[go: up one dir, main page]

WO2023030936A1 - Uracil moiety containing thioether compounds for use as herbicides - Google Patents

Uracil moiety containing thioether compounds for use as herbicides Download PDF

Info

Publication number
WO2023030936A1
WO2023030936A1 PCT/EP2022/073275 EP2022073275W WO2023030936A1 WO 2023030936 A1 WO2023030936 A1 WO 2023030936A1 EP 2022073275 W EP2022073275 W EP 2022073275W WO 2023030936 A1 WO2023030936 A1 WO 2023030936A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
alkyl
thioethers
methyl
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2022/073275
Other languages
French (fr)
Inventor
Tobias SEISER
Matthias Witschel
Thomas Seitz
Trevor William Newton
Ricardo Hugo PAVON ROMERO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2023030936A1 publication Critical patent/WO2023030936A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to thioethers of formula (I) defined below and to their use as herbicides.
  • WO 11/137088 describes structurally similar compounds for which herbicidal action is stated.
  • thioethers of formula (I) having improved herbicidal action.
  • thioethers of formula (I) which have high herbicidal activity, in particular even at low application rates, and which are sufficiently compatible with crop plants for commercial utilization.
  • R 1 hydrogen, halogen Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy
  • R 2 hydrogen, halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy
  • R 3 hydrogen, halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy
  • R 5 halogen, CN, NH 2 , NO 2 ;
  • R 6 H halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy
  • R 9 is hydrogen, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-haloalkyl, C3-C6- haloalkenyl, Cs-Ce-haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, C1- Ce-alkoxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, di(Ci-C6-alkoxy)Ci-C6-alkyl, Ci-Ce-halo- alkoxy-Ci-Ce-alkyl, Cs-Ce-alkenyloxy-Ci-Ce-alkyl, Cs-Ce-haloalkenyloxy-Ci-Ce- alkyl, Cs-Ce-alkenyloxy-Ci-Ce-alkoxy-Ci-Ce-al
  • -N CR 12 R 13 , wherein R 12 and R 13 independently of one another are H, C1-C4- alkyl or phenyl;
  • the present invention provides thioethers of formula (I) wherein the substituents have the following meanings:
  • R 9 is H, Ci-Ce-alkyl or Ci-Ce-alkoxy-Ci-Ce-alkyl; n 1;
  • Z CH or N including their agriculturally acceptable salts, amides, esters or thioesters, provided the thioethers of formula (I) have a carboxyl group.
  • the present invention also provides formulations comprising at least one thioether of formula (I) and auxiliaries customary for formulating crop protection agents.
  • the present invention also provides the use of thioethers of formula (I) as herbicides, i.e. for controlling undesired vegetation.
  • the present invention furthermore provides a method for controlling undesired vegetation where a herbicidal effective amount of at least one thioether of the formula (I) is allowed to act on plants, their seeds and/or their habitat.
  • the invention relates to processes and intermediates for preparing thioethers of formula (I).
  • thioethers of formula (I) 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, according to the invention.
  • thioethers of formula (I) 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, according to the invention.
  • thioethers of formula (I) 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 Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl)ammonium, heptylammonium, dodecylammonium, tetrade
  • 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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • Thioethers of formula (I) 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- Ci-Ce-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 Ci-Cw-alkylthio esters.
  • amides such as mono- and di- Ci-Ce-alkylamides or arylamides
  • esters for example as allyl esters, propargyl esters, C1-C10- alkyl esters, alkoxyalkyl esters, tefuryl ((te
  • Preferred mono- and di-Ci-Ce-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.
  • Ci-C4-alkoxy-Ci-C4-alkyl esters are the straight-chain or branched Ci-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 Ci-Cw-alkylthio ester is the ethylthio ester.
  • the organic moieties mentioned in the definition of the variables R 1 to R 14 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 can be straight-chain or branched, the prefix C n -C m denoting in each case the possible number of carbon atoms in the group.
  • Ci-Cs-alkyl for example CH3, C2H5, n-propyl and CH(CH3)2;
  • Ci-C4-alkyl and also the Ci-C4-alkyl moieties of phenyl-Ci-C4-alkyl for example CH3, C2H5, n-propyl, CH(CH 3 ) 2 , n-butyl, CH(CH 3 )-C 2 H 5 , CH 2 -CH(CH 3 ) 2 and C(CH 3 ) 3 ;
  • Ci-C4-haloalkyl Ci-C4-alkyl 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-fluoropropy
  • Ci-Ce-haloalkyl Ci-C4-haloalkyl as mentioned above, and also, for example,
  • C2-C4-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,
  • Cs-Ce-haloalkenyl and also the Cs-Ce-haloalkenyl moieties of Cs-Ce-haloalkenyloxy-Ci-Ce- alkyl a Cs-Ce-alkenyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 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-tribrom
  • C2-C4-alkynyl for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl ;
  • Cs-Ce-haloalkynyl a Cs-Ce-alkynyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 1 ,1 -difl uoroprop-2-yn-1-yl,
  • Ci-Cs-alkoxy for example methoxy, ethoxy, propoxy
  • Ci-C4-alkoxy and also the Ci-C4-alkoxy moieties of Ci-C4-alkyoxycarbonyl for example methoxy, ethoxy, propoxy, 1 -methylethoxy butoxy, 1 -methylpropoxy, 2-methylpropoxy and 1 ,1- dimethylethoxy;
  • Ci-C4-haloalkoxy a Ci-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2- trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,
  • Ci-C4-alkylthio for example methylthio, ethylthio, propylthio, 1 -methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1 , 1-dimethylethylthio;
  • Ci-Ce-alkylsulfonyl (Ci-Ce-alkyl-S(O)2-) and also the Ci-Ce-alkylsulfonyl moieties of Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1- methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methyl-propylsulfonyl, 1 ,1- dimethylethylsulfonyl, pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl, 1 ,2-dimethylpropy
  • (Ci-C4-alkyl)amino for example methylamino, ethylamino, propylamino, 1 -methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino or 1 ,1 -dimethylethylamino;
  • Ca-Ce-heterocyclyl and also the heterocyclyl moieties of Cs-Ce-heterocyclyl-Ci-Ce-alkyl aliphatic heterocycle having 3 to 6 ring members which, in addition to carbon atoms, containsl to 4 nitrogen atoms, or 1 to 3 nitrogen atoms and an oxygen or sulphur atom, or an oxygen or a sulphur atom, for example three- or four-membered heterocycles like 2-oxetanyl, 3-oxetanyl, 2-thietanyl, 3-thietanyl, 1- azetidinyl, 2-azetidinyl, 1-azetinyl, 2-azetinyl; five-membered saturated heterocycles like 2- tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1 -pyrrolidinyl,2- pyrrol
  • 5- or 6 membered heteroaryl aromatic heteroaryl having 5 or 6 ring members which, in addition to carbon atoms, contains 1 to 4 nitrogen atoms, or 1 to 3 nitrogen atoms and an oxygen or sulphur atom, or an oxygen or a sulphur atom, for example 5-membered aromatic rings like furyl (for example 2-furyl, 3-furyl), thienyl (for example 2-thienyl, 3-thienyl), pyrrolyl (for example pyrrol-2-yl, pyrrol-3-yl), pyrazolyl (for example pyrazol-3-yl, pyrazol-4-yl), isoxazolyl (for example isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl), isothiazolyl (for example isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl), imidazolyl (for example imidazo
  • R 3 is H or halogen; preferably is H, F or Cl; more preferred is F or Cl; especially preferred is F.
  • R 4 is H, F or Cl; particularly preferred is F or Cl; especially preferred is F.
  • R 5 is halogen or CN; preferably F, Cl, Br or CN; particularly preferred is F, Cl or Br; especially preferred is Cl or Br; more preferred is Cl; also more preferred is Br.
  • R 6 is H, F, Cl, Br, CH 3 or OCH 3 ; particularly preferred is H, CH 3 or OCH 3 ; especially preferred is H.
  • R 7 is Ci-C 3 -alkoxy; particularly preferred is OCH 3 .
  • R 8 is OR 9 , SR 9 or NR 9 S(O) 2 R 10 ; particularly preferred is OR 9 .
  • R 9 is hydrogen, Ci-Ce-alkyl, C 3 -Ce-alkenyl, C 3 -Ce-alkynyl, Ci-Ce-haloalkyl, C 3 -Ce-haloalkenyl, C 3 -Ce-haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkoxy-Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci-Ce-alkyl, Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C 3 -C6-cycloalkyl, C 3 -Ce- cyclo
  • R 10 is Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-haloalkyl, Cs-Ce-haloalkenyl, C3-C6- haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkoxy-Ci-Ce-alkoxy- Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci-Ce-alkyl, Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, Cs-Ce-cycloalkyl, C3-C6- cycloalkyl-Ci-C
  • R 11 is H, Ci-Ce-alkyl or Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl; particularly preferred is H or Ci-Ce-alkyl; more preferred is H; also more preferred is Ci-Ce-alkyl.
  • R 12 is phenyl or Ci-C4-alkyl; particularly preferred is phenyl or CH3; also particularly preferred is phenyl; also particularly preferred is Ci-C4-alkyl.
  • R 13 is phenyl or Ci-C4-alkyl; particularly preferred is phenyl or CH 3 ; also particularly preferred is phenyl; also particularly preferred is Ci-C4-alkyl.
  • R 14 is halogen or Ci-Ce-alkyl; particularly preferred is F, Cl or CH3; also particularly preferred is halogen; especially preferred is F or Cl; also particularly preferred is Ci-Ce-alkyl; especially preferred is CH3.
  • Q is O, also preferably is S.
  • W is O, also preferably is S.
  • Y 1 is O, also preferably is S.
  • Y 2 is O, also preferably is S.
  • Z is CH, also preferably is N.
  • R° is CH 3 or NH 2 ;
  • R 1 is halogen
  • R 2 is halogen
  • R 3 is hydrogen or halogen
  • R 4 is H or halogen
  • R 5 is halogen or CN
  • R 6 is H, halogen, Ci-Cs-alkyl or Ci-Cs-alkoxy
  • R 7 is Ci-Cs-alkoxy or Ci-Cs-alkylthio
  • R 8 is OR 9 , SR 9 or NR 9 S(O) 2 R 10 , wherein
  • R 9 is hydrogen, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-haloalkyl, C3-C6- haloalkenyl, Cs-Ce-haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce- alkoxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci- Ce-alkyl, Ci-Ce-alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3-C6- cycloalkyl, Cs-Ce-cycloalkyl-Ci
  • R 10 is Ci-C 6 -alkyl; n is 1 ;
  • Q is O or S
  • W, Y 1 , Y 2 are O;
  • Z is CH or N.
  • R 1 is F
  • R 2 is F
  • R 3 is H, F or Cl
  • R 4 is F or Cl
  • R 5 is halogen or CN
  • R 6 is H, F, Cl, Br, CH 3 or OCH 3 ;
  • R 7 is Ci-C 3 -alkoxy
  • R 8 is OR 9 , SR 9 or NR 9 S(O) 2 R 10 , wherein
  • R 9 is hydrogen, Ci-Ce-alkyl, C 3 -Ce-alkenyl, C 3 -Ce-alkynyl, Ci-Ce-cyanoalkyl, Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C 3 - Ce-cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, C 3 -C6-heterocyclyl, C 3 -C6-heterocyclyl- Ci-Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl;
  • R 10 is Ci-C 6 -alkyl; n is 1 ;
  • Q is O or S
  • W, Y 1 , Y 2 are O;
  • Z is CH or N.
  • R° is CH 3 ;
  • R 1 is F
  • R 2 is F
  • R 3 is F or Cl
  • R 4 is F
  • R 5 is F, Cl or Br
  • R 6 is H
  • R 7 is OCH 3 ;
  • R 8 is OR 9 , wherein
  • R 9 is hydrogen, Ci-Ce-alkyl, C 3 -Ce-alkenyl, C 3 -Ce-alkynyl, Ci-Ce-cyanoalkyl, Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C 3 - Ce-cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, C 3 -C6-heterocyclyl, C 3 -C6-heterocyclyl- Ci-Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl; n is 1 ;
  • Q is O or S
  • W, Y 1 , Y 2 are O;
  • Z is CH or N.
  • R° is CH 3 ;
  • R 1 is F
  • R 2 is F
  • R 3 is F or Cl
  • R 4 is F
  • R 5 is Cl or Br
  • R 6 is H
  • R 7 is OCH 3 ;
  • R 8 is OR 9 , wherein
  • R 9 is hydrogen, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-alkoxy-Ci-Ce- alkyl; n is 1;
  • Z is CH or N.
  • R 2 is H or halogen
  • R 5 is halogen or CN
  • R 7 is Ci-Cs-alkoxy
  • R 8 is OR 9 , wherein
  • R 9 is H, Ci-C4-alkyl or Ci-C 6 -alkoxy-Ci-C 6 -alkyl;
  • Z is CH or N.
  • R 2 is H or F
  • R 5 is F, Cl, BrorCN
  • R 7 is OCH 3 ;
  • R 8 is OR 9 , wherein
  • R 9 is H, CH 3 , C2H5, CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 or CH 2 CH 2 OCH 3 ;
  • thioethers of formula (l.a) corresponds to formula (I) wherein R° is CH3, R 1 is F, R 3 and R 4 are F, R 6 is H, n is 1, Q, W, Y 1 and Y 2 are O and Z is CH
  • R 2 , R 5 , R 7 and R 8 have the meanings, in particular the preferred meanings, as defined above.
  • thioethers of formula (l.b) particularly preferred the thioethers of formulae (l.b.1) to l.b.48, which differ from the corresponding thioethers of formulae (l.a.1) to (I. a.48) only in that Z is N:
  • thioethers of formula (l.c) particularly preferred the thioethers of formulae (l.c.1) to (l.c.48), which differ from the corresponding thioethers of formulae (l.a.1) to (I. a.48) only in that Q is S:
  • thioethers of formula (l.d) particularly preferred the thioethers of formulae (l.d.1) to (l.d.48), which differ from the corresponding thioethers of formulae (l.a.1) to (I. a.48) only in that Q is S and Z is N:
  • the thioethers of formula (I) according to the invention can be prepared by standard processes of organic chemistry, for example by the following processes:
  • the thioethers of formula (I) are obtained from the acid halides of formula (II) by reaction with compounds of formula (III) in the presence of a base:
  • L 1 is halogen; preferably is F, Cl or Br; especially preferred is F or Cl, more preferred is Cl.
  • acid halides of formula (II) instead of the acid halides of formula (II), also the corresponding acid (e.g. acid halide of formula (II), wherein L 1 is OH) in combination with an activating reagent, like carbonyldiimidazole, N,N'-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3- dimethylaminopropyl)- , carbodiimide (EDC) or N-methyl-2-chloropyridinium chloride can be used.
  • an activating reagent like carbonyldiimidazole, N,N'-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3- dimethylaminopropyl)- , carbodiimide (EDC) or N-methyl-2-chloropyridinium chloride.
  • an activating reagent like carbonyldiimidazole, N,N'-
  • the compounds (III) can also be employed in the form of their salts, in particular the sodium and potassium salts, in which case the presence of a base is not necessary.
  • the reaction of acid halides (II) with compounds (III) is usually carried out from 0 °C to the boiling point of the reaction mixture, preferably at from 0 °C to 100 °C, particularly preferably at from 0 °C to 40 °C, in an inert organic solvent in the presence of a base.
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the acid halides (II) with the compounds (III) in an organic solvent. Suitable in principle are all solvents, which are capable of dissolving the acid halides (II) and the compounds (III) at least partly, and preferably fully under reaction conditions.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, nitromethane and mixtures of C5-C8-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene, tolene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetra hydrofuran (THF); esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile; ketones such as acetone, methyl ethyl ketone, diethyl
  • Preferred solvents are halogenated hydrocarbons, ethers and dipolar aprotic solvents as mentioned above.
  • suitable bases include metal-containing bases and nitrogen-containing bases.
  • suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate; alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; and furthermore organic bases, such as tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidinge, ter
  • nitrogen-containing bases are C1-C6-alkylamines, preferably trialkylamines, for example triethylamine, trimethylamine, N-ethyhdiisopropyhamine; pyridine, lutidine, collidine, 4-(dimethylamino)pyridine (DMAP), imidazole, 1 ,8-diazabicyclo[5.4.0]undec-7- ene (DBU) or 1 ,5-diazabhcyclo- , [4.3.0]-'non-5-ene (DBN).
  • C1-C6-alkylamines preferably trialkylamines, for example triethylamine, trimethylamine, N-ethyhdiisopropyhamine
  • pyridine lutidine, collidine, 4-(dimethylamino)pyridine (DMAP), imidazole, 1 ,8-diazabicyclo[5.4.0]undec-7- ene (DBU) or
  • Preferred bases are alkali metal and alkaline earth metal carbonates and nitrogen-containing bases as defined above; especially preferred triethylamine, pyridine or sodium carbonate.
  • base as used herein also includes mixtures of two or more, preferably two of the above compounds. Particular preference is given to the use of one base.
  • the bases are generally used in excess, more preferably with from 1 to 3 equivalents based on the acid halides (II), and they may also be used as the solvent. However, they can also be employed in catalytic amounts.
  • the acid halides (II), the compounds (III) and the base can be brought into contact in any way per se.
  • reaction partners and the base may be introduced into the reaction vessel and reacted separately, simultaneously or successively.
  • the reactants are generally employed in equimolar amounts. It might be advantageous using one of the reactants in excess, for example with a view to complete a reaction of the other reactant.
  • the reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
  • the end of the reaction can easily be determined by the skilled worker by means of routine methods.
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separation of the phases and, if appropriate, chromatographic purification of the crude product.
  • Some of the intermediates and end products are obtained in the form of viscous oils, which can be purified or freed from volatile components under reduced pressure and at moderately elevated temperature.
  • purification can also be carried out by recrystallisation or digestion.
  • the thioethers of formula (I) can also be prepared by reaction of compounds of formula (IV) with alkylating agents of formula (V) in the presence of a base in analogy to known processes (e.g.
  • L 2 is a leaving group such halogen, Ci-Ce-alkyl- sulfonate or arylsulfonate; preferably Cl or Br.
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the compounds of formula (IV) with the alkylating agents of formula (V) in an organic solvent.
  • Suitable in principle are all solvents which can dissolve the compounds of formula (IV) and the alkylating agents of formula (V) at least partly and preferably fully under reaction conditions.
  • suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethyl- acetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2
  • suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as lithium
  • alkylating agents of formula (V) are commercially available or can be prepared by known methods (e.g. Lowell, Andrew N. et al, Tetrahedron, 6(30), 5573-5582, 2010; WO 11/137088).
  • PG is a protecting group selected from the group consisting of Ci-Ce-alkyl, Ci-Ce--cyanoalkyl, Ci-Ce-haloalkyl, Ci-C6-alkylthio-C1-C4-alkyl, Ci-Ce- alkoxy- Ci-C4-alkyl, Ci-Ce-alkoxy- Ci-C4-alkoxy- Ci-C4-alkyl, (tri- Ci-Ce-alkyl)silyl- Ci-C4-alkyl, (tri- Ci-Ce-alkyl)silyl- Ci-C4-alkyoxy- Ci-C4-alkyl, C2-Ce-alkenyl, Cs-Ce-alkynyl, Cs-Ce-cycloalkyl, Cs-Ce-cylcloalkyl- Ci-C4-alkyl, Cs-Ce-cycloalkenyl, tetrahydr
  • PG is Ci-Ce-alkyl, Ci-C6-alkoxy-Ci-C4-alkyl, (tri- Ci-Ce-alkyl)silyl-C1 -C4-alkyl, C2-C6- alkenyl, tetrahydropyranyl, (tri-Ci-C6-alkyl)silyl, [(diphenyl)(Ci-C4-alkyl)]silyl or phenyl-Ci-C4- alkyl.
  • the compounds of formula (IV) can be prepared by treating the compounds of formula (VI), wherein “PG” is methyl, with boron tribromide in a solvent such as dichloromethane, acetonitrile or 1 ,4-dioxane, or without a solvent at temperatures ranging from 0 °C to 150 °C.
  • a solvent such as dichloromethane, acetonitrile or 1 ,4-dioxane
  • compounds of formula (IV) can be prepared by deprotecting compounds of formula (VI), wherein “PG” is a benzyl group, by catalytic hydrogenation in a hydrogen gas atmosphere at a pressure of 70 to 700 kPa, preferably 270 to 350 kPa, in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20% of metal to carrier, suspended in a solvent such as ethanol at ambient temperature.
  • PG is a benzyl group
  • the Sandmeyer reaction is performed by diazotization with an alkyl nitrite (e.g. isoamyl nitrite, tert-Butyl nitrite or NaNO2) followed by treatment with a copper (I) and/or copper (II) halide (e.g. CuCI, CuCh, CuBr, CuBr2 or CuCN) in a solvent such as acetonitrile at a temperature ranging from 0 °C to the reflux temperature of the solvent to give the corresponding phenyluracils of formula (I), wherein R 5 is a Cl, Br or CN (e.g. WO 2011/137088, or L. Kurti, B. Czako Strategic Applications of Named Reactions in Organic Synthesis, Elsevier: San Diego, 2005, p. 394-395)
  • an alkyl nitrite e.g. isoamyl nitrite, tert-Butyl nitrite or NaNO2
  • reaction conditions can be used, adding instead of a copper salt an iodine salt such as potassium iodide after diazotization.
  • tetrafluoroborate salts of the diazonium compound can be used. These are obtained by adding hydrogene tetrafluoroborate during the diazotization. Subsequent thermal or photolytical decomposition delivers the corresponding fluoro compounds (Langlois, B. In Introduction of Fluorine via Diazonium Compounds (Fluorodediazoniation); Baasner, B., Hagemann, H., Tatlow, J. C., Eds.; Houben- Weyl, Methods of Organic Chemistry; Thieme: Stuttgart, 1999; Vol. E10a, Organo-Fluorine Compounds, pp 686-740).
  • the reaction of amino compounds of formula (VII) with a diazotization agent and optionally copper salts is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 0°C to 100°C, particularly preferably from 0°C to 40°C, in an inert solvent.
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the amino compounds of formula (VII) with the copper salts and the diazotization agent in an organic solvent.
  • Suitable in principle are all solvents, which are capable of dissolving the amino compounds of formula (VII), the copper salts and the diazotization agent at least partly, and preferably fully under reaction conditions.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, nitromethane and mixtures of C5-C8-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene, tolene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetra hydrofuran (THF); esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile; ketones such as acetone, methyl ethyl ketone, diethyl
  • Preferred solvents are nitriles or polar protic solvents as mentioned above. It is also possible to use mixtures of the solvents mentioned.
  • the copper salts are generally used in excess, more preferably from 1 to 3 equivalents based on the amino compounds of formula (VII).
  • the diazotization agent is generally used in excess, more preferably from 1 to 3 equivalents based on the amino compounds of formula (VII).
  • the amino compounds of formula (VII), the copper salts and the diazotization agent can be brought into contact in any way per se.
  • the reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
  • the copper salts and the diazotization agents are commercially available.
  • Amino compounds of formula (VII) can be prepared from nitro compounds of formula (VIII) using reduction conditions:
  • the reduction of the nitro group on can be achieved by treatment with iron powder in acetic acid at a temperature ranging from 0 °C to 100 °C.
  • the reduction can be carried out by catalytic hydrogenation in hydrogen gas at a pressure of 70 to 700 kPa, preferably 270 to 350 kPa, in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20% of metal to carrier, suspended in a solvent such as ethanol at ambient temperature (see e.g. WO 2011/137088).
