazole, 2-oxazole, 2-furyl. Especially preferred are: 3-isoxazole, 5-methyl-3-isoxazole, 5-isoxazole, 3-methyl-5-isoxazole, 1-methyl-1H-pyrazole-3,2-methyl-2H-pyrazole-3 and thiazole-2.


In a preferred aspect of the compounds of the formula I, the groups Rc independently of one another are Z—CN, Z—OH, Z—NO2, Z-halogen, oxo (═O), ═N—Rd, C1-C8-alkyl, C1-C4-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, Z—C1-C8-alkoxy, Z—C1-C8-haloalkoxy, Z—C3-C10-cycloalkyl, O—Z—C3-C10-cycloalkyl, Z—C(═O)—Rd, NRiRii, Z-(tri-C1-C4-alkyl)silyl, Z-phenyl or S(O)nRb.


In a preferred aspect of heterocyclic groups R2, the groups Rc independently of one another are preferably C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthio or C1-C4-alkylsulfonyl. Especially preferred are CH3, C2H5, CH2F, CF2H, CF3, OCH3, CH2OCH3, CH2SCH3, SCH3 and SO2CH3.


The group Rb is preferably C1-C8-alkyl.


In a preferred aspect, the group Z1 is a covalent bond.


In a further preferred aspect, the group Z1 is C1-C4-alkyleneoxy, in particular OCH2 or OCH2CH2.


In a further preferred aspect, the group Z1 is C1-C4-oxyalkylene, in particular CH2O or CH2CH2O.


In a further preferred aspect, the group Z1 is C1-C4-alkyleneoxy-C1-C4-alkylene, in particular OCH2OCH2 or OCH2CH2OCH2.


Particularly preferred aspects of heterocycles attached via Z1 include tetrahydrofuran-2-ylmethoxymethyl and [1,3]dioxolan-2-ylmethoxy.


In a further preferred embodiment of the compounds of the formula I, R2 is phenyl which is attached via Z1 or oxygen and is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl or C1-C4-alkoxy-C1-C4-alkoxy.


Particular preference is given in this case to a phenyl group which may be partially or fully substituted—preferably mono-, di- or trisubstituted, in particular monosubstituted—by groups Rc. Groups Rc preferred for this aspect include: C1-C2-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl, C1-C2-alkoxy-C1-C2-alkyl or C1-C2-alkoxy-C1-C2-alkoxy. Particular preference is given to CH3, C2H5, OCH3, OC2H5, CHF2, CF3, OCHF2, OCF3, OCH2OCH3 and OCH2CH2OCH3. Special preference is given to alkoxy, such as OCH3 or OC2H5. A group Rc is preferably in position 4. A particularly preferred phenyl group R2 is a group P:




embedded image


wherein # denotes the bond via which the group R2 is attached and the substituents are selected from Rc and are in particular:


RP2 H or F;

RP3 H, F, Cl or OCH3; and


RP4 H, F, Cl, CH3, CF3, OCH3, OCH2OCH3 or OCH2CH2OCH3.


In a further preferred embodiment of the compounds of the formula I, R3 is hydrogen, halogen, C1-C4-alkyl or Z—C3-C10-cycloalkyl.


More preferably, R3 is hydrogen, halogen, cyclopropyl or C1-C4-alkyl.


Particularly preferred are compounds of formula I wherein R3 is H, Cl, F, CH3, CH2CH3, iso-propyl or cyclopropyl.


Especially preferred are compounds of formula I wherein R3 is H, Cl, CH3 or cyclopropyl.


Most preferably, R3 is H.


In a further preferred embodiment of the compounds of the formula I, R4 is hydrogen, halogen or C1-C4-alkyl, more preferably halogen or C1-C4-alkyl and in particular halogen.


Particularly preferred are compounds of formula I wherein R4 is H, F, Cl, Br or CH3, more preferably F, Cl, Br or CH3 and in particular F, Cl or Br.


In a further preferred aspect, R1 together with R2 or R3 together with R4 forms a 5- to 10-membered mono- or bicyclic saturated, partially unsaturated or fully unsaturated ring which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, said ring optionally being substituted with Rb.


In a particularly preferred aspect, R2 together with R1 or R3 together with R4 forms a 5- to 10-membered mono- or bicyclic, saturated, partially unsaturated or fully unsaturated ring which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S and which may be partially or fully substituted by groups Rc. Suitable are, for example, the following: 4-dihydro-2H-thiopyrano[2,3-b]pyridine 1,1-dioxide, 3,4-dihydro-2H-thiopyrano[3,2-b]pyridine 1,1-dioxide, 2,3-dihydro-[1,4]dithiino[2,3-b]pyridine 1,1,4,4-tetraoxide, 1H-thiazolo[5,4-b]pyridin-2-one, 2,3-dihydrothieno[2,3-b]pyridine 1,1-dioxide, 1,8-naphthyridine, 1,5-naphthyridine, 1,7-naphthyridine and isothiazolo[5,4-b]pyridine.


Preferably, R2 together with R1 or R3 together with R4 forms a five- or six-membered monocyclic, saturated, partially unsaturated or fully unsaturated ring.


In further preferred aspects of the compound of formula I, the groups R1, R2, R3 and R4 together form a substitution pattern selected from the group consisting of:


R1=Cl, R2=H, R3=H, R4=Cl;


R1=Cl, R2=Cl, R3=H, R4=Cl;


R1=Cl, R2=Br, R3=H, R4=Cl;


R1=Cl, R2=OCH3, R3=H, R4=Cl;


R1=Cl, R2=OCH2CH3, R3=H, R4=Cl;


R1=Cl, R2=OCH2CH2OCH3, R3=H, R4=Cl;


R1=Cl, R2=O—CH(CH3)2, R3=H, R4=Cl;


R1=Cl, R2=OCH3, R3=H, R4=F;


R1=Cl, R2=OCH2CH3, R3=H, R4=F;


R1=Cl, R2=OCH2CH2OCH3, R3=H, R4=F;


R1=Cl, R2=O—CH(CH3)2, R3=H, R4=F;


R1=Br, R2=Cl, R3=H, R4=Cl;


R1=Br, R2=Cl, R3=H, R4=F;


R1=Br, R2=OCH3, R3=H, R4=Cl;


R1=Br, R2=OCH2CH3, R3=H, R4=Cl;


R1=Br, R2=OCH2CH2OCH3, R3=H, R4=Cl;


R1=Br, R2=O—CH(CH3)2, R3=H, R4=Cl;


R1=Br, R2=OCH3, R3=H, R4=F;


R1=Br, R2=OCH2CH3, R3=H, R4=F;


R1=Br, R2=OCH2CH2OCH3, R3=H, R4=F;


R1=Br, R2=O—CH(CH3)2, R3=H, R4=F;


R1=OCH3, R2=Cl, R3=H, R4=Cl;


R1=OCH2CH3, R2=Cl, R3=H, R4=Cl;


R1=OCH2CH2OCH3, R2=Cl, R3=H, R4=Cl;


R1=O—CH(CH3)2, R2=Cl, R3=H, R4=Cl;


R1=F, R2=Cl, R3=H, R4=Cl;


R1=CH3, R2=Cl, R3=H, R4=Cl;


R1=CH3, R2=Cl, R3=H, R4=F; and


R1=OCHF2, R2=Cl, R3=H, R4=Cl.


In another preferred embodiment of the compounds of the formula I, R5 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy or C1-C4-haloalkylthio, particularly preferably H, CH3, CF3, CHF2, OCH3, OCF3, OCHF2, SCH3, SCF3 or SCHF2, in particular H.


In further preferred embodiments:


R6 is H, OH, CN, halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, more preferably H or halogen and in particular H or F;


R7 is H, OH, CN, halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, in particular H.


In another preferred embodiment of the compounds of the formula I, at least one of the groups R6 and R7 is hydrogen.


In another preferred embodiment of the compounds of the formula I, at least one of the groups R5 and R7 is hydrogen.


In another preferred embodiment of the compounds of the formula I, R6 and R7 are both hydrogen.


In another preferred embodiment of the compounds of the formula I, R5 and R7 are both hydrogen.


In an especially preferred embodiment of the compounds of the formula I, R5, R6 and R7 are, independently of one another, H or halogen.


In another especially preferred embodiment of the compounds of the formula I, R5 and R7 are both hydrogen and R6 is halogen, in particular fluorine.


Rx and Ry, independently of one another, are preferably H, C1-C5-alkyl (in particular CH3, C2H5, n-C3H7, CH(CH3)2, n-C3H9, or C(CH3)3), C3-C5-alkenyl (in particular CH2CH═CH2, CH2C(CH3)═CH2, CH2CH2H═CH2, CH2CH2C(CH3)═CH2, or CH2CH2CH2CH═CH2), C3-C5-alkynyl (in particular CH2C≡CH), C1-C5-haloalkyl (in particular CH2CF3 or CH2CHF2), or Rx and Ry together form a bridge —CH2—CH2—. More preferably, Rx and Ry are, independently of one another, H, C1-C8-alkyl, or C1-C4-haloalkyl, or Rx and Ry together form a bridge —CH2—CH2—. Particularly preferably, Rx and Ry, independently of one another, are H or C1-C8-alkyl, or Rx and Ry together form a bridge —CH2—CH2—. In one embodiment, Rx and Ry, independently of one another, are H or C1-C8-alkyl, preferably H, CH3, or C2H5 and more preferably H or CH3. In another embodiment, Rx and Ry together form a bridge —CH2—CH2—.


In another preferred embodiment of the compounds of the formula I, R5, R6 and R7 are hydrogen. These compounds correspond to formula I.a




embedded image


in which the variables have the meanings defined at the outset and preferably those mentioned above.


More preferably, in compounds of the formula I.a the group

  • R is hydroxy or O—RA wherein RA is C1-C4-alkyl or C1-C6-alkylcarbonyl (preferably C1-C6-alkylcarbonyl), in particular hydroxy, methoxy, prop-2-ylcarbonyloxy, cyclopropylcarbonyloxy or 2-methyl-prop-2-ylcarbonyloxy and most preferably hydroxy or 2-methyl-prop-2-ylcarbonyloxy;
  • R1 is halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, in particular F, Cl, Br, CH3, CH2CH3, iso-propyl, cyclopropyl, OCH3 or OCHF2;
  • R2 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, NRiSO2Rii or NRiCORii wherein Ri and Rii in the groups NRiSO2Rii or NRiCORii are, independently of one another, hydrogen or C1-C4-alkyl (more preferably C1-C4-alkyl, in particular CH3), in particular H, Cl, Br, OCH3, OCH2CH3, OCH2CH2OCH3, N(CH3)SO2CH3 or N(CH3)COCH3;
  • R3 is hydrogen, halogen or C1-C4-alkyl, in particular hydrogen;
  • R4 is hydrogen or halogen, more preferably halogen and in particular F or Cl; and
  • Rx, Ry are, independently of one another, H or C1-C5-alkyl (in particular H, CH3, or C2H5), or together form a bridge —CH2—CH2—.


Especially preferably, in compounds of the formula I.a the group

  • R is hydroxy or O—RA wherein RA is C1-C4-alkyl or C1-C6-alkylcarbonyl (more preferably C1-C6-alkylcarbonyl), in particular hydroxy, methoxy, prop-2-ylcarbonyloxy, cyclopropylcarbonyloxy or 2-methyl-prop-2-ylcarbonyloxy and most preferably hydroxy or 2-methyl-prop-2-ylcarbonyloxy;
  • R1 is halogen or C1-C4-alkoxy, in particular chloro, bromo or methoxy;
  • R2 is hydrogen, halogen, C1-C4-alkoxy or C1-C4-alkoxy-C1-C4-alkoxy, in particular H, Cl, Br, OCH3, OC2H5 or OCH2CH2OCH3;
  • R3 is hydrogen, halogen or C1-C4-alkyl, in particular hydrogen;
  • R4 is halogen, in particular F or Cl; and
  • Rx, Ry are, independently of one another, H or C1-C5-alkyl (in particular H, CH3, or C2H5), or together form a bridge —CH2—CH2—.


A further embodiment relates to the N-oxides of the compounds of the formula I.


A further embodiment relates to salts of the compounds of the formula I, in particular those which are obtainable by quaternization of a pyridine nitrogen atom, which may preferably take place by alkylation or arylation of the compounds of the formula I. Preferred salts of the compounds are thus the N-alkyl salts, in particular the N-methyl salts, and the N-phenyl salts.


In particular with a view to their use, preference is given to the compounds of the formula I compiled in the Tables below, which compounds correspond to the formula I.a as shown above. The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.


Table 1


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 2


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 3


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 4


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 5


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 6


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 7


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 8


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 9


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 10


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 11


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 12


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 13


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 14


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 15


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 16


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 17


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 18


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 19


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 20


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 21


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 22


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 23


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 24


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 25


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 26


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 27


Compounds of the formula I, in which Rx is H, Ry is H, R is OH, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 28


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 29


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 30


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 31


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 32


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 33


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 34


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 35


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 36


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 37


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 38


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 39


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 40


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 41


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 42


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 43


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 44


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 45


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 46


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 47


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 48


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 49


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 50


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 51


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 52


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 53


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 54


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OH, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 55


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 56


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 57


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 58


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 59


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 60


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 61


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 62


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 63


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 64


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 65


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 66


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 67


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 68


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 69


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 70


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 71


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 72


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 73


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 74


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 75


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 76


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 77


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 78


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 79


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 80


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 81


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OH, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 82


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 83


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 84


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 85


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 86


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 87


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 88


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 89


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 90


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 91


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 92


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 93


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 94


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 95


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 96


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 97


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 98


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 99


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 100


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 101


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 102


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 103


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 104


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 105


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 106


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 107


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 108


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 109


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 110


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 111


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 112


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 113


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 114


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 115


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 116


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 117


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 118


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 119


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 120


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 121


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 122


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 123


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 124


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 125


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 126


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 127


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 128


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 129


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 130


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 131


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 132


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 133


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 134


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 135


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 136


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 137


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 138


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 139


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 140


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 141


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 142


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 143


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 144


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 145


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 146


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 147


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 148


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 149


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 150


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 151


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 152


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 153


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 154


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 155


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 156


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 157


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 158


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 159


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 160


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 161


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 162


Compounds of the formula I, in which Rx is H, Ry is H, R is OC(O)C(CH3)3, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 163


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 164


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 165


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 166


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 167


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 168


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 169


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 170


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 171


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 172


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 173


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 174


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 175


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 176


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 177


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 178


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 179


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 180


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 181


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 182


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 183


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 184


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 185


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 186


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 187


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 188


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 189


Compounds of the formula I, in which Rx is H, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 190


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 191


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 192


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 193


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 194


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 195


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 196


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 197


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 198


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 199


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 200


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 201


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 202


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 203


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 204


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 205


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 206


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 207


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 208


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3OC(O)C(CH3)3, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 209


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 210


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 211


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 212


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 213


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 214


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 215


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 216


Compounds of the formula I, in which Rx is CH3, Ry is CH3, R is OC(O)C(CH3)3, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 217


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 218


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 219


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 220


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 221


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 222


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 223


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 224


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 225


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 226


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 227


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 228


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OH, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 229


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 230


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 231


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 232


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 233


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 234


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 235


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 236


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 237


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 238


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 239


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 240


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 241


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 242


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 243


Compounds of the formula I, in which Rx is H, Ry is CH2CH3, R is OC(O)C(CH3)3, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 244


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is Cl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 245


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 246


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is Br and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 247


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is F and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 248


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 249


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 250


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is O-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 251


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is O-iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 252


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCH2CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 253


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 254


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCH2-cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 255


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 256


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 257


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCH2CHF2 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 258


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is OCH2CH2CF3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 259


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OH, R1 is CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 260


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is iso-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 261


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is cyclopropyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 262


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is n-propyl and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 263


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 264


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is SCH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 265


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is SO2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 266


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is SO2CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 267


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is S(O)CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 268


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is S(O)CH2CH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 269


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is CH2OCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A


Table 270


Compounds of the formula I, in which Rx and Ry together form a bridge —CH2—CH2—, R is OC(O)C(CH3)3, R1 is CH2SCH3 and the combination of R2 to R4 for a compound corresponds in each case to one row of table A









