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WO2001030782A2 - Novel herbicides - Google Patents

Novel 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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Prior art keywords
alkyl
crc
halogen
hydrogen
formula
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PCT/EP2000/010595
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French (fr)
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WO2001030782A3 (en
Inventor
Christoph Lüthy
Kurt Nebel
Jean Wenger
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Syngenta Participations AG
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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/en
Publication of WO2001030782A3 publication Critical patent/WO2001030782A3/en
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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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Abstract

Compounds of formula (I) wherein R1-R4 and W are as defined in the description and the agrochemically acceptable salts and tautomers, enantiomers and stereoisomers of such compounds of formula are suitable for use as herbicides.

Description

Novel herbicides
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.
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
Figure imgf000002_0001
wherein
R, is hydrogen, methyl or halogen;
R2 is hydrogen, Cι-Cι2alkyl, d-Cι2haloalkyl, C2-Cι alkenyl, C2-Cι2alkynyl, C2-C8alkynyl-
C2-C alkenyl, C3-Ci2allenyl, C2-C12haloalkenyl, C2-Cι2haloalkynyl, C3-C6cycloalkyl,
C3-C6cycloalkyl-C C4alkyl, C3-C6halocycloalkyl-CrC4alkyl( tri(Cι-C4alkyl)silyl-C C4alkyl, tri(Cι-C4alkyl)silyl-C2-C4alkenyl, cyano-CrCι2alkyl, CrC6alkoxy-CrC alkyl, C C4alkoxy-Cr or -C2-alkoxy-Cι- or -C2-alkyl, di(Cι-C4alkoxy)-d- or -C2-alkyl, ethylenedioxy-d- or -C2-alkyl,
C2-C6alkenyloxy-C1-C4alkyl, C2-C6haloalkenyloxy-Cι-C4alkyl, Ca-Cβalkynyloxy-CrCalkyl, C3-
Figure imgf000002_0002
d- C6alkylsulfonyl-CrC alkyl, hydroxy-d -Chalky I, d-C-ealkylcarbonyl-d-dalkyl, C C6haloalkylcarbonyI-CrC4alkyl, CrC6alkoxycarbonyl-Cι-C alkyl, d-C6alkoxy-Cι- or -C2- alkoxycarbonyl-Cι-C alkyl, Cι-C6alkoxycarbonyl-CrC4haloalkyl, C3-C6cycloalkylcarbonyl-Cr C4alkyl or benzoyl-d-C alkyl wherein the benzoyl group may be substituted by halogen, Cr C3alkyl, d-C3haloalkyl, d-C3alkoxy or by Cι-C3haloalkoxy, or is C3-C6alkenyloxycarbonyl- Cι-C4alkyl, C3-C6alkynyloxycarbonyl-Cι-C4alkyl, C1-C6alkylcarbonyloxy-C1-C4alkyl, C2- C6alkenylcarbonyloxy-C C4alkyl, C3-C6cycloalkylcarbonyloxy-Cι-C alkyl, benzoyloxy-d- C4alkyl, Cι-C6alkoxycarbonyloxy-CrC4alkyl, carbamoyl-C1-C alkyl, CrC6alkylaminocarbonyl- Cι-C4alkyl, or phenyl- or heterocyclyl-substituted Cι-C alkyl wherein the phenyl and heterocyclyl groups may be substituted by halogen, d-C6alkyl, d-C6alkoxy, Cι-C6haloalkyl, CrC6haloalkoxy, C2-C6alkenyl, C2-C6alkynyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6cycloalkyl-C1-C alkyl, C3-C6halocycloalkyl-Cι-C4alkyl, cyano-CrC4alkyl, Cι-C-6alkoxy-d- C4alkyl, d-Cealkylthio-d-dalkyl, d-C6alkylsulfinyl-C1-C4alkyl, CrC6alkylsulfonyl-C C alkyl, hydroxy-C C alkyl, d-C6alkylcarbonyl-Cι-C4alkyl, d-C6alkoxycarbonyl, d-C6alkoxy- carbonyl-Cι-C alkyl, Ci-Cεalkoxycarbonyl-d-dhaloalkyl, Cι-C6alkoxycarbonyl-C1-C4alkoxy, Cι-C6alkylcarbonyloxy-CrC4alkyl, d-Cealkoxycarbonyloxy-d-dalkyl, d-C alkoxy-d- C2alkoxy-Cι-C2alkyl, Cι-C4alkylaminocarbonyl( d-C6alkylaminocarbonyl-Cι-C alkoxy, phenyl, phenoxy or by benzyloxy, wherein the phenyl ring of the last three definitions may be substituted by halogen, methyl, trifluoromethyl, methylsulfonyl, methoxy, ethoxy or by cyano; or is phenyl-substituted C2-C alkenyl or C2-C4alkynyl, wherein the phenyl group may be substituted by halogen, methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, methoxy, ethoxy, cyano or by nitro;
R3 is hydrogen, Cι-C12alkyl, d-Cι2haloalkyl, C C6alkoxycarbonyl, or phenyl which is unsubstituted or substituted by halogen, methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, methoxy, ethoxy, cyano or by nitro; R4 is hydrogen or d-C6alkyl; W is a group
Figure imgf000003_0001
Figure imgf000004_0001
Figure imgf000005_0001
R11 is hydrogen, d-C3alkyl, halogen, CrC3haloalkyl or cyano;
R12 is C C3alkyl, C C3haloalkyl, d-C3alkyl-S(O) n1-, d-C3haloalkyl-S(O) n1- or cyano; and
R13 is hydrogen, d-C3alkyl, d-C3haloalkyl, allyl, propargyl or amino; or
R12 and Rn or R12 and R13 together form a C3- or C4-alkylene bridge which may be substituted by halogen, d-C3haloalkyl or by cyano;
R14 is hydrogen, d-C3alkyl, halogen, C Cshaloalkyl or cyano; and
R15 is d-C3alkyl, d-C3haloalkyl, d-C3alkyl-S(O)n2-, C C3haloalkyl-S(O)n2- or cyano; or
R15 and Rι4 together form a C3- or C4-alkylene bridge which may be substituted by halogen, d-C3haloalkyl or by cyano;
R16 is hydrogen, d-C3alkyl, halogen, Ci-Cshaloalkyl, C Csalkoxy, d-C3haloalkoxy, hydroxy, mercapto, d-C3alkylthio, CrCsalkylsulfinyl, CrCaalkylsulfonyl, allylthio, propargylthio, amino, d-C3alkylamino, di(d-C3alkyl)amino, allylamino, propargylamino or cyano;
Figure imgf000005_0002
R17 is hydrogen, d-C3alkyl, halogen or cyano; and
R18 is Cι-C3alkyl, halogen, C C3haloalkyl, d-dalkylthio, d-C3alkylsulfinyl, d-
C3alkylsulfonyl or cyano; or
R18 and R17 together form a C3- or C4-alkylene or C3- or C -alkenylene bridge, both of which may be substituted by halogen, Cι-C3alkyl or by d-C3haloalkyl;
R19 is hydrogen, halogen, d-C3alkyl, carboxyl, d-C3alkoxycarbonyl or amino; or
R19 and R18 together form a C3- or C4-alkylene or C3- or C4-alkenylene bridge, both of which may be substituted by halogen, d-C3alkyl or by C C3haloalkyl;
R2o and R21 are each independently of the other hydrogen or Cι-C alkyl; or
R051
R20 and R2ι together are a group =\ ;
■ ■052
R051 and R052 are each independently of the other hydrogen or d-C4alkyl; or
R051 and R052 together form a C4- or C5-alkylene bridge;
R052 and R2 together form a C3alkylene bridge;
R22 is hydrogen or C C3alkyl; or
R22 and R2o or R22 and R2ι together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)- and/or substituted by halogen, d-C4alkyl, Cι-
C3haloalkyl, C2-C4alkenyl, d-C3alkoxycarbonyl, d-C3alkylcarbonyloxy, d-
C3alkylsulfonyloxy or by hydroxy;
R23 and R24 are each independently of the other hydrogen, d-C3alkyl, C C3haloalkyl or propargyl; or
R23 and R24 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)- and/or substituted by halogen, C C4alkyl, hydroxy, d-
C4alkoxy or by Cι-C4alkoxy-C C alkoxy;
R25 is hydrogen, halogen, d-C alkyl, d-C haloalkyl, d-dalkoxy, d-C4haloalkoxy, d-
C alkylthio, d-C4haloalkylthio, Cι-C alkylsulfinyl, d-C4haloalkylsulfinyl, d-C4alkylsulfonyl,
Cι-C4haloalkylsulfonyl, hydroxy or cyano; and
R26 is hydrogen, Cι-C4alkyl or d-C4haloalkyl; or
R26 and R25 together form a C3-Csalkylene bridge which may be interrupted by oxygen,
sulfur, -S(O)-, -S(O)2-, N— C^C^alkyl or by -C(O)- and/or substituted by halogen, C
dalkyl, d-C3haloalkyl, C2-C alkenyl, C C3alkoxycarbonyl, d-C3alkylcarbonyloxy, d- C3alkylsulfonyloxy or by hydroxy; R27 and R 8 are each independently of the other hydrogen or Cι-C alkyl; or
R27 and R28 together form a C3-C5alkylene bridge which may be substituted by halogen or by Cι-C4alkyl 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-C4aIkyl;
R29 and R30 are each independently of the other hydrogen, d-dalkyl or d-C haloalkyl; or
R29 and R30 together form a C3-C5alkylene 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)-;
R31 is hydrogen, C C4alkyl or Cι-C4haloalkyl; and
R32 is hydrogen, d-C4alkyl, C C4haloalkyl, d-C alkylthio, d-C4alkylsulfinyl, d-dalkyl- sulfonyl, cyano or nitro; or
R31 and R32 together form a C3-C5alkylene 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;
R33 is hydrogen, d-C3alkyl, halogen, Cι-C3haloalkyl, hydroxy, d-C3alkoxy, d-
C3haloalkoxy, mercapto, d-C3alkylthio, d-C3alkylsulfinyl, d-C3alkylsulfonyl, amino, Cι-
C3alkylamino, Cι-C3alkylcarbonylamino, d-C3haloalkylcarbonylamino or cyano;
R34 is Cι-C alkyl, d-C haloalkyl, d-C alkoxy or Cι-C4alkylthio;
R36 is hydrogen, Cι-C3alkyl, halogen, Cι-C3haloalkyl or cyano; and
R37 is Cι-C3alkyl, Cι-C3haloalkyl, d-C3alkyl-S(O) n1-, CrC3haloalkyl-S(O) n1- or cyano; or
R37 and R36 together form a C3- or C -alkenylene bridge which may be substituted by halogen, d-C3alkyl, Cι-C3haloalkyl or by cyano;
R38 is d-C3alkyl; and
R39 is hydrogen or d-C3alkyl; or
R39 and R38 together form a C2- or C3-alkylene or C2- or C3-alkenylene bridge which is unsubstituted or substituted by Cι-C alkyl or form an -NH-CH2-, -N=CH- or -N=N- bridge;
R40 and R41 are each independently of the other d-C3alkyl or d-C3haloalkyl; or
R41 and R40 together form a C3-C5alkylene bridge which is unsubstituted or substituted by halogen or by d-C4alkyl;
R42 is hydrogen, d-dalkyl, d-C3haloalkyl, cyano or carboxyl;
R43 is hydrogen, d-C3alkyl, C C3haloalkyl, allyl or propargyl;
R44 is hydrogen, d-dalkyl, halogen, d-C3haloalkyl, hydroxy, mercapto, amino, C1-
C3alkoxy, C C3alkylthio or di(C C4alkyl)amino;
R45 is hydrogen, d-dalkyl, halogen or cyano;
R46 is d-dalkyl, d-C3haloalkyl or cyano;
R47 is hydrogen, Cι-C3alkyl or halogen; R48 is d-dalkyl or C C3haloalkyl;
R49. R50 and R51 are each independently of the others hydrogen, d-C4alkyl, propargyl or Cι-
C haloalkyl;
R52 is C C3alkyl, halogen, d-C3haloalkyl, Cι-C3alkoxy, d-C3haloalkoxy, C C3alkylthio,
Cι-C3alkylsulfinyl, C C3alkylsulfonyl, amino or C C3alkylamino;
R53 is Cι-C3alkyl or d-C3haloalkyl;
R54 is d-dalkyl;
R55 is hydrogen, d-dalkyl, propargyl or C C3haloalkyl;
R56 is d-dalkyl, d-C3haloalkyl, d-C3alkylthio, C C3alkylsulfinyl or d-C3alkylsulfonyl; and
R57 is C C3alkyl or Cι-C3haloalkyl; or
R57 and R5β together form a C2-C4alkylene or C2-C4alkenylene bridge which both are unsubstituted or substituted by halogen or by d-dalkyl;
R58 is hydrogen, d-C3alkyl, d-C3haloalkyl or amino;
R59 is hydrogen, C C3alkyl or d-C3haloalkyl;
R100 is hydrogen, halogen, nitro, amino, cyano, C C3alkyl, C2- or C3-alkenyl or C2- or C3- alkynyl;
R101 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-C3alkyl, d-
C3haloalkyl, C2- or C3-alkenyl, C2- or C3-alkynyl, CrC3alkoxy, d-C3haloalkoxy, d-
C3alkylthio, Cι-C3alkylsulfinyl, C C3alkylsulfonyl, Cι-C3haloalkylthio, d-dhaloalkylsulfinyl,
CrC3haloalkylsulfonyl, FS(O)2-, CIS(O)2-, d-C6alkylsulfonyloxy, d-C6haloalkylsulfonyloxy,
Cι-C3alkylcarbonyl, HC(O)-, HOC(O)-, CIC(O)-, FC(O)-, C C3alkoxycarbonyl, H2NC(O)- or
H2NC(S)-; and
R102 is hydrogen, d-C6alkyl, d-C6alkyl substituted by cyano, HO-, HOC(O)-, C dalkoxycarbonyl or by HC(O)-, or is C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, d-
C6haloalkyl or Cι-C3alkylsulfonyl; or when W is a group W10o,
R102 and R101 together form a C3-C5alkylene 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;
R103 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, Cι-C3alkyl, d- dhaloalkyl, C2- or C3-alkenyl, C2- or C3-aIkynyl, Cι-C3alkoxy, Cι-C3haloalkoxy, Cι-
C3alkylthio, d-C3alkylsulfinyl, C C3alkylsulfonyl, C C3haloalkylthio, d-dhaloalkylsulfinyl,
Cι-C3haloalkylsulfonyl, FS(O)2-, CIS(O)2-, Cι-C6alkylsulfonyloxy, d-C6haloalkylsulfonyloxy, d-C3alkylcarbonyl, HC(O)-, HOC(O)-, CIC(O)-, FC(O)-, d-C3alkoxycarbonyl, H2NC(O)- or
H2NC(S)-; R104 is hydrogen, d-dalkyl, d-C6alkyl substituted by cyano, HO-, HOC(O)-, d-
C3alkoxy-carbonyl or by HC(O)-, or is C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, d-
C6haloalkyl or Cι-C3alkylsulfonyl; and
R105 is hydrogen, halogen, nitro, amino, cyano, d-dalkyl, C2- or C3-alkenyl or C2- or C3- alkynyl; or
Rι04 and Rι03 together form a C3-C5alkylene 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;
R106 is hydrogen, halogen, amino, nitro, hydroxy, Cι-C3alkyl or d-C3alkoxy;
R107 is hydrogen, halogen, amino, hydroxy, d-dalkyl, C C3haloalkyl, HC(O)-, HOC(O)-, hydroxy-Cι-C3alkyl, C C3alkoxy or Cι-C3haloalkoxy; and
R108 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, Cι-C3alkyl, d-C3haloalkyl, C2- or C3-alkenyl, C C3alkoxy, d-
C3haloalkoxy, d-C3alkylcarbonyl, C C3alkoxycarbonyl, C C3alkylthio, d-C3haloalkylthio,
Cι-C3alkylsulfinyl, Cι-C3haloalkylsulfinyl, Cι-C3alkylsulfonyl, C C3haloalkylsulfonyl, d-
C3alkylsulfonyloxy or d-C3haloalkylsulfonyloxy; or
Rioβ and R107 together form a C3-C5alkylene 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;
R10g is hydrogen, halogen, amino, hydroxy, d-dalkyl, C C3haloalkyl, HC(O)-, HOC(O)-, hydroxy-Cι-C3alkyl, d-C3alkoxy or d-C3haloalkoxy; or
R109 and Rioβ together form a C3-C5alkylene 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-C3alkyl, d-dhaloalkyl, C3-C4alkenyl or C3-C4alkynyl;
R„ι is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-C3alkyl, d-C3haloalkyl, C2- or C3-alkenyl, d-C3alkoxy, C1-
C3haloalkoxy, C,-C3alkylcarbonyl, d-C3alkoxycarbonyl, Cι-C3alkylthio, d-C3haloalkylthio, d-C3alkylsulfinyl, d-C3haloalkylsulfinyl, d-dalkylsulfonyl, Cι-C3haloalkylsulfonyl, C1-
C3alkylsulfonyloxy or d-dhaloalkylsulfonyloxy; and
R112 is hydrogen, halogen, amino, hydroxy, d-dalkyl, CrC3haloalkyl, HC(O)-, HOC(O)-, hydroxy-C C3alkyl, d-C3alkoxy or d-C3haloalkoxy; or
R1 t1 and Rn0 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the pyrazinone via a CH2 group; or
Rιι2 and Rm together form a C3-C5alkylene 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; R113 is hydrogen, d-dalkyl, Cι-C3haloalkyl, C3-C4alkenyl or C3-C alkynyl; and
R114 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, C C3alkyl, d-C3haloalkyl, C2- or C3-aIkenyl, Cι-C3alkoxy, d-
C3haloalkoxy, d-C3alkylcarbonyl, d-C3alkoxycarbonyl, C C3alkylthio, C C3haloalkylthio,
Cι-C3alkylsulfinyl, d-dhaloalkylsulfinyl, CrC3alkylsulfonyl, C C3haloalkylsulfonyl, d-
C3alkylsulfonyloxy, d-C3haloalkylsulfonyloxy, Cι-C3alkylamino or di(d-C3alkyl)amino; or
R114 and R1 3 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the triazinone via a CH2 group;
R115 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, Cι-C3alkyl, C C3haloalkyl, C2- or C3-alkenyl, d-C3alkoxy, C
C3haloalkoxy, Cι-C3alkylcarbonyl, d-dalkoxycarbonyl, d-C3alkylthio, Cι-C3haloalkylthio,
CrC3alkylsulfinyl, Cι-C3haloalkylsulfinyl, Cι-C3alkylsulfonyl, Cι-C3haloalkylsulfonyl, d-
C3alkylsulfonyloxy or C C3haloalkylsulfonyloxy; and
R116 is hydrogen, Cι-C3alkyl, Cι-C3haloalkyl, C3-C4alkenyl or C3-C4alkynyl; or
R116 and Rn5 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the triazinone via a CH2 group;
R117 is hydrogen, Cι-C3alkyl, d-C3haloalkyl, C3-C4alkenyl or C3-C4alkynyl;
R118 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, Cι-C3alkyl, d-dhaloalkyl, C2- or C3-alkenyl, C C3aIkoxy, C
C3haloalkoxy, d-C3alkylcarbonyl, Cι-C3alkoxycarbonyl, Cι-C3aIkylthio, C C3haloalkylthio,
CrC3alkylsulfinyl, C -C3haloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, Ci-
C3alkylsulfonyloxy or d-C3haloalkylsulfonyloxy; and
R119 is hydrogen, halogen, amino, nitro, hydroxy, d-C3alkyl or C C3alkoxy; or
Rn8 and Rn7 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the pyrimidinone via a CH2 group;
R120 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, Cι-C3alkyl, d-C3haloalkyl, C2- or C3-alkenyl, d-C3alkoxy, Cr
C3haloalkoxy, d-C3alkylcarbonyl, Cι-C3alkoxycarbonyl, d-C3alkylthio, d-C3haloalkylthio, d-C3aIkylsulfinyl, C C3haloalkylsulfinyl, d-dalkylsulfonyl, CrC3haloalkylsulfonyl, d-
C3alkylsulfonyloxy or d-C3haloalkylsulfonyloxy;
R12ι is hydrogen, d-dalkyl, d-dhaloalkyl, C3- or C -alkenyl or C3- or C4-alkynyl; and
R122 is hydrogen, halogen, amino, nitro, hydroxy, d-C3alkyl or d-C3alkoxy; or R121 and R120 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the pyrimidinone via a CH2 group;
R123 is hydrogen, Cι-C3alkyl, halogen or d-C3haloalkyl;
R124 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, CrC3alkyl, Cι-C3haloalkyl, C2- or C3-alkenyl, C C3alkoxy, d- dhaloalkoxy, d-C3alkylcarbonyl, d-C3alkoxycarbonyl, CrC3alkylthio, Cι-C3haloalkylthio, d-dalkylsulfinyl, d-C3haloalkylsulfinyl, d-C3alkylsulfonyl, d-C3haloalkylsulfonyl, d- dalkylsulfonyloxy or C C3haloalkylsulfonyloxy; and
R125 is hydrogen, d-C3alkyl, halogen, hydroxy, d-C3alkoxy, Cι-C3haloalkoxy, d-
C3alkylthio, d-C3alkylsulfinyl, C C3alkylsulfonyl, amino or cyano;
Xl . 2. 3. X4. Xδi Xδi X7. β. θ, Xl0, Xl1 ι XI2F Xl3, Xl4> Xl5ι Xl6. Xl7ι Xl8. Xl9> X2O1 X21 ι X22, X23.
X24 and X25 are each independently of the others oxygen or sulfur; and
Yt and Y2 are oxygen or sulfur, and also the agrochemically acceptable salts and tautomers, enantiomers and stereoisomers of the compounds of formula I.
In the above definitions, halogen is to be understood as being iodine and also, preferably, fluorine, chlorine or bromine.
The 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.
There may be mentioned as examples of 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. Longer chain alkenyl groups may also contain two or more unsaturated C=C bond groups, for example C2-C8alkenyl-C2-C4alkenyl (for example substituent R2). There may be mentioned as examples of 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.
There may be mentioned as examples of 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.
The cycloalkyl-containing groups and also any alkylene- or alkenylene-containing groups, for example C3- or C4-alkylene or C3- or C -alkenylene bridges, may also be substituted one or more times by further d-dalkyl groups, especially methyl groups, and by halogen and d-dhaloalkyl.
The alkylene and alkenylene bridges, for example in the definitions 'R15 and R 4 together form a C3- or C4-alkylene bridge' or 'R18 and R17 together form a C3- or C -alkylene or C3- or
C -alkenylene bridge' may, as mentioned in the corresponding definitions, be substituted or unsubstituted.
Likewise, in the definitions 'R27 and R28 together form a...', 'R29 and R30 together form a...',
'R31 and R32 together form a...', and 'R41 and R40 together form a C3-C5alkylene bridge', and
'R39 and R38 together form a C2- or C3-alkylene bridge' and 'R57 and R56 together form a C2- dalkylene bridge', those alkylene bridges may be substituted by halogen, C C4alkyl or by d-dhaloalkyl.
Especially in the definitions 'R22 and R20 together form a ...', 'R22 and R2ι together form a...',
'R23 and R24 together form a...', 'R26 and R25 together form a...', 'R27 and R28 together form a...', 'R29 and R30 together form a...', 'R3ι and R32 together form a...' and 'R41 and R40 together form a C3-C5alkylene bridge', and also 'R39 and R38 together form a C2- or C3- alkylene bridge' and 'R57 and R56 together form a C2-C4alkylene 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
(2-methyl-but-3-yn-2-yl)oxycarbonyl.
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 ]oxazin-3-on-2-yl group.
Corresponding meanings may also be given to the substituents in combined definitions, for example alkynylalkenyl, cyanoalkyl, alkoxyalkoxyalkyl, di(alkoxy)alkyl, alkylthioalkyl, alkyl- sulfinylalkyl, alkylsulfonylalkyl, hydroxyalkyl, alkylcarbonylalkyl, haloalkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylhaloalkyl, alkenyloxycarbonylalkyl, alkynyloxycarbonylalkyl, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, cycloalkylcarbonyloxyalkyl, benzoyloxyalkyl, alkoxycarbonyloxyalkyl, cycloalkylcarbonyloxyalkyl, benzoyloxyalkyl, alkylaminocarbonylalkyl, halocycloalkylalkyl, alkylcarbonylamino, alkylsulfonyloxy and haloalkylsulfonyloxy.
In the definitions of 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. in the reagents Rι3-Lι of formula IX, R5-L! of formula IXb (Reaction Scheme 1 ) and R38-Lι of formula IXa, L2 in the reagent R2-L2 of formula IV (Reaction Schemes 1 and 1 a), L3 in the reagent R23-L3 of formula XVa (Reaction Scheme 5), L4 in the reagent R2 -L4 of formula XVb (Reaction Scheme 5), L5 in the reagents R22-L5 of formula X (Reaction Scheme 4) and R26- L5 of formula Xa and L10 in the reagent R102-L10 of formula XVI are leaving groups, for example halogen, especially chlorine, bromine or iodine, or sulfonate, especially CH3S(O)2O- (mesyloxy) or p-tolyl-S(O)2O- (tosyloxy).
L6 and L7 in the reagent of formula XXXVI (Reaction Scheme 8) are leaving groups, for example halogen, especially chlorine or bromine, or, in the case of L7, also hydroxy or alkoxy.
L9 in the reagent of formula XII (Reaction Schemes 1f and 22) is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially mesyloxy, tosyloxy or trifluoromethanesulfonyloxy.
L11 in the reagent of formula XXV (Reaction Scheme 17) is a leaving group, for example hydroxy, C C3alkoxy, chlorine, amino or d-dalkylamino.
L12 and L13 in the reagents of formulae XXVIa, XXVIb, XXVIc and XXVId (Reaction Scheme 17) are leaving groups, for example chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy.
L1 in the reagent of formula XlVa (Reaction Scheme 18) is a leaving group, for example halogen, e.g. chlorine or bromine.
L15 in the reagent of formula XVII (Reaction Scheme 18) 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 (Reaction Scheme 15a) is preferably methyl, chlorine, bromine or carboxy.
A1 in the compound of formula lib (Reaction Scheme 1c) is a leaving group, for example halogen, especially fluorine, chlorine or bromine, alkylsulfonyl, especially methylsulfonyl, sulfonate, especially mesyloxy, trifluoromethylsulfonyloxy or phenylsulfonyloxy, or nitro. A2 in the compound of formula llu (Reaction Scheme 1d) is methyl, cyano, formyl, d- dalkylcarbonyl, carboxyl or d-C4alkoxycarbonyl.
A3 in the compound of formula llv (Reaction Scheme 1e) is either a leaving group, for example halogen, especially chlorine or bromine, or a sulfonate group, especially trifluoromethylsulfonyloxy or a Cι-C4trialkylstannyl or boronic acid group.
B in the reagent B-W of formula V (Reaction Scheme 1e) is, complementarily to A3 in the compound of formula llv, either a d-C4trialkylstannyl 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 (Reaction Scheme 15) is a leaving group, for example alkoxy, especially methoxy or ethoxy, or halogen, especially chlorine or bromine.