  • the reaction of nitro compounds of formula (VIII) with the reducing agent is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 20°C to the boiling point of the reaction mixture, in an inert solvent.
  • the reaction may in principle be carried out in substance.
  • Suitable in principle are all solvents, which can dissolve the nitro compounds of formula (VIII), at least partly, and preferably fully under reaction conditions.
  • Suitable solvents are alcohols such as ethanol.
  • the reducing agents are generally used in excess, more preferably with from 1 to 6 equivalents based on the nitro compounds.
  • the reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
  • the reducing agents are commercially available.
  • Nitro compounds of formula (VIII) can be prepared from compounds of formula (IX) in the presence of a base using compounds of formula (X):
  • L 3 is a leaving group such halogen, Ci-Ce-alkylsulfonate or arylsulfonate; preferably F, Ci-Ce-alkylsulfonate or arylsulfonate; especially preferred F, mesylat or tosylat.
  • reaction of the compounds of formula (IX) with compounds of formula (X) in presence of a base is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 20°C to 100°C.
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the compounds of formula (IX) with the compounds of formula (X) in an organic solvent. Suitable in principle are all solvents which can dissolve the compounds of formula (IX) and the compounds of formula (X) at least partly and preferably fully under reaction conditions.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, nitromethane and mixtures of Cs-Cs-alkanes, aromatic hydrocarbons such as benzene, chlorobenzene, toluene, cresols, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, 1 ,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetra hydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfo
  • Preferred solvents are ethers, nitriles and dipolar aprotic solvents as mentioned above.
  • suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbon
  • L 4 is a leaving group such F, Ci-Ce-alkylsulfonate or arylsulfonate; preferably F, mesylat or tosylat;
  • the reaction of the uracils of formula (XI) with compounds of formula (XII) in presence of a base is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 20°C to 100°C.
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the uracils of formula (XI) with the compounds of formula (XII) in an organic solvent.
  • Suitable in principle are all solvents which can dissolve the uracils of formula (XI) and the compounds of formula (XII) at least partly and preferably fully under reaction conditions.
  • suitable solvents are dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2- imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and 1- methyl-2 pyrrolidinone (NMP).
  • dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2- imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPU
  • suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as lithium
  • reaction of the compounds of formula (XIII) in presence of an acid is usually carried out from 20°C to the boiling point of the reaction mixture, preferably from 50°C to 100°C.
  • the reaction may in principle be carried out in substance. However, preference is given to reacting the compounds of formula (XIII) in an organic solvent.
  • Suitable in principle are all solvents which can dissolve the compounds of formula (XIII) at least partly and preferably fully under reaction conditions.
  • Suitable solvents are alcohols such as ethanol.
  • Suitable acids are Bronsted acids, such as HCI or H2SO4.
  • keto-esters of formula (XIV) with ureas of formula (XV) may in principle be carried out in substance. However, preference is given to reactions in an organic solvent. Suitable in principle are all solvents which can dissolve keto-esters of formula (XIV) and ureas of formula (XV) at least partly and preferably fully under reaction conditions.
  • suitable solvents are aromatic hydrocarbons such as benzene, chlorobenzene, toluene, cresols, o-, m- and p-xylene, nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N '-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
  • aromatic hydrocarbons such as benzene, chlorobenzene, toluene, cresols, o-, m- and p-xylene
  • nitriles such as acetonitrile and propionitrile
  • keto-esters of formula (XIV) with ureas of formula (XV) is usually carried out from 20°C to the boiling point of the reaction mixture, preferably from 60°C to 140°C.
  • Keto-esters of formula (XIV) can be prepared by reaction of esters of formula (XVI) with an acetic acid ester of formula (XVII) in the presence of a base:
  • the reaction may be carried out in substance. However, it also possible reacting the esters of formula (XVI) with an acetic acid ester of formula (XVII) in an organic solvent.
  • Suitable in principle are all solvents which can dissolve esters of formula (XVI) and an acetic acid ester of formula (XVII) at least partly and preferably fully under reaction conditions.
  • Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N- dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
  • ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), di
  • suitable metal-containing bases are alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; metal organic compounds, preferably alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alkoxides such as potassium tert-butoxide.
  • alkali metal and alkaline earth metal hydrides such as lithium hydr
  • Esters of formula (XVI) and acetic acid ester of formula (XVII) are known from literature and/or commercially available.
  • the thioethers of formula (I) may be mixed with many representatives of other herbicidal or growth-regulating active ingredient groups and then applied concomitantly.
  • Suitable components for combinations are, for example, herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenyl
  • thioethers 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.
  • 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 invention also relates to formulations comprising at least an auxiliary and at least one thioethers of formula (I) according to the invention.
  • a formulation comprises a pesticidally effective amount of a thioether of formula (I).
  • effective amount denotes an amount of the combination or of the thioethers of formula (I), which is sufficient for controlling undesired vegetation, especially for controlling undesired vegetation in crops (i.e. cultivated plants) and which does not result in a substantial damage to the treated crop plants.
  • Such an amount can vary in a broad range and is dependent on various factors, such as the undesired vegetation to be controlled, the treated crop plants or material, the climatic conditions and the specific thioether of formula (I) used.
  • the thioethers of formula (I), their N-oxides, salts amides, esters or thioesters can be converted into customary types of formulations, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g.
  • WP 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
  • gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • the formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • toluene paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • alcohols e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol
  • glycols DMSO
  • ketones e.g. cyclohexanone
  • esters e.g. lactates, carbonates, fatty acid esters,
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • 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 thioethers 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 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.
  • a thioether of formula (I) according to the invention 5-25 wt% of a thioether of formula (I) 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.
  • dispersant e. g. polyvinylpyrrolidone
  • organic solvent e.g. cyclohexanone
  • a thioether of formula (I) 5-40 wt% of a thioether of formula (I) according to the invention and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% waterinsoluble organic solvent (e.g. aromatic hydrocarbon).
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • waterinsoluble organic solvent e.g. aromatic hydrocarbon
  • a thioether of formula (I) In an agitated ball mill, 20-60 wt% of a thioether of formula (I) according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type formulation up to 40 wt% binder (e.g. polyvinylalcohol) is added.
  • WG, SG Water-dispersible granules and water-soluble granules
  • thioether of formula (I) 50-80 wt% of a thioether of formula (I) 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.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • a thioether of formula (I) 50-80 wt% of a thioether of formula (I) 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.
  • dispersants e.g. sodium lignosulfonate
  • wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a thioether of formula (I) In an agitated ball mill, 5-25 wt% of a thioether of formula (I) 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.
  • dispersants e.g. sodium lignosulfonate
  • 1-5 wt% thickener e.g. carboxymethylcellulose
  • a thioether of formula (I) 5-20 wt% 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.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a thioether of formula (I) 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.
  • an oil phase comprising 5-50 wt% of a thioether of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g.
  • a thioether of formula (I) according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
  • solid carrier e.g. finely divided kaolin
  • according to the invention is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%.
  • solid carrier e.g. silicate
  • Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • a thioether of formula (I) 1-50 wt% of a thioether of formula (I) according to the invention are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
  • organic solvent e.g. aromatic hydrocarbon
  • the formulation types i) to xi) may optionally comprise further auxiliaries, such as 0,1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1-1 wt% colorants.
  • the formulations 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 thioether of formula (I).
  • the thioethers of formula (I) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the formulations in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • Methods for applying thioethers of formula (I), formulations thereof, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • thioethers of formula (I), formulations 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.
  • oils e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • thioethers of formula (I) may be added to the thioethers of formula (I), the formulations comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the formulations according to the invention in a weight ratio of 1 :100 to 100:1, preferably 1 :10 to 10:1.
  • the user applies the thioethers of formula (I) according to the invention, the formulations comprising them usually from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the formulation is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the formulation according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • either individual components of the formulation according to the invention or partially premixed components e. g. components comprising thioethers of formula (I) may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • individual components of the formulation according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the formulation according to the invention or partially premixed components, e. g components comprising thioethers of formula (I) can be applied jointly (e.g. after tank mix) or consecutively.
  • the thioethers of formula (I), are suitable as herbicides. They are suitable as such or as an appropriately formulation.
  • the thioethers of formula (I), or the formulations comprising the thioethers of formula (I), control undesired vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
  • the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) have an outstanding herbicidal activity against undesired vegetation, i.e. against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous weeds.
  • the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) are used to control monocotyledonous weeds.
  • Examples of monocotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the genera Hordeum spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp., Eriochloa spp., Setaria spp., Pennisetum spp., Eleusine spp., Eragrostis spp., Panicum spp., Lolium spp., Brachiaria spp., Leptochloa spp., Avena spp., Cyperus spp., Axonopris spp., Sorghum spp., and Melinus spp..
  • Preferred examples of monocotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Hordeum murinum, Echinochloa crus-galli, Poa annua, Bromus rubens L., Bromus rigidus, Bromus secalinus L., Digitaria sanguinalis, Digitaria insularis, Eriochloa gracilis, Setaria faberi, Setaria viridis, Pennisetum glaucum, Eleusine indica, Eragrostis pectinacea, Panicum miliaceum, Lolium multiflorum, Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus compressus, Cyperus esculentes, Axonopris offinis, Sorghum halapense, and Melinus repens.
  • Especially preferred examples of monocotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Echinochloa spp., Digitaria spp., Setaria spp., Eleusine spp. and Brachiarium spp.
  • the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) are used to control dicotyledonous weeds.
  • dicotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the genera Amaranthus spp., Erigeron spp., Conyza spp., Polygonum spp., Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp., Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp., Erodium spp., Erigeron spp., Senecio spp., Lamium spp., Kochia spp., Chenopodium spp., Lactuca spp
  • Preferred examples of dicotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Amaranthus spinosus, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum offi cinale, Oenothera laciniata, Amsinckia intermedia, Erodium cicutarium, Erodium moschatum, Erigeron bonariensis (Conyza bonariensis), Senecio vulgaris, Lamium amplexicaule, Erigeron canadensis, Polygonum aviculare, Kochia scoparia, Chenopodium album, Lactuca serriola, Malva parviflora, Malva neglecta, Ipomoea hederacea, Ipomoea
  • dicotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Amaranthus spp., Erigeron spp., Conyza spp., Kochia spp. and Abutilon spp.
  • the thioethers of formula (I), or the formulations comprising them are applied to the plants mainly by spraying the leaves.
  • the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 100 to 1000 l/ha (for example from 300 to 400 l/ha).
  • the thioethers of formula (I), or the formulations comprising them may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.
  • thioethers of formula (I), or the formulations comprising them can be done before, during and/or after, preferably during and/or after, the emergence of the undesired vegetation.
  • thioethers of formula (I), or the formulations can be carried out before or during sowing.
  • the thioethers of formula (I), or the formulations comprising them can be applied pre-, postemergence or pre-plant, or together with the seed of a crop plant. It is also possible to apply the thioethers of formula (I), or the formulations comprising them, by applying seed, pretreated with the thioethers of formula (I), or the formulations comprising them, of a crop plant.
  • application techniques may be used in which the combinations are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesired vegetation growing underneath, or the bare soil surface (post-directed, lay-by).
  • the thioethers of formula (I), or the formulations 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 thioethers of formula (I), or the formulations prepared therefrom.
  • the combinations can be applied diluted or undiluted.
  • seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms.
  • seed describes corns and seeds.
  • the seed used can be seed of the crop plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
  • the amounts of active substances applied i.e. the thioethers of formula (I) 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 0.01 to 0.9 kg per ha and in particular from 0.02 to 0.5 kg per ha.
  • the application rate of the thioethers of formula (I) 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.).
  • the rates of application of the thioethers of formula (I) according to the present invention 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.
  • the application rates of the thioethers 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.
  • the application rate of the thioethers of formula (I) is 0.1 to 1000 g/ha, preferably 1 to 750 g/ha, more preferably 5 to 500 g/ha.
  • 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.
  • the amounts of active substances applied i.e. the thioethers of formula (I) are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
  • 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.
  • the thioethers of formula (I), or the formulations comprising them can additionally be employed in a further number of crop plants for eliminating undesired vegetation.
  • all the crop plants (cultivated plants) mentioned herein are understood to comprise all species, subspecies, variants and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
  • corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn.
  • all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).
  • soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856).
  • the indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (Maturity Group, (MG) 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins.
  • all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
  • 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 s
  • Especially preferred crops are crops of cereals, corn, soybeans, rice, oilseed rape, cotton, peas, lentils, peanuts or permanent crops.
  • thioethers of formula (I) according to the invention can also be used in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
  • crops as used herein includes also (crop) plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
  • Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome.
  • Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
  • Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination.
  • one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants.
  • the process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
  • Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.
  • ALS acetolactate synthase
  • Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4- hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
  • HPPD 4- hydroxyphenylpyruvate dioxygenase
  • Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
  • Transgenic corn events comprising herbicide tolerance genes are for example, but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO- 01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
  • Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS- 81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
  • Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
  • Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1 , MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
  • Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants.
  • Transgenes which have most frequently been used are toxin genes of Bacillus spec, and synthetic variants thereof, like cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.1O5, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), vip3Aa20.
  • genes of plant origin have been transferred to other plants.
  • genes coding for protease inhibitors like CpTI and pinll.
  • a further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes.
  • An example for such a transgene is dvsnf7.
  • Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
  • Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701 , MON87751 and DAS-81419.
  • Transgenic cotton events comprising genes for insecticidal proteins are for example, but not excluding others, SGK321 , MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601 , Eventl , COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
  • Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
  • Crops comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
  • Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb- 4, comprised by soybean event IND-00410-5.
  • Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process.
  • Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.
  • Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art.
  • detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-qmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and W02017/011288.
  • ISAAA International Service for the Acquisition of Agri-biotech Applications
  • CERA Center for Environmental Risk Assessment
  • effects which are specific to a crop comprising a certain gene or event may result in effects which are specific to a crop comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
  • 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).
  • 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).
  • the thioethers of formula (I) according to the invention are also suitable for the defoliation and/or desiccation of plant parts of crops such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton.
  • crops such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton.
  • formulations for the desiccation and/or defoliation of crops processes for preparing these formulations and methods for desiccating and/or defoliating plants using the thioethers of formula (I) have been found.
  • the thioethers of formula (I) are particularly suitable for desiccating the aboveground 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.
  • Example 1 - step 1 6-hydroxy-1-methyl-6-(trifluoromethyl)hexahydropyrimidine-2, 4-dione
  • Example 1 - step 8 methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]sul- fanylphenoxy]-2-methoxy-acetate
  • 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.
  • the active ingredients which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
  • the containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the test plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients.
  • 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.
  • test plants were kept at 10 - 25°C or 20 - 35°C, respectively.
  • the test period extended over 2 to 3weeks. During this time, the test plants were tended, and their response to the individual treatments was evaluated.
  • Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the test plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
  • test plants used in the greenhouse experiments were of the following species:
  • the thioether I. a.38 (example) 1 applied post-emergent showed very good herbicidal activity against AMARE, CHEAL, POLCO and SETVI.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to thioethers of formula (I), or their agriculturally acceptable salts or derivatives, wherein the variables are defined according to the description, compositions comprising them and their use as herbicides, i.e. for control-ling harmful plants, and also a method for controlling unwanted vegetation which comprises allowing a herbicidal effective amount of at least one thioether of formula (I) to act on plants, their seed and/or their habitat.