TABLE A







Compounds of the formula I which correspond to the formula I.a


as shown above










No.
R2
R3
R4





I.a.1
Cl
H
Cl


I.a.2
OCH3
H
Cl


I.a.3
OCH2CH3
H
Cl


I.a.4
O(CH2)2OCH3
H
Cl


I.a.5
OCH2c-Pr
H
Cl


I.a.6
O(CH2)2c-Pr
H
Cl


I.a.7
O(CH2)2i-Pr
H
Cl


I.a.8
O(CH2)2c-Bu
H
Cl


I.a.9
O(CH2)3OCH3
H
Cl


I.a.10
O(CH2)4OCH3
H
Cl


I.a.11
OCH2CHF2
H
Cl


I.a.12
OCHF2
H
Cl


I.a.13
OCH2CON(CH3)2
H
Cl


I.a.14
O(CH2)2CON(CH3)2
H
Cl


I.a.15
O(CH2)-5-pyrrolidin-2-on
H
Cl


I.a.16
O(CH2)-1-pyrrolidin-2-on
H
Cl


I.a.17
OCH(CH3)2
H
Cl


I.a.18
OCH2CH(CH3)2
H
Cl





I.a.19


embedded image


H
Cl





I.a.20
OCH2CF3
H
Cl


I.a.21
O(CH2)2CF3
H
Cl


I.a.22
Oc-Pr
H
Cl


I.a.23
Oc-Bu
H
Cl





I.a.24


embedded image


H
Cl





I.a.25


embedded image


H
Cl





I.a.26
SCH3
H
Cl


I.a.27
S(O)CH3
H
Cl


I.a.28
SO2CH3
H
Cl


I.a.29
S(CH2)2OCH3
H
Cl


I.a.30
SCH2CH3
H
Cl


I.a.31
SO2CH2CH3
H
Cl


I.a.32
SO2(CH2)2OCH3
H
Cl


I.a.33
SO2i-Pr
H
Cl


I.a.34
SO2c-Pr
H
Cl


I.a.35
NHSO2CH3
H
Cl


I.a.36
N(CH3)SO2CH3
H
Cl


I.a.37
S(O)CH2CH3
H
Cl


I.a.38
NHCOCH3
H
Cl


I.a.39
N(CH3)COCH3
H
Cl





I.a.40


embedded image


H
Cl





I.a.41


embedded image


H
Cl





I.a.42


embedded image


H
Cl





I.a.43
CH2OCH3
H
Cl


I.a.44
CH2OCH2CH3
H
Cl


I.a.45
CH2OCH2CH2OCH3
H
Cl


I.a.46
CH2OCH2CF3
H
Cl


I.a.47
CH2OCH2CF2CHCF2
H
Cl


I.a.48
CH2OCH2CHF2
H
Cl





I.a.49


embedded image


H
Cl





I.a.50


embedded image


H
Cl





I.a.51
Cl
Cl
Cl


I.a.52
OCH3
Cl
Cl


I.a.53
OCH2CH3
Cl
Cl


I.a.54
O(CH2)2OCH3
Cl
Cl


I.a.55
OCH2c-Pr
Cl
Cl


I.a.56
O(CH2)2c-Pr
Cl
Cl


I.a.57
O(CH2)2i-Pr
Cl
Cl


I.a.58
O(CH2)2c-Bu
Cl
Cl


I.a.59
O(CH2)3OCH3
Cl
Cl


I.a.60
O(CH2)4OCH3
Cl
Cl


I.a.61
OCH2CHF2
Cl
Cl


I.a.62
OCHF2
Cl
Cl


I.a.63
OCH2CON(CH3)2
Cl
Cl


I.a.64
O(CH2)2CON(CH3)2
Cl
Cl


I.a.65
O(CH2)-5-pyrrolidin-2-on
Cl
Cl


I.a.66
O(CH2)-1-pyrrolidin-2-on
Cl
Cl


I.a.67
OCH(CH3)2
Cl
Cl


I.a.68
OCH2CH(CH3)2
Cl
Cl





I.a.69


embedded image


Cl
Cl





I.a.70
OCH2CF3
Cl
Cl


I.a.71
O(CH2)2CF3
Cl
Cl


I.a.72
Oc-Pr
Cl
Cl


I.a.73
Oc-Bu
Cl
Cl





I.a.74


embedded image


Cl
Cl





I.a.75


embedded image


Cl
Cl





I.a.76
SCH3
Cl
Cl


I.a.77
S(O)CH3
Cl
Cl


I.a.78
SO2CH3
Cl
Cl


I.a.79
S(CH2)2OCH3
Cl
Cl


I.a.80
SCH2CH3
Cl
Cl


I.a.81
SO2CH2CH3
Cl
Cl


I.a.82
SO2(CH2)2OCH3
Cl
Cl


I.a.83
SO2i-Pr
Cl
Cl


I.a.84
SO2c-Pr
Cl
Cl


I.a.85
NHSO2CH3
Cl
Cl


I.a.86
N(CH3)SO2CH3
Cl
Cl


I.a.87
S(O)CH2CH3
Cl
Cl


I.a.88
NHCOCH3
Cl
Cl


I.a.89
N(CH3)COCH3
Cl
Cl





I.a.90


embedded image


Cl
Cl





I.a.91


embedded image


Cl
Cl





I.a.92


embedded image


Cl
Cl





I.a.93
CH2OCH3
Cl
Cl


I.a.94
CH2OCH2CH3
Cl
Cl


I.a.95
CH2OCH2CH2OCH3
Cl
Cl


I.a.96
CH2OCH2CF3
Cl
Cl


I.a.97
CH2OCH2CF2CHCF2
Cl
Cl


I.a.98
CH2OCH2CHF2
Cl
Cl





I.a.99


embedded image


Cl
Cl





I.a.100


embedded image


Cl
Cl





I.a.101
Cl
CH3
Cl


I.a.102
OCH3
CH3
Cl


I.a.103
OCH2CH3
CH3
Cl


I.a.104
O(CH2)2OCH3
CH3
Cl


I.a.105
OCH2c-Pr
CH3
Cl


I.a.106
O(CH2)2c-Pr
CH3
Cl


I.a.107
O(CH2)2i-Pr
CH3
Cl


I.a.108
O(CH2)2c-Bu
CH3
Cl


I.a.109
O(CH2)3OCH3
CH3
Cl


I.a.110
O(CH2)4OCH3
CH3
Cl


I.a.111
OCH2CHF2
CH3
Cl


I.a.112
OCHF2
CH3
Cl


I.a.113
OCH2CON(CH3)2
CH3
Cl


I.a.114
O(CH2)2CON(CH3)2
CH3
Cl


I.a.115
O(CH2)-5-pyrrolidin-2-on
CH3
Cl


I.a.116
O(CH2)-1-pyrrolidin-2-on
CH3
Cl


I.a.117
OCH(CH3)2
CH3
Cl


I.a.118
OCH2CH(CH3)2
CH3
Cl





I.a.119


embedded image


CH3
Cl





I.a.120
OCH2CF3
CH3
Cl


I.a.121
O(CH2)2CF3
CH3
Cl


I.a.122
Oc-Pr
CH3
Cl


I.a.123
Oc-Bu
CH3
Cl





I.a.124


embedded image


CH3
Cl





I.a.125


embedded image


CH3
Cl





I.a.126
SCH3
CH3
Cl


I.a.127
S(O)CH3
CH3
Cl


I.a.128
SO2CH3
CH3
Cl


I.a.129
S(CH2)2OCH3
CH3
Cl


I.a.130
SCH2CH3
CH3
Cl


I.a.131
SO2CH2CH3
CH3
Cl


I.a.132
SO2(CH2)2OCH3
CH3
Cl


I.a.133
SO2i-Pr
CH3
Cl


I.a.134
SO2c-Pr
CH3
Cl


I.a.135
NHSO2CH3
CH3
Cl


I.a.136
N(CH3)SO2CH3
CH3
Cl


I.a.137
S(O)CH2CH3
CH3
Cl


I.a.138
NHCOCH3
CH3
Cl


I.a.139
N(CH3)COCH3
CH3
Cl





I.a.140


embedded image


CH3
Cl





I.a.141


embedded image


CH3
Cl





I.a.142


embedded image


CH3
Cl





I.a.143
CH2OCH3
CH3
Cl


I.a.144
CH2OCH2CH3
CH3
Cl


I.a.145
CH2OCH2CH2OCH3
CH3
Cl


I.a.146
CH2OCH2CF3
CH3
Cl


I.a.147
CH2OCH2CF2CHCF2
CH3
Cl


I.a.148
CH2OCH2CHF2
CH3
Cl





I.a.149


embedded image


CH3
Cl





I.a.150


embedded image


CH3
Cl





I.a.151
Cl
CH2CH3
Cl


I.a.152
OCH3
CH2CH3
Cl


I.a.153
OCH2CH3
CH2CH3
Cl


I.a.154
O(CH2)2OCH3
CH2CH3
Cl


I.a.155
OCH2c-Pr
CH2CH3
Cl


I.a.156
O(CH2)2c-Pr
CH2CH3
Cl


I.a.157
O(CH2)2i-Pr
CH2CH3
Cl


I.a.158
O(CH2)2c-Bu
CH2CH3
Cl


I.a.159
O(CH2)3OCH3
CH2CH3
Cl


I.a.160
O(CH2)4OCH3
CH2CH3
Cl


I.a.161
OCH2CHF2
CH2CH3
Cl


I.a.162
OCHF2
CH2CH3
Cl


I.a.163
OCH2CON(CH3)2
CH2CH3
Cl


I.a.164
O(CH2)2CON(CH3)2
CH2CH3
Cl


I.a.165
O(CH2)-5-pyrrolidin-2-on
CH2CH3
Cl


I.a.166
O(CH2)-1-pyrrolidin-2-on
CH2CH3
Cl


I.a.167
OCH(CH3)2
CH2CH3
Cl


I.a.168
OCH2CH(CH3)2
CH2CH3
Cl





I.a.169


embedded image


CH2CH3
Cl





I.a.170
OCH2CF3
CH2CH3
Cl


I.a.171
O(CH2)2CF3
CH2CH3
Cl


I.a.172
Oc-Pr
CH2CH3
Cl


I.a.173
Oc-Bu
CH2CH3
Cl





I.a.174


embedded image


CH2CH3
Cl





I.a.175


embedded image


CH2CH3
Cl





I.a.176
SCH3
CH2CH3
Cl


I.a.177
S(O)CH3
CH2CH3
Cl


I.a.178
SO2CH3
CH2CH3
Cl


I.a.179
S(CH2)2OCH3
CH2CH3
Cl


I.a.180
SCH2CH3
CH2CH3
Cl


I.a.181
SO2CH2CH3
CH2CH3
Cl


I.a.182
SO2(CH2)2OCH3
CH2CH3
Cl


I.a.183
SO2i-Pr
CH2CH3
Cl


I.a.184
SO2c-Pr
CH2CH3
Cl


I.a.185
NHSO2CH3
CH2CH3
Cl


I.a.186
N(CH3)SO2CH3
CH2CH3
Cl


I.a.187
S(O)CH2CH3
CH2CH3
Cl


I.a.188
NHCOCH3
CH2CH3
Cl


I.a.189
N(CH3)COCH3
CH2CH3
Cl





I.a.190


embedded image


CH2CH3
Cl





I.a.191


embedded image


CH2CH3
Cl





I.a.192


embedded image


CH2CH3
Cl





I.a.193
CH2OCH3
CH2CH3
Cl


I.a.194
CH2OCH2CH3
CH2CH3
Cl


I.a.195
CH2OCH2CH2OCH3
CH2CH3
Cl


I.a.196
CH2OCH2CF3
CH2CH3
Cl


I.a.197
CH2OCH2CF2CHCF2
CH2CH3
Cl


I.a.198
CH2OCH2CHF2
CH2CH3
Cl





I.a.199


embedded image


CH2CH3
Cl





I.a.200


embedded image


CH2CH3
Cl





I.a.201
Cl
c-Pr
Cl


I.a.202
OCH3
c-Pr
Cl


I.a.203
OCH2CH3
c-Pr
Cl


I.a.204
O(CH2)2OCH3
c-Pr
Cl


I.a.205
OCH2c-Pr
c-Pr
Cl


I.a.206
O(CH2)2c-Pr
c-Pr
Cl


I.a.207
O(CH2)2i-Pr
c-Pr
Cl


I.a.208
O(CH2)2c-Bu
c-Pr
Cl


I.a.209
O(CH2)3OCH3
c-Pr
Cl


I.a.210
O(CH2)4OCH3
c-Pr
Cl


I.a.211
OCH2CHF2
c-Pr
Cl


I.a.212
OCHF2
c-Pr
Cl


I.a.213
OCH2CON(CH3)2
c-Pr
Cl


I.a.214
O(CH2)2CON(CH3)2
c-Pr
Cl


I.a.215
O(CH2)-5-pyrrolidin-2-on
c-Pr
Cl


I.a.216
O(CH2)-1-pyrrolidin-2-on
c-Pr
Cl


I.a.217
OCH(CH3)2
c-Pr
Cl


I.a.218
OCH2CH(CH3)2
c-Pr
Cl





I.a.219


embedded image


c-Pr
Cl





I.a.220
OCH2CF3
c-Pr
Cl


I.a.221
O(CH2)2CF3
c-Pr
Cl


I.a.222
Oc-Pr
c-Pr
Cl


I.a.223
Oc-Bu
c-Pr
Cl





I.a.224


embedded image


c-Pr
Cl





I.a.225


embedded image


c-Pr
Cl





I.a.226
SCH3
c-Pr
Cl


I.a.227
S(O)CH3
c-Pr
Cl


I.a.228
SO2CH3
c-Pr
Cl


I.a.229
S(CH2)2OCH3
c-Pr
Cl


I.a.230
SCH2CH3
c-Pr
Cl


I.a.231
SO2CH2CH3
c-Pr
Cl


I.a.232
SO2(CH2)2OCH3
c-Pr
Cl


I.a.233
SO2i-Pr
c-Pr
Cl


I.a.234
SO2c-Pr
c-Pr
Cl


I.a.235
NHSO2CH3
c-Pr
Cl


I.a.236
N(CH3)SO2CH3
c-Pr
Cl


I.a.237
S(O)CH2CH3
c-Pr
Cl


I.a.238
NHCOCH3
c-Pr
Cl


I.a.239
N(CH3)COCH3
c-Pr
Cl





I.a.240


embedded image


c-Pr
Cl





I.a.241


embedded image


c-Pr
Cl





I.a.242


embedded image


c-Pr
Cl





I.a.243
CH2OCH3
c-Pr
Cl


I.a.244
CH2OCH2CH3
c-Pr
Cl


I.a.245
CH2OCH2CH2OCH3
c-Pr
Cl


I.a.246
CH2OCH2CF3
c-Pr
Cl


I.a.247
CH2OCH2CF2CHCF2
c-Pr
Cl


I.a.248
CH2OCH2CHF2
c-Pr
Cl





I.a.249


embedded image


c-Pr
Cl





I.a.250


embedded image


c-Pr
Cl





I.a.251
Cl
i-Pr
Cl


I.a.252
OCH3
i-Pr
Cl


I.a.253
OCH2CH3
i-Pr
Cl


I.a.254
O(CH2)2OCH3
i-Pr
Cl


I.a.255
OCH2c-Pr
i-Pr
Cl


I.a.256
O(CH2)2c-Pr
i-Pr
Cl


I.a.257
O(CH2)2i-Pr
i-Pr
Cl


I.a.258
O(CH2)2c-Bu
i-Pr
Cl


I.a.259
O(CH2)3OCH3
i-Pr
Cl


I.a.260
O(CH2)4OCH3
i-Pr
Cl


I.a.261
OCH2CHF2
i-Pr
Cl


I.a.262
OCHF2
i-Pr
Cl


I.a.263
OCH2CON(CH3)2
i-Pr
Cl


I.a.264
O(CH2)2CON(CH3)2
i-Pr
Cl


I.a.265
O(CH2)-5-pyrrolidin-2-on
i-Pr
Cl


I.a.266
O(CH2)-1-pyrrolidin-2-on
i-Pr
Cl


I.a.267
OCH(CH3)2
i-Pr
Cl


I.a.268
OCH2CH(CH3)2
i-Pr
Cl





I.a.269


embedded image


i-Pr
Cl





I.a.270
OCH2CF3
i-Pr
Cl


I.a.271
O(CH2)2CF3
i-Pr
Cl


I.a.272
Oc-Pr
i-Pr
Cl


I.a.273
Oc-Bu
i-Pr
Cl





I.a.274


embedded image


i-Pr
Cl





I.a.275


embedded image


i-Pr
Cl





I.a.276
SCH3
i-Pr
Cl


I.a.277
S(O)CH3
i-Pr
Cl


I.a.278
SO2CH3
i-Pr
Cl


I.a.279
S(CH2)2OCH3
i-Pr
Cl


I.a.280
SCH2CH3
i-Pr
Cl


I.a.281
SO2CH2CH3
i-Pr
Cl


I.a.282
SO2(CH2)2OCH3
i-Pr
Cl


I.a.283
SO2i-Pr
i-Pr
Cl


I.a.284
SO2c-Pr
i-Pr
Cl


I.a.285
NHSO2CH3
i-Pr
Cl


I.a.286
N(CH3)SO2CH3
i-Pr
Cl


I.a.287
S(O)CH2CH3
i-Pr
Cl


I.a.288
NHCOCH3
i-Pr
Cl


I.a.289
N(CH3)COCH3
i-Pr
Cl





I.a.290


embedded image


i-Pr
Cl





I.a.291


embedded image


i-Pr
Cl





I.a.292


embedded image


i-Pr
Cl





I.a.293
CH2OCH3
i-Pr
Cl


I.a.294
CH2OCH2CH3
i-Pr
Cl


I.a.295
CH2OCH2CH2OCH3
i-Pr
Cl


I.a.296
CH2OCH2CF3
i-Pr
Cl


I.a.297
CH2OCH2CF2CHCF2
i-Pr
Cl


I.a.298
CH2OCH2CHF2
i-Pr
Cl





I.a.299


embedded image


i-Pr
Cl





I.a.300


embedded image


i-Pr
Cl





I.a.301
Cl
H
F


I.a.302
OCH3
H
F


I.a.303
OCH2CH3
H
F


I.a.304
O(CH2)2OCH3
H
F


I.a.305
OCH2c-Pr
H
F


I.a.306
O(CH2)2c-Pr
H
F


I.a.307
O(CH2)2i-Pr
H
F


I.a.308
O(CH2)2c-Bu
H
F


I.a.309
O(CH2)3OCH3
H
F


I.a.310
O(CH2)4OCH3
H
F


I.a.311
OCH2CHF2
H
F


I.a.312
OCHF2
H
F


I.a.313
OCH2CON(CH3)2
H
F


I.a.314
O(CH2)2CON(CH3)2
H
F


I.a.315
O(CH2)-5-pyrrolidin-2-on
H
F


I.a.316
O(CH2)-1-pyrrolidin-2-on
H
F


I.a.317
OCH(CH3)2
H
F


I.a.318
OCH2CH(CH3)2
H
F





I.a.319


embedded image


H
F





I.a.320
OCH2CF3
H
F


I.a.321
O(CH2)2CF3
H
F


I.a.322
Oc-Pr
H
F


I.a.323
Oc-Bu
H
F





I.a.324


embedded image


H
F





I.a.325


embedded image


H
F





I.a.326
SCH3
H
F


I.a.327
S(O)CH3
H
F


I.a.328
SO2CH3
H
F


I.a.329
S(CH2)2OCH3
H
F


I.a.330
SCH2CH3
H
F


I.a.331
SO2CH2CH3
H
F


I.a.332
SO2(CH2)2OCH3
H
F


I.a.333
SO2i-Pr
H
F


I.a.334
SO2c-Pr
H
F


I.a.335
NHSO2CH3
H
F


I.a.336
N(CH3)SO2CH3
H
F


I.a.337
S(O)CH2CH3
H
F


I.a.338
NHCOCH3
H
F


I.a.339
N(CH3)COCH3
H
F





I.a.340


embedded image


H
F





I.a.341


embedded image


H
F





I.a.342


embedded image


H
F





I.a.343
CH2OCH3
H
F


I.a.344
CH2OCH2CH3
H
F


I.a.345
CH2OCH2CH2OCH3
H
F


I.a.346
CH2OCH2CF3
H
F


I.a.347
CH2OCH2CF2CHCF2
H
F


I.a.348
CH2OCH2CHF2
H
F





I.a.349


embedded image


H
F





I.a.350


embedded image


H
F





I.a.351
Cl
Cl
F


I.a.352
OCH3
Cl
F


I.a.353
OCH2CH3
Cl
F


I.a.354
O(CH2)2OCH3
Cl
F


I.a.355
OCH2c-Pr
Cl
F


I.a.356
O(CH2)2c-Pr
Cl
F


I.a.357
O(CH2)2i-Pr
Cl
F


I.a.358
O(CH2)2c-Bu
Cl
F


I.a.359
O(CH2)3OCH3
Cl
F


I.a.360
O(CH2)4OCH3
Cl
F


I.a.361
OCH2CHF2
Cl
F


I.a.362
OCHF2
Cl
F


I.a.363
OCH2CON(CH3)2
Cl
F


I.a.364
O(CH2)2CON(CH3)2
Cl
F


I.a.365
O(CH2)-5-pyrrolidin-2-on
Cl
F


I.a.366
O(CH2)-1-pyrrolidin-2-on
Cl
F


I.a.367
OCH(CH3)2
Cl
F


I.a.368
OCH2CH(CH3)2
Cl
F





I.a.369


embedded image


Cl
F





I.a.370
OCH2CF3
Cl
F


I.a.371
O(CH2)2CF3
Cl
F


I.a.372
Oc-Pr
Cl
F


I.a.373
Oc-Bu
Cl
F





I.a.374


embedded image


Cl
F





I.a.375


embedded image


Cl
F





I.a.376
SCH3
Cl
F


I.a.377
S(O)CH3
Cl
F


I.a.378
SO2CH3
Cl
F


I.a.379
S(CH2)2OCH3
Cl
F


I.a.380
SCH2CH3
Cl
F


I.a.381
SO2CH2CH3
Cl
F


I.a.382
SO2(CH2)2OCH3
Cl
F


I.a.383
SO2i-Pr
Cl
F


I.a.384
SO2c-Pr
Cl
F


I.a.385
NHSO2CH3
Cl
F


I.a.386
N(CH3)SO2CH3
Cl
F


I.a.387
S(O)CH2CH3
Cl
F


I.a.388
NHCOCH3
Cl
F


I.a.389
N(CH3)COCH3
Cl
F





I.a.390


embedded image


Cl
F





I.a.391


embedded image


Cl
F





I.a.392


embedded image


Cl
F





I.a.393
CH2OCH3
Cl
F


I.a.394
CH2OCH2CH3
Cl
F


I.a.395
CH2OCH2CH2OCH3
Cl
F


I.a.396
CH2OCH2CF3
Cl
F


I.a.397
CH2OCH2CF2CHCF2
Cl
F


I.a.398
CH2OCH2CHF2
Cl
F





I.a.399


embedded image


Cl
F





I.a.400


embedded image


Cl
F





I.a.401
Cl
CH3
F


I.a.402
OCH3
CH3
F


I.a.403
OCH2CH3
CH3
F


I.a.404
O(CH2)2OCH3
CH3
F


I.a.405
OCH2c-Pr
CH3
F


I.a.406
O(CH2)2c-Pr
CH3
F


I.a.407
O(CH2)2i-Pr
CH3
F


I.a.408
O(CH2)2c-Bu
CH3
F


I.a.409
O(CH2)3OCH3
CH3
F


I.a.410
O(CH2)4OCH3
CH3
F


I.a.411
OCH2CHF2
CH3
F


I.a.412
OCHF2
CH3
F


I.a.413
OCH2CON(CH3)2
CH3
F


I.a.414
O(CH2)2CON(CH3)2
CH3
F


I.a.415
O(CH2)-5-pyrrolidin-2-on
CH3
F


I.a.416
O(CH2)-1-pyrrolidin-2-on
CH3
F


I.a.417
OCH(CH3)2
CH3
F


I.a.418
OCH2CH(CH3)2
CH3
F





I.a.419


embedded image


CH3
F





I.a.420
OCH2CF3
CH3
F


I.a.421
O(CH2)2CF3
CH3
F


I.a.422
Oc-Pr
CH3
F


I.a.423
Oc-Bu
CH3
F





I.a.424


embedded image


CH3
F





I.a.425


embedded image


CH3
F





I.a.426
SCH3
CH3
F


I.a.427
S(O)CH3
CH3
F


I.a.428
SO2CH3
CH3
F


I.a.429
S(CH2)2OCH3
CH3
F


I.a.430
SCH2CH3
CH3
F


I.a.431
SO2CH2CH3
CH3
F


I.a.432
SO2(CH2)2OCH3
CH3
F


I.a.433
SO2i-Pr
CH3
F


I.a.434
SO2c-Pr
CH3
F


I.a.435
NHSO2CH3
CH3
F


I.a.436
N(CH3)SO2CH3
CH3
F


I.a.437
S(O)CH2CH3
CH3
F


I.a.438
NHCOCH3
CH3
F


I.a.439
N(CH3)COCH3
CH3
F





I.a.440


embedded image


CH3
F





I.a.441


embedded image


CH3
F





I.a.442


embedded image


CH3
F





I.a.443
CH2OCH3
CH3
F


I.a.444
CH2OCH2CH3
CH3
F


I.a.445
CH2OCH2CH2OCH3
CH3
F


I.a.446
CH2OCH2CF3
CH3
F


I.a.447
CH2OCH2CF2CHCF2
CH3
F


I.a.448
CH2OCH2CHF2
CH3
F





I.a.449


embedded image


CH3
F





I.a.450


embedded image


CH3
F





I.a.451
Cl
CH2CH3
F


I.a.452
OCH3
CH2CH3
F


I.a.453
OCH2CH3
CH2CH3
F


I.a.454
O(CH2)2OCH3
CH2CH3
F


I.a.455
OCH2c-Pr
CH2CH3
F


I.a.456
O(CH2)2c-Pr
CH2CH3
F


I.a.457
O(CH2)2i-Pr
CH2CH3
F


I.a.458
O(CH2)2c-Bu
CH2CH3
F


I.a.459
O(CH2)3OCH3
CH2CH3
F


I.a.460
O(CH2)4OCH3
CH2CH3
F


I.a.461
OCH2CHF2
CH2CH3
F


I.a.462
OCHF2
CH2CH3
F


I.a.463
OCH2CON(CH3)2
CH2CH3
F


I.a.464
O(CH2)2CON(CH3)2
CH2CH3
F


I.a.465
O(CH2)-5-pyrrolidin-2-on
CH2CH3
F


I.a.466
O(CH2)-1-pyrrolidin-2-on
CH2CH3
F


I.a.467
OCH(CH3)2
CH2CH3
F


I.a.468
OCH2CH(CH3)2
CH2CH3
F





I.a.469


embedded image


CH2CH3
F





I.a.470
OCH2CF3
CH2CH3
F


I.a.471
O(CH2)2CF3
CH2CH3
F


I.a.472
Oc-Pr
CH2CH3
F


I.a.473
Oc-Bu
CH2CH3
F





I.a.474


embedded image


CH2CH3
F





I.a.475


embedded image


CH2CH3
F





I.a.476
SCH3
CH2CH3
F


I.a.477
S(O)CH3
CH2CH3
F


I.a.478
SO2CH3
CH2CH3
F


I.a.479
S(CH2)2OCH3
CH2CH3
F


I.a.480
SCH2CH3
CH2CH3
F


I.a.481
SO2CH2CH3
CH2CH3
F


I.a.482
SO2(CH2)2OCH3
CH2CH3
F


I.a.483
SO2i-Pr
CH2CH3
F


I.a.484
SO2c-Pr
CH2CH3
F


I.a.485
NHSO2CH3
CH2CH3
F


I.a.486
N(CH3)SO2CH3
CH2CH3
F


I.a.487
S(O)CH2CH3
CH2CH3
F


I.a.488
NHCOCH3
CH2CH3
F


I.a.489
N(CH3)COCH3
CH2CH3
F





I.a.490


embedded image


CH2CH3
F





I.a.491


embedded image


CH2CH3
F





I.a.492


embedded image


CH2CH3
F





I.a.493
CH2OCH3
CH2CH3
F


I.a.494
CH2OCH2CH3
CH2CH3
F


I.a.495
CH2OCH2CH2OCH3
CH2CH3
F


I.a.496
CH2OCH2CF3
CH2CH3
F


I.a.497
CH2OCH2CF2CHCF2
CH2CH3
F


I.a.498
CH2OCH2CHF2
CH2CH3
F





I.a.499


embedded image


CH2CH3
F





I.a.500


embedded image


CH2CH3
F





I.a.501
Cl
c-Pr
F


I.a.502
OCH3
c-Pr
F


I.a.503
OCH2CH3
c-Pr
F


I.a.504
O(CH2)2OCH3
c-Pr
F


I.a.505
OCH2c-Pr
c-Pr
F


I.a.506
O(CH2)2c-Pr
c-Pr
F


I.a.507
O(CH2)2i-Pr
c-Pr
F


I.a.508
O(CH2)2c-Bu
c-Pr
F


I.a.509
O(CH2)3OCH3
c-Pr
F


I.a.510
O(CH2)4OCH3
c-Pr
F


I.a.511
OCH2CHF2
c-Pr
F


I.a.512
OCHF2
c-Pr
F


I.a.513
OCH2CON(CH3)2
c-Pr
F


I.a.514
O(CH2)2CON(CH3)2
c-Pr
F


I.a.515
O(CH2)-5-pyrrolidin-2-on
c-Pr
F


I.a.516
O(CH2)-1-pyrrolidin-2-on
c-Pr
F


I.a.517
OCH(CH3)2
c-Pr
F


I.a.518
OCH2CH(CH3)2
c-Pr
F





I.a.519


embedded image


c-Pr
F





I.a.520
OCH2CF3
c-Pr
F


I.a.521
O(CH2)2CF3
c-Pr
F


I.a.522
Oc-Pr
c-Pr
F


I.a.523
Oc-Bu
c-Pr
F





I.a.524


embedded image


c-Pr
F





I.a.525


embedded image


c-Pr
F





I.a.526
SCH3
c-Pr
F


I.a.527
S(O)CH3
c-Pr
F


I.a.528
SO2CH3
c-Pr
F


I.a.529
S(CH2)2OCH3
c-Pr
F


I.a.530
SCH2CH3
c-Pr
F


I.a.531
SO2CH2CH3
c-Pr
F


I.a.532
SO2(CH2)2OCH3
c-Pr
F


I.a.533
SO2i-Pr
c-Pr
F


I.a.534
SO2c-Pr
c-Pr
F


I.a.535
NHSO2CH3
c-Pr
F


I.a.536
N(CH3)SO2CH3
c-Pr
F


I.a.537
S(O)CH2CH3
c-Pr
F


I.a.538
NHCOCH3
c-Pr
F


I.a.539
N(CH3)COCH3
c-Pr
F





I.a.540


embedded image


c-Pr
F





I.a.541


embedded image


c-Pr
F





I.a.542


embedded image


c-Pr
F





I.a.543
CH2OCH3
c-Pr
F


I.a.544
CH2OCH2CH3
c-Pr
F


I.a.545
CH2OCH2CH2OCH3
c-Pr
F


I.a.546
CH2OCH2CF3
c-Pr
F


I.a.547
CH2OCH2CF2CHCF2
c-Pr
F


I.a.548
CH2OCH2CHF2
c-Pr
F





I.a.549


embedded image


c-Pr
F





I.a.550


embedded image


c-Pr
F





I.a.551
Cl
i-Pr
F


I.a.552
OCH3
i-Pr
F


I.a.553
OCH2CH3
i-Pr
F


I.a.554
O(CH2)2OCH3
i-Pr
F


I.a.555
OCH2c-Pr
i-Pr
F


I.a.556
O(CH2)2c-Pr
i-Pr
F


I.a.557
O(CH2)2i-Pr
i-Pr
F


I.a.558
O(CH2)2c-Bu
i-Pr
F


I.a.559
O(CH2)3OCH3
i-Pr
F


I.a.560
O(CH2)4OCH3
i-Pr
F


I.a.561
OCH2CHF2
i-Pr
F


I.a.562
OCHF2
i-Pr
F


I.a.563
OCH2CON(CH3)2
i-Pr
F


I.a.564
O(CH2)2CON(CH3)2
i-Pr
F


I.a.565
O(CH2)-5-pyrrolidin-2-on
i-Pr
F


I.a.566
O(CH2)-1-pyrrolidin-2-on
i-Pr
F


I.a.567
OCH(CH3)2
i-Pr
F


I.a.568
OCH2CH(CH3)2
i-Pr
F





I.a.569


embedded image


i-Pr
F





I.a.570
OCH2CF3
i-Pr
F


I.a.571
O(CH2)2CF3
i-Pr
F


I.a.572
Oc-Pr
i-Pr
F


I.a.573
Oc-Bu
i-Pr
F





I.a.574


embedded image


i-Pr
F





I.a.575


embedded image


i-Pr
F





I.a.576
SCH3
i-Pr
F


I.a.577
S(O)CH3
i-Pr
F


I.a.578
SO2CH3
i-Pr
F


I.a.579
S(CH2)2OCH3
i-Pr
F


I.a.580
SCH2CH3
i-Pr
F


I.a.581
SO2CH2CH3
i-Pr
F


I.a.582
SO2(CH2)2OCH3
i-Pr
F


I.a.583
SO2i-Pr
i-Pr
F


I.a.584
SO2c-Pr
i-Pr
F


I.a.585
NHSO2CH3
i-Pr
F


I.a.586
N(CH3)SO2CH3
i-Pr
F


I.a.587
S(O)CH2CH3
i-Pr
F


I.a.588
NHCOCH3
i-Pr
F


I.a.589
N(CH3)COCH3
i-Pr
F





I.a.590


embedded image


i-Pr
F





I.a.591


embedded image


i-Pr
F





I.a.592


embedded image


i-Pr
F





I.a.593
CH2OCH3
i-Pr
F


I.a.594
CH2OCH2CH3
i-Pr
F


I.a.595
CH2OCH2CH2OCH3
i-Pr
F


I.a.596
CH2OCH2CF3
i-Pr
F


I.a.597
CH2OCH2CF2CHCF2
i-Pr
F


I.a.598
CH2OCH2CHF2
i-Pr
F





I.a.599


embedded image


i-Pr
F





I.a.600


embedded image


i-Pr
F





I.a.601
Cl
H
Br


I.a.602
OCH3
H
Br


I.a.603
OCH2CH3
H
Br


I.a.604
O(CH2)2OCH3
H
Br


I.a.605
OCH2c-Pr
H
Br


I.a.606
O(CH2)2c-Pr
H
Br


I.a.607
O(CH2)2i-Pr
H
Br


I.a.608
O(CH2)2c-Bu
H
Br


I.a.609
O(CH2)3OCH3
H
Br


I.a.610
O(CH2)4OCH3
H
Br


I.a.611
OCH2CHF2
H
Br


I.a.612
OCHF2
H
Br


I.a.613
OCH2CON(CH3)2
H
Br


I.a.614
O(CH2)2CON(CH3)2
H
Br


I.a.615
O(CH2)-5-pyrrolidin-2-on
H
Br


I.a.616
O(CH2)-1-pyrrolidin-2-on
H
Br


I.a.617
OCH(CH3)2
H
Br


I.a.618
OCH2CH(CH3)2
H
Br





I.a.619


embedded image


H
Br





I.a.620
OCH2CF3
H
Br


I.a.621
O(CH2)2CF3
H
Br


I.a.622
Oc-Pr
H
Br


I.a.623
Oc-Bu
H
Br





I.a.624


embedded image


H
Br





I.a.625


embedded image


H
Br





I.a.626
SCH3
H
Br


I.a.627
S(O)CH3
H
Br


I.a.628
SO2CH3
H
Br


I.a.629
S(CH2)2OCH3
H
Br


I.a.630
SCH2CH3
H
Br


I.a.631
SO2CH2CH3
H
Br


I.a.632
SO2(CH2)2OCH3
H
Br


I.a.633
SO2i-Pr
H
Br


I.a.634
SO2c-Pr
H
Br


I.a.635
NHSO2CH3
H
Br


I.a.636
N(CH3)SO2CH3
H
Br


I.a.637
S(O)CH2CH3
H
Br


I.a.638
NHCOCH3
H
Br


I.a.639
N(CH3)COCH3
H
Br





I.a.640


embedded image


H
Br





I.a.641


embedded image


H
Br





I.a.642


embedded image


H
Br





I.a.643
CH2OCH3
H
Br


I.a.644
CH2OCH2CH3
H
Br


I.a.645
CH2OCH2CH2OCH3
H
Br


I.a.646
CH2OCH2CF3
H
Br


I.a.647
CH2OCH2CF2CHCF2
H
Br


I.a.648
CH2OCH2CHF2
H
Br





I.a.649


embedded image


