WO2003104206A2 - Herbicidally active heterocyclylalkynes - Google Patents

Herbicidally active heterocyclylalkynes Download PDF

Info

Publication number
WO2003104206A2
WO2003104206A2 PCT/EP2003/005703 EP0305703W WO03104206A2 WO 2003104206 A2 WO2003104206 A2 WO 2003104206A2 EP 0305703 W EP0305703 W EP 0305703W WO 03104206 A2 WO03104206 A2 WO 03104206A2
Authority
WO
WIPO (PCT)
Prior art keywords
mono
substituted
dalkyl
hydrogen
halogen
Prior art date
Application number
PCT/EP2003/005703
Other languages
French (fr)
Other versions
WO2003104206A3 (en
Inventor
Jürgen Schaetzer
Jean Wenger
Sabine Berteina-Raboin
Kurt Nebel
André Stoller
Roger Graham Hall
Original Assignee
Syngenta Participations Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to AU2003238179A priority Critical patent/AU2003238179A1/en
Publication of WO2003104206A2 publication Critical patent/WO2003104206A2/en
Publication of WO2003104206A3 publication Critical patent/WO2003104206A3/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/08—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/12—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/16—Halogen atoms; Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
    • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel, herbicidally active heterocyclylalkynes, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
  • Phenyl- and pyridyl-alkynes having herbicidal action are described, for example, in JP-A-11 147 866, WO 01/55066, WO 02/28182 and PCT Application No. 02/14006.
  • the present invention accordingly relates to compounds of formula I
  • n O, 1 , 2, 3 or 4; each Ri independently is halogen, -CN, -SCN, -SF 5 , -NO 2> -NR 5 R 6 , -CO 2 R 7 , -CONR 8 R 9 ,
  • R 3 and R are each independently of the other hydrogen, halogen, -CN, CrC 4 alkyl or CrC 4 alkoxy; or
  • R 3 and R together are C 2 -C 5 alkylene;
  • R 5 is hydrogen or C C 8 alkyl;
  • R 6 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by C ⁇ -C 4 alkyl or mono-, di- or tri-substituted by CrC 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-C 4 alkylthio, d-C alkylsulfinyl or by d-C 4 alkylsulfonyl; or
  • R 5 and R 6 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 7 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C C 8 alkyl.
  • R 8 is hydrogen or d-C 8 alkyl;
  • R 9 is hydrogen or d
  • R 9 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or trisubstituted by C ⁇ -C 4 haloalkyl, d-C 4 alkoxy, -CN, -NO 2 , d-C 4 alkylthio, d-C 4 alkylsulfinyl or by d-C 4 alkylsulfonyl; or R 8 and R 9 together are C 2 -C 5 alkylene; R 10 is hydrogen, d-C alkyl, C ⁇ -C haloalkyl or C 3 -C 6 cycloalkyl;
  • Rn is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 12 is hydrogen, C C 4 alkyl, d-C haloalkyl or C 3 -C 6 cycloalkyl;
  • R 13 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; or
  • R 13 is phenyl or phenyl-d-C ⁇ alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or tri-substituted by d-C halo- alkyl, d-C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 8 alkylthio, C ⁇ -C 8 alkylsulfinyl or by C ⁇ -C 8 alkylsulfonyl, or R 13 is d-C 8 alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, C ⁇ -C 6 alkylamino, di(d-C 6 alkyl)amino or by C C 4 alkoxy;
  • R 14 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C ⁇ -C 8 alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or by C ⁇ -C alkoxy;
  • R 15 , R 16 and R 1 7 are each independently of the others C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by d-C 4 alkoxy;
  • R 18 is hydrogen or d-C 8 alkyl;
  • R 19 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or tri-substituted by d-C 4 haloalkyl, C C 4 alkoxy, -CN, -NO 2 , C C alkylthio, d-C 4 alkylsulfinyl or by C,-C 4 alkylsulfonyl; or
  • R 18 and R 19 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 20 is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C alkyl or mono-, di- or tri-substituted by d-C haloalkyl, d-C alkoxy, -CN, -NO 2 , d-C 4 alkylthio, d-C 4 alkylsulfinyl or by C ⁇ -C 4 alkylsulfonyl;
  • R 21 is hydrogen or d-C 8 alkyl;
  • R 22 is hydrogen or d-C 8 alkyl, or is C ⁇ -C 8 alkyl mono-, di- or tri-substituted by -COOH, C ⁇ -C 8 alkoxycarbonyl or by -CN, or R 22 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or trisubstituted by C ⁇ -C 4 haloalkyl, d-C alkoxy, -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by d-C 4 alkylsulfonyl; or R 21 and R 22 together are C 2 -C 5 alkylene; R 23 is hydrogen, d-C 4 alkyl
  • R 25 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 26 is hydrogen or C ⁇ -C 8 alkyl;
  • R 27 is hydrogen or d-C 8 alkyl, or is C C 8 alkyl mono-, di- or tri-substituted by -COOH, C C 8 - alkoxycarbonyl or by -CN, or
  • R 27 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by C ⁇ -C 4 alkyl or mono-, di- or trisubstituted by d-C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C C 4 alkylthio, C C 4 alkylsulfinyl or by C ⁇ -C alkylsulfonyl; or R 26 and R 27 together are C 2 -C 5 alkylene; R 28 is hydrogen or d-C 8 alkyl;
  • R and R 30 are each independently of the other hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or d-C 8 alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by C C alkoxy;
  • R 31 and R 32 are each independently of the other d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or d-C 8 alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or by d-C 4 alkoxy; m is 0, 1 , 2 or 3; each R 2 independently is halogen, -CN, -SCN, -OCN, -N 3( -SF 5 , -NO 2 , -NR 33 R 34 , -CO 2 R 35 .
  • R 2 is a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono- to penta- substituted by hal
  • R 33 is hydrogen or d-C 8 alkyl;
  • R 34 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, CH 3 C(O)-, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or tri-substituted by C ⁇ -C 4 haloalkyl, d-C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C C 4 alkylsulfinyl or by d-C alky
  • R 33 and R 34 together are a C -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 35 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by d-C 4 alkyl or mono-, di- or tri-substituted by d-C 4 haloalkyl, d-C alkoxy, -CN, -NO 2 , C C 4 alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; R 36 is hydrogen or C ⁇ -C 8 alkyl;
  • R 37 is hydrogen or d-C 8 alkyl, or is d-C 8 alkyl mono-, di- or tri-substituted by -COOH, C ⁇ -C 8 - alkoxycarbonyl or by -CN, or
  • R 37 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or trisubstituted by C ⁇ -C 4 haloalkyl.
  • R 36 and R 37 together are C 3 -C 5 alkylene;
  • R 3 ⁇ is hydrogen, d-C alkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 39 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 4 o is hydrogen, d-C 4 alkyl, C,-C 4 haloalkyl, C ⁇ -C 8 alkylthio, -C(O)-C(O)Od-C 4 alkyl or C 3 -C 6 - cycloalkyl;
  • R 4 ⁇ is hydrogen, d-C 8 alkyl. d-dhaloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-C 6 alkoxy- C ⁇ -C 6 alkyl, C C 8 alkylcarbonyl, CrC 8 alkoxycarbonyl, C 3 -C 8 alkenyloxycarbonyl, C ⁇ -C 6 alkoxy- C ⁇ -C 6 alkoxycarbonyl, C ⁇ -C 6 alkylthio-C ⁇ -C 6 alkyl, d-C 6 alkylsulfinyl-C ⁇ -C 6 alkyl or d-C 6 alkyl- sulfonyl-d-C 6 alkyl; or
  • R 4 ⁇ is phenyl or phenyl-Ci-C ⁇ alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen or by C ⁇ -C alkyl or mono-, di- or tri-substituted by C ⁇ -C halo- alkyl, C C 4 alkoxy, -CN, -NO 2 or by -S(O) 2 C 1 -C 8 alkyl, or
  • R 41 is d-C 8 alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -COOH, C ⁇ -C 8 alkoxycarbonyl, C ⁇ -C 6 alkylamino, di(d-C 6 alkyl)amino or by -CN;
  • R 42 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C ⁇ -C 8 alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or by d-C 4 alkoxy;
  • R,i 3 and R ⁇ are each independently of the other d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or d-C 8 alkyl mono- to penta-substituted by halogen or mono
  • R 5 is C ⁇ -C 8 alkyl, d-C 8 alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by C ⁇ -C 4 alkoxy, or is C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or R 45 is phenyl, it being possible for the phenyl ring to be mono- to penta-substituted by halogen or by d-C 4 alkyl or mono-, di- or tri-substituted by C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, -CN, NO 2> d-C 8 alkylthio, C C 8 alkylsulfinyl or by C,-C 8 alkylsulfonyl; R ⁇ is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkyny
  • R 47 is phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , C C 4 alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; p is 0 or 1 ;
  • R50, R5 1 , R ⁇ 2 and R 53 are each independently of the others hydrogen, C C 8 alkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono- to penta-substituted by halogen or by C ⁇ -C 8 alkyl or mono-, di- or trisubstituted by d-dhaloalkyl, C ⁇ -C 4 alkoxy, d-C 4 alkylamino, di(C ⁇ -C 4 alkyl)amino, -NH 2) -CN, -NO 2> d-dalkylthio, d-C 4 alkylsulfinyl or by C C 4 alkylsulfonyl;
  • R M and R 55 are each independently of the other hydrogen, d-C 8 alkyl, or phenyl which may in turn be mono- to penta-substituted by halogen or by C ⁇ -C 4 alkyl or mono-, di- or trisubstituted by C ⁇ -C 4 haloalkyl, d-C 4 alkoxy, -CN, -NO 2 , C C 8 alkylthio, d-C 8 alkylsulfinyl or by d-C 8 alkylsulfonyl;
  • Rse is hydrogen, d-C 8 alkyl, d-C 4 haloalkyl, C r C 4 alkoxy, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or benzyl, it being possible for benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C haloalkyl.
  • R 57 is d-C 8 alkyl, C C 4 haloalkyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C 4 haloalkyl, d-C 4 alkoxy, C C 4 alkylamino, d d-dalky amino, -NH 2 , -CN, -NO 2) d-dalkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; R 58 and R 59 are each independently of the other CrC 8 alkyl.
  • R 60 and R 6 are each independently of the other hydrogen or d-dalkyl;
  • R 62 , R 63 and R 64 are each independently of the others hydrogen or d-C 8 alkyl, or R 63 and R 64 together form a C 2 -C 5 alkylene bridge;
  • R67, Res. ⁇ 9 and R 70 are each independently of the others hydrogen or d-C 8 alkyl, or
  • each R 2 independently is C C 8 alkyl substituted by a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, hydroxy-d-C 4 alkyl, d-C alkoxy, d-C 4 alkoxy- d-C 4 alkyl.
  • Q 2 , Q 3 or Q 5 , two adjacent R 2 substituents together may form a C 2 -C 7 alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by C ⁇ -C 6 alkyl or mono-, di- or tri-substituted by d-C 6 alkoxy, the total number of ring atoms being at least 5 and at most 9;
  • R 7 ⁇ is hydrogen or C C 8 alkyl;
  • R 72 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by C C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-C 4 alkylthio, C C 4 - alkylsulfinyl or by d-C 4 alkylsulfonyl; or
  • R 71 and R 72 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 73 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C 4 haloalkyl, Ci-dalkoxy, -CN, -NO 2) d-C 4 alkylthio, d-C 4 alkylsulfinyl or by C,-C 4 alkylsulfonyl; R 74 is hydrogen or d-C 8 alkyl;
  • R 75 is hydrogen, C ⁇ -C 8 alkyl or C 3 -C 7 cycloalkyl, or is C ⁇ -C 8 alkyl mono-, di- or tri-substituted by -COOH, d-C 8 alkoxycarbonyl, Ci-dalkoxy or by -CN; or
  • R 75 is C 3 -C 8 alkenyl.
  • R 74 and R 75 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 76 is hydrogen, Crdalkyl, d-C haloalkyl or C 3 -C 6 cycloalkyl
  • R-n is hydrogen, d-dalkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl
  • R 78 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-dhaloalkyl or C 3 -C 6 haloalkenyl;
  • R 79 is hydrogen or C C 8 alkyl
  • R 80 is hydrogen or C C 8 alkyl, or is C ⁇ -C 8 alkyl mono-, di- or tri-substituted by -COOH, d-C 8 - alkoxycarbonyl or by -CN; or R 80 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , Crdalkylthio, d-C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R 79 and R 80 together are C 2 -C 5 alkylene; R 81 is hydrogen or C C 8 alkyl;
  • R 82 is -Si(CrC 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is Crdalkyl which is mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN, -NH 2 , CrC 6 alkylamino, di(CrC 6 alkyl)amino or by C C 4 alkoxy;
  • R ⁇ 3 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is d-C 8 alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH 2 , CrC 6 aIkylamino, di(d-C 6 alkyl)amino or by d-C 4 alkoxy;
  • R-w, Res and R 86 are each independently of the others C C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 - alkynyl, or d-C 8 alkyl which is mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by C C 4 alkoxy;
  • R 87 and Rr ⁇ are each independently of the other hydrogen, d-dalkyl or d-C 8 alkoxy; Rag is d-dalkyl; Rgo is hydrogen or Crdalkyl; R 91 is d-dalkyl;
  • R 92 and R 93 are each independently of the other Crdalkyl
  • R 94 is hydrogen or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by C r C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R 95 is hydrogen or d-dalkyl;
  • R 96 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-C 8 alkoxycarbonyl or by -CN; or
  • R 96 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R 95 and R g6 together are C 2 -C 5 alkylene;
  • R 97 and R 98 are each independently of the other hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl;
  • R 99 is hydrogen, Crdalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-dhaloalkyl or C 3 -C 6 haloalkenyl;
  • R . oo is hydrogen or d-dalkyl;
  • R,o ⁇ is hydrogen or C C 8 alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-C 8 - alkoxycarbonyl or by -CN; or
  • R 101 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, C C 4 alkoxy, -CN, -NO 2 , d-C 4 alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R 100 and R 10 i together are C 2 -C 5 alkylene; R 102 is hydrogen or d-dalkyl;
  • R 103 is hydrogen, C C 8 alkyl, -Si(CrC 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; R l04 is d-C 6 alkyl;
  • R 105 is hydrogen or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by C C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by d-C 4 alkylsulfonyl; R 106 is hydrogen or d-dalkyl;
  • R 10 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
  • R 107 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-C 4 alkoxy, -CN, -NO 2> d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R 10 e and R 107 together are C 2 -C 5 alkylene; R 108 is hydrogen, d-dalkyl, C C 4 haloalkyl or C 3 -C 6 cycloalkyl; R 109 is hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl
  • R 110 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R,n is hydrogen or d-dalkyl;
  • R 112 is hydrogen or d-dalkyl, or is Crdalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
  • R. 12 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R,n and R 112 together are C 2 -C 5 alkylene; R 113 is hydrogen or d-dalkyl; R 11 is hydrogen, d-dalkyl, -S d-dalkyl ⁇ , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; R 115 is CrC 6 alkyl;
  • R 16 is hydrogen or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R 117 is hydrogen or d-dalkyl;
  • R 118 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
  • R 118 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , C C 4 alkylthio, C C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R 117 and Rn 8 together are C 2 -C 5 alkylene; R 119 is hydrogen, d-dalkyl, C C 4 haloalkyl or C 3 -C 6 cycloalkyl; R 120 is hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl;
  • R 12 ⁇ is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 122 is hydrogen or d-dalkyl;
  • R 123 is hydrogen or Crdalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
  • R .23 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by d-dalkylsulfonyl; or
  • R 122 and R ⁇ 23 together are C 2 -C 5 alkylene; and R .24 is hydrogen or d-dalkyl, and to the agrochemically acceptable salts and all stereoisomers and tautomers of the compounds of formula I.
  • substituents that are formed as a result of R 5 and R 6 together or R 18 and R 19 together or R 36 and R 37 together or R 7 and R 75 together being a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom are piperidine, morpholine, thiomorpholine and pyrrolidine.
  • heterocyclic ring systems which may be aromatic or partially or fully saturated in the definition of R 2 are:
  • alkyl groups appearing in the substituent definitions may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the pentyl, hexyl, heptyl and octyl isomers.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro- methyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl.
  • Alkoxy groups have a chain length of preferably from 1 to 6, especially from 1 to 4, carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or the pentyloxy and hexyloxy isomers; preferably methoxy or ethoxy.
  • Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, alkylaminoalkoxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylthio, alkenylsulfonyl, alkenylsulfinyl, alkynylsulfonyl, alkynylthio and alkynylsulfinyl groups are derived from the mentioned alkyl radicals.
  • the alkenyl and alkynyl groups may be mono- or poly-unsaturated.
  • Alkenyl is, for example, vinyl, allyl, methallyl, 1 -methylvinyl or but-2-en-1-yl.
  • Alkynyl is, for example, ethynyl, propargyl, but- 2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl.
  • Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
  • Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • the invention relates also to the salts which the compounds of formula I are able to form preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • Suitable salt formers are described, for example, in WO 98/41089.
  • alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, especially the hydroxides of sodium and potassium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary d-C 18 alkylamines, d-dhydroxyalkylamines and d-dalkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropyl- amine, 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, eth
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R a R b R c R )]OH wherein R a , R b , R c and R d are each independently of the others d-dalkyl.
  • Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • -C(CrC 4 alkylthio) NR 28 , -OR 9 , -SR 30 , -SOR 31 , -SO 2 R 2 or by C 3 -C 6 cycloalkyl; or each Ri independently is C 3 -C 6 cycloalkyl mono-, di- or tri-substituted by halogen, -CN, -NO 2 ,
  • each Ri independently is phenyl which may in turn be mono-, di- or tri-substituted by halogen, d-dalkyl, C,-C 4 haloalkyl, d-dalkoxy, -CN, -NO 2> d-dalkylthio, C r
  • R 3 and R 4 together are C 2 -C 5 alkylene;
  • R 5 is hydrogen or d-dalkyl;
  • R 6 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by d-dalkylsulfonyl; or
  • R 5 and R 6 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 7 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl mono-, di- or tri-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2l d-dalkylthio, C,-C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; R 8 is hydrogen or d-dalkyl;
  • R 9 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
  • R 9 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; or R 8 and R 9 together are C 2 -C 5 alkylene;
  • R 10 is hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl;
  • Rn is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-dhaloalkyl or C 3 -C 8 haloalkenyl;
  • R 12 is hydrogen, d-C alkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl;
  • Ri 3 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; or
  • R 13 is phenyl or phenyl-d-dalkyl, it being possible for the phenyl ring in turn to be mono-, di- or tri-substituted by halogen, Crdalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-C 8 - alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or
  • R 13 is d-dalkyl mono-, di- or tri-substituted by halogen, -CN, CrC 6 alkylamino, di(C r C 6 - alkyl)amino or by d-C 4 alkoxy;
  • R 1 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is d-dalkyl mono-, di- or trisubstituted by halogen, -CN or by C C alkoxy;
  • R 15 , R ⁇ e and R 17 are each independently of the others d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 - alkynyl, or d-C 8 alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C 4 alkoxy;
  • R i8 is hydrogen or d-dalkyl;
  • Rig is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2> d-dalkylthio, d-dalkylsulfinyl or by C C 4 alky
  • R ⁇ 8 and R ⁇ 9 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 20 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , C C 4 alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; 21 is hydrogen or d-C 8 alkyl;
  • R 22 is hydrogen or d-dalkyl, or is d-C 8 alkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
  • R 22 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by d-C 4 alkylsulfonyl; or R 21 and R 22 together are C -C 5 alkylene; R 23 is hydrogen, d-dalkyl, C C 4 haloalkyl or C 3 -C G cycloalkyl; R 2 is hydrogen, d-dalkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 25 is hydrogen, CrC 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, CrC 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 26 is hydrogen or d-C 8 alkyl;
  • R 27 is hydrogen or d-C 8 alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
  • R 27 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C C 4 haloalkyl, d-C 4 alkoxy, -CN, -NO 2 , d-dalkylthio, d-dalkylsulfinyl or by C C 4 alkylsulfonyl; or R 26 and R 27 together are C 2 -C 5 alkylene; R 28 is hydrogen or d-C 8 alkyl;
  • R 29 and R 30 are each independently of the other hydrogen, d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C r C 8 alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C 4 alkoxy;
  • R 31 and R 32 are each independently of the other d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or d-C 8 alkyl mono-, di- or tri-substituted by halogen, -CN or by C C alkoxy;
  • m is 0, 1 , 2 or 3; each R 2 independently is hydrogen, halogen, -CN, -SCN, -OCN, -N 3 , -SF 5 , -NO 2 , -NR 33 R 3 -,, -CO 2 R 35 , -CONR 36 R37, -C(R
  • R 34 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-dalkylsulfinyl or by d-C 4 alkylsulfonyl; or
  • R 33 and R 34 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 35 is hydrogen, Crdalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is Crdalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl mono-, di- or tri-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-C 4 alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl;
  • R 36 is hydrogen or d-dalkyl;
  • R 37 is hydrogen or d-dalkyl, or is d-C 8 alkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
  • R 37 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C haloalkyl, d-dalkoxy, -CN, -NO 2l d-dalkylthio, d-C 4 alkylsulfinyl or by d-C 4 alkylsulfonyl; or R 38 and R 37 together are C 3 -C 5 alkylene; R 3 ⁇ is hydrogen, d-dalkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 39 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R- t o is hydrogen, Crdalkyl, d-dhaloalkyl, d-dalkylthio, -C(O)-C(O)OCrC 4 alkyl or d-C 6 cycloalkyl;
  • R ⁇ is hydrogen, Crdalkyl.. d-dhaloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-dalkoxy- d-dalkyl, C r C 8 alkylcarbonyl, Crdalkoxycarbonyl, C 3 -C 8 alkenyloxycarbonyl, d-dalkoxy- d-dalkoxycarbonyl, CrC 6 alkylthio-C ⁇ -C 6 alkyl, CrC 6 alkylsulfinyl-CrC 6 alkyl or C C 6 alkyl- sulfonyl-d-dalkyl; or
  • R 1 is phenyl or phenyl-d-dalkyl, it being possible for the phenyl ring in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C 4 alkoxy, -CN, -NO 2 or by -S(O) 2 CrC 8 alkyl, or
  • R 4 ⁇ is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl, C C 6 alkyl- amino, di(d-C 6 alkyl)amino or by -CN;
  • R 42 is hydrogen, Crdalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C C 8 alkyl mono-, di- or trisubstituted by halogen, -CN or by d-C alkoxy;
  • R 43 and R ⁇ are each independently of the other d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or d-C 8 alkyl mono-, di- or tri-substituted by halogen, -CN or by C C 4 alkoxy; R ⁇ is d-dalkyl, C C 8 alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C alkoxy, or is C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or
  • R 45 is phenyl, it being possible for the phenyl ring to be mono-, di- or tri-substituted by halogen, d-dalkyl.
  • R 46 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or d-C 4 haloalkyl;
  • R 47 is hydrogen, d-C 8 alkyl, d-dalkoxy, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C C 8 alkyl mono-, di- or tri-substituted by halogen, -CN, d-dalkoxy, Crdalkoxycarbonyl, -NH 2 , d-dalkylamino, di(CrC 4 alkyl)amino, -NR ⁇ COR ⁇ , -NR 50 SO 2 R5i or by -NR52CO 2 R53, or R 47 is phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or trisubstituted by halogen, d-dalky
  • R 4 g. R50, R51, R5 2 and R53 are each independently of the others hydrogen, d-dalkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C alkoxy, d-dalkylamino, di(C C 4 alkyl)amino, -NH 2 , -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by d-dalkylsulfonyl;
  • R 5 --. and R 55 are each independently of the other hydrogen, Crdalkyl, or phenyl which may in turn be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
  • R 56 is hydrogen, Crdalkyl, d-dhaloalkyl, d-dalkoxy, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or benzyl, it being possible for benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C 4 alkoxy, -CN, -NO 2> CrC 8
  • R 57 is d-dalkyl, d-dhaloalkyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy, d-dalkylamino, di(C C 4 alkyl)amino, -NH 2 , -CN, -NO 2 , C C 4 alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
  • Rs ⁇ and R 59 are each independently of the other Crdalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, C C alkoxy, d-dalkylamino, di(CrC 4 alkyl)amino, -NH 2 , -CN, -NO 2 , d-C 4 alkylthio, C C 4 alkylsulfinyl or by d-C 4 alkyl- sulfonyl;
  • R ⁇ o and R 6 ⁇ are each independently of the other hydrogen or d-C 6 alkyl;
  • R 62 , R ⁇ 3 and R 64 are each independently of the others hydrogen or Crdalkyl, or R 63 and R ⁇ together form a C 2 -C 5 alkylene bridge; ⁇ . R-3 6 .
  • Re ⁇ , Reg and R 70 are each independently of the others hydrogen or d-dalkyl, or
  • each R 2 independently is d-C 8 alkyl substituted by a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, hydroxy-d-dalkyl, d-dalkoxy, CrC 4 alkoxy-d-C 4 alkyl, -CN, -NO 2 , d- dalkylthio, C C 6 alkylsulfin
  • R 72 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by d-dalkylsulfonyl; or
  • R 7i and R 72 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 73 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl mono-, di- or tri-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by d-dalkylsulfonyl; R 74 is hydrogen or d-dalkyl;
  • R 75 is hydrogen, d-C 8 alkyl or C 3 -C 7 cycloalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl, d-dalkoxy or by -CN; or
  • R 75 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, C C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R 74 and R 75 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 76 is hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl
  • R- ⁇ is hydrogen, d-dalkyl, d-C haloalkyl or C 3 -C 6 cycloalkyl
  • R 78 is hydrogen, Crdalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 79 is hydrogen or d-dalkyl
  • R ⁇ o is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
  • R 80 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R 79 and R ⁇ together are C 2 -C 5 alkylene; R 8 , is hydrogen or d-dalkyl;
  • R 82 is -Si(CrC 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C C 8 alkyl which is mono-, di- or trisubstituted by halogen, -CN, -NH 2 , Crdalkylamino, di(CrC 6 alkyl)amino or by d-C 4 alkoxy;
  • R 83 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is d-C 8 alkyl which is mono-, di- or tri-substituted by halogen, -CN, -NH 2 , CrC 6 alkylamino, di(d-C 6 alkyl)amino or by d-C 4 alkoxy;
  • Rew, Res and R 86 are each independently of the others d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 - alkynyl, or d-dalkyl which is mono-, di- or tri-substituted by halogen, -CN or by d-dalkoxy;
  • R 87 and Rsg are each independently of the other hydrogen, d-C 8 alkyl or d-C 8 alkoxy;
  • R 88 is d-dalkyl;
  • R 90 is hydrogen or d-C 8 alkyl;
  • R 9 ⁇ is d-C 4 alkyl;
  • R 92 and R 93 are each independently of the other d-dalkyl
  • R 94 is hydrogen or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono-, di- or tri-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by C,-C 4 alkylsulfonyl;
  • R 95 is hydrogen or d-dalkyl;
  • R 96 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
  • R 96 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, d-C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R 95 and R 96 together are C 2 -C 5 alkylene;
  • R 97 and R 98 are each independently of the other hydrogen, d-dalkyl, d-dhaloalkyl or d-C 6 cycloalkyl;
  • R 99 is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 10 o is hydrogen or Crdalkyl;
  • R 101 is hydrogen or d-dalkyl, or is d-C 8 alkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
  • R 101 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C C 4 haloalkyl, d-dalkoxy, -CN, -NO 2 , d-dalkylthio, C,-C 4 alkylsulfinyl or by d-dalkylsulfonyl; or R 10 o and R 10 ⁇ together are C 2 -C 5 alkylene;
  • R. 02 is hydrogen or Crdalkyl;
  • R 103 is hydrogen, d-dalkyl, -Si(CrC 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
  • R10-1 is d-dalkyl;
  • R .05 is hydrogen or is Crdalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono-, di- or tri-substituted by halogen, C C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, C C 4 alkoxy, -CN,
  • 106 is hydrogen or d-dalkyl
  • R ⁇ 07 is hydrogen or d-dalkyl, or is C C 8 alkyl mono-, di- or tri-substituted by -COOH,
  • R 107 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy,
  • R 106 and R 10 7 together are C 2 -C 5 alkylene
  • R. 08 is hydrogen, d-dalkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R. 09 is hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl;
  • Rno is hydrogen, d-dalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 111 is hydrogen or d-C 8 alkyl
  • Rn 2 is hydrogen or d-C 8 alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
  • Rn 2 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy,
  • Rm and R 2 together are C 2 -C 5 alkylene
  • R 113 is hydrogen or d-C 8 alkyl
  • R 114 is hydrogen, CrC 8 alkyl, -Si(CrC 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
  • Rns is d-dalkyl
  • Rue is hydrogen or is d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono-, di- or tri-substituted by halogen, C C alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN,
  • R is hydrogen or d-dalkyl
  • Rns is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
  • Rue is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, C C 4 alkoxy,
  • R 1i7 and R 1i8 together are C 2 -C 5 alkylene
  • R 119 is hydrogen, d-dalkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl
  • R i20 is hydrogen, d-dalkyl, d-dhaloalkyl or C 3 -C 6 cycloalkyl
  • R 12 i is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 122 is hydrogen or d-C 8 alkyl
  • R 123 is hydrogen or C C 8 alkyl, or is C C 8 alkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
  • R .23 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy,
  • R ⁇ 24 is hydrogen or d-dalkyl.
  • R 10 is hydrogen or d- dalkyl; and Rn is d-dalkyl.
  • R ⁇ R 2 , R 3 , R 4 , Z, m and n are as defined for formula I, can be prepared analogously to known methods described, for example, in "Palladium in Heterocyclic Chemistry” from Tetrahedron Organic Chemistry Series 20, A Guide for the Synthetic Chemist, Editors Jie Jack Li and Gordon W. Gribble, Pergamon 2000; Tetrahedron Lett. 1986 (27), 1171 ; Tetrahedron Organic Chemistry 2000 (20), 359-362; ibid. 2000 (20), 390-394; and K. Sonogashira in "Comprehensive Organic Synthesis", Editors I. Fleming et al., Oxford 1991 , Vol. 3, page 521 ff., for example by reacting a compound of formula II
  • R 1 f Z and n are as defined for formula I and X is halogen, with a compound of formula Ilia
  • R 3 and R are as defined for formula I and M + is an alkali metal cation such as, for example, a lithium, sodium or potassium cation, to form a compound of formula IV
  • MCPBA 3-chloroperbenzoic acid
  • Q is a group Q 3 , that is to say compounds of formula lc
  • the compounds of formula la can be obtained, for example, by reaction of substituted propargyl ethers of formula IV with compounds of formula Va by means of Sonogashira coupling.
  • the propargyl ethers of formula IV can, for their part, be obtained by a nucleophilic aromatic
  • Ri C(R ⁇ )-
  • Ri is as defined for formula I and X is a leaving group such as, for example, halogen, -Otosyl (-OTs) or -Omesyl (-OMs), with an alcoholate of formula Ilia (route A in Reaction Scheme 1 ).
  • nucleophilic aromatic substitution reaction is facilitated if they are activated compounds. That is the case when Ri is, for example, a substituent having electron-withdrawing properties (-M and or -I effect), such as, for example, -CN, -NO 2 , -CO 2 R 7 , COR ⁇ 2 .
  • -M and or -I effect electron-withdrawing properties
  • a suitable alternative synthesis method is a nucleophilic aliphatic substitution reaction, wherein a compound of formula II
  • Z C(R ⁇ )-; Ri is as defined for formula I; n is 0, 1 , 2 or 3; and X is OH, is reacted with a compound of formula 11 lb
  • R 3 and R are as defined for formula I and Xi is -Otosyl (-OTs), -Omesyl (-OMs), chlorine, bromine or iodine, in the presence of a base, to form a compound of formula IV
  • R,, R 3 , R 4 , Z and n are as defined (route B in Reaction Scheme 1 ).
  • Such etherification reactions are standard methods and may be carried out, for example, in analogy to Tetrahedron 1997 (53), 12621-12628; J. Chem. Soc. Perkin Trans. 1979, 2756- 2761 ; Synth. Communic. 1988 (18), 1111 -1118; J. Org. Chem. 1996 (61 ), 4258-4261 ; or Synth. Communic. 1994 (24), 1367-1379.
  • the propargyl ethers of formula IV obtained are coupled with substituted pyrazinyl (or 1 ,4-diazinyl) derivatives of formula Va under typical Sonogashira conditions (K. Sonogashira in Comprehensive Organic Synthesis 1991 , Vol. 3, page 521 ff.; and J. Org.
  • the pyrazinyl derivatives of formula Va preferably have a leaving group A, A being, for example, halogen or trifluoromethanesulfonate (Tetrahedron Organic Chemistry 2000 (20),
  • Suitable catalyst mixtures for the Sonogashira reaction are, for example, tetrakis-
  • triphenylphosphine palladium or bis(triphenylphosphine)palladium(ll) dichloride together with copper(l) iodide (Cul);
  • suitable bases are especially amines, for example triethylamine, diethylamine or diisopropylethylamine.
  • solvents there are usually used ethers, for example tetrahydrofuran, chlorinated hydrocarbons, for example chloroform, or dipolar aprotic solvents, for example dimethylformamide or dimethyl sulfoxide, and also amines, for example triethylamine or piperidine.
  • ethers for example tetrahydrofuran
  • chlorinated hydrocarbons for example chloroform
  • dipolar aprotic solvents for example dimethylformamide or dimethyl sulfoxide
  • amines for example triethylamine or piperidine.
  • R 2 , R 3 , R 4 and m are as defined for formula I and Xi is a leaving group such as, for example, halogen, -Otosyl (-OTs) or -Omesyl (-OMs).
  • Xi is a leaving group such as, for example, halogen, -Otosyl (-OTs) or -Omesyl (-OMs).
  • the compound of formula Villa can be obtained, for example, from the compound of formula Vila by means of sulfonylation or halogenation, in accordance with Reaction Scheme 3.
  • Sulfonylation of the alcohol of formula Vila to form the compound of formula Villa is a standard reaction and can be carried out, for example, using a sulfonic acid chloride, for example mesyl chloride (MsCI) or para-toluenesulfonic acid chloride (p-TsCI), in the presence of a tertiary amine, e.g. triethylamine, or an aromatic amine, e.g. pyridine, in a solvent such as, for example, a chlorinated hydrocarbon, e.g. carbon tetrachloride or methylene chloride, or an amine, e.g. pyridine.
  • a sulfonic acid chloride for example mesyl chloride (MsCI) or para-toluenesulfonic acid chloride (p-TsCI)
  • MsCI mesyl chloride
  • p-TsCI para-toluenesulfonic acid chloride
  • Halogenation of the alcohol of formula Vila to form the compound of formula Villa can be carried out in analogy to standard methods.
  • bromination can be successfully carried out using carbon tetrabromide in the presence of triphenylphosphine (Synthesis 1998, 1015-1018) in methylene chloride.
  • Chlorination can be successfully carried out using mineral acids, for example using concentrated hydrochloric acid (J. Org. Chem. 1955 (20), 95), or using para-toluenesulfonic acid chloride in the presence of an amine, for example triethylamine, in a solvent, for example methylene chloride (Tetrahedron Lett. 1984 (25), 2295).
  • Suitable solvents are dimethylformamide and acetonitrile; suitable bases are especially potassium carbonate and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • DBU 1 ,8-diazabicyclo[5.4.0]undec-7-ene
  • the etherification can also be carried out in halogenated or aromatic hydrocarbons as solvent, for example in chloroform or in benzene, in the presence of silver carbonate as base.
  • the reactions resulting in the compounds of formula I are advantageously performed in aprotic, inert, organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitrites, such as acetonitrile or propionitrile, amides, such as N,N-dimethyl- formamide, diethylformamide or N-methylpyrrolidinone.
  • the reaction temperatures are preferably from -20°C to +120°C.
  • the reactions are generally slightly exothermic and can usually be carried out at room temperature.
  • heating, up to the boiling point of the reaction mixture may, where appropriate, be carried out for a short time. It is also possible for the reaction times to be reduced by adding a few drops of base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]- octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec-7-ene.
  • bases inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates, e.g. sodium carbonate or potassium carbonate, or hydrogen carbonates, e.g. potassium hydrogen carbonate or sodium hydrogen carbonate.
  • the compounds of formula I may, in conventional manner, be isolated by concentrating and/or evaporating off the solvent and purified by recrystallising or triturating the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • the compounds of formulae IV and VII are novel.
  • the present invention accordingly relates also to those compounds.
  • the compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or at least one compound of formula I, and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient(s) with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • Suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
  • the surfactants conventionally employed in formulation technology which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques.
  • the weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Panicum, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Euphorbia, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • the reaction mixture is stirred for 3 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C.
  • the solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/2).
  • the desired title compound is obtained as a brown solid having a melting point of 142°C in a yield of 510 mg (84 % of theory).
  • R f 0.50 in ethyl acetate/petroleum ether 1/1 ;
  • the reaction mixture is stirred for 3 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C.
  • the solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/2).
  • the desired title compound is obtained as a beige solid having a melting point of 88°C in a yield of 412 mg (66 % of theory).

Abstract

Compounds of formula (I), wherein Q is a group, (II), (III), (IV), (V), (VI) or (VII); Z is =N-, (VIII) or =C(R1)-; n is 0, 1, 2, 3 or 4; R1 and R2 are as defined in claim 1; R3 and R4 are each independently of the other hydrogen, halogen, -CN, C1-C4alkyl or C1-C4alkoxy; or R3 and R4 together are C2-C5alkylene; m is 0, 1, 2 or 3; and the agrochemically acceptable salts and all stereoisomers and tautomers of the compounds of formula (I) are suitable for use as herbicides.

Description

Novel herbicides
The present invention relates to novel, herbicidally active heterocyclylalkynes, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
Phenyl- and pyridyl-alkynes having herbicidal action are described, for example, in JP-A-11 147 866, WO 01/55066, WO 02/28182 and PCT Application No. 02/14006.