Description

URACIL MOIETY CONTAINING THIOETHER COMPOUNDS FOR USE AS HERBICIDES
The present invention relates to thioethers of formula (I) defined below and to their use as herbicides.
WO 11/137088 describes structurally similar compounds for which herbicidal action is stated.
However, the herbicidal properties of these known compounds regarding the undesired vegetation are not always entirely satisfactory.
It is therefore an object of the present invention to provide thioethers of formula (I) having improved herbicidal action. To be provided are in particular thioethers of formula (I) 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 thioethers of formula (I), defined below, and by their agriculturally suitable salts.
Accordingly, the present invention provides thioethers of formula (I)
Figure imgf000002_0001
wherein the substituents have the following meanings:
R° Ci-C3-alkyl or NH2;
R1 hydrogen, halogen Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; R2 hydrogen, halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; R3 hydrogen, halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; R4 H or halogen;
R5 halogen, CN, NH2, NO2;
R6 H, halogen, Ci-Cs-alkyl, Ci-Cs-alkoxy;
R7 Ci-Cs-alkoxy or Ci-Cs-alkylthio;
R8 OR9, SR9, NR10R11, NR9OR9, NR9S(O)2R10 or NR9S(O)2NR10R11, wherein
R9 is hydrogen, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-haloalkyl, C3-C6- haloalkenyl, Cs-Ce-haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, C1- Ce-alkoxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, di(Ci-C6-alkoxy)Ci-C6-alkyl, Ci-Ce-halo- alkoxy-Ci-Ce-alkyl, Cs-Ce-alkenyloxy-Ci-Ce-alkyl, Cs-Ce-haloalkenyloxy-Ci-Ce- alkyl, Cs-Ce-alkenyloxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci-Ce-alkyl, Ci-Ce-alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce- alkylcarbonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, Ci-Ce- haloalkoxycarbonyl-Ci-Ce-alkyl, Cs-Ce-alkenyloxycarbonyl-Ci-Ce-alkyl, C3-C6- alkynyloxycarbonyl-Ci-Ce-alkyl, amino, (Ci-C6-alkyl)amino, di(Ci-Ce- alkyl)amino, (Ci-C6-alkylcarbonyl)amino, amino-Ci-Ce-alkyl, (C Ce- alkyl)amino-Ci-C6-alkyl, di(Ci-C6-alkyl)amino-Ci-C6-alkyl, aminocarbonyl-Ci- Ce-alkyl, (Ci-C6-alkyl)aminocarbonyl-Ci-C6-alkyl, di(Ci-C6-alkyl)aminocarbonyl- Ci-C6-alkyl,
-N=CR12R13, wherein R12 and R13 independently of one another are H, C1-C4- alkyl or phenyl;
Cs-Ce-cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, Ca-Ce-heterocyclyl, C3-C6- heterocyclyl-Ci-Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl or a 5- or 6 membered heteroaryl, wherein each cycloalkyl, heterocyclyl, phenyl or heteroaryl ring can be substituted by one to four substituents selected from R14 or a 3- to 7- membered carbocyclus, which carbocyclus optionally has in addition to carbon atoms one or two ring members selected from the group consisting of -N(R12)-, -N=N-, -C(=O)-, -O- and -S-, and which carbocyclus is optionally substituted with one to four substituents selected from R14; wherein R14 is halogen, NO2, CN, Ci-C4-alkyl, Ci-C4-halo- alkyl, Ci-C4-alkoxy or Ci-C4-alkoxycarbonyl;
R10, R11 independently of one another are R9, or together form a 3- to 7-membered carbocyclus, which carbocyclus optionally has in addition to carbon atoms one or two ring members selected from the group consisting of -N(R12)-, -N=N-, - C(=O)-, -O- and -S-, and which carbocyclus is optionally substituted with one to four substituents selected from R14; n 1 to 3;
Q, W, Y1, Y2 independently of one another O or S;
Z CH or N; including their agriculturally acceptable salts, amides, esters or thioesters, provided the compounds of formula (I) have a carboxyl group.
Preferably the present invention provides thioethers of formula (I)
Figure imgf000003_0001
wherein the substituents have the following meanings:
R° CH3;
R1 F;
R2 H or halogen;
R3 F;
R4 F; R5 halogen or CN;
R6 H;
R7 Ci-Cs-alkoxy;
R8 OR9, wherein
R9 is H, Ci-Ce-alkyl or Ci-Ce-alkoxy-Ci-Ce-alkyl; n 1;
Q O or S;
W, Y1, Y2 O;
Z CH or N; including their agriculturally acceptable salts, amides, esters or thioesters, provided the thioethers of formula (I) have a carboxyl group.
The present invention also provides formulations comprising at least one thioether of formula (I) and auxiliaries customary for formulating crop protection agents.
The present invention also provides the use of thioethers of formula (I) as herbicides, i.e. for controlling undesired vegetation.
The present invention furthermore provides a method for controlling undesired vegetation where a herbicidal effective amount of at least one thioether of the formula (I) is allowed to act on plants, their seeds and/or their habitat.
Moreover, the invention relates to processes and intermediates for preparing thioethers of formula (I).
If the thioethers of formula (I) 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, according to the invention.
If the thioethers of formula (I) 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, according to the invention.
If the thioethers of formula (I) 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 Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl)ammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium (olamine salt), 2-(2- hydroxyeth-1-oxy)eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (diolamine salt), tris(2-hydroxyethyl)ammonium (trolamine salt), tris(2- hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N- trimethylethanolammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(Ci-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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
Thioethers of formula (I) 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- Ci-Ce-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 Ci-Cw-alkylthio esters. Preferred mono- and di-Ci-Ce-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 Ci-C4-alkoxy-Ci-C4-alkyl esters are the straight-chain or branched Ci-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 Ci-Cw-alkylthio ester is the ethylthio ester.
The organic moieties mentioned in the definition of the variables R1 to R14 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 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:
Ci-Cs-alkyl: for example CH3, C2H5, n-propyl and CH(CH3)2;
Ci-C4-alkyl and also the Ci-C4-alkyl moieties of phenyl-Ci-C4-alkyl: for example CH3, C2H5, n-propyl, CH(CH3)2, n-butyl, CH(CH3)-C2H5, CH2-CH(CH3)2 and C(CH3)3;
Ci-Ce-alkyl and also the Ci-Ce-alkyl moieties of Ci-Ce-cyanoalkyl, Ci-Ce-alkyoxy-Ci-Ce- alkyl, Ci-Ce-alkoxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, di(Ci-C6-alkoxy)Ci-Ce-alkyl, Ci-Ce-haloalkoxy-Ci- Ce-alkyl, Cs-Ce-alkenyloxy-Ci-Ce-alkyl, Cs-Ce-haloalkenyloxy-Ci-Ce-alkyl, Cs-Ce-alkenyloxy-Ci- Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci-Ce-alkyl, Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkylcarbonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C1- Ce-haloalkoxycarbonyl-Ci-Ce-alkyl, Cs-Ce-alkenyloxycarbonyl-Ci-Ce-alkyl, C3-C6- alkynyloxycarbonyl-Ci-Ce-alkyl, (Ci-C6-alkylcarbonyl)amino, amino-Ci-Ce-alkyl, (Ci-Ce- alkyl)amino-Ci-C6-alkyl, di(Ci-C6-alkyl)amino-Ci-C6-alkyl, aminocarbonyl-Ci-Ce-alkyl, (Ci-Ce- alkyl)aminocarbonyl-Ci-C6-alkyl, di(Ci-C6-alkyl)aminocarbonyl-Ci-C6-alkyl, Cs-Ce-cycloalkyl-Ci- Ce-alkyl, Cs-Ce-heterocyclyl-Ci-Ce-alkyl: Ci-C4-alkyl as mentioned above, and also, for example, n-pentyl, 1 -methyl butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1 , 1-dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 , 1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 , 1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably methyl, ethyl, n- propyl, 1 -methylethyl, n-butyl, 1 ,1— dimethylethyl, n-pentyl or n-hexyl;
Ci-C4-haloalkyl: Ci-C4-alkyl 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;
Ci-Ce-haloalkyl: Ci-C4-haloalkyl as mentioned above, and also, for example,
5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl,
6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;
Cs-Ce-alkenyl and also the Cs-Ce-alkenyl moieties of Cs-Ce-alkenyloxy-Ci-Ce-alkyl, C3-C6- alkenyloxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, Cs-Ce-alkenyloxycarbonyl-Ci-Ce-alkyl: for example 1- propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -propenyl, 2- methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2- butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3- methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1- ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1- methyl-1-pentenyl, 2-methyl-1 -pentenyl, 3-methyl- 1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-
2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1- dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3- dimethyl-1-butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3- dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3- dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2- ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1- ethyl-2-methyl-1 -propenyl and 1-ethyl-2-methyl-2-propenyl;
C2-C4-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,
Cs-Ce-haloalkenyl and also the Cs-Ce-haloalkenyl moieties of Cs-Ce-haloalkenyloxy-Ci-Ce- alkyl: a Cs-Ce-alkenyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 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;
C2-C4-alkynyl: for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl ;
Cs-Ce-alkynyl and also the Cs-Ce-alkynyl moieties of Cs-Ce-alkynyloxycarbonyl-Ci-Ce-alkyl: for example 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1- pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3- butynyl, 3-methyl-1-butynyl, 1 ,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl,
2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1- pentynyl, 4-methyl-2-pentynyl, 1 ,1-dimethyl-2-butynyl, 1 ,1-dimethyl-3-butynyl, 1 ,2-dimethyl-3- butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2- ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Cs-Ce-haloalkynyl: a Cs-Ce-alkynyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 1 ,1 -difl uoroprop-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;
Ci-Cs-alkoxy: for example methoxy, ethoxy, propoxy;
Ci-C4-alkoxy and also the Ci-C4-alkoxy moieties of Ci-C4-alkyoxycarbonyl: for example methoxy, ethoxy, propoxy, 1 -methylethoxy butoxy, 1 -methylpropoxy, 2-methylpropoxy and 1 ,1- dimethylethoxy;
Ci-Ce-alkoxy and also the Ci-Ce-alkoxy moieties of Ci-Ce-alkyoxy-Ci-Ce-alkyl, Ci-Ce- alkoxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, di(Ci-C6-alkoxy)Ci-Ce-alkyl, Cs-Ce-alkenyloxy-Ci-Ce-alkoxy-Ci- Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl: Ci-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- methyl pentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethyl butoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl- 1 -methylpropoxy and 1- ethyl-2-methylpropoxy.
Ci-C4-haloalkoxy: a Ci-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 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, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3- dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1 -(fluoromethyl)-2-fluoroethoxy, 1 -(chloromethyl)-2-chloroethoxy, 1 -(bromo- methyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;
Ci-Ce-haloalkoxy and also the Ci-Ce-haloalkoxy moieties of Ci-Ce-haloalkoxy-Ci-Ce-alkyl, Ci-Ce-haloalkoxycarbonyl-Ci-Ce-alkyl: a Ci-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 and dodecafluorohexoxy;
Ci-C4-alkylthio: for example methylthio, ethylthio, propylthio, 1 -methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1 , 1-dimethylethylthio;
Ci-Ce-alkylthio and also the Ci-Ce-alkylthio moieties of Ci-Ce-alkylthio-Ci-Ce-alkyl: C1-C4- alkylthio as mentioned above, and also, for example, pentylthio, 1-methylbutylthio, 2-methyl- butylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1 -ethylpropylthio, hexylthio, 1 ,1-di- methylpropylthio, 1 ,2-dimethylpropylthio, 1 -methylpentylthio, 2-methylpentylthio, 3-methyl- pentylthio, 4-methylpentylthio, 1 , 1-dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3-dimethylbutylthio,
2.2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 -ethylbutylthio, 2- ethylbutylthio, 1 , 1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1- ethyl-2-methylpropylthio;
Ci-Ce-alkylsulfinyl (Ci-Ce-alkyl-S(=O)-) and also the Ci-Ce-alkylsulfinyl moieties of Ci-Ce- alkylsulfinyl-Ci-Ce-alkyl: for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-me- thylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1 ,1-di- methylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3- methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1 , 1-dimethylpropylsulfinyl,
1.2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3- methylpentylsulfinyl, 4-methylpentyl-sulfinyl, 1 , 1-dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl,
1.3-dimethylbutyl-sulfi nyl , 2,2-dimethylbutylsulfi nyl , 2, 3-dimethylbutylsulfinyl , 3,3-dimethylbutyl- sulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1 , 1 ,2-trimethylpropylsulfinyl, 1 ,2,2- trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl;
Ci-Ce-alkylsulfonyl (Ci-Ce-alkyl-S(O)2-) and also the Ci-Ce-alkylsulfonyl moieties of Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1- methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methyl-propylsulfonyl, 1 ,1- dimethylethylsulfonyl, pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3- methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl, 2,2- dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2- methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 ,1 -dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethyl- butylsulfonyl, 3,3-dimethylbutylsulfonyl, 1 -ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 , 1 ,2-trimethyl- propylsulfonyl, 1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl- 1-methylpropylsulfonyl and 1-ethyl-2- methylpropylsulfonyl;
(Ci-C4-alkyl)amino: for example methylamino, ethylamino, propylamino, 1 -methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino or 1 ,1 -dimethylethylamino;