Z2 in the reagent of formula XXXII (Reaction Scheme 15) 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 R2, 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.
Among the 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.
Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary Cι-Cι8alkylamines, Cι-C hydroxyalkyl- amines and C -C4alkoxyalkylamines, 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-octadecylamine, ethyl- butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n- amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n- propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl- ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2- amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec- butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
The presence of an asymmetric carbon atom in the compounds of formula I, for example in the substituent R2, R3 and R4 and also at the R3- and R4-carrying oxazine carbon atom and, in general, in alkylsulfinyl groups, wherein R2, R3 or R is especially a branched alkyl, alkenyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl or alkylsulfinylalkyl group, means that the compounds may be in the form of optically active individual isomers or in the form of racemic mixtures. In the present invention, 'compounds of formula I' is to be understood as including both the pure optical antipodes and the racemates or diastereoisomers or mixtures thereof.
When an aliphatic C=C double bond is present, for example in alkenyl and haloalkenyl groups of the substituent R2, geometric <E/Z>-isomerism may occur. Likewise, in the groups
W,ι, W12 and W2o the exocyclic double bond may be present in the syn/anti
Figure imgf000018_0001
form, as shown by way of example for the compound of formula IW12:
Figure imgf000019_0001
Specific <E>- or <Z>-isomers of that kind can, if desired, be isolated in the pure form.
Moreover, for example, the compounds of formulae IW10oz and IWι0ιz can, with respect to the groups W10o and W10ι, wherein R10o is hydrogen and Rι0ι is hydroxy, be present as keto- enol tautomer mixtures; for the group W100z in the compound of formula IW10oz by way of example:
Figure imgf000019_0002
(I 100Z)
The present invention also includes those specific <E>- and <Z>-isomers, or syn- and anti- isomers, and tautomeric forms and mixtures thereof.
Preference is given to compounds of formula I wherein R, is hydrogen, methyl or halogen;
R2 is hydrogen, d-C12alkyl, Cι-C12haloalkyl, d-C12alkenyl, Cι-C12alkynyl, d- Cι2haloalkenyl, d-C12haloalkynyl, d-C6cycloalkyl-Cι-C4alkyl, d-dhalocycloalkyl-d- C4alkyl, cyano-Cι-Ci2alkyl, Cι-C6alkoxy-d-C4alkyl, d-dalkoxy-d-dalkoxy-d-dalkyl, di(Cι-C4alkoxy)CrC2alkyl, CrC6alkylthio-d-C4alkyl, d-dalkylsulfinyl-d-dalkyl, d- C6alkylsulfonyl-Cι-C4alkyl, hydroxy-Cι-d2alkyl, d-dalkylcarbonyl-d-dalkyl, d- dhaloalkylcarbonyl-d-dalkyl, Cι-C6alkoxycarbonyl-d-C4alkyl, Cι-C6alkoxycarbonyl-Cr C4haloalkyl, d-C6alkoxycarbonyl-benzyl, d-dalkenyloxycarbonyl-d-dalkyl, d- C6alkynyloxycarbonyl-d-C4alkyl, C C6alkylcarbonyloxy-Cι-C alkyl,
Cι-C6alkenylcarbonyloxy-CrC4alkyl, Cι-C6cycloalkylcarbonyloxy-C -C alkyl, benzoyloxy-d- C alkyl, Ci-dalkoxycarbonyloxy-d-dalkyl, Cι-C6alkylaminocarbonyl-Cι-C4alkyl, C dalkylaminocarbonyl-benzyl, or d-C4alkyl substituted by phenyl or by heterocyclyl, wherein the phenyl and heterocyclyl group may be substituted one or more times by halogen, d- dalkyl, Cι-C6haloalkyl, d-C6alkenyl, d-C6alkynyl, d-C6haloalkenyl, Ci-Cehaloalkynyl, d- C6cycloalkyl-Cι-C4alkyl, Cι-C6halocycloalkyl-d-C4alkyl, cyano-d-C12alkyl, d-dalkoxy-d- dalkyl, d-C6alkylthio-Cι-C4alkyl, d-dalkylsulfinyl-d-dalkyl, d-dalkylsulfonyl-d-dalkyl, hydroxy-d-Cι2alkyl, CrC6alkylcarbonyl-Cι-C4alkyl, Cι-C6alkoxycarbonyl-d-C alkyl, d- C6alkoxycarbonyl-CrC4haloalkyl, d-dalkylcarbonyloxy-d-dalkyl, Cι- C6alkoxycarbonyloxy-Cι-C alkyl, Cι-C4alkoxy-Cι-C2alkoxy-d-C2alkyl or by phenyl; R3 is hydrogen, d-C12alkyl, Cι-d ha.oalkyl or unsubstituted or substituted phenyl;
R is hydrogen or d-C6alkyl;
W is a group
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0003
Figure imgf000021_0001
(W105) , ( l06), (W107) or
Figure imgf000021_0002
Figure imgf000021_0004
Figure imgf000021_0003
Figure imgf000021_0005
R11 is hydrogen, d-C3alkyl, halogen, d-dhaloalkyl or cyano;
R12 is d-dalkyl, d-C3haloalkyl, C C3alkyl-S(O) n1-, C C3haloalkyl-S(O) nι- or cyano; and "
Rι3 is d-C3alkyl, d-dhaloalkyl or- amino; or
R12 and R or Rι2and R13 together form a C3- or C4-alkylene bridge which may be substituted by halogen, d-dhaloalkyl or by cyano;
Rι4 is hydrogen, Cι-C3alkyl, halogen, d-C3haloalkyl or cyano; and
Ris is d-dalkyl, d-C3haloalkyl, Cι-C3alkyl-S(O)n2-, d-C3haloalkyl-S(O)n2- or cyano; or
Rι5and R14 together form a C3- or C4-alkylene bridge which may be substituted by halogen,
Cι-C3haloalkyl or by cyano;
R16 is hydrogen, d-dalkyl, halogen, d-dhaloalkyl, d-dalkoxy, C C3haloalkoxy, d-
C3alkylthio, C C3alkylsulfinyl, d-C3alkylsulfonyl or cyano;
Figure imgf000021_0006
R17 is hydrogen, d-C3alkyl, halogen or cyano; and
R18 is d-C3alkyl, halogen, Cι-C3haloalkyl, C C3alkylthio, CrC3alkylsulfinyl, d-
C3alkylsulfonyl or cyano; or
R18 and Rι7 together form a C3- or C4-alkylene or C3- or C4-alkenylene bridge, both of which may be substituted by halogen, d-C3alkyl or by d-C3haloalkyl;
R19 is hydrogen, halogen, d-C3alkyl or amino; or Rι9 and R18 together form a C3- or dalkylene or C3- or C4-alkenylene bridge, both of which may be substituted by halogen, d-C3alkyl or Cι-C3haloalkyl;
R20 and R2i are each independently of the other hydrogen or d-C4alkyl; or
R0S1
R20 and R2ι together are a group = ;
"θ52
R051 and R052 are each independently of the other Cι-C4alkyl; or R051 and R0s2 together form a C4- or C5-alkylene bridge; R051 and R22 together form a dalkylene bridge; R22 is hydrogen or d-dalkyl; or
R22 and R20 or R22 and R2ι together form a C3-C5alkylene bridge which may be interrupted by oxygen or by -C(O)- and/or substituted by halogen, d-dalkyl, d-dhaloalkyl, C2- dalkenyl, d-C3alkoxycarbonyl, d-C3alkylcarbonyloxy, d-C3alkylsulfonyloxy or by hydroxy; R23 is hydrogen, d-C3alkyl or d-C3haloalkyl; or
R23 and R24 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-;
R25 is hydrogen, halogen, Cι-C4alkyl, d-C4haloalkyl, C C4alkoxy, Cι-C4haloalkoxy, d- C alkylthio, d-C4haloalkylthio, C1-C4alkylsulfinyl, Cι-C4haloalkylsulfinyl, d-dalkylsulfonyl, Cι-C haloalkylsulfonyl or cyano; and R26 is hydrogen, Cι-C4alkyl or d-C4haloalkyl; or
R26 and R25 together form a C3-C5alkylene bridge which may be interrupted by oxygen or by -C(O)- and/or substituted by halogen, Cι-C4alkyl, d-C3haloalkyl, C2-C4alkenyl, d-C3alkoxy- carbonyl, d-C3alkylcarbonyloxy, Cι-C3alkylsulfonyloxy or by hydroxy; R27 and R28 are each independently of the other hydrogen or d-dalkyl; or R27 and R28 together form a C3-C5alkylene bridge or a dalkenylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-; R29 and R30 are each independently of the other hydrogen or C C4alkyl; or R29 and R30 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-; R31 is hydrogen, Cι-C alkyl or d-C haloalkyl; and
R32 is hydrogen, d-dalkyl, d-C4haloalkyl, d-C4alkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, cyano or nitro; or
R31 and R32 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-; R33 is hydrogen, d-dalkyl, halogen, d-dhaloalkyl, d-C3alkoxy, d-dhaloalkoxy, d-C3alkylthio, C C3alkylsulfinyl, C C3alkylsulfonyl, amino, d-C3alkylamino, d-C3alkyl- carbonylamino, d-C3haloalkylcarbonylamino or cyano;
R34 is Cι-C4alkyl, Cι-C4haloalkyl, d-C alkoxy or Cι-C4alkylthio;
R100 is hydrogen, halogen, nitro, amino, cyano, d-dalkyl, C2- or C3-alkenyl or C2- or C3- alkynyl;
R10ι is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-dalkyl, C1- dhaloalkyl, C2- or C3-alkenyl, C2- or C3-alkynyl, CrC3alkoxy, CrC3haloalkoxyf C1-
C3alkylthio, Cι-C3alkylsulfinyl, d-C3alkylsulfonyl, C C3haloalkylthio, d-dhaloalkylsulfinyl, d-dhaloalkylsulfonyl, FS(O)2-, CIS(O)2-, Cι-C6alkylsulfonyloxy, d-C6haloalkylsulfonyIoxy,
C,-C3alkylcarbonyl, HC(O)-, HOC(O)-, CIC(O)-, FC(O)-, CrC3alkoxycarbonyl, H2NC(O)- or
H2NC(S)-;
R102 is hydrogen, d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, d-C6haloalkyl,
C C3alkylsulfonyl, or d-C6alkyl which may be substituted by cyano, HO-, HOC(O)-, C C3- alkoxycarbonyl or by HC(O)-; or, when W is a group W10o,
R102 and R10ι together form a C3-C5alkylene 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;
R103 is as defined for R10ι;
R104 is as defined for R102;
R105 is as defined for R10o;
R106 is hydrogen, halogen, amino, nitro, hydroxy, d-C3alkyl or C C3alkoxy;
R107 is hydrogen, halogen, amino, hydroxy, d-dalkyl, C C3haloalkyl, HC(O)-, HOC(O)-, hydroxy-Cι-C3alkyl, d-C3alkoxy or CrC3haloalkoxy; and
R108 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, HS-, d-C3alkyl, d-C3haloalkyl, C2- or C3-alkenyl, d-C3alkoxy, Cι-C3haloalkoxy, d-dalkylcarbonyl, d-dalkoxycarbonyl, CrC3alkylthio, d-C3haloalkylthio, Cι- dalkylsulfinyl, d-dhaloalkylsulfinyl, d-dalkylsulfonyl, Cι-C3haloalkylsulfonyl( d- dalkylsulfonyloxy or Cι-C3haloalkylsulfonyloxy;
R10g is as defined for Rι07;
Rι07 and Rιoβ together form a C3-C5alkylene 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;
Rιos and R109 together form a C3-C5alkylene 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;
R110 is hydrogen, d-C3alkyl, d-C3haloalkyl, C3-C alkenyl or C3-C4alkynyl; Rm is as defined for R108;
R112 is as defined for R10g;
Rm and Rn2 together form a C3-C5alkylene 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;
R110 and Rm together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the pyrazinone;
R113 is as defined for R 10;
R114 is as defined for R108;
R113 and Rn4 together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the triazinone;
R115 is as defined for R108;
R116 is as defined for Rn0;
Rι15 and R116 together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the triazinone;
R117 is as defined for Rno;
R118 is as defined for R108;
R119 is as defined for R10e;
Rn7 and Rn8 together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the pyrimidinone;
Rι20 is as defined for R108;
R121 is as defined for R110;
R122 is as defined for Rioβ!
R121 and R120 together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the pyrimidinone;
Xι. X2, X3, X4, X5, Xβ, X7, Xβ, X9. X10.X11. X12 or Xι3 are each independently of the others oxygen or sulfur; and
Y1 is oxygen or sulfur.
Preference is also given to compounds of formula I wherein Ri is hydrogen or fluorine. In further preferred compounds of formula I, R2 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 -yl, 1-chloro-prop-1-en-3-yl, 2-chloro-prop-1 -en-3-yl, 3-chloro-but-2-en-1-yl, 5- chloropentyl, 2-bromo-prop-1 -en-3-yl, 6,6-dimethyl-hept-2-en-4-yn-1 -yl, dimethylethylsilylmethyl, trimethylsilylmethyl-prop-2-en-1 -yl, cyclopropylmethyl, dichlorocyclopropylmethyl, cyanoethyl, methoxyethyl, ethoxyethyl, ethylthioethyl, 2,2- dimethoxyethyl, 3,3-dimethoxypropyl, ethylcarbonylmethyl, tert.-butylcarbonylmethyl, cyclopropylcarbonylmethyl, oxiranylmethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 1 -(methoxycarbonyl)-ethyl, 1-(ethoxycarbonyl)-ethyl, 1-(methoxycarbonyl)-prop-1 -yl, benzyl or 2-methoxybenzyl; R3 is hydrogen, methyl, ethyl, n-propyl or n-butyl; and R4 is hydrogen or methyl.
In a selected group of compounds of formula I, W is a group Wi to W2.. Of those compounds, special preference is given to those wherein W is a group W], W2, W , W5, W7, n, W12, W14, Wi5, W18 or W21. Of those compounds, very special preference is given to those wherein W is a group Wi, W2, W4, W5, W7 or Wn.
In a further selected group of compounds of formula I, W is a group W3, W6, W8, W9, W10,
Figure imgf000025_0001
In a preferred group of compounds of formula I, W is a group Wi or W2
Figure imgf000025_0002
wherein R11 ( R12, R13, R14, R15, Rι6, X^ X2 and X3 are as defined for formula I. Of those compounds, special preference is given to those wherein X! and X3 are oxygen; Rn and R14 are hydrogen, chlorine or methyl; R12 and R15 are methyl, ethyl, chlorodifluoromethyl, trifluoromethyl, pentafluoroethyl or cyano; R13 is methyl, fluoromethyl, propargyl or amino; and Ri6 is chlorine, methoxy, fluoromethoxy or methylthio.
Of those compounds, very special preference is given to those wherein X^ X2 and X3 are oxygen; R1 t and R14 are hydrogen or methyl; R12 and R15 are trifluoromethyl, pentafluoroethyl or cyano; R13 is methyl or amino; and R16 is chlorine or methoxy. Of those compounds, preference is given more especially to those wherein W is a group W^ Rn is hydrogen; R12 is trifluoromethyl; and R13 is methyl, fluoromethyl or amino.
In a further preferred group of compounds of formula I, W is a group W2 or Wn
Figure imgf000026_0001
wherein R14, R15, R36, R37, R38, R39. X3 and X14 are as defined for formula I; and R16 is amino, d-dalkylamino, di(Cι-C3alkyl)amino, allylamino or propargylamino. Of those compounds, special preference is given to those wherein X3 and X1 are oxygen; Rι4 and R36 are hydrogen, chlorine or methyl; R15 and R37 are methyl, ethyl, chlorodifluoromethyl, trifluoromethyl, pentafluoroethyl or cyano; Rι6 is amino or methylamino; and R39 and R38 together form an unsubstituted or methyl-substituted dalkylene or dalkenylene bridge. Of those compounds, very special preference is given to those wherein R15 and R37 are trifluoromethyl.
In another preferred group of compounds of formula I, W is a group W3
Figure imgf000026_0002
wherein R17, Rι8, R19 and X5 are as defined for formula I. Special preference is given especially to those wherein R17 is hydrogen or Cι-C3alkyl; R18 is trifluoromethyl or methylsulfonyl; R19 is hydrogen, Cι-C3alkyl or amino; and X5 is oxygen. Of those compounds, very special preference is given to those wherein Rι7 is hydrogen; and R19 is methyl or amino.
Special preference is given to compounds of formula I wherein W is a group W3; R17 and R19 are each independently of the other hydrogen or methyl; and R18 is trifluoromethyl, pentafluoroethyl or cyano. Very special preference is given especially to those wherein Rι7 is hydrogen; R18 is trifluoromethyl; and R 9 is hydrogen or methyl. Preference is also given to compounds of formula I wherein W is the group W4
X. R.υ
— N r2R 2 ^22 7
R2o, R21 and R22 are as defined for formula I, and X6 and X7 are oxygen. Of those compounds, special preference is given especially to those wherein R 1 and R22 together form a C3- or C4-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
compounds wherein R2o and R21 together are a group ; R05ι is hydrogen; and
Figure imgf000027_0001
R052 and R22 together form a dalkylene bridge.
In an especially preferred group of compounds, W is a group W4 wherein R2o is hydrogen; and R21 and R22 together form a dalkylene group which is unsubstituted or substituted once or twice by fluorine or chlorine.
Preference is also given to compounds of formula I wherein W is the group W5
Figure imgf000027_0002
R23 and R2 are as defined for formula I; and X8 and/or X9 are oxygen. Of those compounds, special preference is given to those wherein R23 and R2 together form a C3-C5alkylene bridge which may be interrupted by oxygen. Very special preference is given to those wherein R23 and R2 together form a C3- or C -alkylene bridge.
In another preferred group of compounds of formula I, W is a group W6
Figure imgf000027_0003
wherein R25 and R26 are as defined for formula I; and X4 is oxygen. Of those compounds, special preference is given to those wherein R25 and R26 together form a dalkylene bridge. In another especially preferred group, W is a group W6; R25 is methyl, ethyl or trifluoromethyl; and R26 is methyl or difluoromethyl. Of those compounds, very special preference is given to those wherein X4 is oxygen.
In a further preferred group of compounds of formula I, W is a group W7
Figure imgf000028_0001
wherein R2 and R28 are as defined for formula I; and X10 and Xn are oxygen. Of those compounds, special preference is given to those wherein R27 and R28 together form a dalkylene bridge. Special preference is likewise given to those compounds wherein R27 is methyl and R28 is C C3alkyl.
In other preferred groups of compounds of formula I, W is a group W8 or W9
Figure imgf000028_0002
wherein R29, R3o, R31, R32 and R33 are as defined for formula I; and Xι2 is oxygen. Of those compounds, special preference is given to those wherein R29 and R30 together and R31 and R32 together form, in each case, a dalkylene bridge. Of those groups, very special preference is given especially to those wherein W is a group W9 and R33 is chlorine or bromine.
In a further group of preferred compounds, W is a group W9 wherein R31 is hydrogen, chlorine, methyl or trifluoromethyl; R32 is methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro; and R33 is chlorine, amino, methylamino or ethylamino.
In another preferred group of compounds of formula I, W is a group W10
Figure imgf000029_0001
wherein X13 is oxygen; and Ra* and Yi are as defined for formula I. Of those compounds, special preference is given to those wherein R^ is tert-butyl or trifluoromethyl.
Preference is likewise given to compounds of formula I wherein W is a group W 2
Figure imgf000029_0002
X15 is oxygen; Y2 is sulfur; R40 is methyl or ethyl; and R ι is methyl, ethyl or difluoromethyl; or R40 and R ι together form a -(CH2)3-, -CH2CH(CH3)CH2-, -(CH2)4-, -CH2CH2OCH2- or -CH2CH2OCH2CH2- bridge.
In a further preferred group of compounds of formula I, W is a group Wι3
Figure imgf000029_0003
R42 is hydrogen or cyano; R43 is methyl; and Xι6 and Xι7 are oxygen.
In a further preferred group of compounds of formula I, W is a group Wι5
Figure imgf000029_0004
Of those compounds, special preference is given to those wherein R48 is trifluoromethyl.
Preference is also given to compounds of formula I wherein W is a group W16 or Wi7
Figure imgf000030_0001
X18 and X20 are oxygen; R49 is methyl; R50 is methyl or difluoromethyl; and R52 is chlorine or methyl.
Preference is also given to compounds of formula I wherein W is a group W2o
Figure imgf000030_0002
and R56 and R57 together form a -SCH2CH2-, -SCH(CH3)CH2-, -SC(CH3)2CH2-, -SCH2CH2CH2-, -(CH2)3-, -CH2CH(CH3)CH2- or -CH2C(CH3)2CH2- bridge.
In a further preferred group of compounds of formula I, W is a group W21
Figure imgf000030_0003
R58 is methyl or amino; R59 is methyl; and X23 and X 4 are oxygen.
In another selected group of compounds of formula I, W is a group W100, W10ι, W102, W103, W10 , W105, W106, W107, W108 or W109, especially the group W100.
Very special preference is given to those compounds of formula I wherein W is a group
W100
Figure imgf000030_0004
R10o is methyl, chlorine or bromine; R10 is chlorine, bromine, trifluoromethyl, difluoromethoxy, methylsulfonyl, ethylsulfonyl or cyano; and R102 is methyl or ethyl; or R102 and R101 together form a dalkylene bridge.
Preference is also given to compounds of formula I wherein W is a group W102
Figure imgf000031_0001
R103 is methyl, ethyl or trifluoromethyl; and Rιc is methyl, ethyl or difluoromethyl; or R104 and R103 together form a dalkenylene bridge; and R105 is methyl, chlorine or bromine.
The process according to the invention for the preparation of compounds of formula I according to variant a) and Reaction Scheme 1 a is carried out analogously to known processes, as described, for example, in WO 98/42698, and comprises, for the preparation of those compounds of formula I
Figure imgf000031_0002
wherein R1 ? R2, R3, R and W are as defined for formula I with the exception of R2 as hydrogen, reacting a compound of formula la
Figure imgf000031_0003
wherein R1 t R3, R4 and W are as defined, with a suitable alkylating reagent of formula IV
Figure imgf000031_0004
wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially CH3S(O)2O- (mesyloxy) or p-tolyl-S(O)2O- (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:
Figure imgf000032_0001
(la) (1): (Ft other than hydrogen,
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.
The process according to the invention for the preparation of compounds of formula I according to variant b) and Reaction Scheme 1 b Reaction Scheme 1 b:
Figure imgf000032_0002
(lla) (l): (WrW21, W100-W109)
is carried out analogously to known processes, as described, for example, in WO 99/52892, WO 99/52893 and WO 98/27083, and comprises, for the preparation of those compounds of formula I
Figure imgf000033_0001
wherein H,, R2, Rg and R4 are as defined for formula I and W is a group VJ,
Figure imgf000033_0002
wherein Rn, R12, Rι3, Xi and X2 are as defined for formula I, reacting a compound of formula lla
Figure imgf000033_0003
wherein R^ R2, R3 and R4 are as defined, either
1), according to route a) in Reaction Scheme 1 , with a compound of formula VI
(VI),
CI-C-X0R5
wherein X2 is as defined for formula I, X0 is oxygen, sulfur or amino, and R5 is Cι-C4alkyl, to yield the compound of formula lie
Figure imgf000033_0004
wherein Ri, R2, R3, R4, R5, X0 and X2 are as defined, or, as a variant thereof and in cases where X0 in the compound of formula He is sulfur, first of all 1) carrying out a reaction with the reagent of formula Xln
X2=C=S (Xln) and then 2) with the alkylating reagent of formula IXb Rs-L, (IXb) to yield the compound of formula lie, the substituents X2 and R5 in the reagents of formulae Xln and IXb being as defined and Li being a leaving group, for example halogen, especially chlorine, bromine or iodine, or sulfonate, especially mesyloxy or tosyloxy, or 2), according to route b) in Reaction Scheme 1 , carrying out treatment with (thio-)phosgene or oxalyl chloride to yield the compound of formula lid
Figure imgf000034_0001
wherein R^ R2, R3, R4 and X2 are as defined, and then, according to route c) in Reaction Scheme 1 , condensing and cyclising the resulting compounds of formulae He and lid with an enamine of formula VII
Figure imgf000034_0002
wherein Rn, R12 and R13 are as defined, Xi is oxygen or sulfur, and R6 is d-C4alkyl, 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,
Figure imgf000034_0003
wherein R1 ; R2, R3, R , Ru, Rι2, Rι3, Xi and X2 are as defined, and
3) optionally, further functionalising those compounds according to the definition of Ri, R2,
Rn, Rι3> Xi and X2 for formula I according to standard methods (Reaction Scheme 1 ).
Examples of such standard methods for further functionalisation are: aa) thionation of compounds of formula IWι
Figure imgf000035_0001
wherein R1t R2, R3, R , Rn, Rι2 and Rι3 are as defined for formula I and Xi and/or X2 are oxygen, with the aid of a thionating reagent, for example Lawesson's reagent or P2S5 (phosphorus pentasulfide), to form the compound of formula IW!
