EP1076655A1 - N-pyridonyl herbicides - Google Patents

N-pyridonyl herbicides

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Publication number
EP1076655A1
EP1076655A1 EP99919194A EP99919194A EP1076655A1 EP 1076655 A1 EP1076655 A1 EP 1076655A1 EP 99919194 A EP99919194 A EP 99919194A EP 99919194 A EP99919194 A EP 99919194A EP 1076655 A1 EP1076655 A1 EP 1076655A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
compounds
compound
haloalkyl
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.)
Withdrawn
Application number
EP99919194A
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German (de)
French (fr)
Inventor
Kurt Nebel
Walter Kunz
Jean Wenger
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.)
Syngenta Participations AG
Original Assignee
Novartis AG
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Filing date
Publication date
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Publication of EP1076655A1 publication Critical patent/EP1076655A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to novel, herbicidally active substituted N-pyridonyl nitrogen heterocycles, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth, and also in the non-selective control of weeds.
  • crops of useful plants for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth, and also in the non-selective control of weeds.
  • N-Pyridyl-pyrazoles and N-pyridyl-tetramethylenetriazolidine-dione compounds having herbicidal activity are described, for example, in DE-A-3 917 469, DE-A-19 518 054, DE-A-19 530 606 and US-A-5 306 694.
  • N-(2-Pyridyl)-pyridazinone compounds having herbicidal activity are described, for example, in JP-A-58-213 776.
  • the present invention therefore relates to compounds of formula I
  • R-i is hydrogen, fluorine, chlorine, bromine or methyl
  • R 2 is C ⁇ -C alkyl, C ⁇ -C haloalkyl, halogen, nitro, amino, cyano or R 3 O- ;
  • R 43 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, CrC 8 haloalkyl, cyano-CrC 8 alkyl, C 3 -C 8 haloalkenyl, hydroxy-CrC alkyl, C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkyl, C 3 -C 6 - alkenyloxy-C 1 -C 4 alkyl, C 3 -C 6 alkynyloxy-CrC 4 alkyl, C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkoxy-C ⁇ -C 4 -alkyl, C C 4 alkylthio-C ⁇ -C alkyl, C ⁇ -C 8 alkylcarbonyl, CrC 8 alkoxycarbonyl, C 3 -C 8 alkenyl- oxycarbonyl, benzyloxy-Ci- or
  • heteroaromatic rings being unsubstituted or mono- to tri-substituted by halogen, d-dalkyl or by d-C haloalkyl; or
  • R 44 X 16 C(0)-[C 1 -C 8 alkylene]- R 43 is R ⁇ Xie CCOJ-d-Cealkyl- or ;
  • _ ⁇ N — X 16 is oxygen, sulfur or 45 ⁇ ;
  • R 44 is hydrogen, CrC 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, C ⁇ -C 8 haloalkyl, C 3 -C 8 haloalkenyl, d-dalkoxy-d-dalkyl, d-Cealkenyloxy-d-dalkyl, d-C 4 alkylthio-C ⁇ - C 4 alkyl, phenyl, phenyl mono- to tri-substituted by halogen, C ⁇ -C alkyl or by C C -halo- alkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, d-C alkyl or by C ⁇ -C 4 haloalkyl;
  • R 45 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, d-C 8 haloalkyl or benzyl;
  • R 3 is hydroxy, C C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 all ynyloxy, CrC 6 haloalkoxy, C 3 -C 6 - haloalkenyloxy, C ⁇ -C 6 alkoxy-d-C 6 alkyl, C 3 -C 6 alkenyloxy-CrC 6 alkyl, C 3 -C 6 alkynyloxy- C C 6 alkyl, d-Cealkoxy-d-Cealkoxy-d-Cealkyl, B -Cealkoxy, R 4 (R 5 )N-, C C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 - halocycioalkyl
  • B-i is cyano, OHC-, HOC(O)-, C C ⁇ alkylcarbonyl, d-C 6 haloalkylcarbonyl, C C 6 alkoxy- carbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, benzyloxy, benzyloxy- carbonyl, benzyloxycarbonyl mono- to tri-substituted on the phenyl
  • R 4 and R 5 are each independently of the other hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 - alkynyl, C C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy-C ⁇ -C 6 alkyl, OHC-, d-C 6 alkylcarbonyl, C C 6 haloalkylcarbonyl, C r C 6 alkyl-S(O) 2 - or C C 6 haloalkyl- S(O) 2 -;
  • R 6 and R 7 are each independently of the other hydrogen, C C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 - alkynyl, C C 6 haloalkyl, C 3 -C 6 haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, C C alkyl or by d-C 4 haloalkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C C alkyl or by C r C 4 haloalkyl;
  • Xi is oxygen or sulfur
  • W is a group T ? " ( ⁇ )> T jj " (W2)l rl (Wa) '
  • R 8 is CrC 3 alkyl, C C 3 haloalkyl or amino
  • R 9 is d-C 3 haloalkyl, d-C 3 alkyl-S(O) n1 , CrC 3 haloalkyl-S(O) n1 or cyano; or
  • R 8 and Rg together form a C 3 - or C 4 -alkylene bridge or C 3 - or C 4 -alkenylene bridge, each of which may be substituted by halogen, C C 3 haloalkyl or by cyano; n-i is O, 1 or 2; R-io is hydrogen, d-C 3 alkyl, halogen, d-C 3 haloalkyl or cyano; or R 10 and R 9 together form a C 3 - or C -alkylene bridge or C 3 - or C 4 -alkenylene bridge, each of which may be substituted by halogen, C C 3 haloalkyl or by cyano; Rn is hydrogen, C C 3 alkyl, halogen or cyano; R- I2 is d-C 3 haloalkyl;
  • R 12 and Rn together form a C 3 - or C 4 -alkylene bridge or C 3 - or C 4 -alkenylene bridge;
  • R 13 is hydrogen, C C 3 alkyl or halogen;
  • R 13 and R 12 together form a C 3 - or C 4 -alkylene bridge or C 3 - or C 4 -alkenylene bridge;
  • R M is hydrogen, C 1 -C 3 alkyl, halogen, C C 3 haloalkyl, R 33 O-, R 3 S(O) n2 , R 35 (R 36 )N,
  • R 3 ⁇ (R 39 )N-C(R 37 ) N-, hydroxy, nitro or N ⁇ C-S- ;
  • R 33 is C C 3 alkyl, d-C 3 haioalkyl, C 2 -C 4 alkenyl, C 3 - or C -alkynyl or C r C 5 alkoxycarbonyl- C C 4 alkyl;
  • R 34 is C C alkyl or C C 4 haloalkyl; n 2 is 0, 1 or 2;
  • R 35 is hydrogen, C C 4 alkyl, C C 4 haloalkyl, C 3 -C 6 cycloalkyl, OHC- or C C 4 alkylcarbonyl;
  • R 38 is C C 4 alkyl
  • R 15 is hydrogen, C C 4 alkyl, halogen, Crdhaloalkyl, C 2 -C 4 alkenyl, C 3 -C 5 haloalkenyl, C 3 - or C 4 -alkynyl, C C 4 alkoxy, CrC 4 alkylcarbonyl, C C 4 haloaIkylcarbonyl, C 2 -C 4 alkenyl- carbonyl, C 2 -C 4 haioalkenylcarbonyl, C 2 -C alkynyicarbonyl, C -C 4 haloalkynylcarbonyl, d-C 4 alkoxycarbonyl, C C 4 alkylcarbamoyl, C r C 4 alkylS(O) n3 , C 3 - or C -alkynylS(O) n3 ,
  • n 3 is 0, 1 or 2;
  • R ⁇ 6 and R ⁇ 7 are each independently of the other hydrogen, C C 4 alkyl, halogen, C C 4 halo- alkyl or cyano;
  • R 20 and R 2 ⁇ are each independently of the other hydrogen, C C 4 alkyl or C C haloalkyl;
  • R 22 and R 23 are each independently of the other hydrogen, C C 3 alkyl, halogen or hydroxy;
  • R 24 and R 25 are each independently of the other hydrogen or C C 4 alkyl; or
  • R 40 and R 41 are each independently of the other d-C 4 alkyl; or - 5 -
  • R 40 and R together form a C 4 - or C 5 -alkylene bridge
  • R 26 is hydrogen or C C 3 alkyl ;
  • R 29 and R 30 are each independently of the others hydrogen, C C 3 alkyl, C 3 - or C 4 - alkenyl or C 3 -C 5 alkynyl; or R 2 and R 28 together and/or R 2 g and R 30 together in each case form a C 2 -C 5 alkylene bridge or C 3 -C 5 alkenylene bridge, each of which may be interrupted by oxygen, sulfur or -
  • R 31 is hydrogen, d-C 4 alkyl, C C haloalkyl, C 3 - or C 4 -alkenyl, C 3 - or d-haloalkenyl or C 3 - or C -alkynyl;
  • R 32 is hydrogen, d-C 4 alkyl, C C 3 alkoxy-C ⁇ - or -C 2 -alkyl, C C 4 haloalkyl, C 3 - or C 4 -alkenyl,
  • halogen is to be understood as being iodine or, preferably, fluorine, chlorine or bromine.
  • Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyi and the various isomeric pentyl and hexyl radicals. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
  • alkenyl radicals examples include vinyl, allyl, methallyl, 1 -methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals - 6 -
  • alkynyl radicals examples include ethynyl, propargyl, 1 -methyl- propargyl, 3-butynyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-
  • alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
  • Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro- ethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl.
  • Suitable haioalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl,
  • alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms.
  • the alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
  • Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3- fluoropropynyl, 3-chioropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4- trif luoro-but-2-yn-1 -yl.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
  • Alkyisulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri- fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
  • Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
  • Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyi or 3-hydroxypropyl.
  • Alkylamino is, for example, methylamino, ethylamino or an isomer of propylamino or butyl- amino. - 7 -
  • Dialkylamino is, for example, dimethylamino, diethylamino or an isomer of dipropylamino or dibutylamino.
  • Alkenylamino is, for example, allylamino, methallylamino or but-2-en-1-ylamino.
  • Alkynylamino is, for example, propargylamino or 1-methylpropargylamino.
  • Haloalkylamino is, for example, chloroethylamino, trifluoroethylamino or 3-chloropropyl- amino.
  • Di(haloalkyl)amino is, for example, di(2-chloroethyl)amino.
  • Alkylcarbonyl is especially acetyl or propionyl.
  • Haloalkylcarbonyl is especially trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl or
  • Alkenylcarbonyl is especially vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1 - ylcarbonyl, pentenylcarbonyl or 2-hexenylcarbonyl.
  • Alkynylcarbonyl is especially acetylenecarbonyl, propargylcarbonyl, 1 -methyipropargyl- carbonyl, 3-butynylcarbonyl, but-2-yn-1 -ylcarbonyl or pent-4-yn-1-ylcarbonyl.
  • Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy, tert-butoxy or an isomer of pentyloxy or hexyloxy.
  • Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1 -yloxy.
  • Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkenyloxyalkyl is, for example, allyloxyalkyl, methallyloxyalkyl or but-2-en-1-yloxyalkyl.
  • Alkynyloxyalkyl is, for example, propargyloxyalkyl or 1-methylpropargyloxyalkyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
  • Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1- yloxycarbonyl, pentenyloxycarbonyl or 2-hexenyloxycarbonyl.
  • Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1- yloxycarbonyl or 2-methylbutyn-2-yioxycarbonyl.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy.
  • Suitable haloalkenyloxy radicals are alkenyloxy groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyloxy, 2- or 3-chloropropenyloxy, 2- or 3-bromopropenyloxy,
  • cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or up to per-halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl,
  • substituents in combined definitions such as, for example, alkylcarbonyloxy, alkoxyalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxy- carbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, haloalkynylcarbonyl, alkylthio-C(O)-, alkenylthio, alkynylthio, alkyl-S(O)-, alkylsulfonyloxy, R 33 O-, R 4 (R 5 )N-, R 35 (R 36 )N-,
  • L in the reagents of formulae VI, XI, XIX, XXVIII, XXXIa, XXXIb and XXXXII denotes a leaving group, such as, for example, halogen, preferably chlorine, bromine or iodine,
  • L T in the reagent of formula XX denotes a leaving group, such as, for example, HOS(O) 2 O-,
  • L 2 in the reagents of formulae XXXIIa and XXXIIc denotes a leaving group, such as, for example, hydroxy, d-C 4 alkoxy or halogen, preferably chlorine, bromine or iodine.
  • a leaving group such as, for example, hydroxy, d-C 4 alkoxy or halogen, preferably chlorine, bromine or iodine.
  • L 3 in the reagent of formula XXXVIII denotes a leaving group, such as, for example, chlorine
  • cyanoalkyl alkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyl, haloalkenyicarbonyl, alkynylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl and haloalkylcarbonyl
  • the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be.
  • the invention relates also to the salts that the compounds of formula I having azide hydrogen, especially the derivatives with carboxylic acid and sulfonamide groups (e.g.
  • carboxyl-substituted alkyl and alkoxy groups and alkyl-S(O) 2 NH and haloalkyl-S(O) 2 NH groups) are able to form with bases.
  • Those salts are, for example, alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium.
  • Suitable salt formers are described, for example, in WO 97/41112.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C ⁇ -C ⁇ 8 alkylamines, d-C hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methyiamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyloctadecylamine
  • heterocyciic amines for example pyridine, quinoiine, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
  • the salts of compounds of formula I having basic groups, especially having basic pyrazolyl rings (W 3 , W 4 ), or the derivatives with amino groups, for example alkylamino and dialkyl- amino groups, in the definition of R 3 , R 8 or R ⁇ are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid and nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or
  • Ri is hydrogen, fluorine, chlorine, bromine or methyl; R is methyl, halogen, hydroxy, nitro, amino or cyano; and R 3 , Xi and W are as defined for formula I. - 11 -
  • X10 and X15 are as defined for formula I.
  • Preferred compounds of formula I are those wherein W is a group
  • X 8 , Xn and X 12 are as defined for formula I.
  • Ri is hydrogen, fluorine or chlorine
  • R is chlorine, bromine, cyano or CF 3
  • Xi is oxygen
  • R-i is fluorine or chlorine
  • R 2 is chlorine, bromine or cyano
  • Ri is fluorine
  • R is chlorine
  • R 1 f R 2 and W are as defined for formula I;
  • Xi is O or S;
  • R 3 is d-Cealkoxy-Ci-Ce- alkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 - haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, BrC ⁇ -C 6 alkyl,
  • R ⁇ R 2 and W are as defined for formula I and R 03 is a lower alkoxy group, e.g. d- or C -alkoxy, benzyloxy or halogen, e.g. chlorine or bromine, by first reacting a compound of formula IVa with an alkylating agent of formula VI
  • MnO 2 manganese dioxide
  • K 3 Fe(CN) 6 potassium hexacyanoferrate
  • Ri, R 2 and W are as defined for formula I;
  • Xi is S;
  • R 3 is hydroxy, C ⁇ -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 6 haloalkoxy, C 3 -C 6 haloalkenyioxy, B ⁇ -CrC 6 alkoxy, d-C 6 alkyicarbonyloxy, C 3 -C 8 trialkylsilyloxy, (hydroxy-d-C 5 alkyl)-O- or (B ⁇ -C ⁇ -C 5 hydroxy- alkyl)-O-; and B 1 is as defined for formula I is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises first oxidising a compound of formula III
  • X 1 R 3 wherein R ⁇ R 2 , R 3 and W are as defined for formula I and Xi is S is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises treating a compound of formula I - 17 -
  • R 1 ? R 2 , R 3 and W are as defined and X ⁇ is O in an inert solvent with a sulfur reagent, for example phosphorus pentasulfide or Lawesson reagent.
  • a sulfur reagent for example phosphorus pentasulfide or Lawesson reagent.
  • W is a group Wi — R 9 (W T ) and
  • R10, X 2 and X 3 are as defined for formula I (corresponding to the compound of formula Ilia in Reaction Scheme 2), comprises, for example, converting a compound of formula XII
  • Ri and R 2 are as defined and Hal is fluorine, chlorine or bromine, in the presence of an inert solvent and ammonia, if appropriate in an autoclave at temperatures of from -10 to 180°C, into a compound of formula XIII
  • R 1 R 2 , R 9 , Rio, X 2 and X 3 are as defined, and reacting that compound further in the presence of an inert solvent and a base c) with a compound of formula XIX
  • Ri, and R 11 , R 12 , R ⁇ 3 and X 4 are as defined for formula I (corresponding to the compound of formula lllb in Reaction Scheme 3), comprises, for example, either a) converting a compound of formula XII
  • R T and R 2 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent, into a compound of formula XXI - 20 -
  • R ⁇ 3 is as defined and X is oxygen.
  • X, ⁇ , R25, R 2 6, X9 and X10 are as defined for formula I (corresponding to the compound of formula lllg in Reaction Scheme 4), comprises, for example, reacting either a) a compound of formula XVa
  • R 26 -L (XXVIII), wherein R 26 is d-C 3 aIkyl and L is a leaving group.
  • W is a group W ⁇ — N i, (W 8 ) and
  • R27, 2 8, X11 and X ⁇ 2 are as defined for formula I (corresponding to the compound of formula lllh in Reaction Scheme 5), comprises, for example, reacting a) a compound of formula XVb
  • R ⁇ 4 , R 15 and R 16 are as defined for formula I (corresponding to the compound of formula lllc in Reaction Scheme 6), comprises, for example, condensing a compound of formula XXI
  • R 15 wherein R ⁇ is hydrogen, d-C 3 alkyl or d-C 3 haloalkyl; R i5 is hydrogen, d-C 4 alkyl, d-C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 5 haloalkenyl or C 3 - or C 4 -alkynyl and R ⁇ 6 is hydrogen, C ⁇ -C 4 alkyl or d-C 4 haloalkyl, if appropriate in the presence of an acidic, basic or bifunctional catalyst, e.g. p-toluenesulfonic acid, or b) with a compound of formula XXXIIa
  • R ⁇ 8 and R ⁇ 9 are as defined and R ⁇ 7 is hydrogen, d-C 4 alkyl or C ⁇ -C haioalkyl, if appropriate in the presence of a catalyst, or b) with a compound of formula XXXIIc
  • a halogenating agent e.g. a phosphorus oxyhalide or thionyl halide
  • R 1 ( R 2 , R ⁇ 8 and R ⁇ 9 are as defined and R ⁇ 7 is halogen, and optionally reacting that compound with a cyanide of formula XXXIV
  • W is a group W 5 — N
  • formula I (corresponding to the compounds of formulae llle and lllf, respectively, in Reaction Scheme 8), comprises, for example, reacting a) a compound of formula XXXV
  • Ri, R 2 and R 20 to R 23 are as defined and X 5 to X 8 are oxygen, with the aid of a suitable sulfur reagent, into the corresponding thiono compound of formula Hie or lllf wherein X 5 and/or X 6 and X 7 and/or X 8 are sulfur respectively (Reaction Scheme 8).
  • R29, R30, X13 and X ⁇ 4 are as defined for formula I (corresponding to the compound of formula llli in Reaction Scheme 9), comprises, for example, reacting a) a compound of formula XVc - 29 -
  • W is a group W ⁇ 0 N A ⁇ / '31 wh N N (W ⁇ 0 )
  • H 32 and R 31 , R 32 and X ⁇ 5 are as defined for formula I (corresponding to the compound of formula lllk in Reaction Scheme 10), comprises, for example, a) reacting a compound of formula XXI
  • R 3 ⁇ is C ⁇ -C 4 alkyl, C ⁇ -Chaloalkyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl or C 3 - or C 4 -alkynyl and L is a leaving group.
  • Reaction Scheme 2 R, a) CIC(X 2 )0-C 1 -C 4 alkyl or
  • thionation reagent e.g. Lawesson reagent solvent
  • Reaction Scheme 2 shows a selection of suitable preparation procedures, the choice of the reaction routes and the reagents being governed by the reactivities of the substituents in the intermediates.
  • the carbamate and the iso(thio)cyanate of formulae XV and XVI may be cyclised in the presence of an enamine derivative of formula XVII in an inert solvent to form a uracil derivative of formula XVIII, the reaction of the iso(thio)cyanate of formula XVI advantageously being carried out in the presence of from 0.1 to 1.5 equivalents of a base, e.g. sodium hydride, potassium tert-butanolate or an alkaline earth metal oxide or hydroxide, e.g. barium hydroxide.
  • a base e.g. sodium hydride, potassium tert-butanolate or an alkaline earth metal oxide or hydroxide, e.g. barium hydroxide.
  • the compounds of formula lllb may be prepared in accordance with known methods, for example in accordance with Reaction Scheme 3 (variant a)), by reacting a 2-halopyrid ⁇ ne - 36 -
  • the hydrazone derivative of formula XXIV may also be obtained from the 2-aminopyridine derivative of formula XIII via diazotisation, preferably with exclusion of water, and subsequent coupling to the ketonic acid of formula XXIII (Japp-
  • the compounds of formula lllg may be prepared analogously to known methods, for example as described in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509,
  • a carbamate derivative of formula XVa may be cyclised in the presence of a solvent and a base, or - 38 -
  • an iso(thio)cyanate of formula XVIa may be cyclised, if appropriate in a suitable solvent, with an amino acid derivative of formula XXVI via a compound of formula XXVII in the presence of a base and a suitable solvent to form a compound of formula lllg.
  • R 26 is hydrogen and X 9 and/or X ⁇ 0 are oxygen
  • alkylation e.g. ⁇ -L, R 28 -L, or
  • the compounds of formula lllh may be prepared analogously to known procedures, for example as described in EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955.
  • EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955 for example, in accordance with Reaction Scheme 5 either - 40 -
  • a carbamate derivative of formula XVb may be cyclised in the presence of a solvent and a base, or b) an iso(thio)cyanate of formula XVIb may be cyclised, if appropriate in a suitable solvent, with a carbazate of formula XXIX via a compound of formula XXX in the presence of a base and a suitable solvent to form a compound of formula lllh.
  • halogenation reagent e.g. N * '16
  • the pyrazole compounds of formula lllc may be prepared, for example, either from the hydrazinopyridine derivatives of formula XXI by means of condensation with a 1 ,3-dicarbonyl derivative of formula XXXII (variant a)), or by means of condensation with a ⁇ -carbonylcarboxylic acid derivative of formula XXXIIa wherein L 2 is a leaving group, for example d-C 4 alkoxy, hydroxy or halogen, e.g.
  • R ⁇ 5 is hydrogen
  • an electrophilic reagent e.g. a halogenating agent, such as elemental halogen or sulfuryl - 42 -
  • Ri to R 3 , R ⁇ to R ⁇ 6 and Xi are as defined for formula I, may be obtained, as described above, from compounds of formula lllc by means of oxidation of the pyridyl moiety.
  • the pyridono derivatives of formula Ic may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa
  • R 1 R 2 and R 3 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent.
  • the compounds of formula Ic may also be obtained in manner analogous to that described in J. Het. Chem. 15, 1221 (1978) and in Reaction Scheme 11 , by substitution of a pyridonyl derivative of formula Xlla that is provided with a leaving group U, 43
  • a halide e.g. a halide, a d-C alkyl- or phenyl-sulfonyl group or an unsubstituted or substituted d- dalkyl- or phenyl-sulfonyloxy group, (variant c) in Reaction Scheme 11), or by substitution of a pyridine derivative of formula XII that is provided with a leaving group U, e.g.
  • a halide a d-dalkyl- or phenyl-sulfonyl group or an unsubstituted or substituted C ⁇ -C 4 alkyl- or phenyl-sulfonyloxy group, (variant d) in Reaction Scheme 11 ), with a pyrazole of formula W 03 or an alkali metal salt thereof, and in the case of variant d) by subsequent functionalisation (oxidation) of the pyridyl moiety of the compound of formula lllc.
