WO2001030782A2 - Nouveaux herbicides - Google Patents

Nouveaux herbicides Download PDF

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Publication number
WO2001030782A2
WO2001030782A2 PCT/EP2000/010595 EP0010595W WO0130782A2 WO 2001030782 A2 WO2001030782 A2 WO 2001030782A2 EP 0010595 W EP0010595 W EP 0010595W WO 0130782 A2 WO0130782 A2 WO 0130782A2
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alkyl
crc
halogen
hydrogen
formula
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PCT/EP2000/010595
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WO2001030782A3 (fr
Inventor
Christoph Lüthy
Kurt Nebel
Jean Wenger
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Syngenta Participations Ag
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Priority to AU10269/01A priority Critical patent/AU1026901A/en
Publication of WO2001030782A2 publication Critical patent/WO2001030782A2/fr
Publication of WO2001030782A3 publication Critical patent/WO2001030782A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • 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
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00

Definitions

  • the present invention relates to novel, herbicidally active 4H-pyrido[3,2-b][1 ,4]oxazin-3- ones substituted by 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-imides, N-pyridyl-pyrazoles and N-pyridyl-triazolidinones and also N-pyridyl-uracils and N-pyridonyl-uracils having herbicidal activity are described, for example, in DE 3 917 469, WO 98/27082, WO 98/27083, WO 98/52938, WO 98/42698, WO 98/21 199, WO 99/52892 and WO 99/52893.
  • Novel heterocyclic derivatives of 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-one and 3-oxo-3,4- dihydro-2H-pyrido[3,2-b][1 ,4]oxazine-6-carboxylic acid which are substituted in the 6- position and have herbicidal and growth-inhibiting properties have now been found.
  • the present invention accordingly relates to compounds of formula I
  • R is hydrogen, methyl or halogen
  • R 2 is hydrogen, C ⁇ -C ⁇ 2 alkyl, d-C ⁇ 2 haloalkyl, C 2 -C ⁇ alkenyl, C 2 -C ⁇ 2 alkynyl, C 2 -C 8 alkynyl-
  • R 3 is hydrogen, C ⁇ -C 12 alkyl, d-C ⁇ 2 haloalkyl, C C 6 alkoxycarbonyl, or phenyl which is unsubstituted or substituted by halogen, methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, methoxy, ethoxy, cyano or by nitro;
  • R 4 is hydrogen or d-C 6 alkyl;
  • W is a group
  • R 11 is hydrogen, d-C 3 alkyl, halogen, CrC 3 haloalkyl or cyano;
  • R 12 is C C 3 alkyl, C C 3 haloalkyl, d-C 3 alkyl-S(O) n1 -, d-C 3 haloalkyl-S(O) n1 - or cyano;
  • R 13 is hydrogen, d-C 3 alkyl, d-C 3 haloalkyl, allyl, propargyl or amino; or
  • R 12 and Rn or R 12 and R 13 together form a C 3 - or C 4 -alkylene bridge which may be substituted by halogen, d-C 3 haloalkyl or by cyano;
  • R 14 is hydrogen, d-C 3 alkyl, halogen, C Cshaloalkyl or cyano;
  • R 15 is d-C 3 alkyl, d-C 3 haloalkyl, d-C 3 alkyl-S(O)n2-, C C 3 haloalkyl-S(O)n2- or cyano; or
  • R 15 and R ⁇ 4 together form a C 3 - or C 4 -alkylene bridge which may be substituted by halogen, d-C 3 haloalkyl or by cyano;
  • R 16 is hydrogen, d-C 3 alkyl, halogen, Ci-Cshaloalkyl, C Csalkoxy, d-C 3 haloalkoxy, hydroxy, mercapto, d-C3alkylthio, CrCsalkylsulfinyl, CrCaalkylsulfonyl, allylthio, propargylthio, amino, d-C 3 alkylamino, di(d-C 3 alkyl)amino, allylamino, propargylamino or cyano; R 17 is hydrogen, d-C 3 alkyl, halogen or cyano; and
  • R 18 is C ⁇ -C 3 alkyl, halogen, C C 3 haloalkyl, d-dalkylthio, d-C 3 alkylsulfinyl, d-
  • R 18 and R 17 together form a C 3 - or C 4 -alkylene or C 3 - or C -alkenylene bridge, both of which may be substituted by halogen, C ⁇ -C 3 alkyl or by d-C 3 haloalkyl;
  • R 19 is hydrogen, halogen, d-C 3 alkyl, carboxyl, d-C 3 alkoxycarbonyl or amino; or
  • R 19 and R 18 together form a C 3 - or C 4 -alkylene or C 3 - or C 4 -alkenylene bridge, both of which may be substituted by halogen, d-C 3 alkyl or by C C 3 haloalkyl;
  • R 2 o and R 21 are each independently of the other hydrogen or C ⁇ -C alkyl; or
  • R 051 and R 052 are each independently of the other hydrogen or d-C 4 alkyl; or
  • R 051 and R 052 together form a C 4 - or C 5 -alkylene bridge
  • R 052 and R 2 together form a C 3 alkylene bridge
  • R 22 is hydrogen or C C 3 alkyl
  • R 22 and R 2 o or R 22 and R 2 ⁇ together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by halogen, d-C 4 alkyl, C ⁇ -
  • R 23 and R 24 are each independently of the other hydrogen, d-C 3 alkyl, C C 3 haloalkyl or propargyl; or
  • R 23 and R 24 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by halogen, C C 4 alkyl, hydroxy, d-
  • R 25 is hydrogen, halogen, d-C alkyl, d-C haloalkyl, d-dalkoxy, d-C 4 haloalkoxy, d-
  • R 26 is hydrogen, C ⁇ -C 4 alkyl or d-C 4 haloalkyl
  • R 26 and R 2 5 together form a C 3 -Csalkylene bridge which may be interrupted by oxygen
  • R 27 and R 8 are each independently of the other hydrogen or C ⁇ -C alkyl; or
  • R 27 and R 28 together form a C 3 -C 5 alkylene bridge which may be substituted by halogen or by C ⁇ -C 4 alkyl and/or interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- or form a dalkenylene bridge which is unsubstituted or substituted by d-C 4 aIkyl;
  • R 29 and R 30 are each independently of the other hydrogen, d-dalkyl or d-C haloalkyl; or
  • R 29 and R 30 together form a C 3 -C 5 alkylene bridge which may be substituted by halogen or by d-C alkyl and/or interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)-;
  • R 31 is hydrogen, C C 4 alkyl or C ⁇ -C 4 haloalkyl
  • R 32 is hydrogen, d-C 4 alkyl, C C 4 haloalkyl, d-C alkylthio, d-C 4 alkylsulfinyl, d-dalkyl- sulfonyl, cyano or nitro; or
  • R 31 and R 32 together form a C 3 -C 5 alkylene bridge which may be substituted by halogen or by d-dalkyl and/or interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- or form a dalkenylene bridge which is unsubstituted or substituted by d-C alkyl;
  • R 33 is hydrogen, d-C 3 alkyl, halogen, C ⁇ -C 3 haloalkyl, hydroxy, d-C 3 alkoxy, d-
  • R 34 is C ⁇ -C alkyl, d-C haloalkyl, d-C alkoxy or C ⁇ -C 4 alkylthio;
  • R 36 is hydrogen, C ⁇ -C 3 alkyl, halogen, C ⁇ -C 3 haloalkyl or cyano;
  • R 37 is C ⁇ -C 3 alkyl, C ⁇ -C 3 haloalkyl, d-C 3 alkyl-S(O) n1 -, C r C 3 haloalkyl-S(O) n1 - or cyano; or
  • R 37 and R 36 together form a C 3 - or C -alkenylene bridge which may be substituted by halogen, d-C 3 alkyl, C ⁇ -C 3 haloalkyl or by cyano;
  • R 38 is d-C 3 alkyl
  • R 39 is hydrogen or d-C 3 alkyl
  • R 40 and R 41 are each independently of the other d-C 3 alkyl or d-C 3 haloalkyl; or
  • R 41 and R 40 together form a C 3 -C 5 alkylene bridge which is unsubstituted or substituted by halogen or by d-C 4 alkyl;
  • R 42 is hydrogen, d-dalkyl, d-C 3 haloalkyl, cyano or carboxyl;
  • R 43 is hydrogen, d-C 3 alkyl, C C 3 haloalkyl, allyl or propargyl;
  • R 44 is hydrogen, d-dalkyl, halogen, d-C 3 haloalkyl, hydroxy, mercapto, amino, C 1 -
  • R 45 is hydrogen, d-dalkyl, halogen or cyano
  • R 46 is d-dalkyl, d-C 3 haloalkyl or cyano
  • R 47 is hydrogen, C ⁇ -C 3 alkyl or halogen;
  • R 48 is d-dalkyl or C C 3 haloalkyl;
  • R 50 and R51 are each independently of the others hydrogen, d-C 4 alkyl, propargyl or C ⁇ -
  • R 52 is C C 3 alkyl, halogen, d-C 3 haloalkyl, C ⁇ -C 3 alkoxy, d-C 3 haloalkoxy, C C 3 alkylthio,
  • R 53 is C ⁇ -C 3 alkyl or d-C 3 haloalkyl
  • R 54 is d-dalkyl
  • R 55 is hydrogen, d-dalkyl, propargyl or C C 3 haloalkyl
  • R 56 is d-dalkyl, d-C 3 haloalkyl, d-C 3 alkylthio, C C 3 alkylsulfinyl or d-C 3 alkylsulfonyl;
  • R 57 is C C 3 alkyl or C ⁇ -C 3 haloalkyl
  • R 57 and R 5 ⁇ together form a C 2 -C 4 alkylene or C 2 -C 4 alkenylene bridge which both are unsubstituted or substituted by halogen or by d-dalkyl;
  • R 58 is hydrogen, d-C 3 alkyl, d-C 3 haloalkyl or amino
  • R 59 is hydrogen, C C 3 alkyl or d-C 3 haloalkyl
  • R 100 is hydrogen, halogen, nitro, amino, cyano, C C 3 alkyl, C 2 - or C 3 -alkenyl or C 2 - or C 3 - alkynyl;
  • R 101 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-C 3 alkyl, d-
  • R 102 is hydrogen, d-C 6 alkyl, d-C 6 alkyl substituted by cyano, HO-, HOC(O)-, C dalkoxycarbonyl or by HC(O)-, or is C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-
  • R 102 and R101 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 103 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, C ⁇ -C 3 alkyl, d- dhaloalkyl, C 2 - or C 3 -alkenyl, C 2 - or C 3 -aIkynyl, C ⁇ -C 3 alkoxy, C ⁇ -C 3 haloalkoxy, C ⁇ -
  • R 104 is hydrogen, d-dalkyl, d-C 6 alkyl substituted by cyano, HO-, HOC(O)-, d-
  • R 105 is hydrogen, halogen, nitro, amino, cyano, d-dalkyl, C 2 - or C 3 -alkenyl or C 2 - or C 3 - alkynyl; or
  • R ⁇ 04 and R ⁇ 03 together form a C 3 -C 5 alkylene bridge or a dalkenylene bridge which both may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 106 is hydrogen, halogen, amino, nitro, hydroxy, C ⁇ -C 3 alkyl or d-C 3 alkoxy;
  • R 107 is hydrogen, halogen, amino, hydroxy, d-dalkyl, C C 3 haloalkyl, HC(O)-, HOC(O)-, hydroxy-C ⁇ -C 3 alkyl, C C 3 alkoxy or C ⁇ -C 3 haloalkoxy;
  • R 108 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, C ⁇ -C 3 alkyl, d-C 3 haloalkyl, C 2 - or C 3 -alkenyl, C C 3 alkoxy, d-
  • Rio ⁇ and R 10 7 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 10 g is hydrogen, halogen, amino, hydroxy, d-dalkyl, C C 3 haloalkyl, HC(O)-, HOC(O)-, hydroxy-C ⁇ -C 3 alkyl, d-C 3 alkoxy or d-C 3 haloalkoxy; or
  • R 109 and Rio ⁇ together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • Rno is hydrogen, d-C 3 alkyl, d-dhaloalkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl;
  • Rdom ⁇ is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, d-C 3 alkyl, d-C 3 haloalkyl, C 2 - or C 3 -alkenyl, d-C 3 alkoxy, C 1 -
  • R 112 is hydrogen, halogen, amino, hydroxy, d-dalkyl, CrC 3 haloalkyl, HC(O)-, HOC(O)-, hydroxy-C C 3 alkyl, d-C 3 alkoxy or d-C 3 haloalkoxy; or
  • R 1 t1 and Rn 0 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein the
  • C 3 -C 5 alkylene bridge is bonded to the N atom of the pyrazinone via a CH 2 group;
  • R ⁇ 2 and Rm together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 113 is hydrogen, d-dalkyl, C ⁇ -C 3 haloalkyl, C 3 -C 4 alkenyl or C 3 -C alkynyl;
  • R 114 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, C C 3 alkyl, d-C 3 haloalkyl, C 2 - or C 3 -aIkenyl, C ⁇ -C 3 alkoxy, d-
  • R 114 and R 1 3 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein the
  • C 3 -C 5 alkylene bridge is bonded to the N atom of the triazinone via a CH 2 group;
  • R 115 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, C ⁇ -C 3 alkyl, C C 3 haloalkyl, C 2 - or C 3 -alkenyl, d-C 3 alkoxy, C
  • R 116 is hydrogen, C ⁇ -C 3 alkyl, C ⁇ -C 3 haloalkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; or
  • R 116 and Rn 5 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein the
  • C 3 -C 5 alkylene bridge is bonded to the N atom of the triazinone via a CH 2 group;
  • R 117 is hydrogen, C ⁇ -C 3 alkyl, d-C 3 haloalkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl;
  • R 118 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, C ⁇ -C 3 alkyl, d-dhaloalkyl, C 2 - or C 3 -alkenyl, C C 3 aIkoxy, C
  • R 119 is hydrogen, halogen, amino, nitro, hydroxy, d-C 3 alkyl or C C 3 alkoxy; or
  • Rn 8 and Rn 7 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein the
  • C 3 -C 5 alkylene bridge is bonded to the N atom of the pyrimidinone via a CH 2 group;
  • R 120 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, C ⁇ -C 3 alkyl, d-C 3 haloalkyl, C 2 - or C 3 -alkenyl, d-C 3 alkoxy, C r
  • R 12 ⁇ is hydrogen, d-dalkyl, d-dhaloalkyl, C 3 - or C -alkenyl or C 3 - or C 4 -alkynyl;
  • R 122 is hydrogen, halogen, amino, nitro, hydroxy, d-C 3 alkyl or d-C 3 alkoxy; or R 121 and R 120 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein the
  • C 3 -C 5 alkylene bridge is bonded to the N atom of the pyrimidinone via a CH 2 group;
  • R 123 is hydrogen, C ⁇ -C 3 alkyl, halogen or d-C 3 haloalkyl
  • R 124 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, mercapto, CrC 3 alkyl, C ⁇ -C 3 haloalkyl, C 2 - or C 3 -alkenyl, C C 3 alkoxy, d- dhaloalkoxy, d-C 3 alkylcarbonyl, d-C 3 alkoxycarbonyl, CrC 3 alkylthio, C ⁇ -C 3 haloalkylthio, d-dalkylsulfinyl, d-C 3 haloalkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylsulfonyl, d- dalkylsulfonyloxy or C C 3 haloalkylsulfonyloxy; and
  • R 125 is hydrogen, d-C 3 alkyl, halogen, hydroxy, d-C 3 alkoxy, C ⁇ -C 3 haloalkoxy, d-
  • X 24 and X 25 are each independently of the others oxygen or sulfur;
  • Y t and Y 2 are oxygen or sulfur, and also the agrochemically acceptable salts and tautomers, enantiomers and stereoisomers of the compounds of formula I.