H
Br





I.a.650


embedded image


H
Br





I.a.651
Cl
Cl
Br


I.a.652
OCH3
Cl
Br


I.a.653
OCH2CH3
Cl
Br


I.a.654
O(CH2)2OCH3
Cl
Br


I.a.655
OCH2c-Pr
Cl
Br


I.a.656
O(CH2)2c-Pr
Cl
Br


I.a.657
O(CH2)2i-Pr
Cl
Br


I.a.658
O(CH2)2c-Bu
Cl
Br


I.a.659
O(CH2)3OCH3
Cl
Br


I.a.660
O(CH2)4OCH3
Cl
Br


I.a.661
OCH2CHF2
Cl
Br


I.a.662
OCHF2
Cl
Br


I.a.663
OCH2CON(CH3)2
Cl
Br


I.a.664
O(CH2)2CON(CH3)2
Cl
Br


I.a.665
O(CH2)-5-pyrrolidin-2-on
Cl
Br


I.a.666
O(CH2)-1-pyrrolidin-2-on
Cl
Br


I.a.667
OCH(CH3)2
Cl
Br


I.a.668
OCH2CH(CH3)2
Cl
Br





I.a.669


embedded image


Cl
Br





I.a.670
OCH2CF3
Cl
Br


I.a.671
O(CH2)2CF3
Cl
Br


I.a.672
Oc-Pr
Cl
Br


I.a.673
Oc-Bu
Cl
Br





I.a.674


embedded image


Cl
Br





I.a.675


embedded image


Cl
Br





I.a.676
SCH3
Cl
Br


I.a.677
S(O)CH3
Cl
Br


I.a.678
SO2CH3
Cl
Br


I.a.679
S(CH2)2OCH3
Cl
Br


I.a.680
SCH2CH3
Cl
Br


I.a.681
SO2CH2CH3
Cl
Br


I.a.682
SO2(CH2)2OCH3
Cl
Br


I.a.683
SO2i-Pr
Cl
Br


I.a.684
SO2c-Pr
Cl
Br


I.a.685
NHSO2CH3
Cl
Br


I.a.686
N(CH3)SO2CH3
Cl
Br


I.a.687
S(O)CH2CH3
Cl
Br


I.a.688
NHCOCH3
Cl
Br


I.a.689
N(CH3)COCH3
Cl
Br





I.a.690


embedded image


Cl
Br





I.a.691


embedded image


Cl
Br





I.a.692


embedded image


Cl
Br





I.a.693
CH2OCH3
Cl
Br


I.a.694
CH2OCH2CH3
Cl
Br


I.a.695
CH2OCH2CH2OCH3
Cl
Br


I.a.696
CH2OCH2CF3
Cl
Br


I.a.697
CH2OCH2CF2CHCF2
Cl
Br


I.a.698
CH2OCH2CHF2
Cl
Br





I.a.699


embedded image


Cl
Br





I.a.700


embedded image


Cl
Br





I.a.701
Cl
CH3
Br


I.a.702
OCH3
CH3
Br


I.a.703
OCH2CH3
CH3
Br


I.a.704
OCH2OCH3
CH3
Br


I.a.705
O(CH2)2OCH3
CH3
Br


I.a.706
O(CH2)2c-Pr
CH3
Br


I.a.707
O(CH2)2i-Pr
CH3
Br


I.a.708
O(CH2)2c-Bu
CH3
Br


I.a.709
O(CH2)3OCH3
CH3
Br


I.a.710
O(CH2)4OCH3
CH3
Br


I.a.711
OCH2CHF2
CH3
Br


I.a.712
OCHF2
CH3
Br


I.a.713
OCH2CON(CH3)2
CH3
Br


I.a.714
O(CH2)2CON(CH3)2
CH3
Br


I.a.715
O(CH2)-5-pyrrolidin-2-on
CH3
Br


I.a.716
O(CH2)-1-pyrrolidin-2-on
CH3
Br


I.a.717
OCH(CH3)2
CH3
Br


I.a.718
OCH2CH(CH3)2
CH3
Br





I.a.719


embedded image


CH3
Br





I.a.720
OCH2CF3
CH3
Br


I.a.721
O(CH2)2CF3
CH3
Br


I.a.722
Oc-Pr
CH3
Br


I.a.723
Oc-Bu
CH3
Br





I.a.724


embedded image


CH3
Br





I.a.725


embedded image


CH3
Br





I.a.726
SCH3
CH3
Br


I.a.727
S(O)CH3
CH3
Br


I.a.728
SO2CH3
CH3
Br


I.a.729
S(CH2)2OCH3
CH3
Br


I.a.730
SCH2CH3
CH3
Br


I.a.731
SO2CH2CH3
CH3
Br


I.a.732
SO2(CH2)2OCH3
CH3
Br


I.a.733
SO2i-Pr
CH3
Br


I.a.734
SO2c-Pr
CH3
Br


I.a.735
NHSO2CH3
CH3
Br


I.a.736
N(CH3)SO2CH3
CH3
Br


I.a.737
S(O)CH2CH3
CH3
Br


I.a.738
NHCOCH3
CH3
Br


I.a.739
N(CH3)COCH3
CH3
Br





I.a.740


embedded image


CH3
Br





I.a.741


embedded image


CH3
Br





I.a.742


embedded image


CH3
Br





I.a.743
CH2OCH3
CH3
Br


I.a.744
CH2OCH2CH3
CH3
Br


I.a.745
CH2OCH2CH2OCH3
CH3
Br


I.a.746
CH2OCH2CF3
CH3
Br


I.a.747
CH2OCH2CF2CHCF2
CH3
Br


I.a.748
CH2OCH2CHF2
CH3
Br





I.a.749


embedded image


CH3
Br





I.a.750


embedded image


CH3
Br





I.a.751
Cl
CH2CH3
Br


I.a.752
OCH3
CH2CH3
Br


I.a.753
OCH2CH3
CH2CH3
Br


I.a.754
O(CH2)2OCH3
CH2CH3
Br


I.a.755
OCH2c-Pr
CH2CH3
Br


I.a.756
O(CH2)2c-Pr
CH2CH3
Br


I.a.757
O(CH2)2i-Pr
CH2CH3
Br


I.a.758
O(CH2)2c-Bu
CH2CH3
Br


I.a.759
O(CH2)3OCH3
CH2CH3
Br


I.a.760
O(CH2)4OCH3
CH2CH3
Br


I.a.761
OCH2CHF2
CH2CH3
Br


I.a.762
OCHF2
CH2CH3
Br


I.a.763
OCH2CON(CH3)2
CH2CH3
Br


I.a.764
O(CH2)2CON(CH3)2
CH2CH3
Br


I.a.765
O(CH2)-5-pyrrolidin-2-on
CH2CH3
Br


I.a.766
O(CH2)-1-pyrrolidin-2-on
CH2CH3
Br


I.a.767
OCH(CH3)2
CH2CH3
Br


I.a.768
OCH2CH(CH3)2
CH2CH3
Br





I.a.769


embedded image


CH2CH3
Br





I.a.770
OCH2CF3
CH2CH3
Br


I.a.771
O(CH2)2CF3
CH2CH3
Br


I.a.772
Oc-Pr
CH2CH3
Br


I.a.773
Oc-Bu
CH2CH3
Br





I.a.774


embedded image


CH2CH3
Br





I.a.775


embedded image


CH2CH3
Br





I.a.776
SCH3
CH2CH3
Br


I.a.777
S(O)CH3
CH2CH3
Br


I.a.778
SO2CH3
CH2CH3
Br


I.a.779
S(CH2)2OCH3
CH2CH3
Br


I.a.780
SCH2CH3
CH2CH3
Br


I.a.781
SO2CH2CH3
CH2CH3
Br


I.a.782
SO2(CH2)2OCH3
CH2CH3
Br


I.a.783
SO2i-Pr
CH2CH3
Br


I.a.784
SO2c-Pr
CH2CH3
Br


I.a.785
NHSO2CH3
CH2CH3
Br


I.a.786
N(CH3)SO2CH3
CH2CH3
Br


I.a.787
S(O)CH2CH3
CH2CH3
Br


I.a.788
NHCOCH3
CH2CH3
Br


I.a.789
N(CH3)COCH3
CH2CH3
Br





I.a.790


embedded image


CH2CH3
Br





I.a.791


embedded image


CH2CH3
Br





I.a.792


embedded image


CH2CH3
Br





I.a.793
CH2OCH3
CH2CH3
Br


I.a.794
CH2OCH2CH3
CH2CH3
Br


I.a.795
CH2OCH2CH2OCH3
CH2CH3
Br


I.a.796
CH2OCH2CF3
CH2CH3
Br


I.a.797
CH2OCH2CF2CHCF2
CH2CH3
Br


I.a.798
CH2OCH2CHF2
CH2CH3
Br





I.a.799


embedded image


CH2CH3
Br





I.a.800


embedded image


CH2CH3
Br





I.a.801
Cl
c-Pr
Br


I.a.802
OCH3
c-Pr
Br


I.a.803
OCH2CH3
c-Pr
Br


I.a.804
O(CH2)2OCH3
c-Pr
Br


I.a.805
OCH2c-Pr
c-Pr
Br


I.a.806
O(CH2)2c-Pr
c-Pr
Br


I.a.807
O(CH2)2i-Pr
c-Pr
Br


I.a.808
O(CH2)2c-Bu
c-Pr
Br


I.a.809
O(CH2)3OCH3
c-Pr
Br


I.a.810
O(CH2)4OCH3
c-Pr
Br


I.a.811
OCH2CHF2
c-Pr
Br


I.a.812
OCHF2
c-Pr
Br


I.a.813
OCH2CON(CH3)2
c-Pr
Br


I.a.814
O(CH2)2CON(CH3)2
c-Pr
Br


I.a.815
O(CH2)-5-pyrrolidin-2-on
c-Pr
Br


I.a.816
O(CH2)-1-pyrrolidin-2-on
c-Pr
Br


I.a.817
OCH(CH3)2
c-Pr
Br


I.a.818
OCH2CH(CH3)2
c-Pr
Br





I.a.819


embedded image


c-Pr
Br





I.a.820
OCH2CF3
c-Pr
Br


I.a.821
O(CH2)2CF3
c-Pr
Br


I.a.822
Oc-Pr
c-Pr
Br


I.a.823
Oc-Bu
c-Pr
Br





I.a.824


embedded image


c-Pr
Br





I.a.825


embedded image


c-Pr
Br





I.a.826
SCH3
c-Pr
Br


I.a.827
S(O)CH3
c-Pr
Br


I.a.828
SO2CH3
c-Pr
Br


I.a.829
S(CH2)2OCH3
c-Pr
Br


I.a.830
SCH2CH3
c-Pr
Br


I.a.831
SO2CH2CH3
c-Pr
Br


I.a.832
SO2(CH2)2OCH3
c-Pr
Br


I.a.833
SO2i-Pr
c-Pr
Br


I.a.834
SO2c-Pr
c-Pr
Br


I.a.835
NHSO2CH3
c-Pr
Br


I.a.836
N(CH3)SO2CH3
c-Pr
Br


I.a.837
S(O)CH2CH3
c-Pr
Br


I.a.838
NHCOCH3
c-Pr
Br


I.a.839
N(CH3)COCH3
c-Pr
Br





I.a.840


embedded image


c-Pr
Br





I.a.841


embedded image


c-Pr
Br





I.a.842


embedded image


c-Pr
Br





I.a.843
CH2OCH3
c-Pr
Br


I.a.844
CH2OCH2CH3
c-Pr
Br


I.a.845
CH2OCH2CH2OCH3
c-Pr
Br


I.a.846
CH2OCH2CF3
c-Pr
Br


I.a.847
CH2OCH2CF2CHCF2
c-Pr
Br


I.a.848
CH2OCH2CHF2
c-Pr
Br





I.a.849


embedded image


c-Pr
Br





I.a.850


embedded image


c-Pr
Br





I.a.851
Cl
i-Pr
Br


I.a.852
OCH3
i-Pr
Br


I.a.853
OCH2CH3
i-Pr
Br


I.a.854
O(CH2)2OCH3
i-Pr
Br


I.a.855
OCH2c-Pr
i-Pr
Br


I.a.856
O(CH2)2c-Pr
i-Pr
Br


I.a.857
O(CH2)2i-Pr
i-Pr
Br


I.a.858
O(CH2)2c-Bu
i-Pr
Br


I.a.859
O(CH2)3OCH3
i-Pr
Br


I.a.860
O(CH2)4OCH3
i-Pr
Br


I.a.861
OCH2CHF2
i-Pr
Br


I.a.862
OCHF2
i-Pr
Br


I.a.863
OCH2CON(CH3)2
i-Pr
Br


I.a.864
O(CH2)2CON(CH3)2
i-Pr
Br


I.a.865
O(CH2)-5-pyrrolidin-2-on
i-Pr
Br


I.a.866
O(CH2)-1-pyrrolidin-2-on
i-Pr
Br


I.a.867
OCH(CH3)2
i-Pr
Br


I.a.868
OCH2CH(CH3)2
i-Pr
Br





I.a.869


embedded image


i-Pr
Br





I.a.870
OCH2CF3
i-Pr
Br


I.a.871
O(CH2)2CF3
i-Pr
Br


I.a.872
Oc-Pr
i-Pr
Br


I.a.873
Oc-Bu
i-Pr
Br





I.a.874


embedded image


i-Pr
Br





I.a.875


embedded image


i-Pr
Br





I.a.876
SCH3
i-Pr
Br


I.a.877
S(O)CH3
i-Pr
Br


I.a.878
SO2CH3
i-Pr
Br


I.a.879
S(CH2)2OCH3
i-Pr
Br


I.a.880
SCH2CH3
i-Pr
Br


I.a.881
SO2CH2CH3
i-Pr
Br


I.a.882
SO2(CH2)2OCH3
i-Pr
Br


I.a.883
SO2i-Pr
i-Pr
Br


I.a.884
SO2c-Pr
i-Pr
Br


I.a.885
NHSO2CH3
i-Pr
Br


I.a.886
N(CH3)SO2CH3
i-Pr
Br


I.a.887
S(O)CH2CH3
i-Pr
Br


I.a.888
NHCOCH3
i-Pr
Br


I.a.889
N(CH3)COCH3
i-Pr
Br





I.a.890


embedded image


i-Pr
Br





I.a.891


embedded image


i-Pr
Br





I.a.892


embedded image


i-Pr
Br





I.a.893
CH2OCH3
i-Pr
Br


I.a.894
CH2OCH2CH3
i-Pr
Br


I.a.895
CH2OCH2CH2OCH3
i-Pr
Br


I.a.896
CH2OCH2CF3
i-Pr
Br


I.a.897
CH2OCH2CF2CHCF2
i-Pr
Br


I.a.898
CH2OCH2CHF2
i-Pr
Br





I.a.899


embedded image


i-Pr
Br





I.a.900


embedded image


i-Pr
Br





I.a.901
Cl
H
CH3


I.a.902
OCH3
H
CH3


I.a.903
OCH2CH3
H
CH3


I.a.904
O(CH2)2OCH3
H
CH3


I.a.905
OCH2c-Pr
H
CH3


I.a.906
O(CH2)2c-Pr
H
CH3


I.a.907
O(CH2)2i-Pr
H
CH3


I.a.908
O(CH2)2c-Bu
H
CH3


I.a.909
O(CH2)3OCH3
H
CH3


I.a.910
O(CH2)4OCH3
H
CH3


I.a.911
OCH2CHF2
H
CH3


I.a.912
OCHF2
H
CH3


I.a.913
OCH2CON(CH3)2
H
CH3


I.a.914
O(CH2)2CON(CH3)2
H
CH3


I.a.915
O(CH2)-5-pyrrolidin-2-on
H
CH3


I.a.916
O(CH2)-1-pyrrolidin-2-on
H
CH3


I.a.917
OCH(CH3)2
H
CH3


I.a.918
OCH2CH(CH3)2
H
CH3





I.a.919


embedded image


H
CH3





I.a.920
OCH2CF3
H
CH3


I.a.921
O(CH2)2CF3
H
CH3


I.a.922
Oc-Pr
H
CH3


I.a.923
Oc-Bu
H
CH3





I.a.924


embedded image


H
CH3





I.a.925


embedded image


H
CH3





I.a.926
SCH3
H
CH3


I.a.927
S(O)CH3
H
CH3


I.a.928
SO2CH3
H
CH3


I.a.929
S(CH2)2OCH3
H
CH3


I.a.930
SCH2CH3
H
CH3


I.a.931
SO2CH2CH3
H
CH3


I.a.932
SO2(CH2)2OCH3
H
CH3


I.a.933
SO2i-Pr
H
CH3


I.a.934
SO2c-Pr
H
CH3


I.a.935
NHSO2CH3
H
CH3


I.a.936
N(CH3)SO2CH3
H
CH3


I.a.937
S(O)CH2CH3
H
CH3


I.a.938
NHCOCH3
H
CH3


I.a.939
N(CH3)COCH3
H
CH3





I.a.940


embedded image


H
CH3





I.a.941


embedded image


H
CH3





I.a.942


embedded image


H
CH3





I.a.943
CH2OCH3
H
CH3


I.a.944
CH2OCH2CH3
H
CH3


I.a.945
CH2OCH2CH2OCH3
H
CH3


I.a.946
CH2OCH2CF3
H
CH3


I.a.947
CH2OCH2CF2CHCF2
H
CH3


I.a.948
CH2OCH2CHF2
H
CH3





I.a.949


embedded image


H
CH3





I.a.950


embedded image


H
CH3





I.a.951
Cl
Cl
CH3


I.a.952
OCH3
Cl
CH3


I.a.953
OCH2CH3
Cl
CH3


I.a.954
O(CH2)2OCH3
Cl
CH3


I.a.955
OCH2c-Pr
Cl
CH3


I.a.956
O(CH2)2c-Pr
Cl
CH3


I.a.957
O(CH2)2i-Pr
Cl
CH3


I.a.958
O(CH2)2c-Bu
Cl
CH3


I.a.959
O(CH2)3OCH3
Cl
CH3


I.a.960
O(CH2)4OCH3
Cl
CH3


I.a.961
OCH2CHF2
Cl
CH3


I.a.962
OCHF2
Cl
CH3


I.a.963
OCH2CON(CH3)2
Cl
CH3


I.a.964
O(CH2)2CON(CH3)2
Cl
CH3


I.a.965
O(CH2)-5-pyrrolidin-2-on
Cl
CH3


I.a.966
O(CH2)-1-pyrrolidin-2-on
Cl
CH3


I.a.967
OCH(CH3)2
Cl
CH3


I.a.968
OCH2CH(CH3)2
Cl
CH3





I.a.969


embedded image


Cl
CH3





I.a.970
OCH2CF3
Cl
CH3


I.a.971
O(CH2)2CF3
Cl
CH3


I.a.972
Oc-Pr
Cl
CH3


I.a.973
Oc-Bu
Cl
CH3





I.a.974


embedded image


Cl
CH3





I.a.975


embedded image


Cl
CH3





I.a.976
SCH3
Cl
CH3


I.a.977
S(O)CH3
Cl
CH3


I.a.978
SO2CH3
Cl
CH3


I.a.979
S(CH2)2OCH3
Cl
CH3


I.a.980
SCH2CH3
Cl
CH3


I.a.981
SO2CH2CH3
Cl
CH3


I.a.982
SO2(CH2)2OCH3
Cl
CH3


I.a.983
SO2i-Pr
Cl
CH3


I.a.984
SO2c-Pr
Cl
CH3


I.a.985
NHSO2CH3
Cl
CH3


I.a.986
N(CH3)SO2CH3
Cl
CH3


I.a.987
S(O)CH2CH3
Cl
CH3


I.a.988
NHCOCH3
Cl
CH3


I.a.989
N(CH3)COCH3
Cl
CH3





I.a.990


embedded image


Cl
CH3





I.a.991


embedded image


Cl
CH3





I.a.992


embedded image


Cl
CH3





I.a.993
CH2OCH3
Cl
CH3


I.a.994
CH2OCH2CH3
Cl
CH3


I.a.995
CH2OCH2CH2OCH3
Cl
CH3


I.a.996
CH2OCH2CF3
Cl
CH3


I.a.997
CH2OCH2CF2CHCF2
Cl
CH3


I.a.998
CH2OCH2CHF2
Cl
CH3





I.a.999


embedded image


Cl
CH3





I.a.1000


embedded image


Cl
CH3





I.a.1001
Cl
CH3
CH3


I.a.1002
OCH3
CH3
CH3


I.a.1003
OCH2CH3
CH3
CH3


I.a.1004
O(CH2)2OCH3
CH3
CH3


I.a.1005
OCH2c-Pr
CH3
CH3


I.a.1006
O(CH2)2c-Pr
CH3
CH3


I.a.1007
O(CH2)2i-Pr
CH3
CH3


I.a.1008
O(CH2)2c-Bu
CH3
CH3


I.a.1009
O(CH2)3OCH3
CH3
CH3


I.a.1010
O(CH2)4OCH3
CH3
CH3


I.a.1011
OCH2CHF2
CH3
CH3


I.a.1012
OCHF2
CH3
CH3


I.a.1013
OCH2CON(CH3)2
CH3
CH3


I.a.1014
O(CH2)2CON(CH3)2
CH3
CH3


I.a.1015
O(CH2)-5-pyrrolidin-2-on
CH3
CH3


I.a.1016
O(CH2)-1-pyrrolidin-2-on
CH3
CH3


I.a.1017
OCH(CH3)2
CH3
CH3


I.a.1018
OCH2CH(CH3)2
CH3
CH3





I.a.1019


embedded image


CH3
CH3





I.a.1020
OCH2CF3
CH3
CH3


I.a.1021
O(CH2)2CF3
CH3
CH3


I.a.1022
Oc-Pr
CH3
CH3


I.a.1023
Oc-Bu
CH3
CH3





I.a.1024


embedded image


CH3
CH3





I.a.1025


embedded image


CH3
CH3





I.a.1026
SCH3
CH3
CH3


I.a.1027
S(O)CH3
CH3
CH3


I.a.1028
SO2CH3
CH3
CH3


I.a.1029
S(CH2)2OCH3
CH3
CH3


I.a.1030
SCH2CH3
CH3
CH3


I.a.1031
SO2CH2CH3
CH3
CH3


I.a.1032
SO2(CH2)2OCH3
CH3
CH3


I.a.1033
SO2i-Pr
CH3
CH3


I.a.1034
SO2c-Pr
CH3
CH3


I.a.1035
NHSO2CH3
CH3
CH3


I.a.1036
N(CH3)SO2CH3
CH3
CH3


I.a.1037
S(O)CH2CH3
CH3
CH3


I.a.1038
NHCOCH3
CH3
CH3


I.a.1039
N(CH3)COCH3
CH3
CH3





I.a.1040


embedded image


CH3
CH3





I.a.1041


embedded image


CH3
CH3





I.a.1042


embedded image


CH3
CH3





I.a.1043
CH2OCH3
CH3
CH3


I.a.1044
CH2OCH2CH3
CH3
CH3


I.a.1045
CH2OCH2CH2OCH3
CH3
CH3


I.a.1046
CH2OCH2CF3
CH3
CH3


I.a.1047
CH2OCH2CF2CHCF2
CH3
CH3


I.a.1048
CH2OCH2CHF2
CH3
CH3





I.a.1049


embedded image


CH3
CH3





I.a.1050


embedded image


CH3
CH3





I.a.1051
Cl
CH2CH3
CH3


I.a.1052
OCH3
CH2CH3
CH3


I.a.1053
OCH2CH3
CH2CH3
CH3


I.a.1054
O(CH2)2OCH3
CH2CH3
CH3


I.a.1055
OCH2c-Pr
CH2CH3
CH3


I.a.1056
O(CH2)2c-Pr
CH2CH3
CH3


I.a.1057
O(CH2)2i-Pr
CH2CH3
CH3


I.a.1058
O(CH2)2c-Bu
CH2CH3
CH3


I.a.1059
O(CH2)3OCH3
CH2CH3
CH3


I.a.1060
O(CH2)4OCH3
CH2CH3
CH3


I.a.1061
OCH2CHF2
CH2CH3
CH3


I.a.1062
OCHF2
CH2CH3
CH3


I.a.1063
OCH2CON(CH3)2
CH2CH3
CH3


I.a.1064
O(CH2)2CON(CH3)2
CH2CH3
CH3


I.a.1065
O(CH2)-5-pyrrolidin-2-on
CH2CH3
CH3


I.a.1066
O(CH2)-1-pyrrolidin-2-on
CH2CH3
CH3


I.a.1067
OCH(CH3)2
CH2CH3
CH3


I.a.1068
OCH2CH(CH3)2
CH2CH3
CH3





I.a.1069


embedded image


CH2CH3
CH3





I.a.1070
OCH2CF3
CH2CH3
CH3


I.a.1071
O(CH2)2CF3
CH2CH3
CH3


I.a.1072
Oc-Pr
CH2CH3
CH3


I.a.1073
Oc-Bu
CH2CH3
CH3





I.a.1074


embedded image


CH2CH3
CH3





I.a.1075


embedded image


CH2CH3
CH3





I.a.1076
SCH3
CH2CH3
CH3


I.a.1077
S(O)CH3
CH2CH3
CH3


I.a.1078
SO2CH3
CH2CH3
CH3


I.a.1079
S(CH2)2OCH3
CH2CH3
CH3


I.a.1080
SCH2CH3
CH2CH3
CH3


I.a.1081
SO2CH2CH3
CH2CH3
CH3


I.a.1082
SO2(CH2)2OCH3
CH2CH3
CH3


I.a.1083
SO2i-Pr
CH2CH3
CH3


I.a.1084
SO2c-Pr
CH2CH3
CH3


I.a.1085
NHSO2CH3
CH2CH3
CH3


I.a.1086
N(CH3)SO2CH3
CH2CH3
CH3


I.a.1087
S(O)CH2CH3
CH2CH3
CH3


I.a.1088
NHCOCH3
CH2CH3
CH3


I.a.1089
N(CH3)COCH3
CH2CH3
CH3





I.a.1090


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CH2CH3
CH3





I.a.1091


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CH2CH3
CH3





I.a.1092


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CH2CH3
CH3





I.a.1093
CH2OCH3
CH2CH3
CH3


I.a.1094
CH2OCH2CH3
CH2CH3
CH3


I.a.1095
CH2OCH2CH2OCH3
CH2CH3
CH3


I.a.1096
CH2OCH2CF3
CH2CH3
CH3


I.a.1097
CH2OCH2CF2CHCF2
CH2CH3
CH3


I.a.1098
CH2OCH2CHF2
CH2CH3
CH3





I.a.1099


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CH2CH3
CH3





I.a.1100


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CH2CH3
CH3





I.a.1101
Cl
c-Pr
CH3


I.a.1102
OCH3
c-Pr
CH3


I.a.1103
OCH2CH3
c-Pr
CH3


I.a.1104
O(CH2)2OCH3
c-Pr
CH3


I.a.1105
OCH2c-Pr
c-Pr
CH3


I.a.1106
O(CH2)2c-Pr
c-Pr
CH3


I.a.1107
O(CH2)2i-Pr
c-Pr
CH3


I.a.1108
O(CH2)2c-Bu
c-Pr
CH3


I.a.1109
O(CH2)3OCH3
c-Pr
CH3


I.a.1110
O(CH2)4OCH3
c-Pr
CH3


I.a.1111
OCH2CHF2
c-Pr
CH3


I.a.1112
OCHF2
c-Pr
CH3


I.a.1113
OCH2CON(CH3)2
c-Pr
CH3


I.a.1114
O(CH2)2CON(CH3)2
c-Pr
CH3


I.a.1115
O(CH2)-5-pyrrolidin-2-on
c-Pr
CH3


I.a.1116
O(CH2)-1-pyrrolidin-2-on
c-Pr
CH3


I.a.1117
OCH(CH3)2
c-Pr
CH3


I.a.1118
OCH2CH(CH3)2
c-Pr
CH3





I.a.1119


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c-Pr
CH3





I.a.1120
OCH2CF3
c-Pr
CH3


I.a.1121
O(CH2)2CF3
c-Pr
CH3


I.a.1122
Oc-Pr
c-Pr
CH3


I.a.1123
Oc-Bu
c-Pr
CH3





I.a.1124


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c-Pr
CH3





I.a.1125


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c-Pr
CH3





I.a.1126
SCH3
c-Pr
CH3


I.a.1127
S(O)CH3
c-Pr
CH3


I.a.1128
SO2CH3
c-Pr
CH3


I.a.1129
S(CH2)2OCH3
c-Pr
CH3


I.a.1130
SCH2CH3
c-Pr
CH3


I.a.1131
SO2CH2CH3
c-Pr
CH3


I.a.1132
SO2(CH2)2OCH3
c-Pr
CH3


I.a.1133
SO2i-Pr
c-Pr
CH3


I.a.1134
SO2c-Pr
c-Pr
CH3


I.a.1135
NHSO2CH3
c-Pr
CH3


I.a.1136
N(CH3)SO2CH3
c-Pr
CH3


I.a.1137
S(O)CH2CH3
c-Pr
CH3


I.a.1138
NHCOCH3
c-Pr
CH3


I.a.1139
N(CH3)COCH3
c-Pr
CH3





I.a.1140


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c-Pr
CH3





I.a.1141


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c-Pr
CH3





I.a.1142


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c-Pr
CH3





I.a.1143
CH2OCH3
c-Pr
CH3


I.a.1144
CH2OCH2CH3
c-Pr
CH3


I.a.1145
CH2OCH2CH2OCH3
c-Pr
CH3


I.a.1146
CH2OCH2CF3
c-Pr
CH3


I.a.1147
CH2OCH2CF2CHCF2
c-Pr
CH3


I.a.1148
CH2OCH2CHF2
c-Pr
CH3





I.a.1149


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c-Pr
CH3





I.a.1150


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c-Pr
CH3





I.a.1151
Cl
i-Pr
CH3


I.a.1152
OCH3
i-Pr
CH3


I.a.1153
OCH2CH3
i-Pr
CH3


I.a.1154
O(CH2)2OCH3
i-Pr
CH3


I.a.1155
OCH2c-Pr
i-Pr
CH3


I.a.1156
O(CH2)2c-Pr
i-Pr
CH3


I.a.1157
O(CH2)2i-Pr
i-Pr
CH3


I.a.1158
O(CH2)2c-Bu
i-Pr
CH3


I.a.1159
O(CH2)3OCH3
i-Pr
CH3


I.a.1160
O(CH2)4OCH3
i-Pr
CH3


I.a.1161
OCH2CHF2
i-Pr
CH3


I.a.1162
OCHF2
i-Pr
CH3


I.a.1163
OCH2CON(CH3)2
i-Pr
CH3


I.a.1164
O(CH2)2CON(CH3)2
i-Pr
CH3


I.a.1165
O(CH2)-5-pyrrolidin-2-on
i-Pr
CH3


I.a.1166
O(CH2)-1-pyrrolidin-2-on
i-Pr
CH3


I.a.1167
OCH(CH3)2
i-Pr
CH3


I.a.1168
OCH2CH(CH3)2
i-Pr
CH3





I.a.1169


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i-Pr
CH3





I.a.1170
OCH2CF3
i-Pr
CH3


I.a.1171
O(CH2)2CF3
i-Pr
CH3


I.a.1172
Oc-Pr
i-Pr
CH3


I.a.1173
Oc-Bu
i-Pr
CH3





I.a.1174


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i-Pr
CH3





I.a.1175


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i-Pr
CH3





I.a.1176
SCH3
i-Pr
CH3


I.a.1177
S(O)CH3
i-Pr
CH3


I.a.1178
SO2CH3
i-Pr
CH3


I.a.1179
S(CH2)2OCH3
i-Pr
CH3


I.a.1180
SCH2CH3
i-Pr
CH3


I.a.1181
SO2CH2CH3
i-Pr
CH3


I.a.1182
SO2(CH2)2OCH3
i-Pr
CH3


I.a.1183
SO2i-Pr
i-Pr
CH3


I.a.1184
SO2c-Pr
i-Pr
CH3


I.a.1185
NHSO2CH3
i-Pr
CH3


I.a.1186
N(CH3)SO2CH3
i-Pr
CH3


I.a.1187
S(O)CH2CH3
i-Pr
CH3


I.a.1188
NHCOCH3
i-Pr
CH3


I.a.1189
N(CH3)COCH3
i-Pr
CH3





I.a.1190


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i-Pr
CH3





I.a.1191


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i-Pr
CH3





I.a.1192


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i-Pr
CH3





I.a.1193
CH2OCH3
i-Pr
CH3


I.a.1194
CH2OCH2CH3
i-Pr
CH3


I.a.1195
CH2OCH2CH2OCH3
i-Pr
CH3


I.a.1196
CH2OCH2CF3
i-Pr
CH3


I.a.1197
CH2OCH2CF2CHCF2
i-Pr
CH3


I.a.1198
CH2OCH2CHF2
i-Pr
CH3





I.a.1199


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i-Pr
CH3





I.a.1200


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i-Pr
CH3





wherein # denotes the bonding site, c-Pr denotes cyclopropyl, i-Pr denotes iso-propyl and c-Bu denotes cyclobutyl






The substituted pyridine compounds of formula I according to the invention can be prepared by standard processes of organic chemistry, for example by the following processes:


Picolinic acid derivatives of the formula II can be reacted with a thiol compound of the formula III to yield thioether compounds of the formula IV. In the formulae II and III, the variables have the meaning given for the compounds of formula I. The group X is a halogen atom, in particular Cl or Br. Y is a methyl or ethyl group.




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The reaction of the picolinic acid derivative II with the thiol compound III can be carried out according to literature procedures [cf. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999) (1984), (7), 1501-1505] in an organic solvent, such as, for example acetonitrile or dimethylformamide (DMF), at temperatures between −78° C. and reflux of the solvent, preferably in a temperature range of from 10° C. to 50° C. It is also possible to use mixtures of the solvents mentioned. The starting materials II and III are generally reacted with one another in equimolar amounts.