Figure imgf000035_0002
wherein R1 f R2, R3, R , Rn, R12 and R13 are as defined and Xi and/or X2 are sulfur (Reaction
Scheme 1), or when X2 is oxygen, ab) alkylation of compounds of formula IWιa
Figure imgf000035_0003
wherein R1 ( R2, R3, R , Rn, R12 and X! are as defined for formula I and Rι3 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
Figure imgf000035_0004
wherein R13 is as defined for formula I with the exception of Rι3 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 IW1a
Figure imgf000036_0001
wherein Ri, R2, R3, R , Rn, Rι2, Rι3 and Xi are as defined, (Reaction Scheme 1 ), or ac) alkylation of compounds of formula IWι
Figure imgf000036_0002
wherein Ri, R3, R4, Rn, R12, R13, Xi and X2 are as defined for formula I with the exception of R13 as amino, and R2 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
R2-L2 (IV), wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 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 IW1
Figure imgf000036_0003
wherein Ri, R2, R3, R , Rn, Rι2, Rι3, Xi and X2 are as defined (Reaction Scheme 1), with the proviso that, when X2 in the compound of formula IW1 is sulfur, Rι3 must be other than hydrogen (S-alkylation), or ad) amination of compounds of formula IW1
Figure imgf000037_0001
wherein R^ R2, R3, R4, Rn, R12, Xi and X2 are as defined for formula I and R13 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
Figure imgf000037_0002
wherein Ri, R2, R3, R4, Rn, Rι2, Xi and X2 are as defined and R13 is amino (Reaction
Scheme 1 ), or ae) halogenation of compounds of formula IW1
Figure imgf000037_0003
wherein R2, R3, R4, R12, Rι3, Xi and X2 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,
Figure imgf000037_0004
wherein R2, R3, R4, R12, R13, Xi and X2 are as defined and Ri and/or Rn are halogen
(Reaction Scheme 1 ), or af) fluorination of compounds of formula IW1
Figure imgf000038_0001
wherein R2, R3, R , Rι2, R13, X< and X2 are as defined for formula I and Ri and/or Rn are hydrogen, using an electrophilic fluorinating reagent, for example FN(SO2CF3)2 or Selectfluor™ (= 1-chloromethyl-4-fluoro-1 ,4-diazabicyclo[2.2.2]octane bis(tetrafluoroborate); Manufacturer: Air Products European Technology Group, England), preferably after activation by means of a metallation reaction, for example using n-butyllithium, sec- butyllithium or lithium diisopropylamide (LDA), and advantageously with the aid of an ortho- directing group, for example a uracil radical in a compound of formula IW1 or a group A in a compound of formula II
Figure imgf000038_0002
wherein R2, R3 and R4 are as defined for formula I, Ri is hydrogen, and A is, for example, a group -NHC(X2)R5 or -NHC(X2)X0R5, wherein X2 is oxygen or sulfur, X0 is oxygen, sulfur or amino, and R5 is d-C6alkyl or phenyl, to form the compound of formula IW1 wherein R2, R3, R , ι2, R13, Xi and X2 are as defined and Ri and/or R are fluorine, or to form the compound of formula II wherein R2, R3, R4 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. Reaction Scheme 1 :
Figure imgf000039_0001
(IW,): R13=NH2
The process according to the invention for the preparation of compounds of formula I is carried out according to variant b) and Reaction Scheme 1 b) and comprises, for the preparation of those compounds of formula I
Figure imgf000040_0001
wherein Ri, R2, R3 and R4 are as defined for formula I and W is a group W2
Figure imgf000040_0002
wherein Rι , R15 and X3 are as defined for formula I and Ri6 is hydrogen, d-C3alkyl, d- C3haloalkyl, halogen, d-C3alkoxy, Cι-C3haloalkoxy, mercapto, d-C3alkylthio, Ci- C3alkylsulfinyl, Cι-C3alkylsulfonyl, allylthio, propargylthio, amino, d-C3alkylamino, di(d- C3alkyl)amino, allylamino, propargylamino or cyano, treating a compound of formula IWi
Figure imgf000040_0003
wherein R , R2, R3, R l Rn, Rι2, Xi and X2 are as defined for formula I and R13 is hydrogen, either, according to route f) in Reaction Scheme 2, with an alkylating reagent, for example R13-L of formula IX, wherein Rι3 is d-C3alkyl, CrC3haloalkyl, 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 (R2O)2SO2, wherein R2 is as defined for formula I with the exception of R2 as hydrogen, or with a Meerwein's salt (R3O»BF4), wherein R is preferably methyl or ethyl, or a freonising reagent, for example CHF2CI or BrCH2F, and thereby effecting direct conversion into the compound of formula IW2
Figure imgf000040_0004
wherein Ri, R2, R3 and R4 are as defined, R 4, R15 and X3 are as defined for R , Rι2 and X1 t respectively, and Rι6 is d-C3alkoxy, d-C3haloalkoxy, d-C3alkylthio, allylthio or propargylthio, or, according to route d) in Reaction Scheme 2, first of all obtaining, using a halogenating reagent, for example phosphorus oxychloride, the compound of formula IW2
Figure imgf000041_0001
wherein Ri, R2, R3 and R4 are as defined, Ru, Ri5 and X3 are as defined for Rn, Ri2 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-C3alcoholate, a d-C3alkylthiolate or an alkali metal cyanide, into the compound of formula IW2
Figure imgf000041_0002
wherein R1 t R2, R3, R4, R , Rι5 and X3 are as defined and Rι6 is Cι-C3alkoxy, Cι-C3alkylthio or cyano, or, when X2 in the compound of formula IWι is oxygen, first of all converting that compound, according to route e) in Reaction Scheme 2, using a thionating reagent, for example phosphorus pentasulfide (P2S5), into the compound of formula IWig
Figure imgf000041_0003
wherein Ri, R ) R3, R4, Rn, Rι2 and Xi are as defined, and then treating that compound with an alkylating reagent of formula
Figure imgf000041_0004
wherein R 3 is CrC3alkyl, Cι-C3haloalkyl, 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-C3alkyl halide, especially methyl iodide, or Cι-C3alkyl sulfate, especially dimethyl sulfate, and optionally of formula IV R2-L2 (IV), wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or sulfonate, especially mesyloxy or tosyloxy, to thereby yield the compound of formula IW2 wherein Ri to R4, Rι , R15 and X3 are as defined and R 6 is d-C3alkylthio, Cι-C3haloalkylthio, allylthio or propargylthio (route f) in Reaction Scheme 2, or, for the preparation of compounds of formula IWιg according to route ka) in Reaction Scheme 2, reacting a compound of formula llc4
Figure imgf000042_0001
wherein R1 f R2, R3 and R4 are as defined hereinbefore, X0 is oxygen, sulfur or amino, and R5 is C -C4alkyl or phenyl, with an enamine derivative of formula Vila
Figure imgf000042_0002
wherein Rn, Rι2 and Xi are as defined and R6 is Cι-C4alkyl, or, according to route kb) in Reaction Scheme 2, reacting a compound of formula llc6
Figure imgf000042_0003
wherein R1 p R2, R3 and R4 are as defined and Rι6 is Cι-C3alkyl or Cι-C3haloalkyl, with an enamine derivative of formula Vila
Figure imgf000042_0004
wherein Rn, R12 and Xi are as defined and R6 is Cι-C4alkyl, to yield the compounds of formula IW2, wherein Rι4, R15 and X3 are as defined for Rn, R 2 and X respectively, in compounds of formulae Vila and IW1, and Ri6 is as defined. Reaction Scheme 2:
Figure imgf000043_0001
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
Figure imgf000044_0001
wherein R1 f R , R3 and R are as defined for formula I and W is a group W3
Figure imgf000044_0002
wherein Rι7, Rι8, R19 and X5 are as defined for formula I, first of all converting a compound of formula Ha
Figure imgf000044_0003
wherein Ri, R2, R3 and R are as defined for formula I, under standard diazotisation conditions, e.g. using HNO3/H2SO4, and with reduction of the diazonium salt, as described, for example, in 'Methoden der Organischen Chemie (Houben-Weyl)', volume X/2 (Stickstoffverbindungen), Georg Thieme Verlag, Stuttgart, 1967, pages 180 ff., into the hydrazine derivative of formula He
Figure imgf000044_0004
and then condensing that compound with the reagent of formula Xla or Xlb
Figure imgf000044_0005
wherein Rι7 and Rι8 are as defined for formula I and Hal is halogen, especially chlorine or bromine, to form the hydrazone derivative of formula llf
Figure imgf000045_0001
the substituents Ri, R , R3, R4, Rι and Rι8 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
Figure imgf000045_0002
wherein R19 and X5 are as defined for formula I and R8 is Cι-C4alkyl, 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 IW3
Figure imgf000045_0003
wherein Ri, R2, R3, R4, R17, Riβ, R19 and X5 are as defined, and, optionally, further functionalising that compound according to the definitions of Ri, R , Riβ and X5 in analogous manner to that described under aa), ac) or ae). Reaction Scheme 3:
Figure imgf000046_0001
The process according to the invention for the preparation of compounds of formula I according to variant b) and Reaction Scheme 1 b is carried out analogously to known processes, as described, for example, in WO 99/52893, EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, US-A-5 665 681 and US-A-5 661 109, and comprises, for the preparation of those compounds of formula I
Figure imgf000046_0002
wherein R1 ( R2, R3 and R4 are as defined for formula I and W is a group W4
Figure imgf000046_0003
wherein R20, R2ι, R22 and X7 are as defined for formula I, reacting a compound of formula
Figure imgf000047_0001
wherein Ri, R2, R3, R and X7 are as defined for formula I, X0 is oxygen, sulfur or amino, and R5 is d-dalkyl, with an amino acid ester of formula XIII
Figure imgf000047_0002
wherein R20, R21, R22 and X6 are as defined for formula I and R9 is Cι-C4alkyl, to form the compound of formula lig
Figure imgf000047_0003
wherein Ri, R2, R3, R , R9, R2o, R21, R22, Xβ and X7 are as defined, and then cyclising (Reaction Scheme 4) the resulting compound to form the compound of formula IW
Figure imgf000047_0004
and, optionally, further functionalising that compound according to the definitions of R^ R2, R20, R21, R22, XΘ and X7 in analogous manner to that described under aa), ac) or ae). For example, the compound of formula IW4 wherein R22 is hydrogen and X7 is oxygen can, in analogous manner to that described under ac), be further reacted with an alkylating reagent of formula X
Figure imgf000047_0005
wherein R22 is d-C3alkyl and L5 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 IW4 wherein R22 is d-C3alkyl.
Moreover, for example, the compound of formula IW4 wherein R22 and R2o or R22 and R2ι together form a C3-C5alkylene bridge which is, for example,
1 ) interrupted by -C(O)- or substituted by hydroxy, can readily be converted, by standard methods, for example using the reagent DAST (diethylaminosulfur trifluoride) or Deoxyfluor™ (= bis(2-methoxymethyl)aminosulfur trifluoride), into the corresponding derivatives substituted once or twice by fluorine (Example 19), or
2) interrupted by sulfur, can readily be converted, using a suitable oxidising agent, for example sodium pehodate (NalO4), into the corresponding -S(O)- or -S(O)2- derivative.
Reaction Scheme 4:
Figure imgf000048_0001
(IW4): „ other than H The process according to the invention for the preparation of compounds of formula I according to variant b) and Reaction Scheme 1b is carried out analogously to known processes, as described, for example, in WO 99/52893, EP-A-0 210 137, DE-A-2 526 358, EP-A-0 075 267 and EP-A-0 370 955, and comprises, for the preparation of those compounds of formula I
Figure imgf000049_0001
wherein Ri, R2, R3 and R4 are as defined for formula I and W is a group W5
Figure imgf000049_0002
wherein R23, R24, X8 and X9 are as defined for formula I, either, according to Reaction Scheme 5, reacting a compound of formula llc2 or lld2
Figure imgf000049_0003
wherein R , R2, R3, R and X9 are as defined for formula I, X0 is oxygen, sulfur or amino, and R5 is d-C alkyl, with a hydrazide ester of formula XIV
Figure imgf000049_0004
wherein R23, R2 and X8 are as defined for formula I and Rio is Cι-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
Figure imgf000050_0001
wherein R1 t R2, R3, R , Rι0, R23, R2 , Xβ and X9 are as defined, and then cyclising that compound to form the compound of formula IW5
Figure imgf000050_0002
or, according to Reaction Scheme 5a, reacting a compound of formula llc5 or lld5
Figure imgf000050_0003
wherein R1 t R2, R3, R , R5, Xo and X8 are as defined, with a hydrazine of formula XXXVa
R24NHNHR23 (XXXVa), wherein R23 and R2 are as defined, to form the compound of formula lip
Figure imgf000050_0004
and cyclising that compound, according to route r) in Reaction Scheme 5a, with phosgene, thiophosgene or a chloroformate of formula Via
CIC(X9)OR9 (Via) wherein X9 is as defined and R9 is Cι-C4alkyl.
According to Reaction Scheme 5a, route s), starting from the compounds of formula lip
Figure imgf000051_0001
wherein Ri, R2, R3 and R4 are as defined for formula I with the proviso that X8, R23 and R24 are as defined for Y2, R 0 and R4ι, respectively, the compounds of formula I wherein W is a group Wi2
Figure imgf000051_0002
and R40, R4ι, Y2 and X15 are as defined for formula I, can be obtained by reaction with phosgene, thiophosgene or a chloroformate of formula Vlb
CIC(Xι5)OR9 (Vlb), wherein X15 is as defined and R9 is Cι-C4alkyl. For example, the compounds of formula IWι2 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.
The compound of formula IW5 may, optionally, be further functionalised according to the definitions of Ri, R2, R23, R24, X8 and X9 in analogous manner to that described under aa), ac) or ae).
For example, the compound of formula IW5 wherein R23 and/or R24 are hydrogen can be further reacted, in analogous manner to that described under ac), with an alkylating reagent of formula XVa and/or XVb
R23-L3 (XVa) and/or R24-L4 (XVb), wherein R23 and R24 are as defined for formula I with the exception of R23 and R24 as hydrogen, and L3 and L4 are each 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 to form the compound of formula IW5 wherein R23 and/or R24 are Cι-C3alkyl or d-C3haloalkyl. Optionally, the compound of formula IW5 wherein R2 is hydrogen, and R23 and R24 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
R2-L2 (IV), wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group, for example halogen, e.g. chlorine, bromine or iodine, or sulfonate, e.g. mesyloxy or tosyloxy.
Likewise, the compound of formula IW12 may be further functionalised (R1 f R2, R23, R24 or R40 and R ι, and X15) 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.
Reaction Scheme 5:
Figure imgf000052_0001
(IW5): R and/or RP4 other than H (iw5)
24 Reaction Scheme 5a:
Figure imgf000053_0001
(IWι2)
It is also possible to prepare the compounds of formula I wherein W is a group W6, W7, W8, W9 and W12 analogously to the process according to the invention described above according to variant b) and as illustrated in Reaction Scheme 1 b. Such processes are described, for example, in WO 99/52893.
Furthermore, 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,, W2, W3, W4, W5, W6, W7, W8, W9, W10, Wn, W13, Wι5, W,9 or W20.
The process of the invention according to variant b) for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in J. Org. Chem. 56, 5643 (1991 ), J. Heterocycl. Chem. 27, 2017 (1990), DE-OS-3 917 469, WO 94/22828, WO 88/09617 and US-A-5 449 784, and comprises, for the preparation of those compounds of formula I
Figure imgf000054_0001
wherein R f R2, R3 and R4 are as defined for formula I and W is a group W6
Figure imgf000054_0002
wherein R25, R26 and X4 are as defined for formula I, first of all converting a compound of formula Ha
Figure imgf000054_0003
wherein R1 f R2, R3 and R4 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 (Stickstoffverbindungen), Georg Thieme Verlag, Stuttgart, 1967, pages 180 ff., into the hydrazine derivative of formula He
Figure imgf000054_0004
and then, according to route g) in Reaction Scheme 6, condensing that compound with the reagent of formula Xlc
Figure imgf000054_0005
wherein R25, R2β and X4 are as defined, U is oxygen, sulfur or imino, and R84 is d-C4alkyl, 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
Figure imgf000055_0001
and then cyclising that compound either with base catalysis, for example using an alcoholate, e.g. sodium ethanolate, or preferably with acid catalysis, for example using a carboxylic acid, e.g. acetic acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, in a suitable solvent as mentioned above or also, for example, in a carboxylic acid, e.g. acetic acid, or, according to route h) in Reaction Scheme 6, condensing the compound of formula He with the reagent of formula Xld
O
II (Xld),
R 25 COOH
wherein R2s is as defined, with acid catalysis, for example using an Cι-C4alkylcarboxylic 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
Figure imgf000055_0002
and subsequently cyclising that compound in 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
(R6oO)2P(O)N3 (XXXIX), wherein Rεo is d-dalkyl, to form the compound of formula IWβa
Figure imgf000056_0001
wherein Ri, R2, R3, R and R25 are as defined and R26 is hydrogen, and then optionally converting into the compounds of formula IW6 using the reagent of formula Xa
Figure imgf000056_0002
wherein R26 is d-C alkyl or C C4haloalkyl, e.g. methyl or bromodifluoromethyl, and L5 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. toluene or one of the xylene isomers, or in water, or in a two- phase system consisting of a water-immiscible solvent and water, in the presence of a phase-transfer catalyst, for example a quaternary ammonium salt, e.g. tetrabutylammonium bromide, and in the presence of a 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
Figure imgf000056_0003
wherein R25 is C C alkyl or Cι-C4haloalkyl, and R02s is hydrogen, Cι-C4alkyl, 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 lleι
Figure imgf000056_0004
wherein R1 f R2, R3, R4, R25 and R025 are as defined, and then reacting that compound with an isocyanate or isothiocyanate of formula Xlf R26NCX4 (Xlf) wherein R26 is d-dalkyl or Cι-C4haloalkyl and X4 is oxygen or sulfur, or with an alkali metal cyanate or alkali metal thiocyanate of formula Xlei
Figure imgf000057_0001
wherein M+ is an alkali metal ion and X4 is as defined (e.g. Na+ OCN, K+ OCN, or K+ SCN), to thereby yield the compound of formula llmi and/or llm2
Figure imgf000057_0002
wherein Ri, R2, R3, R4, R2 and R025 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.
From compounds of formula llmi and/or llm2, it is possible, according to route k) in Reaction Scheme 6, either 'in situ' or after their isolation, by reaction with a carboxylic acid of formula Xli or an activated form thereof of formula Xli1
R25COOH (Xli) or R25C(O)-Lι6(Xliι), wherein R25 is d-C4alkyl or d-C haloalkyl and Lie is a leaving group, for example halogen, e.g. chlorine (= acid chloride), or a carboxyl group -OC(O)R25 (= anhydride), or with a corresponding ortho ester of formula Xli2
Figure imgf000057_0003
wherein R25 is as defined and R61 is methyl or ethyl, to yield the compounds of formula IW 6
Figure imgf000057_0004
wherein R1 f R2, R3, R4, R25, R26 and X are as defined.
According to route j) in Reaction Scheme 6, the compounds of formula llnrii and/or llm2 can first of all be hydrolysed to form the compound of formula llm
Figure imgf000058_0001
and then, in the presence of a carboxylic acid of formula Xli or an activated form thereof of formula Xliι or Xli2, with heating, cyclised to form the compounds of formula IW6. The reactions with the carboxylic acid of formula Xli are advantageously carried out without isolation of the compounds of formulae llmi and/or llm2 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 llm2 wherein R025 is hydrogen can also, according to route I) in Reaction Scheme 6, be converted into the compounds of formula IW6 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.
Reaction Scheme 6 illustrates those reactions, which are especially suitable for the preparation of compounds of formula IW6 wherein R25 is hydrogen, Cι-C alkyl or C dhaloalkyl or wherein R26 and R25 together form a C3-C5alkylene bridge. The compounds of formulae IW6a and IW6 wherein R26 and/or R2 are hydrogen or R is hydrogen and X is oxygen may optionally be further functionalised, according to the definitions of Ri, R2, R26 and X4, as described above under ab) or ac) using an alkylating reagent, for example R26-Lι and R2-L2, or as described above under ae) or aa).
Reaction Scheme 6:
Figure imgf000059_0001
Starting from the compound of formula He
Figure imgf000059_0002
wherein R1 f R2, R3 and R4 are as defined for formula I, it is also possible to prepare (according to variant b) and Reaction Scheme 1b) the compounds of formula I wherein W is a group W6 (compounds of formula IW6), Wι6 (compounds of formula IWι6) or Wι7 (compounds of formula IWi7) by reacting the compound of formula He first with a chloroformic acid ester of formula XXXIVa
CICOOR84 (XXXIVa), wherein R8 is C C alkyl, and then with an isocyanate or isothiocyanate of formula Xlf or
Xlg
R26N=C=X4 (Xlf) or R50N=C=Xι9 (Xlg), wherein R26 and R50 are Crdalkyl or d-C4haloalkyl and X4 and Xι9 are oxygen or sulfur, to yield the compound of formula Ho or llθ , respectively,
Figure imgf000060_0001
wherein Ri, R2, R3, R4, 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 IW6b or IWι6b
Figure imgf000060_0002
and, using standard processes, carrying out either alkylation (R2, R25 and R26 or R2, R49 and R50 = alkyl) according to ab) or ac) and/or thionation (X4, Xι8 and/or X19 = S) and optionally alkylation (R25) according to aa) and/or optionally halogenation (Ri, R25 = halogen) according to ae), to yield the compounds of formulae IW6 and IWι6
Figure imgf000060_0003
wherein R3, R4, X4, Xι8 and Xi9 are as defined, Ri is hydrogen or halogen, R25 is halogen, d-dalkoxy or C C alkylthio and R2, R26, R49 and R50 are each independently of the others hydrogen or alkyl. For example, the compound of formula IW6 wherein R26 is other than hydrogen and X is sulfur can be alkylated with the reagent of formula IV
Figure imgf000061_0001
wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group, for example halogen, especially chlorine, bromine or iodine, in the presence of an alkali metal carbonate. When R50 in the compound of formula IWι6 is hydrogen, that compound can, according to standard processes, be subsequently alkylated (R52 = Cι- dalkoxy, C C3alkylthio), thionated (X20 = sulfur) and/or halogenated (Ri, R52 = halogen) to yield the compound of formula IWι7
Figure imgf000061_0002
wherein Ri, R2, R3 and R4 are as defined, X20 is oxygen or sulfur, R51 is Crdalkyl and R52 is halogen, d-C3alkoxy or Cι-C3alkylthio. Reaction Scheme 6a illustrates those reactions.
The above reaction sequence is especially suitable for preparing compounds of formula IW6 wherein R25 is hydroxy, halogen, d-C alkoxy, Cι-C4haloalkoxy, d-C alkylthio, C1- dhaloalkylthio, d-dalkylsulfinyl, Cι-C4haloalkylsulfinyl, C C alkylsulfonyl, C dhaloalkylsulfonyl or cyano and also for compounds of formulae IW16 and IWι7 wherein R49, R50, R51, R52, X18, X19 and X2o are as defined above.
Reaction Scheme 6a:
Figure imgf000062_0001
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in DE-OS-3 917 469 and WO 00/15633, and comprises, for the preparation of those compounds of formula
Figure imgf000063_0001
wherein R1 f R2, R3 and R4 are as defined for formula I and W is a group W7
Figure imgf000063_0002
wherein R27, R28, Xι0 and Xn are as defined for formula I, reacting a compound of formula Ha
Figure imgf000063_0003
wherein R1 ( R2, R3 and R4 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
(XXXIII),
Figure imgf000063_0004
wherein R27 and R28 are as defined for formula I, in a temperature range of from 20° to 200°C. Reaction Scheme 7 and Example P15 illustrate that reaction sequence. The resulting compound of formula IW7a
Figure imgf000064_0001
wherein, for example, Ri and/or R2 are hydrogen, may be further functionalised according to the definitions of Ri, R2, Xι0 and Xn in accordance with processes described under aa), ac) and ae) to form compounds of formula IW7. Reaction Scheme 7:
Figure imgf000064_0002
(lla) (XXXIII)
(Xιo> Xn) (IW7)
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in WO 00/15633, and comprises, for the preparation of those compounds of formula I
Figure imgf000064_0003
wherein R1 t R2, R3 and R4 are as defined for formula I and W is a group Wn
Figure imgf000064_0004
wherein R36l R37, R∞ and R39 are as defined for formula I and X 4 is oxygen (compound of formula IWna in Reaction Scheme 17), either, according to route o) in Reaction Scheme 17, reacting a compound of formula lld4
Figure imgf000065_0001
wherein Ri, R2, R3 and R4 are as defined, with a compound of formula XXXVIII
R5X0H (XXXVIII), wherein R5 is d-C4alkyl and X0 is oxygen, sulfur or amino, to yield the compound of formula llc4
Figure imgf000065_0002
and further reacting that compound in succession with the amines of formulae XXXVIIIa and XXXVIIIb
R38NH2 (XXXVIIIa) and R39NH2 (XXXVIIIb), or with the diamine derivative of formula XXXVIIIc
H2N-R38-R39-NH2 (XXXVIIIc), wherein in the compounds of formulae XXXVIIIa and XXXVIIIb R38 is Crdalkyl and R39 is hydrogen or d-dalkyl and in the compound of formula XXXVIIIc R^ and R39 together form a C2- or C3-alkylene bridge, to form the open-chain or cyclic amine derivative of formula llq
Figure imgf000065_0003
wherein R1 ( R2, R3, R4, R38 and R39 are as defined, and then condensing that compound with a compound of formula XXV
Figure imgf000066_0001
wherein 36and R37 are as defined, R6 is d-C4alkyl and Ln is hydroxy, CrC3alkoxy, chlorine, amino or d-C3alkylamino, or, according to route p) in Reaction Scheme 17, first of all reacting a compound of formula IW2
Figure imgf000066_0002
wherein Ri, R2, R3, R4, X3, Rι4 and R15 are as defined for formula I and Rι6 is d-dalkylthio, with an oxidising agent, for example hydrogen peroxide, to form the corresponding d- dalkylsulfonyl derivative of formula IW2 wherein R16 is d-C3alkylsulfonyl, 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
Roι6NH2 (XXXVIIId) or (R0ι6)2NH (XXXVIIId,), wherein R016 is hydrogen, C C3alkyl, allyl or propargyl, into the compound of formula IW2
Figure imgf000066_0003
wherein Ri, R2, R3, R4, X3, Rι4 and Rι5 are as defined and Rι6 is amino, CrC3alkylamino, di(CrC3alkyl)amino, allylamino, diallylamino, propargylamino or dipropargylamino, and then reacting that compound, when R16 is amino, with an aldehyde derivative of formula XXVIa
Figure imgf000066_0004
✓C R038R39" 12 (XXVIa),
R1270
wherein Rι26 is Cr or C2-alkyl and Rι27 is hydrogen or C or C2-alkyl, R038 and R39 together form a C or C2-alkylene bridge and L 2 is a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, or with the reagent of formula XXVIb Li3-R38R39-Lι2 (XXVIb), wherein R^ and R39 together form a C2- or C3-alkylene bridge, L12 and Li3 are each a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, or with the alkylating agent of formula XXVId
R38-Li2 (XXVId), wherein R38 is d-dalkyl and L12 is a leaving group, for example chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy, or, according to route q) in Reaction Scheme 17, first of all reacting the compound of formula IW2 with an oxidising agent, for example hydrogen peroxide, and then with a reagent of formula XXVIc
H2N-R39R38-Lι3 (XXVIc), wherein R38 and R39 together form a C2- or C3-alkylene bridge and L 3 is as defined, wherein according to routes p) and q) in Reaction Scheme 17 the substituents Xι4, R36 and R3 in compounds of formulae IWn and IWna take the meanings of the corresponding substituents X3, RM and Rι5, respectively, in the starting compound IW2, and R38 and R39 together form a C2- or C3-alkylene or -alkenylene bridge.
The resulting compounds of formulae IWn and IW2 wherein R1 t R2, R3, R4, R , R15, R36, R37, R38, R39, X3 and XH are as defined and Rι6 is d-dalkylsulfinyl, C C3alkylsulfonyl, amino, CrC3alkylamino, di(CrC3alkyl)amino, allylamino or propargylamino, may be further functionalised in accordance with the standard methods described above: when X or X3 is oxygen, in accordance with aa) using a thionating reagent; when R38 is hydrogen, in accordance with ab) using an alkylating reagent of formula IXa
R38-Lι (IXa), wherein R38 is as defined for formula I and Li is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy; when R2 is hydrogen, in accordance with ac) using an alkylating reagent of formula IV; and, when Ri and/or R36 are hydrogen, in accordance with ae) using a halogenating reagent. Reaction Scheme 17:
Figure imgf000068_0001
(H 4) (Hc4)
Figure imgf000068_0002
(IW2): R16=amino, C1-C3alkylamino (IW2): R16=C1-C3alkylthio
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in DE-OS-3 917 469, WO 00/15633 and US-A-4 831 150, and comprises, for the preparation of those compounds of formula I
Figure imgf000069_0001
wherein Ri, R2, R3 and R4 are as defined for formula I and W is a group W8 or W9
Figure imgf000069_0002
wherein R29, R30, R3ι, R32, R33 and Xι2 are as defined for formula I, condensing with one another a compound of formula He
Figure imgf000069_0003
wherein Ri, R2, R3 and R4 are as defined, and a compound of formula Xlh
R85OC(Xι2)-CH(R3o)-COR29 (Xlh), wherein R29, R30 and Xι2 are as defined and R85 is C C4alkyl 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 IW8
Figure imgf000069_0004
That compound may be further functionalised in accordance with the standard methods aa), ac) and/or ae) described above. In particular, it is possible, starting from the compound of formula IW8, to obtain, by means of halogenation, for example using phosgene, oxalyl chloride, thionyl chloride, phosphorus oxychloride or phosphorus pentachloride, phosphorus oxybromide or phosphorus tribromide (R1 ( R33), and/or alkylation (R2, R ) and/or thionation and alkylation (R33), the compound of formula IW9
Figure imgf000070_0001
wherein R1 ( R2, R3 and R are as defined, R3ι and R32 have the meanings of R29 and R30, respectively, in the compound of formula IW8 and R33 is halogen, hydroxy, d-C3alkoxy, C C3haloalkoxy, mercapto, CrC3alkylthio, C C3alkylsulfinyl or d-C3alkylsulfonyl. Reaction Scheme 10 illustrates those reaction steps.