  • halogen is to be understood as being iodine and also, preferably, fluorine, chlorine or bromine.
  • alkyl, alkenyl and alkynyl groups appearing in the substituent definitions may be straight-chained or branched, that especially also being true of the alkyl, alkenyl and alkynyl moiety of alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkylS(O) n , alkylsulfonyloxy, alkylthioalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylamino and other alkyl- containing groups.
  • Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl radicals.
  • Preference is given to lower alkyl groups for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2-pentyl and 3-pentyl.
  • alkenyl groups vinyl, allyl, methallyl, 1-methylvinyl, but-3-en-2-yl, n-pent-4-enyl and 2-hexen-5-yl; preferably alkenyl radicals having a chain length of from 3 to 5 carbon atoms.
  • alkynyl radicals ethynyl, propargyl, 2-butyn-1 -yl, 2- butyn-3-yl, but-2-yn-1 -yl, but-3-yn-2-yl, 2-methyl-but-3-yn-2-yl, pent-4-yn-1-yl, hex-4-yn-2-yl and 3-heptyn-2-yl; preferably alkynyl radicals having a chain length of from 3 to 5 carbon atoms.
  • Suitable haloalkyl radicals include alkyl groups substituted one or more times, especially from one to five times, by halogen, halogen being in particular iodine and especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, difluorochloromethyl, 1 -f luoroethyl, 2-fluoroethyl, 1 ,1- difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-difluorochloroethyl, 2-chloroethyl, 2- bromoethyl, pentafluoroethyl, 2-fluoroprop-1-yl, 3-fluoroprop-1-yl, 3,3-dif luoroprop-1 -yl and 2,3,3-trif luoroprop-1 -yl.
  • Suitable haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being in particular bromine or iodine and especially fluorine or chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1-yl and 4-chloro-but- 2-en-1-yl.
  • Preferred alkenyl radicals substituted once, twice or three times by halogen are especially those having a chain length of 3 or 5 carbon atoms.
  • the alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms and may optionally occur in the cis and also trans forms.
  • Suitable haloalkynyl radicals include alkynyl groups substituted one or more times by halogen, halogen being in particular bromine or iodine and especially fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl.
  • Preferred alkynyl groups substituted one or more times by halogen are those having a chain length of from 3 to 5 carbon atoms.
  • cycloalkyl- and halocycloalkyl-containing groups the cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl group.
  • Cycloalkylalkyl is, for example, cyclopropylmethyl, dimethylcyclopropylmethyl, difluorocyclo- propylmethyl, dichlorocyclopropylmethyl, dibromocyclopropylmethyl, 2,2,3,3-tetrafluoro- cyclobutylmethyl and 2,2-difluoro-3,3-dichlorocyclobuty!methyl.
  • cycloalkyl-containing groups and also any alkylene- or alkenylene-containing groups may also be substituted one or more times by further d-dalkyl groups, especially methyl groups, and by halogen and d-dhaloalkyl.
  • alkylene and alkenylene bridges for example in the definitions 'R 15 and R 4 together form a C 3 - or C 4 -alkylene bridge' or 'R 18 and R17 together form a C 3 - or C -alkylene or C 3 - or
  • C -alkenylene bridge' may, as mentioned in the corresponding definitions, be substituted or unsubstituted.
  • 'R 31 and R 32 together form a...'
  • 'R41 and R 40 together form a C 3 -C 5 alkylene bridge'
  • 'R 39 and R 38 together form a C 2 - or C 3 -alkylene bridge' and 'R 57 and R 56 together form a C 2 - dalkylene bridge', those alkylene bridges may be substituted by halogen, C C 4 alkyl or by d-dhaloalkyl.
  • 'R 23 and R 24 together form a...', 'R 26 and R 25 together form a...', 'R 27 and R 28 together form a...', 'R 29 and R 30 together form a...', 'R 3 ⁇ and R 32 together form a...' and 'R 41 and R 40 together form a C 3 -C 5 alkylene bridge', and also 'R 39 and R 38 together form a C 2 - or C 3 - alkylene bridge' and 'R 57 and R 56 together form a C 2 -C 4 alkylene bridge', a carbon atom of such a bridge may be substituted once or twice, geminally or vicinally, by fluorine.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2,2,2-trichloroethylsulfonyl.
  • Alkylcarbonyl is, for example, acetyl, propionyl, pivaloyl and n-propylcarbonyl.
  • Haloalkylcarbonyl is especially chloromethylcarbonyl, bromomethylcarbonyl, trifluoroacetyl, dichloroacetyl, trichloroacetyl, 1-chloroethylcarbonyl, 1-bromoethylcarbonyl and 3,3,3- trifluoropropionyl.
  • Alkoxy perse and alkoxy-containing groups are especially methoxy, ethoxy and propoxy groups.
  • Alkenyloxy and alkynyloxy perse and alkenyloxy- and alkynyloxy-containing groups are especially allyloxy and propargyloxy groups.
  • Haloalkoxy and haloalkoxy-containing groups are especially the fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy and 2-fluoroethoxy groups.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl and isopropoxyethyl.
  • Alkenyloxyalkyl is, for example, allyloxy-methyl, methallyloxy-methyl, allyloxy-ethyl and methallyloxy-ethyl.
  • Haloalkenyloxyalkyl is, for example, 3-chloropropenyloxy-methyl and 3-fluoropropenyloxy- methyl.
  • Alkynyloxyalkyl is, for example, propargyloxy-methyl, propargyloxy-ethyl, 1- methylpropargyloxy-ethyl and methylpropargyloxy-methyl.
  • Haloalkynyloxyalkyl is, for example, 3-chloropropynyloxy-methyl and 3-fluoropropynyloxy- methyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.
  • Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, 1 -propenyloxy- carbonyl and (but-2-en-1-yl)oxycarbonyl.
  • Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, (but-3-yn-2-yl)oxycarbonyl and
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino and isopropylamino.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio and isopropylthio.
  • Alkylthioalkyl is, for example, methylthioethyl, ethylthioethyl, methylthiopropyl and ethylthiopropyl.
  • Haloalkylthio is, for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chloromethylthio, 2-fluoroethylthio, 2,2,2-trifluoroethylthio and 2,2,2-trichloroethylthio.
  • Alkylsulfinyl, alkylsulfinylalkyl, alkylsulfonyl and alkylsulfonylalkyl are, for example, methylsulfinyl, ethylsulfinyl, methylsulfmylethyl, ethylsulfinylethyl, methylsulfonyl, n-propylsulfonyl, methylsulfonylethyl and ethylsulfonylethyl.
  • Haloalkylsulfinyl is, for example, fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethyl- sulfinyl, chloromethylsulfinyl, trichloromethylsulfinyl, 2-fluoroethylsulfinyl and 2,2,2-trifluoro- ethylsulfinyl.
  • Hydroxyalkyl is, for example, 2-hydroxyethyl, 3-hydroxypropyl and 2,3-dihydroxypropyl. Cyanoalkyl is especially cyanomethyl, cyanoethyl, 1 -cyanoethyl and 2-cyanopropyl.
  • a phenyl, benzoyl or heterocyclyl group can be substituted one or more times in dependence upon the substituents indicated; for example, a phenyl or benzoyl ring may be perfluoridated, or carry from 1 to 3 chlorides, alkyl, alkoxy and/or haloalkoxy groups, 1 or 2 bromides and/or nitro groups, and/or 1 cyano and/or haloalkyl group.
  • Heterocyclyl groups may generally be occupied once or twice by the substituents indicated.
  • a heterocyclyl group may be aromatic and also partially or completely saturated and contain from 1 to 4 nitrogen atoms and/or 1 or 2 oxygen atoms or 1 or 2 sulfur atoms.
  • Examples that may be mentioned include the 2- and 3-pyridyl group, the 2- and 4-pyrimidinyl group, the 1- and 3-pyrazolyl group, the 1 - and 2-furyl group, the 1- and 2-thienyl group, the 2- oxazolyl group, the 1 -oxadiazolyl group, the 1 ,2-oxazol-3-yl group, the 1 ,2-oxazolin-3-yl group, the 1 - and 3-triazolyl group, the oxiran-2-yl group, the oxetan-3-yl group, the tetrahydrofur-2-yl group, the tetrahydropyran-2-yl group, the 1 ,3-dioxazolin-2-yl group, the 1 ,3-dioxolan-2-yl group and the 1 ,3-oxathiazol-2-yl group, and also the 4H-pyrido[3,2-b][1 ,4 ]o
  • cyanoalkyl alkylcarbonyl, alkenylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, cycloalkylcarbonyl, alkylaminocarbonyl and haloalkylcarbonyl
  • the carbon atom of the cyano or carbonyl is not included in the lower and upper limits given for the number of carbons in each particular case.
  • L 6 and L 7 in the reagent of formula XXXVI are leaving groups, for example halogen, especially chlorine or bromine, or, in the case of L 7 , also hydroxy or alkoxy.
  • L 9 in the reagent of formula XII is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially mesyloxy, tosyloxy or trifluoromethanesulfonyloxy.
  • L 11 in the reagent of formula XXV (Reaction Scheme 17) is a leaving group, for example hydroxy, C C 3 alkoxy, chlorine, amino or d-dalkylamino.
  • L 12 and L 13 in the reagents of formulae XXVIa, XXVIb, XXVIc and XXVId are leaving groups, for example chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy.
  • L 1 in the reagent of formula XlVa is a leaving group, for example halogen, e.g. chlorine or bromine.
  • L 15 in the reagent of formula XVII is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy.
  • Ao in the compound of formula Hz is preferably methyl, chlorine, bromine or carboxy.
  • a 1 in the compound of formula lib is a leaving group, for example halogen, especially fluorine, chlorine or bromine, alkylsulfonyl, especially methylsulfonyl, sulfonate, especially mesyloxy, trifluoromethylsulfonyloxy or phenylsulfonyloxy, or nitro.
  • a 2 in the compound of formula llu is methyl, cyano, formyl, d- dalkylcarbonyl, carboxyl or d-C 4 alkoxycarbonyl.
  • a 3 in the compound of formula llv is either a leaving group, for example halogen, especially chlorine or bromine, or a sulfonate group, especially trifluoromethylsulfonyloxy or a C ⁇ -C 4 trialkylstannyl or boronic acid group.
  • reaction Scheme 1e is, complementarily to A 3 in the compound of formula llv, either a d-C 4 trialkylstannyl or a boronic acid group, or a leaving group, for example halogen, especially chlorine or bromine, or a sulfonate group, especially trifluoromethylsulfonyloxy.
  • Zi in the reagent of formula XXXII is a leaving group, for example alkoxy, especially methoxy or ethoxy, or halogen, especially chlorine or bromine.
  • Z 2 in the reagent of formula XXXII is a leaving group, for example halogen, especially chlorine or bromine, or a sulfonate, especially mesyloxy or phenylsulfonyloxy.
  • the invention relates also to the salts that the compounds of formula I having acid hydrogen, including especially the carboxylic acid derivatives, for example hydrolysis products of R 2 , to which the present invention also relates, 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, i.e. unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and diisopropylammonium salts; or salts with other organic bases.
  • alkali metal salts e.g. sodium and potassium salts
  • alkaline earth metal salts e.g. calcium and magnesium salts
  • ammonium salts i.e. unsubstituted ammonium salts and mono- or poly-substituted ammonium salts,
  • alkali metal and alkaline earth metal hydroxides used as salt formers emphasis is to be given to, for example, the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium and potassium.
  • Suitable salt formers are described, for example, in WO 97/411 12.
  • Suitable amines for ammonium salt formation are ammonia as well as primary, secondary and tertiary C ⁇ -C ⁇ 8 alkylamines, C ⁇ -C hydroxyalkyl- amines and C -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octa
  • W, ⁇ , W 12 and W 2 o the exocyclic double bond may be present in the syn/anti
  • the compounds of formulae IW 10 o z and IW ⁇ 0 ⁇ z can, with respect to the groups W 10 o and W 10 ⁇ , wherein R 10 o is hydrogen and R ⁇ 0 ⁇ is hydroxy, be present as keto- enol tautomer mixtures; for the group W 100z in the compound of formula IW 10 o z by way of example:
  • the present invention also includes those specific ⁇ E>- and ⁇ Z>-isomers, or syn- and anti- isomers, and tautomeric forms and mixtures thereof.