  • the substitution reactions according to variants c) and d) may optionally be carried out in the presence of a suitable solvent and a base.
  • the tetrahydroindazole compounds of formula llld may be obtained according to known procedures from the hydrazinopyridine derivatives of formula XXI, for example either by condensation with a cyclohexanone derivative of formula XXXIIb that is acylated in the 2-position, wherein R ⁇ 7 is as defined for formula I with the exception of R i7 as halogen or cyano, (variant a)), or by condensation with a cyclohexanone derivative of formula XXXIIc wherein L 2 is a leaving group, for example C ⁇ -C 4 alkoxy, hydroxy or halogen, e.g.
  • the pyrrolinedione derivatives of formula Hie and the tetrahydroisoindolinedione derivatives of formula lllf may be obtained analogously to known procedures, for example by reaction of an anhydride of formula XXXV (variant a)) or XXXVa (variant b)) with an aminopyridine of formula XIII in an inert solvent, for example an ether, e.g. dioxane, or a lower alkylcarboxylic acid, e.g. propionic acid, at temperatures of from 20 to 200°C.
  • an inert solvent for example an ether, e.g. dioxane, or a lower alkylcarboxylic acid, e.g. propionic acid
  • the pyridono derivatives of formulae le and If may also be obtained directly from the corresponding aminopyridone derivatives of formula Xllla
  • the compounds of formula llli may be prepared according to known procedures, for example by first reacting a carbamate of formula XVc (variant a)) or an isothiocyanate of formula XVIc (variant b)) with a hydrazine derivative of formula XXXVI to form a semicarbazide derivative of formula XXXVII and then reacting the latter in the presence of a carbonylating or thiocarbonylating reagent of formula XXXVIII. Both reaction steps are advantageously carried out in a suitable solvent and in the presence of a base.
  • As (thio)carbonylating reagent of formula XXXVIII there come into consideration e.g. phosgene, diphosgene, thiophosgene and carbonyldiimidazole.
  • L 3 in formula XXXVIII is therefore a leaving group, for example halogen, e.g. chlorine or bromine,
  • Ri to R 3 , R 29 , R 30 , Xi, X 13 and X ⁇ are as defined for formula I, may be obtained from the compounds of formula llli in the manner described above, by means of oxidation of the pyridyl moiety.
  • the pyridono derivatives of formula li may also be obtained directly from the corresponding pyridone carbamates of formula XVd
  • the triazolone derivatives of formula lllk may be prepared analogously to known procedures, for example by using as starting material a hydrazinopyridine derivative of formula XXI which, in accordance with variant a), is reacted with a keto acid of formula XXXIX, advantageously in the presence of an acid catalyst, e.g. a lower alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. sulfuric acid or hydrochloric acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, to form a hydrazone derivative of formula XXXX.
  • an acid catalyst e.g. a lower alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. sulfuric acid or hydrochloric acid, or a sulfonic acid, e.g. p-toluenesulf
  • a hydrazinopyridine derivative of formula XXI may be cyclised with an imino ether of formula XXXXIII to form a triazolone derivative of formula lllk wherein X 15 is oxygen and R 31 is hydrogen and then optionally alkylated or thionated as described under variant a).
  • a hydrazinopyridine derivative of formula XXI may be converted first with an aldehyde of formula XXXXIV, then in the presence of a lower alkylcarboxylic acid, e.g. acetic acid, with an alkali metal cyanate to form a compound of formula XXXXV, which may or may not be isolated, and finally cyclised - 50 -
  • a lower alkylcarboxylic acid e.g. acetic acid
  • Ri to R 3 , R 31 , R 32 , Xi and X ⁇ 5 are as defined for formula I, may be obtained from the compounds of formula lllk as described above, by means of oxidation of the pyridyl moiety.
  • the pyridono derivatives of formula Ik may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa
  • the 2-aminopyridines of formula XIII may also be prepared by degradation reactions according to Curtius, Hofmann or Lossen from corresponding pyridine derivatives with carboxylic acid, carboxylic acid chloride, carboxylic acid azide, carboxylic acid ester or carboxylic acid amide functions in the 2-position.
  • reagents of formulae XIV, XVa, XVb, XVIa, XVIb, XVII, XIX, XX, XXII, XXIIa, XXIII, XXV, XXVI, XXVIII, XXIX, XXXIa, XXXIb, XXXII, XXXIIa, XXXIIb, XXXIIc, XXXIV, XXXV, XXXVa, XXXVI, XXVIII, XXXIX, XXXXI, XXXII, XXXIII and XXXXIV used in Reaction Schemes 2 to 10 are either known or may be prepared in analogy to known methods.
  • the reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xyiene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, N,N-diethylformamide or N-methylpyrroiidinone.
  • the reaction temperatures are preferably from -20°C to +120°C.
  • the reactions are generally slightly exothermic and may usually be carried out at room temperature.
  • the reaction mixture may be heated to its boiling point for a short time.
  • the reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5- diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate. - 52 -
  • the compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography and a suitable eluant.
  • the compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of - 53 -
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques.
  • the weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Steliaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. - 54 -
  • a further 5 g of hydrogen peroxide/urea adduct and 3 ml of trifluoroacetic acid anhydride are then added in two portions in the course of 3 hours and after the exothermic reaction has subsided the reaction mixture is heated at 25-35°C until the reaction is complete.
  • the reaction mixture is then cooled and at -5°C adjusted to pH 7.5 first with 2N sodium hydroxide solution and then with saturated sodium hydrogen carbonate solution and partitioned between dichloromethane and ice-water; the organic phase is separated off, dried over sodium sulfate, filtered and concentrated by evaporation.
  • the solid residue that remains is recrystallised from ethyl acetate/n-hexane, yielding the desired product having a melting point of 142- 143°C.
  • Example P6 Preparation of 1-(2-propar ⁇ yloxy-3-chloro-5-fluoro-Pyridin-6-yl)-3-methyl-4- trifluoromethyl-pyrimidine-2.6-dione. 1 -(2-chloro-3-propar ⁇ yloxy-5-fluoro-pyridin-6-yl)-3- methyl-4-trifluoromethyl-pyrimidine-2.6-dione and 1 -(1 -propar ⁇ yloxy-3-chloro-5-fluoro-2- pyridon-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2.6-dione
  • Example P9 Preparation of 2-(5-chloro-3-fluoro-6-hvdroxy-pyridin-2-yl)-4.5.6.7-tetrahvdro- isoindolo-1 ,3-dione and 2-(5-hvdroxy-6-chloro-3-fluoro-pyridin-2-yl)-4.5,6,7-tetrahydro- isoindolo-1 ,3-dione
  • N N ⁇ x R 3 corresponding substituents R 1 t Xi and R 3 are indicated in Table A, so that 423 specific compounds of formula l 2 are disclosed.

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Abstract

Compounds of formula (I), wherein R1 is hydrogen, fluorine, chlorine, bromine or methyl; R2 is C1-C4alkyl, C1-C4haloalkyl, halogen, nitro, amino, cyano or R43O- ; R3 is as in claim 1; X1 is oxygen or sulfur; W is a group (W1), (W2), (W3), (W4), (W5), (W6), (W7), (W8), (W9) or (W10); and R8 to R32, R43 and X2 to X15 are defined in claim 1, and the agrochemically acceptable salts and stereoisomers of such compounds of formula (I), are suitable for use as herbicides.

Description

- 1 -
N-PYRIDONYL HERBICIDES
The present invention relates to novel, herbicidally active substituted N-pyridonyl nitrogen heterocycles, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth, and also in the non-selective control of weeds.
N-Pyridyl-pyrazoles and N-pyridyl-tetramethylenetriazolidine-dione compounds having herbicidal activity are described, for example, in DE-A-3 917 469, DE-A-19 518 054, DE-A-19 530 606 and US-A-5 306 694.
N-(2-Pyridyl)-pyridazinone compounds having herbicidal activity are described, for example, in JP-A-58-213 776.
Novel N-pyridonyi nitrogen heterocycles having herbicidal and growth-inhibiting properties have now been found.
The present invention therefore relates to compounds of formula I
Ft,
(I).
■ N
X, Ft, wherein
R-i is hydrogen, fluorine, chlorine, bromine or methyl;
R2 is Cι-C alkyl, Cι-C haloalkyl, halogen, nitro, amino, cyano or R 3O- ;
R43 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, CrC8haloalkyl, cyano-CrC8alkyl, C3-C8haloalkenyl, hydroxy-CrC alkyl, Cι-C4alkoxy-Cι-C4alkyl, C3-C6- alkenyloxy-C1-C4alkyl, C3-C6alkynyloxy-CrC4alkyl, Cι-C4alkoxy-Cι-C4alkoxy-Cι-C4-alkyl, C C4alkylthio-Cι-C alkyl, Cι-C8alkylcarbonyl, CrC8alkoxycarbonyl, C3-C8alkenyl- oxycarbonyl, benzyloxy-Ci- or -C2-alkyl, benzylcarbonyi, benzyloxycarbonyl, phenyl, phenyl-C2-C8alkyl, benzyl, pyridyl, pyrimidinyl, pyrazinyi or pyridazinyl, those aromatic - 2 -
and heteroaromatic rings being unsubstituted or mono- to tri-substituted by halogen, d-dalkyl or by d-C haloalkyl; or
R44X16C(0)-[C1-C8alkylene]- R43 is R^Xie CCOJ-d-Cealkyl- or ;
(C6H5)
_τN — X16 is oxygen, sulfur or 45 ι ;
R44 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, Cι-C8haloalkyl, C3-C8haloalkenyl, d-dalkoxy-d-dalkyl, d-Cealkenyloxy-d-dalkyl, d-C4alkylthio-Cι- C4alkyl, phenyl, phenyl mono- to tri-substituted by halogen, Cι-C alkyl or by C C -halo- alkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, d-C alkyl or by Cι-C4haloalkyl;
R45 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, d-C8haloalkyl or benzyl;
R3 is hydroxy, C C6alkoxy, C3-C6alkenyloxy, C3-C6all ynyloxy, CrC6haloalkoxy, C3-C6- haloalkenyloxy, Cι-C6alkoxy-d-C6alkyl, C3-C6alkenyloxy-CrC6alkyl, C3-C6alkynyloxy- C C6alkyl, d-Cealkoxy-d-Cealkoxy-d-Cealkyl, B -Cealkoxy, R4(R5)N-, C C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl, C3-C6haloalkenyl, C3-C6cycloalkyl, C3-C6- halocycioalkyl, Brd-Cβalkyl, OHC-, d-C6alkylcarbonyl, Cι-C6alkylcarbonyioxy, CrC6haloalkylcarbonyl, C2-C6alkenylcarbonyl, d-Cβalkoxycarbonyl, C C6alkyl-S(O)2-,
C C6haloalkyl-S(O)2-, C3-C8trialkylsilyloxy, (C1-C6alkyl)2N-N=CH-I > — CH2- , o
τ ^ c c3alky' , B CH=N-, (CH3)2N-CH=N-, (C C5hydroxyalkyl)-CH2-, (B C Cs- CH2— hydroxyalkyl)-CH2-, (B1-C1-C5haloalkyl)-CH2-l (hydroxy-d-Csalkyl -O- or (B C Cs- hydroxyalkyl)-O-; B-i is cyano, OHC-, HOC(O)-, C Cβalkylcarbonyl, d-C6haloalkylcarbonyl, C C6alkoxy- carbonyl, C3-C6alkenyloxycarbonyl, C3-C6alkynyloxycarbonyl, benzyloxy, benzyloxy- carbonyl, benzyloxycarbonyl mono- to tri-substituted on the phenyl ring by halogen, d-C4alkyl or by C1-C4haloalkyl, benzylthio, benzylthiocarbonyl, benzylthiocarbonyl mono- to tri-substituted on the phenyl ring by halogen, C C4alkyl or by Cι-C haloalkyl, C C6haloalkoxycarbonyl, CrC6alkylthio-C(O)-, R6(R7)NC(O)-, phenyl, phenyl mono- to - 3 -
tri-substituted by halogen, C C4alkyl or by C C4haioaikyl, d-C6alkyl-S(O)2-, CrC6- alkyl-S(O)-, C C6alkylthio-, C3-C6cycloalkyl, C C6alkoxy, C3-C6alkenylthio or C3-C6- alkynylthio;
R4 and R5 are each independently of the other hydrogen, d-C6alkyl, C3-C6alkenyl, C3-C6- alkynyl, C C6haloalkyl, C3-C6haloalkenyl, C3-C6cycloalkyl, d-C6alkoxy-Cι-C6alkyl, OHC-, d-C6alkylcarbonyl, C C6haloalkylcarbonyl, CrC6alkyl-S(O)2- or C C6haloalkyl- S(O)2-;
R6 and R7 are each independently of the other hydrogen, C C6alkyl, C3-C6alkenyl, C3-C6- alkynyl, C C6haloalkyl, C3-C6haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, C C alkyl or by d-C4haloalkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C C alkyl or by CrC4haloalkyl;
Xi is oxygen or sulfur;
^9 12 n R
W is a group T ? " ( ι)> T jj " (W2)l rl (Wa)'
1
I23
R21 R* (W4)' x^N χ 5 (W5)' rv (W6)ι I (W7)ι
Raβ FL7 R.
R. 32 R
30 R 31
'29
N- \ / -N
N-N
X1 122 N XH Y X^^Y^^ — N I X« x„13 X ",14„ I
R8 is CrC3alkyl, C C3haloalkyl or amino;
R9 is d-C3haloalkyl, d-C3alkyl-S(O)n1, CrC3haloalkyl-S(O)n1 or cyano; or
R8 and Rg together form a C3- or C4-alkylene bridge or C3- or C4-alkenylene bridge, each of which may be substituted by halogen, C C3haloalkyl or by cyano; n-i is O, 1 or 2; R-io is hydrogen, d-C3alkyl, halogen, d-C3haloalkyl or cyano; or R10 and R9 together form a C3- or C -alkylene bridge or C3- or C4-alkenylene bridge, each of which may be substituted by halogen, C C3haloalkyl or by cyano; Rn is hydrogen, C C3alkyl, halogen or cyano; R-I2 is d-C3haloalkyl;
R12 and Rn together form a C3- or C4-alkylene bridge or C3- or C4-alkenylene bridge; R13 is hydrogen, C C3alkyl or halogen;
R13 and R12 together form a C3- or C4-alkylene bridge or C3- or C4-alkenylene bridge; RM is hydrogen, C1-C3alkyl, halogen, C C3haloalkyl, R33O-, R3 S(O)n2, R35(R36)N,
R3δ(R39)N-C(R37)=N-, hydroxy, nitro or N≡C-S- ;
R33 is C C3alkyl, d-C3haioalkyl, C2-C4alkenyl, C3- or C -alkynyl or CrC5alkoxycarbonyl- C C4alkyl;
R34 is C C alkyl or C C4haloalkyl; n2 is 0, 1 or 2;
R35 is hydrogen, C C4alkyl, C C4haloalkyl, C3-C6cycloalkyl, OHC- or C C4alkylcarbonyl;
R36> R37 and R39 are each independently of the others hydrogen or C C4alkyl;
R38 is C C4alkyl;
R15 is hydrogen, C C4alkyl, halogen, Crdhaloalkyl, C2-C4alkenyl, C3-C5haloalkenyl, C3- or C4-alkynyl, C C4alkoxy, CrC4alkylcarbonyl, C C4haloaIkylcarbonyl, C2-C4alkenyl- carbonyl, C2-C4haioalkenylcarbonyl, C2-C alkynyicarbonyl, C -C4haloalkynylcarbonyl, d-C4alkoxycarbonyl, C C4alkylcarbamoyl, CrC4alkylS(O)n3, C3- or C -alkynylS(O)n3,
OHC-, nitro, amino, cyano or N≡C— S- ; n3 is 0, 1 or 2;
Rι6 and Rι7 are each independently of the other hydrogen, C C4alkyl, halogen, C C4halo- alkyl or cyano; R-iβ and Rι9 are each independently of the other hydrogen, methyl, halogen, hydroxy or =O; R20 and R2ι are each independently of the other hydrogen, C C4alkyl or C C haloalkyl; R22 and R23 are each independently of the other hydrogen, C C3alkyl, halogen or hydroxy; R24 and R25 are each independently of the other hydrogen or C C4alkyl; or
/ R40
R 4 and R25 together form the group ==C N ;
R41
R40 and R41 are each independently of the other d-C4alkyl; or - 5 -
R40 and R together form a C4- or C5-alkylene bridge;
R26 is hydrogen or C C3alkyl ; or
R26 together with R25 forms a C-3-C5alkyiene bridge, which may be interrupted by oxygen and/or substituted by halogen, C C alkyl, C2-C4alkenyl, d-C3haloalkyl, C C3alkyl- carbonyloxy, d-C4alkoxycarbonyl, d-C3alkylsulfonyloxy, hydroxy or by =O; R27. R28. R29 and R30 are each independently of the others hydrogen, C C3alkyl, C3- or C4- alkenyl or C3-C5alkynyl; or R2 and R28 together and/or R2g and R30 together in each case form a C2-C5alkylene bridge or C3-C5alkenylene bridge, each of which may be interrupted by oxygen, sulfur or -
S(O)2- and/or substituted by halogen, C C alkyl, C -C4alkenyl, Cι-C3alkylcarbonyloxy,
Crdalkylsulfonyloxy, hydroxy or by =O; R31 is hydrogen, d-C4alkyl, C C haloalkyl, C3- or C4-alkenyl, C3- or d-haloalkenyl or C3- or C -alkynyl; R32 is hydrogen, d-C4alkyl, C C3alkoxy-Cι- or -C2-alkyl, C C4haloalkyl, C3- or C4-alkenyl,
C3- or C4-haloalkenyl or C3- or C -alkynyl; or R32 and R31 together form a C3-C5alkyiene bridge; and X2> X3, X4, X5, X6, X7, X8, X9, X10, X11, Xι2, X13, X14 and X15 are each independently of the others oxygen or sulfur, and the agrochemically acceptable salts and stereoisomers of those compounds of formula I.
In the above definitions, halogen is to be understood as being iodine or, preferably, fluorine, chlorine or bromine.
The alkyl, alkenyl and alkynyl groups in the substituent definitions may be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of the following groups: alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio, alkenylthio, alkynylthio, alkylthio-C(O)-, alkylsulfinyl, alkylsulfonyl, alkylaminocarbonyl, dialkylaminocarbonyl, (alkyl)2N-N=CH-, alkylcarbamoyl, trialkylsilyloxy, B alkyi and HOC(O)-alkyl.
Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyi and the various isomeric pentyl and hexyl radicals. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
Examples of alkenyl radicals that may be mentioned are vinyl, allyl, methallyl, 1 -methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals - 6 -
having a chain length of from 3 to 5 carbon atoms.
Examples of alkynyl radicals that may be mentioned are ethynyl, propargyl, 1 -methyl- propargyl, 3-butynyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-
1-yl and 2-hexynyl, with preference being given to alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro- ethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl.
Suitable haioalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl,
2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1 -yl and 4,4,4-trichlorobut-2-en-1-yl. Of the alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms. The alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3- fluoropropynyl, 3-chioropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4- trif luoro-but-2-yn-1 -yl.
Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
Alkyisulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri- fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyi or 3-hydroxypropyl.
Alkylamino is, for example, methylamino, ethylamino or an isomer of propylamino or butyl- amino. - 7 -
Dialkylamino is, for example, dimethylamino, diethylamino or an isomer of dipropylamino or dibutylamino.
Alkenylamino is, for example, allylamino, methallylamino or but-2-en-1-ylamino.
Alkynylamino is, for example, propargylamino or 1-methylpropargylamino.
Haloalkylamino is, for example, chloroethylamino, trifluoroethylamino or 3-chloropropyl- amino.
Di(haloalkyl)amino is, for example, di(2-chloroethyl)amino.
Alkylcarbonyl is especially acetyl or propionyl.
Haloalkylcarbonyl is especially trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl or
3,3,3-trichioropropionyl.
Alkenylcarbonyl is especially vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1 - ylcarbonyl, pentenylcarbonyl or 2-hexenylcarbonyl.
Alkynylcarbonyl is especially acetylenecarbonyl, propargylcarbonyl, 1 -methyipropargyl- carbonyl, 3-butynylcarbonyl, but-2-yn-1 -ylcarbonyl or pent-4-yn-1-ylcarbonyl.
Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy, tert-butoxy or an isomer of pentyloxy or hexyloxy.
Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1 -yloxy.
Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Alkenyloxyalkyl is, for example, allyloxyalkyl, methallyloxyalkyl or but-2-en-1-yloxyalkyl.
Alkynyloxyalkyl is, for example, propargyloxyalkyl or 1-methylpropargyloxyalkyl.
Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1- yloxycarbonyl, pentenyloxycarbonyl or 2-hexenyloxycarbonyl.
Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1- yloxycarbonyl or 2-methylbutyn-2-yioxycarbonyl.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy.
Suitable haloalkenyloxy radicals are alkenyloxy groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyloxy, 2- or 3-chloropropenyloxy, 2- or 3-bromopropenyloxy,
2,3,3-trifluoropropenyloxy, 2,3,3-trichloropropenyloxy, 4,4,4-trifluoro-but-2-en-1 -yloxy or - 8 -
4,4,4-trichlorobut-2-en-1 -yloxy.
The cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or up to per-halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl,
2-fluoro-2-chlorocyclopropyl, 2-chloro-2-bromocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl,
2,2,3,3-tetrachlorocyclopropyl, pentafluorocyclopropyl, fluorocyclobutyl, chlorocyclobutyl,
2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, 2,2,3-trifluoro-3-chlorocyclobutyl, 2,2- dichloro-3,3-difluorocyclobutyl, fluorocyclopentyl, difluorocyclopentyl, chlorocyclopentyl, perfluorocyclopentyl, chlorocyclohexyl and pentachlorocyclohexyl.
Corresponding meanings may also be given to the substituents in combined definitions, such as, for example, alkylcarbonyloxy, alkoxyalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxy- carbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, haloalkynylcarbonyl, alkylthio-C(O)-, alkenylthio, alkynylthio, alkyl-S(O)-, alkylsulfonyloxy, R33O-, R4(R5)N-, R35(R36)N-,
R6(R7)NC(O)-, R38(R39)N-C(R37)=N-, R^SfO B alkyl, B alkoxy, B CH=N-, (B haloalkyl)-
CH2- and (B1-hydroxyalkyl)-CH2-.
In the definition of R3, (Cι-C5hydroxyalkyl)-CH2-, (Bι-d-C5hydroxyalkyl)-CH2- and
(BrCi-Cδhaloalky -CH∑- signify that only the C C5alkyl moiety is hydroxylated or halogenated, that is to say the methylene group is not hydroxylated or halogenated.
L in the reagents of formulae VI, XI, XIX, XXVIII, XXXIa, XXXIb and XXXXII denotes a leaving group, such as, for example, halogen, preferably chlorine, bromine or iodine,
d-C3alkyl- or aryl-sulfonyloxy, preferably CH3SO2O- or CH„— ) — S0 0- . or
Cι-C6alkylcarbonyloxy, preferably acetyloxy.
LT in the reagent of formula XX denotes a leaving group, such as, for example, HOS(O)2O-,
CH,
NO, or H3C- VθS(0) 2-
>2O ^°" CH,
L2 in the reagents of formulae XXXIIa and XXXIIc denotes a leaving group, such as, for example, hydroxy, d-C4alkoxy or halogen, preferably chlorine, bromine or iodine. - 9 -
L3 in the reagent of formula XXXVIII denotes a leaving group, such as, for example, chlorine
or bromine, trichloromethoxy or — N ι .