Reaction Scheme 10
Figure imgf000070_0002
(IW9): R33 = alkoxy, alkylthio, Cl, Br (IWβa): R33= CI, Br (IWβ)
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes and comprises, for the preparation of those compounds of formula I
Figure imgf000071_0001
wherein R1 f R2, R3 and R are as defined for formula I and W is a group Wi2
Figure imgf000071_0002
wherein R40, R4ι, X15 and Y2 are as defined for formula I, reacting a compound of formula lld3 or llc3
Figure imgf000071_0003
wherein R1 f R2, R3, R4 and Y2 are as defined for formula I, R5 is d-dalkyl and X0 is oxygen, sulfur or amino, with a compound of formula XXXV
R40-NH-NH-R4ι (XXXV), wherein R40 and R4ι are as defined for formula I, to yield the compound of formula llpι
Figure imgf000071_0004
and further reacting that compound with the compound of formula XXXVI
X |,5
(XXXVI),
'-1 wherein Xi5 is oxygen or sulfur, and L8 and L are leaving groups, for example halogen, e.g. chlorine or bromine (phosgene, thiophosgene), or L7 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 resulting compounds of formula IWi2
Figure imgf000072_0001
wherein, for example, R1 f R2, R 0 and R ι are hydrogen and X15 is oxygen, may be further functionalised according to the definitions of R f R2, R40, R4ι and X15 in accordance with processes described under aa), ac), ad) and ae).
The iso(-thio-)cyanate derivative of formula lld3 may, in addition, be converted into the compound of formula llc3 by reaction with a reagent of formula XXXVIII
R5X0H (XXXVIII), wherein R5 is d-dalkyl and X0 is oxygen, sulfur or amino.
Reaction Scheme 8:
Figure imgf000072_0002
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in Helv. Chim. Acta 61 , 1175 (1978), J. Heterocyd. Chem. 17, 1365 (1980) and WO 97/30980, and comprises, for the preparation of those compounds of formula I
Figure imgf000073_0001
wherein R1f R , R3 and R4 are as defined for formula I and W is a group Wι3
Figure imgf000073_0002
wherein R42, R43, Xiε and Xι7 are as defined for formula I, first of all converting a compound of formula Ha
Figure imgf000073_0003
wherein R1 ( R2, R3 and R4 are as defined for formula I, under diazotisation conditions, into the diazonium salt of formula llee
Figure imgf000073_0004
wherein R R2, R3 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
/ .C-H- NHR, (XXXVIIa), 42 ft
O
wherein R and R 3 are as defined, to form the hydrazone derivative of formula Ilk
Figure imgf000074_0001
and further reacting that derivative with the chloroformic acid ester of formula XXXIVb
CICOOR85 (XXXIVb), wherein R85 is d-dalkyl. to form the compound of formula III
Figure imgf000074_0002
which is cyclised under basic conditions, for example in aqueous sodium or potassium hydroxide solution, to form the compound of formula IWι3a
Figure imgf000074_0003
or, in accordance with route n) in Reaction Scheme 9, the diazonium salt of formula llee may be coupled with the reagent of formula XXXVIIb
(XXXVIIb),
Figure imgf000074_0004
wherein R 2, R43 and R85 are as defined, to form the compound of formula III directly, which may then be cyclised analogously to route m), under basic conditions, to form the compound of formula IWι3a.
The resulting compounds of formula IWι3a wherein, for example, R42 is a carboxyl group may be converted into the compounds of formula IWι3 wherein R42 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. Furthermore, the compounds of formula IWι3a wherein R43 and/or R2 are hydrogen or R, is hydrogen may be further functionalised according to the definitions of R1 f R2, R43, Xι6 and Xι7 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 Xι6 and Xι7 in the compound of formula IWι3 are sulfur, by means of thionation as described under aa). Reaction Scheme 9 illustrates those reaction sequences. Reaction Scheme 9:
Figure imgf000075_0001
Figure imgf000075_0002
(iw13)
Figure imgf000075_0003
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in EP-A-0 726 258, and comprises, for the preparation of those compounds of formula I
Figure imgf000076_0001
wherein Ri, R2, R3 and R4 are as defined for formula I and W is a group Wi8
Figure imgf000076_0002
wherein R53, R5 ) and X2ι are as defined for formula I, reacting a compound of formula Ha
Figure imgf000076_0003
wherein R1 t R2, R3 and R4 are as defined, with a hydrazinecarboxylic acid ester of formula XlVa
Figure imgf000076_0004
wherein R53 and X2ι are as defined, R85 is d-dalkyl and L14 is a leaving group, for example halogen, e.g. chlorine or bromine, to form the compound of formula llr
Figure imgf000076_0005
and heating that compound in the presence of an alkali metal hydroxide solution and cyclising that compound to form the compound of formula IW18
Figure imgf000077_0001
wherein R1 p R2, R3, R4, R53 and X21 are as defined and R5 is hydrogen, and carrying out a further reaction with the alkylating reagent of formula XVII
Figure imgf000077_0002
wherein RM is d-C3alkyl and L15 is a leaving group, for example halogen, especially chlorine, bromine or iodine, or a sulfonate, especially mesyloxy or tosyloxy, and/or, when R2 is hydrogen, optionally carrying out a reaction, as described under ac) above, with the alkylating reagent of formula IV
Figure imgf000077_0003
wherein R2 is as defined for formula I with the exception of R2 as hydrogen and L2 is a leaving group, and/or, when X2ι is oxygen, carrying out thionation as described under aa) above. Reaction Scheme 18 illustrates those reactions.
Reaction Scheme 18:
Figure imgf000078_0001
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described, for example, in J. Pestic. Sci. 18, 309 (1993), and comprises, for the preparation of those compounds of formula I
Figure imgf000078_0002
wherein Ri, R2, R3 and R4 are as defined for formula I and W is a group W20
-N- ,N,
^> -R 56
(W20),
S-N
R 57 wherein R56 and R57 are as defined for formula I, first of all converting a compound of formula lla
Figure imgf000079_0001
wherein Ri, R2, R3 and R4 are as defined, for example using thiophosgene, into the isothiocyanate of formula lld4
Figure imgf000079_0002
and then further reacting that isothiocyanate with an amidine derivative of formula XVIII
(XVIII),
Figure imgf000079_0003
wherein R56 and R57 are as defined, to yield the compound of formula lls
Figure imgf000079_0004
which, on treatment with chlorine or bromine, is cyclised to form the compound of formula IW20
Figure imgf000079_0005
and is optionally alkylated (R2) and/or halogenated (Ri) in accordance with standard processes as described under ac) and ae) and, when R56 is d-dalkylthio, is optionally oxidised using an oxidising agent, for example sodium periodate, to form the corresponding Crdalkylsulfinyl or d-C3alkylsulfonyl derivative. Reaction Scheme 19 illustrates those reactions. Reaction Scheme 19:
Figure imgf000080_0001
(Ha) (llcU)
Figure imgf000080_0002
The process according to the invention for the preparation of compounds of formula I is carried out analogously to known processes, as described for example in DE 3516631 or DE 2718799, or in C. R. Hebd. Seances Acad. Sci., Ser. C (1976), 283, 491 , for the preparation of those compounds of formula I
Figure imgf000080_0003
wherein Ri, R2, R3 and R4 are as defined for formula I, and W is a group W2ι
Figure imgf000080_0004
wherein R58, Rs9) X23, X24 and X25 are as defined for formula I, first of all converting a compound of formula Ha
Figure imgf000081_0001
wherein Ri, R2, R3 and R are as defined for formula I, either, according to Reaction Scheme 21 , by reacting a compound of formula llc7 or lld7
Figure imgf000081_0002
wherein R1 ( R2, R3, R4 and X23 are as defined for formula I, X0 is oxygen, and R5 is d- C alkyl, with an urea of formula XXXVb
(XXXVb) '
Figure imgf000081_0003
wherein R58, R5 and X25 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 lltι
Figure imgf000081_0004
wherein R , R2, R3, R , R58, R59, X23 and X25 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 IW2i
Figure imgf000082_0001
or according to Reaction Scheme 21 , reacting a compound of formula llc7
Figure imgf000082_0002
wherein Ri, R2, R3, R and X23 are as defined for formula I, X0 is oxygen, and R is d- C4alkyl, 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
X24=C=N-R59 (Xlo), wherein R59 and X2 are as defined for formula I, to thereby yield the compound of formula llt2
Figure imgf000082_0003
wherein R1 f R2, R3, R4, R5, R59, X23 and X24 are as defined, X0 is oxygen, and R5 is C dalkyl, and then cyclising that compound in the presence of an isocyanate or an isothiocyanate of formula Xlp
X25=C=N-R58 (Xlp), wherein R58 and X25 are as defined for formula I, to form the. compound of formula IW21
Figure imgf000083_0001
The compound of formula IW2ι may, optionally, be further functionalised according to the definitions of R1 f R2, R58, R59, X23, X2 and X25 in analogous manner to that described under aa), ac) or ae).
For example, the compound of formula IW2ι, wherein R58 and/or R59 are hydrogen, can be further reacted, in analogous manner to that described under ac), with an alkylating reagent of formula XVc and/or XVd
R58-L3 (XVc) and/or R59-L4 (XVd), wherein R58 and R59 are as defined for formula I with the exception of R58 and R59 as hydrogen, and L3 and L are each 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 to form the compound of formula IW2ι, wherein Rsa and/or R59 are CrC3alkyl or d-C3haloalkyl. Optionally, the compound of formula IW2ι, wherein R2 is hydrogen, and R58 and R59 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
Figure imgf000083_0002
wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group, for example halogen, e.g. chlorine, bromine or iodine, or sulfonate, e.g. mesyloxy or tosyloxy.
Reaction Scheme 21:
Figure imgf000084_0001
1)CDI(forX24=0)or
1)X25=C=NR58 CIC(X24)Clor
(Xlp) CIC(X24)OR9 (if (Vic)
2) when R2, R5β, R69=H: ■±xx ... R58≠NH2)
N I
R X 2) when R2=H: alkylation, e.g. using I
R alkylation, e.g. using R58-L3 and/or R59-L4 R2-L2 (XVc) (XVd) (I 21) (IV) and/or amination (R58) and/or when R,=H: and/or when R,=H: halogenation halogenation
The process according to the invention for the preparation of compounds of formula I according to variant c) and Reaction Scheme 1c) is carried out analogously to known processes and comprises, for the preparation of those compounds of formula I
Figure imgf000084_0002
wherein Ri, R2, R3 and R4 are as defined for formula I and W is a group Wi to W21 (C-N- linked ring systems), reacting a compound of formula lib
Figure imgf000085_0001
wherein Ri, R2, R3 and R4 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
H-W (III), wherein W is a group Wi to W21, 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. tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), bis(triphenylphosphine)palladium(ll) dichloride (Pd(PPh3)2CI2) or palladium(ll) acetate (Pd(OAc)2), and/or copper iodide, and further catalytic additives, for example various phosphine ligands, e.g. biphenyl-2-bis-tert-butylphosphine, and in the presence of a suitable diluent, for example an aromatic hydrocarbon, e.g. one of the xylene isomers, or an amide, e.g. NMP or DMF, as illustrated in Reaction Scheme 1c.
Reaction Scheme 1c:
Figure imgf000085_0002
(Mb) solvent, e.g. DMF
The process according to the invention for the preparation of compounds of formula I wherein W is a group W100 to Wι09 (C-C-linked ring systems) is carried out, for example, starting from compounds of formula llu
Figure imgf000086_0001
wherein Ri to R4 are as defined for formula I and A2 is methyl, ethyl, ethynyl, cyano, formyl, acyl, carboxy or d-C4alkoxycarbonyl, according to variant d) and Reaction Scheme 1d Reaction Scheme 1 d:
Figure imgf000086_0002
(llu) (0 (w=w100-w109)
or analogously to known processes, as described, for example, in EP-A-0 839 808,
WO 96/01254 and WO 98/21199, and comprises, for the preparation of those compounds of formula I
Figure imgf000086_0003
wherein Ri, R2, R3 and R are as defined for formula I and W is a group W100
Figure imgf000086_0004
wherein Rioo is hydrogen, chlorine or bromine, R10ι is difluoromethoxy and Ri02 is as defined for formula I, converting a compound of formula llu1
Figure imgf000087_0001
using standard processes, for example using thionyl chloride, oxalyl chloride or phosgene, into the activated form (acid chloride) of formula llu2
Figure imgf000087_0002
the substituents R., R2, R3 and R in the compounds of formulae lluι and llu2 being as defined, and reacting the latter compound with a malonic acid ester of formula XL
Figure imgf000087_0003
wherein Rgo is hydrogen, a sodium, potassium or magnesium cation, trimethylsilyl or d- dalkyl, R9ι is d-C4alkyl and 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
Figure imgf000087_0004
then cyclising that keto ester with a hydrazine derivative of formula XLI
H2NNHRi02 (XLI), wherein Rι02 is as defined for formula I, to form the pyrazolone derivative of formula IWiooz
Figure imgf000088_0001
and finally subjecting that derivative to a freonisation reaction, for example using chlorodifluoromethane or bromodifluoromethane in the presence of a suitable base, for example an alkali metal hydroxide, especially sodium hydroxide, or a carbonate, especially potassium carbonate, and in a suitable solvent, for example an ether, e.g. 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 IW100a
Figure imgf000088_0002
Ri, R2, R3, R4 and R102 in the compounds of formulae IWiooz being IWiooa as defined and R100 being hydrogen or halogen, and, optionally, further functionalising that compound according to the definitions of R1 t R2, R100 and Rι02 given for formula I in accordance with standard methods.
Compounds of formula IW ooa wherein R2 is hydrogen may, for example, be alkylated, according to process variant ac), using an appropriate alkylating reagent of formula IV
Figure imgf000088_0003
wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group; or compounds of formula IWiooa 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. By that means, compounds of formula IWι00a wherein Ri0o is chlorine and Ri is hydrogen are obtained selectively. When the above halogenation reaction is carried out using an excess of halogenating reagent, it is possible to obtain, from compounds of formula IWiooz wherein Ri is hydrogen, the corresponding dihalogenated compound of formula IWiooa wherein Ri and Rioo are halogen, especially chlorine or bromine. Reaction Scheme 1 1 illustrates those reactions. Reaction Scheme 11 : oxalyl chloride or phosgene
Figure imgf000089_0001
Figure imgf000089_0002
Figure imgf000089_0003
Figure imgf000089_0004
Figure imgf000089_0005
If the keto ester of formula llx is reacted with hydrazine (compound of formula XLI wherein R102 is hydrogen) there is formed the pyrazolone derivative of formula IWiooz wherein R102 is hydrogen, which, on subsequent alkylation using the reagent of formula XVI
Figure imgf000090_0001
wherein R102 is as defined for formula I with the exception of Ri02 as hydrogen, and L10 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 R102 is as defined, also yields the isomeric pyrazolone derivative of formula IWι0ιz
Figure imgf000090_0002
and, by means of a freonisation reaction, and when R100 is hydrogen optionally by means of a halogenation reaction, the corresponding isomeric compound of formula IWι0ιa
Figure imgf000090_0003
(Reaction Scheme 12). That compound may optionally be further functionalised according to the definitions of Ri, R2, R100 and Rι02 for formula I by means of standard methods. Reaction Scheme 12:
Figure imgf000090_0004
(I ioiz) (IW,0,a): Rv R1C0=CI, Br
Further synthesis processes for the preparation of compounds of formula IW100
Figure imgf000091_0001
wherein R1 ( R2, R3, R4, Rioo and Rι02 are as defined for formula I and Rι0ι is trifluoromethyl (compound of formula IW oob), cyano (compound of formula IWiooc), or methylthio, methylsulfinyl or methylsulfonyl (compound of formula IWiooa), or Rι0ι and Rι02 together form a C3-C5alkylene bridge (compound of formula IWiooe), may be carried out in analogous manner to that described, for example, in WO 98/21199 and EP-A-0 839 808.
The process according to the invention for the preparation of compounds of formula I according to variant e) and Reaction Scheme 1e is carried out analogously to known processes and comprises, for the preparation of those compounds of formula I
Figure imgf000091_0002
wherein R,, R2, R3, R and W are as defined for formula I, reacting a compound of formula llv
Figure imgf000091_0003
wherein R R2, R3 and R are as defined and A3 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
B-W (V), wherein W is as defined for formula I and B, complementarily to A3 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- dimethylformamide (DMF) (Reaction Scheme 1 e). Reaction Scheme 1e:
Figure imgf000092_0001
solvent e.g. NMP
(llv) (0
The process according to the invention for the preparation of compounds of formula according to variant f) and Reaction Scheme 1f Reaction Scheme 1f:
Figure imgf000092_0002
is carried out analogously to known processes and comprises, for the preparation of those compounds of formula I
Figure imgf000092_0003
wherein Ri, R2, R3, R4 and W are as defined for formula I, but W is especially a group W100, reacting a compound of formula XIW
Figure imgf000093_0001
wherein Ri and W are as defined for formula I, but W is especially a group W100 (compound of formula XIW100 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
Figure imgf000093_0002
wherein R2, R3 and R4 are as defined for formula I, and L9 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
Figure imgf000093_0003
and rearranging and cyclising that compound in the presence of base, for example a carbonate, especially sodium or potassium carbonate, and an inert organic solvent, for example an amide, e.g. N-methylpyrrolidone, at temperatures of from 20° to 250°C and under normal pressure or under slight overpressure but preferably at the boiling point of the solvent used. The above 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:
Figure imgf000094_0001
(XIWioo)
Figure imgf000094_0002
Figure imgf000094_0003
Figure imgf000094_0004
The process according to the invention for the preparation of compounds of formula I according to variant g) and Reaction Scheme 1 g is carried out analogously to known processes, as described, for example, in Acta Chimica Scandinavica 23, 2322 (1969), and comprises, for the preparation of those compounds of formula I or llz
Figure imgf000094_0005
wherein Ri, R3 and R4 are as defined for formula I, R2 is especially hydrogen, W is especially a group W14 or W100-Wι09, and A0 is especially hydrogen, methyl, ethyl, fluorine, chlorine, bromine or carboxy, condensing a compound of formula XXIX
Figure imgf000094_0006
wherein Ri and W are as defined, with an acetic acid derivative of formula XXXII (XXXII) ,
Figure imgf000095_0001
wherein R3 and R are as defined, Zi is a C C4alkoxy group or a leaving group, for example chlorine or bromine, and Z2 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. sodium, potassium or barium hydroxide, and 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. Reaction Scheme 1q:
Figure imgf000095_0003
(XXIX)
Figure imgf000095_0002
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 R1 f R3, R4 and W are as defined for formula I, with an appropriate alkylating reagent of formula IV
Figure imgf000095_0004
wherein R2 is as defined for formula I with the exception of R2 as hydrogen, and L2 is a leaving group, in the presence of a base and a suitable solvent, as illustrated in Reaction Scheme 1a0: Reaction Scheme 1an:
Figure imgf000096_0001
(la) (l): W=W W10, W100-W108 or variant b), converting compounds of formula Ha, wherein Ri to R are as defined for formula I, analogously to known one- or multi-stage synthesis processes, into the corresponding cyclic ring systems Wi to W10 or W 00 to W108 in a multi-stage synthesis according to Reaction Scheme 1 b0:
Reaction Scheme 1bQ:
Figure imgf000096_0002
(lla) ('): W=Wt-W10, W100-W108 or variant c), reacting compounds of formula lib, wherein Ri to R4 are as defined for formula I and Ai is a leaving group, for example fluorine, chlorine, bromine, methylsulfonyl, trifluoromethylsulfonyloxy, methylsulfonyloxy, phenylsulfonyloxy or nitro, in the presence of a base and one or more suitable catalysts and a suitable diluent, with a cyclic compound of formula III, wherein W is as defined for formula I, according to Reaction Scheme 1c0: Reaction Scheme 1 cn:
Figure imgf000096_0003
(lib)
(I): W=W1-W10, W100-W108 or variant d), converting compounds of formula llu, wherein Ri to R4 are as defined for formula I and A2 is methyl, cyano, formyl, acyl, carboxyl or d-C4alkoxycarbonyl, analogously to known one- or multi-stage synthesis processes, according to Reaction Scheme 1d0, into the corresponding cyclic C-C-linked ring systems of formula I wherein W is
Figure imgf000097_0001
Reaction Scheme 1dg:
Figure imgf000097_0002
or variant e), reacting compounds of formula llv, wherein Ri to R4 are as defined for formula I and A3 either is a leaving group, for example chlorine, bromine or trifluoromethylsulfonyloxy or is a trialkylstannyl or boronic acid group, with a corresponding heterocyclic compound of formula V
B-W (V), wherein W is as defined above for Wt to Wi0 or W10o to Wι08, and B, complementarily to A3, 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
Reaction Scheme 1 e0:
Reaction Scheme 1 en:
Figure imgf000097_0003
(llv) (I): rW10, W100-W108 or variant f), reacting compounds of formula XIW, wherein Ri is as defined for formula I, and W is especially a group Wioo, in the presence of a base and an inert solvent at elevated temperatures, with a compound of formula XII, wherein R2 to R4 are as defined for formula and L9 is a leaving group, as illustrated in Reaction Scheme 1f0: Reaction Scheme 1fn:
Figure imgf000098_0001
(XIW)
(I): W=W100-W108
The process according to the invention described under variant b) and in Reaction Scheme 1b for the preparation of compounds of formula I wherein W is a group Wi is carried out analogously to known processes, as described, for example, in WO 99/52892 and WO 98/27083, and comprises converting a compound of formula Ha (Reaction Scheme 10), using a suitable reagent, for example oxalyl chloride, phosgene or thiophosgene, or using a reagent of formula Vl0
CI-C(X2)OR5 (Vlo), wherein X2 is as defined for formula I and R5 is d-dalkyl, into an intermediate of formula lid or llc0, respectively, and then condensing that intermediate with the corresponding enamine of formula Vllb
Figure imgf000098_0002
wherein Rn, Rι2 and Rι3 are as defined for formula I and R6 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
aa) when Xi and/or X2 are sulfur, treatment with a thionating reagent, for example Lawesson's reagent, is carried out, or ab) when Rι3 is hydrogen and X2 is oxygen, reaction with an alkylating reagent of formula IX
Figure imgf000099_0001
wherein Rι3 is as defined above with the exception of R13 as hydrogen, and Li is a leaving group, is carried out, and/or
ac) when R is hydrogen, reaction, according to process variant a), with an appropriate alkylating reagent of formula IV
Figure imgf000099_0002
wherein R2 is as defined for formula I with the exception of R as hydrogen, and L2 is a leaving group, for example chlorine, bromine, methylsulfonyloxy or phenylsulfonyloxy, is carried out, and/or
ad) when Rι3 is amino, treatment with an electrophilic aminating agent, as described, for example, in WO 96/36614, is carried out, and/or
ae) when Ri and/or Rn are chlorine, bromine or iodine, treatment with a corresponding halogenating reagent is carried out.
Those synthesis sequences are illustrated in Reaction Scheme 10-
Reaction Scheme 1n:
Figure imgf000100_0001
Compounds of formula I wherein W is a group W2 can be obtained under particular conversion conditions from compounds of formula IWi wherein Ri3 is hydrogen and X2 is oxygen or sulfur, either using an alkylating reagent or using a chlorinating reagent and a subsequent substitution reaction. Reaction Scheme 20 illustrates that process.
Reaction Scheme 20:
Figure imgf000101_0001
(IW2)
The process according to the invention described under variant b) for the preparation of compounds of formula I wherein W is a group W3 is likewise carried out analogously to known processes and comprises first of all converting a compound of formula lla, under diazotisation and condensation conditions, via a hydrazine derivative of formula He into a hydrazone of formula llf, wherein Rι7 and Rι8 are as defined for formula I, and then condensing that hydrazone with a Wittig reagent of formula Vlll0
(Vlllo),
Figure imgf000101_0002
wherein Rι9 is as defined for formula I and R8 is C C4alkyl, in the presence of from 0.1 to 1.5 equivalents of a suitable base in an inert solvent to form the cyclic group W3, and then, optionally, further reacting in an additional conversion reaction according to the corresponding meanings of Ri, R2, Rι8 and X5 in analogous manner to that described under aa), ac) or ae). Reaction Scheme 30 illustrates that reaction sequence.
Aoo Reaction Scheme 3n
Figure imgf000102_0001
The process according to the invention described under variant b) for the preparation of compounds of formula I wherein W is a group W is likewise carried out analogously to known processes, as described, for example, in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, US-A-5 665 681 and US-A-5 661 109, and comprises reacting a compound of formula llc0ι or lldι with an amino acid ester of formula Xlll0, wherein R20 , R2ι and R2 are as defined for formula I and R is d-dalkyl, and condensing the resulting intermediate of formula llg0 to form the cyclic group of formula W4a and then, optionally, further reacting the resulting compound in an additional conversion reaction according to the corresponding meanings of Ri, R2, R20, R2ι and X7 as described under aa), ac) or ae) or, when R22 is hydrogen, further reacting the resulting compound with an appropriate alkylating agent of formula X
Figure imgf000102_0002
wherein R22 is d-C3alkyl and L5 is a leaving group, for example halogen, especially chlorine, bromine or iodine, in the presence of a base. Reaction Scheme 40 illustrates that reaction sequence. Reaction Scheme 4 :,θi
Figure imgf000103_0001
The process according to the invention described under variant b) for the preparation of compounds of formula I wherein W is a group W5 is carried out analogously to known processes, as described, for example, in EP-A-0 210 137, DE-A-2 526 358, EP-A-0 075 267 and EP-A-0 370 955, and comprises reacting a compound of formula llc02 or lld2 with a hydrazide ester of formula XIV0, wherein R23 and R2 are as defined for formula I and Rι0 is d-dalkyl, in the presence of a base and a suitable solvent, and then condensing the intermediate of formula llh0 to form the cyclic group of formula W5a and then, optionally, further reacting the resulting compound in an additional conversion reaction according to the corresponding meanings of Ri, R2, R23, R24 and X9 in analogous manner to that described under aa), ac) or ae) or, when R23 and/or R24 are hydrogen, further reacting the resulting compound with an appropriate alkylating agent of formula XVa and/or XVb
R23-L3 (XVa) and/or R24-L4 (XVb), wherein R23 and R2 are as defined for formula I with the exception of R23 and R2 as hydrogen, and L3 and L4 are leaving groups, for example halogen, especially chlorine, bromine or iodine, in the presence of a base. Reaction Scheme 50 illustrates that reaction sequence. Reaction Scheme 5 Oi
Figure imgf000104_0001
In analogous manner, compounds of formula I wherein W is a group W6, W7, W8, W9 or W10 can also be prepared in accordance with the processes according to the invention described under variant b).