Novel heterocyclylalkynes that have herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula I
Figure imgf000003_0001
wherein Q is a group
Figure imgf000003_0002
Figure imgf000003_0003
Z is =N-, I + - or =C(Rι)- ;
=N— O n is O, 1 , 2, 3 or 4; each Ri independently is halogen, -CN, -SCN, -SF5, -NO2> -NR5R6, -CO2R7, -CONR8R9,
-C(Rιo)=NOR11, -COR12, -OR13, -SR14, -SOR15, -SO2Rι6, -OSO2Rι7> CrC8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or is Cι-C8alkyl, C2-C8alkenyl or C2-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NO2, -NR18R19> -CO2R2o, -CONR2ιR22, -COR23,
Figure imgf000004_0001
-C(S)NR26R27, -C(CrC4alkylthio)=NR28> - OR29, -SR30> -SOR31, -SO2R32 or by C3-C6cycloalkyl; and/or each Rx independently is C3-C6cycloalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NO2, -NR18R19, -CO2R20, -CONR21R22, -COR23> -C(R24)=NOR25, -C(S)NR26R27, -C(C1-C4alkylthio)=NR28, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; and/or each Ri independently is phenyl which may in turn be mono- to penta-substituted by halogen or by C C4alkyl or mono-, di- or tri-substituted by CrC4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C1-C4alkylsulfinyl or by d-C4alkylsulfonyl; and/or two adjacent Ri substituents together form a Cι-C7alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by Cι-C6alkyl or mono-, di- or tri-substituted by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent Rx substituents together form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by C C6alkyl or mono-, di- or trisubstituted by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9;
R3 and R are each independently of the other hydrogen, halogen, -CN, CrC4alkyl or CrC4alkoxy; or
R3 and R together are C2-C5alkylene; R5 is hydrogen or C C8alkyl;
R6 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by Cι-C4alkyl or mono-, di- or tri-substituted by CrC4haloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, d-C alkylsulfinyl or by d-C4alkylsulfonyl; or
R5 and R6 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl. C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by C C4alkyl or mono-, di- or tri-substituted by d-C4haloalkyl, Cι-C alkoxy, -CN, -NO2( C C4alkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; R8 is hydrogen or d-C8alkyl; R9 is hydrogen or d-C8alkyl, or is d-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl or by -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or trisubstituted by Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, d-C4alkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; R10 is hydrogen, d-C alkyl, Cι-C haloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R12 is hydrogen, C C4alkyl, d-C haloalkyl or C3-C6cycloalkyl; R13 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-d-Cβalkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or tri-substituted by d-C halo- alkyl, d-C4alkoxy, -CN, -NO2, Cι-C8alkylthio, Cι-C8alkylsulfinyl or by Cι-C8alkylsulfonyl, or R13 is d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, Cι-C6alkylamino, di(d-C6alkyl)amino or by C C4alkoxy;
R14 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is Cι-C8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or by Cι-C alkoxy; R15, R16 and R17 are each independently of the others Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by d-C4alkoxy; R18 is hydrogen or d-C8alkyl;
R19 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or tri-substituted by d-C4haloalkyl, C C4alkoxy, -CN, -NO2, C C alkylthio, d-C4alkylsulfinyl or by C,-C4alkylsulfonyl; or
R18 and R19 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R20 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C alkyl or mono-, di- or tri-substituted by d-C haloalkyl, d-C alkoxy, -CN, -NO2, d-C4alkylthio, d-C4alkylsulfinyl or by Cι-C4alkylsulfonyl; R21 is hydrogen or d-C8alkyl;
R22 is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl or by -CN, or R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or trisubstituted by Cι-C4haloalkyl, d-C alkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or R21 and R22 together are C2-C5alkylene; R23 is hydrogen, d-C4alkyl, C C4haloalkyl or C3-C6cycloalkyl; R24 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or Cι-C8alkyl;
R27 is hydrogen or d-C8alkyl, or is C C8alkyl mono-, di- or tri-substituted by -COOH, C C8- alkoxycarbonyl or by -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by Cι-C4alkyl or mono-, di- or trisubstituted by d-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by Cι-C alkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or d-C8alkyl;
R and R30 are each independently of the other hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by C C alkoxy;
R31 and R32 are each independently of the other d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or by d-C4alkoxy; m is 0, 1 , 2 or 3; each R2 independently is halogen, -CN, -SCN, -OCN, -N3( -SF5, -NO2, -NR33R34, -CO2R35. -CONR36R37, -C(R38)=NOR39, -COR^, -OR41, -SR42> -SOR^, -SO2R44, -OSO2R45, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)SO2R57, - (SO2R58)SO2R59,
Figure imgf000006_0001
-CRez^ResJORw, -OC(O)NR65R66, -SC(O)NR67R68, -OC(S)NR69R70 or -N-phthalimide; and/or R2 is a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono- to penta- substituted by halogen or by Cι-C4alkyl or mono-, di- or tri-substituted by d-C4haloalkyl, hydroxy-d-dalkyl, d-C alkoxy. d-dalkoxy-d-dalkyl, -CN, -NO2( C C6alkylthio, d-C6alkylsulfinyl or by C C6alkylsulfonyl; R33 is hydrogen or d-C8alkyl; and R34 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CH3C(O)-, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or tri-substituted by Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or by d-C alkylsulfonyl; or
R33 and R34 together are a C -C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R35 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by d-C4alkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-C alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; R36 is hydrogen or Cι-C8alkyl;
R37 is hydrogen or d-C8alkyl, or is d-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8- alkoxycarbonyl or by -CN, or
R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or trisubstituted by Cι-C4haloalkyl. Cη-C4alkoxy, -CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or by Cι-C alkylsulfonyI; or R36 and R37 together are C3-C5alkylene; R3β is hydrogen, d-C alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R4o is hydrogen, d-C4alkyl, C,-C4haloalkyl, Cι-C8alkylthio, -C(O)-C(O)Od-C4alkyl or C3-C6- cycloalkyl;
R4ι is hydrogen, d-C8alkyl. d-dhaloalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C6alkoxy- Cι-C6alkyl, C C8alkylcarbonyl, CrC8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, Cι-C6alkoxy- Cι-C6alkoxycarbonyl, Cι-C6alkylthio-Cι-C6alkyl, d-C6alkylsulfinyl-Cι-C6alkyl or d-C6alkyl- sulfonyl-d-C6alkyl; or
R4ι is phenyl or phenyl-Ci-Cβalkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen or by Cι-C alkyl or mono-, di- or tri-substituted by Cι-C halo- alkyl, C C4alkoxy, -CN, -NO2 or by -S(O)2C1-C8alkyl, or
R41 is d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl, Cι-C6alkylamino, di(d-C6alkyl)amino or by -CN; R42 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is Cι-C8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or by d-C4alkoxy; R,i3 and R^ are each independently of the other d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or by Cι-C4alkoxy;
R 5 is Cι-C8alkyl, d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by Cι-C4alkoxy, or is C3-C8alkenyl or C3-C8alkynyl, or R45 is phenyl, it being possible for the phenyl ring to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or tri-substituted by Cι-C4haloalkyl, Cι-C alkoxy, -CN, NO2> d-C8alkylthio, C C8alkylsulfinyl or by C,-C8alkylsulfonyl; R^ is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl or C C4haloalkyl; R47 is hydrogen, Cι-C8alkyl, d-C alkoxy, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, d-C4alkoxy, d-C8alkoxycarbonyl, -NH2, Cι-C alkylamino, di(CrC4alkyl)amino, -NR^COR^, -NR50SO2R51
Figure imgf000008_0001
R47 is phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; p is 0 or 1 ;
R-iβ, R49. R50, R51, Rε2 and R53 are each independently of the others hydrogen, C C8alkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono- to penta-substituted by halogen or by Cι-C8alkyl or mono-, di- or trisubstituted by d-dhaloalkyl, Cι-C4alkoxy, d-C4alkylamino, di(Cι-C4alkyl)amino, -NH2) -CN, -NO2> d-dalkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl;
RM and R55 are each independently of the other hydrogen, d-C8alkyl, or phenyl which may in turn be mono- to penta-substituted by halogen or by Cι-C4alkyl or mono-, di- or trisubstituted by Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, C C8alkylthio, d-C8alkylsulfinyl or by d-C8alkylsulfonyl;
Rse is hydrogen, d-C8alkyl, d-C4haloalkyl, CrC4alkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, it being possible for benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C haloalkyl. d-dalkoxy, -CN, -NO2, d-C8alkylthio, C C8alkylsulfinyl or by d-C8alkylsulfonyl;
R57 is d-C8alkyl, C C4haloalkyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-C4alkoxy, C C4alkylamino, d d-dalky amino, -NH2, -CN, -NO2) d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; R58 and R59 are each independently of the other CrC8alkyl. C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, d-C4alkylamino, di(d-C4alkyl)amino. -NH2> -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl;
R60 and R6. are each independently of the other hydrogen or d-dalkyl; R62, R63 and R64 are each independently of the others hydrogen or d-C8alkyl, or R63 and R64 together form a C2-C5alkylene bridge;
Res, Rε6. R67, Res. β9 and R70 are each independently of the others hydrogen or d-C8alkyl, or
R65 and Ree, or R67 and Res, or R69 and R70 in each case together form a C2-C5alkylene bridge; and/or each R2 independently is d-C8alkyl, or is d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -N3, -SCN, -NO2, -OH, -NR71R72, -CO2R73, -CONR74R75) -COR76, -C(R77)=NOR78, -C(S)NR79R80, -C(d-C4alkylthio)=NR81 l -OR,*, -SR^, -SOR84, -SO2R85, -O(SO2)R86. -N(R87)CO2R88, -N(R89)COR90, -S+(R91)2, -N+(R92)3, -Si(R93)3 or by C3-C6cycloalkyl; and/or each R2 independently is C C8alkyl substituted by a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, hydroxy-d-C4alkyl, d-C alkoxy, d-C4alkoxy- d-C4alkyl. -CN, -NO2, d-C6alkylthio, Cι-C6alkylsulfinyl or by d-C6alkylsulfonyl; and/or each R2 independently is C2-C8alkenyl, or is C2-C8alkenyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NO2, -CO2R , -CONR95R96, -COR97, -C(R98)=NOR99, -C(S)NR100Rιoι, -C(C1-C4alkylthio)--NR102, -OR103, -Si(Rl04)3 or by C3-C6- cycloalkyl; and/or each R2 independently is C2-C8alkynyl, or is C -C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -CO2R105, -CONR106Rιo7- -CORι08, -C(Rιo9)=NOR110,
Figure imgf000009_0001
-C(d-C4alkylthio)=NR113> -OR114, -Si(R115)3 or by C3-C6cycloalkyl; and/or each R2 independently is C3-C6cycloalkyl, or is C3-C6cycloalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -CO2R116, -CONR117R118, -COR1 9, -C(Rι20)=NOR121, -C(S)NR122Rι23 or by -C(C1-C4alkylthio)=NR124; or, when Q is a group Q,, Q2, Q3 or Q5, two adjacent R2 substituents together may form a d-C7alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by d-C6alkyl or mono-, di- or tri-substituted by CrC6alkoxy, the total number of ring atoms being at least 5 and at most 9; or, when Q is a group Q1 ? Q2, Q3 or Q5, two adjacent R2 substituents together may form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by Cι-C6alkyl or mono-, di- or tri-substituted by d-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; R7ι is hydrogen or C C8alkyl;
R72 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by C C4haloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, C C4- alkylsulfinyl or by d-C4alkylsulfonyl; or
R71 and R72 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R73 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, Ci-dalkoxy, -CN, -NO2) d-C4alkylthio, d-C4alkylsulfinyl or by C,-C4alkylsulfonyl; R74 is hydrogen or d-C8alkyl;
R75 is hydrogen, Cι-C8alkyl or C3-C7cycloalkyl, or is Cι-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl, Ci-dalkoxy or by -CN; or
R75 is C3-C8alkenyl. C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2> d-C4alkylthio, d-C4alkylsulfinyl or by d-C alkylsulfonyl; or
R74 and R75 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R76 is hydrogen, Crdalkyl, d-C haloalkyl or C3-C6cycloalkyl; R-n is hydrogen, d-dalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl; and
R79 is hydrogen or C C8alkyl;
R80 is hydrogen or C C8alkyl, or is Cι-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or R80 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, Crdalkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or R79 and R80 together are C2-C5alkylene; R81 is hydrogen or C C8alkyl;
R82 is -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl, or is Crdalkyl which is mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, CrC6alkylamino, di(CrC6alkyl)amino or by C C4alkoxy;
Rβ3 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, CrC6aIkylamino, di(d-C6alkyl)amino or by d-C4alkoxy;
R-w, Res and R86 are each independently of the others C C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by C C4alkoxy;
R87 and Rrø are each independently of the other hydrogen, d-dalkyl or d-C8alkoxy; Rag is d-dalkyl; Rgo is hydrogen or Crdalkyl; R91 is d-dalkyl;
R92 and R93 are each independently of the other Crdalkyl;
R94 is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by CrC4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R95 is hydrogen or d-dalkyl;
R96 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or by -CN; or
R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or R95 and Rg6 together are C2-C5alkylene;
R97 and R98 are each independently of the other hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl; R99 is hydrogen, Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl; R.oo is hydrogen or d-dalkyl;
R,oι is hydrogen or C C8alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or
R101 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, C C4alkoxy, -CN, -NO2, d-C4alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R100 and R10i together are C2-C5alkylene; R102 is hydrogen or d-dalkyl;
R103 is hydrogen, C C8alkyl, -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; Rl04 is d-C6alkyl;
R105 is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by C C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; R106 is hydrogen or d-dalkyl;
R10 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
R107 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-C4alkoxy, -CN, -NO2> d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R10e and R107 together are C2-C5alkylene; R108 is hydrogen, d-dalkyl, C C4haloalkyl or C3-C6cycloalkyl; R109 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R110 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; R,n is hydrogen or d-dalkyl;
R112 is hydrogen or d-dalkyl, or is Crdalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R.12 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; or R,n and R112 together are C2-C5alkylene; R113 is hydrogen or d-dalkyl; R11 is hydrogen, d-dalkyl, -S d-dalkyl^, C3-C8alkenyl or C3-C8alkynyl; R115 is CrC6alkyl;
R 16 is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R117 is hydrogen or d-dalkyl;
R118 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R118 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; or R117 and Rn8 together are C2-C5alkylene; R119 is hydrogen, d-dalkyl, C C4haloalkyl or C3-C6cycloalkyl; R120 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R12ι is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; R122 is hydrogen or d-dalkyl;
R123 is hydrogen or Crdalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R.23 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; or
R122 and Rι23 together are C2-C5alkylene; and R.24 is hydrogen or d-dalkyl, and to the agrochemically acceptable salts and all stereoisomers and tautomers of the compounds of formula I.
When m is 0, all free valencies on the heterocyclic groups Qι to Q6 of the compounds of formula I are occupied by hydrogen. When n is 0, all free valencies on the phenyl or pyridyl ring of the compounds of formula I are occupied by hydrogen.
Examples of substituents that are formed as a result of R5 and R6 together or R18 and R19 together or R36 and R37 together or R7 and R75 together being a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom are piperidine, morpholine, thiomorpholine and pyrrolidine.
Examples of heterocyclic ring systems which may be aromatic or partially or fully saturated in the definition of R2 are:
Figure imgf000014_0001
The alkyl groups appearing in the substituent definitions may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the pentyl, hexyl, heptyl and octyl isomers.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro- methyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. Alkoxy groups have a chain length of preferably from 1 to 6, especially from 1 to 4, carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or the pentyloxy and hexyloxy isomers; preferably methoxy or ethoxy.
Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, alkylaminoalkoxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylthio, alkenylsulfonyl, alkenylsulfinyl, alkynylsulfonyl, alkynylthio and alkynylsulfinyl groups are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated. Alkenyl is, for example, vinyl, allyl, methallyl, 1 -methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but- 2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl.
Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Substituents where two adjacent R2 substituents (on the group Q1f Q2, Q3 or Q5) together form a d-C7alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by Crdalkyl or mono-, di- or tri-substituted by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9, or where two adjacent R2 substituents together form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
Figure imgf000016_0001
Figure imgf000016_0002
Substituents where two adjacent Rx substituents together form a d-dalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9, or where two adjacent R, substituents together form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
Figure imgf000017_0001
Figure imgf000017_0002
Figure imgf000017_0003
The invention relates also to the salts which the compounds of formula I are able to form preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt formers are described, for example, in WO 98/41089.
Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, especially the hydroxides of sodium and potassium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary d-C18alkylamines, d-dhydroxyalkylamines and d-dalkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropyl- amine, 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-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl- 2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n- propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n- amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, 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.
Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(RaRbRcR )]OH wherein Ra, Rb, Rc and Rd are each independently of the others d-dalkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
Preference is given to compounds of formula I wherein each Ri independently is hydrogen, halogen, -CN, -SCN, -SF5> -NO2l -NR5R6, -CO2R7, -CONR8R9, -C(Rι0)=NORn, -CORι2, -
ORi3, -SRi4, -SOR15, -SO2Ri6, -OSO2Rι7, d-C8aIkyl, C2-C8alkenyl, C2-C8alkynyl or C3-
C6cycloalkyl; or is d-C8alkyl, C2-C8alkenyl or C2-C8alkynyl mono-, di- or tri-substituted by halogen, -CN, -NO2, -NRι8Rι9, -COzRzo, -CONR2ιR22) -COR23, -C(R24)=NOR25, -C(S)NR2eR27,
-C(CrC4alkylthio)=NR28, -OR 9, -SR30, -SOR31, -SO2R 2 or by C3-C6cycloalkyl; or each Ri independently is C3-C6cycloalkyl mono-, di- or tri-substituted by halogen, -CN, -NO2,
-NR18Ri9, -CO2R2o, -CONR21R22, -COR23,
Figure imgf000018_0001
-C(S)NR26R27, -C(d-C4alkyl- thio)=NR28, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each Ri independently is phenyl which may in turn be mono-, di- or tri-substituted by halogen, d-dalkyl, C,-C4haloalkyl, d-dalkoxy, -CN, -NO2> d-dalkylthio, Cr
C4alkylsulfinyl or by C C4alkylsulfonyl; or two adjacent Ri substituents together form a d-C7alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, d-dalkyl or by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; or two adjacent Ri substituents together form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, d-dalkyl or by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; R3 or R4 are each independently of the other hydrogen, halogen, -CN, d-dalkyl or d-dalkoxy; or
R3 and R4 together are C2-C5alkylene; R5 is hydrogen or d-dalkyl;
R6 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or
R5 and R6 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl mono-, di- or tri-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2l d-dalkylthio, C,-C4alkylsulfinyl or by C C4alkylsulfonyl; R8 is hydrogen or d-dalkyl;
R9 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; R10 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C8haloalkenyl; R12 is hydrogen, d-C alkyl, d-dhaloalkyl or C3-C6cycloalkyl; Ri3 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-d-dalkyl, it being possible for the phenyl ring in turn to be mono-, di- or tri-substituted by halogen, Crdalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C8- alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or
R13 is d-dalkyl mono-, di- or tri-substituted by halogen, -CN, CrC6alkylamino, di(CrC6- alkyl)amino or by d-C4alkoxy;
R1 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl mono-, di- or trisubstituted by halogen, -CN or by C C alkoxy;
R15, Rιe and R17 are each independently of the others d-dalkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C4alkoxy; Ri8 is hydrogen or d-dalkyl; Rig is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2> d-dalkylthio, d-dalkylsulfinyl or by C C4alkylsulfonyl; or
Rι8 and Rι9 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R20 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; 21 is hydrogen or d-C8alkyl;
R22 is hydrogen or d-dalkyl, or is d-C8alkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; or R21 and R22 together are C -C5alkylene; R23 is hydrogen, d-dalkyl, C C4haloalkyl or C3-CGcycloalkyl; R2 is hydrogen, d-dalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or d-C8alkyl;
R27 is hydrogen or d-C8alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C C4haloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by C C4alkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or d-C8alkyl;
R29 and R30 are each independently of the other hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C4alkoxy; R31 and R32 are each independently of the other d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN or by C C alkoxy; m is 0, 1 , 2 or 3; each R2 independently is hydrogen, halogen, -CN, -SCN, -OCN, -N3, -SF5, -NO2, -NR33R3-,, -CO2R35, -CONR36R37, -C(R3β)=NOR39, -COR-to, -OR41, -SR42) -SOR43, -SO^, -OSO2R 5,
Figure imgf000020_0001
-N(OR54)COR55, -N(R56)SO2R57, -N(SO2R58)SO2R59, -N=C(OR60)R6i, -CR62(OR63)OR64, -OC(O)NR65R66, -SC(O)NR67R68, -OC(S)NR69R70 or -N-phthalimide; or R2 is a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono-, di- or trisubstituted by halogen, d-dalkyl, d-dhaloalkyl, hydroxy-d-C4alkyl, d-C alkoxy, d-dalkoxy-d-dalkyl, -CN, -NO2, d-dalkylthio. d-C6alkylsulfinyl or by d-dalkylsulfonyl; R33 is hydrogen or d-C8alkyl; and
R34 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-C4alkylsulfonyl; or
R33 and R34 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R35 is hydrogen, Crdalkyl, C3-C8alkenyl or C3-C8alkynyl, or is Crdalkyl, C3-C8alkenyl or C3-C8alkynyl mono-, di- or tri-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; R36 is hydrogen or d-dalkyl;
R37 is hydrogen or d-dalkyl, or is d-C8alkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C haloalkyl, d-dalkoxy, -CN, -NO2l d-dalkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; or R38 and R37 together are C3-C5alkylene; R3β is hydrogen, d-dalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R-to is hydrogen, Crdalkyl, d-dhaloalkyl, d-dalkylthio, -C(O)-C(O)OCrC4alkyl or d-C6cycloalkyl;
R ι is hydrogen, Crdalkyl.. d-dhaloalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dalkoxy- d-dalkyl, CrC8alkylcarbonyl, Crdalkoxycarbonyl, C3-C8alkenyloxycarbonyl, d-dalkoxy- d-dalkoxycarbonyl, CrC6alkylthio-Cι-C6alkyl, CrC6alkylsulfinyl-CrC6alkyl or C C6alkyl- sulfonyl-d-dalkyl; or
R 1 is phenyl or phenyl-d-dalkyl, it being possible for the phenyl ring in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C4alkoxy, -CN, -NO2 or by -S(O)2CrC8alkyl, or
R4ι is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl, C C6alkyl- amino, di(d-C6alkyl)amino or by -CN; R42 is hydrogen, Crdalkyl, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl mono-, di- or trisubstituted by halogen, -CN or by d-C alkoxy;
R43 and R^ are each independently of the other d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN or by C C4alkoxy; R^ is d-dalkyl, C C8alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C alkoxy, or is C3-C8alkenyl or C3-C8alkynyl, or
R45 is phenyl, it being possible for the phenyl ring to be mono-, di- or tri-substituted by halogen, d-dalkyl. d-dhaloalkyl, d-dalkoxy, -CN, NO2, d-dalkylthio, C C8alkylsulfinyl or by d-dalkylsulfonyl;
R46 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl or d-C4haloalkyl; R47 is hydrogen, d-C8alkyl, d-dalkoxy, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl mono-, di- or tri-substituted by halogen, -CN, d-dalkoxy, Crdalkoxycarbonyl, -NH2, d-dalkylamino, di(CrC4alkyl)amino, -NR^COR^, -NR50SO2R5i or by -NR52CO2R53, or R47 is phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or trisubstituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; p is 0 or 1 ;
R-jβ. R4g. R50, R51, R52 and R53 are each independently of the others hydrogen, d-dalkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C alkoxy, d-dalkylamino, di(C C4alkyl)amino, -NH2, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl;
R5--. and R55 are each independently of the other hydrogen, Crdalkyl, or phenyl which may in turn be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R56 is hydrogen, Crdalkyl, d-dhaloalkyl, d-dalkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, it being possible for benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C4alkoxy, -CN, -NO2> CrC8alkylthio, d-dalkylsulfinyl or by d-C8alkylsulfonyl;
R57 is d-dalkyl, d-dhaloalkyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy, d-dalkylamino, di(C C4alkyl)amino, -NH2, -CN, -NO2, C C4alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
Rsβ and R59 are each independently of the other Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, C C alkoxy, d-dalkylamino, di(CrC4alkyl)amino, -NH2, -CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or by d-C4alkyl- sulfonyl;
Rεo and R6ι are each independently of the other hydrogen or d-C6alkyl; R62, Rβ3 and R64 are each independently of the others hydrogen or Crdalkyl, or R63 and R^ together form a C2-C5alkylene bridge; δδ. R-36. R67. Reβ, Reg and R70 are each independently of the others hydrogen or d-dalkyl, or
R65 and R66, or R67 and R∞, or R69 and R70 in each case together form a C2-C5alkylene bridge; or each R independently is d-dalkyl, or is d-C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -NO2, -NR71R72, -CO2R73, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -C(C,-C4alkylthio)=NR81, -OR82, -SR∞, -SOR^, -SO2R85, -O(SO2)R86. -N(R87)CO2R88, -N(R89)COR90, -S+(R9ι)2, -N+(R92)3, -Si(R93)3 or by C3-C6cycloalkyl; or each R2 independently is d-C8alkyl substituted by a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, hydroxy-d-dalkyl, d-dalkoxy, CrC4alkoxy-d-C4alkyl, -CN, -NO2, d- dalkylthio, C C6alkylsulfinyl or by d-dalkylsulfonyl; or each R2 independently is C2-C8alkenyl, or is C2-C8alkenyl mono-, di- or tri-substituted by -CN, -NO2, -CO2R94, -CONR95R96, -COR97, -C(R98)=NOR99, -C(S)NR100Rιoι. -C(C C4alkyl- thio)=NRι02, -OR103, -Si(Rι04)3 or by C3-C8cycloalkyl; or each R2 independently is C2-C8alkynyl, or is C2-C8alkynyl mono-, di- or tri-substituted by halogen, -CN, -CO2Rιo5, -CONR106Rιo7, -CORι08, -C(R109)=NORno, -C^NRmR^,
Figure imgf000023_0001
-ORn , -Si(Rn5)3 or by C3-C6cycloalkyl; or each R2 independently is C3-C6cycloalkyl, or is C3-C6cycloalkyl mono-, di- or tri-substituted by halogen, -CN, -CO2Rne, -CONR117R,ι8, -CORn9, -C(R12o)=NOR12ι, -C(S)NRι22Rι23 or by -C(Cι-C4alkylthio)=NRι2 ; or, when Q is a group Qι, Q2, Q3 or Q5) two adjacent R substituents together may form a d-dalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, d-dalkyl or by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; or, when Q is a group Q1 F Q2, Q3 or Q5, two adjacent R2 substituents together may form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, d-dalkyl or by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; R7i is hydrogen or d-dalkyl;
R72 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or
R7i and R72 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R73 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl mono-, di- or tri-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; R74 is hydrogen or d-dalkyl;
R75 is hydrogen, d-C8alkyl or C3-C7cycloalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl, d-dalkoxy or by -CN; or
R75 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; or R74 and R75 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R76 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl; R-π is hydrogen, d-dalkyl, d-C haloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; and
R79 is hydrogen or d-dalkyl;
Rβo is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R80 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R79 and R^ together are C2-C5alkylene; R8, is hydrogen or d-dalkyl;
R82 is -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl which is mono-, di- or trisubstituted by halogen, -CN, -NH2, Crdalkylamino, di(CrC6alkyl)amino or by d-C4alkoxy; R83 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-C8alkyl which is mono-, di- or tri-substituted by halogen, -CN, -NH2, CrC6alkylamino, di(d-C6alkyl)amino or by d-C4alkoxy;
Rew, Res and R86 are each independently of the others d-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-dalkyl which is mono-, di- or tri-substituted by halogen, -CN or by d-dalkoxy;
R87 and Rsg are each independently of the other hydrogen, d-C8alkyl or d-C8alkoxy; R88 is d-dalkyl; R90 is hydrogen or d-C8alkyl; R9ι is d-C4alkyl;
R92 and R93 are each independently of the other d-dalkyl;
R94 is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono-, di- or tri-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by C,-C4alkylsulfonyl; R95 is hydrogen or d-dalkyl;
R96 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or R95 and R96 together are C2-C5alkylene;
R97 and R98 are each independently of the other hydrogen, d-dalkyl, d-dhaloalkyl or d-C6cycloalkyl;
R99 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R10o is hydrogen or Crdalkyl;
R101 is hydrogen or d-dalkyl, or is d-C8alkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R101 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C,-C4alkylsulfinyl or by d-dalkylsulfonyl; or R10o and R10ι together are C2-C5alkylene; R.02 is hydrogen or Crdalkyl;
R103 is hydrogen, d-dalkyl, -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; R10-1 is d-dalkyl; R.05 is hydrogen or is Crdalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono-, di- or tri-substituted by halogen, C C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, C C4alkoxy, -CN,
-NO2, d-dalkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; 106 is hydrogen or d-dalkyl;
Rι07 is hydrogen or d-dalkyl, or is C C8alkyl mono-, di- or tri-substituted by -COOH,
Crdalkoxycarbonyl or by -CN, or
R107 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy,
-CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by C,-C4alkylsulfonyl; or
R106 and R107 together are C2-C5alkylene;
R.08 is hydrogen, d-dalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R.09 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
Rno is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl;
R111 is hydrogen or d-C8alkyl;
Rn2 is hydrogen or d-C8alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
Rn2 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy,
-CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or
Rm and R 2 together are C2-C5alkylene;
R113 is hydrogen or d-C8alkyl;
R114 is hydrogen, CrC8alkyl, -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
Rns is d-dalkyl;
Rue is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono-, di- or tri-substituted by halogen, C C alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN,
-NO2, d-dalkylthio, d-C alkylsulfinyl or by d-dalkylsulfonyl;
R is hydrogen or d-dalkyl;
Rns is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
Rue is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, C C4alkoxy,
-CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; or
R1i7 and R1i8 together are C2-C5alkylene;
R119 is hydrogen, d-dalkyl, d-C4haloalkyl or C3-C6cycloalkyl; Ri20 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R12i is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl;
R122 is hydrogen or d-C8alkyl;
R123 is hydrogen or C C8alkyl, or is C C8alkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
R.23 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy,
-CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-C4alkylsulfonyl; or and R123 together are C2-C5alkylene; and
Rι24 is hydrogen or d-dalkyl.
Preference is given also to compounds of formula I wherein each Ri independently is halogen, -CN, -NO2, -C(Rι0)=NORn, -ORι3, -SO2Rι6, -OSO2R17, d-C8alkyl or C2-C8alkenyl, or is d-dalkyl mono-, di- or tri-substituted by halogen or by -CN; R10 is hydrogen or d- dalkyl; and Rn is d-dalkyl.
Preference is given likewise to compounds of formula I wherein Q is a group Qι, Q2, Q3 or Q5. Among those compounds special preference is given to those wherein Q is a group Q,, Q2 or Q3.
Preference is given furthermore to those compounds of formula I wherein each R2 independently is hydrogen (m = 0), halogen, -CN, -SCN, -OCN, -N3, -CONR36R37, -C(R38)=NOR39, -COR-w, -OR41, -OSO2R45, -N([CO]pR46)COR47, -N(R56)SO2R57, -N(SO2R58)SO2R59, -N--C(OR60)R6ι or d-dalkyl, or is C C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -OR82, -SORw, -SO2R85 or by -N(R89)COR9o.
The compounds of formula la
Figure imgf000027_0001
wherein R^ R2, R3, R4, Z, m and n are as defined for formula I, can be prepared analogously to known methods described, for example, in "Palladium in Heterocyclic Chemistry" from Tetrahedron Organic Chemistry Series 20, A Guide for the Synthetic Chemist, Editors Jie Jack Li and Gordon W. Gribble, Pergamon 2000; Tetrahedron Lett. 1986 (27), 1171 ; Tetrahedron Organic Chemistry 2000 (20), 359-362; ibid. 2000 (20), 390-394; and K. Sonogashira in "Comprehensive Organic Synthesis", Editors I. Fleming et al., Oxford 1991 , Vol. 3, page 521 ff., for example by reacting a compound of formula II
Figure imgf000028_0001
wherein R1 f Z and n are as defined for formula I and X is halogen, with a compound of formula Ilia
Figure imgf000028_0002
wherein R3 and R are as defined for formula I and M+ is an alkali metal cation such as, for example, a lithium, sodium or potassium cation, to form a compound of formula IV
Figure imgf000028_0003
wherein Ri, R3, R4, Z and n are as defined for formula I, and then coupling that compound with a compound of formula Va
Figure imgf000028_0004
wherein R2 and m are as defined for formula I and A is a leaving group such as, for example, halogen or trifluoromethanesulfonate, in the presence of a palladium catalyst, and, optionally, oxidising such a compound wherein Z is =N-, for example using hydrogen peroxide or 3-chloroperbenzoic acid (MCPBA), and obtaining the compounds of formula la wherein Z is I + - .
=N-O Preparation of the other compounds of formula I wherein Q is a group Q2, that is to say
compounds of formula lb (Ib);
Figure imgf000029_0001
wherein Q is a group Q3, that is to say compounds of formula lc
(lc); wherein Q is a group Q4, that
Figure imgf000029_0002
is to say compounds of formula Id
Figure imgf000029_0003
wherein Q is a group Q8,
Figure imgf000029_0004
that is to say compounds of formula If
(If), is carried out in a manner analogous
Figure imgf000029_0005
to that described above by way of example for the compounds of formula la (Q = Qι).
These preparation procedures for the compounds of formula I are illustrated in Reaction Schemes 1 , 2, 3 and 4 specifically using the example of the compound of formula la
(Q = Qι).
It is generally true of all four Reaction Schemes that the various substituents Ri and R2 in the compounds of formulae II and Va either are already present at the outset or, however, they may be successively introduced only later in the reaction sequence, for example by means of nucleophilic or electrophilic aromatic substitution.
The same is also true of the analogous preparation of compounds of formulae lb, lc, Id, le and If (Q is a group Q2 to Q6), starting from the respective compounds of formulae Vb, Vc, Vd, Ve and Vf:
Figure imgf000030_0001
In accordance with Reaction Scheme 1 , the compounds of formula la can be obtained, for example, by reaction of substituted propargyl ethers of formula IV with compounds of formula Va by means of Sonogashira coupling.
The pyridine N-oxide function in the compounds of formulae I and la (Z is I + - )
=N-0 can, in dependence upon the reactivity of the substituents already present, be introduced either at the stage of the starting compound of formula II or not until the end of the synthesis sequence, by means of oxidation using standard methods by treating the compound of formula I or II wherein Z is =N- with, for example, hydrogen peroxide or 3-chloroperbenzoic acid (MCPBA).
The propargyl ethers of formula IV can, for their part, be obtained by a nucleophilic aromatic
substitution reaction of a compound of formula II wherein Z is =N-, I + - or
----------N-O
=C(Rι)-, Ri is as defined for formula I and X is a leaving group such as, for example, halogen, -Otosyl (-OTs) or -Omesyl (-OMs), with an alcoholate of formula Ilia (route A in Reaction Scheme 1 ).
For compounds of formula II wherein Z is =C(Rι)-, the nucleophilic aromatic substitution reaction is facilitated if they are activated compounds. That is the case when Ri is, for example, a substituent having electron-withdrawing properties (-M and or -I effect), such as, for example, -CN, -NO2, -CO2R7, CORι2. Such substitution reactions with activated compounds of formula II wherein Z is =N- or =C(Rι)-; and R, is a substituent having an -M and/or -I effect within the framework of the definition of Ri given for formula I, are standard methods and may be carried out, for example, in analogy to Synlett 2000, 874-876; ibid. 1998, 794-796 or J. Org. Chem. 1998 (63), 9594-9596.
For non-activated compounds of formula II wherein Z is =C(R )-; and Rx is as defined for formula I, a suitable alternative synthesis method is a nucleophilic aliphatic substitution reaction, wherein a compound of formula II
Figure imgf000031_0001
wherein Z is =C(Rι)-; Ri is as defined for formula I; n is 0, 1 , 2 or 3; and X is OH, is reacted with a compound of formula 11 lb
Figure imgf000031_0002
wherein R3 and R are as defined for formula I and Xi is -Otosyl (-OTs), -Omesyl (-OMs), chlorine, bromine or iodine, in the presence of a base, to form a compound of formula IV
Figure imgf000031_0003
wherein R,, R3, R4, Z and n are as defined (route B in Reaction Scheme 1 ). Such etherification reactions are standard methods and may be carried out, for example, in analogy to Tetrahedron 1997 (53), 12621-12628; J. Chem. Soc. Perkin Trans. 1979, 2756- 2761 ; Synth. Communic. 1988 (18), 1111 -1118; J. Org. Chem. 1996 (61 ), 4258-4261 ; or Synth. Communic. 1994 (24), 1367-1379.
In the next step, the propargyl ethers of formula IV obtained are coupled with substituted pyrazinyl (or 1 ,4-diazinyl) derivatives of formula Va under typical Sonogashira conditions (K. Sonogashira in Comprehensive Organic Synthesis 1991 , Vol. 3, page 521 ff.; and J. Org.
Chem. 1998 (63), 8551-8553) (Reaction Scheme 1 ).
The pyrazinyl derivatives of formula Va preferably have a leaving group A, A being, for example, halogen or trifluoromethanesulfonate (Tetrahedron Organic Chemistry 2000 (20),
359-362; J. Org. Chem. 1998 (63), 8551-8553; and Tetrahedron Lett. 1986 (27), 1171-
1174). Suitable catalyst mixtures for the Sonogashira reaction are, for example, tetrakis-
(triphenylphosphine)palladium or bis(triphenylphosphine)palladium(ll) dichloride together with copper(l) iodide (Cul); suitable bases are especially amines, for example triethylamine, diethylamine or diisopropylethylamine.
As solvents there are usually used ethers, for example tetrahydrofuran, chlorinated hydrocarbons, for example chloroform, or dipolar aprotic solvents, for example dimethylformamide or dimethyl sulfoxide, and also amines, for example triethylamine or piperidine.
The compounds of formulae lb, lc, Id, le and If are prepared in analogous manner to that described above for the compound of formula la, by coupling the propargyl ethers of formula IV with the appropriate compounds of formulae Vb, Vc, Vd, Ve and Vf under
Sonogashira conditions.
Reaction Scheme 1
Route B: nucleophilic aliphatic substitution:
Figure imgf000033_0001
II: Z is --C(R.)- or =N-
lllb: X, Cl, Br,
Route A: nucleophilic aromatic substitution:
Figure imgf000033_0002
Figure imgf000033_0003
M+ = alkali metal ion, e.g. Na+ l + - IV II: Z is =N-, =N-0 or =C(R-,)-; and R, is preferably a substituent having an -M/-I effect
Figure imgf000033_0004
la: Z is =C(Rιr, =N-, l + - N— O As a variant to the synthesis methods described above, appropriately substituted pyrazinyl derivatives of formula Va may first be reacted, by means of palladium-catalysed cross- coupling, with propargyl alcohols of formula III in accordance with K. Sonogashira to form the compounds of formula Vila. This is illustrated in Reaction Scheme 2. Such reactions are documented, for example, in Tetrahedron Organic Chemistry 2000 (20), 359-362 for pyrazine derivatives and in J. Org. Chem. 1988 (53), 386; ibid. 1998 (63), 8551-8553; and Tetrahedron Lett. 1986 (27), 1171-1174 for phenyl derivatives. Subsequent reaction of the propargyl alcohols of formula Vila with phenyl or pyridyl derivatives of formula II wherein X is a leaving group such as, for example, halogen yields the desired target compound of formula la (Q = Qι).
Reaction Scheme 2
Sonogashira: Nucleophilic aromatic substitution:
Figure imgf000034_0001
Va: A = halogen, -O-SO2-CF3; Vila
Figure imgf000034_0002
la The other compounds of formula I wherein Q is a group Q2 (compounds of formula lb), Q3 (compounds of formula lc), Q4 (compounds of formula Id), Q5 (compounds of formula le) or Q6 (compounds of formula If) can also be prepared in a manner analogous to that shown in Reaction Scheme 2, starting from the corresponding compounds of formula Vb, Vc, Vd, Ve or Vf.