  • R 2 is hydrogen, d-C 12 alkyl, C ⁇ -C 12 haloalkyl, d-C 12 alkenyl, C ⁇ -C 12 alkynyl, d- C ⁇ 2 haloalkenyl, d-C 12 haloalkynyl, d-C 6 cycloalkyl-C ⁇ -C 4 alkyl, d-dhalocycloalkyl-d- C 4 alkyl, cyano-C ⁇ -Ci2alkyl, C ⁇ -C 6 alkoxy-d-C 4 alkyl, d-dalkoxy-d-dalkoxy-d-dalkyl, di(C ⁇ -C 4 alkoxy)CrC 2 alkyl, CrC 6 alkylthio-d-C 4 alkyl, d-dalkylsulfinyl-d-dalkyl, d- C 6 alkylsulfonyl-C ⁇ -C 4 alkyl, hydroxy-C
  • R is hydrogen or d-C 6 alkyl
  • W is a group
  • R 11 is hydrogen, d-C 3 alkyl, halogen, d-dhaloalkyl or cyano;
  • R 12 is d-dalkyl, d-C 3 haloalkyl, C C 3 alkyl-S(O) n1 -, C C 3 haloalkyl-S(O) n ⁇ - or cyano; and "
  • R ⁇ 3 is d-C 3 alkyl, d-dhaloalkyl or- amino
  • R 12 and R or R ⁇ 2 and R 13 together form a C 3 - or C 4 -alkylene bridge which may be substituted by halogen, d-dhaloalkyl or by cyano;
  • R ⁇ 4 is hydrogen, C ⁇ -C 3 alkyl, halogen, d-C 3 haloalkyl or cyano;
  • Ris is d-dalkyl, d-C 3 haloalkyl, C ⁇ -C 3 alkyl-S(O)n 2 -, d-C 3 haloalkyl-S(O) n2 - or cyano; or
  • R ⁇ 5 and R 14 together form a C 3 - or C 4 -alkylene bridge which may be substituted by halogen,
  • R 16 is hydrogen, d-dalkyl, halogen, d-dhaloalkyl, d-dalkoxy, C C 3 haloalkoxy, d-
  • R 17 is hydrogen, d-C 3 alkyl, halogen or cyano
  • R 18 is d-C 3 alkyl, halogen, C ⁇ -C 3 haloalkyl, C C 3 alkylthio, CrC 3 alkylsulfinyl, d-
  • R 18 and R ⁇ 7 together form a C 3 - or C 4 -alkylene or C 3 - or C 4 -alkenylene bridge, both of which may be substituted by halogen, d-C 3 alkyl or by d-C 3 haloalkyl;
  • R 19 is hydrogen, halogen, d-C 3 alkyl or amino; or R ⁇ 9 and R 1 8 together form a C 3 - or dalkylene or C 3 - or C 4 -alkenylene bridge, both of which may be substituted by halogen, d-C 3 alkyl or C ⁇ -C 3 haloalkyl;
  • R 20 and R 2i are each independently of the other hydrogen or d-C 4 alkyl; or
  • R 051 and R 052 are each independently of the other C ⁇ -C 4 alkyl; or R 051 and R 0 s 2 together form a C 4 - or C 5 -alkylene bridge; R 051 and R 22 together form a dalkylene bridge; R 22 is hydrogen or d-dalkyl; or
  • R 22 and R 20 or R 22 and R 2 ⁇ together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen or by -C(O)- and/or substituted by halogen, d-dalkyl, d-dhaloalkyl, C 2 - dalkenyl, d-C 3 alkoxycarbonyl, d-C 3 alkylcarbonyloxy, d-C 3 alkylsulfonyloxy or by hydroxy;
  • R 23 is hydrogen, d-C 3 alkyl or d-C 3 haloalkyl; or
  • R 23 and R 24 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)-;
  • R 25 is hydrogen, halogen, C ⁇ -C 4 alkyl, d-C 4 haloalkyl, C C 4 alkoxy, C ⁇ -C 4 haloalkoxy, d- C alkylthio, d-C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C ⁇ -C 4 haloalkylsulfinyl, d-dalkylsulfonyl, C ⁇ -C haloalkylsulfonyl or cyano; and R 26 is hydrogen, C ⁇ -C 4 alkyl or d-C 4 haloalkyl; or
  • R 26 and R 25 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen or by -C(O)- and/or substituted by halogen, C ⁇ -C 4 alkyl, d-C 3 haloalkyl, C 2 -C 4 alkenyl, d-C 3 alkoxy- carbonyl, d-C 3 alkylcarbonyloxy, C ⁇ -C 3 alkylsulfonyloxy or by hydroxy; R 27 and R 28 are each independently of the other hydrogen or d-dalkyl; or R 27 and R 28 together form a C 3 -C 5 alkylene bridge or a dalkenylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)-; R 29 and R 30 are each independently of the other hydrogen or C C 4 alkyl; or R 29 and R 30 together form a C 3 -C 5 alkylene bridge which may be interrupted by
  • R 32 is hydrogen, d-dalkyl, d-C 4 haloalkyl, d-C 4 alkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, cyano or nitro; or
  • R 31 and R 32 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)-;
  • R 33 is hydrogen, d-dalkyl, halogen, d-dhaloalkyl, d-C 3 alkoxy, d-dhaloalkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl, C C 3 alkylsulfonyl, amino, d-C 3 alkylamino, d-C 3 alkyl- carbonylamino, d-C 3 haloalkylcarbonylamino or cyano;
  • R 34 is C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, d-C alkoxy or C ⁇ -C 4 alkylthio;
  • R 100 is hydrogen, halogen, nitro, amino, cyano, d-dalkyl, C 2 - or C 3 -alkenyl or C 2 - or C 3 - alkynyl;
  • R 10 ⁇ is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-dalkyl, C 1 - dhaloalkyl, C 2 - or C 3 -alkenyl, C 2 - or C 3 -alkynyl, CrC 3 alkoxy, CrC 3 haloalkoxy f C 1 -
  • R 102 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C 6 haloalkyl,
  • R 102 and R 10 ⁇ together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 103 is as defined for R 10 ⁇ ;
  • R 104 is as defined for R 10 2;
  • R 105 is as defined for R 10 o;
  • R 106 is hydrogen, halogen, amino, nitro, hydroxy, d-C 3 alkyl or C C 3 alkoxy;
  • R 107 is hydrogen, halogen, amino, hydroxy, d-dalkyl, C C 3 haloalkyl, HC(O)-, HOC(O)-, hydroxy-C ⁇ -C 3 alkyl, d-C 3 alkoxy or C r C 3 haloalkoxy;
  • R 108 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H 2 NC(O)-, H 2 NC(S)-, hydroxy, HS-, d-C 3 alkyl, d-C 3 haloalkyl, C 2 - or C 3 -alkenyl, d-C 3 alkoxy, C ⁇ -C 3 haloalkoxy, d-dalkylcarbonyl, d-dalkoxycarbonyl, CrC 3 alkylthio, d-C 3 haloalkylthio, C ⁇ - dalkylsulfinyl, d-dhaloalkylsulfinyl, d-dalkylsulfonyl, C ⁇ -C 3 haloalkylsulfonyl ( d- dalkylsulfonyloxy or C ⁇ -C 3 haloalkylsulfonyloxy
  • R 10 g is as defined for R ⁇ 07 ;
  • R ⁇ 07 and R ⁇ o ⁇ together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R ⁇ os and R10 9 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 110 is hydrogen, d-C 3 alkyl, d-C 3 haloalkyl, C 3 -C alkenyl or C 3 -C 4 alkynyl; Rm is as defined for R 108 ;
  • R 112 is as defined for R 10 g;
  • Rm and Rn 2 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen;
  • R 110 and Rm together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein a
  • CH 2 group is bonded to the N atom of the pyrazinone
  • R 113 is as defined for R 10 ;
  • R 114 is as defined for R 108 ;
  • R 113 and Rn 4 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein a
  • CH 2 group is bonded to the N atom of the triazinone
  • R 115 is as defined for R 108 ;
  • R 116 is as defined for Rn 0 ;
  • R ⁇ 15 and R 116 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein a
  • CH 2 group is bonded to the N atom of the triazinone
  • R 117 is as defined for Rno;
  • R 118 is as defined for R 108 ;
  • R 119 is as defined for R 10 e;
  • Rn 7 and Rn 8 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein a
  • CH 2 group is bonded to the N atom of the pyrimidinone
  • R ⁇ 20 is as defined for R 108 ;
  • R121 is as defined for R 110 ;
  • R 122 is as defined for Rio ⁇ !
  • R 121 and R 120 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O) 2 - or by -C(O)- and/or substituted by hydroxy or by halogen, wherein a
  • CH 2 group is bonded to the N atom of the pyrimidinone
  • X12 or X ⁇ 3 are each independently of the others oxygen or sulfur; and
  • Y 1 is oxygen or sulfur.
  • R 2 is hydrogen, methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 3-methylpropyl, n-butyl, 2-butyl, 3-methyl-but-1-yl, 2-pentyl, 3- pentyl, allyl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop-2-en-1 -yl, 3-methyl-prop-2-en-1 -yl, 2- buten-1-yl, 3-buten-1 -yl, 1-buten-3-yl, 4-penten-1-yl, propargyl, 1 -butyn-3-yl, 2,2,2- trifluoroethyl, 2-chloroethyl, 3-fluoroprop-1 -yl, 3-chloroprop-1-yl, 3-chloro-2-methylprop-1-yl, 4-chlorobut-1 -y
  • W is a group Wi to W 2 .
  • W is a group W] W 2 , W , W 5 , W 7 , n, W 12 , W 14 , Wi 5 , W 18 or W 21 .
  • W is a group Wi, W 2 , W 4 , W 5 , W 7 or Wn.
  • W is a group W 3 , W 6 , W 8 , W 9 , W 10 ,
  • W is a group Wi or W 2
  • R 11 R 12 , R 13 , R 14 , R 15 , R ⁇ 6 , X ⁇ X 2 and X 3 are as defined for formula I.
  • Rn and R 14 are hydrogen, chlorine or methyl
  • R 12 and R 15 are methyl, ethyl, chlorodifluoromethyl, trifluoromethyl, pentafluoroethyl or cyano
  • R 13 is methyl, fluoromethyl, propargyl or amino
  • Ri 6 is chlorine, methoxy, fluoromethoxy or methylthio.
  • W is a group W 2 or Wn
  • X3 and X 14 are as defined for formula I; and R 16 is amino, d-dalkylamino, di(C ⁇ -C 3 alkyl)amino, allylamino or propargylamino.
  • X 3 and X 1 are oxygen; R ⁇ 4 and R 36 are hydrogen, chlorine or methyl; R 15 and R 37 are methyl, ethyl, chlorodifluoromethyl, trifluoromethyl, pentafluoroethyl or cyano; R ⁇ 6 is amino or methylamino; and R 39 and R 38 together form an unsubstituted or methyl-substituted dalkylene or dalkenylene bridge.
  • R 15 and R 37 are trifluoromethyl.
  • W is a group W 3
  • R 17 , R ⁇ 8 , R 19 and X 5 are as defined for formula I. Special preference is given especially to those wherein R 17 is hydrogen or C ⁇ -C 3 alkyl; R 18 is trifluoromethyl or methylsulfonyl; R 19 is hydrogen, C ⁇ -C 3 alkyl or amino; and X 5 is oxygen. Of those compounds, very special preference is given to those wherein R ⁇ 7 is hydrogen; and R 19 is methyl or amino.
  • R 2 o, R 21 and R 22 are as defined for formula I, and X 6 and X 7 are oxygen.
  • R 1 and R 22 together form a C 3 - or C 4 -alkylene bridge which is substituted once or twice by fluorine or chlorine or once by hydroxy or is interrupted by a keto group.
  • Special preference is also given to those
  • R 2 o and R 21 together are a group ;
  • R 05 ⁇ is hydrogen;
  • R 052 and R 22 together form a dalkylene bridge.
  • W is a group W 4 wherein R 2 o is hydrogen; and R 21 and R 22 together form a dalkylene group which is unsubstituted or substituted once or twice by fluorine or chlorine.
  • R 23 and R 2 are as defined for formula I; and X 8 and/or X 9 are oxygen. Of those compounds, special preference is given to those wherein R 23 and R 2 together form a C 3 -C 5 alkylene bridge which may be interrupted by oxygen. Very special preference is given to those wherein R 23 and R 2 together form a C 3 - or C -alkylene bridge.
  • W is a group W 6
  • R 25 and R 26 are as defined for formula I; and X 4 is oxygen.
  • R 25 and R 26 together form a dalkylene bridge.
  • W is a group W 6 ;
  • R 25 is methyl, ethyl or trifluoromethyl; and
  • R 26 is methyl or difluoromethyl.
  • X 4 is oxygen.
  • W is a group W 7
  • R 2 and R 28 are as defined for formula I; and X 10 and Xn are oxygen.
  • R 27 and R 28 together form a dalkylene bridge.
  • R 27 is methyl and R 28 is C C 3 alkyl.
  • W is a group W 8 or W 9
  • R 2 9, R 3 o, R31, R32 and R 33 are as defined for formula I; and X ⁇ 2 is oxygen.
  • R 29 and R 30 together and R 31 and R 32 together form, in each case, a dalkylene bridge.
  • W is a group W 9 and R 33 is chlorine or bromine.
  • W is a group W 9 wherein R 31 is hydrogen, chlorine, methyl or trifluoromethyl; R 32 is methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro; and R 33 is chlorine, amino, methylamino or ethylamino.
  • W is a group W 10 wherein X 13 is oxygen; and Ra* and Yi are as defined for formula I.
  • R ⁇ is tert-butyl or trifluoromethyl.
  • X15 is oxygen; Y 2 is sulfur; R 40 is methyl or ethyl; and R ⁇ is methyl, ethyl or difluoromethyl; or R 40 and R ⁇ together form a -(CH 2 ) 3 -, -CH 2 CH(CH 3 )CH 2 -, -(CH 2 ) 4 -, -CH 2 CH 2 OCH 2 - or -CH 2 CH 2 OCH 2 CH 2 - bridge.
  • W is a group W ⁇ 3
  • R 42 is hydrogen or cyano; R 43 is methyl; and X ⁇ 6 and X ⁇ 7 are oxygen.
  • W is a group W ⁇ 5
  • X 18 and X 20 are oxygen; R 49 is methyl; R 50 is methyl or difluoromethyl; and R 52 is chlorine or methyl.
  • R 56 and R 57 together form a -SCH 2 CH 2 -, -SCH(CH 3 )CH 2 -, -SC(CH 3 ) 2 CH 2 -, -SCH 2 CH 2 CH 2 -, -(CH 2 ) 3 -, -CH 2 CH(CH 3 )CH 2 - or -CH 2 C(CH 3 ) 2 CH 2 - bridge.