The picolinic acid derivatives II can be prepared according to literature procedures (cf. Journal of Medicinal Chemistry, 32(4), 827-33; 1989).


The thiol compound III can be prepared from e.g. the corresponding thioacetate by cleavage with an alkali metal hydroxide like sodium hydroxide, potassium hydroxide or lithium hydroxide in water at a temperature of from 0° C. to 100° C., preferably at a temperature of from 10° C. to 30° C. Many benzylthiols can also be acquired from commercial sources. The thioacetate can be prepared from correspondingly substituted benzoic acids or halobenzenes on the basis of syntheses known in the literature [cf. Journal of Medicinal Chemistry 49(12), 3563-3580 (2006); Journal of Medicinal Chemistry 28(10), 1533-6 (1985); US 2004/077901; US 2004/068141; Chemistry—A European Journal 14(26), 7969-7977 (2008); Journal of Enzyme Inhibition and Medicinal Chemistry 17(3), 187-196 (2002)]. Suitably substituted benzoic acids and halobenzenes are known, for example from: WO 2002/006211, WO 2009/058237, WO 98/52926, WO 96/26193, EP-A 352 543, WO 98/52926, WO 97/30986, WO 98/12180.


The thioether compound IV can be reacted with an oxidizing agent to give the sulfone compound V.




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Suitable oxidizing agents include, for example, 3-chloroperoxybenzoic acid or hydrogen peroxide. The oxidation of the thioether compound IV to the sulfone compound V is usually carried out in an organic solvent, such as, for example methylene chloride, at a temperature of from 0° C. to reflux of the solvent, preferably at a temperature of from 10° C. to 25° C. The amount of the oxidizing agent is generally at least 2 molar equivalents relative to the thioether compound IV.


The sulfone compound V can be reacted with a base to give compounds of the formula I.1 (which correspond to compounds of the formula I with R1=hydroxy).




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The cyclization reaction is usually carried out at a temperature of from −78° C. to 0° C., preferably at a temperature of from −60° C. to 0° C. in an inert organic solvent in the presence of a base (analogous to the procedure as described in WO 2010/000892).


Suitable inert organic solvents are tetrahydrofurane (THF), diethyl ether, diisopropyl ether and tert-butyl methyl ether, preferably tetrahydrofurane. It is also possible to use mixtures of the solvents mentioned. Suitable bases are lithiumdiisopropylamide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium methoxide, potassium methoxide, lithium methoxide, triethylamine and tributylamine, preferably lithiumdiisopropylamide. The bases are generally employed in equimolar amounts; however, they can also be used in excess or, if appropriate, as solvents.


The hydroxy compound I.1 can be reacted with a base and an electrophile like an alkyl or acyl halide RA—X (wherein X denotes a halogen atom, in particular Cl or Br) to give compounds of the formula I.2 (which correspond to compounds of the formula I with R1=O—RA).




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The reaction is usually carried out at a temperature of from −78° C. to 80° C., preferably at a temperature of from −60° C. to 0° C. in an inert organic solvent in the presence of a base. Suitable inert organic solvents are tetrahydrofurane (THF), diethyl ether, diisopropyl ether and tert-butyl methyl ether, preferably tetrahydrofurane. It is also possible to use mixtures of the solvents mentioned. Suitable bases are lithiumdiisopropylamide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium methoxide, potassium methoxide, lithium methoxide, triethylamine and tributylamine, preferably lithiumdiisopropylamide. The bases are generally employed in equimolar amounts; however, they can also be used in excess or, if appropriate, as solvents.


In case the preparation of compounds I with Rx and/or Ry=halogen is desired, the compounds I.1 or I.2 which are substituted by hydrogen in the Rx and/or Ry positions can be deprotonated with a base, preferably lithiumdiisopropylamide, in an organic solvent like tetrahydrofurane, methyl-tert-butylether or diethylether at a temperature of from −78° C. to 0° C., preferably at a temperature of from −60° C. to 0° C., and subsequently reacted with a halogenating agent like N-bromosuccinimide or N-fluorodi(benzenesulfonyl)amine at a temperature of from −78° C. to 0° C., preferably at a temperature of from −60° C. to 0° C.


In case the preparation of compounds I with Rx and/or Ry=alkyl or cycloalkyl is desired, the compounds I.1 or I.2 which are substituted by hydrogen in the Rx and/or Ry positions can be deprotonated with a base, preferably potassium-tert-butanolate, in an organic solvent like tetrahydrofurane, methyl-tert-butylether or diethylether at a temperature of from −78° C. to 0° C., preferably at a temperature of from −60° C. to 0° C., and subsequently reacted with an alkylating agent like bromomethane or dibromoethane at a temperature of from −78° C. to 0° C., preferably at a temperature of from −60° C. to 0° C.


With respect to the variables, preferred embodiments of the intermediates II, III, IV and V correspond to those described above for the variables of the compound of formula I.


The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.


If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I.


If the synthesis yields mixtures of isomers, a separation is generally however not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after application, for example in the case of the treatment of plants in the treated plant or in the harmful plant to be controlled.


As shown above the thioether compounds of formula IV are novel thioether compounds and suitable intermediates for the preparation of the compounds of formula I according to the present invention.


Therefore the present invention also provides novel thioether compounds of formula IV




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wherein the variables R1, R2, R3, R4, R5, R6, R7, Rx and Ry have the same meanings given for the compound of formula I and Y is methyl or ethyl.


With respect to the variables R1, R2, R3, R4, R5, R6, R7, Rx and Ry, preferred embodiments of the intermediate IV correspond to those described above for the variables of the compound of formula I.


As shown above the sulfone compounds of formula V are novel compounds and suitable intermediates for the preparation of the compounds of formula I according to the present invention.


Therefore the present invention also provides novel sulfone compounds of formula V




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wherein the variables R1, R2, R3, R4, R5, R6, R7, Rx and Ry have the same meanings given for the compound of formula I and Y is methyl or ethyl.


With respect to the variables R1, R2, R3, R4, R5, R6, R7, Rx and Ry, preferred embodiments of the intermediate V correspond to those described above for the variables of the compound of formula I.


To widen the spectrum of action and to achieve synergistic effects, the compounds of formula (I) may be mixed with a large number of representatives of other herbicidal or growth-regulating active ingredient groups and then applied concomitantly. Suitable components for mixtures 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.


The further herbicidal compound B (component B) is preferably selected from the herbicides of class b1) to b15):

  • b1) lipid biosynthesis inhibitors;
  • b2) acetolactate synthase inhibitors (ALS inhibitors);
  • b3) photosynthesis inhibitors;
  • b4) protoporphyrinogen-lX oxidase inhibitors,
  • b5) bleacher herbicides;
  • b6) enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP inhibitors);
  • b7) glutamine synthetase inhibitors;
  • b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors);
  • b9) mitosis inhibitors;
  • b10) inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors);
  • b11) cellulose biosynthesis inhibitors;
  • b12) decoupler herbicides;
  • b13) auxinic herbicides;
  • b14) auxin transport inhibitors; and
  • b15) other herbicides selected from the group consisting of bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (CAS 499223-49-3) and its salts and esters;


    including their agriculturally acceptable salts or derivatives;


Preference is given to those compositions according to the present invention comprising at least one herbicide B selected from herbicides of class b2, b3, b4, b5, b6, b9 and b10.


Specific preference is given to those compositions according to the present invention which comprise at least one herbicide B selected from the herbicides of class b4, b6 b9 and b10.


Particular preference is given to those compositions according to the present invention which comprise at least one herbicide B selected from the herbicides of class b4, b6 and b10.


Examples of herbicides B which can be used in combination with the compounds 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-2H-pyran-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-methyl-sodium, 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 420138-01-8),


sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazone-sodium, 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. 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, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, 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 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione, 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione (CAS 1258836-72-4), 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, 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, methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-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 212754-02-4);


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, clomazone, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone, bleacher, unknown target: aclonifen, amitrole and flumeturon;


b6) from the group of the EPSP synthase inhibitors:


glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);


b7) from the group of the glutamine synthase inhibitors:


bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;


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: chlorpropham, propham and carbetamide, among these, compounds of group K1, in particular dinitroanilines are preferred;


b10) from the group of the VLCFA inhibitors:


chloroacetamides such as acetochlor, alachlor, 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 and napropamide, tetrazolinones such fentrazamide, and other herbicides such as anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone and isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9




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the isoxazoline compounds of the formulae II.1 to II.9 above are known in the art, e.g. from WO 2006/024820, WO 2006/037945, WO 2007/071900 and WO 2007/096576;


among the VLCFA inhibitors, preference is given to chloroacetamides and oxyacetamides;


b11) from the group of the cellulose biosynthesis inhibitors:


chlorthiamid, dichlobenil, flupoxam, isoxaben and 1-Cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine;


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-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, dichloroprop and its salts and esters, dichloroprop-P and its salts and esters, 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 and triclopyr and its salts and esters;


b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;


b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam and tridiphane.


Preferred herbicides B that can be used in combination with the compounds of the formula (I) according to the present invention are:


b1) from the group of the lipid biosynthesis inhibitors:


clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop-P-ethyl, fluazifop-P-butyl, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, 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-2H-pyran-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); benfuresate, dimepiperate, EPTC, esprocarb, ethofumesate, molinate, orbencarb, prosulfocarb, thiobencarb and triallate;


b2) from the group of the ALS inhibitors:


amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, chlorimuron-ethyl, chlorsulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metosulam, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazon-sodium, propyrisulfuron, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl, tritosulfuron and triafamone;


b3) from the group of the photosynthesis inhibitors:


ametryn, amicarbazone, atrazine, bentazone, bentazone-sodium, bromoxynil and its salts and esters, chloridazone, chlorotoluron, cyanazine, desmedipham, diquat-dibromide, diuron, fluometuron, hexazinone, ioxynil and its salts and esters, isoproturon, lenacil, linuron, metamitron, methabenzthiazuron, metribuzin, paraquat, paraquat-dichloride, phenmedipham, propanil, pyridate, simazine, terbutryn, terbuthylazine and thidiazuron;


b4) from the group of the protoporphyrinogen-lX oxidase inhibitors:


acifluorfen-sodium, bencarbazone, benzfendizone, butafenacil, carfentrazone-ethyl, cinidon-ethyl, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fomesafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraflufen-ethyl, saflufenacil, sulfentrazone, 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 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione, 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione (CAS 1258836-72-4), 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; 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, and 3-[7-Chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (CAS 212754-02-4);


b5) from the group of the bleacher herbicides:


aclonifen, beflubutamid, benzobicyclon, clomazone, diflufenican, flurochloridone, flurtamone, isoxaflutole, mesotrione, norflurazon, picolinafen, pyrasulfotole, pyrazolynate, sulcotrione, tefuryltrione, tembotrione, topramezone, bicyclopyrone, 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7), amitrole and flumeturon;


b6) from the group of the EPSP synthase inhibitors:


glyphosate, glyphosate-isopropylammonium, glyphosate-potassium and glyphosate-trimesium (sulfosate);


b7) from the group of the glutamine synthase inhibitors:


glufosinate, glufosinate-P, glufosinate-ammonium;


b8) from the group of the DHP synthase inhibitors: asulam;


b9) from the group of the mitosis inhibitors:


benfluralin, dithiopyr, ethalfluralin, oryzalin, pendimethalin, thiazopyr and trifluralin;


b10) from the group of the VLCFA inhibitors:


acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethenamid, dimethenamid-P, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, S-metolachlor, naproanilide, napropamide, pretilachlor, fenoxasulfone, ipfencarbazone, pyroxasulfone thenylchlor and isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 as mentioned above;


b11) from the group of the cellulose biosynthesis inhibitors: dichlobenil, flupoxam, isoxaben and 1-Cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine;


b13) from the group of the auxinic herbicides:


2,4-D and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, clopyralid and its salts and esters, dicamba and its salts and esters, dichloroprop-P and its salts and esters, fluroxypyr-meptyl, halauxifen and its salts and esters (CAS 943832-60-8), MCPA and its salts and esters, MCPB and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac and triclopyr and its salts and esters;


b14) from the group of the auxin transport inhibitors: diflufenzopyr and diflufenzopyr-sodium;


b15) from the group of the other herbicides: bromobutide, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, difenzoquat, difenzoquat-metilsulfate, DSMA, dymron (=daimuron), flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, indanofan, indaziflam, metam, methylbromide, MSMA, oxaziclomefone, pyributicarb, triaziflam and tridiphane.


Particularly preferred herbicides B that can be used in combination with the compounds of the formula (I) according to the present invention are:


b1) from the group of the lipid biosynthesis inhibitors: clodinafop-propargyl, cycloxydim, cyhalofop-butyl, fenoxaprop-P-ethyl, pinoxaden, profoxydim, 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-2H-pyran-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); esprocarb, prosulfocarb, thiobencarb and triallate;


b2) from the group of the ALS inhibitors: bensulfuron-methyl, bispyribac-sodium, cyclosulfamuron, diclosulam, flumetsulam, flupyrsulfuron-methyl-sodium, foramsulfuron, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, nicosulfuron, penoxsulam, propoxycarbazon-sodium, propyrisulfuron, pyrazosulfuron-ethyl, pyroxsulam, rimsulfuron, sulfosulfuron, thiencarbazon-methyl, tritosulfuron and triafamone;


b3) from the group of the photosynthesis inhibitors: ametryn, atrazine, diuron, fluometuron, hexazinone, isoproturon, linuron, metribuzin, paraquat, paraquat-dichloride, propanil, terbutryn and terbuthylazine;


b4) from the group of the protoporphyrinogen-IX oxidase inhibitors: flumioxazin, oxyfluorfen, saflufenacil, sulfentrazone, 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), 3-15 [7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione, 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione (CAS 1258836-72-4), and 2-(2,2,7-Trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione, and 1-Methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione;


b5) from the group of the bleacher herbicides: clomazone, diflufenican, flurochloridone, isoxaflutole, mesotrione, picolinafen, sulcotrione, tefuryltrione, tembotrione, topramezone, bicyclopyrone, amitrole and flumeturon;


b6) from the group of the EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate);


b7) from the group of the glutamine synthase inhibitors: glufosinate, glufosinate-P and glufosinate-ammonium;


b9) from the group of the mitosis inhibitors: pendimethalin and trifluralin;


b10) from the group of the VLCFA inhibitors: acetochlor, cafenstrole, dimethenamid-P, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, S-metolachlor, fenoxasulfone, ipfencarbazone and pyroxasulfone; likewise, preference is given to isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9 as mentioned above;


b11) from the group of the cellulose biosynthesis inhibitors: isoxaben;


b13) from the group of the auxinic herbicides: 2,4-D and its salts and esters such as clacyfos, and aminocyclopyrachlor and its salts and esters, aminopyralid and its salts and its esters, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl, quinclorac and quinmerac;


b14) from the group of the auxin transport inhibitors: diflufenzopyr and diflufenzopyr-sodium,


b15) from the group of the other herbicides: dymron (=daimuron), indanofan, indaziflam, oxaziclomefone and triaziflam.