In process variant c), suitable catalysts are especially metal catalysts, for example Pd(PPh3)4, Pd(PPh3)CI2, Pd(OAc)2 and copper iodide. Further 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 process according to the invention described under variant d) for the preparation of compounds of formula I wherein W is, for example, a group Wioo, R101 is difluoromethoxy, R102 is hydrogen, chlorine or bromine and R1( R2, R3, R4 and Rioo are as defined for formula I, is likewise carried out analogously to known synthesis processes, as described, for example, in EP-A-0 839 808 and WO 98/21199, and comprises converting a carboxylic acid of formula lluι, via its acid chloride of formula llu2, using a suitable malonic acid ester of formula XL0
R9oOC(O)CH2C(O)OR9ι (XL0), wherein R90 is hydrogen, trimethylsilyl or d-dalkyl and R91 is Crdalkyl, in the presence of a suitable base and an inert solvent, into the keto ester of formula llx0, and then cyclising that keto ester with a corresponding hydrazine derivative of formula XLI
H2NNHRι02 (XLI), wherein Rι02 is as defined for formula I, to form a pyrazolone derivative of formula IWiooz, which is then subjected to freonisation and subsequently to a halogenation reaction. In the first stage therein, instead of R90 as hydrogen, a sodium, potassium or magnesium salt of the malonic acid monoalkyl ester may also be advantageously used. The freonisation is advantageously performed in the presence of a suitable base in water or in a two-phase system consisting of a chlorinated hydrocarbon and water or, optionally, advantageously in a closed system and under slight overpressure. Reaction Scheme 110 illustrates that reaction sequence for the preparation of compounds of formula IWiooa-
Reaction Scheme 11nl
oxalyl chloride or phosgene
Figure imgf000105_0002
Figure imgf000105_0001
Figure imgf000105_0003
In further conversion reactions, in analogous manner to that described under ac) above, the compounds of formula IWiooa wherein Ri and/or R2 are hydrogen may be further reacted, according to process variant a), with an appropriate alkylating reagent of formula IV R2-L2 (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 R100 are accordingly simultaneously chlorine or bromine. When unsubstituted hydrazine of formula XLI wherein R102 is hydrogen is used, compounds of formula IW10oz are obtained wherein Rι02 is hydrogen. Those compounds can be reacted with an appropriate alkylating agent of formula XVI
Figure imgf000106_0001
wherein Rι02 is as defined for formula I with the exception of Rι02 as hydrogen, and L10 is a leaving group, to form the corresponding compound of formula IWiooa wherein Rι02 is as defined. In addition, in that alkylation reaction there are also formed the isomeric compounds of formula IWι0ιz, which, after the freonisation reaction and, optionally, the halogenation reaction, form the corresponding isomeric compounds of formula IWι0ιa, as illustrated in Reaction Scheme 120. Reaction Scheme 12g:
1 ) freonisation
2) halogenation
Figure imgf000106_0002
Figure imgf000106_0003
Figure imgf000106_0004
Corresponding synthesis processes for the preparation of compounds of formula IW100
Figure imgf000106_0005
wherein R101 is trifluoromethyl (compounds of formula IWioob), cyano (compounds of formula IWiooc), methylthio (n3=0), methylsulfinyl (n3=1 ) or methylsulfonyl (n3=2) (compounds of formula IWiooa), or wherein R101 and Rι02 together form a C3-C5alkylene chain (n4 = 0, 1 or 2) (compounds of formula IWiooe) are known, for example, from WO 98/21 199 and EP-A-0 839 808.
Figure imgf000107_0001
d iooe)
Figure imgf000107_0002
Compounds of formula IW100 may also be prepared according to process variant f) described above by reacting a compound of formula XIW100, wherein Ri and W are as defined for formula I, with a corresponding acetamide of formula XII
Figure imgf000107_0003
wherein R2, R3 and R4 are as defined for formula I and L9 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. Reaction Scheme 220 illustrates that reaction sequence. Reaction Scheme 22,,:
Figure imgf000108_0001
(XIW100) K2C03/temp./NMP
Figure imgf000108_0002
Figure imgf000108_0003
(iw100)
Compounds of formulae XW100 and XIW100 either are known or can be prepared analogously to the processes described in WO 98/42698.
Compounds of formula I wherein W is a group Wι03 (compounds of formula IWι03) can be prepared in analogous manner to that described in WO 99/06394 and WO 98/07720.
Compounds of formula I wherein W is a group \NW (compounds of formula IW104) can be prepared in analogous manner to that described in WO 97/11060.
Compounds of formula I wherein W is a group Wι07 (compounds of formula IWι07), can be prepared in analogous manner to that described in WO 97/06150.
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. Moreover, 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. Where synthesis is not directed at the isolation of pure isomers, 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 (Reaction Scheme 1 b) 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, R2, R3 and R4 are as defined for formula I, under known reaction conditions, for example using iron trichloride (Fe(IH)CI3) 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.
Reaction Scheme 13:
Figure imgf000109_0001
(lln) (lla)
The 6-nitro-4H-pyrido[3,2-b][1 ,4]oxazin-3-ones of formula lln used as starting compounds in Reaction Scheme 13 can be obtained selectively by means of aromatic nitration of compounds of formula XXX
Figure imgf000109_0002
wherein Ri to R4 are as defined for formula I, under standard conditions, for example using HNO3 H2SO , as illustrated in Reaction Scheme 14, and then further functionalised according to the definitions of R and R2 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). Reaction Scheme 14 aromatic nitration, e.g. H CyHoSC
Figure imgf000110_0001
Figure imgf000110_0002
(XXX) (lln)
The 4H-pyrido[3,2-b][1 ,4]oxazin-3-ones of formula XXX used as starting compounds in Reaction Scheme 14 can be obtained analogously to known processes, as described, for example, in Acta Chimica Scandinavica 23, 2322 (1969), from 2-amino-3-hydroxy-pyridine derivatives of formula XXXI
Figure imgf000110_0003
wherein Ri and R2 are as defined for formula I, by reacting such a compound with a compound of formula XXXII
(XXXII),
Figure imgf000110_0004
wherein R3 and R4 are as defined for formula I, Zi is a C C alkoxy group, especially methoxy or ethoxy, or halogen, especially chlorine or bromine, and Z2 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. sodium hydride, and in the presence of a suitable solvent, for example an ether, e.g. tetrahydrofuran or dioxane, an amide, e.g. DMF or NMP, or water, or a mixture of those solvents, as illustrated in Reaction Scheme 15. The compounds of formula XXX thereby obtained may then be further functionalised according to the definitions of Ri and R2 for formula I as described above, for example, under ac) (alkylation using R2-L2 (IV)) and/or ae) (halogenation) and/or af)
(fluorination).
Reaction Scheme 15:
Figure imgf000111_0001
(XXXI) (XXX)
In analogous manner, for example, according to process variant g) and Reaction Scheme 15a, starting from a compound of formula XXVIII
(XXVIII)
Figure imgf000111_0002
and a compound of formula XXXII
(XXXII),
Figure imgf000111_0003
it is also possible to prepare compounds of formula Hz
Figure imgf000111_0004
wherein in the compounds of formulae XXVIII, XXXII and llz the substituents R1 ( R2, R3 and R4 are as defined for formula I, Zi is a d-dalkoxy group, especially methoxy or ethoxy, or halogen, especially chlorine or bromine, Z2 is a leaving group, for example halogen, especially chlorine or bromine, or sulfonate, especially methylsulfonyloxy or phenylsulfonyloxy, and A0 is chlorine or bromine (= compounds of formula lib) or, especially, methyl or carboxy (= compounds of formula llu). Reaction Scheme 15a:
Figure imgf000112_0001
(XXVIII) (llz) The starting compounds of formula lib
Figure imgf000112_0002
wherein Ri to R4 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
Figure imgf000112_0003
wherein Ri to R4 are as defined, by means of standard processes, for example diazotisation and boiling of the resulting diazonium salt (compound of formula llee in Reaction Scheme 16b) to form the compound of formula lib wherein Ai is hydroxy, or by a Sandmeyer reaction of the resulting diazonium salt, for example using copper(l) chloride or copper(l) bromide, to form the compounds of formula lib wherein Ai is halogen, especially chlorine or bromine, and subsequently subjecting the hydroxy compound to treatment with d- dalkylsulfonic acid anhydride or trifluoromethanesulfonic acid anhydride to yield the compounds of formula lib wherein Ai is d-dalkylsulfonyloxy or trifluoromethylsulfonyloxy, or subsequently substituting the halogen compound of formula lib (A = halogen) with d- dalkylthiolates to yield the compounds of formula lib wherein Ai is d-dalkylthio and then optionally converting those compounds by means of oxidation, for example using m- chloroperbenzoic acid or hydrogen peroxide in acetic acid, into the corresponding compounds of formula lib wherein A is d-C alkylsulfonyl.
The hydrazine derivatives of formula He
Figure imgf000113_0001
used in Reaction Schemes 3, 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 (SnCI2), of the resulting diazonium salts of formula llee
Figure imgf000113_0002
the substituents R to R4 in the compounds of formulae He and llee being as defined for formula I, and M is an anion for example hydrogen sulfate or tetrafluoroborate, or halide, for example chloride, or by means of hydrazinolysis of the compounds of formula lib
Figure imgf000113_0003
wherein Ri to R4 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:
Figure imgf000114_0001
(lib): A1=F, Q, Br, N02 (lie)
The starting compounds used for process variant d) above, 3-oxo-3,4-dihydro-2H- pyrido[3,2-b][1 ,4]oxazine-6-carboxylic acids or esters thereof of formula lluι
Figure imgf000114_0002
wherein Ri to R4 are as defined for formula I and R89 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 V2O5, Na2WO4, Co(OAc)3 or K2Cr2O3, starting from compounds of formula llu
Figure imgf000114_0003
wherein Ri to R4 are as defined and A2 is methyl (Reaction Scheme 16a), or bb) by means of hydrolysis of compounds of formula llu wherein Ri to R4 are as defined and A2 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. KMn04 or Oo/cat.
Figure imgf000115_0002
Figure imgf000115_0001
(llu,): R89=H, alkyl
(llu)
Reaction Scheme 16b:
Figure imgf000115_0003
diazotisation + Sandmeyer (llu) bb) hydrolysis reaction using Cu(l)CN
Figure imgf000115_0004
(lib): A1= halogen, e.g Cl, Br
The starting compounds of formula llu
Figure imgf000115_0005
wherein R1 t R2, R3 and R4 are as defined for formula I and A2 is formyl or acyl, used in process variant d) can, for example, be prepared by standard methods, starting from compounds of formula llu
Figure imgf000116_0001
wherein Ri to R4 are as defined and A2 is cyano, by means of reduction of the cyano group, for example using dibutylaluminium hydride (DIBAH), or starting from compounds of formula llu2
Figure imgf000116_0002
wherein Ri to R4 are as defined, by means of a Grignard reaction using methylmagnesium chloride, or using the reagent O,N-dimethyl acetamide.
The compounds of formula II
Figure imgf000116_0003
wherein Ri to R4 are as defined for formula I and A is fluorine, d-C alkylthio, d- dalkylsulfonyl, phenylthio, phenylsulfonyl, CrC4alkylsulfonyloxy, trifluoromethylsulfonyloxy, hydroxy, nitro, amino, isocyanato, isothiocyanato, hydrazino, a group NHC(X2)XoR5, NHC(X7)X0R5, NHC(X8)X0R5, NHC(X9)X0R5, NHC(X3)R16, NHN=C(R,7)C(O)Rι8, NHC(X7)N(R22)C(R2o)R2iC(X6)OR9, NHC(X9)NR2 NR23C(X8)ORιo, NHC(X8)NR23NHR24, NHN=C(R25)COOH, NHN=C(R25)R025, N(C(X4)-NHR26)N=CR25R025, N(C(X4 )NHR26)NH2, NHN=C(R25)N(R26)C(X4)OR84, N(C(X4)NHR26)NHC(O)OR84, N(C(Xι9)NHR5o)NHC(O)OR84, NHC(Xι2)NHR26, NHC(O)C(R28)=C(R27)C(O)OR85, NHC(=NR39)NHR38, NHC(Y2)NR40NHR41, NHC(Y2)NR40NR4ιC(O)OR9, NHN=C(R42)C(O)NHR43, NHN=C(R42)C(O)N(R43)C(O)OR85, N(R43)COOR85, NHC(R53)=NNHC(X2ι)OR85, NHC(S)NHC(=NR57)R56, NHC(X23)NHR58C(X25)NHR59, N(C(X24)NHR59)C(X23)XoR5, ethyl, vinyl, ethynyl, C≡CC(O)OR86, C≡CC(O)R87, acyl, formyl, cyano, carboxy, C(O)OR89, C(O)C(O)OR9o, C(O)CH2COOR9ι,
Figure imgf000117_0002
cyanomethyl, B(OH)2 or , wherein
Figure imgf000117_0001
R16, Ri7, Riβ, R20, R21 , R22, R23, R24, R25, R26, R27, R2β, Rsβi R39, R4o, R411 R42, R43, R50, R53, R56 and R57 are as defined in claim 1 ; R5, R9, R025, R84, R86, Rβ9, R90 and R91 are each independently of the others d-dalkyl or phenyl; R10 and R85 are hydrogen or d-dalkyl; R87 and R88 are d-C4alkyl, formyl, CH(d-C4alkoxy) or d-C4haloalkyl; X2, X3, X4, X6, X7, X8, X9, Xι2, X19, X2ι and Y2 are oxygen or sulfur; and X0 is oxygen, sulfur or amino, are new, and the present invention also relates to those compounds. Of those compounds, preference is given to those wherein A is fluorine, d-dalkylthio, d-C4alkylsulfonyloxy, trifluoromethylsulfonyloxy, hydroxy, nitro, amino, isocyanato, isothiocyanato, hydrazino, a group NHC(X2)OR5, NHC(X7)OR5, NHC(X8)OR5, NHC(X9)OR5, NHN=C(R17)C(O)Rι8, NHC(X7)N(R22)CR2oR2iC(O)OR9, NHC(X9)NR24NR23C(O)ORι0, ethyl, vinyl, ethynyl, C≡CC(O)OR86, C≡CC(O)R87, acyl, formyl, cyano, carboxy, C(O)OR89, C(O)CH2COOR9ι, C(O)CH2C(O)R88, cyanomethyl or B(OH)2, wherein R5, Rg, R10, R86, R8g and R9 are each independently of the others d-dalkyl; Rι7, Rι8, R20, R21, R22, R23 and R24 are as defined for formula I; R87 and R88 are each independently of the other d-dalkyl, formyl, CH(C dalkoxy) or C C haloalkyl; and X2, X7, X8 and X9 are oxygen or sulfur.
The compounds of formula II wherein A is methyl, chlorine or bromine (compounds of formulae llu and lib) are known from CH-A-452 528, CH-A-452 529 and US-A-3 854 926 or can be prepared analogously to the processes described therein or analogously to Reaction Scheme 15.
The compounds of formula II wherein A is hydrogen (compounds of formula XXX) are known, for example, from Acta Chimica Scandinavica 23, 2322 (1969), CH-A-452 528, US- A-3 854 926 and WO 88/08705 or can be prepared analogously to the processes described therein or analogously to Reaction Scheme 15.
The compounds of formula XXVIII wherein, for example, A0 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.
Compounds of formulae XW and XIW are either known or can be prepared analogously to the processes described in WO 98/42698, WO 99/52892 and WO 99/52893.
The other compounds of formulae III, IV, V, VI, Via, Vlb, Vic, Vl0, VII, Vila, Vllb, VIII, Vlll0, IX, IXa, IXb, X, Xa, Xla, Xlb, Xlc, Xld, Xle, Xlet, Xlf, Xlg, Xlh, Xli, Xli,, Xli2, Xln, XII, Xlll, Xlll0, XIV, XlVa, XIVo, XVa, XVb, XVI, XVII, XVIII, XXV, XXVIa, XXVIb, XXVIc, XXVId, XXXII, XXXIII, XXXIVa, XXXIVb, XXXV, XXXVa, XXXVb, XXXVI, XXXVIIa, XXXVIIb, XXXVIII, XXXVIIIa, XXXVIIIb, XXXVIIIc, XXXVIIId, XXXVIIId,, XXXIX, XL and XLI are known or can be prepared analogously to the processes described in the literature.
For the use according to the invention of the compounds of formula I or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques, such as, for example, the controlled release of active ingredient. For that purpose, a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea-formaldehyde) and dried. If desired, it is also possible to apply a coating (coated granules) which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I 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. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound of formula I or at least one compound of formula I and, generally, one or more solid or liquid formulation adjuvants, are prepared in known manner, for example by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Furthermore, surface-active compounds (surfactants) may also be used in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485 on page 6.
Depending on the nature of the compound of formula I being formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8.
Furthermore, the surfactants customarily employed in formulation technology, which are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81 , are also suitable for preparation of the herbicidal compositions according to the invention.
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. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, 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. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters. The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially 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.
The following Examples further illustrate but do not limit the invention.
Preparation Examples:
Example P1 : 6-Nitro-4H-pyridor3.2-b1f1.41oxazin-3-one
At 0-5°C, 150 g (1 mol) of 4H-pyrido[3,2-b][1 ,4]oxazin-3-one are introduced, in portions, into
400 ml of concentrated sulfuric acid. Then, while maintaining the temperature at below
10°C, 200 ml of fuming nitric acid are slowly added dropwise to the red solution and stirring is carried out for a further hour at 10-15°C. The reaction mixture is poured onto ice and the precipitated yellow product is filtered off and washed with cold water. Technical-grade 6- nitro-4H-pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of 247-252°C is thereby obtained which, after recrystallisation from methyl Cellosolve, melts at 254-256°C.
1H-NMR ((CD3)2SO): 12.5 ppm (s, 1 H); 8.00 ppm (d, J=8 Hz); 7.64 ppm (d, J=8.2 Hz); 4.88 ppm (s, 2H).
Example P2: 6-Amino-4H-pyrido.3.2-b]f 1 ,41oxazin-3-one
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. 1H-NMR ((CD3)2SO): 10.78 ppm (s, NH); 7.03 ppm (d, 1 H); 6.01 ppm (d, 1 H); 6.29 ppm (s, 1 H); 5.57 ppm (s, NH2); 4.41 ppm (s, 2H). 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. 150 ml of water are then added to the mixture, the pH is adjusted to 4 using concentrated hydrochloric acid and the precipitated crystals are filtered off. Virtually pure (3-oxo-3,4- dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-carbamic acid ethyl ester is thereby obtained. 1H-NMR ((CD3)2SO): 11.08 ppm (s, NH); 9.78 ppm (s, NH); 7.33 ppm (m, 2H); 4.57 ppm (s, 2H); 4.12 ppm (q, 2H); 1.22 ppm (t, 3H).
Example P4: 3-(3-Oxo-3.4-dihvdro-2H-pyrido.3.2-biri .4loxazin-6-yl)-6-trifluoromethyl-1 H- pyrimidine-2.4-dione
1.5 g (6.3 mmol) of (3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-carbamic acid ethyl ester are introduced into a suspension of 0.36 g (15 mmol) of sodium hydride in N-methylpyrrolidone. Stirring is then carried out for about 30 minutes at 35°C, 1.3 g (7.3 mmol) of 3- amino-4,4,4-trifluoro-but-2-enoic acid ethyl ester are then added thereto, and the reaction mixture is heated at 100°C for 1.5 hours. Ice-water is added, the pH is adjusted to 2 using hydrochloric acid and the mixture is extracted several times with ethyl acetate. The combined organic phases are concentrated by evaporation to a volume of about 50 ml, whereupon 3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-trifluoromethyl-1 H- pyrimidine-2,4-dione precipitates out as an almost pure product.
1H-NMR ((CD3)2SO): 12.65 ppm (broad signal, NH); 11.40 ppm (s, NH); 7.52 ppm (d, 1 H); 7.05 ppm (d, 1 H); 6.36 ppm (s, 1 H); 4.72 ppm (s, 2H).
Example P5: 1-Methyl-3-(4-methyl-3-oxo-3.4-dihvdro-2H-pyridof3.2-biπ .41oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2.4-dione
0.33 g (1.0 mmol) of 3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-trifluoromethyl- 1 H-pyrimidine-2,4-dione is stirred with 0.31 g (2.0 mmol) of methyl iodide in the presence of 0.27 g (2.0 mmol) of potassium carbonate in 5 ml of acetonitrile at 20°C. After then being stirred for about 16 hours at 40-45°C, 30 ml of water are added and the mixture is acidified to pH 5 using hydrochloric acid and extracted with ethyl acetate. The product is purified by column chromatography (mobile phase: ethyl acetate/hexane 1/1). Pure 1 -methyl-3-(4- methyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-trifluoromethyl-1 H-pyrimidine- 2,4-dione having a melting point of 211-211.5°C is obtained. 1H-NMR (CDCI3): 7.38 ppm (d, 1 H); 6.90 ppm (d, 1 H); 6.39 ppm (s, 1 H); 4.74 ppm (s, 2H); 3.57 ppm (s, 3H); 3.41 ppm (s, 3H).
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
0.78 g (2.4 mmol) of 3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-trifluoromethyl-
1 H-pyrimidine-2,4-dione is stirred with 0.37 g (2.4 mmol) of methyl iodide in the presence of
0.25 g of potassium hydrogen carbonate in 5 ml of dimethylformamide at 20°C. After about
6 hours, 30 ml of water are added and the precipitated product is filtered off. Virtually pure
1 -methyl-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-trif luoromethyl-1 H- pyrimidine-2,4-dione is obtained.
1H-NMR ((CD3)2SO): 11.32 ppm (s, NH); 7.53 ppm (d, 1 H); 7.01 ppm (d, 1 H); 6.53 ppm (s,
1 H); 4.74 ppm (s, 2H); 3.32 ppm (s, 3H).
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
0.30 g (0.9 mmol) of 1-methyl-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2,4-dione and 0.11 g (0.9 mmol) of propargyl bromide are heated in the presence of 0.14 g of potassium carbonate and a catalytic amount of 18- crown-6 in 10 ml of acetonitrile for 1 hour at reflux temperature. The solvent is evaporated off and the residue is filtered using a 1 :1 mixture of ethyl acetate/hexane over a small amount of silica gel. The desired 1-methyl-3-(3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-pyrido[3,2- b][1 ,4]oxazin-6-yl)-6-trif luoromethyl-1 H-pyrimidine-2,4-dione is obtained in the pure form having a melting point of 161.5-162°C.
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
0.30 g (0.9 mmol) of 1 -methyl-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2,4-dione and 0.17 g (1.4 mmol) of isopropyl bromide are heated at 120°C in the presence of 0.19 g (1.4 mmol) of potassium carbonate and a catalytic amount of 18-crown-6 and a catalytic amount of potassium iodide in 2 ml of dimethylformamide in a pressure vessel for about 2 hours. The solvent is evaporated off under reduced pressure and the residue is chromatographed using a 1 :2 mixture of ethyl acetate and hexane on silica gel. Pure 3-(4-isopropyl-3-oxo-3,4-dihydro-2H-pyrido[3,2- b][1 ,4]oxazin-6-yl)-1-methyl-6-trifluoromethyl-1 H-pyrimidine-2,4-dione is thereby obtained. 1H-NMR (CDCI3): 7.36 ppm (d, 1 H); 6.87 ppm (d, 1 H); 6.37 ppm (s, 1 H); 5.16 ppm (m, 1 H); 4.64 ppm (s, 2H); 3.57 ppm (s, 3H); 1.50 ppm (d, 6H).
Example P9: 6-(4-Chloro-5-difluoromethoxy-1-methyl-1 H-pyrazol-3-yl)-7-fluoro-4H- pyridof3.2-b]f1.4loxazin-3-one
0.5 g (1.3 mmol) of 2-(3-chloro-6-(4-chloro-5-difluoromethoxy-1-methyl-1 H-pyrazol-3-yl)-5- fluoro-pyridin-2-yloxy)acetamide (WO 98/42698) is heated at 150°C in the presence of 0.18 g (1.3 mmol) of potassium carbonate in 10 ml of N-methylpyrrolidone (NMP) for 2 hours.
The mixture is poured into water and extracted with diethyl ether. The residue that remains is chromatographed on silica gel. Pure 6-(4-chloro-5-difluoromethoxy-1 -methyl-1 H-pyrazol-
3-yl)-7-f luoro-4H-pyrido[3,2-b][1 ,4]oxazin-3-one is thereby obtained as the more polar fraction.
1H-NMR (CDCI3): 8.40 ppm (s, NH); 7.18 ppm (d, 1 H); 6.71 ppm (t, 1 H); 4.74 ppm (s, 2H);
3.85 ppm (s, 3H).
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. 5.4 ml (44 mmol) of bromoacetic acid ethyl ester are then added dropwise. The suspension, which is difficult to stir, is further diluted with 15 ml of dimethylformamide and stirring is carried out for a further 2 hours at 70°C. The mixture is left to warm up to 20°C, water is added and extraction at pH 8 is carried out with diethyl ether. The aqueous phase is adjusted to pH 2.6 using hydrochloric acid and extracted with ethyl acetate. The residue is taken up in diethyl ether and readily soluble components are removed by filtration. Pure 3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazine-6-carboxylic acid having a melting point of 138-140°C is obtained as a crystalline product. 1H-NMR ((CD3)2SO): 12.98 ppm (broad signal, OH); 11.55 ppm (s, NH); 7.66 ppm (d, 1 H); 7.41 ppm (d, 1 H); 4.72 ppm (s, 2H).