In the definitions of cyanoalkyl, alkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyl, haloalkenyicarbonyl, alkynylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl and haloalkylcarbonyl, the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be. The invention relates also to the salts that the compounds of formula I having azide hydrogen, especially the derivatives with carboxylic acid and sulfonamide groups (e.g. carboxyl-substituted alkyl and alkoxy groups and alkyl-S(O)2NH and haloalkyl-S(O)2NH groups) are able to form with bases. Those salts are, for example, alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
Among the alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium. Suitable salt formers are described, for example, in WO 97/41112.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Cι-Cι8alkylamines, d-C hydroxyalkylamines and C2-C4- alkoxyalkylamines, for example methyiamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctyiamine, dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanol- amine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, - 10 -
methoxyethylamine and ethoxyethylamine; heterocyciic amines, for example pyridine, quinoiine, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
The salts of compounds of formula I having basic groups, especially having basic pyrazolyl rings (W3, W4), or the derivatives with amino groups, for example alkylamino and dialkyl- amino groups, in the definition of R3, R8 or Rι are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid and nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid. The presence of an asymmetric carbon atom in the compounds of formula I, e.g. in the substituent R3 where R3 is a branched alkyl, alkenyl, haloalkyi or alkoxyalkyl group or R3 is (Bι-d-C5hydroxyalkyl)-CH2-, wherein e.g. Bi is Cι-C6alkyl-S(O)- , means that the compounds may be in the form of optically active individual isomers or in the form of racemic mixtures. In the present invention, "compounds of formula I" is to be understood as including both the pure optical antipodes and the racemates or diastereoisomers. When an aliphatic C=C or C=N-O double bond (syn/anti) is present, geometric isomerism may occur. The present invention relates to those isomers also.
Preference is given to compounds of formula l0
(lo),
wherein
Ri is hydrogen, fluorine, chlorine, bromine or methyl; R is methyl, halogen, hydroxy, nitro, amino or cyano; and R3, Xi and W are as defined for formula I. - 11 -
Preference is also given to compounds of formula I wherein W is the group
R9
1° ^N'Rβ
I ι (Wi); and R8, R9, R10, X2 and X are as defined for formula I. Of those
X^^N^X,
I compounds, special preference is given to those wherein R8 is methyl; Rg is trifluoromethyl;
Rio is hydrogen; and X2 and X3 are oxygen.
Also preferred are compounds of formula I wherein W is a group
R ?12 "» Ras ^ R31
13 ^ /R11 N— ~ 2A -N
X ^N "N (Wa)' 10L N *9 (W7)or N "N 15 (Wιo);
and R11, R12, R13, 24, R25. 26, R31, R32, X4. X9. X10 and X15 are as defined for formula I. Preferred compounds of formula I are those wherein W is a group
Rl9 .R ^3
R16 R,s - /Ri 188 R„ f . a*o a
IK, (W3)' V V Ni R17 <wα I *. <W5)'
R28 °27
\ / N-N
/ . (W8); and Rι , R15, R16, R17. 18. R19, R201 R2i> R22. R23. R27. 281 Xs> Xβ. X7.
X,2
X8, Xn and X12 are as defined for formula I.
Also preferred are compounds of formula I wherein Ri is hydrogen, fluorine or chlorine; R is chlorine, bromine, cyano or CF3; and Xi is oxygen.
Of those compounds, special preference is given to those wherein R-i is fluorine or chlorine; and R2 is chlorine, bromine or cyano, and of those compounds special importance is attached to those wherein Ri is fluorine; and R is chlorine. - 12 -
The process according to the invention for the preparation of compounds of formula I
Ri
// \\
Rj- -w (I)
X1 R3 wherein R1 f R2 and W are as defined for formula I; Xi is O or S; R3 is d-Cealkoxy-Ci-Ce- alkyl, Cι-C6alkoxy-Cι-C6alkoxy-Cι-C6alkyl, d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6- haloalkyl, C3-C6haloalkenyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, BrCι-C6alkyl,
C.-C3alkyl l>- CH, - , (Cι-C5hydroxyalkyl)-CH2-, (Bι-d-C5hydroxyalkyl)-CH2- or
CH2—
(B1-d-C5haioalkyl)-CH2-; and B is as defined for formula I is carried out analogously to known procedures, for example as described in CH Application No. 695/97 and references given therein, and comprises oxidising a compound of formula III
R1 vv (III).
for example with hydrogen peroxide/urea adduct in the presence of a carboxylic acid and/or a carboxylic acid anhydride, organic peracid or persulfonic acid (Caro's acid) in a suitable solvent, to form a compound of formula V
R1
(V)
and then rearranging that compound in an inert solvent in the presence of an anhydride or in the presence of antimony pentachloride (Katada reaction) to yield, after aqueous working-up and purification, a compound of formula II - 13 -
*2~ ^-w (ii),
OH the radicals Ri, R2 and W in the compounds of formulae II, III and V being as defined, and then alkylating that compound in the presence of an inert solvent and a base with a compound of formula VI
R3-L (VI), wherein R3 is as defined and L is a leaving group, preferably chlorine, bromine, iodine,
CH3SO2O- or in a suitable inert solvent and a base to form the isomeric
CH3 \\ //~S02°-
compounds of formulae I and IV
(I) and (IV),
wherein Ri, R2, R3 and W are as defined and Xi is O, and then, after the compound of formula I has been separated from the pyridol derivative of formula IV, optionally functionalising the pyridono derivative of formula I further in accordance with the definition of X and R3, for example with the aid of a suitable sulfur reagent to form the corresponding pyridinethione derivative (XT = S).
When R3 in the pyridol derivative of formula IV is an allyl group or a homolog thereof (R3 = C3-C6allyl group), those pyridol derivatives of formula IVb in Reaction Scheme 1 may be rearranged in a manner analogous to that described, for example, in J. Org. Chem. 50, 764 (1985) and Tetrahedron Lett. 1979, 3949, in the presence of a suitable catalyst, for example palladium(ll) chloride/diacetonitrile or palladium(ll) chloride/phenylacetonitrile complex, to form the isomeric N-allylated pyridone derivative of formula I (R3 = C3-C6allyl group). That rearrangement reaction is illustrated in Reaction Scheme 1 below.
Reaction Scheme 1 : - 14 -
catalyst, e.g.
PdCLfCHgCN), solvent R2~ \ /— w 0-C3-C6allyl group X, R3
IVb I (X1=0, R3=C3-C6allyl group)
The compounds of formula I wherein R^ R2 and W are as defined for formula I, Xi is oxygen and R3 is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl or C3-C6haloalkenyl may be obtained in a manner analogous to that described in J. Org. Chem. 38, 3268 (1973), ibid 16, 1143 (1951 ), Chem. Communic. 1979, 552 or J. Am. Chem. Soc. 78, 416 (1956) from the compounds of formula IVa
(IVa),
wherein R^ R2 and W are as defined for formula I and R03 is a lower alkoxy group, e.g. d- or C -alkoxy, benzyloxy or halogen, e.g. chlorine or bromine, by first reacting a compound of formula IVa with an alkylating agent of formula VI
R3-L (VI), wherein R3 is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl or C3-C6haloalkenyl and L is a leaving group, and then either heating or treating with dimethyl sulfoxide, if appropriate in the presence of an alkali metal halide, or with iodine or hydrochloric acid.
The compounds of formula I wherein R^ R2 and W are as defined for formula I, X^ is oxygen and R3 is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl, C3-C6haloalkenyl or C3-C6cycloalkyl may, in a further synthesis variant, be obtained in a manner analogous to that described in Heterocycles 45, 1059 (1997) or Chem. Pharm. Bull. 2, 193 (1954) from the compounds of formula III
(Ml), wherein R1 t R2 and W are as defined, by reaction with an alkylating reagent of formula VI - 15 -
R3-L (VI), wherein R3 is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl, C3-C6haloalkenyl or C3-C6cycloalkyl and L is a leaving group, and with an oxidising agent, for example manganese dioxide (MnO2) or potassium hexacyanoferrate (K3Fe(CN)6).
The process according to the invention for the preparation of compounds of formula I a
(I)
wherein Ri, R2 and W are as defined for formula I; Xi is S; R3 is hydroxy, Cι-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Cι-C6haloalkoxy, C3-C6haloalkenyioxy, Bι-CrC6alkoxy, d-C6alkyicarbonyloxy, C3-C8trialkylsilyloxy, (hydroxy-d-C5alkyl)-O- or (Bι-Cι-C5hydroxy- alkyl)-O-; and B1 is as defined for formula I is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises first oxidising a compound of formula III
R,
(III) to yield a compound of formula V
(V),
chlorinating or brominating that compound, for example with phosphorus oxychloride, phosphorus oxybromide, sulfuryl chloride, thionyl chloride or phosphorus pentachloride in phosphorus oxychloride, and then oxidising it again to form a compound of formula VIII - 16 -
(VIII),
the radicals R^ R2 and W in the compounds of formulae III, V and VIII being as defined and Hal in the compound of formula VIII being chlorine or bromine, then converting that compound in the presence of a solvent, e.g. water, an alcohol or a mixture thereof, or an amide, using a suitable sulfur reagent, e.g. hydrogen sulfide, thiourea, sodium hydrogen sulfide (NaSH) or phosphorus pentasulfide (P2S5), into a compound of formula Im
T y-W (Im),
S OH and reacting that compound in the presence of a solvent and a base with a compound of formula XI
R42-L (XI), wherein R42 is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, d-C6haloalkyl, C3-C6haloalkenyl, Bι-Cι-C6alkyl, d-C6alkylcarbonyl, C3-C8trialkylsilyl, hydroxy-Cι-C5alkyl or Brd-C5hydroxy- alkyl; B, is as defined; and L is a leaving group, e.g. halogen, for example chlorine, bromine
or iodine, CH3SO2O-, SO,0- or d-C6alkylcarbonyloxy.
The process according to the invention for the preparation of compounds of formula I
Rr -W 0
X1 R3 wherein R^ R2, R3 and W are as defined for formula I and Xi is S is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises treating a compound of formula I - 17 -
(I)
wherein R1 ? R2, R3 and W are as defined and X^ is O in an inert solvent with a sulfur reagent, for example phosphorus pentasulfide or Lawesson reagent.
For the preparation of the pyridine intermediates of formula III, a large number of known standard procedures of heterocyclic chemistry are available, the choice of a suitable preparation procedure being governed by the properties (reactivities) of the substituents in the respective intermediates.
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 438 209 or DE-OS 19 604 229, and, for the purpose of preparing compounds of formula III
(III)
wherein R, and R2 are as defined for formula I, W is a group Wi — R9 (WT) and
Re. 9, R10, X2 and X3 are as defined for formula I (corresponding to the compound of formula Ilia in Reaction Scheme 2), comprises, for example, converting a compound of formula XII
(XII),
- 18
wherein Ri and R2 are as defined and Hal is fluorine, chlorine or bromine, in the presence of an inert solvent and ammonia, if appropriate in an autoclave at temperatures of from -10 to 180°C, into a compound of formula XIII
(XIII),
converting that compound in the presence of a base and a solvent a) with a chloroformic acid ester of formula XIV
X
C^alkylO ϋ C—- Cl (XIV),
wherein X2 is as defined for formula I, into a compound of formula XV
X2 (XV), or
II -NH-C-OC C4alkyl
b) with oxalyl chloride, phosgene or thiophosgene into a compound of formula XVI
(XVI),
then cyclising the compound of formula XV or XVI in the presence of from 0.1 to 1.5 equivalents of a base in an inert solvent with an enamine derivative of formula XVII
Rn X3
/ N (XVII),
NH l
'2, OC1-C,alky I
R 10 wherein R9 and R10 are as defined for formula I and X3 is oxygen, to yield a compound of formula XVIII - 19 -
(XVIII),
wherein R1 ( R2, R9, Rio, X2 and X3 are as defined, and reacting that compound further in the presence of an inert solvent and a base c) with a compound of formula XIX
R8-L (XIX), wherein R8 is d-C3alkyl or Cι-C3haloalkyl and L is a leaving group, or d) with a hydroxyiamine derivative of formula XX
NH2-L! (XX), wherein Li is a leaving group.
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in DE-A-4 423 934 and JP-A-58 213776, and, for the preparation of compounds of formula III
(HI)
x4 R13 wherein RT and R2 are as defined for formula I, W is a group W2 — N ) — R12 (W )
N=<
Ri, and R11, R12, Rι3 and X4 are as defined for formula I (corresponding to the compound of formula lllb in Reaction Scheme 3), comprises, for example, either a) converting a compound of formula XII
(XII),
Hal wherein RT and R2 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent, into a compound of formula XXI - 20 -
R,
(XXI),
Rό NH-NH2
W •N and reacting that compound further with a compound of formula XXII or XXIIa
0 0
R„ H R11 "
(XXII) or (XXIIa),
' ^ R & "» Hal Hal 12 wherein Rn and R12 are as defined for formula I, and Hal in the compound of formula XXIIa is chlorine or bromine, or b) first diazotising a compound of formula XIII
R,
(XIII),
wherein Ri and R2 are as defined, and then reacting further with a compound of formula XXIII
COOH R /Cl\ /R12 (XXIII),
II o wherein Rn and Rι2 are as defined, to yield a compound of formula XXIV
(XXIV),
which is optionally cyclised in the presence of a base, e.g. 4-dimethylaminopyridine, and a compound of formula XXV
X4 P(phenyl),
II II (XXV),
C C4alkyl-0-C-C-R13
wherein Rι3 is as defined and X is oxygen. - 21 -
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, US-A-5 665 681 and US-A-5 661 109, and, for the preparation of compounds of formula III
Ri
(III)
X9 R, wherein R^ and R2 are as defined for formula M H-\ '24 I, W is a group W7 — N . (W7) and r10' -> '26
X, ∑ , R25, R26, X9 and X10 are as defined for formula I (corresponding to the compound of formula lllg in Reaction Scheme 4), comprises, for example, reacting either a) a compound of formula XVa
R«
X10 (XVa)
R 2— \ /)— NH-C-OC C4alkyl ■ N in the presence of a solvent and a base, or b) a compound of formula XVIa
Ri
(XVIa), / — =C=X 10 N if appropriate in a suitable solvent, the radicals R,, R2 and X10 in the compounds of formulae XVa and XVIa being as defined, with a compound of formula XXVI
R β • 25 ll
R ■ 2266N"H' -C | -C "-OC1 C44alkyl (XXVI),
R24 wherein R , R25, R28 and X9 are as defined, to yield a compound of formula XXVII - 22 -
R
Xιc X9
/T ιι i25 II (xxvii),
F^— C — NH-C— N— C-C-OC C4alkyl ^N R π26 R 24 cyclising that compound in the presence of a suitable solvent and a base and then optionally c) when R26 is hydrogen, reacting with a compound of formula XXVIII
R26-L (XXVIII), wherein R26 is d-C3aIkyl and L is a leaving group.
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 210 137, DE-A-2 526 358, EP-A-0 075 267 and EP-A-0 370 955, and, for the preparation of compounds of formula III
R,
(III)
Xn R27 wherein R, and R2 are as defined for formula I, W is a group Wθ — N i, (W8) and
Y ^28 X12
R27, 28, X11 and Xι2 are as defined for formula I (corresponding to the compound of formula lllh in Reaction Scheme 5), comprises, for example, reacting a) a compound of formula XVb
r=( /Rl X j}12 (XVb)
R 2~Λ\ ~ NH-C-OC C4alkyl \— N in the presence of a solvent and a base, or b) a compound of formula XVIb - 23 -
(XVIb),
the radicals Ri, R2 and X12 in the compounds of formulae XVb and XVIb being as defined, if appropriate in a suitable solvent, with a compound of formula XXIX
X11
R28NH-N-C-OC C4alkyl (XXIX),
R27 wherein R27, R28 and Xn are as defined, to yield a compound of formula XXX
R,
, X Λ112 X "11 r - NH-C ιι — N — N-C n-OC C4alkyl (xxx), N R π28 R π27 cyclising that compound in the presence of a suitable solvent and a base, and then optionally c) when R27 and/or R28 are hydrogen, reacting further with a compound of formula XXXIa or XXXIb
R27-L (XXXIa) or R28-L (XXXIb), wherein R27 and R28 are each independently of the other Cι-C3alkyl and L is a leaving group, or with a Michael acceptor.
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in WO 97/07114, US-A-5 306 694, DE-A-3 832 348, EP-A-0 257 479 and EP-A-0 500 209, and, for the preparation of compounds of formula III
/=r /Rl (III)
Rr\\ />-W V— - 24 -
wherein Ri and R2 are as defined for formula I, W is a group W3 / t^ R 15 (W3) and
M16
Rι4, R15 and R16 are as defined for formula I (corresponding to the compound of formula lllc in Reaction Scheme 6), comprises, for example, condensing a compound of formula XXI
(XXI),
NHNH2 wherein Ri and R2 are as defined, a) with a compound of formula XXXII
0 II i »f
RΓ4%H "Rιe (χχχιι>.
I
R15 wherein Rι is hydrogen, d-C3alkyl or d-C3haloalkyl; Ri5 is hydrogen, d-C4alkyl, d-C4haloalkyl, C2-C4alkenyl, C3-C5haloalkenyl or C3- or C4-alkynyl and Rι6 is hydrogen, Cι-C4alkyl or d-C4haloalkyl, if appropriate in the presence of an acidic, basic or bifunctional catalyst, e.g. p-toluenesulfonic acid, or b) with a compound of formula XXXIIa
0 II ft "
LTC CH e (XXXIIa)> I
R15 wherein R15 and Rι6 are as defined and L2 is a suitable leaving group, to form a compound of formula XXXIII
(XXXIII),
- 25 -
and functionalising the pyrazolone group further in accordance with the definition of Rι analogously to known procedures, for example using a halogenating agent, e.g. phosphorus oxychloride, to form the corresponding halogen derivative of formula lllc
R R 16
(lllc),
wherein Ri, R2, R15 and Rι6 are as defined and Rι4 is halogen (Reaction Scheme 6).
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in EP-A-0 370 332, EP-A-0 370 955 or DE-A-3 917 469, and, for the preparation of compounds of formula III
R,
(III) / ~w
wherein Ri and R2 are as defined for formula I, W is a group W4 N
(W4) and Rι7, R18 and R 9 are as defined for formula I (corresponding to the compound of formula Hid in Reaction Scheme 7), comprises, for example, condensing a compound of formula XXI
(XXI), NHNH2 wherein Ri and R2 are as defined, a) with a compound of formula XXXIIb - 26 -
'17 (XXXIIb),
wherein Rι8 and Rι9 are as defined and Rι7 is hydrogen, d-C4alkyl or Cι-C haioalkyl, if appropriate in the presence of a catalyst, or b) with a compound of formula XXXIIc
'L, (XXXIIc),
wherein Rι8 and Rι9 are as defined and L is a suitable leaving group, to form a compound of formula XXXIIIa
(XXXIIIa)
and treating that compound with a halogenating agent, e.g. a phosphorus oxyhalide or thionyl halide, to yield a compound of formula Hid
Ri
(Hid),
wherein R1 ( R2, Rι8 and Rι9 are as defined and Rι7 is halogen, and optionally reacting that compound with a cyanide of formula XXXIV
M(CN)S (XXXIV), wherein M is an ammonium cation, an alkali metal ion or a metal ion from sub-group I or II of the Periodic Table of the Elements and s is the number 1 or 2, if appropriate in the presence of an alkali metal iodide (Rι7 = cyano) (Reaction Scheme 7). - 27
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in DE-A-3 917 469, WO 92 00976, US-A-5 069 71 1 and EP-A-0 260 228, and, for the preparation of compounds of formula III
(III)
wherein Ri and R2 are as defined for formula I, W is a group W5 — N | (W5) or
R20
Xs
R 22
We — N R23 (W6) and R2o, R21, R22, R23 and X5 to X8 are as defined for
formula I (corresponding to the compounds of formulae llle and lllf, respectively, in Reaction Scheme 8), comprises, for example, reacting a) a compound of formula XXXV
O
'21
(XXXV) or
R
b) a compound of formula XXXVa
(XXXVa),
the radicals R20 to R23 in the compounds of formulae XXXV and XXXVa being as defined, with a compound of formula XIII 28
(XIII), wherein Ri and R2 are as defined, in an inert solvent in the presence of a d-dalkyl- carboxylic acid at temperatures of from 20° to 200°C, and optionally converting the resulting compound of formula Hie or lllf
(llle) or R (lllf),
wherein Ri, R2 and R20 to R23 are as defined and X5 to X8 are oxygen, with the aid of a suitable sulfur reagent, into the corresponding thiono compound of formula Hie or lllf wherein X5 and/or X6 and X7 and/or X8 are sulfur respectively (Reaction Scheme 8).
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in WO 95/00521 , EP-A-0 611 708 and WO 94/25467, and, for the preparation of compounds of formula III
(III)
X 13
'30 wherein Ri and R2 are as defined for formula I, W is a group W9 14 I (W9) and v^N
// '
— N R29
R29, R30, X13 and Xι4 are as defined for formula I (corresponding to the compound of formula llli in Reaction Scheme 9), comprises, for example, reacting a) a compound of formula XVc - 29 -
14 (XVc) °r
b) a compound of formula XVIc
R,
(XVIc), the radicals R R2 and Xu in the compounds of formula XVc and XVIc being as defined, if appropriate in the presence of a solvent and a base, with a compound of formula XXXVI
R3o-NH-NH-R29 (XXXVI), wherein R29 and R30 are as defined for formula I, to yield a compound of formula XXXVII v
Λ14
NH-C-N-NH-Rpo (XXXVII),
I ∞
R30 and then reacting that compound, if appropriate in a solvent and in the presence of a base, with a (thio)carbonylating reagent of formula XXXVIII
,C=Xι3 (XXXVIII),
I-3 wherein Xι3 is as defined and L3 is a leaving group (Reaction Scheme 9).
The process according to the invention for the preparation of compounds of formula III is carried out analogously to known procedures, for example as described in US-A-5 980 480, DE-A-3 917 469, US-A-4 818 275, US-A-5 041 155 and EP-A-0 610 733, and, for the preparation of compounds of formula III
(III)
- 30 -
v15
.R, erein Ri and R2 are as defined for formula I, W is a group Wι0 N A~ / '31 wh N N (Wι0)
H32 and R31, R32 and Xι5 are as defined for formula I (corresponding to the compound of formula lllk in Reaction Scheme 10), comprises, for example, a) reacting a compound of formula XXI
R (XXI),
R2- \ //-NHNH, N if appropriate in the presence of a catalyst, with a compound of formula XXXIX π32
Nc=o (XXXIX)
HOOC to form a compound of formula XXXX
,R32
(XXXX), RHT -NHN = — N XCOOH the radicals Ri, R2 and R32 in the compounds of formulae XXI, XXXIX and XXXX being as defined, and cyclising the compound of formula XXXX by further reaction with an azide of formula XXXXI
O
K N,3 — U P(,«OC« C «4a „lky ,lx)2 (XXXXI)
(Xιs = O, R3i = H), or b) cyclising a compound of formula XXI
(XXI) ■ with a compound of formula XXXXIII - 31 -
OC C4alkyl ^ (XXXXIII),
F N-COOC C4alkyl
the radicals R^ R2 and R32 in the compounds of formulae XXI and XXXXIII being as defined,
(Xιs = O, R3ι = H), or c) reacting a compound of formula XXI
(XXI) first with a compound of formula XXXXIV
R32-CHO (XXXXIV) to form a compound of formula XXXXa
•NH-N=CH-R (XXXXa),
32
\\ //
•N and then with an alkali metal cyanate to form a compound of formula XXXXV
R,
(XXXXV)
and finally cyclising that compound in the presence of an oxidising agent, to yield a compound of formula lllk
(Hlk),
wherein Ri, R2 and R32 are as defined, X15 is oxygen and R3ι is hydrogen, and optionally treating that compound with a sulfur reagent (X15 = S) and, in the presence of a base, with an alkylating reagent of formula XXXXII
R31-L (XXXXII), -32-
wherein R3ι is Cι-C4alkyl, Cι-Chaloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl or C3- or C4-alkynyl and L is a leaving group.