(Ci-Ce-alkyl)amino and also the (Ci-Ce-alkyl)amino moiety in (Ci-Ce-alkyl)amino-Ci-Ce- alkyl: (Ci-C4-alkyl)amino as mentioned above, and also, for example, pentylamino, 1- methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethyl- propylamino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethylpropylamino, 1-methyl- pentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 , 1 -dimethylbutylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3- dimethylbutyl-amino 3,3-dimethylbutylamino, 1 -ethylbutylamino, 2-ethylbutylamino, 1 ,1 ,2- trimethylpropylamino, 1 ,2,2-trimethyl-propylamino, 1-ethyl-1-methylpropylamino or 1-ethyl-2- methylpropylamino; di(Ci-C4-alkyl)amino: for example N,N-dimethylamino, N,N-diethylamino, N,N-di(1- methylethyl)amino, N,N-dipropylamino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N- di(2-methylpropyl)amino, N,N-di(1 ,1-dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N- propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1- methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1 ,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1- methylpropyl)amino, N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1 ,1-dimethylethyl)amino, N- (l-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2- methylpropyl)-N-propylamino, N-(1 ,1-dimethylethyl)-N-propylamino, N-butyl-N-(1- methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methyl- propyl)amino, N-(1 ,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1 ,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2- methylpropyl)amino, N-(1 ,1-dimethylethyl)-N-(1-methylpropyl)amino or N-(1,1-dimethylethyl)-N- (2-methylpropyl)amino; di(Ci-C6-alkyl)amino and also the di(Ci-C6-alkyl)amino moiety of di(Ci-C6-alkyl)amino-Ci- Ce-alkyl: di(Ci-C4-alkyl)amino as mentioned above, and also, for example, N-methyl-N- pentylamino, N-methyl-N-(1-methylbutyl)amino, N-methyl-N-(2-methylbutyl)amino, N-methyl-N- (3-methylbutyl)amino, N-methyl-N-(2,2-dimethylpropyl)amino, N-methyl-N-(1-ethylpropyl)amino, N-methyl-N-hexylamino, N-methyl-N-(1,1-dimethylpropyl)amino, N-methyl-N-(1,2- dimethylpropyl)amino, N-methyl-N-(1-methylpentyl)amino, N-methyl-N-(2-methylpentyl)amino, N-methyl-N-(3-methylpentyl)amino, N-methyl-N-(4-methylpentyl)amino, N-methyl-N-(1 ,1- dimethylbutyl)amino, N-methyl-N-(1 ,2-dimethylbutyl)amino, N-methyl-N-(1 ,3- dimethylbutyl)amino, N-methyl-N-(2,2-dimethylbutyl)amino, N-methyl-N-(2,3- dimethylbutyl)amino, N-methyl-N-(3,3-dimethylbutyl)amino, N-methyl-N- (l-ethylbutyl)amino, N- methyl-N-(2-ethylbutyl)amino, N-methyl-N-(1 ,1 ,2-trimethylpropyl)amino, N-methyl-N- (1 ,2,2- trimethylpropyl)amino, N-methyl-N-(1-ethyl-1-methylpropyl)amino, N-methyl-N- (1 -ethyl-2- methylpropyl)amino, N-ethyl-N-pentylamino, N-ethyl-N-(1-methylbutyl)amino, N-ethyl-N-(2- methylbutyl)amino, N-ethyl-N-(3-methylbutyl)amino, N-ethyl-N-(2,2-dimethylpropyl)amino, N- ethyl-N-(1-ethylpropyl)amino, N-ethyl-N-hexylamino, N-ethyl-N-(1 ,1-dimethylpropyl)amino, N- ethyl-N-(1 ,2-dimethylpropyl)amino, N-ethyl-N-(1-methylpentyl)amino, N-ethyl-N-(2-methyl- pentyl)amino, N-ethyl-N-(3-methylpentyl)amino, N-ethyl-N-(4-methylpentyl)amino, N-ethyl-N- (1,1-dimethylbutyl)amino, N-ethyl-N-(1,2-dimethylbutyl)amino, N-ethyl-N-(1 ,3- dimethylbutyl)amino, N-ethyl-N-(2,2-dimethylbutyl)amino, N-ethyl-N-(2,3-dimethylbutyl)amino, N-ethyl-N-(3,3-dimethylbutyl)amino, N-ethyl-N-(1-ethylbutyl)amino, N-ethyl-N-(2- ethylbutyl)amino, N-ethyl-N-(1 , 1 ,2-trimethylpropyl)amino, N-ethyl-N-(1 ,2,2- trimethylpropyl)amino, N-ethyl-N-(1-ethyl-1-methylpropyl)amino, N-ethyl-N-(1-ethyl-2- methylpropyl)amino, N-propyl-N-pentylamino, N-butyl-N-pentylamino, N,N-dipentylamino, N- propyl-N-hexylamino, N-butyl-N-hexylamino, N-pentyl-N-hexylamino or N,N-dihexylamino;
Cs-Ce-cycloalkyl and also the cycloalkyl moieties of Cs-Ce-cycloalkyl-Ci-Ce-alkyl: monocyclic saturated hydrocarbons having 3 to 6 ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Ca-Ce-heterocyclyl and also the heterocyclyl moieties of Cs-Ce-heterocyclyl-Ci-Ce-alkyl: aliphatic heterocycle having 3 to 6 ring members which, in addition to carbon atoms, containsl to 4 nitrogen atoms, or 1 to 3 nitrogen atoms and an oxygen or sulphur atom, or an oxygen or a sulphur atom, for example three- or four-membered heterocycles like 2-oxetanyl, 3-oxetanyl, 2-thietanyl, 3-thietanyl, 1- azetidinyl, 2-azetidinyl, 1-azetinyl, 2-azetinyl; five-membered saturated heterocycles like 2- tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1 -pyrrolidinyl,2- pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-isothiazolidinyl, 3- isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1-pyrazolidinyl, 3-pyrazolidinyl, 4- pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4- thiazolidinyl, 5-thiazolidinyl, 1-imidazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 3-oxazolidinyl,
1.2.4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 3-thiazolidinyl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4- thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,2,4-oxadiazolidin-2-yl, 1,2,4-oxadiazolidin-4-yl, 1,3,4- oxadiazolidin-2-yl, 1 ,2 ,4-thiadiazol idin-2-yl , 1 ,2, 4-thiadiazol idin-4-yl , 1 ,3,4-thiadiazolidin-2-yl,
1.2.4-triazolidin-1-yl, 1 ,3,4-triazolidin-2-yl; six-membered saturated heterocycles like 1- piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 1,4-dioxanyl, 1 ,3-dithian- 5-yl, 1 ,3-dithianyl, 1 ,3-oxathian-5-yl, 1 ,4-oxathianyl, 2-tetrahydropyranyl, 3-tetrahydopyranyl, 4- tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl,4-tetrahydrothiopyranyl, 1- hexahydropyridazinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 1-hexahydropyrimidinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 1-piperazinyl, 2- piperazinyl, 1 ,3,5-hexahydrotriazin-1-yl, 1 ,3,5-hexahydrotriazin-2-yl, 1 ,2,4-hexahydrotriazin-1-yl, 1 ,2,4-hexahydrotriazin-3-yl, tetrahydro-1 ,3-oxazin-1-yl, tetrahydro-1 ,3-oxazin-2-yl, tetrahydro- 1 ,3-oxazin-6-yl, 1-morpholinyl, 2-morpholinyl, 3-morpholinyl;
5- or 6 membered heteroaryl: aromatic heteroaryl having 5 or 6 ring members which, in addition to carbon atoms, contains 1 to 4 nitrogen atoms, or 1 to 3 nitrogen atoms and an oxygen or sulphur atom, or an oxygen or a sulphur atom, for example 5-membered aromatic rings like furyl (for example 2-furyl, 3-furyl), thienyl (for example 2-thienyl, 3-thienyl), pyrrolyl (for example pyrrol-2-yl, pyrrol-3-yl), pyrazolyl (for example pyrazol-3-yl, pyrazol-4-yl), isoxazolyl (for example isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl), isothiazolyl (for example isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl), imidazolyl (for example imidazole-2-yl, imidazole-4-yl), oxazolyl (for example oxazol-2-yl, oxazol-4-yl, oxazol-5-yl), thiazolyl (for example thiazol-2-yl, thiazol-4- yl, thiazol-5-yl), oxadiazolyl (for example 1 ,2,3-oxadiazol-4-yl, 1 ,2,3-oxadiazol-5-yl, 1 ,2,4- oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl, 1 ,3,4-oxadiazol-2-yl), thiadiazolyl (for example 1 ,2,3- thiadiazol-4-yl, 1 ,2,3-thiadiazol-5-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl, 1 ,3,4-thiadiazolyl- 2-yl), triazolyl (for example 1 ,2,3-triazol-4-yl, 1 ,2,4-triazol-3-yl); 1-tetrazolyl; 6-membered aromatic rings like pyridyl (for example pyridine-2-yl, pyridine-3-yl, pyridine-4-yl), pyrazinyl (for example pyridazin-3-yl, pyridazin-4-yl), pyrimidinyl (for example pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl), pyrazin-2-yl, triazinyl (for example 1 ,3,5-triazin-2-yl, 1 ,2,4— triazin-3-yl, 1 ,2,4- triazin-5-yl, 1 ,2,4-triazin-6-yl);
3- to 7-membered carbocyclus: a three- to seven-membered monocyclic, saturated, partial unsaturated or aromatic cycle having three to seven ring members which comprises apart from carbon atoms optionally one or two ring members selected from the group consisting of -N(R12)- , -N=N-, -C(=O)-, -O- and -S-.
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 thioethers of formula (I), wherein the variables, either independently of one another or in combination with one another, have the following meanings:
Preferred are the thioethers of formula (I) wherein R° is CH3 or NH2; preferably is CH3; also preferably is NH2.
Preferred are the thioethers of formula (I) wherein R1 is halogen; preferably is F.
Also preferred are the thioethers of formula (I) wherein R2 is H or halogen; preferably is H or F; also preferably is halogen; more preferred is F.
Also preferred are the thioethers of formula (I) wherein
R3 is H or halogen; preferably is H, F or Cl; more preferred is F or Cl; especially preferred is F.
Also preferred are the thioethers of formula (I) wherein
R4 is H, F or Cl; particularly preferred is F or Cl; especially preferred is F.
Also preferred are the thioethers of formula (I) wherein
R5 is halogen or CN; preferably F, Cl, Br or CN; particularly preferred is F, Cl or Br; especially preferred is Cl or Br; more preferred is Cl; also more preferred is Br.
Also preferred are the thioethers of formula (I) wherein
R6 is H, F, Cl, Br, CH3 or OCH3; particularly preferred is H, CH3 or OCH3; especially preferred is H.
Also preferred are the thioethers of formula (I) wherein
R7 is Ci-C3-alkoxy; particularly preferred is OCH3.
Also preferred are the thioethers of formula (I) wherein
R8 is OR9, SR9 or NR9S(O)2R10; particularly preferred is OR9.
Also preferred are the p thioethers of formula (I) wherein
R9 is hydrogen, Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Ci-Ce-haloalkyl, C3-Ce-haloalkenyl, C3-Ce-haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkoxy-Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci-Ce-alkyl, Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3-C6-cycloalkyl, C3-Ce- cycloalkyl-Ci-Ce-alkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-Ci-C6-alkyl, phenyl, phenyl-Ci-C4-alkyl; preferably is hydrogen, Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Ci-Ce-cyanoalkyl, Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3- Ce-cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl- Ci-Ce-alkyl, phenyl or phenyl-Ci-C4-alkyl; particularly preferred is hydrogen, Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Ci-Ce-alkoxy- Ci-C6-alkyl; also particularly preferred is hydrogen, Ci-Ce-alkyl or Ci-Ce-alkoxy-Ci-Ce-alkyl; especially preferred is hydrogen or Ci-Ce-alkyl; also especially preferred is hydrogen or Ci-C4-alkyl; also especially preferred is Ci-C4-alkyl; more preferred is hydrogen, CH3 or C2H5; most preferred is OCH.
Also preferred are the thioethers of formula (I) wherein
R10 is Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-haloalkyl, Cs-Ce-haloalkenyl, C3-C6- haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkoxy-Ci-Ce-alkoxy- Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci-Ce-alkyl, Ci-Ce- alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, Cs-Ce-cycloalkyl, C3-C6- cycloalkyl-Ci-Ce-alkyl, Cs-Ce-heterocyclyl, Cs-Ce-heterocyclyl-Ci-Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl; preferably is, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci- Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3-C6- cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, Cs-Ce-heterocyclyl, Cs-Ce-heterocyclyl-Ci- Ce-alkyl, phenyl or phenyl-Ci-C4-alkyl; particularly preferred is Ci-Ce-alkyl; more preferred is CH3.
Also preferred are the thioethers of formula (I) wherein
R11 is H, Ci-Ce-alkyl or Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl; particularly preferred is H or Ci-Ce-alkyl; more preferred is H; also more preferred is Ci-Ce-alkyl.
Also preferred are the thioethers of formula (I) wherein
R12 is phenyl or Ci-C4-alkyl; particularly preferred is phenyl or CH3; also particularly preferred is phenyl; also particularly preferred is Ci-C4-alkyl.
Also preferred are the thioethers of formula (I) wherein
R13 is phenyl or Ci-C4-alkyl; particularly preferred is phenyl or CH3; also particularly preferred is phenyl; also particularly preferred is Ci-C4-alkyl.
Also preferred are the thioethers of formula (I) wherein
R14 is halogen or Ci-Ce-alkyl; particularly preferred is F, Cl or CH3; also particularly preferred is halogen; especially preferred is F or Cl; also particularly preferred is Ci-Ce-alkyl; especially preferred is CH3.
Also preferred are the thioethers of formula (I) wherein n is 1 or 2; particularly preferred is 2; also particularly preferred is 1 .
Also preferred are the thioethers of formula (I) wherein
Q is O, also preferably is S.
Also preferred are the thioethers of formula (I) wherein
W is O, also preferably is S.
Also preferred are the thioethers of formula (I) wherein
Y1 is O, also preferably is S.
Also preferred are the thioethers of formula (I) wherein
Y2 is O, also preferably is S.
Also preferred are the thioethers of formula (I) wherein
Z is CH, also preferably is N.
Also preferred are the thioethers of formula (I) wherein
R° is CH3 or NH2;
R1 is halogen;
R2 is halogen;
R3 is hydrogen or halogen;
R4 is H or halogen;
R5 is halogen or CN;
R6 is H, halogen, Ci-Cs-alkyl or Ci-Cs-alkoxy;
R7 is Ci-Cs-alkoxy or Ci-Cs-alkylthio;
R8 is OR9, SR9 or NR9S(O)2R10, wherein
R9 is hydrogen, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-haloalkyl, C3-C6- haloalkenyl, Cs-Ce-haloalkynyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce- alkoxy-Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkylsulfinyl-Ci- Ce-alkyl, Ci-Ce-alkylsulfonyl-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3-C6- cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, Ca-Ce-heterocyclyl, Ca-Ce-heterocyclyl-Ci- Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl;
R10 is Ci-C6-alkyl; n is 1 ;
Q is O or S;
W, Y1, Y2 are O;
Z is CH or N.
Also preferred are the thioethers of formula (I) wherein R° is CH3;
R1 is F;
R2 is F;
R3 is H, F or Cl;
R4 is F or Cl;
R5 is halogen or CN;
R6 is H, F, Cl, Br, CH3 or OCH3;
R7 is Ci-C3-alkoxy;
R8 is OR9, SR9 or NR9S(O)2R10, wherein
R9 is hydrogen, Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Ci-Ce-cyanoalkyl, Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3- Ce-cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl- Ci-Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl;
R10 is Ci-C6-alkyl; n is 1 ;
Q is O or S;
W, Y1, Y2 are O;
Z is CH or N.
Also preferred are the thioethers of formula (I) wherein
R° is CH3;
R1 is F;
R2 is F;
R3 is F or Cl;
R4 is F;
R5 is F, Cl or Br;
R6 is H;
R7 is OCH3;
R8 is OR9, wherein
R9 is hydrogen, Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Ci-Ce-cyanoalkyl, Ci-Ce- alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-Ce-alkoxycarbonyl-Ci-Ce-alkyl, C3- Ce-cycloalkyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl- Ci-Ce-alkyl, phenyl, phenyl-Ci-C4-alkyl; n is 1 ;
Q is O or S;
W, Y1, Y2 are O;
Z is CH or N.
Also preferred are the thioethers of formula (I) wherein
R° is CH3;
R1 is F;
R2 is F;
R3 is F or Cl;
R4 is F;
R5 is Cl or Br;
R6 is H;
R7 is OCH3; R8 is OR9, wherein
R9 is hydrogen, Ci-Ce-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-Ce-alkoxy-Ci-Ce- alkyl; n is 1;
Q isOorS;
W, Y1,Y2 areO;
Z is CH or N.
Preferred are the phenyluracils of formula (1.1) (corresponds to formula (I) wherein R° is CH3, R1 is F, R3 and R4 are F, R6 is H, n is 1 , W, Y1 and Y2 are O),
Figure imgf000015_0001
wherein
R2 is H or halogen;
R5 is halogen or CN;
R7 is Ci-Cs-alkoxy;
R8 is OR9, wherein
R9 is H, Ci-C4-alkyl or Ci-C6-alkoxy-Ci-C6-alkyl;
Q isOorS;
Z is CH or N.
Especially preferred are the phenyluracils of formula (1.1), wherein
R2 is H or F;
R5 is F, Cl, BrorCN;
R7 is OCH3;
R8 is OR9, wherein
R9 is H, CH3, C2H5, CH(CH3)2, CH2CH(CH3)2 or CH2CH2OCH3;
Q isOorS;
ZisCH orN.
Particular preference is given to thioethers of formula (l.a) (corresponds to formula (I) wherein R° is CH3, R1 is F, R3 and R4 are F, R6 is H, n is 1, Q, W, Y1 and Y2 are O and Z is CH),
Figure imgf000015_0002
wherein the variables R2, R5, R7 and R8 have the meanings, in particular the preferred meanings, as defined above.