Example P11 : 3-.2-Methyl-3-oxo-3.4-dihvdro-2H-pyrido.3.2-biri .41oxazin-6-yl)-3-oxo- propionic acid ethyl ester
1.3 g (7.3 mmol) of the potassium salt of malonic acid monomethyl ester and 0.88 g (9.2 mmol) of magnesium chloride are introduced into 20 ml of acetonitrile at 10°C, 1.5 ml (1.1 mmol) of triethylamine are added and stirring is carried out at 20°C for 1 hour. There is then added 0.96 g (3.7 mmol) of crude 2-methyl-3-oxo-3,4-dihydro-2H-pyrido[3,2- b][1 ,4]oxazine-6-carboxylic acid chloride (1H-NMR (CDCI3): 8.38 ppm (broad signal, NH); 7.88 ppm (d, 1 H); 7.38 ppm (d, 1 H); 4.36 ppm (q, 1 H); 1.63 ppm (d, 3H)), prepared from 0.82 g (4 mmol) of 2-methyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazine-6-carboxylic acid (Example II.026) by heating with 0.45 ml (5 mmol) of oxalyl chloride in 15 ml of hexane and a catalytic amount of dimethylformamide, and stirring is carried out for a further
3 hours. The reaction mixture is then poured into ice-water and adjusted to pH 3 using 32 % hydrochloric acid. Extraction with ethyl acetate is carried out; washing once with 5 % sodium hydrogen carbonate solution and once with saturated sodium chloride solution and concentration by evaporation are carried out. The tautomeric forms of the desired title compound 3-hydroxy-3-(2-methyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-acrylic acid ethyl ester are thereby obtained in the form of an oil. 1H-NMR (CDCI3): 8.02 ppm (broad signal, OH); 7.78 ppm (d, 1 H); 7.32 ppm (d, 1 H); 7.70 ppm (q, 1 H); 4.18 ppm (q, 2H);
4.04 ppm (s, 1 H); 1.62 ppm (d, 3H); 1.24 ppm (t, 3H).
Example P12: 6-(5-Hvdroxy-1 -methyl-1 H-pyrazol-3-yl)-2-methyl-4H-pyridof3,2-blH .41oxazin-
3-one
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
4 hours and the mixture is then concentrated by evaporation. The desired 6-(5-hydroxy-1- methyl-1 H-pyrazol-3-yl)-2-methyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one is obtained in the form of crystals by means of column chromatography (mobile phase: ethyl acetate/hexane 1/1). 1H-NMR ((CD3)2SO): 11.35 ppm (s, NH); 7.58 ppm (d, 1 H); 7.49 ppm (d, 1 H); 5.98 ppm (s, 1 H); 4.92 ppm (q, 1 H); 3.71 ppm (s, 3H); 1.61 ppm (d, 3H).
Example P13: 6-(5-Difluoromethoxy-1 -methyl-1 H-pyrazol-3-yl)-2-methyl-4H-pyrido[3.2-b]-
[1 ,4loxazin-3-one
0.36 g (1.4 mmol) of the product prepared in Example P12 is stirred in the presence of
0.55 g (13.8 mmol) of sodium hydroxide in a mixture of 8 ml of dioxane and 8 ml of water at
70°C for 1 hour while continuously passing gaseous Freon (bromo-difluoromethane) into the mixture. The temperature is maintained at 80°C for a further 30 minutes and the mixture is then adjusted to pH 4 using hydrochloric acid and extracted with ethyl acetate. The desired
6-(5-dif luoromethoxy-1 -methyl-1 H-pyrazol-3-yl)-2-methyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one is thereby obtained.
1H-NMR ((CD3)2SO): 11.60 ppm (s, NH); 7.38 ppm (d, 1 H); 7.32 ppm (d, 1 H); 7.26 ppm (t,
1 H); 5.78 ppm (s, 1 H); 4.68 ppm (q, 1 H); 3.65 ppm (s, 3H); 1.34 ppm (d, 3H). Example P14: 6-.4-Chloro-5-difluoromethoxy-1 -methyl-1 H-pyrazol-3-yl)-2-methyl-4H-pyrido-
[3,2-bl.1 ,41oxazin-3-one
In the presence of 0.09 g (0.11 mmol) of sodium acetate in 4 ml of acetic acid, 0.07 g
(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.
1H-NMR (CDCI3): 8.45 ppm (s, NH); 7.68 ppm (d, 1 H); 7.52 ppm (d, 1 H); 6.68 ppm (t, 1 H);
4.74 ppm (q, 1 H); 3.85 ppm (s, 3H); 1.64 ppm (d, 3H).
Example P15: 2-(3-Oxo-3,4-dihvdro-2H-pyrido.3.2-bl.1.4loxazin-6-yl)-4.5.6.7-tetrahvdro- isoindole-1.3-dione
1.65 g (10 mmol) of 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-one (Example P2) and 1.67 g (10 mmol) of tetrahydrophthalic acid anhydride are heated at boiling point in 10 ml of acetic acid for 7 hours. The mixture is then concentrated by evaporation and stirred in hot ethyl acetate. Pure 2-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro- isoindole-1 ,3-dione is obtained as an insoluble residue having a melting point of 220°C. 1H- NMR (CDCI3): 8.72 ppm (broad signal, NH); 7.38 ppm (d, 1 H); 6.94 ppm (d, 1 H); 4.68 ppm (s, 2H); 2.42 ppm (m, 2H); 1.80 ppm (m, 2H).
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. The product is then extracted with ethyl acetate from an aqueous solution at pH 8 and the residue, after concentration by evaporation, is purified by chromatography. Pure 6-amino-4-prop-2-ynyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of 125.5-126°C is obtained.
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). For the purpose of identification, a sample of the reaction mixture is stirred in methanol in the presence of a small amount of triethylamine. According to a thin-layer chromatogram, 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- biπ .41oxazin-6-yl)-tetrahvdro-imidazo.1.5-alpyridine-1 ,3-dione
0.46 g (2.3 mmol) of 4-hydroxy-piperidine-2-carboxylic acid methyl ester • hydrochloride is introduced into 15 ml of dichloromethane at 20°C. 0.50 g (5 mmol) of triethylamine is added and stirring is then carried out for 5 minutes. A dichloromethane solution of 0.54 g (2.3 mmol) of the 6-isocyanato-4-prop-2-ynyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one prepared above in Example P17 is then introduced dropwise and stirring is carried out at about 35°C for a further 3 hours. The 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
0.16 g (0.45 mmol) of racemic 7-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 (Example P18) is treated in 5 ml of pyridine at -10°C with a solution of 0.11 g (0.68 mmol) of diethylaminosulfur trifluoride (DAST) in 1 ml of dichloromethane. The mixture is left to warm up to 20°C slowly and is stirred overnight. 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). 1H-NMR (CDCI3): 7.38 ppm (d, 1 H); 7.04 ppm (d, 1H); 5.90 ppm (m, 1H); 4.86 ppm (m, 2H); 4.72 ppm (s, 2H). Further elution then yields the second 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. 1H- NMR (CDCI3): 7.36 ppm (d, 1 H); 7.01 ppm (d, 1 H); 5.20 ppm (m, 1 H); 4.86 ppm (m, 2H); 4.73 ppm (s, 2H). Example P20: 1 -Amino-3-.3-oxo-3.4-dihvdro-2H-pyrido.3.2-biri .4.oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2.4-dione
3.28 g (10 mmol) of 3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-trifluoromethyl- 1 H-pyrimidine-2,4-dione (Example P4) are stirred with 2.59 g (13 mmol) of N-2,4- dinitrophenyl-hydroxylamine in the presence of 1.22 g (14.5 mmol) of sodium hydrogen carbonate in 50 ml of dimethylformamide at 20°C for 35 hours. Water is added and extraction with ethyl acetate is carried out; the organic phase is washed twice with small amounts of water, dried over magnesium sulfate and concentrated, in part, by evaporation. The desired title compound, 1-amino-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)- 6-trifluoromethyl-1 H-pyrimidine-2,4-dione having a melting point of >220°C precipitates in the form of crystals from the ethyl acetate phase. 1H-NMR ((CD3)2SO): 11.32 ppm (s, NH); 7.46 ppm (d, 1 H); 6.95 ppm (d, 1 H); 6.29 ppm (s, 1 H); 5.48 ppm (s, NH2); 4.68 ppm (s, 2H).
Example P21 : 6-lsothiocyanato-4H-pyrido.3.2-blH .4]oxazin-3-one
16.5 g (0.1 mol) of 6-amino-4H-pyrido[3,2-b][1 ,4]oxazin-3-one (Example P2) are introduced into 200 ml of ethyl methyl ketone and, over a period of 20 minutes, 13.8 g (0.12 mol) of thiophosgene are added. Stirring is then carried out at 22-28°C for 90 minutes and then 10 g (0.12 mol) of solid sodium hydrogen carbonate are first added to the mixture and then 100 ml of water are added dropwise. After the evolution of gas has ceased, stirring is continued for a further 90 minutes and extraction with 1000 ml of ethyl acetate is carried out. The aqueous phase, which contains solid components, is extracted a further three times, using 200 ml of ethyl acetate each time. The combined organic extracts are dried, filtered over Hyflo™ and concentrated until crystallisation occurs. The title compound is obtained in pure form as an ochre-coloured powder having a melting point of 178-179°C. 1H-NMR ((CD3)2SO): 11.42 ppm (s, NH); 7.34 ppm (d, 1 H); 6.88 ppm (d, 1 H); 4.62 ppm (s, 2H).
Example P22: 6-(6-Oxo-2-thioxo-4-trif luoromethyl-3.6-dihydro-2H-pyrimidin-1 -yl)-4H-pyrido- [3,2-b]f1 ,4]oxazin-3-one
3.3 g (18 mmol) of 3-amino-4,4,4-trifluoro-but-2-enoic acid ethyl ester are added dropwise at 0°C to 1.6 g (37 mmol) of sodium hydride in 15 ml of N-methylpyrrolidone as a 55 % dispersion in oil. After stirring for 15 minutes and after the evolution of hydrogen has ceased, 3.1 g (15 mmol) of 6-isothiocyanato-4H-pyrido[3,2-b][1 ,4]oxazin-3-one (Example P21 ) are added to the mixture, which is heated gradually to 90°C. After a further hour, the mixture is cooled, water is added, the pH is adjusted to 9 and the mixture is washed twice with ethyl acetate. The aqueous phase is then acidified to pH 2 using concentrated hydrochloric acid, whereupon the product precipitates out in the form of crystals, which are filtered off and yield pure 6-(6-oxo-2-thioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)- 4H-pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of >220°C. 1H-NMR ((CD3)2SO): 1 1.39 ppm (s, NH); 7.49 ppm (d, 1 H); 7.01 ppm (d, 1 H); 6.68 ppm (s, 1 H); 4.72 ppm (s, 2H).
Example P23: Tetrahvdro-pyridazine-1 -carbothionic acid (3-oxo-3.4-dihvdro-2H-pyrido- [3.2-biπ .41oxazin-6-yl)-amide
9.15 g (55 mmol) of tetrahydropyridazine dihydrochloride are introduced into 150 ml of ethanol. There are then added, in succession, 1 1.6 g (115 mmol) of triethylamine and then, in portions, 10.4 g (50 ml) of the compound prepared in Example P21 , 6-isothiocyanato-4H- pyrido[3,2-b][1 ,4]oxazin-3-one, the temperature being maintained between 23° and 28°C. After stirring for one hour, the precipitated product is filtered off, washed thoroughly with water and ethanol/water 1/1 and then dried in vacuo at 70°C. Pure tetrahydro-pyridazine-1- carbothionic acid (3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-amide having a melting point of 212-212.5°C is obtained.
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-
[1 ,2.41triazolo[1 ,2-alpyridazin-2-yl)-4H-pyrido[3.2-b1[1 ,4loxazin-3-one
1.47 g (5 mmol) of tetrahydro-pyridazine-1-carbothionic acid (3-oxo-3,4-dihydro-2H-pyrido-
[3,2-b][1 ,4]oxazin-6-yl)-amide (Example P23) and 1.83 g (18 mmol) of triethylamine are introduced into 80 ml of tetrahydrofuran, whereupon a clear solution is obtained. At 5-10°C,
3.1 ml of a 20 % solution of 0.58 g (5.9 mmol) of phosgene in toluene are added slowly thereto and stirring is carried out overnight at 20°C. The solvents are distilled off under reduced pressure and the dry residue is triturated in 100 ml of water. The crystals that precipitate out are filtered off, taken up while hot in 80 ml of fresh tetrahydrofuran and poorly soluble components are removed by filtering again. Pure 6-[3-oxo-tetrahydro-
[1 ,3,4]thiadiazolo[3,4-a]pyridazin-<1 E>- or -<1Z>-ylideneamino]-4H-pyrido[3,2-b][1 ,4]oxazin-
3-one (= product A, Example 12.001) having a melting point of >225°C is thereby obtained. H-NMR ((CD3)2SO): 11.40 ppm (s, NH); 7.51 ppm (d, 1 H); 6.81 ppm (d, 1 H); 4.78 ppm (s,
2H); 3.97 ppm (m, 2H); 3.75 ppm (m, 2H); 1.90 ppm (m, 4H).
The mother liquor is concentrated by evaporation and yields, after filtration over silica gel
(mobile phase hexane/tetrahydrofuran 3/2), approx. 80 % 6-(1 -oxo-3-thioxo-tetrahydro-
[1 ,2,4]triazolo[1 ,2-a]pyridazin-2-yl)-4H-pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of >225°C (= product B), which is contaminated with approx. 20 % product A. 1H-NMR ((CD3)2SO): 11.50 ppm (s, NH); 7.68 ppm (d, 1 H); 7.21 ppm (d, 1 H); 4.91 ppm (s, 2H); 4.56 ppm (m, 2H); 3.68 ppm (m, 2H); 2.02 ppm (m, 4H).
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-π ,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 acetonitrile and 3 ml of N-methylpyrrolidone for 2.5 hours. The mixture is then concentrated by evaporation and the residue is chromatographed on silica gel (mobile phase ethyl acetate/hexane 1/1); pure 6-[3-oxo-tetrahydro-[1 ,3,4]thiadiazolo[3,4-a]pyridazin-<1 E>- and/or -<1 Z>-ylideneamino]-4- prop-2-ynyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one is first isolated as product A having a melting point of >225°C. 1H-NMR ((CD3)2SO): 7.28 ppm (d, 1 H); 6.78 ppm (d, 1 H); 4.92 ppm (d, 2H); 4.68 ppm (s, 2H); 3.90 ppm (m, 2H); 3.74 ppm (m, 2H); 2.20 ppm (t, 2H); 1.90 ppm (m, 4H). Pure 6-(1 -oxo-3-thioxo-tetrahydro-[1 ,2,4]triazolo[1 ,2-a]pyridazin-2-yl)-4-prop-2-ynyl-4H- pyrido[3,2-b][1 ,4]oxazin-3-one having a melting point of >225°C is isolated thereafter as main product B. 1H-NMR ((CD3)2SO): 7.41 ppm (d, 1 H); 7.13 ppm (d, 1 H); 4.88 ppm (d, 2H); 4.77 ppm (s, 2H); 4.04 ppm (m, 2H); 3.74 ppm (m, 2H); 2.17 ppm (t, 2H); 1.98 ppm (m, 4H).
Example P26: (3-Oxo-3.4-dihvdro-2H-pyrido[3.2-biri .4loxazin-6-yl)-thiocarbamic acid O- ethyl ester
15.5 g (75 mmol) of 6-isothiocyanato-4H-pyrido[3,2-b][1 ,4]oxazin-3-one (Example P21) are heated in 300 ml of absolute ethanol at boiling point for 1 hour. From the reaction mixture, which has been cooled to 10°C, there can be obtained pure (3-oxo-3,4-dihydro-2H- pyrido[3,2-b][1 ,4]oxazin-6-yl)-thiocarbamic acid O-ethyl ester having a melting point of 218.5-219°C.
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
3.3 g (14.1 mmol) of 6-(4,5-dihydro-1 H-imidazol-2-ylamino)-4H-pyrido[3,2-b][1 ,4]oxazin-3- one (Example P27) and 3.2 g (16.3 mmol) of 3-amino-4,4,4-trifluoro-but-2-enoic acid ethyl ester are heated in 12 ml of N-methylpyrrolidone at 135°C for 8 hours. Water is added thereto and extraction is carried out several times with warm ethyl acetate. From the combined organic phases there crystallises, on concentration by evaporation, pure 6-(7- oxo-5-trifluoromethyl-2,3-dihydro-7H-imidazo[1 ,2-a]pyrimidin-8-yl)-4H-pyrido[3,2- b][1 ,4]oxazin-3-one having a melting point of >225°C. 1H-NMR ((CD3)2SO): 11.46 ppm (s,
NH); 7.56 ppm (d, 1 H); 7.06 ppm (d, 1 H); 6.02 ppm, (s, 1 H), 4.69 ppm (s, 2H), 4.22 ppm (t,
2H); 3.80 ppm (t, 3H).
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|oxazin-3-one
0.31 g (0.85 mmol) of 6-(2-methyl-7-oxo-5-trifluoromethyl-2,3-dihydro-7H-imidazo[1 ,2-a]- pyrimidin-8-yl)-4H-pyrido[3,2-b][1 ,4]oxazin-3-one (Example 11.002) and 0.28 g (0.19 mmol) of 3-mesyloxy-but-1 -yne are heated in the presence of approx. 0.23 g (1.9 mmol) of potassium carbonate and a catalytic amount of 18-crown-6 in 10 ml of tetrahydrofuran and 5 ml of N-methylpyrrolidone in a small pressure reactor at an internal temperature of 110°C for 4 hours. The 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. Isomer 1: 1H- NMR (CDCI3): 7.32 ppm (d, 1 H); 7.02 ppm (d, 1 H); 6.04 ppm (qxd, 1 H); 5.84 ppm (s, 1 H); 5.88 ppm (s, 1 H); 4.68 ppm (s, 2H), 4.2 ppm (m, 2H); 3.58 ppm (m, 1 H); 2.52 ppm (m, 1 H); 1.61 ppm (d, 3H); 1.30 ppm (m, 3H). Isomer II: 'H-NMR (CDCI3): 7.40 ppm (d, 1 H); 6.98 ppm (d, 1 H); 5.94 ppm (qxd, 1 H); 5.88 ppm (s, 1 H); 4.69 ppm (s, 2H), 4.2 ppm (m, 2H); 3.65 ppm (m, 1 H); 2.30 ppm (m, 1 H); 1.72 ppm (dxd, 3H); 1.30 ppm (m, 3H).
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
0.17 g (0.44 mmol) of 3-(4-n-propyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-1- methyl-6-trifluoromethyl-1 H-pyrimidine-2,4-dione (Example 1.060) is treated, in the presence of 0.15 g (1.7 mmol) of sodium acetate in 5 ml of acetic acid at 40°C, with chlorine gas until all the starting material has completely reacted. Extraction with ethyl acetate is then carried out; washing once with sodium acetate solution, drying and recrystallisation are carried out. Pure 3-(4-n-propyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-5-chloro- 1 -methyl-6-trif luoromethyl-1 H-pyrimidine-2,4-dione having a melting point of 176-178°C is thereby obtained. 1H-NMR (CDCI3): 7.38 ppm (d, 1 H); 6.87 ppm (d, 1 H); 4.72 ppm (s, 2H), 4.01 ppm (m, 2H); 3.62 ppm (s, 3H); 1.67 ppm (m, 2H); 0.90 ppm (t, 3H).
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 of 0.09 g (0.67 mmol) of potassium carbonate and, at 0°C, is treated with 0.25 ml of bromofluoromethane. The mixture is left to warm up to 20°C overnight, with vigorous stirring; the reaction mixture is then taken up in diethyl ether and the diethyl ether phase is washed once with dilute hydrochloric acid and once with sodium chloride solution. The residue is concentrated by evaporation and then separated by HPLC (mobile phase gradient from 30 to 40 % ethyl acetate in hexane) into two products, there being obtained, as less polar component, 6-(2-fluoromethoxy-6-oxo-4-trifluoromethyl-6H- pyrimidin-1-yl)-4-prop-2-ynyl-4H-pyrido[3,2-b][1 ,4]oxazin-3-one having 1H-NMR (CDCI3): 7.46 ppm (d, 1 H); 6.98 ppm (d, 1 H); 6.72 ppm (s, 1 H); 5.95 ppm (d, J=50Hz, 1 H); 4.82 ppm (4H); 2.12 ppm (t, 1 H), and, as more polar component, 1-fluoromethyl-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 having a melting point of 192-193°C and 1H-NMR (CDCI3): 7.41 ppm (d, 1 H); 6.95 ppm (d, 1 H); 6.45 ppm (s, 1 H); 6.01 ppm (d, J=50Hz, 1 H); 4.82 ppm (d, 2H); 4.78 ppm (s, 2H); 2.14 ppm (t, 1 H).
Example P32: 1-Amino-3-(3-oxo-3.4-dihvdro-2H-pyrido.3.2-bl.1.41oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2.4-dione
1.77 g (4.9 mmol) of 1 -methylthio-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2,4-dione (compound no. 2.002) is dissolved in 15 ml chloroform and treated with 2.44 g (9.8 mmol) m-chloroperbenzoic acid stirring and maintaining the temperature at below 30 °C. After 3 hours, according to thin layer chromatography the 1 -methylsulfonyl-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)- 6-trifluoromethyl-1 H-pyrimidine-2,4-dione (compound no. 2.008) can be detected only, the reaction mixture is added under stirring to an ice-cold solution of 25% ammoniumhydroxide. After 5 minutes the crystals formed are filtered, washed with water and dried yielding technical grade 1-amino-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2,4-dione with a melting point of >250°C. 1H-NMR ((CD3)2SO): 10.65 ppm (broad signal, NH); 7.38 ppm (d, 1 H); 7.3 ppm (broad signal, NH2); 6.92 ppm (d, 1 H); 6.02 ppm, (s, 1 H); 4.62 ppm (s, 2H).
Example P33: 6-(7-Oxo-5-trifluoromethyl-7H-imidazo.1.2-alpyrimidin-8-yl,-4H-pyrido.3,2- b][1 ,4]oxazin-3-one
1.15 g (3.5 mmol) 1 -amino-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6- trifluoromethyl-1 H-pyrimidine-2,4-dione (Example P32) is added to a well-stirred mixture of 1 ml 32% hydrochloric acid and 5 ml acetic acid containing 1.12 g (7.0 mmol) bromoacetaldehyde and heated afterwards for 17 hours to refluxing temperature. The cold solution is acidified to pH 3 and extracted with ethylacetate. The organic phase is washed once with sodiumbicarbonate solution and evaporated. By HPLC the pure 6-(7-oxo-5- trifluoromethyl-7H-imidazo[1 ,2-a]pyrimidin-8-yl)-4H-pyrido[3,2-b][1 ,4]oxazin-3-one is obtained. 1H-NMR ((CD3)2SO): 11.23 ppm (s, NH); 7.35 ppm (d, 1 H); 7.32 ppm (b, 1H); 6.91 ppm (d, 1 H); 6.88 ppm (b, 1 H); 6.78 ppm (s, 1 H); 4.53 ppm (s, 2H).
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
0.57 g (2 mmol) (3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-carbamic acid phenyl ester (compound no. II.029) is added to a solution of 0.22 g (2 mmol) N,N'-dimethylthiourea in 10 ml NMP containing a catalytic amount of triethylamine. After 5 minutes 0.65 g (4 mmol) carbonyldiimidazole is added and the mixture heated for 6 hours to 80 °C. Then once again 0.65 g (4 mmol) carbonyldiimidazole is added and the mixture stirred further overnight at 95°C. The reaction mixture is poured into icewater and the crystals of almost pure 1 ,5- dimethyl-3-(3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1 ,4]oxazin-6-yl)-6-thioxo-[1 ,3,5]triazinane- 2,4-dione are filtered off and dried. 1H-NMR ((CD3)2SO): 11.58 ppm (s, NH); 7.68 ppm (d, 1 H); 7.22 ppm (d, 1 H); 4.88 ppm (s, 2H); 3.72 ppm (s, 6H).
The preferred compounds listed in the following Tables 1 , 2, 4, 5, 7, 11 , 12 and 100 can also be obtained in analogous manner or using methods described in the Reaction Schemes and in the mentioned references.
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Table 2: Compounds of formula IW2
Figure imgf000136_0002
comp. no. Ri R2 R3 R< X3 Rl4 R|5 R|6 physical data, remarks
(Example)
2.001 (P22) H H H H O H CF3 SH >220°C, tautomeric form IW1g
2.002 H H H H O H CF3 SCH3 >206°C
2.003 H CH3 H H O H CF3 SCH3 >220°C
2.004 H H H O H CF3 SCH3 143-144°C
2.005 H
Figure imgf000136_0003
H H O H CF3 SCH3 183-184°C
2.006 H CH2CH2CH3 H H O H CF3 SCH3 128-129°C
2.007 (P31) H CH2C≡CH H H O H CF3 OCH2F resin
2.008 H H H H O H CF3 SO2CH3 1H-NMR (DMSO-Dβ): 11.41 ppm (s, 1H); 7.45 ppm (d, 1H); 7.37 ppm (s, 1H); 7.07 ppm (d, 1H); 4.67 ppm (s, 2H); 3.32 ppm (s, 3H).