The preparation of the compounds of formula Ilia
Ri /Rιo
R 2- \ }- -R9 (|lla)
^ )j-N 2 8 wherein Ri, R2, R8, Rg, R10, X2 and X3 are as defined for formula I is illustrated in Reaction Scheme 2 below.
33 -
Reaction Scheme 2: R, a) CIC(X2)0-C1-C4alkyl or
NH3 (autoclave) XIV ► solvent, -10-180°C b) oxalyl chloπde or C(X2)Cl2, base, solvent
XII XIII
R, λ2
R_ ^ Ni^O-C C4al yl d-C.alkyl
^ — N
XV or base, solvent
XVIII c) R8-L or XIX base, solvent d) NH^L. XX
thionation reagent, e.g. Lawesson reagent solvent
Ilia (X3 =S) Ilia (X3 =0)
For the preparation of the compounds of formula Ilia according to the invention, a large number of known standard procedures are available, for example as described in EP-A-0 438 209 and DE-OS-19 604 229 (R9 =cyano). Reaction Scheme 2 shows a selection of suitable preparation procedures, the choice of the reaction routes and the reagents being governed by the reactivities of the substituents in the intermediates.
Starting, for example, from a compound of formula XII, it is possible by reaction with ammonia in an inert solvent, if appropriate in an autoclave at temperatures of from -10 to 180βC, to obtain an aminopyridine of formula XIII. The latter compound may be converted in the presence of a base and a solvent either - 34 -
a) with a chloroformic acid ester of formula XIV (X2 = O or S) into a pyridyl carbamate of formula XV, or b) with oxalyl chloride, phosgene (X2 =O) or thiophosgene (X2 =S) into an iso(thio)cyanate of formula XVI. Such reactions are described, for example, in Angew. 1971 , 407.
The carbamate and the iso(thio)cyanate of formulae XV and XVI may be cyclised in the presence of an enamine derivative of formula XVII in an inert solvent to form a uracil derivative of formula XVIII, the reaction of the iso(thio)cyanate of formula XVI advantageously being carried out in the presence of from 0.1 to 1.5 equivalents of a base, e.g. sodium hydride, potassium tert-butanolate or an alkaline earth metal oxide or hydroxide, e.g. barium hydroxide.
The desired compounds of formula Ilia may be prepared in accordance with standard procedures from the uracils of formula XVIII in the presence of an inert solvent and at least one equivalent of a base, for example an alkali metal carbonate, such as potassium carbonate, c) with an alkylating agent of formula XIX to form the N-alkyl derivative of formula Ilia (R8 =alkyl), or d) analogously to WO 97/05116 with a hydroxylamine derivative of formula XX, wherein Li
CH,
NO π= is a leaving group, e.g. HOS(O)2O-, /^ x _ oorr H r- 3CC—- ^ W / ft/— OS(0) 2-
■* ~j-°-
CH,
for example 2,4-dinitrophenyl-hydroxylamine or hydroxylamine-O-sulfonic acid, to form the N-amino derivative of formula Ilia (R8 =amino). The desired thiono derivatives of formula Ilia (X2, X3 =S) may be obtained by thionation, for example with phosphorus pentasulfide or Lawesson reagent.
The preparation of the compounds of formula lllb
(Hlb),
35
wherein R,, R , Rn, R12, R13 and X4 are as defined for formula I, is illustrated in Reaction Scheme 3 below.
Reaction Scheme 3:
NH2NH2 , NH H2 solvent
XII
'12 ° C/R12 or
Br-C^
,^ \.
11 B 'r R 1i1
XXII XXIIa
X4 '13 c-c.
C C4alkyl-0 \\
P(Ph)
XXV
lllb with exclusion of water)
2) O^ / R12 γ Japp-Klingemann
I . , reaction ^CH
COOH ^Rt1 XXIII
The compounds of formula lllb may be prepared in accordance with known methods, for example in accordance with Reaction Scheme 3 (variant a)), by reacting a 2-halopyridιne - 36 -
derivative of formula XII with hydrazine, preferably in a protic solvent, e.g. an alcohol, analogously to GB-A-2 230 261 to form a 2-hydrazino derivative of formula XXI.
The latter is reacted with a diketone of formula XXII analogously to DE-OS-19 754 348 or with a dihaloketone of formula XXIIa analogously to WO 97/07104 to form a hydrazone derivative of formula XXIV.
The subsequent cyclisation to form the desired compound of formula lllb is carried out in the presence of a phosphorane derivative of formula XXV if appropriate in the presence of a base, for example 4-dimethylaminopyridine. Then, for the case where X4 in a compound of formula lllb = O, thionation (X4 = S) may be carried out in a manner analogous to that described under Reaction Scheme 2.
According to Reaction Scheme 3, the hydrazone derivative of formula XXIV may also be obtained from the 2-aminopyridine derivative of formula XIII via diazotisation, preferably with exclusion of water, and subsequent coupling to the ketonic acid of formula XXIII (Japp-
Klingemann reaction analogously to DE-OS-19 754 348) (variant b) in Reaction Scheme 3).
The preparation of the compounds of formula lllg
(Mg).
wherein Ri, R2, R24> R25, R26, X9 and Xι0 are as defined for formula I, is illustrated in Reaction Scheme 4 below.
- 37
Reaction Scheme 4:
R O
a) R 2— \ //"N C>d-C4alkyl Xg ^— .C^C.alkyl
XVa C^alkyL A °25 R24 °
XXVI base, solvent ■N ^N
*10 "26 b) R N=C=X XXVII
10 base, solvent
XVIa
alkylation, e.g. Fl,6-L XXVIII base, solvent v10 R 2, 6 lllg (e.g. X10 = O) mg thionation e.g. Lawesson reagent
lllg (e.g. X10 = S)
The compounds of formula lllg may be prepared analogously to known methods, for example as described in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509,
US-A-5 665 681 or US-A-5 661 109.
For example, in accordance with Reaction Scheme 4 either a) a carbamate derivative of formula XVa may be cyclised in the presence of a solvent and a base, or - 38 -
b) an iso(thio)cyanate of formula XVIa may be cyclised, if appropriate in a suitable solvent, with an amino acid derivative of formula XXVI via a compound of formula XXVII in the presence of a base and a suitable solvent to form a compound of formula lllg. For the case where in a compound of formula lllg R26 is hydrogen and X9 and/or Xι0 are oxygen, then optionally alkylation may be carried out at the free N atom of the hydantoin ring using an alkylating reagent of formula XXVIII and the ring carbonyl group may be thionated (Xg and/or Xι0 = S).
The preparation of compounds of formula lllh
'2 \\ =< //R' N 5 - (lllh),
■ N Y^. 28
X12
wherein R1 f R2, R27, R28, Xn and Xι2 are as defined for formula I, is illustrated in Reaction Scheme 5 below.
- 39 -
Reaction Scheme 5:
R *12
C.-C.alkyl
W -(/' A »N C C4alkyl
-N H O-
0
N
XVb
R27 C C4alkyl
27 0
XXIX or N
■ Rή base, solvent
X
12 R^j b) XXX
N=C=X 12 base, solvent
alkylation, e.g. ^-L, R28-L, or
XXXIa XXXIb
<
Michael acceptor, base, solvent
X12 R28 lllh lllh (e.g. X12 = 0) thionation, e.g. Lawesson reagent
lllh (e.g. X12 = S)
The compounds of formula lllh may be prepared analogously to known procedures, for example as described in EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955. For example, in accordance with Reaction Scheme 5 either - 40 -
a) a carbamate derivative of formula XVb may be cyclised in the presence of a solvent and a base, or b) an iso(thio)cyanate of formula XVIb may be cyclised, if appropriate in a suitable solvent, with a carbazate of formula XXIX via a compound of formula XXX in the presence of a base and a suitable solvent to form a compound of formula lllh.
For the case where in a compound of formula lllh R27 and/or R28 are hydrogen and Xn and/or Xι2 are oxygen, then alkylation may be carried out at the free N atoms using an alkylating agent of formula XXXIa or XXXIb and the ring carbonyl groups may be thionated (Xn and/or X 2 = S) using a thionating reagent.
For the preparation of compounds of formula lllh in Reaction Scheme 5 wherein R27 and R28 together form an alkylene bridge that is interrupted e.g. by -S(O)2-, for example a compound of formula lllh wherein R27 and R28 are hydrogen may be reacted with a corresponding Michael acceptor, for example CH2=CH-S(O)2CH3 or CH2=CH-S(O)2-CH=CH2, and the resulting Michael addition products may be functionalised further.
The preparation of the compounds of formula lllc
(lllc),
wherein Ri, R2 and Rι4 to Rι6 are as defined for formula I, is illustrated in Reaction Scheme 6 below.
41 -
Reaction Scheme 6:
a) R14 -CH ^R16 l5
XXXII NHNH2
o o
II II ) L CH' ,
Rl5
XXXI la
halogenation reagent, e.g. N* '16
*• R2 POCL ^ n«r R R 15
'«1
XXXIII lllc (R14 = halogen)
In accordance with Reaction Scheme 6, the pyrazole compounds of formula lllc may be prepared, for example, either from the hydrazinopyridine derivatives of formula XXI by means of condensation with a 1 ,3-dicarbonyl derivative of formula XXXII (variant a)), or by means of condensation with a β-carbonylcarboxylic acid derivative of formula XXXIIa wherein L2 is a leaving group, for example d-C4alkoxy, hydroxy or halogen, e.g. chlorine or bromine, (variant b)) and subsequent treatment of the resulting pyridylpyrazolone derivative of formula XXXIII with a halogenating agent, for example phosphorus oxychloride (Rι =halogen). The two reaction steps a) and b) in Reaction Scheme 6 are effected, if appropriate, in the presence of an acidic, basic or bifunctional catalyst, e.g. p- toluenesulfonic acid.
The compounds of formula lllc obtained in this way may be functionalised further in accordance with the definitions of the substituents R 4 to Rι6 by means of standard procedures.
The compounds of formula lllc in Reaction Scheme 6 wherein Rι5 is hydrogen may be functionalised further in accordance with the definition of Rι5, for example with an electrophilic reagent, e.g. a halogenating agent, such as elemental halogen or sulfuryl - 42 -
halide, to form the corresponding compounds of formula lllc wherein R15 is halogen, or with a nitrating agent, such as nitric acid, if appropriate in admixture with a further strong acid, such as sulfuric acid, to form the corresponding compounds of formula lllc wherein Rι5 is nitro.
The corresponding pyridono derivatives of formula Ic
(lc),
wherein Ri to R3, Rι to Rι6 and Xi are as defined for formula I, may be obtained, as described above, from compounds of formula lllc by means of oxidation of the pyridyl moiety.
In a further variant, the pyridono derivatives of formula Ic may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa
R2— — NHNH2 (XXIa),
X1 R3 wherein Ri to R3 and Xi are as defined, analogously to the variants shown in Reaction Scheme 6.
The required pyridonylhydrazine of formula XXIa may readily be obtained from the corresponding pyridonyl halide of formula Xlla
R2— —Ha\ (XHa),
X1 R3 wherein R1 ( R2 and R3 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent.
In certain cases, the compounds of formula Ic may also be obtained in manner analogous to that described in J. Het. Chem. 15, 1221 (1978) and in Reaction Scheme 11 , by substitution of a pyridonyl derivative of formula Xlla that is provided with a leaving group U, 43
e.g. a halide, a d-C alkyl- or phenyl-sulfonyl group or an unsubstituted or substituted d- dalkyl- or phenyl-sulfonyloxy group, (variant c) in Reaction Scheme 11), or by substitution of a pyridine derivative of formula XII that is provided with a leaving group U, e.g. a halide, a d-dalkyl- or phenyl-sulfonyl group or an unsubstituted or substituted Cι-C4alkyl- or phenyl-sulfonyloxy group, (variant d) in Reaction Scheme 11 ), with a pyrazole of formula W03 or an alkali metal salt thereof, and in the case of variant d) by subsequent functionalisation (oxidation) of the pyridyl moiety of the compound of formula lllc. The substitution reactions according to variants c) and d) may optionally be carried out in the presence of a suitable solvent and a base.
Reaction Scheme 11 :
„_// 7^ / 16
) '15 Xri R3 R1 lc solvent, base
W, 03
R
R. 15
'14 XII lllc
The preparation of the compounds of formula Hid
R,
* d)
RSl Gf (Hi
7 R19 wherein Ri, R2 and Ri to R19 are as defined for formula I is illustrated in Reaction Scheme 7 below. - 44
Reaction Scheme 7:
0 0
II II
R 3) R-
XXXI lb ».
R 2- (\ / — NHNH2 \— N
XXI R17 fe ™19 g o llld b)
L J-R18
R19
< XXXIIc
,R18
18 halogenation, e.g. ^ POCIj Or SOCI2
O R 19 XXXIIIa R17 Rg llld (R17 = halogen)
M(CN)S XXXIV
llld (R17 = CN)
In accordance with Reaction Scheme 7, the tetrahydroindazole compounds of formula llld may be obtained according to known procedures from the hydrazinopyridine derivatives of formula XXI, for example either by condensation with a cyclohexanone derivative of formula XXXIIb that is acylated in the 2-position, wherein Rι7 is as defined for formula I with the exception of Ri7 as halogen or cyano, (variant a)), or by condensation with a cyclohexanone derivative of formula XXXIIc wherein L2 is a leaving group, for example Cι-C4alkoxy, hydroxy or halogen, e.g. chlorine or bromine, and subsequent halogenation (variant b)) in a manner analogous to that described under Reaction Scheme 6. The halogen derivatives of formula llld wherein Rι7 is halogen may be converted into the corresponding cyano-substituted derivatives of formula llld (R17 =CN) according to known methods with an alkali metal cyanide, ammonium cyanide or a metal cyanide, the metal being selected from sub-groups I and II of the Periodic Table of the Elements, if appropriate with the addition of an alkali metal iodide. - 45 -
The preparation of the compounds of formulae Hie and lllf
(Hie) and (lllf),
wherein R1 f R2, R20 to R23 and X5 to X8 are as defined for formula I, is illustrated in Reaction Scheme 8 below.
Reaction Scheme 8:
a)
llle (X5, X6 =0)
■NH,
•N b) XIII solvent, propionic acid, 20-200°C
XXXVa lllf (X7, X8 = O)
In accordance with Reaction Scheme 8, the pyrrolinedione derivatives of formula Hie and the tetrahydroisoindolinedione derivatives of formula lllf may be obtained analogously to known procedures, for example by reaction of an anhydride of formula XXXV (variant a)) or XXXVa (variant b)) with an aminopyridine of formula XIII in an inert solvent, for example an ether, e.g. dioxane, or a lower alkylcarboxylic acid, e.g. propionic acid, at temperatures of from 20 to 200°C.
The compounds of formulae Hie and lllf (X5 to X8 = O) obtained in accordance with Reaction Scheme 8 may optionally be thionated with a suitable sulfur reagent (X5 to X8 = S). - 46 -
The corresponding pyridono derivatives of formulae le and If
may be obtained from the compounds of formulae Hie and lllf as described above, by means of oxidation of the pyridyl moiety.
In a further variant, the pyridono derivatives of formulae le and If may also be obtained directly from the corresponding aminopyridone derivatives of formula Xllla
R,
(Xllla),
wherein Ri, R2, R3 and Xi are as defined for formula I, analogously to the method as described in Reaction Scheme 8.
The preparation of the compounds of formula llli
R I4 ^X 1133
R- ■ N=τ
W / (llli)
■N N -N
R R∞
H29 wherein Ri, R2, R29, R30, Xι3 and Xι4 are as defined for formula I is illustrated in Reaction Scheme 9 below.
- 47 -
Reaction Scheme 9: R
*1 a) R2-Λ\ //— [j— "-OC^C.alkyl
■ N l
R,
XVc R^NH-NHR,*, NHR XXXVI 29
N solvent, base " R 30
XXXVII solvent, 1-3 base
XVIc V= l3 "-3
XXXVIII
X14 y
*HT ^VN N N-Nχ - R™
R 29
In accordance with Reaction Scheme 9, the compounds of formula llli may be prepared according to known procedures, for example by first reacting a carbamate of formula XVc (variant a)) or an isothiocyanate of formula XVIc (variant b)) with a hydrazine derivative of formula XXXVI to form a semicarbazide derivative of formula XXXVII and then reacting the latter in the presence of a carbonylating or thiocarbonylating reagent of formula XXXVIII. Both reaction steps are advantageously carried out in a suitable solvent and in the presence of a base. As (thio)carbonylating reagent of formula XXXVIII there come into consideration e.g. phosgene, diphosgene, thiophosgene and carbonyldiimidazole. L3 in formula XXXVIII is therefore a leaving group, for example halogen, e.g. chlorine or bromine,
/=N trichloromethoxy or .^ \ .
The corresponding pyridono derivatives of formula li - 48
O-
wherein Ri to R3, R29, R30, Xi, X13 and Xι are as defined for formula I, may be obtained from the compounds of formula llli in the manner described above, by means of oxidation of the pyridyl moiety.
In a further variant, the pyridono derivatives of formula li may also be obtained directly from the corresponding pyridone carbamates of formula XVd
R 14
NH-C-OC^alkyl (XVd)
or from the iso(thio)cyanates of formula XVId
N=C=X 14 (XVId),
X, R, the radicals Ri to R3, Xi and X 4 in the compounds of formulae XVd and XVId being as defined for formula I, in a manner analogous to that described in Reaction Scheme 9. The required starting compounds of formulae XVc and XVIc are known and are described, for example, in EP-A-0 468 924 and EP-A-0 304 920.
The preparation of the compounds of formula lllk
R, N '32
R
^ N Y (lllk), N
Xi R 31
wherein R1 f R2, R3ι, R32 and Xi5 are as defined for formula I, is illustrated in Reaction Scheme 10 below. - 49
Reaction Scheme 10:
a) B32 *x
NHN= COOH
^f Rsi
XXXX Xis lllk ^5=0, R31=H)
La» b> 1
NHNH, y N, T
>- f . -N'
XXI x.„ ".. lllk (X15=0, R31=H) lllk (X1^S. R31)
CJDR^ O
[C1 e.g. aθα — → R,— (\ />— N-N=CHF , -•► e.g. NaOC '' I afcylcartxnylic aα , e.g. ^^N f
C-*ONH2 xxxxv x,c 31 lllk (X16=0, R31=H)
In accordance with Reaction Scheme 10, the triazolone derivatives of formula lllk may be prepared analogously to known procedures, for example by using as starting material a hydrazinopyridine derivative of formula XXI which, in accordance with variant a), is reacted with a keto acid of formula XXXIX, advantageously in the presence of an acid catalyst, e.g. a lower alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. sulfuric acid or hydrochloric acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, to form a hydrazone derivative of formula XXXX. The latter may then be cyclised with an azide of formula XXXXI to form a triazolone derivative of formula lllk wherein X15 is oxygen and R31 is hydrogen and then optionally derivatised further in accordance with standard procedures with an alkylating reagent of formula XXXXII or with a sulfur reagent. In accordance with variant b), a hydrazinopyridine derivative of formula XXI may be cyclised with an imino ether of formula XXXXIII to form a triazolone derivative of formula lllk wherein X15 is oxygen and R31 is hydrogen and then optionally alkylated or thionated as described under variant a).
In accordance with variant c), in Reaction Scheme 10 a hydrazinopyridine derivative of formula XXI may be converted first with an aldehyde of formula XXXXIV, then in the presence of a lower alkylcarboxylic acid, e.g. acetic acid, with an alkali metal cyanate to form a compound of formula XXXXV, which may or may not be isolated, and finally cyclised - 50 -
with an oxidising agent, e.g. an alkali metal hypochlorite (Javelle), to form a compound of formula lllk wherein X 5 is oxygen and R3i is hydrogen. The resulting compound of formula lllk may then optionally be alkylated or thionated as described under variant a). The corresponding pyridono derivatives of formula Ik
R
. R,
N /
X1 R 3 xιs' R31
wherein Ri to R3, R31, R32, Xi and Xι5 are as defined for formula I, may be obtained from the compounds of formula lllk as described above, by means of oxidation of the pyridyl moiety.
As a further variant, the pyridono derivatives of formula Ik may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa
NHNH2 (χχ,a)ι
wherein Ri to R3 and Xi are as defined, in a manner analogous to the variants shown in
Reaction Scheme 10.
The compounds of formulae XII and XIII are known or may be prepared in accordance with known methods, for example as described in DE-A-3 917 469; WO 97/07114; WO
92/00976; JP-A-58-213 776; EP-A-0 012 117; EP-A-0 306 547; EP-A-0 030 215; EP-A-0
272 824; EP-A-0 500 209; US-A-4 996 323; US-A-5 017 705; WO 97/05112; J. Het. Chem.
11 , 889 (1974); J. Het. Chem 21 , 97 (1984); Tetrahedron 41 , 4057 (1985); Heterocycles
22,1 17; Synth. 1988, 938; J. Med. Chem. 25, 96.
The 2-aminopyridines of formula XIII may also be prepared by degradation reactions according to Curtius, Hofmann or Lossen from corresponding pyridine derivatives with carboxylic acid, carboxylic acid chloride, carboxylic acid azide, carboxylic acid ester or carboxylic acid amide functions in the 2-position.
The compounds of formulae XII and Xlla in Reaction Scheme 11 wherein U is a leaving group, e.g. a Cι-C alkyl- or phenyl-sulfonyl group, are known or may be prepared in accordance with known methods, for example by oxidation of the corresponding thioethers - 51 -
with hydrogen peroxide or Javelle water or by means of the synthesis of the heterocycle. Such syntheses are described, for example, in Synthesis 1989, 623 or in WO 98/11071.
The reagents of formulae XIV, XVa, XVb, XVIa, XVIb, XVII, XIX, XX, XXII, XXIIa, XXIII, XXV, XXVI, XXVIII, XXIX, XXXIa, XXXIb, XXXII, XXXIIa, XXXIIb, XXXIIc, XXXIV, XXXV, XXXVa, XXXVI, XXXVIII, XXXIX, XXXXI, XXXXII, XXXXIII and XXXXIV used in Reaction Schemes 2 to 10 are either known or may be prepared in analogy to known methods.
The intermediates of formula II
(II). in which Ri, R2 and W are as defined for formula I and which may be in the tautomeric keto-enol form, are novel. The invention therefore relates to those compounds also.
The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xyiene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, N,N-diethylformamide or N-methylpyrroiidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions are generally slightly exothermic and may usually be carried out at room temperature. In order to shorten the reaction time or alternatively to initiate the reaction, the reaction mixture may be heated to its boiling point for a short time. The reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5- diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate. - 52 -
The compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography and a suitable eluant.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485. Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of - 53 -
WO 97/34485.
In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Steliaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. - 54 -
The following Examples further illustrate but do not limit the invention.
Preparation Examples:
Example P1 : Preparation of 2-N-ethoxycarbonylamino-3-fluoro-5-chloro-pyridine C ^\ ^F O
N,x' xNhT SOC2H5
294 g of 2-amino-3-fluoro-5-chloro-pyridine are dissolved in 1 litre of dry pyridine and cooled to 0°C; 220 g of ethyl chloroformate are added dropwise, with stirring, and the mixture is stirred at 22°C until reaction is complete. The reaction mixture is then poured into ice-water, adjusted to pH 4-5 with 2N hydrochloric acid and extracted with ethyl acetate. The combined extracts are washed with water, dried over sodium sulfate, concentrated by evaporation and caused to crystallise by the addition of n-hexane. The resulting precipitate is filtered off, washed with n-hexane and dried in vacuo, yielding the desired title compound having a melting point of 132°C.