Particularly preferred herbicides B are the herbicides B as defined above; in particular the herbicides B.1-B.187 listed below in table B:










TABLE B






Herbicide B







B.1
clethodim


B.2
clodinafop-propargyl


B.3
cycloxydim


B.4
cyhalofop-butyl


B.5
fenoxaprop-ethyl


B.6
fenoxaprop-P-ethyl


B.7
metamifop


B.8
pinoxaden


B.9
profoxydim


B.10
sethoxydim


B.11
tepraloxydim


B.12
tralkoxydim


B.13
esprocarb


B.14
ethofumesate


B.15
molinate


B.16
prosulfocarb


B.17
thiobencarb


B.18
triallate


B.19
bensulfuron-methyl


B.20
bispyribac-sodium


B.21
cloransulam-methyl


B.22
chlorsulfuron


B.23
clorimuron


B.24
cyclosulfamuron


B.25
diclosulam


B.26
florasulam


B.27
flumetsulam


B.28
flupyrsulfuron-methyl-sodium


B.29
foramsulfuron


B.30
imazamox


B.31
imazamox-ammonium


B.32
imazapic


B.33
imazapic-ammonium


B.34
imazapic-isopropylammonium


B.35
imazapyr


B.36
imazapyr-ammonium


B.37
imazapyr-isopropylammonium


B.38
imazaquin


B.39
imazaquin-ammonium


B.40
imazethapyr


B.41
imazethapyr-ammonium


B.42
imazethapyr-isopropylammonium


B.43
imazosulfuron


B.44
iodosulfuron-methyl-sodium


B.45
iofensulfuron


B.46
iofensulfuron-sodium


B.47
mesosulfuron-methyl


B.48
metazosulfuron


B.49
metsulfuron-methyl


B.50
metosulam


B.51
nicosulfuron


B.52
penoxsulam


B.53
propoxycarbazon-sodium


B.54
pyrazosulfuron-ethyl


B.55
pyribenzoxim


B.56
pyriftalid


B.57
pyroxsulam


B.58
propyrisulfuron


B.59
rimsulfuron


B.60
sulfosulfuron


B.61
thiencarbazone-methyl


B.62
thifensulfuron-methyl


B.63
tribenuron-methyl


B.64
tritosulfuron


B.65
triafamone


B.66
ametryne


B.67
atrazine


B.68
bentazon


B.69
bromoxynil


B.70
bromoxynil-octanoate


B.71
bromoxynil-heptanoate


B.72
bromoxynil-potassium


B.73
diuron


B.74
fluometuron


B.75
hexazinone


B.76
isoproturon


B.77
linuron


B.78
metamitron


B.79
metribuzin


B.80
propanil


B.81
simazin


B.82
terbuthylazine


B.83
terbutryn


B.84
paraquat-dichloride


B.85
acifluorfen


B.86
butafenacil


B.87
carfentrazone-ethyl


B.88
flumioxazin


B.89
fomesafen


B.90
oxadiargyl


B.91
oxyfluorfen


B.92
saflufenacil


B.93
sulfentrazone


B.94
ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-di-



oxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyl-



oxy]acetate (CAS 353292-31-6)


B.95
1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-



3,4-dihydro-2H-benzo[b][1,4]-oxazin-6-yl)-1,3,5-triazinane-



2,4-dione


B.96
benzobicyclon


B.97
clomazone


B.98
diflufenican


B.99
flurochloridone


B.100
isoxaflutole


B.101
mesotrione


B.102
norflurazone


B.103
picolinafen


B.104
sulcotrione


B.105
tefuryltrione


B.106
tembotrione


B.107
topramezone


B.108
topramezone-sodium


B.109
bicyclopyrone


B.110
amitrole


B.111
fluometuron


B.112
glyphosate


B.113
glyphosate-ammonium


B.114
glyphosate-dimethylammonium


B.115
glyphosate-isopropylammonium


B.116
glyphosate-trimesium (sulfosate)


B.117
glyphosate-potassium


B.118
glufosinate


B.119
glufosinate-ammonium


B.120
glufosinate-P


B.121
glufosinate-P-ammonium


B.122
pendimethalin


B.123
trifluralin


B.124
acetochlor


B.125
butachlor


B.126
cafenstrole


B.127
dimethenamid-P


B.128
fentrazamide


B.129
flufenacet


B.130
mefenacet


B.131
metazachlor


B.132
metolachlor


B.133
S-metolachlor


B.134
pretilachlor


B.135
fenoxasulfone


B.136
isoxaben


B.137
ipfencarbazone


B.138
pyroxasulfone


B.139
2,4-D


B.140
2,4-D-isobutyl


B.141
2,4-D-dimethylammonium


B.142
2,4-D-N,N,N-trimethylethanolammonium


B.143
aminopyralid


B.144
aminopyralid-methyl


B.145
aminopyralid-tris(2-hydroxypropyl)ammonium


B.146
clopyralid


B.147
clopyralid-methyl


B.148
clopyralid-olamine


B.149
dicamba


B.150
dicamba-butotyl


B.151
dicamba-diglycolamine


B.152
dicamba-dimethylammonium


B.153
dicamba-diolamine


B.154
dicamba-isopropylammonium


B.155
dicamba-potassium


B.156
dicamba-sodium


B.157
dicamba-trolamine


B.158
dicamba-N,N-bis-(3-aminopropyl)methylamine


B.159
dicamba-diethylenetriamine


B.160
fluroxypyr


B.161
fluroxypyr-meptyl


B.162
MCPA


B.163
MCPA-2-ethylhexyl


B.164
MCPA-dimethylammonium


B.165
quinclorac


B.166
quinclorac-dimethylammonium


B.167
quinmerac


B.168
quinmerac-dimethylammonium


B.169
aminocyclopyrachlor


B.170
aminocyclopyrachlor-potassium


B.171
aminocyclopyrachlor-methyl


B.172
diflufenzopyr


B.173
diflufenzopyr-sodium


B.174
dymron


B.175
indanofan


B.176
indaziflam


B.177
oxaziclomefone


B.178
triaziflam


B.179
II.1


B.180
II.2


B.181
II.3


B.182
II.4


B.183
II.5


B.184
II.6


B.185
II.7


B.186
II.8


B.187
II.9









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 unwanted plants. 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.


Suitable 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 preferred safeners 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 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4) and N-(2-Methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide (CAS 129531-12-0).


Especially preferred safeners C are benoxacor, cloquintocet, cyprosulfamide, dichlormid, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4) and N-(2-Methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide (CAS 129531-12-0).


Particularly preferred safeners C are benoxacor, cloquintocet, cyprosulfamide, dichlormid, fenchlorazole, fenclorim, furilazole, isoxadifen, mefenpyr, naphthalic anhydride, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4) and N-(2-Methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide (CAS 129531-12-0).


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. 71526-07-3] 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.


Particularly preferred safeners C, which, as component C, are constituent of the composition according to the invention are the safeners C as defined above; in particular the safeners C.1-C.17 listed below in table C:










TABLE C






Safener C







C.1
benoxacor


C.2
cloquintocet


C.3
cloquintocet-mexyl


C.4
cyprosulfamide


C.5
dichlormid


C.6
fenchlorazole


C.7
fenchlorazole-ethyl


C.8
fenclorim


C.9
furilazole


C.10
isoxadifen


C.11
isoxadifen-ethyl


C.12
mefenpyr


C.13
mefenpyr-diethyl


C.14
naphtalic acid anhydride


C.15
4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660,



CAS 71526-07-3)


C.16
2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148,



CAS 52836-31-4)


C.17
N-(2-Methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzene-



sulfonamide (CAS 129531-12-0)









Active compounds B and C having a carboxyl group can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative in the compositions according to the invention.


In the case of dicamba, suitable salts include those, where the counterion is an agriculturally acceptable cation. For example, suitable salts of dicamba are dicamba-sodium, dicamba-potassium, dicamba-methylammonium, dicamba-dimethylammonium, dicamba-isopropylammonium, dicamba-diglycolamine, dicamba-olamine, dicamba-diolamine, dicamba-trolamine, dicamba-N,N-bis-(3-aminopropyl)methylamine and dicamba-diethylenetriamine. Examples of a suitable ester are dicamba-methyl and dicamba-butotyl.


Suitable salts of 2,4-D are 2,4-D-ammonium, 2,4-D-dimethylammonium, 2,4-D-diethylammonium, 2,4-D-diethanolammonium (2,4-D-diolamine), 2,4-D-triethanolammonium, 2,4-D-isopropylammonium, 2,4-D-triisopropanolammonium, 2,4-D-heptylammonium, 2,4-D-dodecylammonium, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-tris(isopropyl)ammonium, 2,4-D-trolamine, 2,4-D-lithium, 2,4-D-sodium. Examples of suitable esters of 2,4-D are 2,4-D-butotyl, 2,4-D-2-butoxypropyl, 2,4-D-3-butoxypropyl, 2,4-D-butyl, 2,4-D-ethyl, 2,4-D-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D-isopropyl, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-propyl, 2,4-D-tefuryl and clacyfos.


Suitable salts of 2,4-DB are for example 2,4-DB-sodium, 2,4-DB-potassium and 2,4-DB-dimethylammonium. Suitable esters of 2,4-DB are for example 2,4-DB-butyl and 2,4-DB-isoctyl.


Suitable salts of dichloroprop are for example dichloroprop-sodium, dichloroprop-potassium and dichloroprop-dimethylammonium. Examples of suitable esters of dichloroprop are dichloroprop-butotyl and dichloroprop-isoctyl.


Suitable salts and esters of MCPA include MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-thioethyl, MCPA-2-ethylhexyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-isopropylammonium, MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium and MCPA-trolamine.


A suitable salt of MCPB is MCPB sodium. A suitable ester of MCPB is MCPB-ethyl.


Suitable salts of clopyralid are clopyralid-potassium, clopyralid-olamine and clopyralid-tris-(2-hydroxypropyl)ammonium. Example of suitable esters of clopyralid is clopyralid-methyl.


Examples of a suitable ester of fluroxypyr are fluroxypyr-meptyl and fluroxypyr-2-butoxy-1-methylethyl, wherein fluroxypyr-meptyl is preferred.


Suitable salts of picloram are picloram-dimethylammonium, picloram-potassium, picloram-triisopropanolammonium, picloram-triisopropylammonium and picloram-trolamine. A suitable ester of picloram is picloram-isoctyl.


A suitable salt of triclopyr is triclopyr-triethylammonium. Suitable esters of triclopyr are for example triclopyr-ethyl and triclopyr-butotyl.


Suitable salts and esters of chloramben include chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium and chloramben-sodium. Suitable salts and esters of 2,3,6-TBA include 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium and 2,3,6-TBA-sodium.


Suitable salts and esters of aminopyralid include aminopyralid-potassium and aminopyralid-tris(2-hydroxypropyl)ammonium.


Suitable salts of glyphosate are for example glyphosate-ammonium, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-sodium, glyphosate-trimesium as well as the ethanolamine and diethanolamine salts, preferably glyphosate-diammonium, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate).


A suitable salt of glufosinate is for example glufosinate-ammonium.


A suitable salt of glufosinate-P is for example glufosinate-P-ammonium.


Suitable salts and esters of bromoxynil are for example bromoxynil-butyrate, bromoxynil-heptanoate, bromoxynil-octanoate, bromoxynil-potassium and bromoxynil-sodium.


Suitable salts and esters of ioxonil are for example ioxonil-octanoate, ioxonil-potassium and ioxonil-sodium.


Suitable salts and esters of mecoprop include mecoprop-butotyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-2-ethylhexyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium and mecoprop-trolamine.


Suitable salts of mecoprop-P are for example mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-isobutyl, mecoprop-P-potassium and mecoprop-P-sodium.


A suitable salt of diflufenzopyr is for example diflufenzopyr-sodium.


A suitable salt of naptalam is for example naptalam-sodium.


Suitable salts and esters of aminocyclopyrachlor are for example aminocyclopyrachlor-dimethylammonium, aminocyclopyrachlor-methyl, aminocyclopyrachlor-triisopropanolammonium, aminocyclopyrachlor-sodium and aminocyclopyrachlor-potassium.


A suitable salt of quinclorac is for example quinclorac-dimethylammonium.


A suitable salt of quinmerac is for example quinclorac-dimethylammonium.


A suitable salt of imazamox is for example imazamox-ammonium.


Suitable salts of imazapic are for example imazapic-ammonium and imazapic-isopropylammonium.


Suitable salts of imazapyr are for example imazapyr-ammonium and imazapyr-isopropylammonium.


A suitable salt of imazaquin is for example imazaquin-ammonium.


Suitable salts of imazethapyr are for example imazethapyr-ammonium and imazethapyr-isopropylammonium.


A suitable salt of topramezone is for example topramezone-sodium.


According to a preferred embodiment of the invention, the composition comprises as herbicidal active compound B or component B at least one, preferably exactly one herbicide B.


According to another preferred embodiment of the invention, the composition comprises as herbicidal active compounds B or component B at least two, preferably exactly two herbicides B different from each other.


According to another preferred embodiment of the invention, the composition comprises as herbicidal active compounds B or component B at least three, preferably exactly three herbicides B different from each other.


According to another preferred embodiment of the invention, the composition comprises as safening component C or component C at least one, preferably exactly one safener C.


According to another preferred embodiment of the invention, the composition comprises as component B at least one, preferably exactly one herbicide B, and as component C at least one, preferably exactly one, safener C.


According to another preferred embodiment of the invention, the composition comprises at least two, preferably exactly two, herbicides B different from each other, and as component C at least one, preferably exactly one, safener C.


According to another preferred embodiment of the invention, the composition comprises at least three, preferably exactly three, herbicides B different from each other, and as component C at least one, preferably exactly one, safener C.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), and as component B at least one, preferably exactly one, herbicide B.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), and at least two, preferably exactly two, herbicides B different from each other.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), and at least three, preferably exactly three, herbicides B different from each other.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), and as component C at least one, preferably exactly one, safener C.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), as component B at least one, preferably exactly one, herbicide B, and as component C at least one, preferably exactly one safener C.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), at least two, preferably exactly two herbicides B different from each other, and as component C at least one, preferably exactly one, safener C.


According to another preferred embodiment of the invention, the composition comprises as component A at least one, preferably exactly one compound of formula (I), preferably of formula (I.a), at least three, preferably exactly three herbicides B different from each other, and as component C at least one, preferably exactly one, safener C.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b1), in particular selected from the group consisting of clodinafop-propargyl, cycloxydim, cyhalofop-butyl, fenoxaprop-P-ethyl, pinoxaden, profoxydim, tepraloxydim, tralkoxydim, esprocarb, prosulfocarb, thiobencarb and triallate.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b2), in particular selected from the group consisting of bensulfuron-methyl, bispyribac-sodium, cyclosulfamuron, diclosulam, flumetsulam, flupyrsulfuron-methyl-sodium, foramsulfuron, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, nicosulfuron, penoxsulam, propoxycarbazon-sodium, pyrazosulfuron-ethyl, pyroxsulam, rimsulfuron, sulfosulfuron, thiencarbazon-methyl and tritosulfuron.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b3), in particular selected from the group consisting of ametryn, atrazine, diuron, fluometuron, hexazinone, isoproturon, linuron, metribuzin, paraquat, paraquat-dichloride, propanil, terbutryn and terbuthylazine.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b4), in particular selected from the group consisting of flumioxazin, oxyfluorfen, saflufenacil, sulfentrazone, 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), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione, 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione (CAS 1258836-72-4), 2-(2,2,7-Trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione and 1-Methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b5), in particular selected from the group consisting of clomazone, diflufenican, flurochloridone, isoxaflutole, mesotrione, picolinafen, sulcotrione, tefuryltrione, tembotrione, topramezone, bicyclopyrone, amitrole and flumeturon.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b6), in particular selected from the group consisting of glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate).


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b7), in particular selected from the group consisting of glufosinate, glufosinate-P and glufosinate-ammonium.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b9), in particular selected from the group consisting of pendimethalin and trifluralin.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b10), in particular selected from the group consisting of acetochlor, cafenstrole, dimethenamid-P, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, S-metolachlor, fenoxasulfone and pyroxasulfone. Likewise, preference is given to compositions comprising in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b10), in particular selected from the group consisting of isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9, as defined above.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b11), in particular isoxaben.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b13), in particular selected from the group consisting of 2,4-D and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl, quinclorac and quinmerac.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b14), in particular selected from the group consisting of diflufenzopyr and diflufenzopyr-sodium.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a), at least one and especially exactly one herbicidally active compound from group b15), in particular selected from the group consisting of dymron (=daimuron), indanofan, indaziflam, oxaziclomefone and triaziflam.


According to another preferred embodiment of the invention, the composition comprises, in addition to a compounds A of formula (I), especially an active compound of formula (I.a) of formula (I.a), at least one and especially exactly one herbicidally active compound from the safeners C, in particular selected from the group consisting of benoxacor, cloquintocet, cyprosulfamide, dichlormid, fenchlorazole, fenclorim, furilazole, isoxadifen, mefenpyr, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4).


Further preferred embodiments relate to ternary compositions which correspond to the binary compositions mentioned above and additionally comprise a safener C, in particular selected from the group consisting of benoxacor, cloquintocet, cyprosulfamide, dichlormid, fenchlorazole, fenclorim, furilazole, isoxadifen, mefenpyr, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4).


Here and below, the term “binary compositions” includes compositions comprising one or more, for example 1, 2 or 3, active compounds of the formula (I) and either one or more, for example 1, 2 or 3, herbicides B or one or more safeners. Correspondingly, the term “ternary compositions” includes compositions comprising one or more, for example 1, 2 or 3, active compounds of the formula (I), one or more, for example 1, 2 or 3, herbicides B and one or more, for example 1, 2 or 3, safeners C.


In binary compositions comprising at least one compound of the formula (I) as component A and at least one herbicide B, the weight ratio of the active compounds A:B is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.


In binary compositions comprising at least one compound of the formula (I) as component A and at least one safener C, the weight ratio of the active compounds A:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.


In ternary compositions comprising both at least one compound of formula (I) as component A, at least one herbicide B and at least one safener C, the relative proportions by weight of the components A:B are generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1, the weight ratio of the components A:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1, and the weight ratio of the components B:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1. The weight ratio of components A+B to component C is preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.


The weight ratios of the individual components in the preferred mixtures mentioned below are within the limits given herein, in particular within the preferred limits.


Particularly preferred are the compositions mentioned below comprising the compounds of formula (I) as defined and the substance(s) as defined in the respective row of table 1; especially preferred comprising as only herbicidal active compounds the compounds of formula (I) as defined and the substance(s) as defined in the respective row of table 1; most preferably comprising as only active compounds the compounds of formula (I) as defined and the substance(s) as defined in the respective row of table 1.


Particularly preferred are compositions 1.1 to 1.3383, comprising the compounds of formula (Ia) and the substance(s) as defined in the respective row of table 1:









TABLE 1







(compositions 1.1 to 1.3383)