A further synthesis variant for preparation of compounds of formula I is shown in Reaction Scheme 3, using the example of the compound of formula la. This synthesis variant proceeds via an activated compound of formula Villa
(Villa),
Figure imgf000035_0001
wherein R2, R3, R4 and m are as defined for formula I and Xi is a leaving group such as, for example, halogen, -Otosyl (-OTs) or -Omesyl (-OMs). The compound of formula Villa can be obtained, for example, from the compound of formula Vila by means of sulfonylation or halogenation, in accordance with Reaction Scheme 3.
Reaction Scheme 3
Sonogashira:
sulfonylation or halogenation
Figure imgf000036_0001
Va: A = halogen, -0-S02-CF3 Vila
Figure imgf000036_0002
Villa: X, = halogen, -OTs, -OMs la
Sulfonylation of the alcohol of formula Vila to form the compound of formula Villa is a standard reaction and can be carried out, for example, using a sulfonic acid chloride, for example mesyl chloride (MsCI) or para-toluenesulfonic acid chloride (p-TsCI), in the presence of a tertiary amine, e.g. triethylamine, or an aromatic amine, e.g. pyridine, in a solvent such as, for example, a chlorinated hydrocarbon, e.g. carbon tetrachloride or methylene chloride, or an amine, e.g. pyridine. Such reactions are generally known and are described, for example, in J. Org. Chem. 1997 (62), 8987; J. Het. Chem. 1995 (32), 875- 882; and Tetrahedron Lett. 1997 (38), 8671 -8674.
Halogenation of the alcohol of formula Vila to form the compound of formula Villa can be carried out in analogy to standard methods. For example, bromination can be successfully carried out using carbon tetrabromide in the presence of triphenylphosphine (Synthesis 1998, 1015-1018) in methylene chloride. Chlorination can be successfully carried out using mineral acids, for example using concentrated hydrochloric acid (J. Org. Chem. 1955 (20), 95), or using para-toluenesulfonic acid chloride in the presence of an amine, for example triethylamine, in a solvent, for example methylene chloride (Tetrahedron Lett. 1984 (25), 2295). Preparation of the desired target compound of formula la according to Reaction Scheme 3 can be carried out analogously to Synthesis 1995, 707-712; Tetrahedron Lett. 1994 (35), 6405-6408; Helv. Chim. Acta 2000 (83), 650-657; or Synth. Communic. 1996 (26), 4267- 4273, for example by means of copper iodide-catalysed etherification of the phenol or hydroxy-pyridine of formula II wherein Ri, Z and n are as defined for formula I and X is OH, in the presence of the tosylate (Xi = -OTs) or mesylate (Xt = -OMs) or halide (Xi = halogen) of formula Villa. Suitable solvents are dimethylformamide and acetonitrile; suitable bases are especially potassium carbonate and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The etherification can also be carried out in halogenated or aromatic hydrocarbons as solvent, for example in chloroform or in benzene, in the presence of silver carbonate as base. Such selective O-alkylation reactions (in preference to N-alkylation, which is not desired in this case) in the presence of a ring nitrogen atom (Z is =N-) are described, for example, in Synth. Commun. 1994 (24), 1367-1379 and Heterocycles 1990 (31 ), 819-824.
A further method by which the desired target compound of formula I can be prepared is performed with the aid of the Mitsunobu reaction in a manner analogous to that described, for example, in Synthesis 1981 (1 ); Tetrahedron Lett. 35, 2819-2822 (1994); and Chem. Letters 1994, 539 (with TMAD reagent as a replacement for the DEAD in the two aforesaid references). This synthesis route uses, as intermediate, the compound of formula II
Figure imgf000037_0001
wherein Ri, Z and n are as defined for formula I and X is OH, and the propargyl alcohol of formula Vila
Figure imgf000037_0002
wherein R2, R3, R4 and m are as defined for formula I. The desired compound of formula la is obtained under typical Mitsunobu conditions in the presence of triphenylphosphine and DEAD or TMAD reagent in a suitable solvent such as, for example, an ether, e.g. tetrahydrofuran (THF). This reaction step is illustrated in Reaction Scheme 4 using the example of the compounds of formula la (pyrazinylalkyne derivatives; Q = Qι). Reaction Scheme 4 Mitsunobu:
Figure imgf000038_0001
ll: X = OH la
The following applies to the individual reaction steps according to Reaction Schemes 1 to 4: The reactions resulting in the compounds of formula I (and la to If) are advantageously performed in aprotic, inert, organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitrites, such as acetonitrile or propionitrile, amides, such as N,N-dimethyl- formamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions are generally slightly exothermic and can usually be carried out at room temperature. For reducing the reaction time or also for initiation of the reaction, heating, up to the boiling point of the reaction mixture, may, where appropriate, be carried out for a short time. It is also possible for the reaction times to be reduced by adding a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]- octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec-7-ene. However, there may also be used as bases inorganic bases, such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates, e.g. sodium carbonate or potassium carbonate, or hydrogen carbonates, e.g. potassium hydrogen carbonate or sodium hydrogen carbonate.
The compounds of formula I may, in conventional manner, be isolated by concentrating and/or evaporating off the solvent and purified by recrystallising or triturating the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons. The starting compounds of formula Va used in Reaction Schemes 1 , 2, 3 and 4, and the corresponding starting compounds of formulae Vb, Vc, Vd, Ve and Vf for preparation of the compounds of formulae la, lb, lc, Id, le and If are for the most part known or they can be prepared in analogy to known methods as described, for example, in J. Org. Chem. 1997 (62), 9112; ibid. 1958 (23), 1522; J. Chem. Soc. 1948, 2191 ; Bull. Soc. Chim. Fr. 1957, 1009; J. Am. Chem. Soc. 74, 1580-1582 (1952); US-A-5 547 919; J. Chem. Soc. 1960, 4590; J. Org. Chem. 1963 (28), 1682; J. Heterocycl. Chem. 1994 (31), 1177; and ibid 1982 (19), 1061.
The starting compounds of formulae III, Ilia and 1Mb are likewise known and in some cases are commercially available, or they can be prepared in analogy to known methods.
The compounds of formula II are known and in some cases are commercially available. Examples of substituted compounds of formula II wherein Z is =N- are described, for example, in Tetrahedron Organic Chemistry 20, 209 (2000).
The compounds of formulae IV and VII (and Vila to Vllf) are novel. The present invention accordingly relates also to those compounds.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or at least one compound of formula I, and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient(s) with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending upon the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be in the form of 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), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters. The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques. The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Panicum, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Euphorbia, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following Examples further illustrate but do not limit the invention.
Preparation Examples:
Example P1 : Preparation of 2-f3-(4-fluoro-2-methoxy-phenoxy)-prop-1-vnyll-5-bromo- pyrimidine
(compound no. 2.088)
Figure imgf000041_0001
2.1 ml of tetrabutylammonium fluoride (1 M solution in tetrahydrofuran) are added to a solution of 300 mg (1.05 mmol) of 2-iodo-5-bromopyrimidine, 190 mg (1.05 mmol) of 4- fluoro-2-methoxyphenyl-prop-2-ynyl ether, 40 mg (0.21 mmol) of copper(l) iodide (Cul) and 74 mg (0.105 mmol) of Pd(PPh3)2CI2 in 15 ml of dioxane. The reaction mixture is stirred for 2.5 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvents are evaporated off under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/5). The desired target compound is obtained as a white solid having a melting point of 105°C in a yield of 80 mg (23 % of theory). R, value in ethyl acetate/petroleum ether 1/5: 0.26. MS (IS): m/z=337 and 339 (M+1). 1H NMR (CDCI3): 8.75 ppm (s, 2H); 7.05 ppm (dxd; J=5.4 Hz and 8.7 Hz, 1 H); 6.55-6.69 ppm (m, 2H); 4.96 ppm (s, 2H); 3.86 ppm (s, 3H).
Example P2: Preparation of 2-r3-(4-methyleneiminomethoxy-2-methoxy-phenoxy)-prop-1- ynyll-5-bromo-pyrimidine
(compound no. 2.094)
Figure imgf000042_0001
2.1 ml of tetrabutylammonium fluoride (1 M solution in tetrahydrofuran) are added to a solution of 300 mg (1.05 mmol) of 2-iodo-5-bromopyrimidine, 230 mg (1.05 mmol) of 3- methoxy-4-(prop-2-ynyloxy)-benzaldehyde O-methyloxime, 40 mg (0.21 mmol) of copper(l) iodide (Cul) and 74 mg (0.105 mmol) of Pd(PPh3)2CI2 in 15 ml of dioxane. The reaction mixture is stirred for 2.5 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvents are evaporated off under reduced pressure and the crude product obtained is purified using flash chromatography (eluant: ethyl acetate/petroleum ether 1/3). The desired target compound is obtained as a beige solid having a melting point of 121 °C in a yield of 102 mg (26 % of theory). Rf value in ethyl acetate/petroleum ether 1/3: 0.25. MS (IS): m/z=376 and 378 (M+1 ).
1H NMR (CDCI3): 8.75 ppm (s, 2H); 7.99 ppm (s, 1 H); 7.26 ppm (s, 1 H); 7.00-7.10 ppm (m, 2H); 5.03 ppm (s, 2H); 3.96 ppm (s, 3H); 3.93 ppm (s, 3H).
Example P3: Preparation of 3-(2-methoxy)-O-proparqylphenol ether
Figure imgf000042_0002
4.17 g of 2-methoxyphenol and 4.64 g of potassium carbonate are suspended in 95 ml of acetone. 10.0 g of propargyl bromide are then added dropwise at reflux temperature (56°C), with stirring, and the reaction mixture is subsequently stirred for 2.5 hours. The reaction mixture is analysed by means of analytical thin-layer chromatography (TLC) (eluant: 10 % ethyl acetate/n-hexane). After the reaction is complete, the mixture is cooled, filtered and then concentrated until an oily residue is obtained, which is purified on a silica gel column (eluant: ethyl acetate/n-hexane 1/9). After concentration of the collected fractions, 2.65 g (89 % of theory) of an oil are obtained. NMR (CDCI3): 6.70-7.05 ppm (m, 4H); 4.75 ppm (d, 2H); 4.65 ppm (t, 1 H); 3.85 ppm (s, 3H); 2.50 ppm (t, 1 H).
Example P4: Preparation of 3.5-dichloro-2-(prop-2-vnyloxy)-pyridine:
Figure imgf000043_0001
1.25 g (0.029 mol) of NaH (55 %) are introduced into 30 ml of pentane. After stirring for 15 minutes under nitrogen, the solvent is removed by means of a syringe. 20 ml of absolute THF are then added and, within a period of about 5 minutes, 1.65 ml (0.028 mol) of propargyl alcohol are added dropwise at a temperature of 0°C. After the addition, the ice cooling is removed, and stirring is continued for a further hour at a temperature of about 45°C until the evolution of gas has ceased. Then 4.8 g (0.025 mol) of 2,3,5-trichloropyridine dissolved in 5 ml of THF are added dropwise at 45°C, with stirring. Then stirring is carried out for 6 hours at a temperature of 45°C and for 18 hours at a temperature of 20°C until gas chromatography indicates that conversion is complete. The reaction mixture is then cautiously neutralised with 1 N HCI; a small amount of saturated aqueous sodium chloride is added and extraction with ethyl acetate is carried out three times in total. The combined organic phases are dried over magnesium sulfate. After filtration and after the ethyl acetate has been evaporated off, 5.0 g of 3,5-dichloro-2-(prop-2-ynyloxy)-pyridine are obtained as a light-yellow oil, which corresponds to quantitative conversion.
Example P5: Preparation of 5-bromo-2-(prop-2-vnyloxy)-pyridine:
Figure imgf000043_0002
0.54 g (0.011 mol) of NaH (55 %) are suspended in 15 ml of absolute THF under nitrogen.
Then, within a period of about 5 minutes, 0.67 ml (0.011 mol) of propargyl alcohol is added dropwise at a temperature of 0°C. After the addition, the ice cooling is removed and stirring is carried out at a temperature of about 20°C for 30 minutes until the evolution of gas has ceased. Then 2.0 g (0.011 mol) of 5-bromo-2-fluoropyridine dissolved in 5 ml of THF are added dropwise at 20-30°C, with stirring and ice cooling. Stirring is carried out for a further 2 hours at room temperature until gas chromatography indicates that conversion is complete. The reaction mixture is then cautiously added to 40 ml of water and extraction with ethyl acetate is carried out three times in total. The combined organic phases are dried over sodium sulfate. After filtration and after the ethyl acetate has been evaporated off, 2.1 g of 5- bromo-2-(prop-2-ynyloxy)-pyridine are obtained as beige crystals having a melting point of 58-60°C.
Example P6: Preparation of 5-chloro-3-fluoro-2-(prop-2-vnyloxy)-pyridine:
Figure imgf000044_0001
8.0 g (0.167 mol) of NaH (55 %) are suspended in 200 ml of absolute THF under nitrogen. Then, within a period of about 10 minutes, 9.9 ml (0.167 mol) of propargyl alcohol dissolved in 10 ml of absolute THF are added dropwise at a temperature of 0°C. After the addition, the ice cooling is removed and stirring is carried out at room temperature for 45 minutes until the evolution of gas has ceased. Then 25 g (0.167 mol) of 5-chloro-2,5-difluoropyridine dissolved in 50 ml of THF are added dropwise at 20-30°C, with stirring and ice cooling. Stirring is carried out for a further 3 hours at room temperature until gas chromatography indicates that conversion is complete. The reaction mixture is then cautiously added to 250 ml of water and extraction with ethyl acetate is carried out three times in total. After separating off the organic phase, drying over sodium sulfate and filtration, concentration by evaporation is carried out. The yellow residue is purified by chromatography (eluant: ethyl acetate/hexane 1/4). 19.1 g of 5-chloro-3-fluoro-2-(prop-2-ynyloxy)-pyridine are obtained as a colourless oil.
Example P7: Preparation of 5-chloro-3-methoxy-2-(prop-2-vnyloxy)-pyridine:
Figure imgf000044_0002
1.0 g (5.4 mmol) of 5-chloro-3-fluoro-2-(prop-2-ynyloxy)-pyridine (Example P6) is introduced into 15 ml of methanol under nitrogen. Then, within a period of about 5 minutes, 2.0 ml (10.8 mmol) of 30 % sodium methanolate solution in methanol are added dropwise at room temperature. After the addition, the reaction mixture is heated at reflux and is stirred at that temperature for a further 18 hours. The reaction mixture is cooled to room temperature and 30 ml of water are cautiously added. Extraction with ethyl acetate is then carried out three times. After separating off the organic phase, drying over sodium sulfate and filtration, concentration by evaporation is carried out. The yellowish residue is purified by chromatography (eluant: ethyl acetate/hexane 1/4). 0.65 g of 5-chloro-3-methoxy-2-(prop-2-ynyloxy)- pyridine is obtained as colourless crystals having a melting point of 62-64°C.
Example P8: Preparation of 5-(3-pyrimidinyl-prop-2-vnyloxy)-5-chloro-3-methoxypyridine
Figure imgf000045_0001
12.58 ml of tetrabutylammonium fluoride (1 M solution in THF) are added to a solution of
1.00 g (6.29 mmol) of 5-bromopyrimidine, 1.86 g (9.43 mmol) of 5-chloro-3-methoxy-2-(prop-
2-ynyloxy)-pyridine (Example P7), 239 mg (1.26 mmol) of copper(l) iodide and 442 mg
(0.629 mmol) of bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2CI2) in 25 ml of dioxane. The reaction mixture is stirred for 5 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/5). The desired title compound is obtained as a white solid in a yield of 215 mg (13 % of theory).
Rf = 0.19 in ethyl acetate/petroleum ether 1/3;
1H NMR (CDCI3): δ(ppm)= 3.90 (s, 3H); 5.27 (s, 2H); 7.09 (d, J=1.9 Hz, 1H); 7.72 (d,
J=1.9 Hz, 1 H); 8.77 (s, 2H); 9.13 (s, 1 H). Example P9: Preparation of 5-f3-(4-methyleneiminomethoxy-2-methoxy-phenoxy)-prop-1 - ynvn-pyrimidine
(compound no. 11.122)
Figure imgf000046_0001
3.76 ml of tetrabutylammonium fluoride (1 M solution in THF) are added to a solution of 300 mg (1.88 mmol) of 5-bromopyrimidine, 620 mg (2.82 mmol) of 3-methoxy-4-(prop-2- ynyloxy)-benzaldehyde O-methyloxime, 71 mg (0.38 mmol) of copper(l) iodide and 132 mg (0.188 mmol) of bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2CI2) in 15 ml of dioxane. The reaction mixture is stirred for 5 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 2/3). The desired title compound is obtained as a brown solid in a yield of 80 mg (14 % of theory). Rf = 0.24 in ethyl acetate/petroleum ether 3/7;
1H NMR (CDCI3): δ(ppm)= 3.94 (s, 3H); 3.96 (s, 3H); 5.03 (s, 2H); 7.03 (s, 2H); 7.28 (s, 1H); 8.00 (s, 1 H); 8.75 (s, 2H); 9.15 (s, 1 H).
Example P10: Preparation of 5-f3-(4-fluoro-2-methoxy-phenoxy)-prop-1 -vnyll-pyrimidine
Figure imgf000046_0002
6.28 ml of tetrabutylammonium fluoride (1 M solution in THF) are added to a solution of 500 mg (3.14 mmol) of 5-bromopyrimidine, 850 mg (4.71 mmol) of 4-f luoro-2-methoxy-1 - prop-2-ynyloxy-benzene, 120 mg (0.63 mmol) of copper(l) iodide and 221 mg (0.32 mmol) of bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2CI2) in 18 ml of dioxane. The reaction mixture is stirred for 5 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/3). The desired title compound is obtained as a beige solid in a yield of 223 mg (27 % of theory). R, = 0.32 in ethyl acetate/petroleum ether 3/7;
1H NMR (CDCI3): δ(ppm)= 3.88 (s, 3H); 4.96 (s, 2H); 6.57-6.71 (m, 2H); 7.00 (dxd, J=5.3 and 8.8 Hz, 1 H); 8.74 (s, 2H); 9.14 (s, 1 H).
Figure imgf000047_0001
4.4 ml of tetrabutylammonium fluoride (1 M solution in THF) are added to a solution of 450 mg (2.18 mmol) of iodopyrazine, 647 mg (3.28 mmol) of 5-chloro-3-methoxy-2-(prop-2- ynyloxy)-pyridine (Example P7), 83 mg (0.44 mmol) of copper(l) iodide and 153 mg (0.22 mmol) of bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2CI2) in 14 ml of dioxane. The reaction mixture is stirred for 3 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/2). The desired title compound is obtained as a brown solid having a melting point of 142°C in a yield of 510 mg (84 % of theory). Rf = 0.50 in ethyl acetate/petroleum ether 1/1 ;
1H NMR (CDCI3): δ(ppm)= 3.89 (s, 3H); 5.29 (s, 2H); 7.08 (d, J=2.2 Hz, 1H); 7.71 (d, J=2.2 Hz, 1 H); 8.48 (d, J=2.5 Hz, 1 H); 8.52 (dxd, J=1.3 and 2.5 Hz, 1 H); 8.66 (d, J=1.3 Hz, 1 H).