Example P2: Preparation of 1-(3-fluoro-5-chloro-pyridin-2-vπ-3-methyl-4-trifluoromethyl- pyrimidine-2,6-dione
Cl O 3
N . J N .CH,
CF 3
Under a nitrogen atmosphere, with cooling and stirring, a solution of 22.7 g of 4,4,4-trifluoro- 3-amino-2-butenoic acid ethyl ester is added dropwise at 0-5°C to 5.1 g of a previously prepared sodium hydride dispersion (60%) in 60 ml of N-methylpyrrolidine and the mixture is stirred at 22°C until the evolution of hydrogen has ceased. 23.7 g of 2- ethoxycarbonylamino-3-fluoro-5-chloro-pyridine (Example P1 ) are then added and the reaction mixture is heated at 120°C for about 5 hours. The mixture is then cooled, 16.7 g of methyl iodide are added dropwise and stirring is carried out at 22°C overnight. The reaction mixture is taken up in ethyl acetate and then washed with ice-water, dried over sodium sulfate, filtered and concentrated by evaporation. The resulting residue is recrystallised from ethyl acetate/n-hexane, yielding the desired title compound having a melting point of 133- 134°C. - 55 -
Example P3: Preparation of 1-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-3-methyl-4- trifluoromethyl-pyrimidine-2.6-dione
Cl o s .CH3 N N 3 o- o " ° CrF3,
24 g of 1-(3-fluoro-5-chloro-pyridin-2-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione (Example P2) in 150 ml of dichloromethane are cooled to -5°C and 2 g of hydrogen peroxide/urea adduct are added. 2.7 ml of trifluoroacetic acid anhydride dissolved in 2 ml of dichloromethane are then metered in dropwise and after the exothermic reaction has subsided the reaction mixture is stirred overnight to complete the reaction. A further 5 g of hydrogen peroxide/urea adduct and 3 ml of trifluoroacetic acid anhydride are then added in two portions in the course of 3 hours and after the exothermic reaction has subsided the reaction mixture is heated at 25-35°C until the reaction is complete. The reaction mixture is then cooled and at -5°C adjusted to pH 7.5 first with 2N sodium hydroxide solution and then with saturated sodium hydrogen carbonate solution and partitioned between dichloromethane and ice-water; the organic phase is separated off, dried over sodium sulfate, filtered and concentrated by evaporation. The solid residue that remains is recrystallised from ethyl acetate/n-hexane, yielding the desired product having a melting point of 142- 143°C.
Example P4: Preparation of 1-(3-fluoro-5.6-dichloro-2-pyridvD-3-methyl-4-trifluoromethyl- pyrimidine-2.6-dione
Cl F O A\..CH, C| N N N 3 o^\^Cp3
6.8 g of 1-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-3-methyl-4-trifluoromethyl-pyrimidine-2,6- dione (Example P3) are added in portions to a solution, heated to 70°C, of 2.4 ml of phosphorus oxytrichloride in 20 ml of 1 ,2-dichloroethane and the mixture is maintained at that temperature overnight; a further 4.0 ml of phosphorus oxytrichloride is added and the mixture is heated for a further 20 hours. The mixture is then cooled, poured into ice-water and extracted with dichloroethane and the combined extracts are washed with ice-cold 2N - 56 -
sodium hydroxide solution and water, dried over sodium sulfate and concentrated by evaporation. The residue is purified by means of silica gel chromatography (eluant: hexane/ethyl acetate 9/1 ), yielding the desired title compound having a melting point of 113-115°C.
Example P5: Preparation of 1 -(2-hvdroxy-3-chloro-5-fluoro-pyridin-6-vπ-3-methyl-4- trifluoromethyl-pyrimidine-2.6-dione
Cl
.CH,
HO' A '.NAN NΛ *N'
O - CF3
182 g of trifluoroacetic acid anhydride are added dropwise to a solution, cooled to -30°C, of 29.6 g of 1-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-3-methyl-4-trifluoromethyl-pyrimidine-2,6- dione (Example P3) in 400 ml of dimethylformamide and the mixture is then stirred overnight at -30°C and on the following day at 22°C. The mixture is then freed of excess trifluoroacetic acid anhydride in vacuo, cooled to -5°C and cautiously neutralised first with dilute sodium hydroxide solution and then with sodium hydrogen carbonate solution. After the addition of ice-water, extraction is carried out with ethyl acetate and the combined extracts are washed with water and dried over sodium sulfate. Filtration is then carried out and the filtrate is concentrated by evaporation; the resulting residue is purified over a column of silica gel (eluant: n-hexane/ethyl acetate 8/2, with an increasing gradient with respect to ethyl acetate). The desired title compound having a melting point of 178°C is obtained.
- 57
Example P6: Preparation of 1-(2-proparαyloxy-3-chloro-5-fluoro-Pyridin-6-yl)-3-methyl-4- trifluoromethyl-pyrimidine-2.6-dione. 1 -(2-chloro-3-proparαyloxy-5-fluoro-pyridin-6-yl)-3- methyl-4-trifluoromethyl-pyrimidine-2.6-dione and 1 -(1 -proparαyloxy-3-chloro-5-fluoro-2- pyridon-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2.6-dione
HC,
\
CH , A .CH,
O r . N
CR and CH,
O CF, Cl' N N A. N
C \W CH CF,
Cl ^ F
O^ N N.CH3
CH,
CF, c" o
CH
4.5 ml of propargyl bromide are added dropwise to a suspension of 10.2 g of a mixture of 1- (2-hydroxy-3-chloro-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione and 1 -(2-chloro-3-hydroxy-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6- dione (Example P5), 7.5 g of potassium carbonate and 0.08 g of 18-crown-6 in 180 ml of acetonitrile and the mixture is then heated at 65°C overnight. Concentration by evaporation in vacuo is then carried out, and an ethyl acetate/ice-water mixture and 1 N hydrochloric acid are added to the resulting residue until a pH of 7 is obtained; the aqueous phase is separated off and extracted with ethyl acetate and the combined organic phases are washed with water, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by silica gel chromatography (eluant: n-hexane/ethyl acetate 8/2), yielding the desired isomers 1 -(2-propargyloxy-3-chloro-5-f luoro-pyridin-6-yl)-3-methyl-4- trifluoromethyl-pyrimidine-2,6-dione having a melting point of 121-122°C, 1 -(2-chloro-3- propargyloxy-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2,6-dione having a melting point of 69-71 CC and 1-(1 -propargyloxy-3-chloro-5-fluoro-2-pyridon-6-yl)-3-methyl-4- trifluoromethyl-pyrimidine-2,6-dione having a melting point of 223-224°C. - 58 -
Example P7: Preparation of 1 -(1 -allyloxy-3-chloro-5-f luoro-2-pyridon-6-yl)-3-methyl-4- trifluoromethyl-pyrimidine-2.6-dione
A solution of 0.62 g of 1 -(2-allyloxy-3-chloro-5-fluoro-pyridin-6-yl)-3-methyl-4-trifluoromethyl- pyrimidine-2,6-dione in 5 ml of dioxane is stirred at 20°C with 0.02 g of palladium(ll) chloride/diacetonitrile complex until reaction is complete. The reaction mixture is then filtered over silica gel and concentrated by evaporation. The title compound is purified by silica gel chromatography (eluant: ethyl acetate/hexane). The title compound is obtained in pure form with a melting point of 115-117CC.
Example P8: Preparation of 2-(5-chloro-3-fluoro-1 -oxy-pyridin-2-v0-4.5.6.7-tetrahydro- isoindolo-1 ,3-dione (intermediate)
With cooling at -25° to -15°C, 15 g of trifluoroacetic acid anhydride are added in the course of 30 minutes to a suspension of 10.1 g of 2-(5-chloro-3-fluoro-pyridin-2-yl)-4,5,6,7-tetra- hydroisoindolo-1 ,3-dione (prepared analogously to Chem. Abstr. 114, 164251f) and 6.6 g of hydrogen peroxide/urea adduct in 100 ml of 1 ,2-dichloroethane. Stirring is carried out at +10°C overnight, and then a further 3.3 g of hydrogen peroxide/urea adduct is added and stirring is continued at 20°C until reaction is complete. Everything is then poured into ice- water and neutralised with aqueous 2N sodium hydroxide solution. The product is extracted with ethyl acetate, washed with water and dried. Concentration by evaporation yields a solid, which is purified by means of silica gel chromatography (eluant: hexane/ethyl acetate 7/3). The desired 2-(5-chloro-3-fluoro-1-oxy-pyridin-2-yl)-4,5,6,7-tetrahydroisoindolo-1 ,3- dione having a melting point of 162-164°C is obtained. - 59
Example P9: Preparation of 2-(5-chloro-3-fluoro-6-hvdroxy-pyridin-2-yl)-4.5.6.7-tetrahvdro- isoindolo-1 ,3-dione and 2-(5-hvdroxy-6-chloro-3-fluoro-pyridin-2-yl)-4.5,6,7-tetrahydro- isoindolo-1 ,3-dione
and
3.6 ml of trifluoroacetic acid anhydride are added dropwise, with cooling at -30° to -20°C, to a solution of 0.79 g of 2-(5-chloro-3-fluoro-1-oxy-pyridin-2-yl)-4,5,6,7-tetrahydroisoindolo- 1 ,3-dione (Example P8) in 12 ml of dimethylformamide and the mixture is stirred at +10°C overnight. A further 3 ml of trifluoroacetic acid anhydride is then added dropwise and stirring is continued at +10°C for 15 hours. Concentration by evaporation is then carried out; ethyl acetate is added to the resulting residue and the mixture is rendered basic with aqueous 1N sodium hydroxide solution. Extraction is then carried out with ethyl acetate and the combined extracts are washed with water, dried and concentrated by evaporation. The residue is purified by silica gel chromatography, yielding the isomeric mixture of the two title compounds having a melting point of 190-193°C. The mixture can either be separated or further reacted directly.
In an analogous manner, and in accordance with methods as shown in the general Reaction Schemes 1-10 and in the references indicated, it is also possible to obtain the preferred compounds listed in the following Tables.
Table 1 : A preferred group of compounds of formula I corresponds to general formula
Cl ^-F (lϊ), wherein the meanings of the corresponding
substituents R1 ( Xi and R3 are given in Table A, so that 423 specific compounds of formula li are disclosed. - 60
Table 2: A further preferred group of compounds of formula I corresponds to general
R 1 °\ formula Br — (? y — N y -F (l2), wherein the meanings of the corresponding
X [' -". R 3 o ^ CH3 F
substituents Ri, X and R3 are indicated in Table A, so that 423 specific compounds of formula l2 are disclosed.
Table 3: A further preferred group of compounds of formula I corresponds to general
R 1°\ formula NC — ( y — N y -F (l3), wherein the meanings of the corresponding
X R 3 o ^ CH3 p substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l3 are disclosed.
Table 4: A further preferred group of compounds of formula I corresponds to general
R r^« O..
formula CH ~ ^ \ (U) wherein the meanings of the
N - ,
X R 3 o CH,
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l4 are disclosed.
Table 5: A further preferred group of compounds of formula I corresponds to general
R T O
formula Cl — ( ) — N ^-F (|5), wherein the meanings of the corresponding - N -NN F x R 3 S CH3
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l5 are disclosed. - 61 -
Table 6: A further preferred group of compounds of formula I corresponds to general
- N ^r-N F
X R 3 CH3
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l6 are disclosed.
Table 7: A further preferred group of compounds of formula I corresponds to general
F F formula Cl — ( y — N y F (l7), wherein the meanings of the
F F ι R 3 o CH,
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l7 are disclosed.
Table 8: A further preferred group of compounds of formula I corresponds to general / R 1 I S \v\
F formula Cl — ( — N y — ^F (l8), wherein the meanings of the corresponding
X R 3 s CH3
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l8 are disclosed.
Table 9: A further preferred group of compounds of formula I corresponds to general
R 1 °\ formula CH3 — ( — N y — \ F (Ig), wherein the meanings of the V- N -N F F
X R 3 O CH3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l9 are disclosed. - 62 -
Table 10: A further preferred group of compounds of formula I corresponds to general
R 11 ° \v\ Cl
formula Cl — N y ^-H (|10), wherein the meanings of the corresponding y-N. ^-N F
R „ o CHF,
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι0 are disclosed.
Table 1 1 : A further preferred group of compounds of formula I corresponds to general
I R 11 ° \v\ / CR 3 formula Cl 7 wherein the meanings of the corresponding / x R o CH,
substituents R1 f X, and R3 are indicated in Table A, so that 423 specific compounds of formula In are disclosed.
Table 12: A further preferred group of compounds of formula I corresponds to general
R , O Cl
formula Cl -s R> , O CH - _ _
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l12 are disclosed.
Table 13: A further preferred group of compounds of formula I corresponds to general
R 1°\ formula Cl — ( y — N y — CN (1,3), wherein the meanings of the corresponding
X R 3 O CH3
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι3 are disclosed. - 63
Table 14: A further preferred group of compounds of formula I corresponds to general
R < 0, CH,
formula Br — (^ N) — N — CN (lι4), wherein the meanings of the corresponding - N X X D R O H CH
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula li4 are disclosed.
Table 15: A further preferred group of compounds of formula I corresponds to general
formula NC CN C15), wherein the meanings of the corresponding
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι5 are disclosed.
Table 16: A further preferred group of compounds of formula I corresponds to general
F^ formula CH3 — y — N y — CN (|16), wherein the meanings of the corresponding
N
X R 0 y-N CH
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι6 are disclosed.
Table 17: A further preferred group of compounds of formula I corresponds to general
formula Cl (lι7), wherein the meanings of the corresponding
X V R R β - o O < CH3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι7 are disclosed. 64 -
Table 18: A further preferred group of compounds of formula I corresponds to general
-.. 70f , . — _ .
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula e are disclosed.
Table 19: A further preferred group of compounds of formula I corresponds to general
R 1 °\
formula Cl ) — N y — v (|19), wherein the meanings of the corresponding
XιH .H -> substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula g are disclosed.
Table 20: A further preferred group of compounds of formula I corresponds to general
formula Cl — ( ) — N^ y ^-F (|20), wherein the meanings of the corresponding - N N= F
X 1 R 3 CH3
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l20 are disclosed.
Table 21 : A further preferred group of compounds of formula I corresponds to general
R , 0. r formula Cl N Λ , wherein the meanings of the corresponding
N:
X 1 R g CH3
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l21 are disclosed. - 65 -
Table 22: A further preferred group of compounds of formula I corresponds to general
F formula BBrr- — — ^-F (i^), wherein the meanings of the
X 1 R 3 CHg
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l22 are disclosed.
Table 23: A further preferred group of compounds of formula I corresponds to general
r formula ,_ (l23), wherein the meanings of the corresponding
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l23 are disclosed.
Table 24: A further preferred group of compounds of formula I corresponds to general
R , θ,
F formula Br — ^ — N y ^-F (|24)f wherein the meanings of the
N N^ x R 3 corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2 are disclosed.
Table 25: A further preferred group of compounds of formula I corresponds to general
formula Br — ( — N^ / ~ \ F C25)' wherein the meanings of the corresponding
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2s are disclosed. - 66
Table 26: A further preferred group of compounds of formula I corresponds to general
CH,
F formula Br- -N Λ (l26), wherein the meanings of the
N N
X R
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l26 are disclosed.
Table 27: A further preferred group of compounds of formula I corresponds to general
R ^.
O- formula - f (l27), wherein the meanings of
/ - N N=
X R
the corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l27 are disclosed.
Table 28: A further preferred group of compounds of formula I corresponds to general
R formula Cl1 Δ- (l2s)> wherein the meanings of the
X R 3 corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l28 are disclosed.
Table 29: A further preferred group of compounds of formula I corresponds to general
F formula Cl \ F (|29), wherein the meanings of the corresponding F substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l29 are disclosed. 67
Table 30: A further preferred group of compounds of formula I corresponds to general
R Λ S CH3
formula C| — \ ) — h- N 1 NH y N=^ ' ( ' (|30), wherein the meanings of the corresponding F
X 1 R 3 CH3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l30 are disclosed.
Table 31 : A further preferred group of compounds of formula I corresponds to general
(l3ι), wherein the meanings of the corresponding
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l3ι are disclosed.
Table 32: A further preferred group of compounds of formula I corresponds to general
formula (l32), wherein the meanings of the corresponding
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l32 are disclosed.
Table 33: A further preferred group of compounds of formula I corresponds to general
R 1
formula (I33), wherein the meanings of the corresponding
CH,
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l∞ are disclosed. - 68 -
Table 34: A further preferred group of compounds of formula I corresponds to general R , 0.
formula oi — <^ ^ — N \ — (IM), wherein the meanings of the corresponding
X 1 R 3 substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l^ are disclosed.
Table 35: A further preferred group of compounds of formula I corresponds to general
formula C wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l35 are disclosed.
Table 36: A further preferred group of compounds of formula I corresponds to general
formula yy (|36)? wherein the meanings of the
V- N F
X 1 R 3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l36 are disclosed.
Table 37: A further preferred group of compounds of formula I corresponds to general
R ,° P formula Cl ( y — N y ^ (|37), wherein the meanings of the corresponding -- NN N=^ F X R 3 CN
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l37 are disclosed. - 69
Table 38: A further preferred group of compounds of formula I corresponds to general
R ι C-
(l3s), wherein the meanings of the
corresponding substituents R f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l^ are disclosed.
Table 39: A further preferred group of compounds of formula I corresponds to general
(l39), wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l39 are disclosed.
Table 40: A further preferred group of compounds of formula I corresponds to general
F
formula F (l40), wherein the meanings of the
CH,
corresponding substituents R f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula Uo are disclosed.
Table 41 : A further preferred group of compounds of formula I corresponds to general
- ~ 7rO fc .„_ _ «
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l ι are disclosed. - 70 -
Table 42: A further preferred group of compounds of formula I corresponds to general
formula Cl — P - V (l 2), wherein the meanings of the corresponding N N=
X R
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l42 are disclosed.
Table 43: A further preferred group of compounds of formula I corresponds to general
formula Cl (Lu), wherein the meanings of the corresponding R
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l43 are disclosed.
Table 44: A further preferred group of compounds of formula I corresponds to general
R , l Q formula NC- -N (I44), wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula are disclosed.
Table 45: A further preferred group of compounds of formula I corresponds to general
R CH,
Br formula ci \ -N (l45), wherein the meanings of the corresponding
N N-^CH
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l45 are disclosed. 71
Table 46: A further preferred group of compounds of formula I corresponds to general
,CI formula ci — y — N (l46), wherein the meanings of the corresponding
VN v 'CH,
X R
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l46 are disclosed.
Table 47: A further preferred group of compounds of formula I corresponds to general 1 C 3
,C\ formula ci N (l47), wherein the meanings of the corresponding N- CH,
X
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l 7 are disclosed.
Table 48: A further preferred group of compounds of formula I corresponds to general
R 1 Cl
,CH, formula NC N (l48), wherein the meanings of the corresponding N ^CH3 ,
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l48 are disclosed.
Table 49: A further preferred group of compounds of formula I corresponds to general
R 1
,Br formula Cl — 7~ N x (l4g), wherein the meanings of the corresponding
'CH,
X 1 R g
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l 9 are disclosed. - 72 -
Table 50: A further preferred group of compounds of formula I corresponds to general
R 1 CH3 COOEt formula Cl — ( y — N^ ^ (i^), wherein the meanings of the corresponding
N N- 'CH,
X R
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l50 are disclosed.
Table 51 : A further preferred group of compounds of formula I corresponds to general
R 1 N02
CH3 formula Cl — (^ — N I (l5ι), wherein the meanings of the corresponding
^ N NN^ C| X 1 R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l5ι are disclosed.
Table 52: A further preferred group of compounds of formula I corresponds to general
R 1 C2H5 formula J / //r-l ^λ N x -CH3 (l52), wherein the meanings of the corresponding r- N C2H5
X 1 R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l52 are disclosed.
Table 53: A further preferred group of compounds of formula I corresponds to general
R , C2H5 formula i-f // W ^ /=^= :::1 (I53), wherein the meanings of the corresponding -N ^C2H5
X 1 R 3
substituents R1 f X and R3 are indicated in Table A, so that 423 specific compounds of formula l53 are disclosed. - 73 -
Table 54: A further preferred group of compounds of formula I corresponds to general
R 1 N02
CH3 formula NC (/ \ N (IM), wherein the meanings of the corresponding
N 'CH,
'/
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l^ are disclosed.
Table 55: A further preferred group of compounds of formula I corresponds to general R< CH30
,CH ' '3, formula Cl - -N (l55), wherein the meanings of the corresponding - N ^CH3
X 1 R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l55 are disclosed.
Table 56: A further preferred group of compounds of formula I corresponds to general
R 1 C2H '55 .Br formula . // ' |T ^'56^' wherein the meanings of the corresponding
^- N S ^CH3
X 1 R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l56 are disclosed.
Table 57: A further preferred group of compounds of formula I corresponds to general
R 1 NH2
formula Q\ — (f ^ — N | (l57), wherein the meanings of the corresponding
X 1 R 3 substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l57 are disclosed. - 74
Table 58: A further preferred group of compounds of formula I corresponds to general
CH,
CH3-N.
R , N formula — / (Isβ), wherein the meanings of the corresponding
ClA
CH,
X y, \ R .
substituents Ri ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I58 are disclosed.
Table 59: A further preferred group of compounds of formula I corresponds to general
R 1 N02
.Cl formula (l59), wherein the meanings of the corresponding - N N- C2H5
X 1 R 3
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l59 are disclosed.
Table 60: A further preferred group of compounds of formula I corresponds to general R< Cl
formula Cl ■ N (l6o). wherein the meanings of the corresponding
■ N N'
X 1 R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l6o are disclosed.
Table 61 : A further preferred group of compounds of formula I corresponds to general
/ R , I C \N
formula Cl — V— N. (I6ι), wherein the meanings of the corresponding
N N- χ R 3 substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l6ι are disclosed. - 75 -
Table 62: A further preferred group of compounds of formula I corresponds to general
R 1 Cl
formula NC N, (l62), wherein the meanings of the corresponding
N-
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l62 are disclosed.
Table 63: A further preferred group of compounds of formula I corresponds to general
R 1 Cl
formula Cl — P (l63>, wherein the meanings of the
X R
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l63 are disclosed.
Table 64: A further preferred group of compounds of formula I corresponds to general
R , I C
formula NC (IM), wherein the meanings of the
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lM are disclosed.
Table 65: A further preferred group of compounds of formula I corresponds to general
formula Cl (l65>, wherein the meanings of the
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l65 are disclosed. - 76
Table 66: A further preferred group of compounds of formula I corresponds to general
R .1 c
formula Cl (Iββ), wherein the meanings of the corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l66 are disclosed.
Table 67: A further preferred group of compounds of formula I corresponds to general
R
.CH, formula Cl (l6 ), wherein the meanings of the corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l67 are disclosed.
Table 68: A further preferred group of compounds of formula I corresponds to general
formula Cl (i^,), wherein the meanings of the
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l6β are disclosed.
Table 69: A further preferred group of compounds of formula I corresponds to general
R 1 ^ V, ^'CH, formula Cl — N (l6g), wherein the meanings of the
CH,
N R O
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l6g are disclosed. 77 -
Table 70: A further preferred group of compounds of formula I corresponds to general
R
>^CH,
N (l70), wherein the meanings of the corresponding y^cπ3
substituents R ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l70 are disclosed.