Special preference is given to the thioethers of the formulae I .a.1 to I. a.48 of table A, where the definitions of the variables R2, R5 ,R7 and R8 are of particular importance for the compounds according to the invention not only in combination with one another but in each case also on their own:
Table A
Figure imgf000016_0001
Figure imgf000017_0003
Also preferred are the thioethers of formula (l.b), particularly preferred the thioethers of formulae (l.b.1) to l.b.48, which differ from the corresponding thioethers of formulae (l.a.1) to (I. a.48) only in that Z is N:
Figure imgf000017_0001
Also preferred are the thioethers of formula (l.c), particularly preferred the thioethers of formulae (l.c.1) to (l.c.48), which differ from the corresponding thioethers of formulae (l.a.1) to (I. a.48) only in that Q is S:
Figure imgf000017_0002
Also preferred are the thioethers of formula (l.d), particularly preferred the thioethers of formulae (l.d.1) to (l.d.48), which differ from the corresponding thioethers of formulae (l.a.1) to (I. a.48) only in that Q is S and Z is N: The thioethers of formula (I) according to the invention can be prepared by standard processes of organic chemistry, for example by the following processes:
Process A)
The thioethers of formula (I) are obtained from the acid halides of formula (II) by reaction with compounds of formula (III) in the presence of a base:
Figure imgf000018_0001
Within the acid halides of formula (II), L1 is halogen; preferably is F, Cl or Br; especially preferred is F or Cl, more preferred is Cl.
Instead of the acid halides of formula (II), also the corresponding acid (e.g. acid halide of formula (II), wherein L1 is OH) in combination with an activating reagent, like carbonyldiimidazole, N,N'-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3- dimethylaminopropyl)-,carbodiimide (EDC) or N-methyl-2-chloropyridinium chloride can be used. The reaction conditions are the same as described for the acid halides of formula (II).
The compounds (III) can also be employed in the form of their salts, in particular the sodium and potassium salts, in which case the presence of a base is not necessary.
The reaction of acid halides (II) with compounds (III) is usually carried out from 0 °C to the boiling point of the reaction mixture, preferably at from 0 °C to 100 °C, particularly preferably at from 0 °C to 40 °C, in an inert organic solvent in the presence of a base.
The reaction may in principle be carried out in substance. However, preference is given to reacting the acid halides (II) with the compounds (III) in an organic solvent. Suitable in principle are all solvents, which are capable of dissolving the acid halides (II) and the compounds (III) at least partly, and preferably fully under reaction conditions.
Examples of suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, nitromethane and mixtures of C5-C8-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene, tolene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetra hydrofuran (THF); esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile; ketones such as acetone, methyl ethyl ketone, diethyl ketone, tertbutyl methyl ketone, cyclohexanone; dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2- imidazolidinone (DMI), N,N'-dimethyhpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
Preferred solvents are halogenated hydrocarbons, ethers and dipolar aprotic solvents as mentioned above.
It is also possible to use mixtures of the solvents mentioned.
Examples of suitable bases include metal-containing bases and nitrogen-containing bases.
Examples of suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate; alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; and furthermore organic bases, such as tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidinge, lutidine, N-methylmorpholine and 4-dimethylaminopyridine and also bicyclic amines.
Examples of suitable nitrogen-containing bases are C1-C6-alkylamines, preferably trialkylamines, for example triethylamine, trimethylamine, N-ethyhdiisopropyhamine; pyridine, lutidine, collidine, 4-(dimethylamino)pyridine (DMAP), imidazole, 1 ,8-diazabicyclo[5.4.0]undec-7- ene (DBU) or 1 ,5-diazabhcyclo-,[4.3.0]-'non-5-ene (DBN).
Preferred bases are alkali metal and alkaline earth metal carbonates and nitrogen-containing bases as defined above; especially preferred triethylamine, pyridine or sodium carbonate.
The term base as used herein also includes mixtures of two or more, preferably two of the above compounds. Particular preference is given to the use of one base.
The bases are generally used in excess, more preferably with from 1 to 3 equivalents based on the acid halides (II), and they may also be used as the solvent. However, they can also be employed in catalytic amounts.
For the reaction, the acid halides (II), the compounds (III) and the base can be brought into contact in any way per se.
Accordingly, the reaction partners and the base may be introduced into the reaction vessel and reacted separately, simultaneously or successively.
The reactants are generally employed in equimolar amounts. It might be advantageous using one of the reactants in excess, for example with a view to complete a reaction of the other reactant. The reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
The end of the reaction can easily be determined by the skilled worker by means of routine methods.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, separation of the phases and, if appropriate, chromatographic purification of the crude product. Some of the intermediates and end products are obtained in the form of viscous oils, which can be purified or freed from volatile components under reduced pressure and at moderately elevated temperature.
If the intermediates and the end products are obtained as solid, purification can also be carried out by recrystallisation or digestion.
The compounds of formula (III) are commercially available.
Process B)
The thioethers of formula (I) can also be prepared by reaction of compounds of formula (IV) with alkylating agents of formula (V) in the presence of a base in analogy to known processes (e.g.
WO 11/137088):
Figure imgf000020_0001
Within the alkylating agents of formula (V), L2 is a leaving group such halogen, Ci-Ce-alkyl- sulfonate or arylsulfonate; preferably Cl or Br.
The reaction may in principle be carried out in substance. However, preference is given to reacting the compounds of formula (IV) with the alkylating agents of formula (V) in an organic solvent.
Suitable in principle are all solvents which can dissolve the compounds of formula (IV) and the alkylating agents of formula (V) at least partly and preferably fully under reaction conditions. Examples of suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethyl- acetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP). Examples of suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; metal organic compounds, preferably alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, potassium tertpentoxide and dimethoxymagnesium; and furthermore organic bases, such as tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine, N-methylmorpholine and 4- dimethylaminopyridine and also bicyclic amines.
The alkylating agents of formula (V) are commercially available or can be prepared by known methods (e.g. Lowell, Andrew N. et al, Tetrahedron, 6(30), 5573-5582, 2010; WO 11/137088).
Compounds of formula (IV) can be prepared from compounds of formula (VI):
Figure imgf000021_0001
Within the compounds of formula (VI) “PG” is a protecting group selected from the group consisting of Ci-Ce-alkyl, Ci-Ce--cyanoalkyl, Ci-Ce-haloalkyl, Ci-C6-alkylthio-C1-C4-alkyl, Ci-Ce- alkoxy- Ci-C4-alkyl, Ci-Ce-alkoxy- Ci-C4-alkoxy- Ci-C4-alkyl, (tri- Ci-Ce-alkyl)silyl- Ci-C4-alkyl, (tri- Ci-Ce-alkyl)silyl- Ci-C4-alkyoxy- Ci-C4-alkyl, C2-Ce-alkenyl, Cs-Ce-alkynyl, Cs-Ce-cycloalkyl, Cs-Ce-cylcloalkyl- Ci-C4-alkyl, Cs-Ce-cycloalkenyl, tetrahydropyranyl, (tri-Ci-C6-alkyl)silyl, [(diphenyl)(Ci-C4-alkyl)]silyl, formyl, Ci-Ce-alkyl-carbonyl, Ci-Ce-alkyl-O-carbonyl, C2-Ce-alkenyl- Ocarbonyl, [(diphenyl)(Ci-C4-alkyl)]silyl- Ci-C4-alkyl, phenyl-Ci-C4-alkyl, phenylthio-Ci-Ce-alkyl, phenylcarbonyl, wherein each phenyl ring can be substituted by one to three substituents selected from the group consisting of halogen, CN, NO2, Ci-C4-alkyl and C1-C4-alkoxy. Preferably PG is Ci-Ce-alkyl, Ci-C6-alkoxy-Ci-C4-alkyl, (tri- Ci-Ce-alkyl)silyl-C1 -C4-alkyl, C2-C6- alkenyl, tetrahydropyranyl, (tri-Ci-C6-alkyl)silyl, [(diphenyl)(Ci-C4-alkyl)]silyl or phenyl-Ci-C4- alkyl. For example, the compounds of formula (IV) can be prepared by treating the compounds of formula (VI), wherein “PG” is methyl, with boron tribromide in a solvent such as dichloromethane, acetonitrile or 1 ,4-dioxane, or without a solvent at temperatures ranging from 0 °C to 150 °C.
Alternatively, compounds of formula (IV) can be prepared by deprotecting compounds of formula (VI), wherein “PG” is a benzyl group, by catalytic hydrogenation in a hydrogen gas atmosphere at a pressure of 70 to 700 kPa, preferably 270 to 350 kPa, in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20% of metal to carrier, suspended in a solvent such as ethanol at ambient temperature.
The process, use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: New York, 2007).
Compounds of formula (VI) wherein R5 is halogen or CN can be prepared from amino compounds of formula (VII) using the “Sandmeyer” reaction:
Figure imgf000022_0001
The Sandmeyer reaction is performed by diazotization with an alkyl nitrite (e.g. isoamyl nitrite, tert-Butyl nitrite or NaNO2) followed by treatment with a copper (I) and/or copper (II) halide (e.g. CuCI, CuCh, CuBr, CuBr2 or CuCN) in a solvent such as acetonitrile at a temperature ranging from 0 °C to the reflux temperature of the solvent to give the corresponding phenyluracils of formula (I), wherein R5 is a Cl, Br or CN ( e.g. WO 2011/137088, or L. Kurti, B. Czako Strategic Applications of Named Reactions in Organic Synthesis, Elsevier: San Diego, 2005, p. 394-395)
To obtain compounds of formula (VI), wherein R5 is iodine, no copper salts are required.
The below mentioned reaction conditions can be used, adding instead of a copper salt an iodine salt such as potassium iodide after diazotization.
To obtain compounds of formula (VI), wherein R5 is fluorine, tetrafluoroborate salts of the diazonium compound can be used. These are obtained by adding hydrogene tetrafluoroborate during the diazotization. Subsequent thermal or photolytical decomposition delivers the corresponding fluoro compounds (Langlois, B. In Introduction of Fluorine via Diazonium Compounds (Fluorodediazoniation); Baasner, B., Hagemann, H., Tatlow, J. C., Eds.; Houben- Weyl, Methods of Organic Chemistry; Thieme: Stuttgart, 1999; Vol. E10a, Organo-Fluorine Compounds, pp 686-740). The reaction of amino compounds of formula (VII) with a diazotization agent and optionally copper salts is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 0°C to 100°C, particularly preferably from 0°C to 40°C, in an inert solvent.
The reaction may in principle be carried out in substance. However, preference is given to reacting the amino compounds of formula (VII) with the copper salts and the diazotization agent in an organic solvent.
Suitable in principle are all solvents, which are capable of dissolving the amino compounds of formula (VII), the copper salts and the diazotization agent at least partly, and preferably fully under reaction conditions.
Examples of suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, nitromethane and mixtures of C5-C8-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene, tolene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetra hydrofuran (THF); esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile; ketones such as acetone, methyl ethyl ketone, diethyl ketone, tertbutyl methyl ketone, cyclohexanone; dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3- dimethyl-2-imidazolidino-ne (DMI), N,N'-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP) and polar protic solvents as water.
Preferred solvents are nitriles or polar protic solvents as mentioned above. It is also possible to use mixtures of the solvents mentioned.
The copper salts are generally used in excess, more preferably from 1 to 3 equivalents based on the amino compounds of formula (VII).
The diazotization agent is generally used in excess, more preferably from 1 to 3 equivalents based on the amino compounds of formula (VII).
For the reaction, the amino compounds of formula (VII), the copper salts and the diazotization agent can be brought into contact in any way per se.
The reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
The copper salts and the diazotization agents are commercially available.
Amino compounds of formula (VII) can be prepared from nitro compounds of formula (VIII) using reduction conditions:
Figure imgf000024_0001
The reduction of the nitro group on can be achieved by treatment with iron powder in acetic acid at a temperature ranging from 0 °C to 100 °C. Alternatively, the reduction can be carried out by catalytic hydrogenation in hydrogen gas at a pressure of 70 to 700 kPa, preferably 270 to 350 kPa, in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20% of metal to carrier, suspended in a solvent such as ethanol at ambient temperature (see e.g. WO 2011/137088).
The reaction of nitro compounds of formula (VIII) with the reducing agent is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 20°C to the boiling point of the reaction mixture, in an inert solvent. The reaction may in principle be carried out in substance.
However, preference is given to reacting the nitro compounds of formula (VIII) with the reducing agent in an organic solvent. Suitable in principle are all solvents, which can dissolve the nitro compounds of formula (VIII), at least partly, and preferably fully under reaction conditions.
Examples of suitable solvents are alcohols such as ethanol.
The reducing agents are generally used in excess, more preferably with from 1 to 6 equivalents based on the nitro compounds.
The reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
The reducing agents are commercially available.
Nitro compounds of formula (VIII) can be prepared from compounds of formula (IX) in the presence of a base using compounds of formula (X):
Figure imgf000024_0002
Within the compounds of formula (IX), L3 is a leaving group such halogen, Ci-Ce-alkylsulfonate or arylsulfonate; preferably F, Ci-Ce-alkylsulfonate or arylsulfonate; especially preferred F, mesylat or tosylat.
The reaction of the compounds of formula (IX) with compounds of formula (X) in presence of a base is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 20°C to 100°C.