comp.
herbicide
safener



no.
B
C







1.1
B.1
—



1.2
B.2
—



1.3
B.3
—



1.4
B.4
—



1.5
B.5
—



1.6
B.6
—



1.7
B.7
—



1.8
B.8
—



1.9
B.9
—



1.10
B.10
—



1.11
B.11
—



1.12
B.12
—



1.13
B.13
—



1.14
B.14
—



1.15
B.15
—



1.16
B.16
—



1.17
B.17
—



1.18
B.18
—



1.19
B.19
—



1.20
B.20
—



1.21
B.21
—



1.22
B.22
—



1.23
B.23
—



1.24
B.24
—



1.25
B.25
—



1.26
B.26
—



1.27
B.27
—



1.28
B.28
—



1.29
B.29
—



1.30
B.30
—



1.31
B.31
—



1.32
B.32
—



1.33
B.33
—



1.34
B.34
—



1.35
B.35
—



1.36
B.36
—



1.37
B.37
—



1.38
B.38
—



1.39
B.39
—



1.40
B.40
—



1.41
B.41
—



1.42
B.42
—



1.43
B.43
—



1.44
B.44
—



1.45
B.45
—



1.46
B.46
—



1.47
B.47
—



1.48
B.48
—



1.49
B.49
—



1.50
B.50
—



1.51
B.51
—



1.52
B.52
—



1.53
B.53
—



1.54
B.54
—



1.55
B.55
—



1.56
B.56
—



1.57
B.57
—



1.58
B.58.
—



1.59
B.59
—



1.60
B.60
—



1.61
B.61
—



1.62
B.62
—



1.63
B.63
—



1.64
B.64
—



1.65
B.65
—



1.66
B.66
—



1.67
B.67
—



1.68
B.68
—



1.69
B.69
—



1.70
B.70
—



1.71
B.71
—



1.72
B.72
—



1.73
B.73
—



1.74
B.74
—



1.75
B.75
—



1.76
B.76
—



1.77
B.77
—



1.78
B.78
—



1.79
B.79
—



1.80
B.80
—



1.81
B.81
—



1.82
B.82
—



1.83
B.83
—



1.84
B.84
—



1.85
B.85
—



1.86
B.86
—



1.87
B.87
—



1.88
B.88
—



1.89
B.89
—



1.90
B.90
—



1.91
B.91
—



1.92
B.92
—



1.93
B.93
—



1.94
B.94
—



1.95
B.95
—



1.96
B.96
—



1.97
B.97
—



1.98
B.98
—



1.99
B.99
—



1.100
B.100
—



1.101
B.101
—



1.102
B.102
—



1.103
B.103
—



1.104
B.104
—



1.105
B.105
—



1.106
B.106
—



1.107
B.107
—



1.108
B.108
—



1.109
B.109
—



1.110
B.110
—



1.111
B.111
—



1.112
B.112
—



1.113
B.113
—



1.114
B.114
—



1.115
B.115
—



1.116
B.116
—



1.117
B.117
—



1.118
B.118
—



1.119
B.119
—



1.120
B.120
—



1.121
B.121
—



1.122
B.122
—



1.123
B.123
—



1.124
B.124
—



1.125
B.125
—



1.126
B.126
—



1.127
B.127
—



1.128
B.128
—



1.129
B.129
—



1.130
B.130
—



1.131
B.131
—



1.132
B.132
—



1.133
B.133
—



1.134
B.134
—



1.135
B.135
—



1.136
B.136
—



1.137
B.137
—



1.138
B.138
—



1.139
B.139
—



1.140
B.140
—



1.141
B.141
—



1.142
B.142
—



1.143
B.143
—



1.144
B.144
—



1.145
B.145
—



1.146
B.146
—



1.147
B.147
—



1.148
B.148
—



1.149
B.149
—



1.150
B.150
—



1.151
B.151
—



1.152
B.152
—



1.153
B.153
—



1.154
B.154
—



1.155
B.155
—



1.156
B.156
—



1.157
B.157
—



1.158
B.158
—



1.159
B.159
—



1.160
B.160
—



1.161
B.161
—



1.162
B.162
—



1.163
B.163
—



1.164
B.164
—



1.165
B.165
—



1.166
B.166
—



1.167
B.167
—



1.168
B.168
—



1.169
B.169
—



1.170
B.170
—



1.171
B.171
—



1.172
B.172
—



1.173
B.173
—



1.174
B.174
—



1.175
B.175
—



1.176
B.176
—



1.177
B.177
—



1.178
B.178
—



1.179
B.179
—



1.180
B.180
—



1.181
B.181
—



1.182
B.182
—



1.183
B.183
—



1.184
B.184
—



1.185
B.185
—



1.186
B.186
—



1.187
B.187
—



1.188
B.1
C.1



1.189
B.2
C.1



1.190
B.3
C.1



1.191
B.4
C.1



1.192
B.5
C.1



1.193
B.6
C.1



1.194
B.7
C.1



1.195
B.8
C.1



1.196
B.9
C.1



1.197
B.10
C.1



1.198
B.11
C.1



1.199
B.12
C.1



1.200
B.13
C.1



1.201
B.14
C.1



1.202
B.15
C.1



1.203
B.16
C.1



1.204
B.17
C.1



1.205
B.18
C.1



1.206
B.19
C.1



1.207
B.20
C.1



1.208
B.21
C.1



1.209
B.22
C.1



1.210
B.23
C.1



1.211
B.24
C.1



1.212
B.25
C.1



1.213
B.26
C.1



1.214
B.27
C.1



1.215
B.28
C.1



1.216
B.29
C.1



1.217
B.30
C.1



1.218
B.31
C.1



1.219
B.32
C.1



1.220
B.33
C.1



1.221
B.34
C.1



1.222
B.35
C.1



1.223
B.36
C.1



1.224
B.37
C.1



1.225
B.38
C.1



1.226
B.39
C.1



1.227
B.40
C.1



1.228
B.41
C.1



1.229
B.42
C.1



1.230
B.43
C.1



1.231
B.44
C.1



1.232
B.45
C.1



1.233
B.46
C.1



1.234
B.47
C.1



1.235
B.48
C.1



1.236
B.49
C.1



1.237
B.50
C.1



1.238
B.51
C.1



1.239
B.52
C.1



1.240
B.53
C.1



1.241
B.54
C.1



1.242
B.55
C.1



1.243
B.56
C.1



1.244
B.57
C.1



1.245
B.58.
C.1



1.246
B.59
C.1



1.247
B.60
C.1



1.248
B.61
C.1



1.249
B.62
C.1



1.250
B.63
C.1



1.251
B.64
C.1



1.252
B.65
C.1



1.253
B.66
C.1



1.254
B.67
C.1



1.255
B.68
C.1



1.256
B.69
C.1



1.257
B.70
C.1



1.258
B.71
C.1



1.259
B.72
C.1



1.260
B.73
C.1



1.261
B.74
C.1



1.262
B.75
C.1



1.263
B.76
C.1



1.264
B.77
C.1



1.265
B.78
C.1



1.266
B.79
C.1



1.267
B.80
C.1



1.268
B.81
C.1



1.269
B.82
C.1



1.270
B.83
C.1



1.271
B.84
C.1



1.272
B.85
C.1



1.273
B.86
C.1



1.274
B.87
C.1



1.275
B.88
C.1



1.276
B.89
C.1



1.277
B.90
C.1



1.278
B.91
C.1



1.279
B.92
C.1



1.280
B.93
C.1



1.281
B.94
C.1



1.282
B.95
C.1



1.283
B.96
C.1



1.284
B.97
C.1



1.285
B.98
C.1



1.286
B.99
C.1



1.287
B.100
C.1



1.288
B.101
C.1



1.289
B.102
C.1



1.290
B.103
C.1



1.291
B.104
C.1



1.292
B.105
C.1



1.293
B.106
C.1



1.294
B.107
C.1



1.295
B.108
C.1



1.296
B.109
C.1



1.297
B.110
C.1



1.298
B.111
C.1



1.299
B.112
C.1



1.300
B.113
C.1



1.301
B.114
C.1



1.302
B.115
C.1



1.303
B.116
C.1



1.304
B.117
C.1



1.305
B.118
C.1



1.306
B.119
C.1



1.307
B.120
C.1



1.308
B.121
C.1



1.309
B.122
C.1



1.310
B.123
C.1



1.311
B.124
C.1



1.312
B.125
C.1



1.313
B.126
C.1



1.314
B.127
C.1



1.315
B.128
C.1



1.316
B.129
C.1



1.317
B.130
C.1



1.318
B.131
C.1



1.319
B.132
C.1



1.320
B.133
C.1



1.321
B.134
C.1



1.322
B.135
C.1



1.323
B.136
C.1



1.324
B.137
C.1



1.325
B.138
C.1



1.326
B.139
C.1



1.327
B.140
C.1



1.328
B.141
C.1



1.329
B.142
C.1



1.330
B.143
C.1



1.331
B.144
C.1



1.332
B.145
C.1



1.333
B.146
C.1



1.334
B.147
C.1



1.335
B.148
C.1



1.336
B.149
C.1



1.337
B.150
C.1



1.338
B.151
C.1



1.339
B.152
C.1



1.340
B.153
C.1



1.341
B.154
C.1



1.342
B.155
C.1



1.343
B.156
C.1



1.344
B.157
C.1



1.345
B.158
C.1



1.346
B.159
C.1



1.347
B.160
C.1



1.348
B.161
C.1



1.349
B.162
C.1



1.350
B.163
C.1



1.351
B.164
C.1



1.352
B.165
C.1



1.353
B.166
C.1



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1.1410
B.101
C.7



1.1411
B.102
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1.1412
B.103
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1.1413
B.104
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1.1414
B.105
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1.1415
B.106
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1.1416
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1.1417
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1.1418
B.109
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1.1419
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1.1420
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1.1421
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B.114
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1.1424
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1.1425
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1.1426
B.117
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1.1427
B.118
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1.1428
B.119
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1.1429
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1.1430
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1.1431
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1.1432
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1.1433
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1.1434
B.125
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1.1435
B.126
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1.1436
B.127
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1.1437
B.128
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1.1438
B.129
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1.1439
B.130
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1.1440
B.131
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1.1441
B.132
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1.1442
B.133
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1.1443
B.134
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1.1444
B.135
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1.1445
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1.1446
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1.1447
B.138
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1.1448
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1.1449
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1.1450
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1.1451
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1.1452
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1.1453
B.144
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1.1454
B.145
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1.1455
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1.1456
B.147
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B.148
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1.1458
B.149
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1.1459
B.150
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1.1460
B.151
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B.156
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1.1467
B.158
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1.1468
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1.1469
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1.1470
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1.1471
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1.1472
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1.1473
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1.1474
B.165
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1.1475
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1.1476
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1.1478
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1.1479
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1.1480
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1.1490
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1.1504
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1.1505
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1.1516
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1.1517
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1.1518
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1.1540
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1.1541
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1.1545
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1.1549
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1.1550
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B.57
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B.58.
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1.1555
B.59
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1.1556
B.60
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1.1557
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1.1558
B.62
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1.1559
B.63
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1.1560
B.64
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1.1561
B.65
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1.1562
B.66
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1.1563
B.67
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1.1564
B.68
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1.1565
B.69
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1.1566
B.70
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1.1567
B.71
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1.1568
B.72
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1.1569
B.73
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1.1570
B.74
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1.1571
B.75
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1.1572
B.76
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1.1573
B.77
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1.1574
B.78
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1.1575
B.79
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1.1576
B.80
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1.1577
B.81
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1.1578
B.82
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1.1579
B.83
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1.1580
B.84
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1.1581
B.85
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1.1582
B.86
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1.1583
B.87
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1.1584
B.88
C.8



1.1585
B.89
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1.1586
B.90
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1.1587
B.91
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1.1588
B.92
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1.1589
B.93
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1.1590
B.94
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1.1591
B.95
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1.1592
B.96
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1.1593
B.97
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1.1594
B.98
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1.1595
B.99
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1.1596
B.100
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1.1597
B.101
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1.1598
B.102
C.8



1.1599
B.103
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1.1600
B.104
C.8



1.1601
B.105
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1.1602
B.106
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1.1603
B.107
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1.1604
B.108
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1.1605
B.109
C.8



1.1606
B.110
C.8



1.1607
B.111
C.8



1.1608
B.112
C.8



1.1609
B.113
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1.1610
B.114
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1.1611
B.115
C.8



1.1612
B.116
C.8



1.1613
B.117
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1.1614
B.118
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1.1615
B.119
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1.1616
B.120
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1.1617
B.121
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1.1618
B.122
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1.1619
B.123
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1.1620
B.124
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1.1621
B.125
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1.1622
B.126
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1.1623
B.127
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1.1624
B.128
C.8



1.1625
B.129
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1.1626
B.130
C.8



1.1627
B.131
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1.1628
B.132
C.8



1.1629
B.133
C.8



1.1630
B.134
C.8



1.1631
B.135
C.8



1.1632
B.136
C.8



1.1633
B.137
C.8



1.1634
B.138
C.8



1.1635
B.139
C.8



1.1636
B.140
C.8



1.1637
B.141
C.8



1.1638
B.142
C.8



1.1639
B.143
C.8



1.1640
B.144
C.8



1.1641
B.145
C.8



1.1642
B.146
C.8



1.1643
B.147
C.8



1.1644
B.148
C.8



1.1645
B.149
C.8



1.1646
B.150
C.8



1.1647
B.151
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1.1648
B.152
C.8



1.1649
B.153
C.8



1.1650
B.154
C.8



1.1651
B.155
C.8



1.1652
B.156
C.8



1.1653
B.157
C.8



1.1654
B.158
C.8



1.1655
B.159
C.8



1.1656
B.160
C.8



1.1657
B.161
C.8



1.1658
B.162
C.8



1.1659
B.163
C.8



1.1660
B.164
C.8



1.1661
B.165
C.8



1.1662
B.166
C.8



1.1663
B.167
C.8



1.1664
B.168
C.8



1.1665
B.169
C.8



1.1666
B.170
C.8



1.1667
B.171
C.8



1.1668
B.172
C.8



1.1669
B.173
C.8



1.1670
B.174
C.8



1.1671
B.175
C.8



1.1672
B.176
C.8



1.1673
B.177
C.8



1.1674
B.178
C.8



1.1675
B.179
C.8



1.1676
B.180
C.8



1.1677
B.181
C.8



1.1678
B.182
C.8



1.1679
B.183
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1.1680
B.184
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1.1681
B.185
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1.1682
B.186
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1.1683
B.187
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1.1684
B.1
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B.2
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1.1686
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1.1687
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1.1691
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1.1692
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1.1693
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1.1699
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1.1702
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1.1703
B.20
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1.1704
B.21
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1.1705
B.22
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1.1706
B.23
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1.1707
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1.1708
B.25
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1.1709
B.26
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1.1710
B.27
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1.1711
B.28
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1.1713
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1.1714
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B.32
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B.34
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1.1720
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1.1721
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1.1724
B.41
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1.1725
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1.1726
B.43
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1.1727
B.44
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1.1728
B.45
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1.1729
B.46
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1.1731
B.48
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1.1732
B.49
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1.1733
B.50
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1.1734
B.51
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1.1735
B.52
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1.1736
B.53
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1.1737
B.54
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1.1738
B.55
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1.1739
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1.1740
B.57
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B.58.
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1.1742
B.59
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1.1743
B.60
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1.1744
B.61
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1.1745
B.62
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1.1746
B.63
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1.1747
B.64
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1.1748
B.65
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1.1749
B.66
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1.1750
B.67
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1.1751
B.68
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1.1752
B.69
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1.1753
B.70
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1.1754
B.71
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1.1755
B.72
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1.1756
B.73
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1.1757
B.74
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1.1758
B.75
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1.1759
B.76
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1.1760
B.77
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1.1761
B.78
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1.1762
B.79
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1.1763
B.80
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1.1764
B.81
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1.1765
B.82
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1.1766
B.83
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1.1767
B.84
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1.1768
B.85
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1.1769
B.86
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1.1770
B.87
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1.1771
B.88
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1.1772
B.89
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1.1773
B.90
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1.1774
B.91
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1.1775
B.92
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1.1776
B.93
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1.1777
B.94
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1.1778
B.95
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1.1779
B.96
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1.1780
B.97
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1.1781
B.98
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1.1782
B.99
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1.1783
B.100
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1.1784
B.101
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1.1785
B.102
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1.1786
B.103
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1.1787
B.104
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1.1788
B.105
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1.1789
B.106
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1.1790
B.107
C.9



1.1791
B.108
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1.1792
B.109
C.9



1.1793
B.110
C.9



1.1794
B.111
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1.1795
B.112
C.9



1.1796
B.113
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1.1797
B.114
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1.1798
B.115
C.9



1.1799
B.116
C.9



1.1800
B.117
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1.1801
B.118
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1.1802
B.119
C.9



1.1803
B.120
C.9



1.1804
B.121
C.9



1.1805
B.122
C.9



1.1806
B.123
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1.1807
B.124
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1.1808
B.125
C.9



1.1809
B.126
C.9



1.1810
B.127
C.9



1.1811
B.128
C.9



1.1812
B.129
C.9



1.1813
B.130
C.9



1.1814
B.131
C.9



1.1815
B.132
C.9



1.1816
B.133
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1.1817
B.134
C.9



1.1818
B.135
C.9



1.1819
B.136
C.9



1.1820
B.137
C.9



1.1821
B.138
C.9



1.1822
B.139
C.9



1.1823
B.140
C.9



1.1824
B.141
C.9



1.1825
B.142
C.9



1.1826
B.143
C.9



1.1827
B.144
C.9



1.1828
B.145
C.9



1.1829
B.146
C.9



1.1830
B.147
C.9



1.1831
B.148
C.9



1.1832
B.149
C.9



1.1833
B.150
C.9



1.1834
B.151
C.9



1.1835
B.152
C.9



1.1836
B.153
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1.1837
B.154
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1.1838
B.155
C.9



1.1839
B.156
C.9



1.1840
B.157
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1.1841
B.158
C.9



1.1842
B.159
C.9



1.1843
B.160
C.9



1.1844
B.161
C.9



1.1845
B.162
C.9



1.1846
B.163
C.9



1.1847
B.164
C.9



1.1848
B.165
C.9



1.1849
B.166
C.9



1.1850
B.167
C.9



1.1851
B.168
C.9



1.1852
B.169
C.9



1.1853
B.170
C.9



1.1854
B.171
C.9



1.1855
B.172
C.9



1.1856
B.173
C.9



1.1857
B.174
C.9



1.1858
B.175
C.9



1.1859
B.176
C.9



1.1860
B.177
C.9



1.1861
B.178
C.9



1.1862
B.179
C.9



1.1863
B.180
C.9



1.1864
B.181
C.9



1.1865
B.182
C.9



1.1866
B.183
C.9



1.1867
B.184
C.9



1.1868
B.185
C.9



1.1869
B.186
C.9



1.1870
B.187
C.9



1.1871
B.1
C.10



1.1872
B.2
C.10



1.1873
B.3
C.10



1.1874
B.4
C.10



1.1875
B.5
C.10



1.1876
B.6
C.10



1.1877
B.7
C.10



1.1878
B.8
C.10



1.1879
B.9
C.10



1.1880
B.10
C.10



1.1881
B.11
C.10



1.1882
B.12
C.10



1.1883
B.13
C.10



1.1884
B.14
C.10



1.1885
B.15
C.10



1.1886
B.16
C.10



1.1887
B.17
C.10



1.1888
B.18
C.10



1.1889
B.19
C.10



1.1890
B.20
C.10



1.1891
B.21
C.10



1.1892
B.22
C.10



1.1893
B.23
C.10



1.1894
B.24
C.10



1.1895
B.25
C.10



1.1896
B.26
C.10



1.1897
B.27
C.10



1.1898
B.28
C.10



1.1899
B.29
C.10



1.1900
B.30
C.10



1.1901
B.31
C.10



1.1902
B.32
C.10



1.1903
B.33
C.10



1.1904
B.34
C.10



1.1905
B.35
C.10



1.1906
B.36
C.10



1.1907
B.37
C.10



1.1908
B.38
C.10



1.1909
B.39
C.10



1.1910
B.40
C.10



1.1911
B.41
C.10



1.1912
B.42
C.10



1.1913
B.43
C.10



1.1914
B.44
C.10



1.1915
B.45
C.10



1.1916
B.46
C.10



1.1917
B.47
C.10



1.1918
B.48
C.10



1.1919
B.49
C.10



1.1920
B.50
C.10



1.1921
B.51
C.10



1.1922
B.52
C.10



1.1923
B.53
C.10



1.1924
B.54
C.10



1.1925
B.55
C.10



1.1926
B.56
C.10



1.1927
B.57
C.10



1.1928
B.58.
C.10



1.1929
B.59
C.10



1.1930
B.60
C.10



1.1931
B.61
C.10



1.1932
B.62
C.10



1.1933
B.63
C.10



1.1934
B.64
C.10



1.1935
B.65
C.10



1.1936
B.66
C.10



1.1937
B.67
C.10



1.1938
B.68
C.10



1.1939
B.69
C.10



1.1940
B.70
C.10



1.1941
B.71
C.10



1.1942
B.72
C.10



1.1943
B.73
C.10



1.1944
B.74
C.10



1.1945
B.75
C.10



1.1946
B.76
C.10



1.1947
B.77
C.10



1.1948
B.78
C.10



1.1949
B.79
C.10



1.1950
B.80
C.10



1.1951
B.81
C.10



1.1952
B.82
C.10



1.1953
B.83
C.10



1.1954
B.84
C.10



1.1955
B.85
C.10



1.1956
B.86
C.10



1.1957
B.87
C.10



1.1958
B.88
C.10



1.1959
B.89
C.10



1.1960
B.90
C.10



1.1961
B.91
C.10



1.1962
B.92
C.10



1.1963
B.93
C.10



1.1964
B.94
C.10



1.1965
B.95
C.10



1.1966
B.96
C.10



1.1967
B.97
C.10



1.1968
B.98
C.10



1.1969
B.99
C.10



1.1970
B.100
C.10



1.1971
B.101
C.10



1.1972
B.102
C.10



1.1973
B.103
C.10



1.1974
B.104
C.10



1.1975
B.105
C.10



1.1976
B.106
C.10



1.1977
B.107
C.10



1.1978
B.108
C.10



1.1979
B.109
C.10



1.1980
B.110
C.10



1.1981
B.111
C.10



1.1982
B.112
C.10



1.1983
B.113
C.10



1.1984
B.114
C.10



1.1985
B.115
C.10



1.1986
B.116
C.10



1.1987
B.117
C.10



1.1988
B.118
C.10



1.1989
B.119
C.10



1.1990
B.120
C.10



1.1991
B.121
C.10



1.1992
B.122
C.10



1.1993
B.123
C.10



1.1994
B.124
C.10



1.1995
B.125
C.10



1.1996
B.126
C.10



1.1997
B.127
C.10



1.1998
B.128
C.10



1.1999
B.129
C.10



1.2000
B.130
C.10



1.2001
B.131
C.10



1.2002
B.132
C.10



1.2003
B.133
C.10



1.2004
B.134
C.10



1.2005
B.135
C.10



1.2006
B.136
C.10



1.2007
B.137
C.10



1.2008
B.138
C.10



1.2009
B.139
C.10



1.2010
B.140
C.10



1.2011
B.141
C.10



1.2012
B.142
C.10



1.2013
B.143
C.10



1.2014
B.144
C.10



1.2015
B.145
C.10



1.2016
B.146
C.10



1.2017
B.147
C.10



1.2018
B.148
C.10



1.2019
B.149
C.10



1.2020
B.150
C.10



1.2021
B.151
C.10



1.2022
B.152
C.10



1.2023
B.153
C.10



1.2024
B.154
C.10



1.2025
B.155
C.10



1.2026
B.156
C.10



1.2027
B.157
C.10



1.2028
B.158
C.10



1.2029
B.159
C.10



1.2030
B.160
C.10



1.2031
B.161
C.10



1.2032
B.162
C.10



1.2033
B.163
C.10



1.2034
B.164
C.10



1.2035
B.165
C.10



1.2036
B.166
C.10



1.2037
B.167
C.10



1.2038
B.168
C.10



1.2039
B.169
C.10



1.2040
B.170
C.10



1.2041
B.171
C.10



1.2042
B.172
C.10



1.2043
B.173
C.10



1.2044
B.174
C.10



1.2045
B.175
C.10



1.2046
B.176
C.10



1.2047
B.177
C.10



1.2048
B.178
C.10



1.2049
B.179
C.10



1.2050
B.180
C.10



1.2051
B.181
C.10



1.2052
B.182
C.10



1.2053
B.183
C.10



1.2054
B.184
C.10



1.2055
B.185
C.10



1.2056
B.186
C.10



1.2057
B.187
C.10



1.2058
B.1
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1.2059
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1.2060
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1.2061
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1.2062
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1.2063
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1.2064
B.7
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1.2065
B.8
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1.2066
B.9
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1.2067
B.10
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1.2068
B.11
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1.2069
B.12
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1.2070
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1.2071
B.14
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1.2072
B.15
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1.2073
B.16
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1.2074
B.17
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1.2075
B.18
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1.2076
B.19
C.11



1.2077
B.20
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1.2078
B.21
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1.2079
B.22
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1.2080
B.23
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1.2081
B.24
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1.2082
B.25
C.11



1.2083
B.26
C.11



1.2084
B.27
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1.2085
B.28
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1.2086
B.29
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1.2087
B.30
C.11



1.2088
B.31
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1.2089
B.32
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1.2090
B.33
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1.2091
B.34
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1.2092
B.35
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1.2093
B.36
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1.2094
B.37
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1.2095
B.38
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1.2096
B.39
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1.2097
B.40
C.11



1.2098
B.41
C.11



1.2099
B.42
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1.2100
B.43
C.11



1.2101
B.44
C.11



1.2102
B.45
C.11



1.2103
B.46
C.11



1.2104
B.47
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1.2105
B.48
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1.2106
B.49
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1.2107
B.50
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1.2108
B.51
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1.2109
B.52
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1.2110
B.53
C.11



1.2111
B.54
C.11



1.2112
B.55
C.11



1.2113
B.56
C.11



1.2114
B.57
C.11



1.2115
B.58.
C.11



1.2116
B.59
C.11



1.2117
B.60
C.11



1.2118
B.61
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1.2119
B.62
C.11



1.2120
B.63
C.11



1.2121
B.64
C.11



1.2122
B.65
C.11



1.2123
B.66
C.11



1.2124
B.67
C.11



1.2125
B.68
C.11



1.2126
B.69
C.11



1.2127
B.70
C.11



1.2128
B.71
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1.2129
B.72
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1.2130
B.73
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1.2131
B.74
C.11



1.2132
B.75
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1.2133
B.76
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1.2134
B.77
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1.2135
B.78
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1.2136
B.79
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1.2137
B.80
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1.2138
B.81
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1.2139
B.82
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1.2140
B.83
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1.2141
B.84
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1.2142
B.85
C.11



1.2143
B.86
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1.2144
B.87
C.11



1.2145
B.88
C.11



1.2146
B.89
C.11



1.2147
B.90
C.11



1.2148
B.91
C.11



1.2149
B.92
C.11



1.2150
B.93
C.11



1.2151
B.94
C.11



1.2152
B.95
C.11



1.2153
B.96
C.11



1.2154
B.97
C.11



1.2155
B.98
C.11



1.2156
B.99
C.11



1.2157
B.100
C.11



1.2158
B.101
C.11



1.2159
B.102
C.11



1.2160
B.103
C.11



1.2161
B.104
C.11



1.2162
B.105
C.11



1.2163
B.106
C.11



1.2164
B.107
C.11



1.2165
B.108
C.11



1.2166
B.109
C.11



1.2167
B.110
C.11



1.2168
B.111
C.11



1.2169
B.112
C.11



1.2170
B.113
C.11



1.2171
B.114
C.11



1.2172
B.115
C.11



1.2173
B.116
C.11



1.2174
B.117
C.11



1.2175
B.118
C.11



1.2176
B.119
C.11



1.2177
B.120
C.11



1.2178
B.121
C.11



1.2179
B.122
C.11



1.2180
B.123
C.11



1.2181
B.124
C.11



1.2182
B.125
C.11



1.2183
B.126
C.11



1.2184
B.127
C.11



1.2185
B.128
C.11



1.2186
B.129
C.11



1.2187
B.130
C.11



1.2188
B.131
C.11



1.2189
B.132
C.11



1.2190
B.133
C.11



1.2191
B.134
C.11



1.2192
B.135
C.11



1.2193
B.136
C.11



1.2194
B.137
C.11



1.2195
B.138
C.11



1.2196
B.139
C.11



1.2197
B.140
C.11



1.2198
B.141
C.11



1.2199
B.142
C.11



1.2200
B.143
C.11



1.2201
B.144
C.11



1.2202
B.145
C.11



1.2203
B.146
C.11



1.2204
B.147
C.11



1.2205
B.148
C.11



1.2206
B.149
C.11



1.2207
B.150
C.11



1.2208
B.151
C.11



1.2209
B.152
C.11



1.2210
B.153
C.11



1.2211
B.154
C.11



1.2212
B.155
C.11



1.2213
B.156
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1.2214
B.157
C.11



1.2215
B.158
C.11



1.2216
B.159
C.11



1.2217
B.160
C.11



1.2218
B.161
C.11



1.2219
B.162
C.11



1.2220
B.163
C.11



1.2221
B.164
C.11



1.2222
B.165
C.11



1.2223
B.166
C.11



1.2224
B.167
C.11



1.2225
B.168
C.11



1.2226
B.169
C.11



1.2227
B.170
C.11



1.2228
B.171
C.11



1.2229
B.172
C.11



1.2230
B.173
C.11



1.2231
B.174
C.11



1.2232
B.175
C.11



1.2233
B.176
C.11



1.2234
B.177
C.11



1.2235
B.178
C.11



1.2236
B.179
C.11



1.2237
B.180
C.11



1.2238
B.181
C.11



1.2239
B.182
C.11



1.2240
B.183
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1.2241
B.184
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1.2242
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1.2243
B.186
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1.2244
B.187
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1.2245
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1.2246
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1.2247
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1.2248
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1.2249
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1.2250
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1.2251
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1.2252
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1.2253
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1.2254
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1.2255
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1.2256
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1.2257
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1.2258
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1.2259
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1.2260
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1.2261
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1.2262
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1.2263
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1.2264
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1.2265
B.21
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1.2266
B.22
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1.2267
B.23
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1.2268
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1.2269
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1.2270
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1.2271
B.27
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1.2272
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1.2273
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1.2274
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1.2275
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1.2276
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1.2277
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1.2278
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1.2279
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1.2280
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1.2281
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1.2282
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1.2283
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1.2284
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1.2285
B.41
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1.2286
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1.2287
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1.2288
B.44
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1.2289
B.45
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1.2290
B.46
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1.2291
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1.2292
B.48
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1.2293
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1.2294
B.50
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1.2295
B.51
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1.2296
B.52
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1.2297
B.53
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1.2298
B.54
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1.2299
B.55
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1.2300
B.56
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1.2301
B.57
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1.2302
B.58.
C.12



1.2303
B.59
C.12



1.2304
B.60
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1.2305
B.61
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1.2306
B.62
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1.2307
B.63
C.12



1.2308
B.64
C.12



1.2309
B.65
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1.2310
B.66
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1.2311
B.67
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1.2312
B.68
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1.2313
B.69
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1.2314
B.70
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1.2315
B.71
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1.2316
B.72
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1.2317
B.73
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1.2318
B.74
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1.2319
B.75
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1.2320
B.76
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1.2321
B.77
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1.2322
B.78
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1.2323
B.79
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1.2324
B.80
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1.2325
B.81
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1.2326
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1.2327
B.83
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1.2328
B.84
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1.2329
B.85
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1.2330
B.86
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1.2331
B.87
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1.2332
B.88
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1.2333
B.89
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1.2334
B.90
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1.2335
B.91
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1.2336
B.92
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1.2337
B.93
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1.2338
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1.2339
B.95
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1.2340
B.96
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1.2341
B.97
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1.2342
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1.2343
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1.2344
B.100
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1.2345
B.101
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1.2346
B.102
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1.2347
B.103
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1.2348
B.104
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1.2349
B.105
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1.2350
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1.2351
B.107
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1.2352
B.108
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1.2353
B.109
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1.2354
B.110
C.12



1.2355
B.111
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1.2356
B.112
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1.2357
B.113
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1.2358
B.114
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1.2359
B.115
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1.2360
B.116
C.12



1.2361
B.117
C.12



1.2362
B.118
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1.2363
B.119
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1.2364
B.120
C.12



1.2365
B.121
C.12



1.2366
B.122
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1.2367
B.123
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1.2368
B.124
C.12



1.2369
B.125
C.12



1.2370
B.126
C.12



1.2371
B.127
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1.2372
B.128
C.12



1.2373
B.129
C.12



1.2374
B.130
C.12



1.2375
B.131
C.12



1.2376
B.132
C.12



1.2377
B.133
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1.2378
B.134
C.12



1.2379
B.135
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1.2380
B.136
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1.2381
B.137
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1.2382
B.138
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1.2383
B.139
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1.2384
B.140
C.12