  • W is a group W 21
  • R 58 is methyl or amino; R 59 is methyl; and X 23 and X 4 are oxygen.
  • W is a group W 100 , W 10 ⁇ , W 102 , W 103 , W 10 , W 105 , W 106 , W 107 , W 108 or W 109 , especially the group W100.
  • R 10 o is methyl, chlorine or bromine; R 10 is chlorine, bromine, trifluoromethyl, difluoromethoxy, methylsulfonyl, ethylsulfonyl or cyano; and R 102 is methyl or ethyl; or R 102 and R 101 together form a dalkylene bridge.
  • R 103 is methyl, ethyl or trifluoromethyl; and R ⁇ c is methyl, ethyl or difluoromethyl; or R 104 and R 103 together form a dalkenylene bridge; and R 105 is methyl, chlorine or bromine.
  • R 1 ? R 2 , R 3 , R and W are as defined for formula I with the exception of R 2 as hydrogen, reacting a compound of formula la
  • R 1 t R 3 , R 4 and W are as defined, with a suitable alkylating reagent of formula IV wherein R 2 is as defined for formula I with the exception of R 2 as hydrogen, and L 2 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially CH 3 S(O) 2 O- (mesyloxy) or p-tolyl-S(O) 2 O- (tosyloxy), in the presence of a base and, optionally, one or more catalysts preferably in an inert diluent at temperatures of from 20° to 250°C, preferably from 20°C to the boiling point of the solvent or alkylating agent used, and at normal pressure or optionally under a slightly elevated pressure.
  • Reaction Scheme 1 a :
  • W vv -Wvv , -W v» 21 , W vv 100 -W» 109 ; .
  • Bases that are suitable for that alkylating reaction are, for example, alkali or alkaline earth metal hydrides, especially sodium hydride; alkali or alkaline earth metal carbonates, especially sodium hydrogen carbonate or sodium or potassium carbonate; trialkylamines, especially triethylamine or ethyl-diisopropylamine; aromatic amines, especially pyridine or N,N-dimethylaminopyridine; or caesium fluoride.
  • Suitable catalysts are, for example, crown ethers, especially 15-crown-5 or 18-crown-6; alkali metal halides, especially sodium or potassium iodide; or copper(l) iodide.
  • Suitable diluents are, for example, aromatic or heteroaromatic hydrocarbons, for example toluene, one of the xylene isomers, or 5-ethyl-2- methylpyridine; ketones, especially acetone or methyl ethyl ketone; ethers, especially tetrahydrofuran (THF), dimethoxyethane or diethoxymethane; esters, especially ethyl acetate; nitriles, especially acetonitrile; amides, especially N,N-dimethylformamide (DMF) or N-methylpyrrolidone (NMP); or sulfoxides, especially dimethyl sulfoxide.
  • aromatic or heteroaromatic hydrocarbons for example toluene, one of the xylene isomers, or 5-ethyl-2- methylpyridine
  • ketones especially acetone or methyl ethyl ketone
  • ethers especially tetrahydrofur
  • R ⁇ R 2 , R 3 and R 4 are as defined, either
  • Ri, R 2 , R 3 , R 4 , R 5 , X 0 and X 2 are as defined, or, as a variant thereof and in cases where X 0 in the compound of formula He is sulfur, first of all 1) carrying out a reaction with the reagent of formula Xln
  • Rn, R 12 and R 13 are as defined, Xi is oxygen or sulfur, and R 6 is d-C 4 alkyl, in the presence of from 0.01 to 1.5 equivalents of a suitable base, for example an alkali metal hydroxide or hydride, e.g. sodium hydroxide or sodium hydride, or an alcoholate, e.g. sodium ethanolate or potassium tert-butanolate, in an inert solvent, for example an aromatic hydrocarbon, e.g. toluene or one of the xylene isomers, a nitrile, e.g. acetonitrile, or an amide, e.g. DMF or NMP (see also Example P4), to form the compound of formula IW,
  • a suitable base for example an alkali metal hydroxide or hydride, e.g. sodium hydroxide or sodium hydride, or an alcoholate, e.g. sodium ethanolate or potassium tert-butanolate, in an
  • R 1 ; R 2 , R 3 , R , Ru, R ⁇ 2 , R ⁇ 3 , Xi and X 2 are as defined, and
  • R 1 ( R 2 , R 3 , R , Rn, R 12 and X! are as defined for formula I and R ⁇ 3 is hydrogen, in the presence of a base, for example an alkali metal carbonate, e.g. potassium carbonate or sodium hydrogen carbonate, using an alkylating reagent of formula IX wherein R 13 is as defined for formula I with the exception of R ⁇ 3 as hydrogen and amino, and L, is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy, to form the compound of formula IW 1a wherein Ri, R 2 , R 3 , R , Rn, R ⁇ 2 , R ⁇ 3 and Xi are as defined, (Reaction Scheme 1 ), or ac) alkylation of compounds of formula IW ⁇
  • Ri, R 3 , R 4 , Rn, R 12 , R 13 , Xi and X 2 are as defined for formula I with the exception of R 13 as amino, and R 2 is hydrogen, in the presence of a base, for example an alkali metal carbonate, especially potassium carbonate, and a catalyst, for example 18-crown-6 or potassium iodide, using an alkylating reagent of formula IV
  • Ri, R 2 , R 3 , R , Rn, R ⁇ 2 , R ⁇ 3 , Xi and X 2 are as defined (Reaction Scheme 1), with the proviso that, when X 2 in the compound of formula IW 1 is sulfur, R ⁇ 3 must be other than hydrogen (S-alkylation), or ad) amination of compounds of formula IW 1 wherein R ⁇ R 2 , R 3 , R 4 , Rn, R12, Xi and X 2 are as defined for formula I and R 13 is hydrogen, using an electrophilic aminating reagent, for example 1-aminooxy-2,4-dinitrobenzene, in analogous manner to that described, for example, in WO 96/36614, to form the compound of formula
  • R 2 , R 3 , R 4 , R 12 , R ⁇ 3 , Xi and X 2 are as defined for formula I and Ri and/or R are hydrogen, using a halogenating reagent, for example chlorine, bromine or iodine, to form the compound of formula WN,
  • a halogenating reagent for example chlorine, bromine or iodine
  • R 2 , R3, R 4 , R12, R13, Xi and X 2 are as defined and Ri and/or Rn are halogen
  • R 2 , R 3 and R 4 are as defined for formula I
  • Ri is hydrogen
  • A is, for example, a group -NHC(X 2 )R 5 or -NHC(X 2 )X 0 R 5 , wherein X 2 is oxygen or sulfur, X 0 is oxygen, sulfur or amino, and R 5 is d-C 6 alkyl or phenyl, to form the compound of formula IW 1 wherein R 2 , R 3 , R , ⁇ 2 , R13, Xi and X 2 are as defined and Ri and/or R are fluorine, or to form the compound of formula II wherein R 2 , R 3 , R 4 and A are as defined and Ri is fluorine (Reaction Scheme 1 ).
  • the fluorination may advantageously be carried out in an organic solvent, for example a cyclic ether, e.g. tetrahydrofuran, in the presence of an auxiliary base, for example tetramethylethylenediamine, and a further polar, aprotic solvent.
  • an organic solvent for example a cyclic ether, e.g. tetrahydrofuran
  • an auxiliary base for example tetramethylethylenediamine
  • a further polar, aprotic solvent for example a further polar, aprotic solvent.
  • R ⁇ , R 15 and X 3 are as defined for formula I and Ri 6 is hydrogen, d-C 3 alkyl, d- C 3 haloalkyl, halogen, d-C 3 alkoxy, C ⁇ -C 3 haloalkoxy, mercapto, d-C 3 alkylthio, Ci- C 3 alkylsulfinyl, C ⁇ -C 3 alkylsulfonyl, allylthio, propargylthio, amino, d-C 3 alkylamino, di(d- C 3 alkyl)amino, allylamino, propargylamino or cyano, treating a compound of formula IWi
  • R , R 2 , R 3 , R l Rn, R ⁇ 2 , Xi and X 2 are as defined for formula I and R 13 is hydrogen, either, according to route f) in Reaction Scheme 2, with an alkylating reagent, for example R 13 -L of formula IX, wherein R ⁇ 3 is d-C 3 alkyl, CrC 3 haloalkyl, allyl or propargyl, and Li is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy, or with a dialkyl sulfate of formula (R 2 O) 2 SO 2 , wherein R 2 is as defined for formula I with the exception of R 2 as hydrogen, or with a Meerwein's salt (R 3 O»BF 4 ), wherein R is preferably methyl or ethyl, or a freonising reagent, for example CHF 2 CI or BrCH 2 F
  • Ri, R 2 , R 3 and R 4 are as defined, Ru, R i5 and X 3 are as defined for Rn, R i2 and Xi, respectively, and R 6 is halogen, especially chlorine, and then converting that compound via a nucleophilic substitution reaction, for example with a d-C 3 alcoholate, a d-C 3 alkylthiolate or an alkali metal cyanide, into the compound of formula IW 2
  • R 1 t R 2 , R 3 , R 4 , R , R ⁇ 5 and X 3 are as defined and R ⁇ 6 is C ⁇ -C 3 alkoxy, C ⁇ -C 3 alkylthio or cyano, or, when X 2 in the compound of formula IW ⁇ is oxygen, first of all converting that compound, according to route e) in Reaction Scheme 2, using a thionating reagent, for example phosphorus pentasulfide (P 2 S 5 ), into the compound of formula IW ig
  • a thionating reagent for example phosphorus pentasulfide (P 2 S 5 )
  • Ri, R ) R 3 , R 4 , Rn, R ⁇ 2 and Xi are as defined, and then treating that compound with an alkylating reagent of formula wherein R 3 is C r C 3 alkyl, C ⁇ -C 3 haloalkyl, allyl or propargyl, and Li is a leaving group, for example halogen, especially chlorine, bromine or iodine, or sulfonate, especially mesyloxy or tosyloxy, for example a d-C 3 alkyl halide, especially methyl iodide, or C ⁇ -C 3 alkyl sulfate, especially dimethyl sulfate, and optionally of formula IV R 2 -L 2 (IV), wherein R 2 is as defined for formula I with the exception of R 2 as hydrogen, and L 2 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or sulfonate, especially mesyloxy or tosyl
  • R 1 f R 2 , R 3 and R 4 are as defined hereinbefore, X 0 is oxygen, sulfur or amino, and R 5 is C -C 4 alkyl or phenyl, with an enamine derivative of formula Vila
  • Rn, R ⁇ 2 and Xi are as defined and R 6 is C ⁇ -C 4 alkyl, or, according to route kb) in Reaction Scheme 2, reacting a compound of formula llc 6
  • R 1 p R 2 , R 3 and R 4 are as defined and R ⁇ 6 is C ⁇ -C 3 alkyl or C ⁇ -C 3 haloalkyl, with an enamine derivative of formula Vila
  • the process according to the invention for the preparation of compounds of formula I according to variant b) and Reaction Scheme 1 b) comprises, for the preparation of those compounds of formula I wherein R 1 f R , R 3 and R are as defined for formula I and W is a group W 3
  • R ⁇ 7 , R ⁇ 8 , R 19 and X 5 are as defined for formula I, first of all converting a compound of formula Ha
  • Ri, R 2 , R 3 and R are as defined for formula I, under standard diazotisation conditions, e.g. using HNO 3 /H 2 SO 4 , and with reduction of the diazonium salt, as described, for example, in 'Methoden der Organischen Chemie (Houben-Weyl)', volume X/2 (Stickstoffijn Chemie), Georg Thieme Verlag, Stuttgart, 1967, pages 180 ff., into the hydrazine derivative of formula He
  • R ⁇ 7 and R ⁇ 8 are as defined for formula I and Hal is halogen, especially chlorine or bromine, to form the hydrazone derivative of formula llf the substituents Ri, R , R 3 , R 4 , R ⁇ and R ⁇ 8 in the compounds of formulae lie and llf being defined as indicated, and then condensing and cyclising (as illustrated in Reaction Scheme 3) the compound of formula llf with the Wittig reagent of formula VIII
  • R 19 and X 5 are as defined for formula I and R 8 is C ⁇ -C 4 alkyl, in the presence of from 0.01 to 1.5 equivalents of a suitable base, for example an alkali metal hydride or alcoholate, e.g. sodium hydride or potassium tert-butanolate, in an inert solvent, for example an ether, e.g. THF, an aromatic hydrocarbon, e.g. toluene or one of the xylene isomers, or an amide, e.g. NMP, to form the compound of formula IW 3
  • a suitable base for example an alkali metal hydride or alcoholate, e.g. sodium hydride or potassium tert-butanolate
  • an inert solvent for example an ether, e.g. THF, an aromatic hydrocarbon, e.g. toluene or one of the xylene isomers, or an amide, e.g. NMP, to form the compound of formula IW
  • R 1 R 2 , R 3 and R 4 are as defined for formula I and W is a group W 4
  • R 20 , R 2 ⁇ , R 22 and X 7 are as defined for formula I, reacting a compound of formula wherein Ri, R 2 , R 3 , R and X 7 are as defined for formula I, X 0 is oxygen, sulfur or amino, and R 5 is d-dalkyl, with an amino acid ester of formula XIII
  • R 20 , R 21 , R 22 and X 6 are as defined for formula I and R 9 is C ⁇ -C 4 alkyl, to form the compound of formula lig
  • the compound of formula IW 4 wherein R 22 is hydrogen and X 7 is oxygen can, in analogous manner to that described under ac), be further reacted with an alkylating reagent of formula X wherein R 22 is d-C 3 alkyl and L 5 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy, in the presence of a suitable base, for example a trialkylamine or an alkali metal carbonate, to form the compound of formula IW 4 wherein R 22 is d-C 3 alkyl.