Table 71 : A further preferred group of compounds of formula I corresponds to general
R . O.
.CH, formula 'N ^< (l7ι), wherein the meanings of the corresponding
CH,
X R O
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l7ι are disclosed.
Table 72: A further preferred group of compounds of formula I corresponds to general
formula Cl (l72), wherein the meanings of the
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l72 are disclosed.
Table 73: A further preferred group of compounds of formula I corresponds to general
R 1
formula NC (I73), wherein the meanings of the corresponding
X -N- R 3 0
substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l73 are disclosed. 78 -
Table 74: A further preferred group of compounds of formula I corresponds to general
R s
CH, formula Cl N (l7 ), wherein the meanings of the corresponding CH,
X R 3 s substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l7 are disclosed.
Table 75: A further preferred group of compounds of formula I corresponds to general
R 1 O
CH, formula NC (l75), wherein the meanings of the corresponding CH,
X o
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l75 are disclosed.
Table 76: A further preferred group of compounds of formula I corresponds to general
R
formula Cl (l76), wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l76 are disclosed.
Table 77: A further preferred group of compounds of formula I corresponds to general
R 1 °
formula Cl (I ), wherein the meanings of the correspo r nding
X , NW- i R 3 ° Y
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula \τ, are disclosed. 79
Table 78: A further preferred group of compounds of formula I corresponds to general
R 1
'CCI, formula Cl (I78), wherein the meanings of the
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l78 are disclosed.
Table 79: A further preferred group of compounds of formula I corresponds to general
R
formula Cl (l79), wherein the meanings of the corresponding
CF,
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l79 are disclosed.
Table 80: A further preferred group of compounds of formula I corresponds to general
R , o
.CH, formula Cl
"VN ^— (Iβo), wherein the meanings of the
X R o O
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l80 are disclosed.
Table 81 : A further preferred group of compounds of formula I corresponds to general
R 1 formula Cl (l8ι), wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l8ι are disclosed. - 80 -
Table 82: A further preferred group of compounds of formula I corresponds to general
formula CH (l82), wherein the meanings of the corresponding N-_
X O
substituents R1? Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l82 are disclosed.
Table 83: A further preferred group of compounds of formula I corresponds to general
R 1 9, formula (l83), wherein the meanings of the corresponding
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l83 are disclosed.
Table 84: A further preferred group of compounds of formula I corresponds to general
formula Cl — < V- N' (IM), wherein the meanings of the N ^
X R 30
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I are disclosed.
Table 85: A further preferred group of compounds of formula I corresponds to general
R ι formula NC (las), wherein the meanings of the
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l8s are disclosed. 81
Table 86: A further preferred group of compounds of formula I corresponds to general
formula Cl ( (l86), wherein the meanings of the
N n
X O
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l86 are disclosed.
Table 87: A further preferred group of compounds of formula I corresponds to general
R , o,
.CH, formula NC— ^ y— (l87), wherein the meanings of the
X R 3 0 corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l87 are disclosed.
Table 88: A further preferred group of compounds of formula I corresponds to general
R o,
CH, formula Cl (l88), wherein the meanings of the
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l88 are disclosed.
Table 89: A further preferred group of compounds of formula I corresponds to general
R 1 formula Br — (l89), wherein the meanings of the - N
X f R 3 corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l89 are disclosed. 82
Table 90: A further preferred group of compounds of formula I corresponds to general
R 1 S
formula Cl — T y— N ■, (Igo), wherein the meanings of the corresponding
X f R 3 S
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula Igo are disclosed.
Table 91 : A further preferred group of compounds of formula I corresponds to general
R 9v
CH, formula Cl N (l9ι), wherein the meanings of the
CH,
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I9 are disclosed.
Table 92: A further preferred group of compounds of formula I corresponds to general
R <
^CH3 formula Cl -N I (l92), wherein the meanings of the corresponding
N
R
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l92 are disclosed.
Table 93: A further preferred group of compounds of formula I corresponds to general
R . °v formula Cl f the corresponding N
R V (l93), wherein the meanings o
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l93 are disclosed. - 83 -
Table 94: A further preferred group of compounds of formula I corresponds to general
-CH, ~N' formula Cl — (? y — (lM), wherein the meanings of the corresponding
^ N
X1 R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l94 are disclosed.
Table 95: A further preferred group of compounds of formula I corresponds to general
formula Cl _ — (7~ ) — N °K J CH> (|95), wherein the meanings of the corresponding
X, R 3 O CH2CH3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lg5 are disclosed.
Table 96: A further preferred group of compounds of formula I corresponds to general
R , Q
/CH3 formula Cl — (f y — N J (l^), wherein the meanings of the
X1 R 3 O CH 2CH2CH3
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula Ige are disclosed.
Table 97: A further preferred group of compounds of formula I corresponds to general
formula Cl — ( y — N J (l97), wherein the meanings of the y p fj CHgCHjCHgCH,
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l97 are disclosed. - 84 -
Table 98: A further preferred group of compounds of formula I corresponds to general
formula Cl — ( y — N «CH (l98), wherein the meanings of the
X y-N R O Y \ CH2CH 3 2CH2CH3
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l98 are disclosed.
Table 99: A further preferred group of compounds of formula I corresponds to general
formula NC — ( — N J (|99), wherein the meanings of the
X1 R 3 O CH 2CH2CH3
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l99 are disclosed.
Table 100: A further preferred group of compounds of formula I corresponds to general R , P. CH2CH3 formula Cl — ( y — •N l ^-CH CH doo), wherein the meanings of the
corresponding substituents R1 t X1 and R3 are indicated in Table A, so that 423 specific compounds of formula \\∞ are disclosed.
Table 101 : A further preferred group of compounds of formula I corresponds to general
_ ~ ^NH formula Cl — ( y— N J ( oi), wherein the meanings of the
X1 R 3 O CH 2CH2CH3
corresponding substituents R^ Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I101 are disclosed. - 85 -
Table 102: A further preferred group of compounds of formula I corresponds to general
R , s
.CH,
A^N'
(lι02), wherein the meanings of the corresponding
X1 R 3 S
substituents R1 ? Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι02 are disclosed.
Table 103: A further preferred group of compounds of formula I corresponds to general
formula NC ( — N L-CH O103), wherein the meanings of the corresponding
X1 R 3 O CH
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι03 are disclosed.
Table 104: A further preferred group of compounds of formula I corresponds to general
R , Q
NC- ^ -N formula \ j . ^ ('1 4)1 wherein the meanings of the corresponding
X1 R 3 O substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lιM are disclosed.
Table 105: A further preferred group of compounds of formula I corresponds to general
formula d05)* where'n the meanings of the corresponding
substituents R^ Xi and R3 are indicated in Table A, so that 423 specific compounds of formula 1105 are disclosed. - 86
Table 106: A further preferred group of compounds of formula I corresponds to general
formula (hoe), wherein the meanings of the
CH ,
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l106 are disclosed.
Table 107: A further preferred group of compounds of formula I corresponds to general
R < S,
.CH, formula Br -0T7 (lι07), wherein the meanings of the corresponding
CH,
X, R
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι07 are disclosed.
Table 108: A further preferred group of compounds of formula I corresponds to general
,/CH3 formula (hoe), wherein the meanings of the corresponding X1 R substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula oe are disclosed.
Table 109: A further preferred group of compounds of formula I corresponds to general
formula C 'l —W (^ ^) " —■ N. O | | (|109), wherein the meanings of the corresponding
X, R 3 ° substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι09 are disclosed. - 87
Table 1 10: A further preferred group of compounds of formula I corresponds to general
(I110), wherein the meanings of the corresponding
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln0 are disclosed.
Table 111 : A further preferred group of compounds of formula I corresponds to general
formula Cl (Im), wherein the meanings of the
OH corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula Im are disclosed.
Table 112: A further preferred group of compounds of formula I corresponds to general
R , Q
N formula Cl (I112), wherein the meanings of the
Cl
X< R o O
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι12 are disclosed.
Table 113: A further preferred group of compounds of formula I corresponds to general
R ,
formula B (I113), wherein the meanings of the
R
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln3 are disclosed. 88
Table 114: A further preferred group of compounds of formula I corresponds to general
R < Q
formula NC (lιι ), wherein the meanings of the Cl
R
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l are disclosed.
Table 115: A further preferred group of compounds of formula I corresponds to general ι formula NC -N (I115), wherein the meanings of the corresponding N xι R 3 substituents R1 τ Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln5 are disclosed.
Table 116: A further preferred group of compounds of formula I corresponds to general
R , Q
formula B jrι (/ V) — N (hie), wherein the meanings of the corresponding
X1 R 3 substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln6 are disclosed.
Table 117: A further preferred group of compounds of formula I corresponds to general
formula Cl (l ι ), wherein the meanings of the corresponding
substituents R^ Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln7 are disclosed. 89
Table 118: A further preferred group of compounds of formula I corresponds to general
formula Cl - — (rC y — NVo I /. (ln8), wherein the meanings of the corresponding -N. y-^^
X, R 3 o
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln8 are disclosed.
Table 119: A further preferred group of compounds of formula I corresponds to general
R ,
•N formula NC ( ) — N I / (ln9), wherein the meanings of the
x. R o o
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula ln9 are disclosed.
Table 120: A further preferred group of compounds of formula I corresponds to general
R ?
Λ^N' formula NC N (I120), wherein the meanings of the N
X,
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l120 are disclosed.
Table 121 : A further preferred group of compounds of formula I corresponds to general
formula Cl (lι2ι), wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l 2ι are disclosed. - 90 -
Table 122: A further preferred group of compounds of formula I corresponds to general
o
Λ (lι22), wherein the meanings of the o - CH
X1 R 3 ° corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι22 are disclosed.
Table 123: A further preferred group of compounds of formula I corresponds to general
formula cι (I123), wherein the meanings of the
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι23 are disclosed.
Table 124: A further preferred group of compounds of formula I corresponds to general
R , Q
formula Br - ι2 ), wherein the meanings of the
CH,
X0 (l
, R o o
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι24 are disclosed.
Table 125: A further preferred group of compounds of formula I corresponds to general
formula Cl ^^ wnΘrein the meanings of the CH . 1 R 3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι25 are disclosed. 91
Table 126: A further preferred group of compounds of formula I corresponds to general
R ,
N' formula Br (Ii26), wherein the meanings of the
V-N y xι R 3 ° corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι26 are disclosed.
Table 127: A further preferred group of compounds of formula I corresponds to general
R < Q
formula Cl (I127), wherein the meanings of the corresponding
X, R O
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι27 are disclosed.
Table 128: A further preferred group of compounds of formula I corresponds to general
R , ° formula Cl <ϊP (lι28), wherein the meanings of the "° CH,
X, R o O
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι28 are disclosed.
Table 129: A further preferred group of compounds of formula I corresponds to general
formula Cl — — N I > (|129), wherein the meanings of the corresponding .
X, R 3 O Y^
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula 29 are disclosed. - 92
Table 130: A further preferred group of compounds of formula I corresponds to general
formula C 1l- \ ) — N I /==0 (lι30), wherein the meanings of the
X, N. R 3 O Y^
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula li∞ are disclosed
Table 131 : A further preferred group of compounds of formula I corresponds to general R
formula Cl (lι3ι), wherein the meanings of the corresponding
N
X, R 3 ° substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I131 are disclosed. Table 132: A further preferred group of compounds of formula I corresponds to general
formula C -liΑ → (lι32), wherein the meanings of the
Xi R 3 ° corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι32 are disclosed.
Table 133: A further preferred group of compounds of formula I corresponds to general
formula NC — ( — N I ) — F (i^), wherein the meanings of the
X V, N. R 3 O Y^
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι33 are disclosed. 93 -
Table 134: A further preferred group of compounds of formula I corresponds to general
R < Q
formula CH f l3 — \ ) " —' V^, J^ / — ■ F (IIM), wherein the meanings of the N
R 3 ° corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula IIM are disclosed.
Table 135: A further preferred group of compounds of formula I corresponds to general
formula Cl W ( y — N J \ (1,35), wherein the meanings of the corresponding
xι R 3 ° O substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι35 are disclosed.
Table 136: A further preferred group of compounds of formula I corresponds to general
R , P.
formula Cl ling
R 3 O
substituents R1( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι36 are disclosed
Table 137: A further preferred group of compounds of formula I corresponds to general
R < Q
formula Cl - XP, R N
R 3 O )YO j )= -n^-ro C137), wherein the meanings of the
. . corresponding substituents R1f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula h37 are disclosed. 94
Table 138: A further preferred group of compounds of formula I corresponds to general
formula Cl ( /~~ \ ) — ci daβ), wherein the meanings of the
VH
X, R 3 O γn-j
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula li38 are disclosed.
Table 139: A further preferred group of compounds of formula I corresponds to general
formula Cl ( y — N J \ — F (1,39), wherein the meanings of the
VN. v-/ x, R 3 o corresponding substituents R1f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι39 are disclosed.
Table 140: A further preferred group of compounds of formula I corresponds to general
formula ^ Cl — / (/ V y —_ N / "N I H (I140), wherein the meanings of the corresponding -N YH^ Z i R3 S
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l140 are disclosed.
Table 141 : A further preferred group of compounds of formula I corresponds to general
R , P.
formula Cl (I141), wherein the meanings of the
Xi f R, γ* corresponding substituents R Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l141 are disclosed. - 95
Table 142: A further preferred group of compounds of formula I corresponds to general
R H
formula Cl -r r (lι42), wherein the meanings of the
•CH,
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι42 are disclosed.
Table 143: A further preferred group of compounds of formula I corresponds to general p n ^ ^N" ^CH3 formula Cl — < y — N I (|143), wherein the meanings of the
X V, K R3 O y-N-cH»
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l143 are disclosed.
Table 144: A further preferred group of compounds of formula I corresponds to general
R < P.
formula CH3 3- ( ~ y N I (li44), wherein the meanings of the
V \ N .. \^-N^CH3 xι R ^,3 o
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l144 are disclosed.
Table 145: A further preferred group of compounds of formula I corresponds to general
formula Cl — ( / ~N '. (I1 5), wherein the meanings of the y-N^
Xι Ro 3 S
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula li 5 are disclosed. - 96
Table 146: A further preferred group of compounds of formula I corresponds to general
R < P
formula Cl -r (lι46), wherein the meanings of the corresponding -T RVΛi O
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι46 are disclosed.
Table 147: A further preferred group of compounds of formula I corresponds to general
R « P
formula Cl -r# o ( 47), wherein the meanings of the corresponding
R3 ° substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula 47 are disclosed.
Table 148: A further preferred group of compounds of formula I corresponds to general
R o CH 3
CH, formula Cl /T -N I I (l148), wherein the meanings of the -N.
CH,
Xi Ro o
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι 8 are disclosed.
Table 149: A further preferred group of compounds of formula I corresponds to general
R , P
formula NC -f - ( (lι49), wherein the meanings of the corresponding
x, R3 o
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι49 are disclosed. - 97 -
Table 150: A further preferred group of compounds of formula I corresponds to general
formula Cl w — N I > (|150), wherein the meanings of the corresponding
X VI H R3 O Y
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι50 are disclosed.
Table 151 : A further preferred group of compounds of formula I corresponds to general
R 1 <&
formula CH. ,77- (lι51), wherein the meanings of the corresponding
Xi R, o "
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I151 are disclosed.
Table 152: A further preferred group of compounds of formula I corresponds to general
R 1 S formula Cl / '/ ^ —^ κ ^N I s° (|152), wherein the meanings of the
/ 0
■N y
X, R3 θ
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι52 are disclosed.
Table 153: A further preferred group of compounds of formula I corresponds to general
formula Cl —V ~N ' β (I153), wherein the meanings of the corresponding -N yH^
X, R3 θ
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι53 are disclosed. - 98 -
Table 154: A further preferred group of compounds of formula I corresponds to general
R . Q
formula Cl — ( y — N \f O (|154), wherein the meanings of the corresponding
x V, N R3 O )
substituents R1 r Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l154 are disclosed.
Table 155: A further preferred group of compounds of formula I corresponds to general
R < P
K- .CH, formula Cl — ( y — N I (|155), wherein the meanings of the corresponding - N ^N"^CH3
X1 R3 substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι55 are disclosed.
Table 156: A further preferred group of compounds of formula I corresponds to general
,R 1 ?
.CH3 formula NC (l156), wherein the meanings of the corresponding
"CH, x. 3 ° substituents Ru Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι56 are disclosed.
Table 157: A further preferred group of compounds of formula I corresponds to general
R < P
.CH,
(I157), wherein the meanings of the corresponding
•CH3 substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι57 are disclosed. - 99 -
Table 158: A further preferred group of compounds of formula I corresponds to general
R ■ ■ « P
,CH, formula Br — ^ N I^ J I( (|158), wherein the meanings of the corresponding
VN " •CCHH,, ι R3 °' substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι58 are disclosed.
Table 159: A further preferred group of compounds of formula I corresponds to general
R 1 P
formula NC (Γ~\ y — N / ^ I H (|159), wherein the meanings of the corresponding
V y- CH»
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι59 are disclosed.
Table 160: A further preferred group of compounds of formula I corresponds to general
/R ' \ formula Cl — ( — N I (|160), wherein the meanings of the
^- N -N^CH(CH3)2 1 R 3 ° corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l16o are disclosed.
Table 161 : A further preferred group of compounds of formula I corresponds to general
formula Cl — ( — N I O (|161)f wherein the meanings of the corresponding
VN -N- x, R3 ° substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι6ι are disclosed. - 100 -
Table 162: A further preferred group of compounds of formula I corresponds to general
R « S
.CH, formula Cl — ( y — N I (l162), wherein the meanings of the corresponding
VN - , x, R3 s substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula 62 are disclosed.
Table 163: A further preferred group of compounds of formula I corresponds to general R , P
formula Cl — < y — N J| — CH3 (l^), wherein the meanings of the
VN
Xi R3 ° VN-/
corresponding substituents R^ Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι63 are disclosed.
Table 164: A further preferred group of compounds of formula I corresponds to general
~ I (|164), wherein the meanings of the corresponding ^N^CH3 o substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l164 are disclosed.
Table 165: A further preferred group of compounds of formula I corresponds to general
formula NC — — N I S (|165), wherein the meanings of the corresponding
X V, H R3 0 YN^
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lies are disclosed. - 101 -
Table 166: A further preferred group of compounds of formula I corresponds to general
R , S
formula Cl i- — V y —- N I S (|166), wherein the meanings of the corresponding
Xi R3 S substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l166 are disclosed.
Table 167: A further preferred group of compounds of formula I corresponds to general
formula CH3-^ y — N I S (|167), wherein the meanings of the N / O
R π3 O
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l167 are disclosed.
Table 168: A further preferred group of compounds of formula I corresponds to general
formula Cl _ (7~i y N7-N I^7 I (|168)ι wherein the meanings of the corresponding
>-N y-N^°
X, R3 o
substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι68 are disclosed.
Table 169: A further preferred group of compounds of formula I corresponds to general
formula Cl < / ~N I I (|169), wherein the meanings of the corresponding
Xi R3 O
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι69 are disclosed. - 102 -
Table 170: A further preferred group of compounds of formula I corresponds to general
R , P
formula Cl |Λ — if y —N NN I ==0 (lι o), wherein the meanings of the y-»N > X, R3 O Y*^
corresponding substituents R1 t X and R3 are indicated in Table A, so that 423 specific compounds of formula l170 are disclosed.
Table 171 : A further preferred group of compounds of formula I corresponds to general
R < P
formula NC — v y — N \f yS (|171), wherein the meanings of the
x V, N R3 O
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula h7ι are disclosed.
Table 172: A further preferred group of compounds of formula I corresponds to general
R « P
A^N' formula NC ^ y — NN I I (|172)j wherein the meanings of the corresponding
N yu. ^ ^
X, R3 O
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι72 are disclosed.
Table 173: A further preferred group of compounds of formula I corresponds to general
N^k 3 formula CH3 — / </ y — ^=\ / N( (lι73), wherein the meanings of the — N S"^^ Ό-o
X 1 R 3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι73 are disclosed. - 103 -
Table 174: A further preferred group of compounds of formula I corresponds to general
R T CH3- y \ / N formula Cl — <? — ^=\ I ( 74), wherein the meanings of the
V- N S^s
X 1 R 3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l 74 are disclosed.
Table 175: A further preferred group of compounds of formula I corresponds to general
R 1 formula ^ / O N (lι75), wherein the meanings of the corresponding
N
X R 3 substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι75 are disclosed.
Table 176: A further preferred group of compounds of formula I corresponds to general
formula Nπ N (I ), wherein the meanings of the corresponding
S' substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι76 are disclosed.
Table 177: A further preferred group of compounds of formula I corresponds to general
formula QJ __// \v__N__/ ^ (Im), wherein the meanings of the corresponding X— N s^^s
X 1 R 3 substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula I are disclosed. 104
Table 178: A further preferred group of compounds of formula I corresponds to general
R 1 formula (Ii7β), wherein the meanings of the corresponding
Cl \
N ■N=< S
X R
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι78 are disclosed.
Table 179: A further preferred group of compounds of formula I corresponds to general
O
R formula (lι79), wherein the meanings of the corresponding
Cl ~ N S^>0 x V '/' D R
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l179 are disclosed.
Table 180: A further preferred group of compounds of formula I corresponds to general
R formula cι-r '/ \ y- Ci8o), wherein the meanings of the corresponding
N
N x R
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l180 are disclosed.
Table 181 : A further preferred group of compounds of formula I corresponds to general
formula (l18ι), wherein the meanings of the corresponding
Cl -1 R 3 - 105 -
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι8ι are disclosed.
Table 182: A further preferred group of compounds of formula I corresponds to general
R 1 formula r. — Λ. ^'182^' w'ιere'n t e meanings of the corresponding
CI_ yy—1 N N=<S s ^o
X 1 R 3
substituents R1t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι82 are disclosed.
Table 183: A further preferred group of compounds of formula I corresponds to general
R <
(I183), wherein the meanings of the corresponding
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι83 are disclosed.
Table 184: A further preferred group of compounds of formula I corresponds to general
formula QJ // N-_/ J (IIM), wherein the meanings of the corresponding
VN S^O
X , R 3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l^ are disclosed. - 106 -
Table 185: A further preferred group of compounds of formula I corresponds to general
R formula // / (l185), wherein the meanings of the corresponding
N S^^s x l' R 3 substituents R1( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι85 are disclosed.
Table 186: A further preferred group of compounds of formula I corresponds to general
formula _μ __/ ('186)' wherein the meanings of the
3^ N S^ ;
X 1 R 3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l18β are disclosed.
Table 187: A further preferred group of compounds of formula I corresponds to general
formula QJ_J // N__ T (I187), wherein the meanings of the
V- N S^^o
X 1 R 3
corresponding substituents R1f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι87 are disclosed.
Table 188: A further preferred group of compounds of formula I corresponds to general
formula _ ,7 //7 * 7 K1 /-χ N (l188), wherein the meanings of the corresponding
X 1 R 3 - 107 -
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι88 are disclosed.
Table 189: A further preferred group of compounds of formula I corresponds to general
R , P \ -N K /CH3 formula Cl — ( — (|189), wherein the meanings of the corresponding
N N' "CH. 3
X, R R3„
1 substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι89 are disclosed.
Table 190: A further preferred group of compounds of formula I corresponds to general
formula NC ( y — N \ (|190), wherein the meanings of the corresponding - N N^^CH3
X1 Rg
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l190 are disclosed.