Example P12: Preparation of 3-(4-fluoro-2-methoxy-phenoxy)-prop-1-ynyl-pyrazine
(compound no. 1.100)
Figure imgf000047_0002
4.90 ml of tetrabutylammonium fluoride (1 M solution in THF) are added to a solution of 500 mg (2.43 mmol) of iodopyrazine, 655 mg (3.64 mmol) of 4-fluoro-2-methoxy-1-prop-2- ynyloxy-benzene, 92 mg (0.48 mmol) of copper(l) iodide and 170 mg (0.24 mmol) of bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2CI2) in 16 ml of dioxane. The reaction mixture is stirred for 3 hours at 50°C under an argon atmosphere and is then allowed to cool to 20°C. The solvent is removed under reduced pressure and the crude product obtained is purified by means of flash chromatography (eluant: ethyl acetate/petroleum ether 1/2). The desired title compound is obtained as a beige solid having a melting point of 88°C in a yield of 412 mg (66 % of theory).
Rf = 0.28 in ethyl acetate/petroleum ether 1/2;
1H NMR (CDCI3): δ(ppm)= 3.87 (s, 3H); 4.98 (s, 2H); 6.56-6.69 (m, 2H); 7.04 (dxd, J=5.6 and
8.8 Hz, 1 H); 8.48 (d, J=2.5 Hz, 1 H); 8.52 (dxd, J=1.3 and 2.5 Hz, 1 H); 8.62 (d, J=1.3 Hz,
1 H).
It is also possible for the preferred compounds listed in the following Tables to be obtained in a manner analogous to that described in Examples P1 and P2 or by the methods shown in Reaction Schemes 1 -4 and in the references indicated. In the column "Phys. data", the indicated temperatures denote the melting point (m.p.) of the compounds in question. Table 1 : Compounds of formula Ia1
Figure imgf000048_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
1.001 2-OCH3, 4-CN 6-CI H H
1.002 2-F, 4-CI 6-CI H H
1.003 2-CI, 4-CI 6-CI H H
1.004 2-OCH3> 4-F 6-CI H H
1.005 2-OCH3, 4-CI 6-CI H H
1.006 2-OCH3, 4-Br 6-CI H H
1.007 2-CI, 4-CF3 6-CI H H
1.008 2-OCH3, 4-CF3 6-CI H H
1.009 2-OCH3, 4-CH3 6-CI H H
1.010 2-OCH3, 4-CH=NOCH3 6-CI H H Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
1.011 2-F, 4-CF3 6-CI H H
1.012 2-OCH3 6-CI H H
1.013 2-OCH3, 4-CN 6-CH2CN, 5-F H H
1.014 2-F, 4-CI 6-CH2CN, 5-F H H
1.015 2-CI, 4-CI 6-CH2CN, 5-F H H
1.016 2-OCH3, 4-F 6-CH2CN, 5-F H H
1.017 2-OCH3, 4-CI 6-CH2CN, 5-F H H
1.018 2-OCH3, 4-Br 6-CH2CN, 5-F H H
1.019 2-CI, 4-CF3 6-CH2CN, 5-F H H
1.020 2-OCH3, 4-CF3 6-CH2CN, 5-F H H
1.021 2-OCH3, 4-CH3 6-CH2CN, 5-F H H
1.022 2-OCH3, 4-CH=NOCH3 6-CH2CN, 5-F H H
1.023 2-F, 4-CF3 6-CH2CN, 5-F H H
1.024 2-OCH3 6-CH2CN, 5-F H H
1.025 2-OCH3, 4-CN 6-CH(CH3)CN H H
1.026 2-F, 4-CI 6-CH(CH3)CN H H
1.027 2-CI, 4-CI 6-CH(CH3)CN H H
1.028 2-OCH3, 4-F 6-CH(CH3)CN H H
1.029 2-OCH3, 4-CI 6-CH(CH3)CN H H
1.030 2-OCH3, 4-Br 6-CH(CH3)CN H H
1.031 2-CI, 4-CF3 6-CH(CH3)CN H H
1.032 2-OCH3, 4-CF3 6-CH(CH3)CN H H
1.033 2-OCH3, 4-CH3 6-CH(CH3)CN H H
1.034 2-OCH3, 4-CH=NOCH3 6-CH(CH3)CN H H
1.035 2-F, 4-CF3 6-CH(CH3)CN H H
1.036 2-OCH3 6-CH(CH3)CN H H
1.037 2-OCH3, 4-CN 6-CH2CN H H
1.038 2-F, 4-CI 6-CH2CN H H
1.039 2-CI, 4-CI 6-CH2CN H H
1.040 2-OCH3, 4-F 6-CH2CN H H
1.041 2-OCH3, 4-CI 6-CH2CN H H
1.042 2-OCH3, 4-Br 6-CH2CN H H Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
1.043 2-CI, 4-CF3 6-CH2CN H H
1.044 2-OCH3, 4-CF3 6-CH2CN H H
1.045 2-OCH3, 4-CH3 6-CH2CN H H
1.046 2-OCH3, 4-CH=NOCH3 6-CH2CN H H
1.047 2-F, 4-CF3 6-CH2CN H H
1.048 2-OCH3 6-CH2CN H H
1.049 2-OCH3, 4-F 6-CH2CN CH3 H
1.050 2-OCH3, 4-CI 6-CH2CN CH3 H
1.051 2-OCH3, 4-CF3 6-CH2CN CH3 H
1.052 2-OCH3, 4-Br 6-CH2CN CH3 H
1.053 2-CI, 4-CF3 6-CH2CN CH3 H
1.054 2-OCH3, 4-CN 6-CH2CN CH3 H
1.055 2-OCH3, 4-F 6-CHF2 H H
1.056 2-OCH3, 4-CI 6-CHF2 H H
1.057 2-OCH3, 4-CF3 6-CHF2 H H
1.058 2-OCH3, 4-Br 6-CHF2 H H
1.059 2-CI, 4-CF3 6-CHF2 H H
1.060 2-OCH3, 4-CN 6-CHF2 H H
1.061 2-OCH3, 4-F 6-CH3 H H
1.062 2-OCH3, 4-CI 6-CH3 H H
1.063 2-OCH3, 4-CF3 6-CH3 H H
1.064 2-OCH3, 4-Br 6-CH3 H H
1.065 2-CI, 4-CF3 6-CH3 H H
1.066 2-OCH3, 4-CN 6-CH3 H H
1.067 2-OCH3, 4-F 6-CH2-CN F F
1.068 2-OCH3, 4-CI 6-CH2-CN F F
1.069 2-OCH3, 4-CF3 6-CH2-CN F F
1.070 2-OCH3, 4-Br 6-CH2-CN F F
1.071 2-CI, 4-CF3 6-CH2-CN F F
1.072 2-OCH3, 4-CN 6-CH2-CN F F
1.073 2-OCH3, 4-CN 5-CI H H
1.074 2-F, 4-CI 5-CI H H
Figure imgf000051_0001
Figure imgf000052_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
1.138 2-OCH3, 4-F 5-I H H
1.139 2-OCH3, 4-CI 5-I H H
1.140 2-OCH3, 4-CN 5-I H H
1.141 2-OCH3, 4-CH=NOCH3 5-I H H
1.142 2-OCH3, 4-Br 5-I H H
1.143 2-OCH3, 4-I 5-I H H
1.144 2-OCH3, 4-CH3 5-I H H
1.145 2-OCH3, 4-NH2 5-I H H
1.146 2-OCH3, 4-CHO 5-I H H
1.147 2-OCH3, 4-NO2 5-I H H
1.148 2-F, 4-NO2 5-I H H
1.149 2-OCH3 5-CH3 H H
1.150 2-OCH3, 4-CF3 5-CH3 H H
1.151 2-F, 4-CF3 5-CH3 H H
1.152 2-OCH3, 4-CHF2 5-CH3 H H
1.153 2-OCH3, 4-F 5-CH3 H H
1.154 2-OCH3, 4-CI 5-CH3 H H
1.155 2-OCH3, 4-CN 5-CH3 H H
1.156 2-OCH3, 4-CH=NOCH3 5-CH3 H H
1.157 2-OCH3, 4-Br 5-CH3 H H
1.158 2-OCH3, 4-I 5-CH3 H H
1.159 2-OCH3, 4-CH3 5-CH3 H H
1.160 2-OCH3, 4-NH2 5-CH3 H H
1.161 2-OCH3, 4-CHO 5-CH3 H H
1.162 2-OCH3, 4-NO2 5-CH3 H H
1.163 2-F, 4-NO2 5-CH3 H H
1.164 2-OCH3 5-CF3 H H
1.165 2-OCH3, 4-CF3 5-CF3 H H
1.166 2-F, 4-CF3 5-CF3 H H
1.167 2-OCH3, 4-CHF2 5-CF3 H H
1.168 2-OCH3, 4-F 5-CF3 H H
Figure imgf000054_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
1 .200 2-OCH3, 4-CN 5-NH2 H H
1 .201 2-OCH3, 4-CH=NOCH3 5-NH2 H H
1.202 2-OCH3, 4-Br 5-NH2 H H
1.203 2-OCH3, 4-I 5-NH2 H H
1.204 2-OCH3, 4-CH3 5-NH2 H H
1.205 2-OCH3, 4-CHO 5-NH2 H H
1.206 2-OCH3, 4-NO2 5-NH2 H H
1.207 2-F, 4-NO2 5-NH2 H H
1.208 2-OCH3 5-CI, 6-CI H H
1 .209 2-OCH3, 4-CF3 5-CI, 6-CI H H
1.210 2-OCH3, 4-F 5-CI, 6-CI H H
1.211 2-OCH3, 4-I 5-CI, 6-CI H H
1.212 2-OCH3, 4-CH3 5-CI, 6-CI H H
1.213 2-OCH3, 4-CN 5-CI, 6-CI H H
1.214 2-OCH3, 4-CH=NOCH3 5-CI, 6-CI H H
1.215 2-OCH3 6-I H H
1.216 2-OCH3, 4-CF3 6-I H H
1.217 2-OCH3, 4-CHF2 6-I H H
1.218 2-OCH3, 4-F 6-I H H
1.219 2-OCH3, 4-Br 6-I H H
1.220 2-OCH3, 4-CH3 6-I H H
1.221 2-OCH3, 4-CN 6-I H H
1.222 2-OCH3 6-NH2 H H
1.223 2-OCH3, 4-CF3 6-NH2 H H
1.224 2-OCH3, 4-CHF2 6-NH2 H H
1.225 2-OCH3, 4-F 6-NH2 H H
1.226 2-OCH3, 4-I 6-NH2 H H
1.227 2-OCH3, 4-CH3 6-NH2 H H
1.228 2-OCH3, 4-CN 6-NH2 H H
1.229 2-OCH3 5-CH3, 6-F H H
1.230 2-OCH3, 4-F 5-CH3, 6-F H H Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
1.231 2-OCH3, 4-CN 5-CH3, 6-F H H
1.232 2-OCH3, 4-CF3 5-CH3, 6-F H H
1.233 2-OCH3, 4-Br 5-CH3, 6-F H H
1.234 2-F, 4-CF3 5-CH3, 6-F H H
1.235 2-OCH3 5-CH3, 6-CI H H
1.236 2-OCH3, 4-F 5-CH3, 6-CI H H
1.237 2-OCH3, 4-CN 5-CH3, 6-CI H H
1.238 2-OCH3, 4-CF3 5-CH3, 6-CI H H
1.239 2-OCH3, 4-Br 5-CH3, 6-CI H H
1.240 2-F, 4-CF, 5-CH3, 6-CI H H
1.241 2-OCH3 5-F, 6-CH3 H H
1.242 2-OCH3, 4-F 5-F, 6-CH3 H H
1.243 2-OCH3, 4-CN 5-F, 6-CH3 H H
1.244 2-OCH3, 4-CF3 5-F, 6-CH3 H H
1.245 2-OCH3, 4-Br 5-F, 6-CH3 H H
1.246 2-F, 4-CF3 5-F, 6-CH3 H H
1.247 2-OCH3 5-CI, 6-CH3 H H
1.248 2-OCH3, 4-F 5-CI, 6-CH3 H H
1.249 2-OCH3, 4-CN 5-CI, 6-CH3 H H
1.250 2-OCH3, 4-CF3 5-CI, 6-CH3 H H
1.251 2-OCH3, 4-Br 5-CI, 6-CH3 H H
1.252 2-F, 4-CF3 5-CI, 6-CH3 H H
1.253 2-OCH3 5-CN H H
1.254 2-OCH3, 4-F 5-CN H H
1.255 2-OCH3, 4-CN 5-CN H H
1.256 2-OCH3, 4-CF3 5-CN H H
1.257 2-OCH3, 4-Br 5-CN H H
1.258 2-F, 4-CF3 5-CN H H Table 2: Compounds of formula lb?1
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. ro
2.090 2-OCH3> 4-Br 5-Br H H
2.091 2-CI, 4-CF3 5-Br H H
2.092 2-OCH3, 4-CF3 5-Br H H
2.093 2-OCH3, 4-CH3 5-Br H H
2.094 2-OCH3, 4-CH=NOCH3 5-Br H H crystalline (121°C)
2.095 2-F, 4-CF3 5-Br H H
2.096 2-OCH3 5-Br H H
2.097 2-OCH3, 4-CN H (m=0) H H
2.098 2-F, 4-CI H (m=0) H H
2.099 2-CI, 4-CI H (m=0) H H
2.100 2-OCH3, 4-F H (m=0) H H
2.101 2-OCH3, 4-CI H (m=0) H H
2.102 2-OCH3, 4-Br H (m=0) H H
2.103 2-CI, 4-CF3 H (m=0) H H
2.104 2-OCH3, 4-CF3 H (m=0) H H
2.105 2-OCH3, 4-CH3 H (m=0) H H
2.106 2-OCH3, 4-CH=NOCH3 H (m=0) H H
2.107 2-F, 4-CF3 H (m=0) H H
2.108 2-OCH3 H (m=0) H H
2.109 2-OCH3, 4-CN 5-CH3 H H
2.110 2-F, 4-CI 5-CH3 H H
2.111 2-CI, 4-CI 5-CH3 H H
2.112 2-OCH3, 4-F 5-CH3 H H
2.113 2-OCH3, 4-CI 5-CH3 H H
2.114 2-OCH3> 4-Br 5-CH3 H H
2.115 2-CI, 4-CF3 5-CH3 H H
2.116 2-OCH3, 4-CF3 5-CH3 H H
2.117 2-OCH3, 4-CH3 5-CH3 H H
2.118 2-OCH3, 4-CH=NOCH3 5-CH3 H H
2.119 2-F, 4-CF3 5-CH3 H H
2.120 2-OCH3 5-CH3 H H
Figure imgf000061_0001
Figure imgf000062_0001
Table 3: Compounds of formula Ia2
Figure imgf000063_0002
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. (°C)
3.217 3-OCH3, 4-CI 5-CH3, 6-CI H H
3.218 3-OCH3> 4-CN 5-CH3, 6-CI H H
3.219 3-OCH3, 4-CF3 5-CH3, 6-CI H H
3.220 3-OCH3, 4-Br 5-CH3, 6-CI H H
3.221 3-F, 4-CF3 5-CH3> 6-CI H H
3.222 3-F, 5-F 5-CH3, 6-CI H H
3.223 3-F 5-CH3, 6-CI H H
3.224 5-CF3 5-CH3, 6-CI H H
3.225 5-CI 5-CH3, 6-CI H H
3.226 3-OCH3 5-F, 6-CH3 H H
3.227 3-OCH3, 4-CI 5-F, 6-CH3 H H
3.228 3-OCH3, 4-CN 5-F, 6-CH3 H H
3.229 3-OCH3, 4-CF3 5-F, 6-CH3 H H
3.230 3-OCH3, 4-Br 5-F, 6-CH3 H H
3.231 3-F, 4-CF3 5-F, 6-CH3 H H
3.232 3-F, 5-F 5-F, 6-CH3 H H
3.233 3-F 5-F, 6-CH3 H H
3.234 5-CF3 5-F, 6-CH3 H H
3.235 5-CI 5-F, 6-CH3 H H
3.236 3-OCH3 5-CI, 6-CH3 H H
3.237 3-OCH3, 4-CI 5-CI, 6-CH3 H H
3.238 3-OCH3, 4-CN 5-CI, 6-CH3 H H
3.239 3-OCH3, 4-CF3 5-CI, 6-CH3 H H
3.240 3-OCH3, 4-Br 5-CI, 6-CH3 H H
3.241 3-F, 4-CF3 5-CI, 6-CH3 H H
3.242 3-F, 5-F 5-CI, 6-CH3 H H
3.243 3-F 5-CI, 6-CH3 H H
3.244 5-CF3 5-CI, 6-CH3 H H
3.245 5-CI 5-CI, 6-CH3 H H
3.246 3-OCH3 5-CN H H
3.247 3-OCH3, 4-CI 5-CN H H
3.248 3-OCH3, 4-CN 5-CN H H Comp. Ri R2 R3 R4 Phys. data no. m.p. o
3.249 3-OCH3, 4-CF3 5-CN H H
3.250 3-OCH3, 4-Br 5-CN H H
3.251 3-F, 4-CF3 5-CN H H
3.252 3-F, 5-F 5-CN H H
3.253 3-F 5-CN H H
3.254 5-CF3 5-CN H H
3.255 5-CI 5-CN H H
3.256 3-OCH3 6-CH3 H H
3.257 3-OCH3, 4-CI 6-CH3 H H
3.258 3-OCH3, 4-CN 6-CH3 H H
3.259 3-OCH3, 4-CF3 6-CH3 H H
3.260 3-OCH3, 4-Br 6-CH3 H H
3.261 3-F, 4-CF3 6-CH3 H H
3.262 3-F, 5-F 6-CH3 H H
3.263 3-F 6-CH3 H H
3.264 5-CF3 6-CH3 H H
3.265 5-CI 6-CH3 H H
Table 4: Compounds of formula lb?2
Figure imgf000071_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. (°C)
4.001 3-OCH3, 5-CN 5-CH3 H H
4.002 3-F, 5-CI 5-CH3 H H
4.003 3-CI, 5-CI 5-CH3 H H
4.004 3-OCH3, 5-F 5-CH3 H H
4.005 3-OCH3, 5-CI 5-CH3 H H
Figure imgf000072_0001
Comp. Ri R2 R3 R4 Phys. data no rap. rθ
4.038 3-F, 5-CI 6-CH(CH3)CN H H
4.039 3-CI, 5-CI 6-CH(CH3)CN H H
4.040 3-OCH3, 5-F 6-CH(CH3)CN H H
4.041 3-OCH3, 5-CI 6-CH(CH3)CN H H
4.042 3-OCH3, 5-Br 6-CH(CH3)CN H H
4.043 3-CI, 5-CF3 6-CH(CH3)CN H H
4.044 3-OCH3, 5-CF3 6-CH(CH3)CN H H
4.045 3-OCH3, 5-CH3 6-CH(CH3)CN H H
4.046 3-OCH3, 5-CH=NOCH3 6-CH(CH3)CN H H
4.047 3-F, 5-CF3 6-CH(CH3)CN H H
4.048 3-OCH3 6-CH(CH3)CN H H
4.049 3-OCH3, 5-F 6-CH2-CN F F
4.050 3-OCH3, 5-CI 6-CH2-CN F F
4.051 3-OCH3, 5-CF3 6-CH2-CN F F
4.052 3-OCH3, 5-Br 6-CH2-CN F F
4.053 3-CI, 5-CF3 6-CH2-CN F F
4.054 3-OCH3, 5-CN 6-CH2-CN F F
4.055 3-F, 5-F 5-CH3 H H
4.056 3-F, 5-Br 5-CH3 H H
4.057 3-F, 5-NH2 5-CH3 H H
4.058 3-OCH3, 5-NH2 5-CH3 H H
4.059 3-F 5-CH3 H H
4.060 3-CI 5-CH3 H H
4.061 5-F 5-CH3 H H
4.062 5-CI 5-CH3 H H
4.063 5-Br 5-CH3 H H
4.064 5-CF3 5-CH3 H H
4.065 5-CN 5-CH3 H H
4.066 5-NH2 5-CH3 H H
4.067 3-F, 5-F 5-CI H H
4.068 3-F, 5-Br 5-CI H H
4.069 3-F, 5-NH2 5-CI H H
Figure imgf000074_0001
Comp R3 R4 Phys. data no m.p. ro
4.102
4.103
4.104
4.105
4.106
4.107
4.108
4.109
4.1 10
4.111
4.112
4.113
4.1 14
4.115
4.1 16
4.117
4.1 18 3-CI 5-Br H H
4.1 19 5-F 5-Br H H
4.120 5-CI 5-Br H H
4.121 5-Br 5-Br H H
4.122 5-CF3 5-Br H H
4.123 5-CN 5-Br H H
4.124 5-NH2 5-Br H H
4.125 3-OCH3, 5-CN 5-CF3 H H
4.126 3-F, 5-CI 5-CF3 H H
4.127 3-OCH3, 5-F 5-CF3 H H
4.128 3-OCH3, 5-CI 5-CF3 H H
4.129 3-OCH3, 5-Br 5-CF3 H H
4.130 3-CI, 5-CF3 5-CF3 H H
4.131 3-OCH3, 5-CF3 5-CF3 H H
4.132 3-OCH3> 5-CH3 5-CF3 H H
4.133 3-F, 5-CF3 5-CF3 H H
Figure imgf000076_0001
Figure imgf000077_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. ro
4.198 3-F, 4-CF3 5-CH3, 6-F H H