  • a suitable base for example a trialkylamine or an alkali metal carbonate
  • R 23 , R 24 , X 8 and X 9 are as defined for formula I, either, according to Reaction Scheme 5, reacting a compound of formula llc 2 or lld 2
  • R , R 2 , R 3 , R and X 9 are as defined for formula I, X 0 is oxygen, sulfur or amino, and R 5 is d-C alkyl, with a hydrazide ester of formula XIV
  • R 23 , R 2 and X 8 are as defined for formula I and Rio is C ⁇ -C alkyl, in the presence of a base, for example a trialkylamine, and a suitable solvent, for example a chlorinated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. DMF or NMP, to thereby yield the compound of formula llh wherein R 1 t R 2 , R 3 , R , R ⁇ 0 , R23, R2 , X ⁇ and X 9 are as defined, and then cyclising that compound to form the compound of formula IW 5
  • a base for example a trialkylamine
  • a suitable solvent for example a chlorinated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. DMF or NMP
  • R 40 , R 4 ⁇ , Y 2 and X 15 are as defined for formula I, can be obtained by reaction with phosgene, thiophosgene or a chloroformate of formula Vlb
  • the compounds of formula IW ⁇ 2 can be obtained by reacting compounds of formula lip with phosgene in an aromatic hydrocarbon, e.g. toluene, and preferably in an additional solvent, for example an ether, e.g. tetrahydrofuran, and in the presence of a base as acid-binding agent, at temperatures of from 5° to 20°C.
  • an aromatic hydrocarbon e.g. toluene
  • an additional solvent for example an ether, e.g. tetrahydrofuran, and in the presence of a base as acid-binding agent, at temperatures of from 5° to 20°C.
  • the compound of formula IW 5 may, optionally, be further functionalised according to the definitions of Ri, R 2 , R 23 , R 24 , X 8 and X 9 in analogous manner to that described under aa), ac) or ae).
  • the compound of formula IW 5 wherein R 23 and/or R 24 are hydrogen can be further reacted, in analogous manner to that described under ac), with an alkylating reagent of formula XVa and/or XVb
  • R 23 and R 24 are C ⁇ -C 3 alkyl or d-C 3 haloalkyl.
  • the compound of formula IW 5 wherein R 2 is hydrogen, and R 23 and R 24 are other than hydrogen can be alkylated, in the presence of a base, for example an alkali metal carbonate, e.g. potassium carbonate, as acid-binding agent, with the reagent of formula IV
  • halogen e.g. chlorine, bromine or iodine
  • sulfonate e.g. mesyloxy or tosyloxy.
  • the compound of formula IW 12 may be further functionalised (R 1 f R 2 , R 23 , R 24 or R 40 and R ⁇ , and X 15 ) in Reaction Scheme 5a according to the standard methods described under aa), ac) and ae). That possibility is also illustrated in Reaction Schemes 5 and 5a.
  • WO 00/15633 describes general processes according to variant b) above, according to which processes it is also possible to prepare the compounds of formula I wherein W is a group W,, W 2 , W 3 , W 4 , W 5 , W 6 , W 7 , W 8 , W 9 , W 10 , Wn, W 13 , W ⁇ 5 , W, 9 or W 20 .
  • R f R 2 , R 3 and R 4 are as defined for formula I and W is a group W 6
  • R 25 , R 26 and X 4 are as defined for formula I, first of all converting a compound of formula Ha
  • R 1 f R 2 , R 3 and R 4 are as defined for formula I, under diazotisation conditions and with reduction of the diazonium salt, as described, for example, in 'Methoden der Organischen Chemie (Houben-Weyl)', volume X/2 (Stickstofftagenen), Georg Thieme Verlag, Stuttgart, 1967, pages 180 ff., into the hydrazine derivative of formula He
  • R 25 , R 2 ⁇ and X 4 are as defined, U is oxygen, sulfur or imino, and R 84 is d-C 4 alkyl, optionally in the presence of a base, for example an alcoholate, e.g. sodium ethanolate or potassium tert-butanolate, or an amine, e.g. triethylamine or pyridine, or a carbonate, e.g. potassium carbonate, in a suitable solvent, for example an alcohol, e.g. ethanol, an amide, e.g. DMF or NMP, or pyridine, at temperatures from 20° to the boiling point of the solvent used, to yield the hydrazone derivative of formula llj
  • a base for example an alcoholate, e.g. sodium ethanolate or potassium tert-butanolate, or an amine, e.g. triethylamine or pyridine, or a carbonate, e.g. potassium carbonate
  • a suitable solvent for example an alcohol
  • R 2 s is as defined, with acid catalysis, for example using an C ⁇ -C 4 alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. hydrochloric or sulfuric acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, to yield the hydrazone derivative of formula llw
  • acid catalysis for example using an C ⁇ -C 4 alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. hydrochloric or sulfuric acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, to yield the hydrazone derivative of formula llw
  • a solvent for example a halogenated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. NMP, under basic conditions, for example in the presence of an alkali metal hydroxide or alcoholate, e.g. potassium hydroxide or potassium tert-butanolate, with an azide of formula XXXIX
  • R 6 oO 2 P(O)N 3 (XXXIX), wherein R ⁇ o is d-dalkyl, to form the compound of formula IW ⁇ a wherein Ri, R 2 , R 3 , R and R 25 are as defined and R 26 is hydrogen, and then optionally converting into the compounds of formula IW 6 using the reagent of formula Xa wherein R 26 is d-C alkyl or C C 4 haloalkyl, e.g.
  • L 5 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy, in an inert organic solvent, for example a nitrile, e.g. acetonitrile, an amide, e.g. DMF or NMP, a chlorinated hydrocarbon, e.g. chloroform, an aromatic hydrocarbon, e.g.
  • a nitrile e.g. acetonitrile
  • an amide e.g. DMF or NMP
  • chlorinated hydrocarbon e.g. chloroform
  • aromatic hydrocarbon e.g.
  • phase-transfer catalyst for example a quaternary ammonium salt, e.g. tetrabutylammonium bromide
  • base for example a hydroxide, e.g. an alkali metal hydroxide, or a carbonate, e.g.
  • an alkali metal carbonate or, according to route i) in Reaction Scheme 6, condensing the compound of formula He with a compound of formula Xle wherein R 25 is C C alkyl or C ⁇ -C 4 haloalkyl, and R 02 s is hydrogen, C ⁇ -C 4 alkyl, furyl or phenyl, in a suitable solvent, for example an aromatic hydrocarbon, e.g. one of the xylene isomers, a halogenated hydrocarbon, e.g. chlorobenzene, a ketone, e.g. methyl ethyl ketone, or an amide, e.g. NMP, and optionally with acid catalysis, e.g. using p-toluenesulfonic acid, and at elevated temperatures, advantageously with removal by azeotropic distillation of water of reaction that is formed, to form the hydrazone of formula lle ⁇
  • a suitable solvent for example an aromatic hydrocarbon, e.g
  • R 1 f R 2 , R 3 , R 4 , R 25 and R 025 are as defined, and then reacting that compound with an isocyanate or isothiocyanate of formula Xlf R 26 NCX 4 (Xlf) wherein R 26 is d-dalkyl or C ⁇ -C 4 haloalkyl and X 4 is oxygen or sulfur, or with an alkali metal cyanate or alkali metal thiocyanate of formula Xlei wherein M + is an alkali metal ion and X 4 is as defined (e.g. Na + OCN, K + OCN, or K + SCN), to thereby yield the compound of formula llmi and/or llm 2
  • Ri, R 2 , R 3 , R 4 , R 2 and R 02 5 are as defined.
  • This reaction is advantageously carried out in a suitable solvent, for example a ketone, e.g. acetone, an alcohol, e.g. ethanol, a nitrile, e.g. acetonitrile, an amide, e.g. DMF or NMP, or in water, and optionally with addition of a base, for example an amine, e.g. triethylamine, or pyridine, or an acid, e.g. acetic acid or p-toluenesulfonic acid, at temperatures of from 20° to 180°C.
  • a suitable solvent for example a ketone, e.g. acetone, an alcohol, e.g. ethanol, a nitrile, e.g. acetonitrile, an amide, e.g. DMF or NMP, or in water, and optionally with addition
  • R 1 f R 2 , R 3 , R 4 , R25, R26 and X are as defined.
  • the compounds of formula llnrii and/or llm 2 can first of all be hydrolysed to form the compound of formula llm and then, in the presence of a carboxylic acid of formula Xli or an activated form thereof of formula Xli ⁇ or Xli 2 , with heating, cyclised to form the compounds of formula IW 6 .
  • the reactions with the carboxylic acid of formula Xli are advantageously carried out without isolation of the compounds of formulae llmi and/or llm 2 or of formula llm.
  • the acid of formula Xli can be used in an equimolar amount and also as a solvent, for example acetic or propionic acid.
  • the compounds of formulae llmi and/or llm 2 wherein R 025 is hydrogen can also, according to route I) in Reaction Scheme 6, be converted into the compounds of formula IW 6 in the presence of an oxidising agent, e.g. 2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone (DDQ) or Javelle water, in a suitable solvent, for example a halogenated hydrocarbon, e.g. chlorobenzene, a carboxylic acid, e.g. acetic acid, an amide, e.g. NMP, or water, or a mixture thereof, at temperatures of from 0° to 130°C.
  • an oxidising agent e.g. 2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone (DDQ) or Javelle water
  • a suitable solvent for example a halogenated hydrocarbon, e.g. chlorobenzene, a carboxylic acid
  • Reaction Scheme 6 illustrates those reactions, which are especially suitable for the preparation of compounds of formula IW 6 wherein R 25 is hydrogen, C ⁇ -C alkyl or C dhaloalkyl or wherein R 26 and R 25 together form a C 3 -C 5 alkylene bridge.
  • the compounds of formulae IW 6a and IW 6 wherein R 26 and/or R 2 are hydrogen or R is hydrogen and X is oxygen may optionally be further functionalised, according to the definitions of Ri, R 2 , R 26 and X 4 , as described above under ab) or ac) using an alkylating reagent, for example R 26 -L ⁇ and R 2 -L 2 , or as described above under ae) or aa).
  • Ri, R 2 , R3, R 4 , R26, R50, R ⁇ , X and X19 are as defined, and then, under acid conditions, for example in the presence of acetic acid or propionic acid, and optionally at an elevated temperature of up to 130°C, converting that compound into the compound of formula IW 6 b or IW ⁇ 6b
  • R 3 , R 4 , X 4 , X ⁇ 8 and X i9 are as defined
  • Ri is hydrogen or halogen
  • R 25 is halogen
  • d-dalkoxy or C C alkylthio R 2 , R 26 , R 49 and R 50 are each independently of the others hydrogen or alkyl.
  • the compound of formula IW 6 wherein R 26 is other than hydrogen and X is sulfur can be alkylated with the reagent of formula IV wherein R 2 is as defined for formula I with the exception of R 2 as hydrogen, and L 2 is a leaving group, for example halogen, especially chlorine, bromine or iodine, in the presence of an alkali metal carbonate.
  • R 50 in the compound of formula IW ⁇ 6 is hydrogen
  • Ri, R 2 , R 3 and R 4 are as defined, X 20 is oxygen or sulfur, R 51 is Crdalkyl and R 52 is halogen, d-C 3 alkoxy or C ⁇ -C 3 alkylthio.
  • Reaction Scheme 6a illustrates those reactions.
  • the above reaction sequence is especially suitable for preparing compounds of formula IW 6 wherein R 25 is hydroxy, halogen, d-C alkoxy, C ⁇ -C 4 haloalkoxy, d-C alkylthio, C 1 - dhaloalkylthio, d-dalkylsulfinyl, C ⁇ -C 4 haloalkylsulfinyl, C C alkylsulfonyl, C dhaloalkylsulfonyl or cyano and also for compounds of formulae IW 16 and IW ⁇ 7 wherein R49, R50, R51, R52, X18, X19 and X 2 o are as defined above.
  • R 1 R 2 , R 3 and R 4 are as defined for formula I, in the presence of a d-dalkylcarboxylic acid, for example acetic acid or propionic acid, optionally in an inert solvent, for example a halogenated hydrocarbon, e.g. chlorobenzene, with a compound of formula XXXIII
  • Reaction Scheme 7 illustrates that reaction sequence.
  • the resulting compound of formula IW 7a wherein, for example, Ri and/or R 2 are hydrogen, may be further functionalised according to the definitions of Ri, R 2 , X ⁇ 0 and Xn in accordance with processes described under aa), ac) and ae) to form compounds of formula IW 7 .
  • R 1 t R 2 , R 3 and R 4 are as defined for formula I and W is a group Wn
  • R 36l R 37 , R ⁇ and R 39 are as defined for formula I and X 4 is oxygen (compound of formula IWn a in Reaction Scheme 17), either, according to route o) in Reaction Scheme 17, reacting a compound of formula lld 4
  • R 1 R 2 , R 3 , R 4 , R 38 and R 39 are as defined, and then condensing that compound with a compound of formula XXV wherein 36 and R 37 are as defined, R 6 is d-C 4 alkyl and Ln is hydroxy, CrC 3 alkoxy, chlorine, amino or d-C 3 alkylamino, or, according to route p) in Reaction Scheme 17, first of all reacting a compound of formula IW 2
  • Ri, R 2 , R 3 , R 4 , X 3 , R ⁇ 4 and R 15 are as defined for formula I and R ⁇ 6 is d-dalkylthio, with an oxidising agent, for example hydrogen peroxide, to form the corresponding d- dalkylsulfonyl derivative of formula IW 2 wherein R 16 is d-C 3 alkylsulfonyl, and converting that derivative, by means of aminolysis, for example using gaseous ammonia in ethanol, or using aqueous ammonium hydroxide, or using an amine of formula XXXVIIId or XXXVIIId
  • Ri, R 2 , R 3 , R 4 , X 3 , R ⁇ 4 and R ⁇ 5 are as defined and R ⁇ 6 is amino, CrC 3 alkylamino, di(CrC 3 alkyl)amino, allylamino, diallylamino, propargylamino or dipropargylamino, and then reacting that compound, when R 16 is amino, with an aldehyde derivative of formula XXVIa
  • R ⁇ 26 is Cr or C 2 -alkyl and R ⁇ 27 is hydrogen or C or C 2 -alkyl
  • R 038 and R 39 together form a C or C 2 -alkylene bridge
  • L 2 is a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, or with the reagent of formula XXVIb Li3-R 38 R 39 -L ⁇ 2 (XXVIb), wherein R ⁇ and R 39 together form a C 2 - or C 3 -alkylene bridge
  • L 12 and L i3 are each a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, or with the alkylating agent of formula XXVId
  • R 85 OC(X ⁇ 2 )-CH(R 3 o)-COR 29 (Xlh), wherein R 29 , R 30 and X ⁇ 2 are as defined and R 85 is C C 4 alkyl or phenyl, optionally in an organic acid, for example acetic acid or propionic acid, and a further inert solvent, for example a halogenated hydrocarbon, e.g. chlorobenzene, by heating at from 20° to 200°C to yield the compound of formula IW 8
  • That compound may be further functionalised in accordance with the standard methods aa), ac) and/or ae) described above.