Table 191 : A further preferred group of compounds of formula I corresponds to general
formula CH3 — ( y— N \ (|191), wherein the meanings of the corresponding - N N-~^CH3
X1 R3 substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l191 are disclosed.
Table 192: A further preferred group of compounds of formula I corresponds to general
/R - \ formula Cl — ( — N I (|192), wherein the meanings of the corresponding - N N^-C2H5
X1 Rg
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula 92 are disclosed. 108
Table 193: A further preferred group of compounds of formula I corresponds to general 1 P
~rO - .CHF2
■N formula NC — ( — N^ l^ (|193), wherein the meanings of the corresponding
^- N N"^CH3
X1 R3
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι93 are disclosed.
Table 194: A further preferred group of compounds of formula I corresponds to general
R S
formula Cl — ( y — N^ l ^ (|194), wherein the meanings of the corresponding
^- N N^^CH3
X1 R3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l194 are disclosed.,
Table 195: A further preferred group of compounds of formula I corresponds to general
R < P
formula Cl C195). wherein the meanings of the corresponding - N N-^ •CH,
X1 R3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι95 are disclosed.
Table 196: A further preferred group of compounds of formula I corresponds to general
R < P
.CH, formula Cl — y— Nχ | (Ii9β). wherein the meanings of the corresponding - N ^ "CF,
X1 R3 substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula dgβ are disclosed. - 109 -
Table 197: A further preferred group of compounds of formula I corresponds to general
R « P
,CH(CH3)2 formula Cl — if — N I (|197), wherein the meanings of the
VH N •CHF,
Ro
corresponding substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι97 are disclosed.
Table 198: A further preferred group of compounds of formula I corresponds to general
formula CF 3 — if — N^ I (|198), wherein the meanings of the - N N"^CH3
X1 R3
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι98 are disclosed.
Table 199: A further preferred group of compounds of formula I corresponds to general
R < P
formula Cl — if y — N^ l^ ^> (|199), wherein the meanings of the u N- •CH,
X, R3
corresponding substituents R f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula lι99 are disclosed.
Table 200: A further preferred group of compounds of formula I corresponds to general
formula Cl — if — N^ I (|200), wherein the meanings of the N N^^-CH "33
X, corresponding substituents R1 f X and R3 are indicated in Table A, so that 423 specific compounds of formula l200 are disclosed. 110 -
Table 201 : A further preferred group of compounds of formula I corresponds to general
formula Cl — ( y — N^ \ \ (i^), wherein the meanings of the - N N-^-CH3
X1 R3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l20ι are disclosed.
Table 202: A further preferred group of compounds of formula I corresponds to general
formula CH3 (l202), wherein the meanings of the
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l202 are disclosed.
Table 203: A further preferred group of compounds of formula I corresponds to general
R < P
,CHF 2 formula CF 3 ,00 -— f ifT ) — -NN^ ϊ (l203), wherein the meanings of the
^- N N^^CH3
X1 R3 corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l203 are disclosed.
Table 204: A further preferred group of compounds of formula I corresponds to general
,R 1 <?* formula Cl — — N | (l204), wherein the meanings of the corresponding - N N
X1 Rg
substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l20 are disclosed. - 111 -
Table 205: A further preferred group of compounds of formula I corresponds to general
R < P
formula Cl ~ — (c y —£ N^ j0 y (|205), wherein the meanings of the corresponding
X1 R3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l205 are disclosed.
Table 206: A further preferred group of compounds of formula I corresponds to general
R < P CH'
formula Br —f y — N | (i206), wherein the meanings of the corresponding
V-- NN N^^CHF2 X1 R3
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l206 are disclosed.
Table 207: A further preferred group of compounds of formula I corresponds to general
formula NC—f "—' 7 (l207), wherein the meanings of the corresponding N N
Xι R 3 substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l207 are disclosed.
Table 208: A further preferred group of compounds of formula I corresponds to general
formula Cl —f y— N I > (|20a), wherein the meanings of the corresponding
V ^^
X1 Rg
substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l208 are disclosed. - 112 -
Table 209: A further preferred group of compounds of formula I corresponds to general
R « Q. CH,
formula 0 if N ~F O209), wherein the meanings of the corresponding c^ 3 - N NN=/ F
X 1 R g substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l209 are disclosed.
Table 210: A further preferred group of compounds of formula I corresponds to general
formula P~ \ ' — N \ / \ ('21°)' here'n the meanings of the
N≡ — ' ^r- N N=/ F
X 1 R g
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι0 are disclosed.
Table 21 1 : A further preferred group of compounds of formula I corresponds to general
R formula CH v CH0 (/ \\ ^ _F (l2n), wherein the meanings of the
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2n are disclosed.
Table 212: A further preferred group of compounds of formula I corresponds to general
R 10 CH3 — F
~~ F O212), wherein the meanings of the
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι2are disclosed. - 113 -
Table 213: A further preferred group of compounds of formula I corresponds to general
R formula (C ) c N | \ (l213), wherein the meanings of the
N N-^
Xi >, R3 o Y corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι3are disclosed.
Table 214: A further preferred group of compounds of formula I corresponds to general
R , 0 CH3 ^ formula CH \ c // \\ N' Z_F (l2ι4), wherein the meanings of the
X 1 R g corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι4 are disclosed.
Table 215: A further preferred group of compounds of formula I corresponds to general
formula Cl — (( y — N y ^-F (|215), wherein the meanings of the
N N=/ F
corresponding substituents R1 t Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι5are disclosed.
Table 216: A further preferred group of compounds of formula I corresponds to general
formula F-^ if y — I (l216), wherein the meanings of the corresponding
substituents R1 ( Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι6 are disclosed. - 114 -
Table 217: A further preferred group of compounds of formula I corresponds to general
R < P
N CHF, ^S / /// \ \\ /^*N formula ^ O — \ — N \ AL (l2ι7), wherein the meanings of the y N N--^CH3
X1 R3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι7 are disclosed.
Table 218: A further preferred group of compounds of formula I corresponds to general
formula O — ( y — N y -F (|218) wherein the meanings of the
F VN. N= F
F X f R 3
corresponding substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι8 are disclosed.
Table 219: A preferred group of compounds of formula I corresponds to general formula
F (\2^)t wherein the meanings of the corresponding F substituents Ri, Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l2ι9 are disclosed.
Table 220: A preferred group of compounds of formula I corresponds to general formula R ι
O — <^ y — N y — ^-F (|220)? wherein the meanings of the
/ '/7/ '/ λ-N
N x ;' R 3 d Y CH3
corresponding substituents R1 f Xi and R3 are indicated in Table A, so that 423 specific compounds of formula l220 are disclosed. 115
Table A
Comp. No. Xi
.001 H O CH3
.002 F O CH3
.003 Cl O CH3
.004 F O CH2OH3
.005 Cl O CH2CH3
.006 H O CH2CH3
.007 F O CH2CH2CH3
.008 Cl O CH2CH2CH3
.009 H O CH2CH2CH3
.010 F O CH2CH2CH2CH3
.011 Cl O CH2CH2CH2CH3
.012 F O CH2CH2CH2CH2CH3
.013 Cl O CH2CH2CH2CH2CH3
.014 F O CH2CH2CH2CH2CH2CH3
.015 F O CH2CH2CH(CH3)2
.016 Cl O CH2CH2CH(CH3)2
.017 H O CH2CH2CH(CH3)2
.018 F O CH2CH(CH3)CH2CH3
.019 Cl O CH2CH(CH3)CH2CH3
.020 H O CH2CH(CH3)CH2CH3
.021 F O CH2CH(CH3)CH2CH2CH3
.022 F O CH2CH2CH(CH3)CH2CH3
.023 F O CH2CH2CH2CH(CH3)2
.024 F O CH(CH3)CH2CH2CH2CH3
.025 Cl O CH(CH3)CH2CH2CH2CH3
.026 H O CH(CH3)CH2CH2CH2CH3
.027 F O CH2C(CH3)3
.028 Cl O CH2C(CH3)3
.029 H O CH2CH(CH3)2
.030 Cl O CH2CH(CH3)2
.031 F O CH2CH(CH3)2
.032 F O CH2C(CH3)2CH2CH3
.033 Cl O CH2C(CH3)2CH2CH3 .034 H O CH2C(CH3)2CH2CH3 - 116
Comp. No. Ri Xi
.035 F O CH2CH2C(CH3)3
.036 Cl O CH2CH2C(CH3)3
.037 F O CH2CH2CHCH2
.038 F O CH2CH2CH2CH3
.039 F O CH(CH3)2
.040 Cl O CH(CH3)2
.041 H O CH(CH3)2
.042 F O CH2CF3
.043 Cl O CH2CF3
.044 H O CH2CF3
.045 F O CH2CCI3
.046 F O CH2CH2CF3
.047 F O CH2CH2CH(OH)CH3
.048 F O CH2CH(OH)CH2CH3
.049 Cl O CH2CH(OH)CH2CH3
.050 F O CH2CH(OH)CH3
.051 H O CH2CH2CHCICH3
.052 Cl O CH2CH2CHCICH3
.053 F O CH CH2CHCICH3
.054 F O CH2CH2CHFCH3
.055 F O CH2CHFCH2CH3
.056 Cl O CH2CHFCH2CH3
.057 H O CH2CHFCH2CH3
.058 F O CH2CHCICH2CH3
.059 F O CH2CH2F
.060 Cl O CH2CH2F
.061 F O CH2CHF2
.062 H O CH2CHCH2
.063 Cl O CH2CHCH2
.064 F O CH2CHCH2
.065 F O CH2CH(CH3)CH2
.066 F O CH2CHCH(CH3)
.067 Cl O CH2CH2OH
.068 F O CH2CH2OH .069 F O CH2CHCHCI - 117
Comp. No. Ri Xi R3
.070 Cl O CH2CHCHCI
.071 F O CH2OCH2CβH5
.072 H O CH2CCH
.073 Cl O CH2CCH
.074 F O CH2CCH
.075 F O CH2CH2CCH
.076 Cl O CH2CH2CeH5
.077 F O CH2CH2CβH5
.078 F O CH2CH2CH2CβH5
.079 F O CH2CH2CH(CH3)CβH5
.080 F O CH2CH2CH2CH2(p-F-C6H4)
.081 H O CH2CβH5
.082 Cl O CH2CβH5
.083 F O CH2C8Hs
.084 F O CH2(o-F-C6H4)
.085 H O CH2(p-CI-C6H4)
.086 F O CH2(m-CF3-C6H5)
.087 H O CH2CN
.088 Cl O CH2CN
.089 F O CH2CN
.090 F O CH2CH2CN
.091 F O cyclopropyl
.092 F O cyclopentyl
.093 F O CH2-cyclopentyl
.094 F O CH2-cyclopropyl
.095 F O CH2CH2CI
.096 F O CH2CHCI2
.097 H O CH2OCH3
.098 Cl O CH2OCH3
.099 F O CH2OCH3
.100 F O CH2CH2OCH3
.101 F O CH2CH2OCH2CH3
.102 F O CH2CH(CH3)OCH3
.103 H O CH2CH2OCH2CH2OCH3 .104 Cl O CH2CH2OCH2CH2OCH3 118 -
Comp. No. Ri Xi R3
.105 F O CH2CH2OCH2CH2OCH3
.106 H O CH2SCH3
.107 Cl O CH2SCH3
.108 F O CH2SCH3
.109 H O CH2S(O)CH3
.110 Cl O CH2S(O)CH3
.111 F O CH2S(O)CH3
.112 H O CH2S(O)2CH3
.113 Cl O CH2S(O)2CH3
.114 F O CH2S(O)2CH3
.115 F O CH2SCH2CH3
.116 F O CH2CH2SCH3
.117 F O CH2CH2SCH2CH3
.118 Cl O CH2CH2SCH2CH3
.119 H O CH2CH2SCH2CH3
.120 Cl O CH2CH2SCH3
.121 H O CH2CH2SCH3
.122 F O CH2CH2S(O)CH3
.123 F O CH2CH2S(O)2CH3
.124 Cl O CH2CH2S(O)CH3
.125 Cl O CH2CH2S(O)2CH3
.126 F O CH2CH2S(O)CH2CH3
.127 Cl O CH2CH2S(O)CH2CH3
.128 H O CH2CH2S(O)CH2CH3
.129 F O CH2CH2S(O)2CH2CH3
.130 Cl O CH2CH2S(O)2CH2CH3
.131 H O CH2CH2S(O)2CH2CH3
.132 F O CH2CH(CH3)SCH3
.133 H O CH2COOH
.134 Cl O CH2COOH
.135 F O CH2COOH
.136 F O CH2COOCH3
.137 H O CH2COOCH2CH3
.138 Cl O CH2COOCH2CH3 .139 F O CH2COOCH2CH3 O o j | i oι θ) θ) oι α (» σ) θ) θ) θ) θi ϋi θι ( ϋi ui ui ( ϋi uι j- ^ ^ 4 j. ^ 4 ^ 4> rσ 3 ω M ^ o o α> ^ OT θι ^ ω iN3 ^ o co oo ^ σ) CΛ ω iN3 ^ o o oo -«j cn uι ^- ω ι\3 --' θ z o --
■π -π o θ "π -π o x τι τι o τι o τι χ o τι o τι τι τι -π o x "n -π o χ τι o χ τι -π τι -π
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O X
o o o o o o 3 ro X X o o X X o o o ro roo o r Xo r X o o r X o o ro X o o r Xo ro X o o o o o r Xo ro X o r X o o ro X o o o r X o o o ro X o ro X o rx oo rox o x x o o rox o o ro ro rx o o rox x o o ro rox ox x x o rx o o r Xo X o ro ro X ro X ro X
CD r Xo r Xo r Xo ω X o X Xo Xo Xo o ro X o o r X o o X o o o o o o o o roo roo roo o o oo o o o X X o o o o o o o o ro O
X o o o z z c Oo O co O co co O co ~ "y ϋ o X o o o o o i o o roo ro zz o o o o o o o
O X X V.
X X o o o z o
X Xz z z o o o o o o o o o o δ r Io ω z z z o o o ro z o o o o o o o o o o o o o o ao o o o X X -r X o -— — «- *■— *- ro ωx cxo ω X r Xo r X X X ,? ? r x x x x x r Xo r Xo r Xo ^J zzo z~* o X X rroo rroo c X r n o oo
O O O X
I oo o o *«. -* o r X o o o X X X % _l_- ω X ω X o o o ω X ω X - o x a* o o X <? x o ω X ω X
-a n
H pi
"0 o
- 120 -
Comp. No. Ri Xi R3
.175 Cl O CH2CH2C(O)CH3
.176 F O CH2COCH2CH3
.177 Cl O CH2COCH2CH3
.178 H O CH2COCH2CH3
.179 F O CH2COCH2CH2CH3
.180 F O CH2CH2COCH2CH3
.181 F O CH2CH2COCH2CF3
.182 F O CH2CHCICOCH2CH3
.183 F O CH2CH2COCHCICH3
.184 F O CH2CH(CH3)COOCH3
.185 F O CH2CH2CH2COOCH3
.186 F O CH2CH2CH2COSCH2CH3
.187 F O CH2CH2CH2CON(CH3)2
.188 F O CH2CH2CH(CH3)COOCH2CH3
.189 H O CH2CH(OH)COOH
.190 Cl O CH2CH(OH)COOH
.191 F O CH2CH(OH)COOH
.192 Cl O CH2CH(CI)COOH
.193 F O CH2CH(CI)COOH
.194 Cl O CH2CH(CI)COOCH2CH3
.195 F O CH2CH(CI)COOCH2CH3
.196 F O CH2CH(CI)COOH
.197 F O CH2C(CH3)(CI)COOH
.198 F O CH2CH(CI)COOCH2CHCH2
.199 F O CH2CH(CI)COOCH2CCH
.200 F O CH2CH(CI)COOCH2C6H5
.201 F O CH2CH(CI)C(O)SCH(CH3)2
.202 F O CH2CH(CI)C(O)NH(CH2CCH)
.203 F O CH2CH(CH3)C(O)N(CH3)(CH2CHCH2)
.204 F O CH2CH(Br)COOC(CH3)3
.205 F O CH2CH(Br)COOCH2CHCH2
.206 F O CH2COOCH2CH2CI
.207 F O CH2COOCH2CF3
.208 H O CH2 10 121
Comp. No. Ri Xi R3
.209 H O
.210 Cl O * CHH2 1Q
.211 F O CH2 10
.212 F O
™
.213 F O S(O)2CH3
.214 F O S(O)2CH2CH3
.215 Cl O S(O)2CF3
.216 Cl O S(O)2CH2CH3
.217 F O S(O)2CH(CH3)2
.218 H O C(O)CH3
.219 Cl O C(O)CH3
.220 F O C(O)CH3
.221 F O C(O)CF3
.222 F O C(O)CH2CH3
.223 Cl O OH
.224 F O OH
.225 H O OCH3
.226 Cl O OCH3
.227 F O OCH3
.228 H O OCH2CH3
.229 Cl O OCH2CH3
.230 F O OCH2CH3
.231 F O OCH2CH(CH3)2
.232 F O OCF3
.233 F O OCHF2
.234 F O OCH2CHCH2
.235 F O OCH2C(CH3)CH2
.236 F O OCH2CHCHCI
.237 Cl O OCH2OCH3
.238 F O OCH2OCH3 .239 F O OCH2SCH3 - 122 -
Comp. No. Ri Xi R3
.240 F O OCH2CCH
.241 F O OCH2COOH
.242 F O OCH2COOCH3
.243 F O OCH2COOCH2CH3
.244 F O OCH2COOCH(CH3)2
.245 Cl O OCH(CH3)COOH
.246 F O OCH(CH3)COOH
.247 F O OCH(CH3)COOCH2CH3
.248 F O OCH(CH3)COOCH2CCH
.249 F O OCH(CH3)COOCH2CHCH2
.250 F O OCH2COSCH2CH3
.251 F O OCH2COSCH(CH3)2
.252 F O OCH2COSCH2C6H5
.253 F O OCH2CONH2
.254 F O OCH2CON(CH3)2
.255 Cl O OCH2CONHCH2CCH
.256 F O OCH2CONHCH2CCH
.257 F O OCH2CβH5
.258 F O OCH2(p-CH3O-C6H4)
.259 F O OCH2(o-F-C6H4)
.260 Cl O OCH2(m-CF3-C6H4)
.261 F O OCH2CH2CβH5
.262 H O OCH2CN
.263 F O OCH2CN
.264 F O OCH2CH2CI
.265 Cl O OCH2CH2OH
.266 F O OCH2CH2OH
.267 H O OCH2CH2CN
.268 Cl O OCH2CH2CN
.269 F O OCH2CH2CN
.270 Cl O OCH2CH(OCH3)(CH3)
.271 F O OCH2CH(OCH3)(CH3)
.272 H O OC(O)CH3
.273 Cl O OC(O)CH3 .274 F O OC(O)CH3 123
Comp. No. Ri Xi R3
.275 H s CH3
.276 Cl s CH3
.277 F s CH3
.278 H s CH2CH3
.279 Cl s CH2CH3
.280 F s CH2CH3
.281 F s CH CH2CH3
.282 F s CH2CH(CH3)2
.283 F s CH2CH2CF3
.284 F s CH(CH3)2
.285 F s CH2CH(CH3)2
.286 F s CH2CH(CI)CH3
.287 Cl s CH2CHCH2
.288 F s CH2CHCH2
.289 F s CH2C(CH3)CH2
.290 H s CH2CCH
.291 Cl s CH2CCH
.292 F s CH2CCH
.293 F s CH2CH2CCH
.294 F s CH(CH3)CCH
.295 H s CH2CH2OH
.296 Cl s CH2CH2OH
.297 F s CH2CH2OH
.298 F s CH2CH(OH)CH3
.299 H s CH2CβH5
.300 Cl s CH2CβH5
.301 F s CH2CβH5
.302 Cl s CH2(o-F-C6H4)
.303 F s CH2(o-F-C6H4)
.304 F s CH2(m-CF3-CβH4)
.305 F s CH2(p-CH3-C6H4)
.306 F s CH2(2,4-di-F-C6H3)
.307 F s CH CH2CH(CH3)CβH5
.308 F s CH2CH2CH2CH2(p-F-C6H4) .309 Cl s CH2CN 124
Comp. No. Ri Xi R3
.310 F s CH2CN
.311 F s cyclopropyl
.312 Cl s CH2-cyclopropyl
.313 F s CH2-cyclopropyl
.314 F s CH2CI
.315 H s CH2OCH3
.316 Cl s CH2OCH3
.317 F s CH2OCH3
.318 F s CH2OCH2CHCH2
.319 F s CH2CH2OCH3
.320 F s CH2CH(OCH3)CH3
.321 F s CH2CH(OCH2CCH)CH3
.322 H s CH2CH2OCH2CH2OCH3
.323 Cl s CH2CH2OCH2CH2OCH3
.324 F s CH2CH2OCH2CH2OCH3
.325 H s CH2SCH3
.326 Cl s CH2SCH3
.327 F s CH2SCH3
.328 F s CH2SCH2CHCH2
.329 F s CH2SCH2CCH
.330 F s CH2CH2SCH3
.331 F s CH2CH2S(O)CH3
.332 F s CH2CH2S(O)2CH3
.333 F s CH2COOH
.334 F s CH2COOCH3
.335 F s CH2COOCH2CH3
.336 F s CH2COOC(CH3)3
.337 F s CH2COOCH2C6H5
.338 F s CH2COOCH2(p-CI-C6H4)
.339 F s CH2C(O)SCH3
.340 F s CH2C(O)SCH(CH3)2
.341 F s CH2C(O)SCH2C6H5
.342 F s CH2C(O)NH2
.343 F s CH2C(O)NH(CH3) .344 Cl s CH2C(O)NH(CH2CCH) 125 -
Comp. No. Ri
.345 F S CH2C(O)NH(CH2CCH)
.346 F S CH2C(O)N(CH2CH3)2
.347 F S CH2CHO
.348 F S CH2C(O)CH3
.349 H S CH2CH2COOH
.350 Cl s CH2CH2COOH
.351 F s CH2CH2COOH
.352 F s CH2CH2COOCH3
.353 F s CH2CH2COOCH2C6H5
.354 Cl s CH2CH2C(O)SCH2CH3
.355 F s CH2CH2C(O)SCH2CH3
.356 F s CH2CH(OH)COOH
.357 F s CH2CH(CI)COOH
.358 Cl s CH2CH(CI)COOCH2CH3
.359 F s CH2CH(CI)COOCH2CH3
.360 F s CH2CH(CI)COOH
.361 F s CH2C(CH3)(CI)COOH
.362 F s CH2CH(CI)COOCH2CHCH2
.363 Cl s CH2CH(CI)COOCH2CCH
.364 F s CH2CH(CI)COOCH2CCH
.365 F s CH2CH(CI)COOCH2C6H5
.366 F s CH2CH(Br)COOH
.367 F s CH2CH(CI)C(O)SCH(CH3)2
.368 F s CH2CH(CI)C(O)NH(CH2CCH)
.369 F s CH2CH(CH3)C(O)N(CH3)(CH2CHCH2)
.370 F s CH2CH2C(O)NH(CH2CCH) .371 H s CH,
.372 Cl
CH >kl
.373 F s CH2<Q .374 Cl s CH2 1 O .375 F s
CH , l 126
Comp. No. Ri Xi R3
.376 F s OH
.377 H s OCH3
.378 Cl s OCH3
.379 F s OCH3
.380 F s OCH2CH3
.381 Cl s OCH2CH(CH3)2
.382 F s OCH2CH(CH3)2
.383 F s OCH(CH3)2
.384 F s OCF3
.385 H s OCH2OCH3
.386 Cl s OCH2OCH3
.387 F s OCH2OCH3
.388 F s OCH2SCH3
.389 Cl s OCH2CHCH2
.390 F s OCH2CHCH2
.391 Cl s OCH2CCH
.392 F s OCH2CCH
.393 F s OCH(CH3)CHCH2
.394 F s OCH(CH3)CCH
.395 F s OCH2CHCH(CI)
.396 F s OCH2COOH
.397 F s OCH2COOCH2CH3
.398 F s OCH(CH3)COOH
.399 F s OCH(CH3)COOCH2CCH
.400 F s OCH2C(O)NH2
.401 F s OCH2C(O)NH(CH3)
.402 F s OCH2C(O)NH(CH2CCH)
.403 F s OCH2C(O)SCH3
.404 F s OCH2C(O)SCH2CH3
.405 F s OCH2C(O)SCH(CH3)2
.406 Cl s OCH2C(O)SCH2C6H5
.407 F s OCH(CH3)C(O)SCH2C6H5
.408 F s OCH2CH2OH
.409 F s OCH2CH(CH3)OH I .410 F s OCH2CH2CI - 127
Comp. No. Ri Xi R3
.411 Cl s OCH2CH2CN
.412 F s OCH2CH2CN
.413 Cl s OCH2CH2CF3
.414 F s OCH2CH2CF3
.415 F s OCH2CH(OH)(C6H5)
.416 F O CH2COCH3
.417 F O CH2CONHCH2CH=CH2
.418 Cl O CH2CONHCH2CH=CH2
.419 Cl s CH2CONHCH2CH3
.420 Cl O CH2CONHCH2CH3
.421 F O CH2CONHCH2CH3
.422 F O CH2CONHCH3 .423 Cl O CH2CONHCH3
Table B: Prepared compounds from the preceding Tables with physico-chemical data. The figure before the point indicates the number of the Table, e.g. 1.002 indicates in Table 1 compound No. 002 of Table A.