4.199 3-F, 5-F 5-CH3, 6-F H H
4.200 3-F 5-CH3, 6-F H H
4.201 5-CF3 5-CH3, 6-F H H
4.202 5-CI 5-CH3, 6-F H H
4.203 3-OCH3 5-CH3, 6-CI H H
4.204 3-OCH3, 4-CI 5-CH3, 6-CI H H
4.205 3-OCH3, 4-CN 5-CH3, 6-CI H H
4.206 3-OCH3, 4-CF3 5-CH3, 6-CI H H
4.207 3-OCH3, 4-Br 5-CH3, 6-CI H H
4.208 3-F, 4-CF3 5-CH3, 6-CI H H
4.209 3-F, 5-F 5-CH3, 6-CI H H
4.210 3-F 5-CH3, 6-CI H H
4.21 1 5-CF3 5-CH3, 6-CI H H
4.212 5-CI 5-CH3, 6-CI H H
4.213 3-OCH3 5-F, 6-CH3 H H
4.214 3-OCH3, 4-CI 5-F, 6-CH3 H H
4.215 3-OCH3, 4-CN 5-F, 6-CH3 H H
4.216 3-OCH3, 4-CF3 5-F, 6-CH3 H H
4.217 3-OCH3, 4-Br 5-F, 6-CH3 H H
4.218 3-F, 4-CF3 5-F, 6-CH3 H H
4.219 3-F, 5-F 5-F, 6-CH3 H H
4.220 3-F 5-F, 6-CH3 H H
4.221 5-CF3 5-F, 6-CH3 H H
4.222 5-CI 5-F, 6-CH3 H H
4.223 3-OCH3 5-CI, 6-CH3 H H
4.224 3-OCH3, 4-CI 5-CI, 6-CH3 H H
4.225 3-OCH3, 4-CN 5-CI, 6-CH3 H H
4.226 3-OCH3, 4-CF3 5-CI, 6-CH3 H H
4.227 3-OCH3, 4-Br 5-CI, 6-CH3 H H
4.228 3-F, 4-CF3 5-CI, 6-CH3 H H
4.229 3-F, 5-F 5-CI, 6-CH3 H H Comp. Ri R2 R3 R4 Phys. data no m.p. ro
4.230 3-F 5-CI, 6-CH3 H H
4.231 5-CF3 5-CI, 6-CH3 H H
4.232 5-CI 5-CI, 6-CH3 H H
Figure imgf000079_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. ro
5.001 2-OCH3, 4-CN 5-CI H H
5.002 2-F, 4-CI 5-CI H H
5.003 2-CI, 4-CI 5-CI H H
5.004 2-OCH3, 4-F 5-CI H H
5.005 2-OCH3, 4-CI 5-CI H H
5.006 2-OCH3, 4-Br 5-CI H H
5.007 2-CI, 4-CF3 5-CI H H
5.008 2-OCH3, 4-CF3 5-CI H H
5.009 2-OCH3, 4-CH3 5-CI H H
5.010 2-OCH3, 4-CH=NOCH3 5-CI H H
5.011 2-F, 4-CF3 5-CI H H
5.012 2-OCH3 5-CI H H
5.013 2-OCH3, 4-CN 5-CH2CN, 6-F H H
5.014 2-F, 4-CI 5-CH2CN, 6-F H H
5.015 2-CI, 4-CI 5-CH2CN, 6-F H H
5.016 2-OCH3, 4-F 5-CH2CN, 6-F H H
5.017 2-OCH3, 4-CI 5-CH2CN, 6-F H H
5.018 2-OCH3, 4-Br 5-CH2CN, 6-F H H
5.019 2-CI, 4-CF3 5-CH2CN, 6-F H H Comp. Ri R2 R3 R4 Phys. data no m.p. (°C)
5.020 2-OCH3, 4-CF3 5-CH2CN, 6-F H H
5.021 2-OCH3, 4-CH3 5-CH2CN, 6-F H H
5.022 2-OCH3, 4-CH=NOCH3 5-CH2CN, 6-F H H
5.023 2-F, 4-CF3 5-CH2CN, 6-F H H
5.024 2-OCH3 5-CH2CN, 6-F H H
5.025 2-OCH3, 4-CN 5-CH(CH3)CN H H
5.026 2-F, 4-CI 5-CH(CH3)CN H H
5.027 2-CI, 4-CI 5-CH(CH3)CN H H
5.028 2-OCH3, 4-F 5-CH(CH3)CN H H
5.029 2-OCH3, 4-CI 5-CH(CH3)CN H H
5.030 2-OCH3, 4-Br 5-CH(CH3)CN H H
5.031 2-CI, 4-CF3 5-CH(CH3)CN H H
5.032 2-OCH3, 4-CF3 5-CH(CH3)CN H H
5.033 2-OCH3, 4-CH3 5-CH(CH3)CN H H
5.034 2-OCH3, 4-CH=NOCH3 5-CH(CH3)CN H H
5.035 2-F, 4-CF3 5-CH(CH3)CN H H
5.036 2-OCH3 5-CH(CH3)CN H H
5.037 2-OCH3, 4-CN 5-CH2CN H H
5.038 2-F, 4-CI 5-CH2CN H H
5.039 2-CI, 4-CI 5-CH2CN H H
5.040 2-OCH3, 4-F 5-CH2CN H H
5.041 2-OCH3, 4-CI 5-CH2CN H H
5.042 2-OCH3, 4-Br 5-CH2CN H H
5.043 2-CI, 4-CF3 5-CH2CN H H
5.044 2-OCH3, 4-CF3 5-CH2CN H H
5.045 2-OCH3, 4-CH3 5-CH2CN H H
5.046 2-OCH3, 4-CH=NOCH3 5-CH2CN H H
5.047 2-F, 4-CF3 5-CH2CN H H
5.048 2-OCH3 5-CH2CN H H
5.049 2-OCH3, 4-F 5-CH2CN CH3 H
5.050 2-OCH3, 4-CI 5-CH2CN CH3 H
5.051 2-OCH3, 4-CF3 5-CH2CN CH3 H Comp. Ri R2 R3 R4 Phys. data no m.p. ro
5.052 2-OCH3, 4-Br 5-CH2CN CH3 H
5.053 2-CI, 4-CF3 5-CH2CN CH3 H
5.054 2-OCH3, 4-CN 5-CH2CN CH3 H
5.055 2-OCH3, 4-F 5-CHF2 H H
5.056 2-OCH3, 4-CI 5-CHF2 H H
5.057 2-OCH3, 4-CF3 5-CHF2 H H
5.058 2-OCH3> 4-Br 5-CHF2 H H
5.059 2-CI, 4-CF3 5-CHF2 H H
5.060 2-OCH3, 4-CN 5-CHF2 H H
5.061 2-OCH3, 4-F 5-CH3 H H
5.062 2-OCH3, 4-CI 5-CH3 H H
5.063 2-OCH3, 4-CF3 5-CH3 H H
5.064 2-OCH3, 4-Br 5-CH3 H H
5.065 2-CI, 4-CF3 5-CH3 H H
5.066 2-OCH3, 4-CN 5-CH3 H H
5.067 2-OCH3, 4-F 5-CH2-CN F F
5.068 2-OCH3, 4-CI 5-CH2-CN F F
5.069 2-OCH3, 4-CF3 5-CH2-CN F F
5.070 2-OCH3, 4-Br 5-CH2-CN F F
5.071 2-CI, 4-CF3 5-CH2-CN F F
5.072 2-OCH3, 4-CN 5-CH2-CN F F
5.073 2-OCH3, 4-CN 6-CI H H
5.074 2-F, 4-CI 6-CI H H
5.075 2-CI, 4-CI 6-CI H H
5.076 2-OCH3, 4-F 6-CI H H
5.077 2-OCH3, 4-CI 6-CI H H
5.078 2-OCH3, 4-Br 6-CI H H
5.079 2-CI, 4-CF3 6-CI H H
5.080 2-OCH3, 4-CF3 6-CI H H
5.081 2-OCH3, 4-CH3 6-CI H H
5.082 2-OCH3, 4-CH=NOCH3 6-CI H H
5.083 2-F, 4-CF3 6-CI H H
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. ro
5.180 2-OCH3, 4-Br 6-Br H H
5.181 2-CI, 4-CF3 6-Br H H
5.182 2-OCH3, 4-CF3 6-Br H H
5.183 2-OCH3, 4-CH3 6-Br H H
5.184 2-OCH3, 4-CH=NOCH3 6-Br H H
5.185 2-F, 4-CF3 6-Br H H
5.186 2-OCH3 6-Br H H
5.187 2-OCH3, 4-CHF2 6-Br H H
5.188 2-OCH3, 4-CHO 6-Br H H
5.189 2-OCH3, 4-NH2 6-Br H H
5.190 2-F, 4-NO2 6-Br H H
5.191 2-OCH3, 4-1 6-Br H H
5.192 2-OCH3 5-CH3, 6-F H H
5.193 2-OCH3, 4-F 5-CH3, 6-F H H
5.194 2-OCH3, 4-CN 5-CH3, 6-F H H
5.195 2-OCH3, 4-CF3 5-CH3, 6-F H H
5.196 2-OCH3, 4-Br 5-CH3, 6-F H H
5.197 2-F, 4-CF3 5-CH3, 6-F H H
5.198 2-OCH3 5-CH3, 6-CI H H
5.199 2-OCH3, 4-F 5-CH3, 6-CI H H
5.200 2-OCH3, 4-CN 5-CH3, 6-CI H H
5.201 2-OCH3, 4-CF3 5-CH3, 6-CI H H
5.202 2-OCH3, 4-Br 5-CH3, 6-CI H H
5.203 2-F, 4-CF3 5-CH3, 6-CI H H
5.204 2-OCH3 5-F, 6-CH3 H H
5.205 2-OCH3, 4-F 5-F, 6-CH3 H H
5.206 2-OCH3, 4-CN 5-F, 6-CH3 H H
5.207 2-OCH3, 4-CF3 5-F, 6-CH3 H H
5.208 2-OCH3, 4-Br 5-F, 6-CH3 H H
5.209 2-F, 4-CF3 5-F, 6-CH3 H H
5.210 2-OCH3 5-CI, 6-CH3 H H
5.21 1 2-OCH3, 4-F 5-CI, 6-CH3 H H Comp. Ri R2 R3 R4 Phys. data no m.p. ro
5.212 2-OCH3, 4-CN 5-CI, 6-CH3 H H
5.213 2-OCH3, 4-CF3 5-CI, 6-CH3 H H
5.214 2-OCH3, 4-Br 5-CI, 6-CH3 H H
5.215 2-F, 4-CF3 5-CI, 6-CH3 H H
Table 6: Compounds of formula ler-,1
Figure imgf000086_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. ro
6.020 2-OCH3, 4-CF3 5-CH2CN, 6-F H H
6.021 2-OCH3, 4-CH3 5-CH2CN, 6-F H H
6.022 2-OCH3, 4-CH=NOCH3 5-CH2CN, 6-F H H
6.023 2-F, 4-CF3 5-CH2CN, 6-F H H
6.024 2-OCH3 5-CH2CN, 6-F H H
6.025 2-OCH3, 4-CN 5-CH(CH3)CN H H
6.026 2-F, 4-CI 5-CH(CH3)CN H H
6.027 2-CI, 4-CI 5-CH(CH3)CN H H
6.028 2-OCH3, 4-F 5-CH(CH3)CN H H
6.029 2-OCH3) 4-CI 5-CH(CH3)CN H H
6.030 2-OCH3, 4-Br 5-CH(CH3)CN H H
6.031 2-CI, 4-CF3 5-CH(CH3)CN H H
6.032 2-OCH3, 4-CF3 5-CH(CH3)CN H H
6.033 2-OCH3, 4-CH3 5-CH(CH3)CN H H
6.034 2-OCH3, 4-CH=NOCH3 5-CH(CH3)CN H H
6.035 2-F, 4-CF3 5-CH(CH3)CN H H
6.036 2-OCH3 5-CH(CH3)CN H H
6.037 2-OCH3, 4-CN 5-CH2CN H H
6.038 2-F, 4-CI 5-CH2CN H H
6.039 2-CI, 4-CI 5-CH2CN H H
6.040 2-OCH3, 4-F 5-CH2CN H H
6.041 2-OCH3, 4-CI 5-CH2CN H H
6.042 2-OCH3, 4-Br 5-CH2CN H H
6.043 2-CI, 4-CF3 5-CH2CN H H
6.044 2-OCH3, 4-CF3 5-CH2CN H H
6.045 2-OCH3, 4-CH3 5-CH2CN H H
6.046 2-OCH3, 4-CH=NOCH3 5-CH2CN H H
6.047 2-F, 4-CF3 5-CH2CN H H
6.048 2-OCH3 5-CH2CN H H
6.049 2-OCH3, 4-F 5-CH2CN CH3 H
6.050 2-OCH3, 4-CI 5-CH2CN CH3 H
6.051 2-OCH3, 4-CF3 5-CH2CN CH3 H Comp. Ri R2 R3 R4 Phys. data no m.p. r
6.052 2-OCH3, 4-Br 5-CH2CN CH3 H
6.053 2-CI, 4-CF3 5-CH2CN CH3 H
6.054 2-OCH3, 4-CN 5-CH2CN CH3 H
6.055 2-OCH3, 4-F 5-CHF2 H H
6.056 2-OCH3, 4-CI 5-CHF2 H H
6.057 2-OCH3, 4-CF3 5-CHF2 H H
6.058 2-OCH3, 4-Br 5-CHF2 H H
6.059 2-CI, 4-CF3 5-CHF2 H H
6.060 2-OCH3, 4-CN 5-CHF2 H H
6.061 2-OCH3, 4-F 5-CH3 H H
6.062 2-OCH3, 4-CI 5-CH3 H H
6.063 2-OCH3, 4-CF3 5-CH3 H H
6.064 2-OCH3, 4-Br 5-CH3 H H
6.065 2-CI, 4-CF3 5-CH3 H H
6.066 2-OCH3, 4-CN 5-CH3 H H
6.067 2-OCH3, 4-F 5-CH2-CN F F
6.068 2-OCH3, 4-CI 5-CH2-CN F F
6.069 2-OCH3, 4-CF3 5-CH2-CN F F
6.070 2-OCH3, 4-Br 5-CH2-CN F F
6.071 2-CI, 4-CF3 5-CH2-CN F F
6.072 2-OCH3, 4-CN 5-CH2-CN F F
6.073 2-OCH3, 4-CN 6-CI H H
6.074 2-F, 4-CI 6-CI H H
6.075 2-CI, 4-CI 6-CI H H
6.076 2-OCH3, 4-F 6-CI H H
6.077 2-OCH3, 4-CI 6-CI H H
6.078 2-OCH3, 4-Br 6-CI H H
6.079 2-CI, 4-CF3 6-CI H H
6.080 2-OCH3, 4-CF3 6-CI H H
6.081 2-OCH3, 4-CH3 6-CI H H
6.082 2-OCH3, 4-CH=NOCH3 6-CI H H
6.083 2-F, 4-CF3 6-CI H H
Figure imgf000089_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. r
6.116 2-OCH3, 4-F 6-F H H
6.117 2-OCH3, 4-CF3 6-F H H
6.118 2-OCH3 6-F H H
6.119 2-OCH3, 4-CH=NOCH3 6-F H H
6.120 2-OCH3, 4-CN 6-Br H H
6.121 2-OCH3, 4-F 6-Br H H
6.122 2-OCH3, 4-CF3 6-Br H H
6.123 2-OCH3 6-Br H H
6.124 2-OCH3, 4-CH=NOCH3 6-Br H H
6.125 2-OCH3, 4-CN 6-NH2 H H
6.126 2-OCH3, 4-F 6-NH2 H H
6.127 2-OCH3, 4-CF3 6-NH2 H H
6.128 2-OCH3 6-NH2 H H
6.129 2-OCH3, 4-CH=NOCH3 6-NH2 H H
Table 7: Compounds of formula Icy-
Figure imgf000090_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. ro
7.001 3-OCH3, 5-CN 6-CH3 H H
7.002 3-F, 5-CI 6-CH3 H H
7.003 3-CI, 5-CI 6-CH3 H H
7.004 3-OCH3, 5-F 6-CH3 H H
7.005 3-OCH3, 5-CI 6-CH3 H H
7.006 3-OCH3, 5-Br 6-CH3 H H
7.007 3-CI, 5-CF3 6-CH3 H H
7.008 3-OCH3, 5-CF3 6-CH3 H H
Figure imgf000091_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. ro
7.041 3-OCH3, 5-CI 5-CH(CH3)CN H H
7.042 3-OCH3, 5-Br 5-CH(CH3)CN H H
7.043 3-CI, 5-CF3 5-CH(CH3)CN H H
7.044 3-OCH3, 5-CF3 5-CH(CH3)CN H H
7.045 3-OCH3, 5-CH3 5-CH(CH3)CN H H
7.046 3-OCH3, 5-CH=NOCH3 5-CH(CH3)CN H H
7.047 3-F, 5-CF3 5-CH(CH3)CN H H
7.048 3-OCH3 5-CH(CH3)CN H H
7.049 3-OCH3, 5-F 5-CH2-CN F F
7.050 3-OCH3, 5-CI 5-CH2-CN F F
7.051 3-OCH3, 5-CF3 5-CH2-CN F F
7.052 3-OCH3, 5-Br 5-CH2-CN F F
7.053 3-CI, 5-CF3 5-CH2-CN F F
7.054 3-OCH3, 5-CN 5-CH2-CN F F
7.055 3-OCH3, 5-CN 5-CI H H
7.056 3-F, 5-CI 5-CI H H
7.057 3-CI, 5-CI 5-CI H H
7.058 3-OCH3, 5-F 5-CI H H
7.059 3-OCH3, 5-CI 5-CI H H
7.060 3-OCH3, 5-Br 5-CI H H
7.061 3-CI, 5-CF3 5-CI H H
7.062 3-OCH3, 5-CF3 5-CI H H
7.063 3-OCH3, 5-CH3 5-CI H H
7.064 3-OCH3, 5-CH=NOCH3 5-CI H H
7.065 3-F, 5-CF3 5-CI H H
7.066 3-OCH3 5-CI H H
7.067 3-F 6-CH3 H H
7.068 3-F, 5-F 6-CH3 H H
7.069 5-CF3 6-CH3 H H
7.070 5-CI 6-CH3 H H
7.071 3-F 6-CI H H
7.072 3-F, 5-F 6-CI H H
Figure imgf000093_0001
Figure imgf000094_0001
Comp. Ri R2 R3 R4 Phys. data no m.p. (°C)
7.137 3-F 5-CH3, 6-F H H
7.138 5-CF3 5-CH3) 6-F H H
7.139 5-CI 5-CH3, 6-F H H
7.140 3-OCH3 5-CH3, 6-CI H H
7.141 3-OCH3, 4-CI 5-CH3, 6-CI H H
7.142 3-OCH3, 4-CN 5-CH3, 6-CI H H
7.143 3-OCH3, 4-CF3 5-CH3, 6-CI H H
7.144 3-OCH3, 4-Br 5-CH3, 6-CI H H
7.145 3-F, 4-CF3 5-CH3, 6-CI H H
7.146 3-F, 5-F 5-CH3, 6-CI H H
7.147 3-F 5-CH3, 6-CI H H
7.148 5-CF3 5-CH3, 6-CI H H
7.149 5-CI 5-CH3, 6-CI H H
7.150 3-OCH3 5-F, 6-CH3 H H
7.151 3-OCH3, 4-CI 5-F, 6-CH3 H H
7.152 3-OCH3, 4-CN 5-F, 6-CH3 H H
7.153 3-OCH3, 4-CF3 5-F, 6-CH3 H H
7.154 3-OCH3) 4-Br 5-F, 6-CH3 H H
7.155 3-F, 4-CF3 5-F, 6-CH3 H H
7.156 3-F, 5-F 5-F, 6-CH3 H H
7.157 3-F 5-F, 6-CH3 H H
7.158 5-CF3 5-F, 6-CH3 H H
7.159 5-CI 5-F, 6-CH3 H H
7.160 3-OCH3 5-CI, 6-CH3 H H
7.161 3-OCH3, 4-CI 5-CI, 6-CH3 H H
7.162 3-OCH3, 4-CN 5-CI, 6-CH3 H H
7.163 3-OCH3, 4-CF3 5-CI, 6-CH3 H H
7.164 3-OCH3, 4-Br 5-CI, 6-CH3 H H
7.165 3-F, 4-CF3 5-CI, 6-CH3 H H
7.166 3-F, 5-F 5-CI, 6-CH3 H H
7.167 3-F 5-CI, 6-CH3 H H
7.168 5-CF3 5-CI, 6-CH3 H H Comp. Ri R2 R3 R4 Phys. data no m.p. r
7.169 5-CI 5-CI, 6-CH3 H H
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. r
8.151 3-OCH3 5-CH3 H H
8.152 3-F, 5-F 5-CH3 H H
8.153 3-F 5-CH3 H H
8.154 5-CF3 5-CH3 H H
8.155 5-CN 5-CH3 H H
8.156 5-CH3 5-CH3 H H
8.157 5-CI 5-CH3 H H
8.158 3-OCH3, 5-CHO 5-CH3 H H
Figure imgf000101_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. ro
9.015 3-CI, 5-CI 6-CH2-CN H H
9.016 3-OCH3, 5-F 6-CH2-CN H H
9.017 3-OCH3, 5-CI 6-CH2-CN H H
9.018 3-OCH3, 5-Br 6-CH2-CN H H
9.019 3-CI, 5-CF3 6-CH2-CN H H
9.020 3-OCH3, 5-CF3 6-CH2-CN H H
9.021 3-OCH3, 5-CH3 6-CH2-CN H H
9.022 3-OCH3, 5-CH=NOCH3 6-CH2-CN H H
9.023 3-F, 5-CF3 6-CH2-CN H H
9.024 3-OCH3 6-CH2-CN H H
9.025 3-OCH3, 5-F 6-CH2-CN F F
9.026 3-OCH3, 5-CI 6-CH2-CN F F
9.027 3-OCH3, 5-CF3 6-CH2-CN F F
9.028 3-OCH3, 5-Br 6-CH2-CN F F
9.029 3-CI, 5-CF3 6-CH2-CN F F
9.030 3-OCH3, 5-CN 6-CH2-CN F F
9.031 3-OCH3, 5-F 6-CHF2 H H
9.032 3-OCH3, 5-CI 6-CHF2 H H
9.033 3-OCH3, 5-CF3 6-CHF2 H H
9.034 3-OCH3, 5-Br 6-CHF2 H H
9.035 3-CI, 5-CF3 6-CHF2 H H
9.036 3-OCH3, 5-CN 6-CHF2 H H
9.037 3-OCH3, 5-CN 2-Br H H
9.038 3-F, 5-CI 2-Br H H
9.039 3-CI, 5-CI 2-Br H H
9.040 3-OCH3> 5-F 2-Br H H
9.041 3-OCH3, 5-CI 2-Br H H
9.042 3-OCH3, 5-Br 2-Br H H
9.043 3-CI, 5-CF3 2-Br H H
9.044 3-OCH3, 5-CF3 2-Br H H
9.045 3-OCH3, 5-CH3 2-Br H H
9.046 3-OCH3, 5-CH=NOCH3 2-Br H H Comp. Ri R2 R3 R4 Phys. data no. m.p.