The reaction may in principle be carried out in substance. However, preference is given to reacting the compounds of formula (IX) with the compounds of formula (X) in an organic solvent. Suitable in principle are all solvents which can dissolve the compounds of formula (IX) and the compounds of formula (X) at least partly and preferably fully under reaction conditions.
Examples of suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, nitromethane and mixtures of Cs-Cs-alkanes, aromatic hydrocarbons such as benzene, chlorobenzene, toluene, cresols, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, 1 ,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetra hydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3- dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPLI), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
Preferred solvents are ethers, nitriles and dipolar aprotic solvents as mentioned above. Examples of suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; metal organic compounds, preferably alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, potassium tertpentoxide and dimethoxymagnesium.
Compounds of formula (X) are known from literature and/or commercially available.
Compounds of formula (IX), can be prepared by reaction of uracils of formula (XI) with compounds of formula (XII) in the presence of a base:
Figure imgf000026_0001
Within the compounds of formula (XII), L4 is a leaving group such F, Ci-Ce-alkylsulfonate or arylsulfonate; preferably F, mesylat or tosylat;
The reaction of the uracils of formula (XI) with compounds of formula (XII) in presence of a base is usually carried out from 0°C to the boiling point of the reaction mixture, preferably from 20°C to 100°C.
The reaction may in principle be carried out in substance. However, preference is given to reacting the uracils of formula (XI) with the compounds of formula (XII) in an organic solvent.
Suitable in principle are all solvents which can dissolve the uracils of formula (XI) and the compounds of formula (XII) at least partly and preferably fully under reaction conditions. Examples of suitable solvents are dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2- imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and 1- methyl-2 pyrrolidinone (NMP).
Examples of suitable metal-containing bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, and other metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide; alkali metal and alkaline earth metal oxide, and other metal oxides, such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and magnesium oxide, iron oxide, silver oxide; alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; metal organic compounds, preferably alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, potassium tertpentoxide and dimethoxymagnesium.
Compounds of formula (XII) are known from literature and/or commercially available. Uracils of formula (XI) can be prepared from compounds of formula (XIII) via dehydration reactions:
Figure imgf000027_0001
For dehydration of compounds of formula (XIII) usually acids are used.
The reaction of the compounds of formula (XIII) in presence of an acid is usually carried out from 20°C to the boiling point of the reaction mixture, preferably from 50°C to 100°C.
The reaction may in principle be carried out in substance. However, preference is given to reacting the compounds of formula (XIII) in an organic solvent.
Suitable in principle are all solvents which can dissolve the compounds of formula (XIII) at least partly and preferably fully under reaction conditions.
Examples of suitable solvents are alcohols such as ethanol.
Examples of suitable acids are Bronsted acids, such as HCI or H2SO4.
Compounds of formula (XIII) can be prepared from keto-esters of formula (XIV) and urea compounds of formula (XV):
Figure imgf000027_0002
The condensation of keto-esters of formula (XIV) with ureas of formula (XV) may in principle be carried out in substance. However, preference is given to reactions in an organic solvent. Suitable in principle are all solvents which can dissolve keto-esters of formula (XIV) and ureas of formula (XV) at least partly and preferably fully under reaction conditions.
Examples of suitable solvents are aromatic hydrocarbons such as benzene, chlorobenzene, toluene, cresols, o-, m- and p-xylene, nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone (DMI), N,N '-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
The reaction of keto-esters of formula (XIV) with ureas of formula (XV) is usually carried out from 20°C to the boiling point of the reaction mixture, preferably from 60°C to 140°C.
Ureas of formula (XV) are known from literature and/or commercially available. Keto-esters of formula (XIV) can be prepared by reaction of esters of formula (XVI) with an acetic acid ester of formula (XVII) in the presence of a base:
Figure imgf000028_0001
The reaction may be carried out in substance. However, it also possible reacting the esters of formula (XVI) with an acetic acid ester of formula (XVII) in an organic solvent.
Suitable in principle are all solvents which can dissolve esters of formula (XVI) and an acetic acid ester of formula (XVII) at least partly and preferably fully under reaction conditions.
Examples of suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran (THF), esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile, as well as dipolar aprotic solvents such as sulfolane, dimethylsulfoxide, N,N-dimethylformamide (DMF), N,N- dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).
Examples of suitable metal-containing bases are alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, cesium carbonate and calcium carbonate, as well as alkali metal hydrogen carbonates (bicarbonates) such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal and alkaline earth metal phosphates such as potassium phosphate, calcium phosphate; metal organic compounds, preferably alkali metal alkyls such as methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alkoxides such as potassium tert-butoxide.
Esters of formula (XVI) and acetic acid ester of formula (XVII) are known from literature and/or commercially available.
To widen the spectrum of action and to achieve synergistic effects, the thioethers of formula (I) may be mixed with many representatives of other herbicidal or growth-regulating active ingredient groups and then applied concomitantly. Suitable components for combinations are, for example, herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.
It may furthermore be beneficial to apply the thioethers 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 invention also relates to formulations comprising at least an auxiliary and at least one thioethers of formula (I) according to the invention.
A formulation comprises a pesticidally effective amount of a thioether of formula (I). The term "effective amount" denotes an amount of the combination or of the thioethers of formula (I), which is sufficient for controlling undesired vegetation, especially for controlling undesired vegetation in crops (i.e. cultivated plants) and which does not result in a substantial damage to the treated crop plants. Such an amount can vary in a broad range and is dependent on various factors, such as the undesired vegetation to be controlled, the treated crop plants or material, the climatic conditions and the specific thioether of formula (I) used.
The thioethers of formula (I), their N-oxides, salts amides, esters or thioesters can be converted into customary types of formulations, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further formulation types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of 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 thioethers of formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for formulation types and their preparation are: i) Water-soluble concentrates (SL, LS)
10-60 wt% of a thioether of formula (I) 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 thioether of formula (I) 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 a thioether of formula (I) 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 a thioether of formula (I) according to the invention and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% waterinsoluble 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 thioether of formula (I) according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type formulation up to 40 wt% binder (e.g. polyvinylalcohol) is added. vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a thioether of formula (I) 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 thioether of formula (I) 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 thioether of formula (I) 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 thioether of formula (I) 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 thioether of formula (I) 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 thioether of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4’-diisocyanate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt%. The wt% relate to the total CS formulation. ix) Dustable powders (DP, DS)
1-10 wt% of a thioether of formula (I) 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 thioether of formula (l)| 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 thioether of formula (I) according to the invention are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%. The formulation types i) to xi) may optionally comprise further auxiliaries, such as 0,1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1-1 wt% colorants.
The formulations 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 thioether of formula (I).
The thioethers of formula (I) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The formulations in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
Methods for applying thioethers of formula (I), formulations thereof, on to plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, thioethers of formula (I), formulations thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
Various types of oils, wetting agents, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the thioethers of formula (I), the formulations comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the formulations according to the invention in a weight ratio of 1 :100 to 100:1, preferably 1 :10 to 10:1.
The user applies the thioethers of formula (I) according to the invention, the formulations comprising them usually from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the formulation is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the formulation according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, either individual components of the formulation according to the invention or partially premixed components, e. g. components comprising thioethers of formula (I) may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, individual components of the formulation according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the formulation according to the invention or partially premixed components, e. g components comprising thioethers of formula (I) can be applied jointly (e.g. after tank mix) or consecutively.
The thioethers of formula (I), are suitable as herbicides. They are suitable as such or as an appropriately formulation.
The thioethers of formula (I), or the formulations comprising the thioethers of formula (I), control undesired vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
The thioethers of formula (I), or the formulations comprising the thioethers of formula (I) have an outstanding herbicidal activity against undesired vegetation, i.e. against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous weeds.
Mentioned below are some representatives of monocotyledonous and dicotyledonous weeds, which can be controlled by the thioethers of formula (I), or the formulations comprising the thioethers of formula (I), without the enumeration being a restriction to certain species.
Preferably the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) are used to control monocotyledonous weeds.
Examples of monocotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the genera Hordeum spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp., Eriochloa spp., Setaria spp., Pennisetum spp., Eleusine spp., Eragrostis spp., Panicum spp., Lolium spp., Brachiaria spp., Leptochloa spp., Avena spp., Cyperus spp., Axonopris spp., Sorghum spp., and Melinus spp..
Preferred examples of monocotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Hordeum murinum, Echinochloa crus-galli, Poa annua, Bromus rubens L., Bromus rigidus, Bromus secalinus L., Digitaria sanguinalis, Digitaria insularis, Eriochloa gracilis, Setaria faberi, Setaria viridis, Pennisetum glaucum, Eleusine indica, Eragrostis pectinacea, Panicum miliaceum, Lolium multiflorum, Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus compressus, Cyperus esculentes, Axonopris offinis, Sorghum halapense, and Melinus repens.
Especially preferred examples of monocotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Echinochloa spp., Digitaria spp., Setaria spp., Eleusine spp. and Brachiarium spp.
Also preferably the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) are used to control dicotyledonous weeds. Examples of dicotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the genera Amaranthus spp., Erigeron spp., Conyza spp., Polygonum spp., Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp., Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp., Erodium spp., Erigeron spp., Senecio spp., Lamium spp., Kochia spp., Chenopodium spp., Lactuca spp., Malva spp., Ipomoea spp., Brassica spp., Sinapis spp., llrtica spp., Sida spp, Portulaca spp., Richardia spp., Ambrosia spp., Calandrinia spp., Sisymbrium spp., Sesbania spp., Capsella spp., Sonchus spp., Euphorbia spp., Helianthus spp., Coronopus spp., Salsola spp., Abutilon spp., Vicia spp., Epilobium spp., Cardamine spp., Pieris spp., Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria spp., Plantago spp., Tribulus spp., Cenchrus spp. Bidens spp., Veronica spp., and Hypochaeris spp..
Preferred examples of dicotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Amaranthus spinosus, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum offi cinale, Oenothera laciniata, Amsinckia intermedia, Erodium cicutarium, Erodium moschatum, Erigeron bonariensis (Conyza bonariensis), Senecio vulgaris, Lamium amplexicaule, Erigeron canadensis, Polygonum aviculare, Kochia scoparia, Chenopodium album, Lactuca serriola, Malva parviflora, Malva neglecta, Ipomoea hederacea, Ipomoea lacunose, Brassica nigra, Sinapis arvensis, Urtica dioica, Amaranthus blitoides, Amaranthus retroflexus, Amaranthus hybridus, Amaranthus lividus, Sida spinosa, Portulaca oleracea, Richardia scabra, Ambrosia artemisiifolia, Calandrinia caulescens, Sisymbrium irio, Sesbania exaltata, Capsella bursa- pastoris, Sonchus oleraceus, Euphorbia maculate, Helianthus annuus, Coronopus didymus, Salsola tragus, Abutilon theophrasti, Vicia benghalensis L., Epilobium paniculatum, Cardamine spp, Pieris echioides, Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria matriccarioides, Plantago spp., Tribulus terrestris, Salsola kali, Cenchrus spp., Bidens bipinnata, Veronica spp., and Hypochaeris radicata.