2.009 (P32) H H H H O H CF3 NH2 >250°C Table 4: Compounds of formula IW
Figure imgf000137_0001
comp. no. Ri R2 R3 R X. χ7 R20 R21 R22 physical data
(Example)
4.001 H H H H O O H -CH2CH(OH)CH2CH2- 225°C (isomer I)
4.002 H H H H O O H -CH2CH(OH)CH2CH2- 225°C (isomer II)
4.003 (P18) H CH2C≡CH H H O O H -CH2CH(OH)CH2CH2- 205.5-206°C
4.004 (P19) H CH2C≡CH H H O O H -CH2CH(F)CH2CH2- 205°C (isomer I)
4.005 (P19) H CH2C≡CH H H O O H -CH2CH(F)CH2CH2- 205°C (isomer II)
Table 5: Compounds of formula IW5
Figure imgf000137_0002
comp. no. Ri R2 R3 R X. X. R23 R24 physical data
(Example)
5.001 (P24) H H H H S 0 -Cπ2CH2CH2CH2" >225°C
5.002 (P25) H CH.C≡CH H H S 0 -CH2CH2CH2CH2- >225°C
5.003 H Ch_2CH=CH2 H H S 0 -CH2Crl2Crl2CH2- 186-187°C
5.004 H CH2CH2CH3 H H S 0 -CH2CH2CH2CH2- 210-210.5°C
5.005 H CH2CH3 H H S 0 -CH_CH2CH2CH2- 197-197.5°C
5.006 H H H H S 0 -CH2CH2OCH2CH2- >225°C
5.007 H
Figure imgf000137_0003
H H S 0 -CH2Crl2OCH2Cr.2" 192-193X
5.008 H CH2C≡CH H H S 0 -CH2CH2OCH2CH2- >225°C
5.009 H CH2CH2CH3 H H S 0 -CH2CH2θCr. CH - 172-173°C
5.010 H CH2CH3 H H S 0 *Crl2CH2OCH2CH2- 223-224°C
5.011 H CH2CH2CH2CH3 H H S 0 -CH2CH2CH2CH2- 153-154°C
5.012 H
Figure imgf000137_0004
H H s 0 -CH2Cπ2Crl2CH2* 153-154°C
5.013 H Cπ2CH2CH2CH=CH2 H H s 0 -CH2CH2Crl2CH2- 177-178°C Table 7: Compounds of formula IW7
Figure imgf000138_0001
comp. no. Rt R2 R3 R_7 R28 X10 X11 physical data
(Example)
7.001 H CH2C=CH H H -CH2CH2CH2CH2- O 0 181-182°C
7.002 H CH(CH3)C-iCH H H -CH2CH_Cπ2CH2- O 0 69-70°C
7.003 H isopropyl H H -CH2CH2Crl2CH2- O 0 137-138°C
7.004 H CH2CH=CHCI (cis) H H -CH2CH2CH2CH2- O 0 resin
7.005 H CH2CH=CHCI (trans) H H -CH2Crl2Cπ2CH2" O 0 141-142°C
7.006 H benzyl H H -CH2CH2Cr.2CH2- O 0 178-179°C
7.007 (P 15) H H H H -CH2CH2CH2CH2" O 0 220°C
7.008 H H H H -CH=CH-CH=CH- O 0 >220°C
7.009 H CHzC≡CH H H -CH=CH-CH=CH- O 0 >220°C
7.010 H
Figure imgf000138_0002
H H -CH=CH-CH=CH- O 0 183-184°C
Table 11 : Compounds of formula IWn
Figure imgf000138_0003
comp. no. Ri R2 R3 R4 Xt4 R36 R37 R38 R39 physical data, remarks
(Example)
11.001 (P28) H H H H O H CF3 -CH2CH2. >225°C
11.002 H H H H O H CF3 -CH2CH(CH3). >225°C
11.003 H CH2C≡CH H H O H CF3 -CH2CH2- 223-224°C
11.004 H Cπ2CH=Cr.2 H H O H CF3 -CH2CH - 152-153°C
11.005 H CH CH2CH3 H H O H CF3 -CH2CH2. 137-137.5°C
11.006 H CH2Cr.3 H H O H CF3 -CH2CH2- 159.5-160°C
11.007 H CH(CH3)C≡CH H H O H CF3 -CH2CH2- 206.5-207.5°C
11.008 H CHjC≡CH H H O H CF3 -CH2CH(CH3). 191-191.5°C
11.009 H
Figure imgf000138_0004
H H O H CF3 -CH2CH(CH3). 143-143.5°C
11.010 H CH2CH3 H H O H CF3 -CH2CH(CH3). 115-117°C, 126-128°C (dual melting point)
11.011 H CH2CH2CH3 H H O H CF3 -CH2CH(CH3). 122-122.5°C 11.012 (P29) H CH(CH3)C≡CH H H O H CF3 -CH2CH(CH3). resin, isomer I
11.013 (P29) H CH(CH3)C≡CH H H O H CF3 -CH2CH(CH3). >200°C (decomp.), isomer II
11.014 H CH2C(0)C(CH3)3 H H 0 H CF3 -CH2CH2- resin
11.015 H CH2C(0)OC(CH3)3 H H O H CF3 -CH2CH2. resin
11.016 H CH2CH=C(CI)CH3 H H O H CF3 -CH2CH2- resin, <E>/<Z>-mixture
11.017 H CH2CH2CH2CI H H O H CF3 -CH2CH2- resin
11.018 H CH CH2CH2CH2CH2CI H H O H CF3 -CH2CH2- resin
11.019 H CH2Si(Cπ3)2CH2Cπ3 H H 0 H CF3 -CH2CH2- resin
11.020 H CH2CH(CH3)CH2CI H H O H CF3 -CH2CH2- resin
11.021 H
Figure imgf000139_0001
H H O H CF3 -CH2CH2- resin
11.022 H CH2CH2CH2F H H O H CF3 -CH2CH2- resin
11.023 H H H O H CF3 -CH2CH2- resin
11.024 H
Figure imgf000139_0002
H H O H CF3 -CH2CH2- resin
11.025 H CH2C(0)CH2CH3 H H 0 H CF3 -CH2CH2- resin
11.026 H CH2C(Br)=CH2 H H O H CF3 -CH2CH2- resin
11.027 H CH_CH(COOCH3)CH2CH3 H H O H CF3 -CH2CH2- resin
11.028 H H H O H CF3 -CH2CH2. resin
~\»
11.029 H CH2Cri2CH(CH3)2 H H O H CF3 -CH2CH2- resin
11.030 H H H O H , CF3 -CH2CH2- resin
Cl
11.031 H CH2CH2CH2C≡N H H O H CF3 -CH2CH2- resin
11.032 H CH2CH2OCH2CH2OCH3 H H O H CF3 -CH2CH2- resin
11.033 H CH(CH3)CH=CH2 H H O H CF3 -CH2CH2- resin
11.034 H CH2CH=CHCOOCH3 H H O H CF3 -CH2CH2- resin
11.035 H CH2C(CH3)=CH2 H H O H CF3 -CH2CH2- resin
11.036 H
Figure imgf000139_0003
H H 0 H CF3 -GrfeCr * resin
11.037 (P33) H H H H O H CF3 -CH=CH- >225°C
11.038 H CH C≡CH H H O H CF3 -CH=CH- 208-210 °C
Table 12: Compounds of formula IW12
Figure imgf000139_0004
comp. no. Ri R2 3 R Yz X15 R40 R41 physical data
(Example)
12.001 (P24) H H H H S O -CH2CH2CH2Cr.2- >225°C, <E> or <Z> isomer
12.002 (P25) H CH2C≡CH H H S O -CH2CH2CH2CH2- >225°C, <E> or <Z> isomer
12.003 H
Figure imgf000139_0005
H H S O -CH2CH Cπ CH2- 197-198°C, <E> or <Z> isomer
12.004 H CH2CH2CH3 H H S O -Cπ2CH2CH2CH2- 188-189°C, <E> or <Z> isomer 12.005 H CH2CH3 H H S O -CH2CH2CH2CH2- >220°C, <E> or <Z isomer
12.006 H H H H S 0 -CH2CH20CH2CH2- >225°C, <E> or <Z> isomer
12.007 H Cr_2CH=Cπ2 H H S O -CH CH2OCH2CH2~ 221-22°C,<E> or <Z> isomer
12.008 H CH2C≡CH H H S O -CH2CH2OCH2CH2- >225°C, <E> or <Z> isomer
12.009 H CrkCr^CHs H H S 0 -CH2CH2OCH2CH2- 214-215°C, <E> or <Z> isomer
12.010 H CH2CH2CH2CH3 H H S 0 -CH2CH2CH2CH2- 129-130°C, <E> or <Z> isomer
12.011 H
Figure imgf000140_0001
H H S 0 -CH2CH2CH2CH2- 154-165°C, <E> or <Z> isomer
12.012 H Cπ2Cπ2CH2CH=:CH H H S 0 -Cπ2CH2CH2CH2 141-142°C, <E> or <Z> isomer
Table 21 : Compounds of formula IW2ι
Figure imgf000140_0002
comp. no. Ri R2 R3 4 X23 X24 X25 R_8 R59 physical data
(Example)
21.001 (P34) H H H H O O s CH3 CH3 >225°C
21.002 H CH2C≡CH H H O O s CH3 CH3
21.003 H CH2CH=CH2 H H O O s CH3 CH3
Table 100: Compounds of formula IW10o
Figure imgf000140_0003
comp. no. Ri R2 R3 R4 Rioo Riot Rιo2 physical data
(Example)
100.001 F CH2C≡CH H H Cl OCHF2 CH3 127-128°C
100.002 F CH3 H H Cl OCHF2 CH3 138-139°C
100.003 (P9) F H H H Cl OCHF2 CH3 solid
100.004 F isopropyl H H Cl OCHF2 CH3 123-124°C
100.005 F CH(CH3)COOCH3 H H Cl OCHF2 CH3 93-95°C
100.006 F
Figure imgf000140_0004
H H Cl OCHF2 CH3 oil 100.007 (P13) H H H CH3 H OCHF2 CH3 solid
100.008 (P14) H H H CH3 Cl OCHF2 CH3 solid
100.009 (P12) H H H CH3 H OH CH3 solid; tautomeric form IWι_o_
Table II: Compounds of formula II:
Figure imgf000141_0001
comp. no. Ri R2 R3 R4 A physical data
(Example)
11.001 (P1) H H H H N02 247-252°C
II.002 (P2) H H H H NH2 279-281°C
II.003 (P21) H H H H N=C=S 178-179°C
11.004 Br H H H N02 solid
II.005 Cl H H H Cl solid
11.006 Cl H H H N02 206-207°C
II.007 H H CH3 H N02 186-187°C
II.008 H H n-butyl H N02 solid
II.009 H H CH3 H N=C=S solid
11.010 H H n-butyl H NH2 >235°C
11.011 H H n-butyl H N=C=S solid
11.012 H H n-butyl H NHCSNHC(CH3)3 solid
11.013 H H CH3 H NH2 >230°C
11.014 H H H H NHCSNHC(CH3)3 solid
11.015 H H n-decyl H N=C=S solid
11.016 Cl H n-butyl H N02 solid
11.017 H H CH2CH3 H CH3 solid
11.018 H H CH3 CH3 CH3 solid
11.019 Cl H CH2CH3 H CH3 solid
II.020 Cl H CH3 H CH3 solid
11.021 Cl H CH3 CH3 CH3 solid
II.022 Cl H n-butyl H N=C=S solid
II.023 H H 2,4-CI2-6- H N02 solid
N02- phenyl
II.024 H H H H Br solid
II.025 (P10) H H H H COOH 138-140°C
11.026 H H CH3 H COOH H-NMR ((CD3.2SO)): 11.80 ppm (s, NH); 7.68 ppm (d, 1H); 7.45 ppm (d, 1H); 4.88 ppm (q, 1H); 1.47 ppm (d, 3H).
II.027 (P11) H H CH3 H COCH2COOEt oil
II.028 Br H H H NH2 220°C
II.029 H H H H NHCOO-phenyl >225°C
II.030 (P16) H CH2C≡CH H H NH2 125-126°C
Figure imgf000142_0001
Biological Examples:
Example B1: Herbicidal action before emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a 25 % wettable powder (Example F3, b) according to WO 97/34485), or in the form of an emulsion (prepared from a 25 % emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in a concentration corresponding to 250 g of active ingredient/ha (500 litres water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Panicum, Digitaria, Sida, Ipomea, Amaranthus, Chenopodium, Stellaria, Veronica.
The compounds according to the invention exhibit good herbicidal action.
Examples of the good herbicidal action of compounds of formula I are given in Table B1.
Table B1 : Pre-emerqence action (at 250 q a.i./ha) comp. Setaria Panicum Digitaria Sida Ipomea Amaranthus Chenopodium Stellari Veronica no. a
100.001 1 1 1 2 4 1 1 1 1
100.002 1 1 2 5 5 1 1 4 5
100.003 1 1 1 3 2 1 2 1
100.004 6 2 2 2 4 1 1 1
100.005 2 1 2 2 6 1 1 4 4
1.002 5 2 6 2 1 3 1 4
1.003 2 1 2 1 1 1 1 2
1.004 2 1 1 1 1 1 1 1
1.005 1 1 1 1 1 1 1 1
1.012 1 1 1 1 2 1 1 1
1.013 1 1 1 1 1 1 1 1
1.014 1 1 1 1 2 1 1 4
1.015 1 1 1 1 1 1 1 1
1.016 1 1 1 1 1 1 1 1
1.017 3 1 3 2 1 1 1 7
1.018 1 1 1 1 2 1 1 1
1.019 3 3 1 1 1 1 1 4
1.023 2 1 1 3 3 1 2 3
1.024 1 1 1 1 2 1 1 1
1.027 1 1 1 1 1 1 1 4
1.034 2 1 2 3 4 1 1 7
1.035 2 1 3 4 5 1 1 5
1.041 1 1 1 1 1 1 1 5
Figure imgf000144_0001
The same results are obtained when the compounds of formula I are formulated in accordance with Examples F2 and F4 to F8 according to WO 97/34485.
Example B2: Post-emergence herbicidal action
In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastics pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I, prepared from a 25 % wettable powder (Example F3, b) according to WO 97/34485), or with an emulsion of the test compounds of formula I, prepared from a 25 % emulsifiable concentrate (Example F1 , c) according to
WO 97/34485), in a concentration corresponding to 250 g of active ingredient/ha (500 litres water/ha). The test plants are then grown on in a greenhouse under optimum conditions.
After a test duration of about 18 days, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Panicum, Digitaria, Euphorbia, Ipomea, Amaranthus, Chenopodium, Polygonum, Veronica.
In this test too, the compounds of formula I exhibit strong herbicidal action.
Examples of the good herbicidal action of compounds of formula I are given in Table B2.
Figure imgf000145_0001
Figure imgf000146_0001
The same results are obtained when the compounds of formu la 1 are formulated in accorda nce with Examples F2 and F4 to F8 according to WO 97/34485.
The compounds of formula I according to the invention can also be used for weed control in admixture with known herbicides as co-herbicides, for example in the form of ready- prepared formulations or in the form of a 'tank-mix'. Suitable mixing partners for the compounds of formula I include, for example, the following co-herbicides: compound of formula I + acetochlor; compound of formula I + acifluorfen; compound of formula I + aclonifen; compound of formula I + alachlor; compound of formula I + ametryn; compound of formula I + aminotriazole; compound of formula I + amidosulfuron; compound of formula I + asulam; compound of formula I + atrazine; compound of formula I + BAY FOE 5043; compound of formula I + benazolin; compound of formula I + bensulfuron; compound of formula I + bentazone; compound of formula I + bifenox; compound of formula I + bispyribac-sodium; compound of formula I + bialaphos; compound of formula I + bromacil; compound of formula I + bromoxynil; compound of formula I + bromophenoxim; compound of formula I + butachlor; compound of formula I + butylate; compound of formula I + cafenstrole; compound of formula I + carbetamide; compound of formula I + chloridazone; compound of formula I + chlorimuron-ethyl; compound of formula I + chlorbromuron; compound of formula I + chlorsulfuron; compound of formula I + chlortoluron; compound of formula I + cinosulfuron; compound of formula I + clethodim; compound of formula I + clodinafop; compound of formula I + clomazone; compound of formula I + clopyralid; compound of formula I + cloransulam; compound of formula I + cyanazine; compound of formula I + cyhalofop; compound of formula I + dalapon; compound of formula I + 2,4-D; compound of formula I + 2,4-DB; compound of formula I + desmetryn; compound of formula I + desmedipham; compound of formula I + dicamba; compound of formula I + diclofop; compound of formula I + difenzoquat metilsulfate; compound of formula I + diflufenican; compound of formula I + dimefuron; compound of formula I + dimepiperate; compound of formula I + dimethachlor; compound of formula I + dimethametryn; compound of formula I + dimethenamid; compound of formula I + S-dimethenamid; compound of formula I + dinitramine; compound of formula I + dinoterb; compound of formula I + dipropetryn; compound of formula I + diuron; compound of formula I + diquat; compound of formula I + DSMA; compound of formula I + EPTC; compound of formula I + esprocarb; compound of formula I + ethalfluralin; compound of formula I + ethametsulfuron; compound of formula I + ethephon; compound of formula I + ethofumesate; compound of formula I + ethoxysulfuron; compound of formula I + fenclorim; compound of formula I + flamprop; compound of formula I + fluazasulfuron; compound of formula I + fluazifop; compound of formula I + flumetralin; compound of formula I + flumetsulam; compound of formula I + fluometuron; compound of formula I + flurochloridone; compound of formula I + fluoxaprop; compound of formula I + fluroxypyr; compound of formula I + fluthiacet-methyl; compound of formula I + fluxofenim; compound of formula I + fomesafen; compound of formula I + glufosinate; compound of formula I + glyphosate; compound of formula I + halosulfuron; compound of formula I + haloxyfop; compound of formula I + hexazinone; compound of formula I + imazamethabenz; compound of formula I + imazapyr; compound of formula I + imazaquin; compound of formula I + imazethapyr; compound of formula I + imazosulfuron; compound of formula I + ioxynil; compound of formula I + isoproturon; compound of formula I + isoxaben; compound of formula I + isoxaflutole; compound of formula I + karbutylate; compound of formula I + lactofen; compound of formula I + lenacil; compound of formula I + linuron; compound of formula I + MCPP; compound of formula I + metamitron; compound of formula I + metazachlor; compound of formula I + methabenzthiazuron; compound of formula I + methazole; compound of formula I + metobromuron; compound of formula I + metolachlor; compound of formula I + S-metolachlor; compound of formula I + metosulam; compound of formula I + metribuzin; compound of formula I + metsulfuron- methyl; compound of formula I + molinate; compound of formula I + MCPA; compound of formula I + MSMA; compound of formula I + napropamide; compound of formula I + NDA- 402989; compound of formula I + nefenacet; compound of formula I + nicosulfuron; compound of formula I + norflurazon; compound of formula I + oryzalin; compound of formula I + oxadiazon; compound of formula I + oxasulfuron; compound of formula I + oxyfluorfen; compound of formula I + paraquat; compound of formula I + pendimethalin; compound of formula I + phenmedipham; compound of formula I + phenoxaprop-P-ethyl (R); compound of formula I + picloram; compound of formula I + pretilachlor; compound of formula I + primisulfuron; compound of formula I + prometon; compound of formula I + prometryn; compound of formula I + propachlor; compound of formula I + propanil; compound of formula I + propazine; compound of formula I + propaquizafop; compound of formula I + propyzamide; compound of formula I + prosulfuron; compound of formula I + pyrazolynate; compound of formula I + pyrazosulfuron-ethyl; compound of formula I + pyrazoxyphen; compound of formula I + pyridate; compound of formula I + pyriminobac- methyl; compound of formula I + pyrithiobac-sodium; compound of formula I + quinclorac; compound of formula I + quizalofop; compound of formula I + rimsulfuron; compound of formula I + sequestrene; compound of formula I + sethoxydim; compound of formula I + simetryn; compound of formula I + simazine; compound of formula I + sulcotrione; compound of formula I + sulfosate; compound of formula I + sulfosulfuron-methyl; compound of formula I + tebutam; compound of formula I + tebuthiuron; compound of formula I + terbacil; compound of formula I + terbumeton; compound of formula I + terbuthylazine; compound of formula I + terbutryn; compound of formula I + thiazafluron; compound of formula I + thiazopyr; compound of formula I + thifensulfuron-methyl; compound of formula I + thiobencarb; compound of formula I + tralkoxydim; compound of formula I + triallate; compound of formula I + triasulfuron; compound of formula I -»- trifluralin; compound of formula I + tribenuron-methyl; compound of formula I + triclopyr; compound of formula I + triflusulfuron; and compound of formula I + trinexapac-ethyl, and esters and salts of those mixing partners for the compound of formula I that are mentioned e.g. in The Pesticide Manual, Eleventh Edition, 1997, BCPC.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000149_0001
wherein
R, is hydrogen, methyl or halogen;
R2 is hydrogen, C.-C12alkyl, CrCι2haloalkyl, C2-Cι2alkenyl, C2-Cι2alkynyl, C2-C8alkynyl- C2-C4alkenyl, C3-Cι2allenyl, C2-C12haloalkenyl, C2-Cι2haloalkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-Cι-C4alkyl, C3-C6halocycloalkyl-Cι-C4alkyl, tri(C1-C4alkyl)silyl-C1-C4alkyl, tri(C C alkyl)silyl-C2-C4alkenyl,
Figure imgf000149_0002
CrC6alkoxy-CrC4alkyl, d-C alkoxy-Cι- or -C2-alkoxy-Cι- or -C2-alkyl, di(Cι-C alkoxy)-Cι- or -C2-alkyl, ethylenedioxy-C or -C2-alkyl, C2-C6alkenyloxy-C1-C4alkyl, C2-C6haloalkenyloxy-Cι-C4alkyl, C2-C6alkynyloxy-d-dalkyl, C3- C6haloalkynyloxy-C C4alkyl, d-Cealkylthio-d-dalkyl, Cι-C6alkylsulfinyl-d-C4alkyl, C C6alkylsulfonyl-C C alkyl, hydroxy-C Cι2alkyl, d-Cβalkylcarbonyl-d-dalkyl, C C6haloalkylcarbonyl-d-C alkyl, Ci-Cealkoxycarbonyl-Crdalkyl, d-C6alkoxy-d- or -C2- alkoxycarbonyl-Cι-C4alkyl, d-C6alkoxycarbonyl-Cι-C4haloalkyl, C3-C6cycloalkylcarbonyl-d- C4alkyl or benzoyl-Cι-C4alkyl wherein the benzoyl group may be substituted by halogen, Ci- C3alkyl, Cι-C3haloalkyl, d-C3alkoxy or by d-C3haloalkoxy, or is C3-C6alkenyloxycarbonyl- C1-C alkyl, C3-C6alkynyloxycarbonyl-CrC4alkyl, CrC6alkylcarbonyloxy-CrC4alkyl, C2- C6alkenylcarbonyloxy-d-C alkyl, C3-C6cycloalkylcarbonyloxy-Cι-C4alkyl, benzoyloxy-Cι- C alkyl, d-Cβalkoxycarbonyloxy-d-dalkyl, carbamoyl-C C4alkyl, C C6alkylaminocarbonyl- Cι-C4alkyl, or phenyl- or heterocyclyl-substituted Cι-C4alkyl, wherein the phenyl and heterocyclyl groups may be substituted by halogen, Cι-C6alkyl, CrC6alkoxy, Cι-C6haloalkyl, CrCehaloalkoxy, C2-C6alkenyl, C2-C6alkynyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6cycloalkyl-Cι-C4alkyl, C3-C6halocycloalkyl-CrC4alkyl, cyano-d-C4alkyl, Cι-C6alkoxy-Cr C4alkyl, C Cealkylthio-d-C^lkyl, d-Cealkylsulfinyl-d-C^lkyl, Cι-C6alkylsulfonyl-C C4alkyl, hydroxy-d-C4alkyl, d-C6alkylcarbonyl-d-C4alkyl, d-Cealkoxycarbonyl, d-C6alkoxy- carbonyl-Cι-C4alkyl, d-C6alkoxycarbonyl-Cι-C haloalkyl, d-Cβalkoxycarbonyl-d-dalkoxy, Ci-Cealkylcarbonyloxy-d-dalkyl, d-Cealkoxycarbonyloxy-d-dalkyl, d-C4alkoxy-d- C2alkoxy-Cι-C2alkyl, d-C4alkylaminocarbonyl, Ci-Cealkylaminocarbonyl-d-dalkoxy, phenyl, phenoxy or by benzyloxy, wherein the phenyl ring of the last three definitions may be substituted by halogen, methyl, trifluoromethyl, methylsulfonyl, methoxy, ethoxy or by cyano; or is phenyl-substituted C2-C4alkenyl or C -C4alkynyl, wherein the phenyl group may be substituted by halogen, methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, methoxy, ethoxy, cyano or by nitro;
R3 is hydrogen, d-C^alkyl, d-d2haloalkyl, CrC6alkoxycarbonyl, or phenyl which is unsubstituted or substituted by halogen, methyl, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, methoxy, ethoxy, cyano or by nitro; R4 is hydrogen or d-C6alkyl; W is a group
Figure imgf000150_0001
(Wi2),
Figure imgf000150_0002
Figure imgf000150_0003
Figure imgf000151_0001
<Wl03> ' <Wl<*) •
Figure imgf000151_0003
Figure imgf000151_0002
Figure imgf000151_0004
R11 is hydrogen, C.-C3alkyl, halogen, d-C3haloalkyl or cyano;
R12 is d-C3alkyl, d-C3haloalkyl, d-C3alkyl-S(O) „.-, C C3haloalkyl-S(O) n1- or cyano; and
R13 is hydrogen, CrC3alkyl, Ci-Cshaloalkyl, allyl, propargyl or amino; or R12 and Rn or R12 and R13 together form a C3- or C -alkylene bridge which may be substituted by halogen, d-C3haloalkyl or by cyano;
Ri4 is hydrogen, d-C3alkyl, halogen, C C3haloalkyl or cyano; and
R15 is Cι-C3alkyl, Cι-C3haloalkyl, Cι-C3alkyl-S(O)n2-, C C3haloalkyl-S(O)n2- or cyano; or
R15 and RM together form a C3- or C4-alkylene bridge which may be substituted by halogen,
Cι-C3ha.oalkyl or by cyano;
Rie is hydrogen, CrC3alkyl, halogen, d-C3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, hydroxy, mercapto, d-C3alkylthio, allylthio, propargylthio, CrC3alkylsulfinyl, d-
C3alkylsulfonyl, amino, d-C3alkylamino, di(CrC3alkyl)amino, allylamino, propargylamino or cyano;
Figure imgf000152_0001
Ri7 is hydrogen, d-C3alkyl, halogen or cyano; and
R18 is Cι-C3alkyl, halogen, d-C3haloalkyl, Cι-C3alkylthio, d-C3alkylsulfinyl, d-
C3alkylsulfonyl or cyano; or
Riβ and R 7 together form a C3- or C -alkylene or C3- or C4-alkenylene bridge, both of which may be substituted by halogen, d-C3alkyl or by Ci-Cshaloalkyl;
R19 is hydrogen, halogen, d-C3alkyl, carboxyl, d-dalkoxycarbonyl or amino; or
R19 and R18 together form a C3- or C4-alkylene or C3- or C4-alkenylene bridge, both of which may be substituted by halogen, d-C3alkyl or by d-C3haloalkyl;
R2o and R21 are each independently of the other hydrogen or d-C4alkyl; or
O51
R20 and R2ι together are a group =
™052
R05i and R052 are each independently of the other hydrogen or d-C4alkyl; or R05i and R052 together form a C4- or C5-alkylene bridge; R052 and R22 together form a C3alkylene bridge; R22 is hydrogen or d-C3alkyl; or
R22 and R20 or R22 and R21 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)- and/or substituted by halogen, d-dalkyl, Ci- Cshaloalkyl, C2-C alkenyl, d-C3alkoxycarbonyl, CrC3alkylcarbonyloxy, C1- C3alkylsulfonyloxy or by hydroxy;
R23 and R are each independently of the other hydrogen, d-dalkyl, C C3haloalkyl or propargyl; or R23 and R24 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)- and/or substituted by halogen, Cι-C4alkyl, hydroxy, C
C4alkoxy or by Cι-C4alkoxy-Cι-C alkoxy;
R 5 is hydrogen, halogen, Cι-C alkyl, C C4haloalkyl, Cι-C4alkoxy, C C4haloalkoxy, C
C4alkylthio, Cι-C4haloalkylthio, d-C alkylsulfinyl, Cι-C haloalkylsulfinyl, C C4alkylsulfonyl,