  • R 40 , R 4 ⁇ , X 15 and Y 2 are as defined for formula I, reacting a compound of formula lld 3 or llc 3
  • R 1 f R 2 , R 3 , R 4 and Y 2 are as defined for formula I, R 5 is d-dalkyl and X 0 is oxygen, sulfur or amino, with a compound of formula XXXV
  • X i5 is oxygen or sulfur
  • L 8 and L are leaving groups, for example halogen, e.g. chlorine or bromine (phosgene, thiophosgene), or L 7 may additionally be hydroxy or d- dalkoxy (haloformic acid or an ester thereof).
  • That (thio)phosgenation reaction is carried out at temperatures of from 0° to 80°C, preferably from 5° to 25°C.
  • Reaction Scheme 8 illustrates that reaction sequence.
  • the iso(-thio-)cyanate derivative of formula lld 3 may, in addition, be converted into the compound of formula llc 3 by reaction with a reagent of formula XXXVIII
  • R5X0H (XXXVIII), wherein R 5 is d-dalkyl and X 0 is oxygen, sulfur or amino.
  • R 1f R , R 3 and R 4 are as defined for formula I and W is a group W ⁇ 3
  • R 1 R 2 , R 3 and R 4 are as defined for formula I, under diazotisation conditions, into the diazonium salt of formula llee
  • R R 2 , R 3 and R are as defined and Mr is an anion, for example hydrogen sulfate or tetrafluoroborate, or halide, for example chloride, and then, in accordance with route m) in Reaction Scheme 9, coupling that salt with the reagent of formula XXXVIIa
  • the diazonium salt of formula llee may be coupled with the reagent of formula XXXVIIb
  • the resulting compounds of formula IW ⁇ 3a wherein, for example, R 42 is a carboxyl group may be converted into the compounds of formula IW ⁇ 3 wherein R 42 is hydrogen using standard decarboxylation methods, for example by heating in an aqueous mineral acid, e.g. hydrochloric acid, or in the presence of a carboxylic acid, e.g. oxalic acid or thioglycolic acid, in an organic solvent, for example a halogenated hydrocarbon, e.g. chlorobenzene.
  • an aqueous mineral acid e.g. hydrochloric acid
  • a carboxylic acid e.g. oxalic acid or thioglycolic acid
  • organic solvent for example a halogenated hydrocarbon, e.g. chlorobenzene.
  • the compounds of formula IW ⁇ 3a wherein R 43 and/or R 2 are hydrogen or R, is hydrogen may be further functionalised according to the definitions of R 1 f R 2 , R 43 , X ⁇ 6 and X ⁇ 7 by means of alkylation and/or halogenation, as described under ab) and ac) in the former case and ae) in the latter case, or, when X ⁇ 6 and X ⁇ 7 in the compound of formula IW ⁇ 3 are sulfur, by means of thionation as described under aa).
  • Reaction Scheme 9 illustrates those reaction sequences. Reaction Scheme 9:
  • R 1 t R 2 , R 3 and R 4 are as defined, with a hydrazinecarboxylic acid ester of formula XlVa
  • R 53 and X 2 ⁇ are as defined, R 85 is d-dalkyl and L 14 is a leaving group, for example halogen, e.g. chlorine or bromine, to form the compound of formula llr
  • R 56 and R 57 are as defined for formula I, first of all converting a compound of formula lla wherein Ri, R 2 , R 3 and R 4 are as defined, for example using thiophosgene, into the isothiocyanate of formula lld 4
  • Reaction Scheme 19 illustrates those reactions. Reaction Scheme 19:
  • R 1 ( R 2 , R 3 , R 4 and X 23 are as defined for formula I, X 0 is oxygen, and R 5 is d- C alkyl, with an urea of formula XXXVb
  • R 58 , R 5 and X 25 are as defined for formula I, in the presence of a base, for example a trialkylamine, and a suitable solvent, for example a chlorinated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. DMF or NMP, to thereby yield the compound of formula llt ⁇
  • a base for example a trialkylamine
  • a suitable solvent for example a chlorinated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. DMF or NMP
  • R , R 2 , R 3 , R , R 58 , R 59 , X 23 and X 25 are as defined, and then cyclising that compound in the presence of a carbonyl equivalent like phosgene, diphosgene, ethylchloroformiate (compound of formula Vic), carbonyldiimidazol (CDI), carbonylbistriazol, to form the compound of formula IW 2i or according to Reaction Scheme 21 , reacting a compound of formula llc 7
  • Ri, R 2 , R 3 , R and X 23 are as defined for formula I, X 0 is oxygen, and R is d- C 4 alkyl, firstly in a suitable solvent, for example a chlorinated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. DMF or NMP, with an isocyanate or an isothiocyanate of the formula Xlo
  • a suitable solvent for example a chlorinated hydrocarbon, e.g. chlorobenzene, or an amide, e.g. DMF or NMP, with an isocyanate or an isothiocyanate of the formula Xlo
  • R 1 f R 2 , R 3 , R 4 , R 5 , R59, X 2 3 and X 24 are as defined, X 0 is oxygen, and R 5 is C dalkyl, and then cyclising that compound in the presence of an isocyanate or an isothiocyanate of formula Xlp
  • the compound of formula IW 2 ⁇ may, optionally, be further functionalised according to the definitions of R 1 f R 2 , R 58 , R 59 , X 23 , X 2 and X 25 in analogous manner to that described under aa), ac) or ae).
  • the compound of formula IW 2 ⁇ , wherein R 58 and/or R 59 are hydrogen can be further reacted, in analogous manner to that described under ac), with an alkylating reagent of formula XVc and/or XVd
  • the compound of formula IW 2 ⁇ , wherein R 2 is hydrogen, and R 58 and R 59 are other than hydrogen can be alkylated in the presence of a base, for example an alkali metal carbonate, e.g. potassium carbonate as acid-binding agent, with the reagent of formula IV wherein R 2 is as defined for formula I with the exception of R 2 as hydrogen, and L 2 is a leaving group, for example halogen, e.g. chlorine, bromine or iodine, or sulfonate, e.g. mesyloxy or tosyloxy.
  • a base for example an alkali metal carbonate, e.g. potassium carbonate as acid-binding agent
  • L 2 is a leaving group, for example halogen, e.g. chlorine, bromine or iodine, or sulfonate, e.g. mesyloxy or tosyloxy.
  • Ri, R 2 , R 3 and R 4 are as defined for formula I and W is a group Wi to W 21 (C-N- linked ring systems), reacting a compound of formula lib wherein Ri, R 2 , R 3 and R 4 are as defined and Ai is a leaving group, for example halogen, especially fluorine, chlorine or bromine, sulfonyl, especially methylsulfonyl, sulfonate, especially trifluoromethylsulfonyloxy, methylsulfonyloxy or phenylsulfonyloxy, or nitro, with an N-heterocyclic compound of formula III
  • W is a group Wi to W 21 , in the presence of a base, for example a trialkylamine, especially triethylamine, a carbonate, especially sodium and potassium carbonate, or also caesium fluoride, in the presence of one or more suitable catalysts, for example metal catalysts, especially palladium catalysts, e.g.
  • Rgo is hydrogen, a sodium, potassium or magnesium cation, trimethylsilyl or d- dalkyl
  • R 9 ⁇ is d-C 4 alkyl
  • R100 is as defined for formula I, in the presence of a suitable base, for example an alkylamine, e.g. triethylamine, and an inert solvent, for example an amide, e.g. DMF, and subsequent hydrolysis to form the keto ester of formula llx
  • tetrahydrofuran or dioxane or water, or in a two-phase system containing water and a chlorinated hydrocarbon at temperatures of from -10° to 110°C or advantageously in a closed system under slight overpressure and, when Rioo is hydrogen, optionally to a halogenation reaction, for example using halogen, e.g. chlorine or bromine, or using sulfuryl halide, e.g. sulfuryl chloride, to thereby yield the compound of formula IW 100a
  • halogen e.g. chlorine or bromine
  • sulfuryl halide e.g. sulfuryl chloride
  • Compounds of formula IW ooa wherein R 2 is hydrogen may, for example, be alkylated, according to process variant ac), using an appropriate alkylating reagent of formula IV wherein R 2 is as defined for formula I with the exception of R 2 as hydrogen, and L 2 is a leaving group; or compounds of formula IWioo a wherein R ⁇ is hydrogen may, for example, be halogenated according to process variant ae), using a suitable halogenating reagent.
  • the halogenation reaction can advantageously be carried out 'in situ', following on from the freonisation reaction.
  • Chlorination is carried out, for example, by passing an equimolar amount or slight excess of chlorine gas into a suitable solvent system, for example a carboxylic acid, e.g. acetic acid, in the presence of a weak base, for example sodium acetate, at temperatures of from 5° to 70°C.
  • a suitable solvent system for example a carboxylic acid, e.g. acetic acid
  • a weak base for example sodium acetate
  • keto ester of formula llx is reacted with hydrazine (compound of formula XLI wherein R 102 is hydrogen) there is formed the pyrazolone derivative of formula IWiooz wherein R 102 is hydrogen, which, on subsequent alkylation using the reagent of formula XVI wherein R 102 is as defined for formula I with the exception of R i0 2 as hydrogen, and L 10 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or sulfonate, especially mesyloxy or tosyloxy, in addition to the compound of formula IWiooz, wherein R 102 is as defined, also yields the isomeric pyrazolone derivative of formula IW ⁇ 0 ⁇ z
  • Reaction Scheme 12 That compound may optionally be further functionalised according to the definitions of Ri, R 2 , R100 and R ⁇ 02 for formula I by means of standard methods. Reaction Scheme 12:
  • R R 2 , R 3 and R are as defined and A 3 either is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially trifluoromethylsulfonyloxy, or is a trialkylstannyl or boronic acid group, with a corresponding heterocyclic compound of formula V
  • W is as defined for formula I and B, complementarily to A 3 in the compound of formula llv, either is a trialkylstannyl or boronic acid group or is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially trifluoromethylsulfonyloxy, in the presence of a metal catalyst from the noble metals group that is suitable for C-N or C- C linkages for example palladium, in the presence of a suitable activation ligand, for example triphenylphosphine or 2-(di-tert-butyl)diphenylphosphine, in the presence of a copper salt, for example copper iodide, in the presence of a suitable base, for example a trialkylamine, especially triethylamine, or a carbonate, especially sodium or potassium carbonate, and in a suitable solvent, for example N-methylpyrrolidone (NMP) or N,N- dimethylform
  • NMP N-methyl
  • Ri and W are as defined for formula I, but W is especially a group W 100 (compound of formula XIW 100 in Reaction Scheme 22), in the presence of a base, for example a carbonate, especially sodium or potassium carbonate, and an inert organic solvent, for example N-methylpyrrolidone, at temperatures of from -20° to 250°C and normal pressure or under slight overpressure, but preferably at the boiling point of the solvent in question, with a compound of formula XII
  • R 2 , R 3 and R 4 are as defined for formula I, and L 9 is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially mesyloxy, tosyloxy or trifluoromethanesulfonyloxy, to yield the compound of formula XW
  • reaction sequence consisting of nucleophilic substitution, subsequent rearrangement and ring-closure reaction may proceed in the same reaction vessel, as a so-called One-pot reaction', as illustrated in Reaction Scheme 22.
  • Reaction Scheme 22
  • R 2 is especially hydrogen
  • W is especially a group W 14 or W 100 -W ⁇ 0 9
  • a 0 is especially hydrogen, methyl, ethyl, fluorine, chlorine, bromine or carboxy, condensing a compound of formula XXIX
  • Ri and W are as defined, with an acetic acid derivative of formula XXXII (XXXII) , wherein R 3 and R are as defined, Zi is a C C 4 alkoxy group or a leaving group, for example chlorine or bromine, and Z 2 is a leaving group, for example chlorine or bromine, or a sulfonate, for example mesyloxy or tosyloxy, in the presence of a suitable base, for example an alkali metal carbonate, e.g. potassium carbonate, an alcoholate, e.g. sodium methanolate or potassium tert-butanolate, a hydride, e.g. sodium hydride, or a hydroxide, e.g.
  • a suitable base for example an alkali metal carbonate, e.g. potassium carbonate, an alcoholate, e.g. sodium methanolate or potassium tert-butanolate, a hydride, e.g. sodium hydride, or
  • a suitable solvent for example an alcohol, e.g. methanol, ethanol or methyl Cellosolve, an ether, e.g. tetrahydrofuran, diethoxymethane or dioxane, an aromatic hydrocarbon, e.g. toluene, a nitrile, e.g. acetonitrile, an amide, e.g. DMF or NMP, a sulfoxide, e.g. dimethyl sulfoxide, or water.
  • a suitable solvent for example an alcohol, e.g. methanol, ethanol or methyl Cellosolve, an ether, e.g. tetrahydrofuran, diethoxymethane or dioxane, an aromatic hydrocarbon, e.g. toluene, a nitrile, e.g. acetonitrile, an amide, e.g. DMF or NMP, a sulfoxide, e
  • the process according to the invention for the preparation of compounds of formula I comprises, in accordance with variant a), reacting compounds of formula la, wherein R 1 f R 3 , R 4 and W are as defined for formula I, with an appropriate alkylating reagent of formula IV
  • R 2 is as defined for formula I with the exception of R 2 as hydrogen, and L 2 is a leaving group, in the presence of a base and a suitable solvent, as illustrated in Reaction Scheme 1a 0 : Reaction Scheme 1a n :
  • B-W (V) wherein W is as defined above for W t to W i0 or W 10 o to W ⁇ 08 , and B, complementarily to A 3 , either is a trialkylstannyl or boronic acid group, or is a leaving group, for example chlorine, bromine or trifluoromethylsulfonyloxy, in the presence of a metal catalyst from the noble metals group that is suitable for C-N or C-C linkages, for example palladium, in the presence of a suitable activation ligand, for example triphenylphosphine or 2-(di-tert- butyl)diphenylphosphine, in the presence of a copper salt, for example copper iodide, and in the presence of a suitable base, for example potassium carbonate or triethylamine, in a suitable inert solvent, for example N-methylpyrrolidone or dimethylformamide, according to
  • Rn, R ⁇ 2 and R ⁇ 3 are as defined for formula I and R 6 is d-C alkyl, in the presence of from 0.1 to 1.5 equivalents of a suitable base in an inert solvent to form the group Wi and then, optionally, in an additional standard conversion reaction, either
  • Ri and/or Rn are chlorine, bromine or iodine, treatment with a corresponding halogenating reagent is carried out.