1.2385
B.141
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1.2386
B.142
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1.2387
B.143
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1.2388
B.144
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1.2389
B.145
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1.2390
B.146
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1.2391
B.147
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1.2392
B.148
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1.2393
B.149
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1.2394
B.150
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1.2395
B.151
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1.2396
B.152
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1.2397
B.153
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1.2398
B.154
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1.2399
B.155
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1.2400
B.156
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1.2401
B.157
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1.2402
B.158
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1.2403
B.159
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1.2404
B.160
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1.2405
B.161
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1.2406
B.162
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1.2407
B.163
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1.2408
B.164
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1.2409
B.165
C.12



1.2410
B.166
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1.2411
B.167
C.12



1.2412
B.168
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1.2413
B.169
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1.2414
B.170
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1.2415
B.171
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1.2416
B.172
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1.2417
B.173
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1.2418
B.174
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1.2419
B.175
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1.2420
B.176
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1.2421
B.177
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1.2422
B.178
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1.2423
B.179
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1.2424
B.180
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1.2425
B.181
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1.2426
B.182
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1.2427
B.183
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1.2428
B.184
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1.2429
B.185
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1.2430
B.186
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1.2431
B.187
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1.2432
B.1
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1.2433
B.2
C.13



1.2434
B.3
C.13



1.2435
B.4
C.13



1.2436
B.5
C.13



1.2437
B.6
C.13



1.2438
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1.2451
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1.2454
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1.2534
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1.2536
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1.2537
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1.2538
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1.2539
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1.2540
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1.2541
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1.2542
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1.2543
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1.2544
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1.2548
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1.2554
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1.2555
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1.2563
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1.2578
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1.2579
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1.2592
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1.2597
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1.2602
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1.2607
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B.91
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B.92
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1.2716
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1.2718
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1.2719
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1.2720
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1.2721
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1.2722
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1.2723
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1.2724
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1.2725
B.107
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1.2726
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1.2727
B.109
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1.2728
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1.2729
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1.2730
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1.2731
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1.2732
B.114
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1.2733
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1.2735
B.117
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1.2736
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1.2738
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1.2740
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1.2741
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1.2743
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1.2744
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1.2745
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1.2747
B.129
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1.2748
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1.2749
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1.2750
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1.2751
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1.2752
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1.2753
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1.2754
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1.2755
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1.2756
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1.2757
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1.2758
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1.2759
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1.2760
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1.2764
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1.2781
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1.2787
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1.2788
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1.2789
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1.2797
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1.2871
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1.2872
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1.2876
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1.2882
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1.2883
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1.2884
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1.2887
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1.2888
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1.2890
B.85
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1.2891
B.86
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1.2892
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1.2893
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B.89
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B.90
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1.2896
B.91
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1.2897
B.92
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1.2898
B.93
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1.2900
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1.2901
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1.2902
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1.2905
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1.2906
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1.2907
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1.2909
B.104
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1.2910
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1.2911
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1.2912
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1.2913
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1.2914
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1.2915
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1.2916
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1.2917
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1.2918
B.113
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B.114
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1.2920
B.115
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1.2921
B.116
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1.2922
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1.2923
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1.2924
B.119
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1.2925
B.120
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1.2926
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1.2927
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1.2928
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1.2929
B.124
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1.2930
B.125
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1.2931
B.126
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1.2932
B.127
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1.2933
B.128
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1.2934
B.129
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1.2935
B.130
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1.2936
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1.2937
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1.2938
B.133
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1.2939
B.134
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1.2940
B.135
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1.2941
B.136
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1.2942
B.137
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1.2943
B.138
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1.2944
B.139
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1.2945
B.140
C.15



1.2946
B.141
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1.2947
B.142
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1.2948
B.143
C.15



1.2949
B.144
C.15



1.2950
B.145
C.15



1.2951
B.146
C.15



1.2952
B.147
C.15



1.2953
B.148
C.15



1.2954
B.149
C.15



1.2955
B.150
C.15



1.2956
B.151
C.15



1.2957
B.152
C.15



1.2958
B.153
C.15



1.2959
B.154
C.15



1.2960
B.155
C.15



1.2961
B.156
C.15



1.2962
B.157
C.15



1.2963
B.158
C.15



1.2964
B.159
C.15



1.2965
B.160
C.15



1.2966
B.161
C.15



1.2967
B.162
C.15



1.2968
B.163
C.15



1.2969
B.164
C.15



1.2970
B.165
C.15



1.2971
B.166
C.15



1.2972
B.167
C.15



1.2973
B.168
C.15



1.2974
B.169
C.15



1.2975
B.170
C.15



1.2976
B.171
C.15



1.2977
B.172
C.15



1.2978
B.173
C.15



1.2979
B.174
C.15



1.2980
B.175
C.15



1.2981
B.176
C.15



1.2982
B.177
C.15



1.2983
B.178
C.15



1.2984
B.179
C.15



1.2985
B.180
C.15



1.2986
B.181
C.15



1.2987
B.182
C.15



1.2988
B.183
C.15



1.2989
B.184
C.15



1.2990
B.185
C.15



1.2991
B.186
C.15



1.2992
B.187
C.15



1.2993
B.1
C.16



1.2994
B.2
C.16



1.2995
B.3
C.16



1.2996
B.4
C.16



1.2997
B.5
C.16



1.2998
B.6
C.16



1.2999
B.7
C.16



1.3000
B.8
C.16



1.3001
B.9
C.16



1.3002
B.10
C.16



1.3003
B.11
C.16



1.3004
B.12
C.16



1.3005
B.13
C.16



1.3006
B.14
C.16



1.3007
B.15
C.16



1.3008
B.16
C.16



1.3009
B.17
C.16



1.3010
B.18
C.16



1.3011
B.19
C.16



1.3012
B.20
C.16



1.3013
B.21
C.16



1.3014
B.22
C.16



1.3015
B.23
C.16



1.3016
B.24
C.16



1.3017
B.25
C.16



1.3018
B.26
C.16



1.3019
B.27
C.16



1.3020
B.28
C.16



1.3021
B.29
C.16



1.3022
B.30
C.16



1.3023
B.31
C.16



1.3024
B.32
C.16



1.3025
B.33
C.16



1.3026
B.34
C.16



1.3027
B.35
C.16



1.3028
B.36
C.16



1.3029
B.37
C.16



1.3030
B.38
C.16



1.3031
B.39
C.16



1.3032
B.40
C.16



1.3033
B.41
C.16



1.3034
B.42
C.16



1.3035
B.43
C.16



1.3036
B.44
C.16



1.3037
B.45
C.16



1.3038
B.46
C.16



1.3039
B.47
C.16



1.3040
B.48
C.16



1.3041
B.49
C.16



1.3042
B.50
C.16



1.3043
B.51
C.16



1.3044
B.52
C.16



1.3045
B.53
C.16



1.3046
B.54
C.16



1.3047
B.55
C.16



1.3048
B.56
C.16



1.3049
B.57
C.16



1.3050
B.58.
C.16



1.3051
B.59
C.16



1.3052
B.60
C.16



1.3053
B.61
C.16



1.3054
B.62
C.16



1.3055
B.63
C.16



1.3056
B.64
C.16



1.3057
B.65
C.16



1.3058
B.66
C.16



1.3059
B.67
C.16



1.3060
B.68
C.16



1.3061
B.69
C.16



1.3062
B.70
C.16



1.3063
B.71
C.16



1.3064
B.72
C.16



1.3065
B.73
C.16



1.3066
B.74
C.16



1.3067
B.75
C.16



1.3068
B.76
C.16



1.3069
B.77
C.16



1.3070
B.78
C.16



1.3071
B.79
C.16



1.3072
B.80
C.16



1.3073
B.81
C.16



1.3074
B.82
C.16



1.3075
B.83
C.16



1.3076
B.84
C.16



1.3077
B.85
C.16



1.3078
B.86
C.16



1.3079
B.87
C.16



1.3080
B.88
C.16



1.3081
B.89
C.16



1.3082
B.90
C.16



1.3083
B.91
C.16



1.3084
B.92
C.16



1.3085
B.93
C.16



1.3086
B.94
C.16



1.3087
B.95
C.16



1.3088
B.96
C.16



1.3089
B.97
C.16



1.3090
B.98
C.16



1.3091
B.99
C.16



1.3092
B.100
C.16



1.3093
B.101
C.16



1.3094
B.102
C.16



1.3095
B.103
C.16



1.3096
B.104
C.16



1.3097
B.105
C.16



1.3098
B.106
C.16



1.3099
B.107
C.16



1.3100
B.108
C.16



1.3101
B.109
C.16



1.3102
B.110
C.16



1.3103
B.111
C.16



1.3104
B.112
C.16



1.3105
B.113
C.16



1.3106
B.114
C.16



1.3107
B.115
C.16



1.3108
B.116
C.16



1.3109
B.117
C.16



1.3110
B.118
C.16



1.3111
B.119
C.16



1.3112
B.120
C.16



1.3113
B.121
C.16



1.3114
B.122
C.16



1.3115
B.123
C.16



1.3116
B.124
C.16



1.3117
B.125
C.16



1.3118
B.126
C.16



1.3119
B.127
C.16



1.3120
B.128
C.16



1.3121
B.129
C.16



1.3122
B.130
C.16



1.3123
B.131
C.16



1.3124
B.132
C.16



1.3125
B.133
C.16



1.3126
B.134
C.16



1.3127
B.135
C.16



1.3128
B.136
C.16



1.3129
B.137
C.16



1.3130
B.138
C.16



1.3131
B.139
C.16



1.3132
B.140
C.16



1.3133
B.141
C.16



1.3134
B.142
C.16



1.3135
B.143
C.16



1.3136
B.144
C.16



1.3137
B.145
C.16



1.3138
B.146
C.16



1.3139
B.147
C.16



1.3140
B.148
C.16



1.3141
B.149
C.16



1.3142
B.150
C.16



1.3143
B.151
C.16



1.3144
B.152
C.16



1.3145
B.153
C.16



1.3146
B.154
C.16



1.3147
B.155
C.16



1.3148
B.156
C.16



1.3149
B.157
C.16



1.3150
B.158
C.16



1.3151
B.159
C.16



1.3152
B.160
C.16



1.3153
B.161
C.16



1.3154
B.162
C.16



1.3155
B.163
C.16



1.3156
B.164
C.16



1.3157
B.165
C.16



1.3158
B.166
C.16



1.3159
B.167
C.16



1.3160
B.168
C.16



1.3161
B.169
C.16



1.3162
B.170
C.16



1.3163
B.171
C.16



1.3164
B.172
C.16



1.3165
B.173
C.16



1.3166
B.174
C.16



1.3167
B.175
C.16



1.3168
B.176
C.16



1.3169
B.177
C.16



1.3170
B.178
C.16



1.3171
B.179
C.16



1.3172
B.180
C.16



1.3173
B.181
C.16



1.3174
B.182
C.16



1.3175
B.183
C.16



1.3176
B.184
C.16



1.3177
B.185
C.16



1.3178
B.186
C.16



1.3179
B.187
C.16



1.3180
B.1
C.17



1.3181
B.2
C.17



1.3182
B.3
C.17



1.3183
B.4
C.17



1.3184
B.5
C.17



1.3185
B.6
C.17



1.3186
B.7
C.17



1.3187
B.8
C.17



1.3188
B.9
C.17



1.3189
B.10
C.17



1.3190
B.11
C.17



1.3191
B.12
C.17



1.3192
B.13
C.17



1.3193
B.14
C.17



1.3194
B.15
C.17



1.3195
B.16
C.17



1.3196
B.17
C.17



1.3197
B.18
C.17



1.3198
B.19
C.17



1.3199
B.20
C.17



1.3200
B.21
C.17



1.3201
B.22
C.17



1.3202
B.23
C.17



1.3203
B.24
C.17



1.3204
B.25
C.17



1.3205
B.26
C.17



1.3206
B.27
C.17



1.3207
B.28
C.17



1.3208
B.29
C.17



1.3209
B.30
C.17



1.3210
B.31
C.17



1.3211
B.32
C.17



1.3212
B.33
C.17



1.3213
B.34
C.17



1.3214
B.35
C.17



1.3215
B.36
C.17



1.3216
B.37
C.17



1.3217
B.38
C.17



1.3218
B.39
C.17



1.3219
B.40
C.17



1.3220
B.41
C.17



1.3221
B.42
C.17



1.3222
B.43
C.17



1.3223
B.44
C.17



1.3224
B.45
C.17



1.3225
B.46
C.17



1.3226
B.47
C.17



1.3227
B.48
C.17



1.3228
B.49
C.17



1.3229
B.50
C.17



1.3230
B.51
C.17



1.3231
B.52
C.17



1.3232
B.53
C.17



1.3233
B.54
C.17



1.3234
B.55
C.17



1.3235
B.56
C.17



1.3236
B.57
C.17



1.3237
B.58.
C.17



1.3238
B.59
C.17



1.3239
B.60
C.17



1.3240
B.61
C.17



1.3241
B.62
C.17



1.3242
B.63
C.17



1.3243
B.64
C.17



1.3244
B.65
C.17



1.3245
B.66
C.17



1.3246
B.67
C.17



1.3247
B.68
C.17



1.3248
B.69
C.17



1.3249
B.70
C.17



1.3250
B.71
C.17



1.3251
B.72
C.17



1.3252
B.73
C.17



1.3253
B.74
C.17



1.3254
B.75
C.17



1.3255
B.76
C.17



1.3256
B.77
C.17



1.3257
B.78
C.17



1.3258
B.79
C.17



1.3259
B.80
C.17



1.3260
B.81
C.17



1.3261
B.82
C.17



1.3262
B.83
C.17



1.3263
B.84
C.17



1.3264
B.85
C.17



1.3265
B.86
C.17



1.3266
B.87
C.17



1.3267
B.88
C.17



1.3268
B.89
C.17



1.3269
B.90
C.17



1.3270
B.91
C.17



1.3271
B.92
C.17



1.3272
B.93
C.17



1.3273
B.94
C.17



1.3274
B.95
C.17



1.3275
B.96
C.17



1.3276
B.97
C.17



1.3277
B.98
C.17



1.3278
B.99
C.17



1.3279
B.100
C.17



1.3280
B.101
C.17



1.3281
B.102
C.17



1.3282
B.103
C.17



1.3283
B.104
C.17



1.3284
B.105
C.17



1.3285
B.106
C.17



1.3286
B.107
C.17



1.3287
B.108
C.17



1.3288
B.109
C.17



1.3289
B.110
C.17



1.3290
B.111
C.17



1.3291
B.112
C.17



1.3292
B.113
C.17



1.3293
B.114
C.17



1.3294
B.115
C.17



1.3295
B.116
C.17



1.3296
B.117
C.17



1.3297
B.118
C.17



1.3298
B.119
C.17



1.3299
B.120
C.17



1.3300
B.121
C.17



1.3301
B.122
C.17



1.3302
B.123
C.17



1.3303
B.124
C.17



1.3304
B.125
C.17



1.3305
B.126
C.17



1.3306
B.127
C.17



1.3307
B.128
C.17



1.3308
B.129
C.17



1.3309
B.130
C.17



1.3310
B.131
C.17



1.3311
B.132
C.17



1.3312
B.133
C.17



1.3313
B.134
C.17



1.3314
B.135
C.17



1.3315
B.136
C.17



1.3316
B.137
C.17



1.3317
B.138
C.17



1.3318
B.139
C.17



1.3319
B.140
C.17



1.3320
B.141
C.17



1.3321
B.142
C.17



1.3322
B.143
C.17



1.3323
B.144
C.17



1.3324
B.145
C.17



1.3325
B.146
C.17



1.3326
B.147
C.17



1.3327
B.148
C.17



1.3328
B.149
C.17



1.3329
B.150
C.17



1.3330
B.151
C.17



1.3331
B.152
C.17



1.3332
B.153
C.17



1.3333
B.154
C.17



1.3334
B.155
C.17



1.3335
B.156
C.17



1.3336
B.157
C.17



1.3337
B.158
C.17



1.3338
B.159
C.17



1.3339
B.160
C.17



1.3340
B.161
C.17



1.3341
B.162
C.17



1.3342
B.163
C.17



1.3343
B.164
C.17



1.3344
B.165
C.17



1.3345
B.166
C.17



1.3346
B.167
C.17



1.3347
B.168
C.17



1.3348
B.169
C.17



1.3349
B.170
C.17



1.3350
B.171
C.17



1.3351
B.172
C.17



1.3352
B.173
C.17



1.3353
B.174
C.17



1.3354
B.175
C.17



1.3355
B.176
C.17



1.3356
B.177
C.17



1.3357
B.178
C.17



1.3358
B.179
C.17



1.3359
B.180
C.17



1.3360
B.181
C.17



1.3361
B.182
C.17



1.3362
B.183
C.17



1.3363
B.184
C.17



1.3364
B.185
C.17



1.3365
B.186
C.17



1.3366
B.187
C.17



1.3367
—
C.1



1.3368
—
C.2



1.3369
—
C.3



1.3370
—
C.4



1.3371
—
C.5



1.3372
—
C.6



1.3373
—
C.7



1.3374
—
C.8



1.3375
—
C.9



1.3376
—
C.10



1.3377
—
C.11



1.3378
—
C.12



1.3379
—
C.13



1.3380
—
C.14



1.3381
—
C.15



1.3382
—
C.16



1.3383
—
C.17










The specific number for each single composition is deductible as follows:


Composition 1.777 for example comprises the compound I.a, foramsulfuron (B.29) and cyprosulfamide (C.4) (see table 1, entry 1.777; as well as table B, entry B.29 and table C, entry C.4).


Composition 2.777 for example comprises the compound I.a (see the definition for compositions 2.1 to 2.3383 below), foramsulfuron (B.29) and cyprosulfamide (C.4) (see table 1, entry 1.777; as well as table B, entry B.29 and table C, entry C.4).


Composition 7.777 for example comprises imazapyr (B.35) (see the definition for compositions 7.1 to 7.3383 below), and the compound I.a, foramsulfuron (B.29) and cyprosulfamide (C.4) (see table 1, entry 1.777; as well as table B, entry B.29 and table C, entry C.4).


The invention also relates to agrochemical compositions comprising at least an auxiliary and at least one compound of formula (I) according to the invention.


An agrochemical composition comprises a pesticidally effective amount of a compound of formula (I). The term “effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling unwanted plants, especially for controlling unwanted plants in cultivated plants and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the plants to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound of formula (I) used.


The compounds of formula (I), their N-oxides, salts or derivatives can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for agrochemical composition 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 agrochemical compositions 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 agrochemical compositions 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, wetters, 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 dodecyl- and 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 agrochemical composition types and their preparation are:


i) Water-Soluble Concentrates (SL, LS)


10-60 wt % of a compound of formula (I) or a herbicidal composition 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 and 5-15 wt % wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt %. The active substance dissolves upon dilution with water.


ii) Dispersible Concentrates (DC)


5-25 wt % of a compound of formula (I) or a herbicidal composition 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 and 1-10 wt % dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.


iii) Emulsifiable concentrates (EC)


15-70 wt % of compound of formula (I) or a herbicidal composition 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 and 5-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %. Dilution with water gives an emulsion.


iv) Emulsions (EW, EO, ES)


5-40 wt % of compound of formula (I) or a herbicidal composition 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 and 1-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt % by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.


v) Suspensions (SC, OD, FS)


In an agitated ball mill, 20-60 wt % of a compound of formula (I) or a herbicidal composition 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 composition up to 40 wt % binder (e.g. polyvinylalcohol) is added.


vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)


50-80 wt % of a compound of formula (I) or a herbicidal composition 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 with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt % and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.


vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)


50-80 wt % of a compound of formula (I) or a herbicidal composition 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 in a rotor-stator mill with addition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt %. Dilution with water gives a stable dispersion or solution of the active substance.


viii) Gel (GW, GF)


In an agitated ball mill, 5-25 wt % of a compound of formula (I) or a herbicidal composition 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.


iv) Microemulsion (ME)


5-20 wt % of a compound of formula (I) or a herbicidal composition 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.


iv) Microcapsules (CS)


An oil phase comprising 5-50 wt % of a compound of formula (I) or a herbicidal composition 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 composition.


ix) Dustable Powders (DP, DS)


1-10 wt % of a compound of formula (I) or a herbicidal composition 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 %.


x) Granules (GR, FG)


0.5-30 wt % of a compound of formula (I) or a herbicidal composition 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.


xi) Ultra-Low Volume Liquids (UL)


1-50 wt % of a compound of formula (I) or a herbicidal composition 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 agrochemical compositions 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 agrochemical compositions and/or herbicidal compositions 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 compound of formula (I). The compound 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 agrochemical compositions 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. Application can be carried out before or during sowing.


Methods for applying compounds of formula (I), agrochemical compositions and/or herbicidal compositions 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), agrochemical compositions and/or herbicidal compositions 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, wetters, 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 agrochemical compositions and/or the herbicidal compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the agrochemical compositions 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 agrochemical compositions and/or the herbicidal compositions comprising them usually from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition 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 agrochemical composition 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 agrochemical composition 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 agrochemical composition 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 appropriately formulated composition (agrochemical composition) or as an herbicidal composition 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 agrochemical compositions and/or herbicidal compositions comprising the compounds of formula (I), control 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 formula (I), or the agrochemical compositions and/or the herbicidal compositions 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 I/ha (for example from 300 to 400 I/ha).


The compounds of formula (I), or the agrochemical compositions and/or the herbicidal compositions 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 agrochemical compositions and/or the herbicidal compositions comprising them, can be done before, during and/or after, preferably during and/or after, the emergence of the undesirable plants.


The compounds of formula (I), or the agrochemical compositions and/or the herbicidal compositions 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 agrochemical compositions and/or the herbicidal compositions comprising them, by applying seed, pretreated with the compounds of formula (I), or the agrochemical compositions and/or the herbicidal compositions 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 herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).


In a further embodiment, the compounds of formula (I), or the agrochemical compositions and/or the herbicidal compositions 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 agrochemical compositions and/or the herbicidal compositions prepared therefrom. Here, the herbicidal compositions can be applied diluted or undiluted.


The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.


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, preferably 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 herbicidal compositions 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 agrochemical compositions and/or herbicidal compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:



Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.


Preferred crops are Arachis hypogaea, Beta vulgaris spec. altissima, Brassica napus var. napus, Brassica oleracea, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cynodon dactylon, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hordeum vulgare, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Medicago sativa, Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Pistacia vera, Pisum sativum, Prunus dulcis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Triticale, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.


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 agrochemical compositions and/or herbicidal compositions comprising them, can also be used in genetically modified plants. The term “genetically modified plants” is to be understood as plants whose genetic material has been modified by the use of recombinant DNA techniques to include an inserted sequence of DNA that is not native to that plant species' genome or to exhibit a deletion of DNA that was native to that species' genome, wherein the modification(s) cannot readily be obtained by cross breeding, mutagenesis or natural recombination alone. Often, a particular genetically modified plant will be one that has obtained its genetic modification(s) by inheritance through a natural breeding or propagation process from an ancestral plant whose genome was the one directly treated by use of a recombinant DNA technique. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted posttranslational modification of protein(s), oligo- or polypeptides. e. g., by inclusion therein of amino acid mutation(s) that permit, decrease, or promote glycosylation or polymer additions such as prenylation, acetylation farnesylation, or PEG moiety attachment.


Plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvyl shikimate 3-phosphate synthase (EPSP) inhibitors such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering; furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are, for example, described in Pest Management Science 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Science 57, 2009, 108; Australian Journal of Agricultural Research 58, 2007, 708; Science 316, 2007, 1185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by mutagenesis and conventional methods of breeding, e. g., Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g., imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g., tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate, imidazolinones and glufosinate, some of which are under development or commercially available under the brands or trade names RoundupReady® (glyphosate tolerant, Monsanto, USA), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate tolerant, Bayer CropScience, Germany).


Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as delta-endotoxins, e. g., CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e. g., VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g., Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxy-steroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as including pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g., WO 02/015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g., in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CryIAb toxin), YieldGard® Plus (corn cultivars producing CryIAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivars producing the Cry1Ac toxin), Bollgard® II (cotton cultivars producing Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIPtoxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e. g., Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CryIAb toxin and PAT enzyme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1F toxin and PAT enzyme).


Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, e.g., EP-A 392 225), plant disease resistance genes (e. g., potato culti-vars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato, Solanum bulbocastanum) or T4-lyso-zym (e.g., potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylovora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g., in the publications mentioned above.


Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g., bio-mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.


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 human or animal nutrition, e. g., oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g., Nexera® rape, Dow AgroSciences, Canada).


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 agrochemical compositions and/or herbicidal compositions comprising them, are also suitable for the defoliation and/or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable. In this regard, agrochemical compositions and/or herbicidal compositions for the desiccation and/or defoliation of plants, processes for preparing these agrochemical compositions and/or herbicidal compositions 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.


The preparation of the compounds of formula (I) is illustrated by examples; however, the subject matter of the present invention is not limited to the examples given.







I. SYNTHESIS EXAMPLES

With appropriate modification of the starting materials, the procedures given in the synthesis examples below were used to obtain further compounds I. The compounds obtained in this manner are listed in the table that follows, together with physical data.


The products shown below were characterized by determination of the melting point, NMR spectroscopy or the masses ([m/z]) determined by HPLC-MS spectrometry.


HPLC-MS=high performance liquid chromatography coupled with mass spectrometry; HPLC column:


RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50*4.6 mm; mobile phase: acetonitrile+0.1% trifluoroacetic acid (TFA)/water+0.1% TFA, using a gradient from 5:95 to 100:0 over 5 minutes at 40° C., flow rate 1.8 ml/min.


MS: quadrupole electrospray ionization, 80 V (positive mode).