Comp. No. physical data
1.002 m.p. 159-160°C
1.007 m.p. 123-125°C
1.064 m.p. 115-116°C
1.071 nD(30°C) 1.5431
1.074 m.p. 218-220°C
1.139 nD(30°C) 1.5131
34.074 1H-NMR (CDCI3): 8,14 ppm (s, 1 H); 7,72 ppm (d, 1H); 7,36 ppm (s, 1 H); 4,90 ppm (s, 2H); 2,21 ppm (s, 1 H)
Examples of specific formulations for compounds of formula I, such as emulsifiable concentrates, solutions, wettable powders, coated granules, extruder granules, dusts and suspension concentrates, are described on pages 9 to 13 of WO 97/34485.
Biological Examples
Example B1 : Herbicidal action prior to emergence of the plants (pre-emeroence action) - 128 -
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a 25 % wettable powder (Example F3, b), as described, for example, in WO 97/34485), or in the form of an emulsion (prepared from a 25 % emulsifiable concentrate (Example F1 , c), as described, for example, in WO 97/34485), are applied by spraying in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action. In this test the compounds of formula I exhibit strong herbicidal action.
Test plants: Lolium, Setaria, Sinapis, Solanum, Ipomoea
Examples of the good herbicidal activity of the compounds of formula I are given in Table B1.
Table B1 : Pre- emerαence action:
Test plant: Lolium Setaria Sinap is Solanum Ipomoea cone, [g a.i./ha]
Comp. No.
1.002 1 1 1 1 2 2000
1.007 3 1 1 1 1 2000
1.064 3 1 1 1 1 2000
1.071 6 1 1 1 3 2000
1.074 1 1 1 1 1 2000 1.139 1 1 1 1 1 2000
The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 and F4 to F8 according to WO 97/34485.
Example B2: Post-emergence herbicidal action
In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastics pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I, prepared from a 25 % wettable powder (Example F3, b) according to WO 97/34485), or with an emulsion of the test compounds of formula I, prepared from a 25 % emulsifiable concentrate (Example F1 , c) according to 129
WO 97/34485), in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Lolium, Setaria, Sinapis, Solanum, Ipomoea
In this test too, the compounds of formula I according to the invention exhibit strong herbicidal action.
Examples of the good herbicidal activity of the compounds of formula I are given in Table B2.
Table B2: Post-emergence action:
Test plant: Lolium Setaria Sinapis Solanum Ipomoea cone.
[g a.i./ha]
Comp. No.
1.002 1 1 1 I 1 2000
1.007 2 2 1 I 1 2000
1.064 4 4 3 I 1 2000
1.071 2 2 1 I 3 2000
1.074 1 1 1 I 1 2000 1.139 1 1 1 1 1 2000
The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 and F4 to F8 according to WO 97/34485.
The compounds of formula I according to the invention can also be used for weed control in admixture with known herbicides as co-herbicides, for example in the form of ready- prepared formulations or in the form of a 'tank-mix'. Suitable mixing partners for the compounds of formula I include, for example, the following co-herbicides: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + aclonifen, compound of formula I + alachlor, compound of formula I + ametryn, compound of formula I + aminotriazole, compound of formula I + amidosulfuron, compound of formula I + asulam, compound of formula I + atrazine, compound of formula I + BAY FOE 5043, compound of formula I + benazolin, compound of formula I + bensulfuron, compound of - 130 -
formula I + bentazone, compound of formula I + bifenox, compound of formula I + bispyribac-sodium, compound of formula I + bialaphos, compound of formula I + bromacil, compound of formula I + bromoxynil, compound of formula I + bromophenoxim, compound of formula I + butachlor, compound of formula I + butylate, compound of formula I + cafenstrole, compound of formula I + carbetamide, compound of formula I + chloridazone, compound of formula I + chlorimuron-ethyl, compound of formula I + chlorbromuron, compound of formula I + chlorsulfuron, compound of formula I + chiortoluron, compound of formula I + cinosulfuron, compound of formula I + clethodim, compound of formula I + clodinafop, compound of formula I + clomazone, compound of formula I + clopyralid, compound of formula I + cloransulam, compound of formula I + cyanazine, compound of formula I + cyhalofop, compound of formula I + dalapon, compound of formula I + 2,4-D, compound of formula I + 2,4-DB, compound of formula I + desmetryn, compound of formula I + desmedipham, compound of formula I + dicamba, compound of formula I + diclofop, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + dimefuron, compound of formula I + dimepiperate, compound of formula I + dimethachlor, compound of formula I + dimethametryn, compound of formula I + dimethenamid, compound of formula I + S-dimethenamid, compound of formula I + dinitramine, compound of formula I + dinoterb, compound of formula I + dipropetryn, compound of formula I + diuron, compound of formula I + diquat, compound of formula I + DSMA, compound of formula I + EPTC, compound of formula I + esprocarb, compound of formula I + ethalfluralin, compound of formula I + ethametsulfuron, compound of formula I + ethephon, compound of formula I + ethofumesate, compound of formula I + ethoxysulfuron, compound of formula I + fenclorim, compound of formula I + flamprop, compound of formula I + fluazasulfuron, compound of formula I + fluazifop, compound of formula I + flumetralin, compound of formula I + flumetsulam, compound of formula I + fluometuron, compound of formula I + flurochloridone, compound of formula I + fluoxaprop, compound of formula I + fluroxypyr, compound of formula I + fluthiacet-methyl, compound of formula I + fluxofenim, compound of formula I + fomesafen, compound of formula I + glufosinate, compound of formula I + glyphosate, compound of formula I + halosulfuron, compound of formula I + haloxyfop, compound of formula I + hexazinone, compound of formula I + imazamethabenz, compound of formula I + imazapyr, compound of formula I + imazaquin, compound of formula I + imazethapyr, compound of formula I + imazosulfuron, compound of formula I + ioxynil, compound of formula I + isoproturon, compound of formula I + isoxaben, compound of formula I + isoxaflutole, compound of formula I + karbutylate, compound of formula I + lactofen, compound of formula I + lenacil, compound of formula I + linuron, compound of formula I + MCPP, compound of formula I + metamitron, - 131 -
compound of formula I + metazachlor, compound of formula I + methabenzthiazuron, compound of formula I + methazole, compound of formula I + metobromuron, compound of formula I + metolachlor, compound of formula I + S-metolachlor, compound of formula I + metosulam, compound of formula I + metribuzin, compound of formula I + metsuifuron- methyl, compound of formula I + molinate, compound of formula I + MCPA, compound of formula I + MSMA, compound of formula I + napropamide, compound of formula I + NDA- 402989, compound of formula I + nefenacet, compound of formula I + nicosulfuron, compound of formula I + norflurazon, compound of formula I + oryzalin, compound of formula I + oxadiazon, compound of formula I + oxasulfuron, compound of formula I + oxyfluorfen, compound of formula I + paraquat, compound of formula I + pendimethalin, compound of formula I + phenmedipham, compound of formula I + phenoxaprop-P-ethyl (R), compound of formula I + picloram, compound of formula I + pretilachlor, compound of formula I + primisulfuron, compound of formula I + prometon, compound of formula I + prometryn, compound of formula I + propachlor, compound of formula I + propanil, compound of formula I + propazine, compound of formula I + propaquizafop, compound of formula I + propyzamide, compound of formula I + prosulfuron, compound of formula I + pyrazolynate, compound of formula I + pyrazosulfuron-ethyl, compound of formula I + pyrazoxyphen, compound of formula I + pyridate, compound of formula I + pyriminobac- methyl, compound of formula I + pyrithiobac-sodium, compound of formula I + quinclorac, compound of formula I + quizalofop, compound of formula I + rimsulfuron, compound of formula I + sequestrene, compound of formula I + sethoxydim, compound of formula I + simetryn, compound of formula I + simazine, compound of formula I + sulcothone, compound of formula I + sulfosate, compound of formula I + sulfosulfuron-methyl, compound of formula I + tebutam, compound of formula I + tebuthiuron, compound of formula I + terbacil, compound of formula I + terbumeton, compound of formula I + terbuthylazine, compound of formula I + terbutryn, compound of formula I + thiazafluron, compound of formula I + thiazopyr, compound of formula I + thifensulfuron-methyl, compound of formula I + thiobencarb, compound of formula I + tralkoxydim, compound of formula I + thallate, compound of formula I + triasulfuron, compound of formula I + trifluralin, compound of formula I + tribenuron-methyl, compound of formula I + triclopyr, compound of formula I + triflusulfuron, and compound of formula I + trinexapac-ethyl, and esters and salts of those mixing partners for the compound of formula I that are mentioned e.g. in The Pesticide Manual, Eleventh Edition, 1997, BCPC.

Claims

- 132 -What is claimed is:
1. A compound of formula I
R1
R2 1 W
(0.
X y1 \ R 3
wherein
R-i is hydrogen, fluorine, chlorine, bromine or methyl;
R2 is C╬╣-C4alkyl, d-C4haloalkyl, halogen, nitro, amino, cyano or R43O- ;
R43 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, C╬╣-C8haloalkyl, cyano-C C8alkyl, C3-C8haloalkenyl, hydroxy-C╬╣-C alkyl, C╬╣-C4alkoxy-C╬╣-C4alkyl, C3-C6- alkenyloxy-C C4alkyl, QrCealkynyioxy-d-dalkyl, CrC4alkoxy-C╬╣-C alkoxy-CrC -alkyl, C╬╣-C alkylthio-C C4alkyl, C╬╣-C8alkylcarbonyl, d-C8alkoxycarbonyl, C3-C8alkenyl- oxycarbonyl, benzyloxy-Ci- or -C2-alkyl, benzylcarbonyl, benzyloxycarbonyl, phenyl, phenyl-C2-C8alkyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by halogen, d-C alkyl or by C C haloalkyl; or
R44X16C(0)-[C1-C8alkylene]- R43 is R44X16C(O)-C1-C8alkyl- or I ;
(C6H5)
Xi6 is oxygen, sulfur or R_r5 N i ΓÇö ;
R,M is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, C C8haloalkyl, C3-C8haloalkenyl, C╬╣-C alkoxy-d-C4aikyl, C3-C╬▓alkenyloxy-CrC4alkyl, d-dalkylthio-Cr C alkyl, phenyl, phenyl mono- to tri-substituted by halogen, d-dalkyl or by d-C -halo- alkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C╬╣-C alkyl or by C╬╣-C haloalkyl;
R45 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, C C8haloalkyl or benzyl; - 133 -
R3 is hydroxy, C╬╣-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C6haloalkoxy, C3-C6- haloalkenyloxy, C╬╣-C6alkoxy-C╬╣-C6alkyl, C3-C6alkenyloxy-C C6alkyl, C3-C6alkynyloxy- d-C6alkyl, d-Cealkoxy-d-Cealkoxy-d-Cealkyl, B -Cealkoxy, R4(R5)N-, C C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl, C3-C6haloalkenyl, C3-C6cycloalkyl, C3-C6- halocycloalkyl, B C C6alkyl, OHC-, C C6alkylcarbonyl, C C6alkylcarbonyloxy, C C6haloalkylcarbonyl, C2-C6alkenylcarbonyl, C C6alkoxycarbonyl, C C6alkyl-S(O)2-,
C C6haloalkyl-S(O)2-, C3-C8trialkylsilyloxy, (C C6alkyl)2N-N=CH-, ΓÇö CH2- , o
0 V^c C3a,ky| , B CH=N-, (CH3)2N-CH=N-, (CrC5hydroxyalkyl)-CH2-, (Brd-Cg- CH2ΓÇö hydroxyalkyl)-CH2-, (B C C5haloalkyl)-CH2-, (hydroxy-C C5alkyl)-O- or (B d-Cs- hydroxyalkyl)-O-;
BT is cyano, OHC-, HOC(O)-, C C6alkylcarbonyl, d-Cehaloalkylcarbonyl, C C6alkoxy- carbonyl, C3-C6alkenyloxycarbonyl, C3-C6alkynyloxycarbonyl, benzyloxy, benzyloxy- carbonyl, benzyloxycarbonyl mono- to tri-substituted on the phenyl ring by halogen, CrC4alkyl or by C C4haloalkyl, benzylthio, benzylthiocarbonyl, benzylthiocarbonyl mono- to tri-substituted on the phenyl ring by halogen, d-djalkyl or by C-|-C4haloalkyl, d-C6haloalkoxycarbonyl, d-Cealkylthio-CfO)-, R6(R7)NC(O)-, phenyl, phenyl mono- to tri-substituted by halogen, C C4alkyl or by C C4haloalkyl, CrC6alkyl-S(O)2-, C C6- alkyl-S(O)-, C C6alkylthio-, C3-C6cycloalkyi, C C6alkoxy, C3-C6alkenylthio or C3-C6- alkynylthio;
R4 and R5 are each independently of the other hydrogen, d-C6alkyl, C3-C6alkenyl, C3-C6- alkynyl, C╬╣-C6haloalkyl, C3-C6haloalkenyl, C3-C6cycloalkyl, C C╬▓alkoxy-C C╬▓alkyl, OHC-, C C6alkylcarbonyl, C C6haloalkylcarbonyl, C C6alkyl-S(O)2- or C C6haloalkyl- S(O)2-;
R6 and R7 are each independently of the other hydrogen, Ci-CealkyI, C3-C6alkenyl, C3-C6- alkynyl, C╬╣-C6haloalkyl, C3-C6haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, C1-C4alkyl or by C╬╣-C4haloalkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C C alkyl or by d-C haloalkyl;
Xi is oxygen or sulfur; -134-
RQ '12
R,, R '115£
'10 'i1e6 ' '
*RQ 13 JL R \" /
*N' \ π π .\
W is a group (Wi), (W2). (Wa),
X3 N X, X4 N |
R« J*" "22 ^Jfc-
^4), JT Y (W5), ( (W╬▓), 1 )1 (W7), ^ X X1^0 R N^X,
'ΓÇ₧17 I X╬▓ N 7 I
V <W╬▓)' I" (W9)or NT X
I Λ13 Λ1 I ^
R8 is C╬╣-C3alkyl, C╬╣-C3haloalkyl or amino;
R9 is CrC3haloalkyl, C C3alkyl-S(O)n╬╣, CrC3haloalkyl-S(O)n╬╣ or cyano; or
R8 and R9 together form a C3- or C4-alkylene bridge or C3- or C4-alkenylene bridge, each of which may be substituted by halogen, C C3haloalkyl or by cyano; r\╬╣ is 0, 1 or 2;
R10 is hydrogen, C╬╣-C3alkyl, halogen, C C3haloalkyl or cyano; or R10 and R9 together form a C3- or C4-alkylene bridge or C3- or C-alkenylene bridge, each of which may be substituted by halogen, CrC3haloalkyl or by cyano; Rn is hydrogen, C C3alkyl, halogen or cyano; R-I2 is C C3haloalkyl;
R╬╣2 and Rn together form a C3- or C4-alkylene bridge or C3- or C-alkenylene bridge; R╬╣3 is hydrogen, d-C3alkyl or halogen;
R╬╣3 and R12 together form a C3- or C-alkylene bridge or C3- or C-alkenylene bridge; R-╬╣4 is hydrogen, C C3alkyl, halogen, C C3haloalkyl, R33O-, R34S(O)n2, R_5(R36)N,
R38(R39)N-C(R37)=N-, hydroxy, nitro or NΓëíC-S- ;
R33 is C C3alkyl, C╬╣-C3haloalkyl, C2-C4alkenyl, C3- or C4-alkynyl or C C5alkoxycarbonyl- d-C4alkyl; - 135 -
R34 is d-C4alkyl or CrC4haloalkyl; n2 is O, 1 or 2;
R35 is hydrogen, C C4alkyl, C C4haloalkyl, C3-C6cycloalkyl, OHC- or C C4alkylcarbonyl;
R36. R37 and R39 are each independently of the others hydrogen or d-C4alkyl;
R38 is C C4alkyl;
R-I5 is hydrogen, C C alkyl, halogen, C C4haloalkyl, C2-C alkenyl, C3-C5haloalkenyl, C3- or C4-alkynyl, C C alkoxy, C C4alkylcarbonyl, C C4haloalkylcarbonyl, C2-C alkenyl- carbonyl, C2-C haloalkenylcarbonyl, C2-C4alkynylcarbonyl, C2-C4haloalkynylcarbonyl, C C4alkoxycarbonyl, CrC4alkylcarbamoyl, C C4alkylS(O)n3, C3- or C4-alkynylS(O)n3,
OHC-, nitro, amino, cyano or NΓëíCΓÇö S- ; n3 is O, 1 or 2;
R16 and R17 are each independently of the other hydrogen, d-C alkyl, halogen, d-C4halo- alkyl or cyano; R╬╣8 and R-|9 are each independently of the other hydrogen, methyl, halogen, hydroxy or =O; R20 and R21 are each independently of the other hydrogen, CrC alkyl or CrC haloalkyl; R22 and R23 are each independently of the other hydrogen, d-C3alkyl, halogen or hydroxy; R24 and R25 are each independently of the other hydrogen or C C alkyl; or
/ R 0
R24 and R25 together form the group =C ;
R4╬╣
R40 and R4-╬╣ are each independently of the other C C alkyl; or
R40 and R41 together form a C4- or C5-all<ylene bridge;
R26 is hydrogen or C C3alkyl; or
R26 together with R25 forms a C3-C5alkylene bridge, which may be interrupted by oxygen and/or substituted by halogen, C╬╣-C4alkyl, C2-C4alkenyl, C╬╣-C3haloalkyl, d-C3alkyl- carbonyloxy, d-C alkoxycarbonyl, C C3alkylsulfonyloxy, hydroxy or by =O;
R27. R28. R29 and R30 are each independently of the others hydrogen, CrC3alkyl, C3- or C4- alkenyl or C3-C5alkynyl; or
R27 and R28 together and/or R29 and R30 together in each case form a C2-C5alkylene bridge or C3-C5alkenylene bridge, each of which may be interrupted by oxygen, sulfur or - S(O)2- and/or substituted by halogen, C╬╣-C alkyl, C2-C4alkenyl, C╬╣-C3alkylcarbonyloxy, C╬╣-C3alkylsulfonyloxy, hydroxy or by =O; - 136 -
R31 is hydrogen, C╬╣-C4alkyl, C1-C4haloalkyl, C3- or C4-alkenyl, C3- or C -haloalkenyl or C3- or C -alkynyl; R32 is hydrogen, C C4alkyl, d-Caalkoxy-d- or -C2-alkyl, C C4haloalkyl, C3- or C -alkenyl,
C3- or C -haloalkenyl or C3- or C4-alkynyl; or R32 and R3-t together form a C3-C5alkylene bridge; and X2. 3. 4. X5. Xe- X7. X╬▓. X9. X10. X11. X12. X13. X14 and X15 are each independently of the others oxygen or sulfur, or an agrochemically acceptable salt or stereoisomer of such a compound of formula I.
2. A compound according to claim 1 of formula l0
R1
(lo), *s
wherein R is hydrogen, fluorine, chlorine, bromine or methyl; R2 is methyl, halogen, hydroxy, nitro, amino or cyano; and R3, Xi and W are as defined in claim 1.
3. A process for the preparation of a compound of formula I
(I),
wherein R^ R2 and W are as defined in claim 1 ; Xt is O or S; R3 is Ci-C╬▓alkoxy-d-CealkyI, C╬╣-C6alkoxy-C╬╣-C6alkoxy-C╬╣-C6alkyl, CrC6alkyl, C3-C6alkenyl, C3-C6alkynyl, C2-C6haloalkyl,
C3-C6haloalkenyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, B╬╣-C╬╣-C6alkyl, >ΓÇö CH 137 -
C C3alkyl , (C╬╣-C5hydroxyalkyl)-CH2-, (B d-Cshydroxyalky -CH^ or
CH2ΓÇö
(B C CshaloalkylJ-CHΓêæ-; and B! is as defined in claim 1 , which process comprises oxidising a compound of formula III
(III) vv
in a suitable solvent to form a compound of formula V
(V)
and then rearranging that compound in an inert solvent in the presence of an anhydride or in the presence of antimony pentachloride to yield, after aqueous working-up, a compound of formula II
(II), the radicals R1 f R2 and W in the compounds of formulae II, III and V being as defined, and then alkylating that compound in the presence of an inert solvent and a base with a compound of formula VI
R3-L (VI), wherein R3 is as defined and L is a leaving group, in a suitable inert solvent and a base to form the compounds of formulae I and IV
,R1 ,R1
// \\ ΓÇóW (I) and (IV),
X1 ^ R3 OR3 - 138 -
wherein R^ R2, R3 and W are as defined and Xi is O, and then, after the compound of formula I has been separated from the pyridol derivative of formula IV, optionally functionalising the pyridono derivative of formula I further in accordance with the definitions of Xi and R3.
4. A compound of formula II
R1 W Γûáw (ll). OH O
wherein RL R2 and W are as defined in claim 1.
5. A herbicidal and plant-growth-inhibiting composition, comprising a herbicidally effective amount of a compound of formula I on an inert carrier.
6. A herbicidal and plant-growth-inhibiting composition according to claim 5, comprising at least one further co-herbicide as additional component.
7. A method of controlling undesired plant growth, which method comprises applying a compound of formula I, or a composition comprising such a compound, in a herbicidally effective amount to plants or to the locus thereof.
8. Use of a composition according to claim 5 in the control of undesired plant growth.
EP99919194A 1998-04-08 1999-04-06 N-pyridonyl herbicides Withdrawn EP1076655A1 (en)

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CH84098 1998-04-08
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JP2002511461A (en) 2002-04-16
CN1295570A (en) 2001-05-16
BR9909487A (en) 2000-12-12
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KR20010042521A (en) 2001-05-25
AU738222B2 (en) 2001-09-13
AU3705699A (en) 1999-11-01

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