Cι-C4haloalkylsulfonyl, hydroxy or cyano; and
R26 is hydrogen, d-C alkyl or CrC haloalkyl; or
R26 and R25 together form a C3-C5alkylene bridge which may be interrupted by oxygen,
sulfur, -S(O)-, -S(O)2-, N— C^C^alkyl or by -C(O)- and/or substituted by halogen, C
C4alkyl, d-dhaloalkyl, C2-C alkenyl, Cι-C3alkoxycarbonyl, Cι-C3alkylcarbonyloxy, C C3alkylsulfonyloxy or by hydroxy;
R2 and R28 are each independently of the other hydrogen or d-C4alkyl; or R27 and R28 together form a C3-C5alkylene 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 Crdalkyl; R29 and R30 are each independently of the other hydrogen, C C alkyl or Cι-C4haloalkyl; or R29 and R30 together form a C3-C5alkylene 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)-; R31 is hydrogen, d-C4alkyl or C1-C haloalkyl; and
R32 is hydrogen, Cι-C4alkyl, d-C4haloalkyl, Cι-C4alkylthio, C dalkylsulfinyl, d-dalkylsulfonyl, cyano or nitro; or
R3i and R32 together form a C3-C5alkylene bridge which may be substituted by halogen or by d-C4alkyl 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-C4alkyl; R33 is hydrogen, CrC3alkyl, halogen, CrCshaloalkyl, hydroxy, CrC3alkoxy, d- Cshaloalkoxy, mercapto, CrC3alkylthio, CrC3alkylsulfinyl, CrC3alkylsulfonyl, amino, C C3alkylamino, CrC3alkylcarbonylamino, C C3haloalkylcarbonylamino or cyano; R34 is C C alkyl, d-C4haloalkyl, CrC4alkoxy or d-dalkylthio; R36 is hydrogen, d-C3alkyl, halogen, CrC3haloalkyl or cyano; and R37 is C C3alkyl, CrC3haloalkyl, d-C3alkyl-S(O) nr, CrC3haloalkyl-S(O) n1- or cyano; or R37 and R36 together form a C3- or C -alkenylene bridge which may be substituted by halogen, d-C3alkyl, d-C3haloalkyl or by cyano; R38 is d-C3alkyl; and R39 is hydrogen or d-C3alkyl; or
R39 and R38 together form a C2- or C3-alkylene or C2- or C3-alkenylene bridge which is unsubstituted or substituted by d-dalkyl or form an -NH-CH2-, -N=CH- or -N=N- bridge; R40 and R are each independently of the other d-dalkyl or C C3haloalkyl; or R 1 and R40 together form a C3-C5alkylene bridge which is unsubstituted or substituted by halogen or by d-dalkyl;
R42 is hydrogen, CrC3alkyl, Ci-Cshaloalkyl, cyano or carboxyl; R43 is hydrogen, d-C3alkyl, d-dhaloalkyl, allyl or propargyl; R44 is hydrogen, d-dalkyl, halogen, d-C3haloalkyl, hydroxy, mercapto, amino, Cr dalkoxy, d-C3alkylthio or di(C C4alkyl)amino; R45 is hydrogen, Cι-C3alkyl, halogen or cyano; R 6 is d-C3alkyl, d-C3haloalkyl or cyano; R47 is hydrogen, d-dalkyl or halogen; R48 is d-dalkyl or C C3haloalkyl;
R49, R50 and R51 are each independently of the others hydrogen, d-dalkyl, propargyl or d- C4haloalkyl;
R52 is d-C3alkyl, halogen, CrC3haloalkyl, d-C3alkoxy, CrC3haloalkoxy, CrC3alkylthio, d-C3alkylsulfinyl, CrC3alkylsulfonyl, amino or d-C3alkylamino; R53 is d-dalkyl or d-C3haloalkyl; RM is d-dalkyl;
R55 is hydrogen, d-dalkyl, propargyl or d-dhaloalkyl;
R56 is Crdalkyl, d-C3haloalkyl, C C3alkylthio, d-C3alkylsulfinyl or d-dalkylsulfonyl; and
R57 is d-C3alkyl or d-dhaloalkyl; or
R57 and R56 together form a C2-C alkylene or C2-C4alkenylene bridge which both are unsubstituted or substituted by halogen or by d-dalkyl; R58 is hydrogen, Crdalkyl, CrC3haloalkyl or amino; R59 is hydrogen, d-C3alkyl or CrC3haloalkyl;
R 100 is hydrogen, halogen, nitro, amino, cyano, d-C3alkyl, C2- or C3-alkenyl or C2- or C3- alkynyl;
R101 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-dalkyl, Ci- Cshaloalkyl, C2- or C3-alkenyl, C2- or C3-alkynyl, CrC3alkoxy, CrC3haloalkoxy, d- dalkylthio, C C3alkylsulfinyl, CrC3alkylsulfonyl, C C3haloalkylthio, d-C3haloalkylsulfinyl, d-dhaloalkylsulfonyl, FS(O)2-, CIS(O)2-, CrC6alkylsulfonyloxy, CrC6haloalkylsulfonyloxy, d-dalkylcarbonyl, HC(O)-, HOC(O)-, CIC(O)-, FC(O)-, C C3alkoxycarbonyl, H2NC(O)- or H2NC(S)-; and Rι02 is hydrogen, d-dalkyl, d-dalkyl substituted by cyano, HO-, HOC(O)-, C,- dalkoxycarbonyl or by HC(O)-, or is C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, d- dhaloalkyl or Cι-C3alkylsulfonyl; or when W is a group W100,
Ri02 and R10ι together form a C3-C5alkylene 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; R103 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-dalkyl, Ci- Cshaloalkyl, C2- or d-alkenyl, C2- or C3-alkynyl, CrC3alkoxy, CrC3haloalkoxy, d- C3alkylthio, CrC3alkylsulfinyl, CrC3alkylsulfonyl, CrC3haloalkylthio, CrC3haloalkylsulfinyl, Ci-Cshaloalkylsulfonyl, FS(O)2-, CIS(O)2-, CrC6alkylsulfonyloxy, d-dhaloalkylsulfonyloxy, CrC3alkylcarbonyl, HC(O)-, HOC(O)-, CIC(O)-, FC(O)-, CrC3alkoxycarbonyl, H2NC(O)- or H2NC(S)-;
RKM is hydrogen, d-dalkyl, d-dalkyl substituted by cyano, HO-, HOC(O)-, C,- dalkoxy-carbonyl or by HC(O)-, or is C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, d- dhaloalkyl or CrC3alkylsulfonyl; and
R105 is hydrogen, halogen, nitro, amino, cyano, d-dalkyl, C2- or C3-alkenyl or C2- or C3- alkynyl; or
RKM and R103 together form a C3-C5alkylene 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;
R106 is hydrogen, halogen, amino, nitro, hydroxy, d-dalkyl or d-C3alkoxy; Rι07 is hydrogen, halogen, amino, hydroxy, d-dalkyl, d-dhaloalkyl, HC(O)-, HOC(O)-, hydroxy-Crdalkyl, d-C3alkoxy or C C3haloalkoxy; and
Rioβ is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-dalkyl, d-dhaloalkyl, C2- or d-alkenyl, d-C3alkoxy, d- C3haloalkoxy, d-dalkylcarbonyl, CrC3alkoxycarbonyl, CrC3alkylthio, CrC3haloalkylthio, CrC3alkylsulfinyl, d-dhaloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, d- C3alkylsulfonyloxy or d-dhaloalkylsulfonyloxy; or
Rioβ and Rι0 together form a C3-C5alkylene 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; R109 is hydrogen, halogen, amino, hydroxy, d-dalkyl, d-C3haloalkyl, HC(O)-, HOC(O)-, hydroxy-Crdalkyl, C C3alkoxy or CrC3haloalkoxy; or
R109 and Rι08 together form a C3-C5alkylene 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; R110 is hydrogen, d-dalkyl, d-C3haloalkyl, C3-C4alkenyl or C3-C alkynyl; Rm is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-dalkyl, d-dhaloalkyl, C2- or d-alkenyl, d-dalkoxy, d-
C3haloalkoxy, C C3alkylcarbonyl, CrC3alkoxycarbonyl, CrC3alkylthio, CrC3haloalkylthio,
CrC3alkylsulfinyl, Crdhaloalkylsulfinyl, CrC3alkylsulfonyl, CrC3haloalkylsulfonyl, d-
C3alkylsulfonyloxy or d-dhaloalkylsulfonyloxy; and
Ri 12 is hydrogen, halogen, amino, hydroxy, d-dalkyl, d-dhaloalkyl, HC(O)-, HOC(O)-, hydroxy-C C3alkyl, Cι-C3alkoxy or d-dhaloalkoxy; or
Rm and R110 together form a C3-C5alkylene 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 d-dalkylene bridge is bonded to the N atom of the pyrazinone via a CH2 group; or
R112 and Rm together form a C3-C5alkylene 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;
R113 is hydrogen, d-dalkyl, d-C3haloalkyl, C3-C alkenyl or C3-C4alkynyl; and
Rn4 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-C3alkyl, CrC3haloalkyl, C2- or d-alkenyl, d-dalkoxy, d-
C3haloalkoxy, d-C3alkylcarbonyl, d-C3alkoxycarbonyl, C C3alkylthio, CrC3haloalkylthio,
CrC3alkylsulfinyl, d-dhaloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, d-
C3alkylsulfonyloxy, d-dhaloalkylsulfonyloxy, d-C3alkylamino or di(CrC3alkyl)amino; or
R114 and Rn3 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the triazinone via a CH2 group;
Rns is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-dalkyl, C C3haloalkyl, C2- or C3-alkenyl, d-C3alkoxy, d-
C3haloalkoxy, d-dalkylcarbonyl, CrC3alkoxycarbonyl, CrC3alkylthio, C C3haloalkylthio,
CrC3alkylsulfinyl, d-dhaloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, d-
C3alkylsulfonyloxy or d-dhaloalkylsulfonyloxy; and
R116 is hydrogen, d-dalkyl, CrC3haloalkyl, C3-C4alkenyl or C3-C4alkynyl; or
R116 and Rn5 together form a C3-C5alkylene 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 d-dalkylene bridge is bonded to the N atom of the triazinone via a CH2 group;
R117 is hydrogen, d-dalkyl, d-C3haloalkyl, C3-C alkenyl or C3-C4alkynyl;
Rue is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, CrC3alkyl, d-C3haloalkyl, C2- or C3-alkenyl, Cι-C3alkoxy, C
C3haloalkoxy, CrC3alkylcarbonyl, d-dalkoxycarbonyl, d-C3alkylthio, d-dhaloalkylthio, d-dalkylsulfinyl, C C3haloalkylsulfinyl, C C3alkylsulfonyl, CrC3haloalkylsulfonyl, d-
C3alkylsulfonyloxy or d-dhaloalkylsulfonyloxy; and
Rug is hydrogen, halogen, amino, nitro, hydroxy, C C3alkyl or d-C3alkoxy; or
Ri 18 and R,17 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the pyrimidinone via a CH2 group;
Ri2o is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-dalkyl, d-dhaloalkyl, C2- or d-alkenyl, d-C3alkoxy, d-
C3haloalkoxy, C C3alkylcarbonyl, C C3alkoxycarbonyl, Cι-C3alkylthio, d-C3haloalkylthio,
CrC3alkylsulfinyl, d-C3haloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, C
C3alkylsulfonyloxy or d-dhaloalkylsulfonyloxy;
R121 is hydrogen, d-C3alkyl, d-dhaloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl; and
R122 is hydrogen, halogen, amino, nitro, hydroxy, d-dalkyl or C C3alkoxy; or
R12ι and Rι20 together form a C3-C5alkylene 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
C3-C5alkylene bridge is bonded to the N atom of the pyrimidinone via a CH2 group;
R123 is hydrogen, d-dalkyl, halogen or d-dhaloalkyl;
Rι24 is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, mercapto, d-dalkyl, d-C3haloalkyl, C2- or C3-alkenyl, CrC3alkoxy, d-
C3haloalkoxy, CrC3aIkylcarbonyl, d-C3alkoxycarbonyl, CrC3alkylthio, C C3haloalkylthio, d-C3alkylsulfinyl, C C3haloalkylsulfinyl, CrC3alkylsulfonyl, d-C3haloalkylsulfonyl, C
C3alkylsulfonyloxy or C C3haloalkylsulfonyloxy; and
R125 is hydrogen, d-C3alkyl, halogen, hydroxy, d-C3alkoxy, d-C3haloalkoxy, C
C3alkylthio, d-C3alkylsulfinyl, C C3alkylsulfonyl, amino or cyano;
X . i X2, X31 X ι Xδi Xε, X7. Xβ. Xθ. XlO, Xl1 » Xl2. Xl3. Xl > Xl5ι X .6. Xl7. Xl8, Xl9. X∑O, X2L X∑2, X23,
X24 and X25 are each independently of the others oxygen or sulfur; and
Y1 and Y2 are oxygen or sulfur, or an agrochemically acceptable salt or tautomer, enantiomer or stereoisomer of such a compound of formula I.
2. A compound of formula I according to claim 1 wherein
R, is hydrogen, methyl or halogen;
R2 is hydrogen, d-d∑alkyl, Ci-Cshaloalkyl, CrCι2alkenyl, d-C^alkynyl, d-
Cι2haloalkenyl, d-C^haloalkynyl, CrC6cycloalkyl-CrC4alkyl, d-dhalocycloalkyl-d-
C4alkyl, cyano-Crd2alkyl, CrC6alkoxy-CrC4alkyl, Cι-C4alkoxy-Crdalkoxy-Cι-C2alkyl, d d-dalkoxyJd-dalkyl, d-dalkylthio-Crdalkyl, Crdalkylsulfinyl-d-dalkyl, d- C6alkylsulfonyl-CrC alkyl, hydroxy-d-Cι2alkyl, d-dalkylcarbonyl-Crdalkyl, d- C6haloalkylcarbonyl-CrC alkyl, CrC6alkoxycarbonyl-CrC4alkyl, Crdalkoxycarbonyl-d- dhaloalkyl, CrC6alkoxycarbonyl-benzyl, CrC6alkenyloxycarbonyl-Cι-C4alkyl, d- C6alkynyloxycarbonyl-CrC4alkyl, Cι-C6alkylcarbonyloxy-CrC4alkyl,
Cι-C6alkenylcarbonyloxy-CrC alkyl, CrC6cycloalkylcarbonyloxy-CrC4alkyl, benzoyloxy-C C alkyl, CrC6alkoxycarbonyloxy-CrC4alkyl, Ci-C6alkylaminocarbonyl-CrC4alkyl, d- C6alkylaminocarbonyl-benzyl, or d-dalkyl substituted by phenyl or by heterocyclyl, wherein the phenyl and heterocyclyl group may be substituted one or more times by halogen, d- C6alkyl, d-dhaloalkyl, d-dalkenyl, d-dalkynyl, d-C6haloalkenyl, d-dhaloalkynyl, d- dcycloalkyl-d-dalkyl, CrC6halocycloalkyl-CrC4alkyl, cyano-CrCι2alkyl, Crdalkoxy-d- C4alkyl, CrC6alkylthio-Cι-C4alkyl, CrC6alkylsulfinyl-C C4alkyl, Cι-C6alkylsulfonyl-CrC4alkyl, hydroxy-d-Cι2alkyl, Cι-C6alkylcarbonyl-CrC4alkyl, CrC6alkoxycarbonyl-CrC4alkyl, d- C6alkoxycarbonyl-CrC4haloalkyl, CrC6alkylcarbonyloxy-Cι-C alkyl, d- C6alkoxycarbonyloxy-CrC4alkyl, Cι-C4alkoxy-Cι-C2alkoxy-CrC2alkyl or by phenyl; R3 is hydrogen, d-Cι2alkyl, d-Cι2haloalkyl or unsubstituted or substituted phenyl; R4 is hydrogen or d-dalkyl;
W is a group
Figure imgf000158_0001
Figure imgf000158_0002
Figure imgf000158_0003
Figure imgf000159_0001
Figure imgf000159_0002
(W106), (Wι07) or
Figure imgf000159_0003
Figure imgf000159_0004
Rn is hydrogen, d-dalkyl, halogen, d-dhaloalkyl or cyano;
Ri2 is d-dalkyl, d-C3haloalkyl, d-C3alkyl-S(O) n1-, C C3haloalkyl-S(O) n1- or cyano; and
Ri3 is d-dalkyl, d-dhaloalkyl or amino; or
Rι2and Rn or Rι2and Rι3 together form a C3- or C4-alkylene bridge which may be substituted by halogen, d-C3haloalkyl or by cyano;
Ru is hydrogen, C C3alkyl, halogen, C C3haloalkyl or cyano; and
Ris is CrC3alkyl, C C3haloalkyl, d-C3alkyl-S(O)n2-, CrC3haloalkyl-S(O)n2- or cyano; or
Rι5and R together form a C3- or C -alkylene bridge which may be substituted by halogen, d-dhaloalkyl or by cyano;
Rie is hydrogen, Cι-C3alkyl, halogen, d-dhaloalkyl, d-dalkoxy, d-C3haloalkoxy, d-
C3alkylthio, CrC3alkylsulfinyl, CrC3alkylsulfonyl or cyano;
Figure imgf000159_0005
R17 is hydrogen, d-dalkyl, halogen or cyano; and Ri8 is d-dalkyl, halogen, d-C3haloalkyl, d-C3alkylthio, d-dalkylsulfinyl, d-
C3alkylsulfonyl or cyano; or
Riβ and Rι7 together form a C3- or C -alkylene or C3- or C4-alkenylene bridge, both of which may be substituted by halogen, d-dalkyl or by d-C3haloalkyl;
R19 is hydrogen, halogen, d-dalkyl or amino; or
R19 and Rι8 together form a C3- or dalkylene or C3- or C -alkenylene bridge, both of which may be substituted by halogen, d-dalkyl or d-C3haloalkyl;
R20 and R2ι are each independently of the other hydrogen or d-dalkyl; or
"051
R20 and R21 together are a group ==\
"θ52
R05i and R052 are each independently of the other d-dalkyl; or
R05i and R052 together form a C4- or C5-alkylene bridge;
R05i and R22 together form a dalkylene bridge;
R22 is hydrogen or C C3alkyl; or
R22 and R2o or R22 and R2ι together form a C3-C5alkylene bridge which may be interrupted by oxygen or by -C(O)- and/or substituted by halogen, d-dalkyl, C C3haloalkyl, C2- dalkenyl, d-C3alkoxycarbonyl, d-C3alkylcarbonyloxy, d-C3alkylsulfonyloxy or by hydroxy;
R23 is hydrogen, d-dalkyl or d-C3haloalkyl; or
R23 and R2 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-;
R25 is hydrogen, halogen, d-dalkyl, d-C4haloalkyl, d-C4alkoxy, Crdhaloalkoxy, d- dalkylthio, CrC4haloalkylthio, d-C alkylsulfinyl, CrC haloalkylsulfinyl, CrC4alkylsulfonyl, d-dhaloalkylsulfonyl or cyano; and
R26 is hydrogen, d-dalkyl or d-dhaloalkyl; or
R26 and R25 together form a C3-C5alkylene bridge which may be interrupted by oxygen or by
-C(O)- and/or substituted by halogen, d-dalkyl, d-C3haloalkyl, C2-C4alkenyl, d-C3alkoxy- carbonyl, CrC3alkylcarbonyloxy, CrC3alkylsulfonyloxy or by hydroxy;
R2 and R28 are each independently of the other hydrogen or d-dalkyl; or
R27 and R28 together form a C3-C5alkylene bridge or a dalkenylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-;
R29 and R30 are each independently of the other hydrogen or d-dalkyl; or
R29 and R30 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-;
R3i is hydrogen, d-dalkyl or d-dhaloalkyl; and R32 is hydrogen, C C4alkyl, d-dhaloalkyl, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, cyano or nitro; or
R3ι and R32 together form a C3-C5alkylene bridge which may be interrupted by oxygen, sulfur, -S(O)-, -S(O)2- or by -C(O)-;
R33 is hydrogen, d-dalkyl, halogen, d-dhaloalkyl, d-C3alkoxy, d-C3haloalkoxy, d-dalkylthio, d-C3alkylsulfinyl, CrC3alkylsulfonyl, amino, d-C3alkylamino, C C3alkyl- carbonylamino, Cι-C3haloalkylcarbonylamino or cyano; Ra* is C C4alkyl, CrC haloalkyl, Cι-C4alkoxy or d-dalkylthio;
R100 is hydrogen, halogen, nitro, amino, cyano, d-C3alkyl, C2- or C3-alkenyl or C2- or C3- alkynyl;
R101 is hydrogen, halogen, nitro, amino, cyano, hydroxy, mercapto, d-dalkyl, Ci- Cshaloalkyl, C2- or d-alkenyl, C2- or C3-alkynyl, d-dalkoxy, d-dhaloalkoxy, d- C3alkylthio, d-dalkylsulfinyl, Crdalkylsulfonyl, d-dhaloalkylthio, CrC3haloalkylsulfinyl, d-C3haloalkylsulfonyl, FS(O)2-, CIS(O)2-, C C6alkylsulfonyloxy, d-C6haloalkylsulfonyloxy, d-C3alkylcarbonyl, HC(O)-, HOC(O)-, CIC(O)-, FC(O)-, d-C3alkoxycarbonyl, H2NC(O)- or H2NC(S)-;
R102 is hydrogen, d-dalkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, d-dhaloalkyl, d-dalkylsulfonyl, or d-dalkyl which may be substituted by cyano, HO-, HOC(O)-, d-C3- alkoxycarbonyl or by HC(O)-; or, when W is a group W10o,
R102 and R101 together form a C3-C5alkylene 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; R103 is as defined for R101; R10 is as defined for Rι02; R105 is as defined for R100;
R106 is hydrogen, halogen, amino, nitro, hydroxy, d-dalkyl or d-dalkoxy; R107 is hydrogen, halogen, amino, hydroxy, d-dalkyl, d-dhaloalkyl, HC(O)-, HOC(O)-, hydroxy-d-dalkyl, d-C3alkoxy or d-C3haloalkoxy; and
Rioβ is hydrogen, halogen, nitro, amino, cyano, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, hydroxy, HS-, d-C3alkyl, CrC3haloalkyl, C2- or d-alkenyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylcarbonyl, CrC3alkoxycarbonyl, Cι-C3alkylthio( CrC3haloalkylthio, d- C3alkylsulfinyl, d-C3haloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, d- C3alkylsulfonyloxy or CrC3haloalkylsulfonyloxy; R109 is as defined for Rι07;
R107 and Rioβ together form a C3-C5alkylene 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; R108 and R109 together form a C3-C5alkylene 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;
R110 is hydrogen, Crdalkyl, d-dhaloalkyl, C3-C alkenyl or C3-C4alkynyl;
Rm is as defined for Rι08;
Rι12 is as defined for R109;
Rm and Rn2 together form a C3-C5alkylene 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;
R110 and Rm together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the pyrazinone;
Rιι3 is as defined for Rn0;
Rn4 is as defined for Rio8;
Rn3 and R together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the triazinone;
Rι15 is as defined for Rι08;
Rue is as defined for Rn0;
R115 and Rue together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the triazinone;
Rι17 is as defined for Ri ι0;
Rιι8 is as defined for Rι08;
R119 is as defined for Rioβ;
R117 and Rn8 together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the pyrimidinone;
R120 is as defined for Rι08;
R121 is as defined for Ri ι0;
Rι22 is as defined for Rioβ;
Ri2i and Rι20 together form a C3-C5alkylene 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
CH2 group is bonded to the N atom of the pyrimidinone;
Xi, X2, X3. X4. X5. Xβ, X7. Xβ. X9. X10. X11. X12 and Xι3 are each independently of the others oxygen or sulfur; and
Yi is oxygen or sulfur.
3. A process for the preparation of compounds of formula I according to claim 1 , which process comprises, for the preparation of compounds of formula I
Figure imgf000163_0001
wherein Ri, R2, R3 and R are as defined in claim 1 and W is a group Wi
Figure imgf000163_0002
wherein Rn, Rι2, Rι3, Xi and X2 are as defined in claim 1 , converting a compound of formula XXX
Figure imgf000163_0003
wherein R1f R2, R3 and R4 are as defined, by means of aromatic nitration, into the compound of formula lln
Figure imgf000163_0004
and subjecting that compound to reduction to yield the compound of formula lla
Figure imgf000163_0005
which is either a) reacted with a compound of formula VI
Figure imgf000164_0001
wherein X2 is as defined in claim 1 , X0 is oxygen, sulfur or amino and R5 is d-Calkyl, to form the compound of formula lie
Figure imgf000164_0002
wherein Ri, R2, R3, R4, R5, X0 and X2 are as defined, or b) treated with phosgene (X2=O) or thiophosgene (X2=S) of formula C(X2)CI or oxalyl chloride, to obtain the compound of formula lid
Figure imgf000164_0003
wherein R1 f R2, R3, R4 and X are as defined, and condensing and cyclising the compounds of formulae lie and lid thereby obtained with an enamine of formula VII
Figure imgf000164_0004
wherein Rn, R12, Rι3 and Xi are as defined and R6 is d-dalkyl, in an inert solvent in the presence of from 0.01 to 1.5 equivalents of a suitable base, and then, optionally, further functionalising the substituents Xi, X2, Ri, R2, Rn and Rι3 according to their definitions.
4. A compound of formula II
Figure imgf000165_0001
wherein R^ to R4 are as defined for formula I and A is fluorine, d-dalkylthio, d- dalkylsulfonyl, phenylthio, phenylsulfonyl, d-C alkylsulfonyloxy, trifluoromethylsulfonyloxy, hydroxy, nitro, amino, isocyanato, isothiocyanato, hydrazino, a group NHC(X2)XoR5, NHC(X7)X0R5, NHC(X8)X0R5, NHC(X9)X0R5, NHC(X3)R16, NHN=C(R,7)C(O)Rι8, NHC(X7)N(R22)C(R20)R2ιC(X6)OR9, NHC(X9)NR24NR23C(X8)ORιo, NHC(X8)NR23NHR24, NHN=C(R25)COOH, NHN=C(R25)Ro25, N(C(X4)-NHR26)N=CR25Ro25, N(C(X4 )NHR26)NH2, NHN=C(R25)N(R26)C(X4)OR8 , N(C(X4)NHR26)NHC(O)OR84, N(C(Xι9)NHR50)NHC(O)OR84, NHC(Xι2)NHR26, NHC(O)C(R28)=C(R27)C(O)OR85,
Figure imgf000165_0002
NHC(Y2)NR40NHR41, NHC(Y2)NR40NR41C(O)OR9, NHN=C(R42)C(O)NHR43, NHN=C(R42)C(O)N(R43)C(O)OR85, N(R43)COOR85, NHC(R5s)=NNHC(X21)OR86,
Figure imgf000165_0003
NHC(X2s)NHR58C(X25)NHR59, N(C(X24)NHR59)C(X23)XoR5, ethyl, vinyl, ethynyl, C≡CC(O)OR86, C=CC(O)R87, acyl, formyl, cyano, carboxy, C(O)OR89, C(O)C(O)OR9o,
C(O)CH2COOR9ι, C(O)CH2C(O)R88, cyanomethyl, B(OH)2 or N J, 025 , wherein
R .6, Ri7, Riβ, R20, R21. R22. R23. R24, R25. R26. R27, R28. R38, R39, R40, R4ι . R42, R43, R50, R53, R56 and R57 are as defined in claim 1 ; R5, R9, R025. Rβ , Rβ6. Rβ9. R90 and R91 are each independently of the others d-dalkyl or phenyl; R10 and R85 are hydrogen or d-dalkyl; R87 and R88 are d-C4alkyl, formyl, CH(d-C4alkoxy) or d-C4haloalkyl; X,, X2, X3, X4, X6, X7, Xβ, Xg. X12, X19, X21 and Y2 are oxygen or sulfur; and X0 is oxygen, sulfur or amino.
5. A herbicidal and plant-growth-inhibiting composition, comprising a herbicidally effective amount of a compound of formula I on an inert carrier.
6. A herbicidal and plant-growth-inhibiting composition according to claim 5, comprising at least one further co-herbicide as additional component.
7. A method of controlling undesired plant growth, which method comprises applying a compound of formula I, or a composition comprising such a compound, in a herbicidally effective amount to plants or to the locus thereof.
8. Use of a composition according to claim 5 in the control of undesired plant growth.
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