  • R ⁇ 9 is as defined for formula I and R 8 is C C 4 alkyl, in the presence of from 0.1 to 1.5 equivalents of a suitable base in an inert solvent to form the cyclic group W 3 , and then, optionally, further reacting in an additional conversion reaction according to the corresponding meanings of Ri, R 2 , R ⁇ 8 and X 5 in analogous manner to that described under aa), ac) or ae).
  • Reaction Scheme 3 0 illustrates that reaction sequence.
  • Reaction Scheme 5 0 illustrates that reaction sequence.
  • suitable catalysts are especially metal catalysts, for example Pd(PPh 3 ) 4 , Pd(PPh 3 )CI 2 , Pd(OAc) 2 and copper iodide.
  • metal catalysts for example Pd(PPh 3 ) 4 , Pd(PPh 3 )CI 2 , Pd(OAc) 2 and copper iodide.
  • suitable catalytic additives include various phosphine ligands, for example biphenyl-2-bis-tert-butylphosphine, and various bases, for example triethylamine, potassium carbonate and caesium fluoride.
  • the compounds of formula IWiooa wherein Ri and/or R 2 are hydrogen may be further reacted, according to process variant a), with an appropriate alkylating reagent of formula IV R 2 -L 2 (IV) or, as described under ae), with a corresponding halogenating reagent. If the halogenation reaction is performed in the presence of an excess of halogenating reagent, there are formed, from compounds of formula IWiooz wherein Ri is hydrogen, compounds of formula IWiooa wherein both Ri and R 100 are accordingly simultaneously chlorine or bromine.
  • Compounds of formula IW 100 may also be prepared according to process variant f) described above by reacting a compound of formula XIW 100 , wherein Ri and W are as defined for formula I, with a corresponding acetamide of formula XII
  • R 2 , R 3 and R 4 are as defined for formula I and L 9 is a leaving group, for example chlorine, bromine, mesyloxy, tosyloxy or trifluoromethylsulfonyloxy, in the presence of a base and an inert solvent, for example N-methylpyrrolidone (NMP), at temperatures of from 20° to 250°C and at normal pressure or under slight overpressure, but preferably at the boiling point of the solvent in question.
  • NMP N-methylpyrrolidone
  • the resulting compounds of formula I and salts thereof can be isolated in customary manner by concentrating or evaporating off the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, for example ethers or aromatic or chlorinated hydrocarbons.
  • solvents in which they are not readily soluble, for example ethers or aromatic or chlorinated hydrocarbons.
  • the person skilled in the art will be familiar with the sequence in which certain reactions among the process variants described should be advantageously performed in order to avoid possible undesired competing reactions.
  • the product may be in the form of a mixture of two or more isomers.
  • the isomers can be separated according to methods known perse. If desired, pure optically active isomers can, for example, also be prepared by synthesis starting from corresponding optically active starting materials.
  • the 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-ones of formula Ha used as starting compounds can be prepared by reducing 6-nitro-4H-pyrido[3,2-b][1 ,4]oxazin-3- one of formula lln, wherein Ri, R 2 , R 3 and R 4 are as defined for formula I, under known reaction conditions, for example using iron trichloride (Fe(IH)CI 3 ) in acetic acid according to Bechamps or in the presence of hydrogen and a metal catalyst, for example Raney nickel or palladium on activated carbon, in an inert diluent, for example an ether, especially tetrahydrofuran or dioxane, an alcohol, especially ethanol, an amide, especially N,N- dimethylformamide (DMF) or N-methylpyrrolidone (NMP) or water, as illustrated in Reaction Scheme 13.
  • Fe(IH)CI 3 iron trichloride
  • Ri to R 4 are as defined for formula I, under standard conditions, for example using HNO 3 H 2 SO , as illustrated in Reaction Scheme 14, and then further functionalised according to the definitions of R and R 2 for formula I in accordance with standard processes, for example alkylation and halogenation as described under ac) and ae).
  • the aromatic nitration proceeds selectively in the 6-position of the 4-H-pyrido[1 ,4]oxazinone ring independently of the substituent Ri (cf., in that respect, the analogous halogenation reaction, which, in contrast, takes place predominantly in the 7-position, e.g. US-A-3 854 926 and WO 88/08705).
  • XXXII wherein R 3 and R 4 are as defined for formula I, Zi is a C C alkoxy group, especially methoxy or ethoxy, or halogen, especially chlorine or bromine, and Z 2 is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially methylsulfonyloxy or phenylsulfonyloxy, in the presence of a suitable base, for example a carbonate, e.g. sodium or potassium carbonate, an alkali metal hydroxide, e.g. sodium or potassium hydroxide, or an alkali or alkaline earth metal hydride, e.g.
  • a suitable base for example a carbonate, e.g. sodium or potassium carbonate, an alkali metal hydroxide, e.g. sodium or potassium hydroxide, or an alkali or alkaline earth metal hydride, e.g.
  • Ri to R 4 are as defined for formula I and Ai is halogen, d-dalkylthio, C C alkyl- sulfonyl, CrC alkylsulfonyloxy, hydroxy or trifluoromethylsulfonyloxy, used for process variant c) above can be prepared, for example, from compounds of formula Ha
  • 6, 6a and 10 can be obtained either by means of diazotisation of compounds of formula Ha, for example using sodium nitrite in hydrochloric acid or sulfuric acid, and reduction, for example using sodium sulfite or tin(ll) chloride (SnCI 2 ), of the resulting diazonium salts of formula llee
  • Ri to R 4 are as defined and Ai is fluorine, chlorine, bromine or nitro, using hydrazine in water, ethanol or NMP, or in a mixture of those solvents, at temperatures of from 10° to 100°C, according to Reaction Scheme 15b.
  • Reaction Scheme 15b Reaction Scheme 15b:
  • Ri to R 4 are as defined for formula I and R 89 is hydrogen or d-dalkyl, can be prepared either ba) by means of oxidation, using potassium permanganate, nitric acid or oxygen in the presence of a suitable metal catalyst, for example V 2 O 5 , Na 2 WO 4 , Co(OAc) 3 or K 2 Cr 2 O 3 , starting from compounds of formula llu
  • Ri to R 4 are as defined and A 2 is methyl (Reaction Scheme 16a), or bb) by means of hydrolysis of compounds of formula llu wherein Ri to R 4 are as defined and A 2 is cyano, or be) by means of carbonylation of compounds of formula lib wherein Ri to R are as defined and Ai is chlorine or bromine, or bd) by means of 1 ) diazotisation of the amines of formula Ha and 2) subsequent carbonylation of the diazonium salts of formula llee obtained.
  • the cyano compounds of formula llu used in process bb) can be obtained by means of diazotisation and a Sandmeyer reaction with addition of copper cyanide (Cu(l)CN).
  • Reaction Schemes 16a and 16b illustrate those conversions in diagrammatic form. Reaction Scheme 16a:
  • ba oxidation: e.g. KMn0 4 or Oo/cat.
  • R 1 t R 2 , R 3 and R 4 are as defined for formula I and A 2 is formyl or acyl, used in process variant d) can, for example, be prepared by standard methods, starting from compounds of formula llu wherein Ri to R 4 are as defined and A 2 is cyano, by means of reduction of the cyano group, for example using dibutylaluminium hydride (DIBAH), or starting from compounds of formula llu 2
  • DIBAH dibutylaluminium hydride
  • Ri to R 4 are as defined, by means of a Grignard reaction using methylmagnesium chloride, or using the reagent O,N-dimethyl acetamide.
  • R16, Ri7, Ri ⁇ , R20, R21 , R22, R23, R2 4 , R25, R26, R27, R2 ⁇ , Rs ⁇ i R39, R 4 o, R411 R42, R43, R50, R53, R56 and R 57 are as defined in claim 1 ;
  • R 5 , R 9 , R025, R 84 , R 8 6, R ⁇ 9, R90 and R91 are each independently of the others d-dalkyl or phenyl;
  • R 10 and R 85 are hydrogen or d-dalkyl;
  • R 87 and R 88 are d-C 4 alkyl, formyl, CH(d-C 4 alkoxy) or d-C 4 haloalkyl;
  • X 2 , X 3 , X 4 , X 6 , X 7 , X 8 , X 9 , X ⁇ 2 , X 19 , X 2 ⁇ and Y 2 are oxygen or sulfur
  • the compounds of formula XXVIII wherein, for example, A 0 is methyl or carboxy are known from CH-A-452 528 and J. Heterocyclic Chem. 13, 1103 (1976) or can be prepared analogously to the processes described therein.
  • the compounds of formula XXXI are either known, for example, where Ri is hydrogen, from Acta Chimica Scandinavica, 23, 1785 (1969) and, where Ri is chlorine or bromine, from Helv. Chim. Acta 60, 2062 (1977), or can be prepared analogously to the processes described therein.
  • the compounds of formula I can be used as herbicides in unmodified form, that is to say as they are obtained in synthesis, but they are preferably formulated in customary manner, together with the adjuvants conventionally employed in formulation technology, for example into emulsif iable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, in WO 97/34485 on pages 9 to 13.
  • 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 of formula I or at least one compound of formula I and, generally, one or more solid or liquid formulation adjuvants
  • formulation adjuvants for example solvents or solid carriers.
  • surface-active compounds surfactants
  • solvents and solid carriers are given, for example, in WO 97/34485 on page 6.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8.
  • the herbicidal formulations generally comprise 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 solid or liquid formulation adjuvant especially from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • compositions may also comprise further ingredients such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients.
  • the compounds of formula I or a composition comprising that compound are generally applied to the plant or to 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 in cereals, cotton, soybeans, sugar beet, sugar cane, sorghum, plantation crops, rape, maize, sunflowers, vegetables, fodder plants and rice, and also for inhibiting plant growth and for non-selective weed control.
  • Crops are 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 monocotyledonous or dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Brachiaria, Euphorbia, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus,
  • Example P1 156 g (0.8 mol) of the product obtained in Example P1 are dissolved in 2 litres of dimethylformamide and hydrogenated in the presence of 16 g of Raney nickel at 35-45°C until 53.8 litres of hydrogen have been absorbed. The mixture is then separated from the catalyst by filtration and diluted with water. Pure 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of 279-281 °C is thereby obtained.
  • Example P3 (3-Oxo-3.4-dihydro-2H-pyridof3.2-bl.1.41oxazin-6-yl)-carbamic acid ethyl ester 1.45 g (8.8 mmol) of 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-one are dissolved in 60 ml of pyridine and treated with 0.96 g (8.8 mmol) of chloroformic acid ethyl ester at 45°C. Stirring is then carried out for about 3 hours at that temperature, the precipitated pyridine hydrochloride is filtered off and the mixture is concentrated a little by evaporation.
  • Example P4 3-(3-Oxo-3.4-dihvdro-2H-pyrido.3.2-biri .4loxazin-6-yl)-6-trifluoromethyl-1 H- pyrimidine-2.4-dione
  • Example P5 1-Methyl-3-(4-methyl-3-oxo-3.4-dihvdro-2H-pyridof3.2-bi ⁇ .41oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2.4-dione
  • Example P6 1 -Methyl-3-.3-oxo-3.4-dihvdro-2H-pyridof3.2-biri .41oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2.4-dione
  • Example P7 1-Methyl-3-(3-oxo-4-prop-2-vnyl-3.4-dihvdro-2H-pyridor3.2-bl.1.41oxazin-6-yl)- 6-trifluoromethyl-1 H-pyrimidine-2.4-dione
  • Example P8 3-(4-lsopropyl-3-oxo-3.4-dihydro-2H-pyrido[3,2-b1[1 ,41oxazin-6-yl)-1-methyl-6- trifluoromethyl-1 H-pyrimidine-2.4-dione
  • Example P10 3-Oxo-3.4-dihydro-2H-pyrido[3.2-bl[1.41oxazine-6-carboxylic acid 3.66 g (84 mmol) of sodium hydride in the form of a 55 % dispersion in oil are introduced into 30 ml of dimethylformamide; then, 6.2 g of (40 mmol) of 2-amino-3-hydroxypyridin-6-yl- carboxylic acid (known from J. Heterocyd. Chem. 13, 1103 (1976)) are introduced, in portions, below 10°C and stirring is then carried out for 2 hours at 45°C until the evolution of hydrogen has ceased.
  • 2-amino-3-hydroxypyridin-6-yl- carboxylic acid known from J. Heterocyd. Chem. 13, 1103 (1976)
  • Example P11 3-.2-Methyl-3-oxo-3.4-dihvdro-2H-pyrido.3.2-biri .41oxazin-6-yl)-3-oxo- propionic acid ethyl ester
  • Example P11 0.82 g (2.9 mmol) of the product prepared in Example P11 is dissolved in 5 ml of acetic acid, and 0.19 ml (3.5 mmol) of methylhydrazine is added. Heating at 80°C is carried out for
  • Example P13 (0.22 mmol) of the product prepared in Example P13 is treated, dropwise, at 60°C, with a solution of 0.015 g (0.22 mmol) of chlorine gas in acetic acid. After the reaction has terminated, the mixture is concentrated by evaporation and purified by chromatography on silica gel. The desired 6-(4-chloro-5-difluoromethoxy-1 -methyl-1 H-pyrazol-3-yl)-2-methyl-4H- pyrido[3,2-b][1 ,4]oxazin-3-one is thereby obtained.
  • Example P16 6-Amino-4-prop-2-vnyl-4H-pyrido.3,2-b]f 1 ,4loxazin-3-one 4.95 g (30 mmol) of 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-one (Example P2) and 3.75 g (31 mmol) of propargyl bromide are heated at boiling point in 30 ml of acetonitrile in the presence of 4.15 g (30 mmol) of potassium carbonate and a catalytic amount of 18-crown-6 for 5 hours.