DBU: 1,8-Diazabicyclo[5.4.0]undec-7-ene


EtOAc: acetic acid ethyl ester


Example 1
Preparation of 6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)-5H-thiopyrano[4,3-b]pyridin-8-ol (Compound I-3 in Table I below)
Step 1: Preparation of methyl 3-[(2,3,5-trichloro-4-pyridyl)methylsulfanylmethyl]pyridine-2-carboxylate



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To a solution of S-[(2,3,5-trichloro-4-pyridyl)methyl]ethanethioate (17.7 g, 65.4 mmol) in methanol (200 ml) was added potassium carbonate (10.9 g, 78.9 mmol) and the mixture stirred for 5 min at room temperature. Methyl-3-(bromomethyl)pyridine-2-carboxylate (16.6 g, 72.2 mmol) was then added and the reaction mixture was stirred at room temperature for 1 h. Water was added and the organic phase separated. The aqueous phase was extracted with ethyl acetate and the combined organic phases were washed with brine and dried over sodium sulfate. The residue after filtration and evaporation of the solvent was chromatographed on silica gel eluted with hexane:ethyl acetate (1:1) to give 21.7 g (88%) of the desired product.



1H NMR (CDCl3): 8.62 (d, 1H); 8.25 (s, 1H); 7.87 (d, 1H); 7.41 (dd, 1H); 4.27 (s, 2H), 3.98 (s, 5H)


Step 2: Preparation of methyl 3-[(2,3,5-trichloro-4-pyridyl)methylsulfonylmethyl]pyridine-2-carboxylate



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A solution of methyl 3-[(2,3,5-trichloro-4-pyridyl)methylsulfanylmethyl]pyridine-2-carboxylate (21.7 g, 57.4 mmol) prepared as described in step 1, example 1 in dichloromethane (100 mL) was cooled to 0° C. and 3-chloroperbenzoic acid (27 g, 156.4 mmol) was added portionwise. The reaction mixture was stirred at room temperature until deemed complete by LC-MS. The mixture was extracted three times with a 2.5% aqueous sodium hydroxide solution. The organic phase was washed with water, brine and dried over sodium sulfate. The residue after evaporation of the solvent was chromatographed on silica gel eluted with hexane/ethyl acetate (1:1) to give 18.8 g (80%) of the desired product.



1H NMR (CDCl3): 8.80 (d, 1H); 8.39 (s, 1H); 8.00 (d, 1H); 7.57 (dd, 1H); 5.07 (s, 2H); 4.86 (s, 2H); 4.02 (s, 3H)


Step 3: Preparation of 6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)-5H-thiopyrano[4,3-b]pyridin-8-ol (Compound I-3 in Table I Below)



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To a solution of methyl 3-[(2,3,5-trichloro-4-pyridyl)methylsulfonylmethyl]pyridine-2-carboxylate (18.8 g, 45.9 mmol) prepared as described in step 2, example 1 in acetonitrile (50 ml) was added 1,8-Diazabicycloundec-7-ene (14 g, 92 mmol). The resultant mixture was heated under reflux for 5 h, cooled to room temperature and diluted with an aqueous solution of 15% citric acid. The aqueous phase was extracted with ethyl acetate and the combined organic phases were washed with brine and dried over sodium sulfate. The residue after evaporation of the solvent was triturated with diisopropyl ether, filtered and dried to give 16.3 g (94%) of the desired product.



1H NMR (CDCl3): 8.71 (d, 1H); 8.47 (s, 1H); 7.83 (d, 1H), 7.58 (dd, 1H), 4.66 (s, 2H)


Example 2
Preparation of [6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)-5H-thiopyrano[4,3-b]pyridin-8-yl]2,2-dimethylpropanoate (Compound I-4 in Table I Below)



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To a solution of 6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)-5H-thiopyrano[4,3-b]pyridin-8-ol (16.3 g, 43.3 mmol) prepared as described in example 1 in dichloromethane (50 ml) were added pyridine (4.1 g, 51.8 mmol) and pivaloyl chloride (5.73 g, 47.3 mmol) successively. The resulting solution was stirred at room temperature for 3 h. A 5% aqueous hydrochloric acid solution was added and the organic layer separated. The aqueous phase was extracted with ethyl acetate and the combined organic phases were washed with brine and dried over sodium sulfate. The residue after filtration and evaporation of the solvent was chromatographed on silica gel eluted with hexane:ethyl acetate (1:1) to give 15.3 g (77%) of the desired product.



1H NMR (CDCl3): 8.68 (d, 1H); 8.47 (s, 1H); 7.74 (d, 1H); 7.41 (dd, 1H); 4.69 (s, 2H); 1.15 (s, 9H)


Example 3
Preparation of [5,5-dimethyl-6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)thiopyrano[4,3-b]pyridin-8-yl]2,2-dimethylpropanoate (Compound I-5 in Table I Below)



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To a solution of [6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)-5H-thiopyrano[4,3-b]pyridin-8-yl]2,2-dimethylpropanoate (200 mg, 0.43 mmol) prepared as described in example 2 in dimethylformamide (5 ml) were added caesium carbonate (43 mg, 1.3 mmol) and methyl iodide (246 mg, 1.7 mmol) successively. The resultant mixture was stirred at room temperature for 4 h. Water was added and the organic layer was separated. The aqueous phase was extracted with ethyl acetate and the combined organic phases were washed with brine and dried over sodium sulfate. The residue after filtration and evaporation of the solvent was chromatographed on silica gel eluted with hexane:ethyl acetate (1:1) to give 140 mg (66%) of the desired compound.



1H NMR (CDCl3): 8.64 (d, 1H); 8.46 (s, 1H); 7.85 (d, 1H); 7.45 (dd, 1H); 1.96 (s, 6H); 1.19 (s, 9H)


Example 4
Preparation of 5,5-dimethyl-6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)thiopyrano[4,3-b]pyridin-8-ol (Compound I-6 in Table I Below)



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To a stirred solution of [5,5-dimethyl-6,6-dioxo-7-(2,3,5-trichloro-4-pyridyl)thiopyrano[4,3-b]pyridin-8-yl]2,2-dimethylpropanoate (500 mg, 1.02 mmol) prepared as described in example 3 in tetrahydrofuran (6 ml) and water (3 ml) was added lithium hydroxide (73 mg, 3 mmol). The resultant mixture was stirred at room temperature for 2 h. Water was added and the solution acidified to pH 3 with aqueous hydrochloric acid (6N). The resulting mixture was extracted with ethyl acetate and the combined organic phases were washed with brine and dried over sodium sulfate. The residue after filtration and evaporation of the solvent was chromatographed on silica gel eluted with ethyl acetate to give 310 mg (77%) of the desired product.



1H NMR (CDCl3): 8.65 (d, 1H); 8.45 (s, 1H), 7.94 (d, 1H), 7.60 (dd, 1H), 1.89 (s, 6H)









TABLE I







Compounds of the formula I.a as shown above























LC-










MS










(M +


No.
R
R1
R2
R3
R4
Rx
Ry
H)


















I-1
OH
Cl
H
H
Cl
H
H
343.0


I-2
OCOtBu
Cl
H
H
Cl
Me
Me
455.0


I-3
OH
Cl
Cl
H
Cl
H
H
376.9


I-4
OCOtBu
Cl
Cl
H
Cl
H
H
461.0


I-5
OCOtBu
Cl
Cl
H
Cl
Me
Me
489.1


I-6
OH
Cl
Cl
H
Cl
Me
Me
405.0


I-7
OCOtBu
Cl
Cl
H
Cl
Me
H
475.1


I-8
OH
Cl
Cl
H
Cl
Me
H
391.0


I-9
OCOtBu
Cl
Cl
H
Cl
Et
H
489.0


I-10
OH
Cl
Cl
H
Cl
Et
H
405.0














I-11
OCOtBu
Cl
Cl
H
Cl
CH2CH2
487.1


I-12
OH
Cl
Cl
H
Cl
CH2CH2
403.0















I-13
OCOtBu
OCH3
Cl
H
Cl
H
H
457.0


I-14
OH
OCH3
Cl
H
Cl
H
H
373.0


I-15
OCOtBu
OCH3
Cl
H
Cl
Me
Me
485.1


I-16
OH
OCH3
Cl
H
Cl
Me
Me
401.0


I-17
OCOtBu
OCH3
Cl
H
Cl
Me
H
471.1


I-18
OH
OCH3
Cl
H
Cl
Me
H
387.0














I-19
OCOtBu
OCH3
Cl
H
Cl
CH2CH2
483.1


I-20
OH
OCH3
Cl
H
Cl
CH2CH2
399.0















I-21
OH
Cl
OCH3
H
Cl
H
H
373.0


I-22
OH
Cl
OCH3
H
Cl
Me
Me
401.0


I-23
OH
Cl
OCH2CH3
H
Cl
H
H
387.0


I-24
OH
Cl
OCH2CH3
H
Cl
Me
Me
415.0


I-25
OH
Cl
OCH2CH2OCH3
H
Cl
H
H
417.0


I-26
OH
Cl
OCH2CH2OCH3
H
Cl
Me
Me
444.9


I-27
OH
Br
Cl
H
F
H
H
405.0


I-28
OH
Br
Cl
H
F
Me
Me
432.8


I-29
OH
Cl
Br
H
Cl
H
H
421.0


I-30
OH
Cl
Br
H
Cl
Me
Me
448.9


I-31
OH
Me
Cl
H
Cl
H
H
357.0


I-32
OH
Me
Cl
H
Cl
Me
Me
385.0


I-33
OH
Br
Cl
H
Cl
H
H
422.7


I-34
OH
Br
Cl
H
Cl
Me
Me
451.0














I-35
OH
Me
Cl
H
Cl
CH2CH2
383.0















I-36
OH
Me
Cl
H
F
H
H
340.9


I-37
OH
Me
Cl
H
F
Me
Me
369.0


I-38
OH
F
Cl
H
Cl
H
H
361.0


I-39
OH
F
Cl
H
Cl
Me
Me
389.0


I-40
OH
F
Cl
H
Br
H
H
404.9


I-41
OH
F
Cl
H
Br
Me
Me
433.0


I-42
OH
OCHF2
Cl
H
Cl
H
H
408.9


I-43
OH
OCHF2
Cl
H
Cl
Me
Me
437.0


I-44
OH
Cl
Cl
H
Br
H
H
422.8


I-45
OH
Cl
Cl
H
Br
Me
Me
448.9


I-46
OH
Me
Cl
H
Cl
Me
H
371.0


I-47
OH
cPr
Cl
H
Cl
H
H
383.0


I-48
OH
cPr
Cl
H
Cl
Me
Me
411.0


I-49
OH
Cl
N(CH3)SO2CH3
H
H
H
H
416.0


I-50
OH
Cl
N(CH3)SO2CH3
H
H
Me
Me
441.1


I-51
OH
F
Br
H
Cl
H
H
406.9


I-52
OH
F
Br
H
Cl
Me
Me
433.0


I-53
OH
Cl
Br
H
F
H
H
406.8


I-54
OH
Cl
Br
H
F
Me
Me
434.8


I-55
OH
Cl
N(CH3)COCH3
H
Cl
H
H
414.0


I-56
OH
Cl
N(CH3)COCH3
H
Cl
Me
Me
442.0


I-57
OH
Et
Cl
H
Cl
H
H
370.9


I-58
OH
Et
Cl
H
Cl
Me
Me
399.0


I-59
OH
iPr
Cl
H
Cl
H
H
384.9


I-60
OH
iPr
Cl
H
Cl
Me
Me
413.0





wherein tBu denotes tert-butyl, Me denotes CH3, Et denotes CH2CH3, iPr denotes iso-propyl and cPr denotes cyclopropyl






II. USE EXAMPLES

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 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 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 plants were tended, and their response to the individual treatments was evaluated.


Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.


The plants used in the greenhouse experiments were of the following species:













Bayer code
Scientific name







ABUTH

Abutilon theophrasti



AMARE

Amaranthus retroflexus



CAPBP

Capsella bursa-pastoris


CHEAL

Chenopodium album



ECHCG

Echinocloa crus-galli


POLCO

Polygonum convolvulus



SETFA

Setaria faberi



SETVI

Setaria viridis



STEME

Stellaria media



THLAR

Thlaspi arvense










At an application rate of 0.125 kg/ha, the compound I-16, applied by the post-emergence method, showed very good herbicidal activity against ABUTH.


At an application rate of 0.25 kg/ha, the compound I-1, applied by the post-emergence method, showed very good herbicidal activity against ABUTH.


At an application rate of 0.271 kg/ha, the compound I-19, applied by the post-emergence method, showed very good herbicidal activity against ABUTH.


At an application rate of 0.50 kg/ha, the compound I-11, applied by the post-emergence method, showed very good herbicidal activity against ABUTH.


At an application rate of 1.0 kg/ha, the compounds I-3, I-18, I-20, I-31, I-32, I-34, I-35, I-37, I-46 and I-48, applied by the post-emergence method, showed very good herbicidal activity against ABUTH.


At an application rate of 0.125 kg/ha, the compounds I-15, I-21, I-22, I-25, I-28, I-29, I-39, I-41, I-42, I-44, I-47, I-50, I-52, I-53, I-55 and I-57, applied by the post-emergence method, showed very good herbicidal activity against AMARE.


At an application rate of 0.125 kg/ha, the compounds I-23, I-38 and I-40, applied by the post-emergence method, showed good herbicidal activity against AMARE.


At an application rate of 0.25 kg/ha, the compounds I-1, I-2, I-4, I-5, I-6, I-9, I-13, I-14, I-17, I-22 and I-27, applied by the post-emergence method, showed very good herbicidal activity against AMARE.


At an application rate of 0.271 kg/ha, the compound I-19, applied by the post-emergence method, showed very good herbicidal activity against AMARE.


At an application rate of 1.0 kg/ha, the compounds I-3, I-20, I-31, I-35, I-36 and I-48, applied by the post-emergence method, showed very good herbicidal activity against AMARE.


At an application rate of 0.125 kg/ha, the compounds I-22 and I-26, applied by the post-emergence method, showed very good herbicidal activity against CAPBP.


At an application rate of 0.25 kg/ha, the compound I-7, applied by the post-emergence method, showed very good herbicidal activity against CAPBP.


At an application rate of 0.125 kg/ha, the compounds I-15, I-21, I-25, I-26, I-28, I-29, I-30, I-38, I-39, I-40, I-41, I-42, I-43, I-45, I-47, I-49, I-50, I-51, I-52, I-53, I-54, I-55, I-57 and I-58, applied by the post-emergence method, showed very good herbicidal activity against CHEAL.


At an application rate of 0.25 kg/ha, the compounds I-1, I-2, I-4, I-6, I-7, I-8, I-9, I-12, I-13, I-14, I-17, I-22 and I-27, applied by the post-emergence method, showed very good herbicidal activity against CHEAL.


At an application rate of 0.125 kg/ha, the compounds I-23, I-25, I-41, I-49, I-50, I-51, I-52, I-53, I-55 and I-57, applied by the post-emergence method, showed very good herbicidal activity against ECHCG.


At an application rate of 0.125 kg/ha, the compound I-40, applied by the post-emergence method, showed good herbicidal activity against ECHCG.


At an application rate of 0.25 kg/ha, the compound I-27, applied by the post-emergence method, showed very good herbicidal activity against ECHCG.


At an application rate of 0.50 kg/ha, the compound I-11, applied by the post-emergence method, showed very good herbicidal activity against ECHCG.


At an application rate of 1.0 kg/ha, the compounds I-3, I-18, I-32, I-34, I-37 and I-46, applied by the post-emergence method, showed very good herbicidal activity against ECHCG.


At an application rate of 1.0 kg/ha, the compound I-36, applied by the post-emergence method, showed good herbicidal activity against ECHCG.


At an application rate of 0.125 kg/ha, the compounds I-38, I-42, I-43, I-44, I-45, I-51, I-54 and I-58, applied by the post-emergence method, showed very good herbicidal activity against POLCO.


At an application rate of 0.125 kg/ha, the compound I-39, applied by the post-emergence method, showed good herbicidal activity against POLCO.


At an application rate of 0.25 kg/ha, the compounds I-4, I-5 and I-17, applied by the post-emergence method, showed very good herbicidal activity against POLCO.


At an application rate of 0.125 kg/ha, the compound I-28, applied by the post-emergence method, showed very good herbicidal activity against SETFA.


At an application rate of 0.125 kg/ha, the compounds I-21, I-23, I-26, I-29, I-30, I-43, I-44, I-45, I-47, I-54 and I-58, applied by the post-emergence method, showed very good herbicidal activity against SETVI.


At an application rate of 0.25 kg/ha, the compounds I-2, I-5, I-6, I-8, I-14 and I-22, applied by the post-emergence method, showed very good herbicidal activity against SETVI.


At an application rate of 0.25 kg/ha, the compound I-13, applied by the post-emergence method, showed good herbicidal activity against SETVI.


At an application rate of 0.271 kg/ha, the compound I-19, applied by the post-emergence method, showed very good herbicidal activity against SETVI.


At an application rate of 0.50 kg/ha, the compound I-11, applied by the post-emergence method, showed very good herbicidal activity against SETVI.


At an application rate of 1.0 kg/ha, the compounds I-18, I-20, I-31, I-32, I-34, I-35, I-36, I-37, I-46 and I-48, applied by the post-emergence method, showed very good herbicidal activity against SETVI.


At an application rate of 0.125 kg/ha, the compounds I-15, I-16, I-22 and I-30, applied by the post-emergence method, showed very good herbicidal activity against STEME.


At an application rate of 0.25 kg/ha, the compounds I-7, I-8, I-9 and I-12, applied by the post-emergence method, showed very good herbicidal activity against STEME.


At an application rate of 0.25 kg/ha, the compound I-12, applied by the post-emergence method, showed very good herbicidal activity against THLAR.

Claims
  • 1-15. (canceled)
  • 16: A substituted pyridine compound of the formula I
  • 17: The compound according to claim 16, wherein R is hydroxy or O—RA wherein RA is C1-C6-alkylcarbonyl.
  • 18: The compound according to claim 17, wherein R is hydroxy or 2-methyl-prop-2-ylcarbonyloxy.
  • 19: The compound according to claim 16, wherein R1 is halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • 20: The compound according to claim 19, wherein R1 is selected from the group consisting of F, Cl, Br, CH3, CH2CH3, iso-propyl, cyclopropyl, OCH3 and OCHF2.
  • 21: The compound according to claim 19, wherein R2 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, NRiSO2Rii or NRiCORii wherein Ri and Rii in the groups NRiSO2Rii or NRiCORii are, independently of one another, hydrogen or C1-C4-alkyl.
  • 22: The compound according to claim 21, wherein R2 is selected from the group consisting of H, Cl, Br, OCH3, OCH2CH3, OCH2CH2OCH3, N(CH3)SO2CH3 and N(CH3)COCH3.
  • 23: The compound according to claim 16 wherein R3 is hydrogen, halogen or C1-C4-alkyl.
  • 24: The compound according to claim 16, wherein R4 is hydrogen or halogen.
  • 25: The compound according to claim 16, wherein the groups R1, R2, R3 and R4 together form a substitution pattern selected from the group consisting of: R1=Cl, R2=H, R3=H, R4=Cl;R1=Cl, R2=Cl, R3=H, R4=Cl;R1=Cl, R2=Br, R3=H, R4=Cl;R1=Cl, R2=OCH3, R3=H, R4=Cl;R1=Cl, R2=OCH2CH3, R3=H, R4=Cl;R1=Cl, R2=OCH2CH2OCH3, R3=H, R4=Cl;R1=Cl, R2=O—CH(CH3)2, R3=H, R4=Cl;R1=Cl, R2=OCH3, R3=H, R4=F;R1=Cl, R2=OCH2CH3, R3=H, R4=F;R1=Cl, R2=OCH2CH2OCH3, R3=H, R4=F;R1=Cl, R2=O—CH(CH3)2, R3=H, R4=F;R1=Br, R2=Cl, R3=H, R4=Cl;R1=Br, R2=Cl, R3=H, R4=F;R1=Br, R2=OCH3, R3=H, R4=Cl;R1=Br, R2=OCH2CH3, R3=H, R4=Cl;R1=Br, R2=OCH2CH2OCH3, R3=H, R4=Cl;R1=Br, R2=O—CH(CH3)2, R3=H, R4=Cl;R1=Br, R2=OCH3, R3=H, R4=F;R1=Br, R2=OCH2CH3, R3=H, R4=F;R1=Br, R2=OCH2CH2OCH3, R3=H, R4=F;R1=Br, R2=O—CH(CH3)2, R3=H, R4=F;R1=OCH3, R2=Cl, R3=H, R4=Cl;R1=OCH2CH3, R2=Cl, R3=H, R4=Cl;R1=OCH2CH2OCH3, R2=Cl, R3=H, R4=Cl;R1=O—CH(CH3)2, R2=Cl, R3=H, R4=Cl;R1=F, R2=Cl, R3=H, R4=Cl;R1=CH3, R2=Cl, R3=H, R4=Cl;R1=CH3, R2=Cl, R3=H, R4=F; andR1=OCHF2, R2=Cl, R3=H, R4=Cl.
  • 26: The compound according to claim 16, wherein R5, R6 and R7 are, independently of one another, H or halogen.
  • 27: The compound according to claim 26, wherein R5, R6 and R7 are H.
  • 28: The compound according to claim 16, wherein Rx and Ry independently of one another are H or C1-C5-alkyl, or Rx and Ry together form a bridge —CH2—CH2—.
  • 29: A composition comprising a herbicidally effective amount of at least one compound of the formula I or an agriculturally suitable salt or N-oxide thereof as defined in claim 16 and auxiliaries customary for formulating crop protection agents.
  • 30: A method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one compound of the formula I or of an agriculturally suitable salt or N-oxide thereof as defined in claim 16 to act on plants, their seed and/or their habitat.
  • 31: The method of claim 30, wherein, in the compound of formula I, R is hydroxy or O—RA wherein RA is C1-C6-alkylcarbonyl.
  • 32: The method of claim 31, wherein, in the compound of formula I, R is hydroxy or 2-methyl-prop-2-ylcarbonyloxy.
  • 33: The method of claim 30, wherein, in the compound of formula I, R1 is halogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • 35: The method of claim 33, wherein, in the compound of formula I, R1 is selected from the group consisting of F, Cl, Br, CH3, CH2CH3, iso-propyl, cyclopropyl, OCH3 and OCHF2.
  • 35: The method of claim 33, wherein, in the compound of formula I, R2 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, NRiSO2Rii or NRiCORii wherein Ri and Rii in the groups NRiSO2Rii or NRiCORii are, independently of one another, hydrogen or C1-C4-alkyl.
  • 36: The method of claim 35, wherein, in the compound of formula I, R2 is selected from the group consisting of H, Cl, Br, OCH3, OCH2CH3, OCH2CH2OCH3, N(CH3)SO2CH3 and N(CH3)COCH3.
  • 37: The method of claim 30, wherein, in the compound of formula I, R3 is hydrogen, halogen or C1-C4-alkyl.
  • 24: The method of claim 30, wherein, in the compound of formula I, R4 is hydrogen or halogen.
  • 38: The method of claim 30, wherein, in the compound of formula I, the groups R1, R2, R3 and R4 together form a substitution pattern selected from the group consisting of: R1=Cl, R2=H, R3=H, R4=Cl;R1=Cl, R2=Cl, R3=H, R4=Cl;R1=Cl, R2=Br, R3=H, R4=Cl;R1=Cl, R2=OCH3, R3=H, R4=Cl;R1=Cl, R2=OCH2CH3, R3=H, R4=Cl;R1=Cl, R2=OCH2CH2OCH3, R3=H, R4=Cl;R1=Cl, R2=O—CH(CH3)2, R3=H, R4=Cl;R1=Cl, R2=OCH3, R3=II, R4=F;R1=Cl, R2=OCH2CH3, R3=H, R4=F;R1=Cl, R2=OCH2CH2OCH3, R3=H, R4=F;R1=Cl, R2=O—CH(CH3)2, R3=H, R4=F;R1=Br, R2=Cl, R3=H, R4=Cl;R1=Br, R2=Cl, R3=H, R4=F;R1=Br, R2=OCH3, R3=H, R4=Cl;R1=Br, R2=OCH2CH3, R3=H, R4=Cl;R1=Br, R2=OCH2CH2OCH3, R3=H, R4=Cl;R1=Br, R2=O—CH(CH3)2, R3=H, R4=Cl;R1=Br, R2=OCH3, R3=H, R4=F;R1=Br, R2=OCH2CH3, R3=H, R4=F;R1=Br, R2=OCH2CH2OCH3, R3=H, R4=F;R1=Br, R2=O—CH(CH3)2, R3=H, R4=F;R1=OCH3, R2=Cl, R3=H, R4=Cl;R1=OCH2CH3, R2=Cl, R3=H, R4=Cl;R1=OCH2CH2OCH3, R2=Cl, R3=H, R4=Cl;R1=O—CH(CH3)2, R2=Cl, R3=H, R4=Cl;R1=F, R2=Cl, R3=H, R4=Cl;R1=CH3, R2=Cl, R3=H, R4=Cl;R1=CH3, R2=Cl, R3=H, R4=F; andR1=OCHF2, R2=Cl, R3=H, R4=Cl.
  • 39: The method of claim 30, wherein, in the compound of formula I, R5, R6 and R7 are, independently of one another, H or halogen.
  • 40: The method of claim 30, wherein, in the compound of formula I, R5, R6 and R7 are H.
  • 41: The method of claim 30, wherein, in the compound of formula I, Rx and Ry independently of one another are H or C1-C5-alkyl, or Rx and Ry together form a bridge —CH2—CH2—.
Priority Claims (1)
Number Date Country Kind
13169234.5 May 2013 EP regional
PCT Information
Filing Document Filing Date Country Kind
PCT/EP2014/059809 5/14/2014 WO 00