Especially preferred examples of dicotyledonous weeds on which the thioethers of formula (I), or the formulations comprising the thioethers of formula (I) act efficiently are selected from the species Amaranthus spp., Erigeron spp., Conyza spp., Kochia spp. and Abutilon spp.
The thioethers of formula (I), or the formulations comprising them, are applied to the plants mainly by spraying the leaves. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 100 to 1000 l/ha (for example from 300 to 400 l/ha). The thioethers of formula (I), or the formulations 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 thioethers of formula (I), or the formulations comprising them, can be done before, during and/or after, preferably during and/or after, the emergence of the undesired vegetation.
Application of the thioethers of formula (I), or the formulations can be carried out before or during sowing. The thioethers of formula (I), or the formulations comprising them, can be applied pre-, postemergence or pre-plant, or together with the seed of a crop plant. It is also possible to apply the thioethers of formula (I), or the formulations comprising them, by applying seed, pretreated with the thioethers of formula (I), or the formulations comprising them, of a crop plant. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the combinations are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesired vegetation growing underneath, or the bare soil surface (post-directed, lay-by).
In a further embodiment, the thioethers of formula (I), or the formulations 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 thioethers of formula (I), or the formulations prepared therefrom. Here, the combinations can be applied diluted or undiluted.
The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the crop plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
When employed in plant protection, the amounts of active substances applied, i.e. the thioethers of formula (I) 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 0.01 to 0.9 kg per ha and in particular from 0.02 to 0.5 kg per ha.
In another embodiment of the invention, the application rate of the thioethers of formula (I) 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 thioethers of formula (I) according to the present invention (total amount of thioethers 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 thioethers 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 thioethers of formula (I) is 0.1 to 1000 g/ha, preferably 1 to 750 g/ha, more preferably 5 to 500 g/ha.
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 thioethers of formula (I) 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.
Depending on the application method in question, the thioethers of formula (I), or the formulations comprising them, can additionally be employed in a further number of crop plants for eliminating undesired vegetation.
According to the invention all the crop plants (cultivated plants) mentioned herein are understood to comprise all species, subspecies, variants and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
For example, corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).
Further, most soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856). The indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (Maturity Group, (MG) 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
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, peas, lentils, peanuts or permanent crops.
The thioethers of formula (I) according to the invention, or the formulations comprising them, can also be used in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
The term "crops" as used herein includes also (crop) plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.
Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4- hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
Transgenic corn events comprising herbicide tolerance genes are for example, but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO- 01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS- 81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1 , MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec, and synthetic variants thereof, like cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.1O5, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particular genes coding for protease inhibitors, like CpTI and pinll. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes. An example for such a transgene is dvsnf7.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701 , MON87751 and DAS-81419.
Transgenic cotton events comprising genes for insecticidal proteins are for example, but not excluding others, SGK321 , MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601 , Eventl , COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
Crops comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb- 4, comprised by soybean event IND-00410-5.
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-qmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and W02017/011288.
The use of the compounds of formula (I) or formulations or combinations comprising them according to the invention on crops may result in effects which are specific to a crop comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of ingredients or new ingredients, specifically to improve raw material production, e.g., potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
Furthermore, it has been found that the thioethers of formula (I) according to the invention, or the formulations comprising them, are also suitable for the defoliation and/or desiccation of plant parts of crops such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton. In this regard, formulations for the desiccation and/or defoliation of crops, processes for preparing these formulations and methods for desiccating and/or defoliating plants using the thioethers of formula (I) have been found.
As desiccants, the thioethers of formula (I) are particularly suitable for desiccating the aboveground 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.
A Preparation examples
Example 1 :
Methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1- yl]phenyl]sulfanylphenoxy]-2-methoxy-acetate
Figure imgf000041_0001
Example 1 - step 1 : 6-hydroxy-1-methyl-6-(trifluoromethyl)hexahydropyrimidine-2, 4-dione
Figure imgf000041_0002
To a solution of ethyl 4,4,4-trifluoroacetoacetate (CAS 372-31-62; 3.9 g, 130 mmol) in dimethylformamide (51.6 mL) was added methylurea (CAS 598-50-5; 7.4 g 100 mmol) in one portion. Then the mixture was stirred at 110°C for 4 hours. The mixture was concentrated by oil pump to give 6-hydroxy-1-methyl-6-(trifluoromethyl)hexahydropyrimidine-2, 4-dione (25 g, crude) as a yellow oil, which was directly used in the next step.
Example 1 - step 2:
1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione
Figure imgf000041_0003
A mixture of 6-hydroxy-1-methyl-6-(trifluoromethyl)hexahydropyrimidine-2, 4-dione
(25 g, 0.118 mol) in H2SO4 (4.5 M, 125 mL) was stirred at 90°C for 16 hours. The mixture was cooled down at 10°C. The formed solid was filtered and the filter cake was dried by oil pump to give 1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione (11.2 g). The filtrate was extracted with ethyl acetate, dried and concentrated to give additional amounts of 1-methyl-6- (trifluoromethyl)pyrimidine-2, 4-dione (2.63 g, crude). Combined yield, over two steps, are 13.83 g (65.4%). 1H NMR (400 MHz, DMSO-cfe): 6 ppm = 11.84 (br s, 1 H), 6.21 (s, 1 H), 3.30 (s, 3H)
Example 1 - step 3:
3-(2,5-difluoro-4-nitro-phenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione
Figure imgf000043_0001
To a solution of 1 ,2,4-Trifluoro-5-nitrobenzene (CAS 2105-61-5; 70 g, 0.4 mmol) in N-methyl-2- pyrrolidon (2 L) was added CS2CO3 (130 g, 0.4 mmol) and 1-methyl-6-(trifluoromethyl)pyrimi- dine-2, 4-dione (78 g, 0.4 mmol). The mixture was stirred at 50°C for 16 hours. The mixture was poured into 1 N HCI, extracted with ethyl acetate, washed with brine, filtered and concentrated. The residue was purified by column chromatography to give a yellow solid. The solid was triturated with methyl-terf-butyl-ether (65 mL) to give the pure 3-(2,5-difluoro-4-nitro-phenyl)-1-me- thyl-6-(trifluoromethyl)pyrimidine-2, 4-dione (83 g, 59.1 %) as a yellow solid.
1H NMR (400 MHz, DMSO-cfe): 6 ppm = 8.41 (dd, J=8.91 , 6.78 Hz, 1 H), 7.89 (dd, J=10.85, 5.96 Hz, 1 H), 6.68 (s, 1 H), 3.44 (s, 3 H).
Example 1 - step 4:
3-[2-fluoro-5-(2-methoxyphenyl)sulfanyl-4-nitro-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-
2,4-dione
Figure imgf000043_0002
To a solution of 3-(2,5-difluoro-4-nitro-phenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione (20 g, 57 mmol) in dimethylformamide (200 mL) was added K2CO3 (15.7 g, 114 mmol) and 2- methoxybenzenethiol (CAS 7217-59-6, 8.8 g, 62.7 mmol). The resulting mixture was stirred at 90°C for 16 hours. The mixture was poured into 1 N HCI, extracted with ethyl acetate and the combined organic layers were washed with brine, dried over Na2SC>4 and concentrated. The residue was purified by column chromatography to give 3-[2-fluoro-5-(2-methoxyphenyl)sulfa- nyl-4-nitro-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione (25 g, 93.2%) as yellow solid.
1H NMR (400 MHz, DMSO-cfe): 6 ppm = 8.38 (d, J=9.38 Hz, 1 H), 7.50 - 7.59 (m, 2 H), 7.14 - 7.18 (m, 1 H), 7.02 - 7.08 (m, 2 H), 6.54 (s, 1 H), 3.70 (s, 3 H), 3.34 (s, 3 H). Example 1 - step 5:
3-[4-amino-2-fluoro-5-(2-methoxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-
2, 4-dione
Figure imgf000044_0001
To a solution of 3-[2-fluoro-5-(2-methoxyphenyl)sulfanyl-4-nitro-phenyl]-1-methyl-6-(trifluorome- thyl)pyrimidine-2 , 4-dione (25 g, 53 mmol) in ethanol (250 mL) and water (50 mL) was added NH4CI (14.2 g, 265 mmol) and Fe (14.2 g, 265 mmol). The mixture was stirred at 80°C for 4 hours. The mixture was then filtered and concentrated. The residue was purified by column chromatography to give 3-[4-amino-2-fluoro-5-(2-methoxyphenyl)sulfanyl-phenyl]-1-methyl-6- (trifluoromethyl)pyrimidine-2, 4-dione (23.5 g, crude) as brown solid.
1H NMR (400 MHz, DMSO-cfe): 6 ppm = 7.34 (d, J = 8.4 Hz, 1 H), 7.17 - 7.12 (m, 1 H), 7.01 (d, J = 7.4 Hz, 1 H), 6.85 (dt, J = 1.0, 7.6 Hz, 1 H), 6.71 (d, J = 12.5 Hz, 1 H), 6.62 (dd, J = 1.5, 7.8 Hz, 1 H), 6.50 (s, 1 H), 5.87 (s, 2H), 3.85 (s, 3H), 3.39 (s, 3H).
Example 1 - step 6:
3-[4-bromo-2-fluoro-5-(2-methoxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-
2,4-dione
Figure imgf000044_0002
To a solution of 3-[4-amino-2-fluoro-5-(2-methoxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoro- methyl)pyrimidine-2, 4-dione (23.5 g, 53.3 mmol) in acetonitrile (250 mL) was added CuBr2 (24.7 g, 106.6 mmol) in a portion at 15 °C and the mixture was heated to 60 °C. Then tert-BuONO (8.3 g, 79.95 mmol) was added drop-wise at 60 °C and the mixture was stirred at 60 °C for 1 hour. The mixture was poured into an aqueous NH4OH solution, extracted with ethylacetate and the combined organic layers were washed with brine, dried over Na2SO4 and concentrated. The residue was purified by preparative MPLC (MeCN-H2O, HCI) to give 3-[4-bromo-2-fluoro-5-(2- methoxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione (11.8 g, 38.2%) as yellow solid.
1H NMR (400 MHz, DMSO-cfe): 6 ppm = 7.51 (d, J=8.76 Hz, 1 H), 7.40 - 7.34 (m, 2 H), 7.00 - 6.93 (m, 2 H) 6.78 (d, J=7.38 Hz, 1 H), 6.29 (s, 1 H), 3.83 (s, 3 H), 3.51 (s, 3 H). Example 1 - step 7:
3-[4-bromo-2-fluoro-5-(2-hydroxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-
2, 4-dione
Figure imgf000045_0001
To a solution of 3-[4-bromo-2-fluoro-5-(2-methoxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoro- methyl)pyrimidine-2, 4-dione (11.8 g, 23.4 mmol) in dichloromethane (120 mL) was added BBr3 (11 .6 g, 46.8 mmol) at 0 °C and the mixture was stirred at 0°C to 25 °C for 2 hours. The mixture was poured into H2O, extracted with dichloromethane, the combined organic layers were washed with brine, dried over Na2SC>4 and concentrated to give 3-[4-bromo-2-fluoro-5-(2-hy- droxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2, 4-dione (13 g, crude) as yellow solid.
The crude 3-[4-bromo-2-fluoro-5-(2-hydroxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluorome- thyl)pyrimidine-2, 4-dione (300 mg) was purified by prep-HPLC (MeCN-H2O,HCI) to give 3-[4- bromo-2-fluoro-5-(2-hydroxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4- dione (130 mg, 3.3%) as yellow solid.
1H NMR (400 MHz, CDCI3): 5 ppm = 7.55 - 7.49 (m, 2 H), 7.45 - 7.39 (m, 1 H), 7.10 (dd, J=8.25, 1.13 Hz, 1 H), 6.99 (td, J=7.54, 1.19 Hz, 1 H), 6.50 (d, J=7.13 Hz, 1 H), 6.33 (br s, 1 H), 6.28 (s, 1 H), 3.50 (s, 3 H).
Example 1 - step 8: methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]sul- fanylphenoxy]-2-methoxy-acetate
Figure imgf000045_0002
To a mixture of 3-[4-bromo-2-fluoro-5-(2-hydroxyphenyl)sulfanyl-phenyl]-1-methyl-6-(trifluorome- thyl)pyrimidine-2, 4-dione (8.3 g, 16.9 mmol), K2CO3 (4.68 g, 33.8 mmol) in dimethylformamide (80 mL) was added methyl 2-bromo-2-methoxy-acetate (CAS 5193-96-4, 4.1 g, 22.1 mmol) drop-wise with stirring at 0 °C and the mixture was stirred for 4 hours at 20 °C. The mixture was poured into water, extracted with ethylacetate and the combined organic layers were washed with brine, dried over Na2SO4 and concentrated. The crude product was purified by prep-HPLC (MeCN-H2O, NH4HCO3) to give methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluo- romethyl)pyrimidin-1-yl]phenyl]sulfanylphenoxy]-2-methoxy-acetate (6.8 g, 68%) as a yellow solid.
1H NMR (400 MHz, CDCI3): 5 ppm = 7.53 (d, J=8.91 Hz, 1 H), 7.36 - 7.29 (m, 2 H), 7.16 (dd, J=8.22, 0.94 Hz, 1 H), 7.06 (td, J=7.56, 1.07 Hz, 1 H), 7.00 (dd, J=7.34, 5.21 Hz, 1 H), 6.29 (s, 1 H), 5.52 (s, 1 H), 3.77 (s, 3 H), 3.51 (s, 3 H), 3.45 (s, 3 H). B Use examples
The herbicidal activity of the thioethers of formula (I) was demonstrated by the following greenhouse experiments:
The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the test plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
Depending on the species, the test plants were kept at 10 - 25°C or 20 - 35°C, respectively. The test period extended over 2 to 3weeks. During this time, the test plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the test plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
The test plants used in the greenhouse experiments were of the following species:
Figure imgf000046_0001
At an application rate of 16 g/ha, the thioether I. a.38 (example) 1 applied post-emergent, showed very good herbicidal activity against AMARE, CHEAL, POLCO and SETVI.