  • Example P17 6-lsocvanato-4-prop-2-vnyl-4H-pyrido.3.2-b]f1 ,4loxazin-3-one 3.5 g (17.2 mmol) of the above product from Example P16 are dissolved in 40 ml of ethyl acetate and treated with 1.87 g (9.5 mmol) of diphosgene. After the slightly exothermic reaction has subsided, the mixture is heated at 60°C for 2 hours, a clear solution being obtained.
  • the reaction mixture is concentrated by evaporation and the crude 6-isocyanato- 4-prop-2-ynyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one in the form of amorphous crystals is used directly for subsequent reactions (e.g. in Example P18).
  • a sample of the reaction mixture is stirred in methanol in the presence of a small amount of triethylamine.
  • the precipitated product is (3-oxo- 3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-carbamic acid methyl ester.
  • Example P18 7- ⁇ R.S>-Hvdroxy-2-(3-oxo-4-prop-2-vnyl-3.4-dihvdro-2H-pyrido.3.2- bi ⁇ .41oxazin-6-yl)-tetrahvdro-imidazo.1.5-alpyridine-1 ,3-dione
  • reaction mixture is then concentrated by evaporation and, in order to remove insoluble components, it is filtered directly with ethyl acetate over a silica gel column.
  • Pure 7- ⁇ R,S>-hydroxy-2-(3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-pyrido[3,2- b][1 ,4]oxazin-6-yl)-tetrahydro-imidazo[1 ,5-a]pyridine-1 ,3-dione is obtained as an isomeric mixture having a melting point of 205.5-206°C.
  • Example P19 7- ⁇ R> and 7- ⁇ S>-Fluoro-2-(3-oxo-4-prop-2-vnyl-3.4-dihvdro-2H-pyridof3.2-bl- .1.41oxazin-6-yl)-tetrahvdro-imidazof 1 ,5-a1pyridine-1 ,3-dione
  • the mixture is then concentrated by evaporation and the aqueous solution at pH 6 is extracted with ethyl acetate, dried and concentrated by evaporation again.
  • the first isomer, 7- ⁇ R> or 7- ⁇ S>-fluoro-2-(3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-pyrido[3,2- b][1 ,4]oxazin-6-yl)-tetrahydro-imidazo[1 ,5-a]pyridine-1 ,3-dione, is obtained by column chromatography (mobile phase: ethyl acetate/hexane 1/1).
  • Example P23 Tetrahvdro-pyridazine-1 -carbothionic acid (3-oxo-3.4-dihvdro-2H-pyrido- [3.2-bi ⁇ .41oxazin-6-yl)-amide
  • Example P24 6-.3-Oxo-tetrahvdro-[1.3.4]thiadiazolo[3.4-alpyridazin- ⁇ 1 E>- and - ⁇ 1Z>- ylideneaminol-4H-pyrido[3.2-b1f1 ,4]oxazin-3-one and 6-(1 -oxo-3-thioxo-tetrahvdro-
  • the mother liquor is concentrated by evaporation and yields, after filtration over silica gel
  • Example P25 6-.3-Oxo-tetrahydro-f1 ,3.4]thiadiazolo.3.4-alpyridazin- ⁇ 1 E>- and/or - ⁇ 1Z>- ylideneaminol-4-prop-2-vnyl-4H-pyrido[3.2-b][1 ,41oxazin-3-one and 6-(1 -oxo-3-thioxo-tetra- hydro- ⁇ ,2.4ltriazolo[1.2-alpyridazin-2-yl)-4-prop-2-ynyl-4H-pyridof3.2-b1f 1.41oxazin-3-one 0.35 g (1.1 mmol) of the 4/1 mixture of product B isolated in Example P24 is heated at boiling point in the presence of 0.15 g (1.3 mmol) of propargyl bromide, 0.18 g (1.3 mmol) of potassium carbonate and a catalytic amount of 18-crown-6 in 10 ml of
  • Example P27 6-(4.5-Dihvdro-1 H-imidazol-2-ylamino)-4H-pyridor3.2-blf1 ,41oxazin-3-one 5.7 g (20 mmol) of (3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-thiocarbamic acid O- ethyl ester (Example P26) are heated in 20 ml of ethylenediamine at 80°C for 90 minutes.
  • the solid product that precipitates out is pure 6-(4,5-dihydro-1 H-imidazol-2-ylamino)-4H- pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of >225°C.
  • Example P28 6-.7-Oxo-5-trifluoromethyl-2.3-dihvdro-7H-imidazori .2-alpyrimidin-8-yl)-4H- pyridof3.2-blf 1 ,41oxazin-3-one
  • Example P29 6-(2-Methyl-7-oxo-5-trifluoromethyl-2,3-dihydro-7H-imidazo.1.2-alpyrimidin-8- yl)-4-(1 -methyl-prop-2-ynyl)-4H-pyrido[3.2-biri .4
  • reaction mixture is then extracted from an aqueous phase by shaking with ethyl acetate and is separated by chromatography over silica gel using ethyl acetate/methanol 9/1 as mobile phase into the two racemic ⁇ S,S> or ⁇ R,R> and ⁇ S,R> or ⁇ R,S> isomers of 6-(2-methyl-7-oxo-5-trifluoromethyl-2,3-dihydro-7H-imidazo[1 ,2- a]pyrimidin-8-yl)-4-(1 -methyl-prop-2-ynyl)-4H-pyrido[3,2-b][1 ,4]oxazin-3-one.
  • Example P30 3-(4-n-Propyl-3-oxo-3.4-dihvdro-2H-pyrido.3.2-bl.1.41oxazin-6-yl)-5-chloro-1 - methyl-6-trifluoromethyl-1 H-pyrimidine-2.4-dione
  • Example P31 6-(2-Fluoromethoxy-6-oxo-4-trifluoromethyl-6H-pyrimidin-1-yl)-4-prop-2-vnyl- 4H-pyrido[3.2-bir 1.4]oxazin-3-one and 1 -f luoromethyl-3-.3-oxo-4-prop-2-ynyl-3.4-dihydro- 2H-pyrido[3.2-b1[1.4]oxazin-6-yD-6-trif luoromethyl-1 H-pyrimidine-2.4-dione 0.19 g (0.52 mmol) of 3-(3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)- 6-trifluoromethyl-1 H-pyrimidine-2,4-dione (Example 1.006) is introduced into 5 ml of dimethylformamide in the presence
  • Example P33 6-(7-Oxo-5-trifluoromethyl-7H-imidazo.1.2-alpyrimidin-8-yl,-4H-pyrido.3,2- b][1 ,4]oxazin-3-one
  • Example P34 1 ⁇ 5-Dimethyl-3-.3-oxo-3.4-dihvdro-2H-pyridor3.2-bin .41oxazin-6-yl)-6-thioxo- [1 ,3.5 ltriazinane-2.4-dione

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne des composés de la formule (1) dans laquelle R1-R4 sont tels que définis dans la description, et les sels agrochimiquement acceptables et tautomères, énantiomères et stéréoisomères des composés précités, qui sont utilisés comme herbicides.
PCT/EP2000/010595 1999-10-29 2000-10-27 Nouveaux herbicides WO2001030782A2 (fr)

Priority Applications (1)

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AU10269/01A AU1026901A (en) 1999-10-29 2000-10-27 Novel herbicides

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CH198899 1999-10-29
CH1988/99 1999-10-29

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024709A2 (fr) * 2000-09-22 2002-03-28 Syngenta Participations Ag Nouveaux herbicides
US7122542B2 (en) 2003-07-30 2006-10-17 Rigel Pharmaceuticals, Inc. Methods of treating or preventing autoimmune diseases with 2,4-pyrimidinediamine compounds
US7329672B2 (en) 2002-02-01 2008-02-12 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US7449458B2 (en) 2005-01-19 2008-11-11 Rigel Pharmaceuticals, Inc. Prodrugs of 2,4-pyrimidinediamine compounds and their uses
WO2009044777A1 (fr) * 2007-10-02 2009-04-09 Research Foundation Itsuu Laboratory Dérivé d'oxazolidinone avec hétérocycle à 7 chaînons
US7517886B2 (en) 2002-07-29 2009-04-14 Rigel Pharmaceuticals, Inc. Methods of treating or preventing autoimmune diseases with 2,4-pyrimidinediamine compounds
WO2010027002A1 (fr) * 2008-09-05 2010-03-11 塩野義製薬株式会社 Derive de morpholine à cycles condensés ayant une activite inhibitrice de pi3k
US8349828B2 (en) 2008-02-20 2013-01-08 Actelion Pharmaceuticals Ltd. Azatricyclic antibiotic compounds
US8349826B2 (en) 2008-02-22 2013-01-08 Actelion Pharmaceuticals Ltd. Oxazolidinone derivatives
US8618092B2 (en) 2008-10-07 2013-12-31 Actelion Pharmaceuticals Ltd. Tricyclic oxazolidinone antibiotic compounds
WO2014108836A1 (fr) 2013-01-09 2014-07-17 Actelion Pharmaceuticals Ltd Dérivés d'oxadiazolone antibactériens
WO2014170821A1 (fr) 2013-04-16 2014-10-23 Actelion Pharmaceuticals Ltd Dérivés bi-aromatiques antibactériens
US10287299B2 (en) * 2015-06-08 2019-05-14 Ucb Biopharma Sprl Substituted benzo[b][1,4]oxazines and pyrido[3,2-b][1,4]oxazines as modulators of tumor necrosis factor activity

Citations (2)

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US3854926A (en) * 1973-06-04 1974-12-17 Dow Chemical Co METHOD OF CONTROLLING UNDESIRED VEGETATION WITH 2H-PYRIDO (3,2-b)--1,4-OXAZIN-3(4H) ONES
EP0406993A2 (fr) * 1989-07-07 1991-01-09 Schering Aktiengesellschaft Dérivés de benzoxazolinone et benzoxazinone substituées, leur procédé de préparation et leur utilisation comme agent à activité herbicide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3854926A (en) * 1973-06-04 1974-12-17 Dow Chemical Co METHOD OF CONTROLLING UNDESIRED VEGETATION WITH 2H-PYRIDO (3,2-b)--1,4-OXAZIN-3(4H) ONES
EP0406993A2 (fr) * 1989-07-07 1991-01-09 Schering Aktiengesellschaft Dérivés de benzoxazolinone et benzoxazinone substituées, leur procédé de préparation et leur utilisation comme agent à activité herbicide

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024709A2 (fr) * 2000-09-22 2002-03-28 Syngenta Participations Ag Nouveaux herbicides
WO2002024709A3 (fr) * 2000-09-22 2002-06-27 Syngenta Participations Ag Nouveaux herbicides
US7329672B2 (en) 2002-02-01 2008-02-12 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US7329671B2 (en) 2002-02-01 2008-02-12 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US7332484B2 (en) 2002-02-01 2008-02-19 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US10709703B2 (en) 2002-02-01 2020-07-14 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US10682350B2 (en) 2002-02-01 2020-06-16 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US7906644B2 (en) * 2002-02-01 2011-03-15 Rigel Pharmaceuticals, Inc. 2,4-pyrimidinediamine compounds and their uses
US20110144330A1 (en) * 2002-02-01 2011-06-16 Rigel Pharmaceuticals, Inc. 2,4-Pyrimidinediamine Compounds and their Uses
US7517886B2 (en) 2002-07-29 2009-04-14 Rigel Pharmaceuticals, Inc. Methods of treating or preventing autoimmune diseases with 2,4-pyrimidinediamine compounds
US7122542B2 (en) 2003-07-30 2006-10-17 Rigel Pharmaceuticals, Inc. Methods of treating or preventing autoimmune diseases with 2,4-pyrimidinediamine compounds
US9751893B2 (en) 2003-07-30 2017-09-05 Rigel Pharmaceuticals, Inc. Methods of treating or preventing autoimmune diseases with 2,4-pyrimidinediamine compounds
US9266912B2 (en) 2005-01-19 2016-02-23 Rigel Pharmaceuticals, Inc. Prodrugs of 2,4-pyrimidinediamine compounds and their uses
US7449458B2 (en) 2005-01-19 2008-11-11 Rigel Pharmaceuticals, Inc. Prodrugs of 2,4-pyrimidinediamine compounds and their uses
US10577381B2 (en) 2005-01-19 2020-03-03 Rigel Pharmaceuticals, Inc. Prodrugs of 2,4-pyrimidinediamine compounds and their uses
US8530646B2 (en) 2007-10-02 2013-09-10 Research Foundation Itsuu Laboratory Oxazolidinone derivative having 7-membered hetero ring
WO2009044777A1 (fr) * 2007-10-02 2009-04-09 Research Foundation Itsuu Laboratory Dérivé d'oxazolidinone avec hétérocycle à 7 chaînons
US8349828B2 (en) 2008-02-20 2013-01-08 Actelion Pharmaceuticals Ltd. Azatricyclic antibiotic compounds
US8349826B2 (en) 2008-02-22 2013-01-08 Actelion Pharmaceuticals Ltd. Oxazolidinone derivatives
WO2010027002A1 (fr) * 2008-09-05 2010-03-11 塩野義製薬株式会社 Derive de morpholine à cycles condensés ayant une activite inhibitrice de pi3k
US9822114B2 (en) 2008-10-07 2017-11-21 Idorsia Pharmaceuticals Ltd Tricyclic oxazolidinone antibiotic compounds
US9346804B2 (en) 2008-10-07 2016-05-24 Actelion Pharmaceuticals Ltd. Tricyclic oxazolidinone antibiotic compounds
US8618092B2 (en) 2008-10-07 2013-12-31 Actelion Pharmaceuticals Ltd. Tricyclic oxazolidinone antibiotic compounds
WO2014108836A1 (fr) 2013-01-09 2014-07-17 Actelion Pharmaceuticals Ltd Dérivés d'oxadiazolone antibactériens
US9527867B2 (en) 2013-04-16 2016-12-27 Actelion Pharmaceuticals Ltd. Antibacterial biaromatic derivatives
WO2014170821A1 (fr) 2013-04-16 2014-10-23 Actelion Pharmaceuticals Ltd Dérivés bi-aromatiques antibactériens
US10287299B2 (en) * 2015-06-08 2019-05-14 Ucb Biopharma Sprl Substituted benzo[b][1,4]oxazines and pyrido[3,2-b][1,4]oxazines as modulators of tumor necrosis factor activity

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