Claims

Claims
1. Thioethers of formula (I)
Figure imgf000047_0001
wherein the substituents have the following meanings:
R° CH3;
R1 F;
R2 hydrogen or halogen;
R3 F;
R4 F;
R5 halogen or CN;
R6 H;
R7 Ci-Cs-alkoxy;
R8 OR9, wherein
R9 is hydrogen, Ci-Ce-alkyl or Ci-Ce-alkoxy-Ci-Ce-alkyl; n 1;
Q O or S;
W, Y1, Y2 O;
Z CH or N; including their agriculturally acceptable salts, amides, esters or thioesters, provided the compounds of formula (I) have a carboxyl group.
2. Thioethers of formula (I) according to claim 1 , wherein R2 is H or F.
3. Thioethers of formula (I) according to claim 1 or 2, wherein R2 is F.
4. Thioethers of formula (I) according to any of claims 1 to 3, wherein R5 is F, Cl, Br or CN.
5. Thioethers of formula (I) according to any of claims 1 to 4, wherein R5 is Br.
6. Thioethers of formula (I) according to any of claims 1 to 5, wherein R7 is OCH3.
7. Thioethers of formula (I) according to any of claims 1 to 6 wherein R8 is OR9, wherein R9 is hydrogen or Ci-Ce-alkyl.
8. Thioethers of formula (I) according to any of claims 1 to 7 wherein R8 is OR9, wherein R9 is Ci-C4-alkyl.
9. Thioethers of formula (I) according to any of claims 1 to 8, wherein Qis O.
10. Thioethers of formula (I) according to any of claims 1 to 9, wherein Z is CH. Thioethers of formula (I) according to any of claims 1 to 9, wherein Z is N. A herbicidal composition comprising an herbicidally active amount of at least one thioether of formula (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if appropriate, at least one surface-active substance. A process for the preparation of herbicidal active compositions, which comprises mixing an herbicidally active amount of at least one thioether of formula (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one surface-active substance. A method of controlling undesired vegetation, which comprises allowing an herbicidally active amount of at least one thioether of formula (I) as claimed in claim 1 to act on plants, their environment or on seed. The use of the thioethers of formula (I) as claimed in claim 1 as herbicides.
PCT/EP2022/073275 2021-09-02 2022-08-22 Uracil moiety containing thioether compounds for use as herbicides Ceased WO2023030936A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21194499.6 2021-09-02
EP21194499 2021-09-02

Publications (1)

Publication Number Publication Date
WO2023030936A1 true WO2023030936A1 (en) 2023-03-09

Family

ID=77626980

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/073275 Ceased WO2023030936A1 (en) 2021-09-02 2022-08-22 Uracil moiety containing thioether compounds for use as herbicides

Country Status (1)

Country Link
WO (1) WO2023030936A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040198607A1 (en) * 2001-09-28 2004-10-07 Nobuaki Mito Herbicide composition
US20040204318A1 (en) * 2001-09-28 2004-10-14 Nobuaki Mito Sumitomo chemical company limited
WO2011137088A1 (en) 2010-04-27 2011-11-03 E. I. Du Pont De Nemours And Company Herbicidal uracils
EP3028573A1 (en) 2014-12-05 2016-06-08 Basf Se Use of a triazole fungicide on transgenic plants
WO2017011288A1 (en) 2015-07-13 2017-01-19 E I Du Pont De Nemours And Company Aryloxypyrimidinyl ethers as herbicides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040198607A1 (en) * 2001-09-28 2004-10-07 Nobuaki Mito Herbicide composition
US20040204318A1 (en) * 2001-09-28 2004-10-14 Nobuaki Mito Sumitomo chemical company limited
WO2011137088A1 (en) 2010-04-27 2011-11-03 E. I. Du Pont De Nemours And Company Herbicidal uracils
EP3028573A1 (en) 2014-12-05 2016-06-08 Basf Se Use of a triazole fungicide on transgenic plants
WO2017011288A1 (en) 2015-07-13 2017-01-19 E I Du Pont De Nemours And Company Aryloxypyrimidinyl ethers as herbicides

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
CAS, no. 7217-59-6
GREENE, T. W.WUTS, P. G. M.: "Protective Groups in Organic Synthesis", 2007, WILEY
L. KURTIB. CZAKO: "Strategic Applications of Named Reactions in Organic Synthesis", 2005, T&F INFORMA, article "New developments in crop protection product formulation", pages: 394 - 395
LANGLOIS, B.: "Houben-Weyl, Methods of Organic Chemistry", vol. E10a, 1999, THIEME, article "In Introduction of Fluorine via Diazonium Compounds (Fluorodediazoniation", pages: 686 - 740
LOWELL, ANDREW N. ET AL., TETRAHEDRON, vol. 6, no. 30, 2010, pages 5573 - 5582
MCCUTCHEON: "Emulsifiers & Detergents", vol. 1, 2008, MCCUTCHEON'S DIRECTORIES
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
PNAS, vol. 107, no. 19, 2010, pages 8563 - 856

Similar Documents

Publication Publication Date Title
AU2016212053B2 (en) Herbicidal phenylpyrimidines
KR102420191B1 (en) Herbicidal uracilpyrid
US20240287028A1 (en) Herbicidal phenyluracils
CN104884441B (en) Herbicidal azines
JP6441334B2 (en) Herbicidal azine
AU2021230070A1 (en) Herbicidal phenyluracils
BR112019010732B1 (en) PHENYLTRIAZOLINONES, PROCESS FOR THE PREPARATION OF PHENYLTRIAZOLINONES, HERBICIDIAL COMPOSITIONS, PROCESS FOR THE PREPARATION OF ACTIVE HERBICIDIAL COMPOSITIONS, METHOD FOR CONTROLLING UNDESIRED VEGETATION AND USE OF PHENYLTRIAZOLINONES
WO2013092244A1 (en) Herbicidal triazines
WO2023030935A1 (en) Method for controlling ppo-i resistant weeds
WO2023030936A1 (en) Uracil moiety containing thioether compounds for use as herbicides
CA3025223C (en) Herbicidal uracilpyridines
EA045807B1 (en) HERBICIDAL URACILPYRIDINES

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22768378

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22768378

Country of ref document: EP

Kind code of ref document: A1