9.047 3-F, 5-CF3 2-Br H H
9.048 3-OCH3 2-Br H H
9.049 3-OCH3) 5-CN 2-CI H H
9.050 3-F, 5-CI 2-CI H H
9.051 3-CI, 5-CI 2-CI H H
9.052 3-OCH3, 5-F 2-CI H H
9.053 3-OCH3, 5-CI 2-CI H H
9.054 3-OCH3, 5-Br 2-CI H H
9.055 3-CI, 5-CF3 2-CI H H
9.056 3-OCH3, 5-CF3 2-CI H H
9.057 3-OCH3, 5-CH3 2-CI H H
9.058 3-OCH3, 5-CH=NOCH3 2-CI H H
9.059 3-F, 5-CF3 2-CI H H
9.060 3-OCH3 2-CI H H
9.061 3-OCH3, 5-CN 2-CH3 H H
9.062 3-F, 5-CI 2-CH3 H H
9.063 3-CI, 5-CI 2-CH3 H H
9.064 3-OCH3, 5-F 2-CH3 H H
9.065 3-OCH3, 5-CI 2-CH3 H H
9.066 3-OCH3, 5-Br 2-CH3 H H
9.067 3-CI, 5-CF3 2-CH3 H H
9.068 3-OCH3, 5-CF3 2-CH3 H H
9.069 3-OCH3, 5-CH3 2-CH3 H H
9.070 3-OCH3, 5-CH=NOCH3 2-CH3 H H
9.071 3-F, 5-CF3 2-CH3 H H
9.072 3-OCH3 2-CH3 H H
9.073 3-OCH3, 5-CN 2-CH2-CN H H
9.074 3-F, 5-CI 2-CH2-CN H H
9.075 3-CI, 5-CI 2-CH2-CN H H
9.076 3-OCH3, 5-F 2-CH2-CN H H
9.077 3-OCH3, 5-CI 2-CH2-CN H H
9.078 3-OCH3, 5-Br 2-CH2-CN H H
Figure imgf000104_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. r
9.111 3-OCH3, 5-CH3 2-F H H
9.1 12 3-OCH3, 5-CH=NOCH3 2-F H H
9.113 3-F, 5-CF3 2-F H H
9.114 3-OCH3 2-F H H
9.1 15 3-F 2-F H H
9.1 16 3-F, 5-F 2-F H H
9.117 5-F 2-F H H
9.118 5-CI 2-F H H
9.119 5-CF3 2-F H H
9.120 5-CH3 2-F H H
9.121 3-OCH3, 5-CN 2-F, 6-F H H
9.122 3-F, 5-CI 2-F, 6-F H H
9.123 3-CI, 5-CI 2-F, 6-F H H
9.124 3-OCH3, 5-F 2-F, 6-F H H
9.125 3-OCH3, 5-CI 2-F, 6-F H H
9.126 3-OCH3, 5-Br 2-F, 6-F H H
9.127 3-CI, 5-CF3 2-F, 6-F H H
9.128 3-OCH3, 5-CF3 2-F, 6-F H H
9.129 3-OCH3, 5-CH3 2-F, 6-F H H
9.130 3-OCH3, 5-CH=NOCH3 2-F, 6-F H H
9.131 3-F, 5-CF3 2-F, 6-F H H
9.132 3-OCH3 2-F, 6-F H H
9.133 3-F 2-F, 6-F H H
9.134 3-F, 5-F 2-F, 6-F H H
9.135 5-F 2-F, 6-F H H
9.136 5-CI 2-F, 6-F H H
9.137 5-CF3 2-F, 6-F H H
9.138 5-CH3 2-F, 6-F H H
9.139 3-F, 5-CF3 6-CH3 H H
9.140 3-OCH3 6-CH3 H H
9.141 3-F 6-CH3 H H
9.142 3-F, 5-F 6-CH3 H H
Figure imgf000106_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. r
9.175 3-OCH3, 5-CI 2-CN H H
9.176 3-OCH3, 5-CH3 2-CN H H
9.177 3-F, 5-F 2-CN H H
9.178 3-OCH3, 5-CF3 2-CN H H
9.179 3-OCH3 2-CN H H
9.180 3-CI 2-CN H H
9.181 5-CF3 2-CN H H
9.182 3-OCH3, 5-CI 2-CH3, 6-CH3 H H
9.183 3-OCH3, 5-CH3 2-CH3, 6-CH3 H H
9.184 3-F, 5-F 2-CH3, 6-CH3 H H
9.185 3-OCH3, 5-CF3 2-CH3, 6-CH3 H H
9.186 3-OCH3 2-CH3, 6-CH3 H H
9.187 3-CI 2-CH3, 6-CH3 H H
9.188 5-CF3 2-CH3, 6-CH3 H H
9.189 3-OCH3, 5-CI 2-F, 6-CH3 H H
9.190 3-OCH3, 5-CH3 2-F, 6-CH3 H H
9.191 3-F, 5-F 2-F, 6-CH3 H H
9.192 3-OCH3, 5-CF3 2-F, 6-CH3 H H
9.193 3-OCH3 2-F, 6-CH3 H H
9.194 3-CI 2-F, 6-CH3 H H
9.195 5-CF3 2-F, 6-CH3 H H
9.196 3-OCH3, 5-CI 2-CI, 6-CH3 H H
9.197 3-OCH3, 5-CH3 2-CI, 6-CH3 H H
9.198 3-F, 5-F 2-CI, 6-CH3 H H
9.199 3-OCH3, 5-CF3 2-CI, 6-CH3 H H
9.200 3-OCH3 2-CI, 6-CH3 H H
9.201 3-CI 2-CI, 6-CH3 H H
9.202 5-CF3 2-CI, 6-CH3 H H able 10: Compounds of formula lbg1
Figure imgf000108_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. ro
10.001 2-OCH3 H (m=0) H H
10.002 2-OCH3, 4-F H (m=0) H H crystalline
10.003 2-OCH3, 4-Br H (m=0) H H
10.004 2-OCH3, 4-1 H (m=0) H H
10.005 2-OCH3, 4-CH3 H (m=0) H H
10.006 2-OCH3, 4-CN H (m=0) H H
10.007 2-OCH3, 4-CF3 H (m=0) H H
10.008 2-OCH3, 4-CHF2 H (m=0) H H
10.009 2-OCH3, 4-CHO H (m=0) H H
10.010 2-F, 4-NO2 H (m=0) H H
10.01 1 2-F, 4-CN H (m=0) H H
10.012 2-OCH3, 4-NH2 H (m=0) H H
10.013 2-OCH3, 4-CH=NOCH3 H (m=0) H H crystalline
10.014 2-OCH3 2-CI H H
10.015 2-OCH3, 4-F 2-CI H H
10.016 2-OCH3, 4-Br 2-CI H H
10.017 2OCH3) 4-1 2-CI H H
10.018 2-OCH3, 4-CH3 2-CI H H
10.019 2-OCH3, 4-CN 2-CI H H
10.020 2-OCH3, 4-CF3 2-CI H H
10.021 2-OCH3, 4-CHF2 2-CI H H
10.022 2-OCH3. 4-CHO 2-CI H H
10.023 2-F, 4-NO2 2-CI H H
10.024 2-F, 4-CN 2-CI H H
10.025 2-OCH3, 4-NH2 2-CI H H
Figure imgf000109_0001
Figure imgf000110_0001
able 11 : Compounds of formula Ib-ς2
Figure imgf000111_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. ro
11.001 3-OCH3 H (m=0) H H
11.002 3-F H (m=0) H H
11.003 3-CI H (m=0) H H
11.004 3-NH2 H (m=0) H H
11.005 3-OCH3, 5-F H (m=0) H H
11.006 3-OCH3, 5-CI H (m=0) H H crystalline
11.007 3-OCH3, 4-Br H (m=0) H H
11.008 3-OCH3, 5-CH3 H (m=0) H H
1 1.009 3-OCH3, 5-CN H (m=0) H H
11.010 3-OCH3, 5-CF3 H (m=0) H H
11.011 3-OCH3, 5-COOH H (m=0) H H
11.012 3-OCH3, 5-COOCH3 H (m=0) H H
11.013 3-F, 5-F H (m=0) H H
11.014 3-F, 5-CI H (m=0) H H
11.015 3-F, 4-Br H (m=0) H H
11.016 3-F, 5-CN H (m=0) H H
11.017 3-F, 5-CF3 H (m=0) H H
11.018 3-F, 5-CH3 H (m=0) H H
11.019 3-F, 5-COOH H (m=0) H H
11.020 3-F, 5-COOCH3 H (m=0) H H
11.021 3-CI, 5-COOCH3 H (m=0) H H
11.022 3-OCH3, 5-NH2 H (m=0) H H
11.023 3-F, 5-NH2 H (m=0) H H
11.024 3-CI, 5-CF3 H (m=0) H H
11.025 3-CI, 5-CN H (m=0) H H Comp. Ri R2 R3 R4 Phys. data no. m.p. ro
11.026 5-F H (m=0) H H
11.027 5-CI H (m=0) H H
11.028 5-Br H (m=0) H H
11.029 5-CF3 H (m=0) H H
11.030 5-CN H (m=0) H H
11.031 5-CH3 H (m=0) H H
11.032 5-NH2 H (m=0) H H
11.033 5-COOH H (m=0) H H
11.034 5-COOCH3 H (m=0) H H
11.035 3-OCH3 2-CI H H
11.036 3-F 2-CI H H
11.037 3-CI 2-CI H H
11.038 3-NH2 2-CI H H
11.039 3-OCH3, 5-F 2-CI H H
11.040 3-OCH3, 5-CI 2-CI H H
11.041 3-OCH3, 4-Br 2-CI H H
11.042 3-OCH3, 5-CH3 2-CI H H
11.043 3-OCH3, 5-CN 2-CI H H
11.044 3-OCH3, 5-CF3 2-CI H H
11.045 3-OCH3, 5-COOH 2-CI H H
11.046 3-OCH3, 5-COOCH3 2-CI H H
11.047 3-F, 5-F 2-CI H H
11.048 3-F, 5-CI 2-CI H H
11.049 3-F, 4-Br 2-CI H H
11.050 3-F, 5-CN 2-CI H H
11.051 3-F, 5-CF3 2-CI H H
11.052 3-F, 5-CH3 2-CI H H
11.053 3-F, 5-COOH 2-CI H H
11.054 3-F, 5-COOCH3 2-CI H H
11.055 3-CI, 5-COOCH3 2-CI H H
11.056 3-OCH3, 5-NH2 2-CI H H
11.057 3-F, 5-NH2 2-CI H H
Figure imgf000113_0001
Comp. Ri R2 R3 R4 Phys. data no. m.p. o
11.090 3-OCH3, 5-CI
11.091 3-OCH3, 5-Br
11.092 3-OCH3, 5-CF3
11.093 3-OCH3, 5-CH3
11.094 3-OCH3, 5-CN
11.095 3-F, 5-F
11.096 3-F, 5-CI
11.097 3-F, 5-CF3
11.098 3-CI, 5-CN
11.099 3-F 11.100 3-CI 11.101 5-F 11.102 5-CI 11.103 5-Br 11.104 5-CF3 11.105 5-CN 11.106 5-CH3 11.107 3-OCH3 11.108 3-OCH3, 5-F 11.109 3-OCH3, 5-CI 11.110 3-OCH3, 5-Br 11.111 3-OCH3, 5-CF3 11.112 3-OCH3> 5-CH3 11.113 3-F, 5-CI 2-NH2 H H 11.114 3-F, 5-F 2-NH2 H H 11.115 3-CI, 5-CF3 2-NH2 H H 11.116 3-F 2-NH2 H H 11.117 3-CI 2-NH2 H H 11.118 5-F 2-NH2 H H 11.119 5-CI 2-NH2 H H 11.120 5-CN 2-NH2 H H 11.121 5-CF3 2-NH2 H H Comp. Ri R2 R3 R4 Phys. data no. m.p. ro
11.122 3-OCH3, 5-CH=NOCH3 H(m=0) H H crystalline
Biological Examples
Example B1 : Herbicidal action prior to emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 4 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: Brachiaria, Sorghum bicolor
Table B1 : Concentration: 1000 g of active ingredient per ha
Test plant: Brachiaria Sorghum bicolor
Comp. no.
11.006
The same results are obtained when the compounds of formula I are formulated analogously to the other Examples of WO 97/34485.
Example B2: Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at the 2- to 3-leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of 2 to 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: Panicum, Scirpus
Table B2: Concentration: 1000 g of active ingredient per ha
Test plant: Panicum Scirpus
Comp. no.
2.088
The same results are obtained when the compounds of formula I are formulated analogously to the other Examples of WO 97/34485.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000117_0001
wherein Q is a group
(Q3).
Figure imgf000117_0002
Figure imgf000117_0003
Z is =N-, l + - or =C(R,)- ^N-O n is O, 1 , 2, 3 or 4; each Rx independently is halogen, -CN, -SCN, -SF5, -NO2, -NR5R6, -CO2R7, -CONR8R9,
Figure imgf000117_0004
-COR12, -OR13, -SR14, -SOR15, -SO2R16, -OSO2R17, CrCβalkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or is CrC8alkyl, C2-C8alkenyl or C2-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NO2, -NRι8R19, -CO2R20, -CONR21R22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(C1-C4alkylthio)=NR28, - OR∑g, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; and/or each Ri independently is C3-C6cycloalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NO2, -NR18Rι9, -CO2R20, -CONR^R^, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(C1-C4alkylthio)=NR28) -SR30, -SOR3ι, -SO2R32 or by C3-C6cycloalkyl; and/or each Ri independently is phenyl which may in turn be mono- to penta-substituted by halogen or by Cι-C4alkyl or mono-, di- or tri-substituted by 0-C4haloalkyl, C C4alkoxy, -CN, -NO2, O-Calkylthio, 0-C4alkylsulfinyl or by d-C alkylsulfonyl; and/or two adjacent Rx substituents together form a C C7alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by 0-C6alkyl or mono-, di- or tri-substituted by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R, substituents together form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by CrC6alkyl or mono-, di- or trisubstituted by CrC6alkoxy, the total number of ring atoms being at least 5 and at most 9;
R3 and R4 are each independently of the other hydrogen, halogen, -CN, d-C4alkyl or C C4alkoxy; or
R3 and R together are C2-C5alkylene; R5 is hydrogen or 0-C8alkyl;
R6 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-C4alkyl or mono-, di- or tri-substituted by C1-C haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, CrC4alkylsulfinyl or by d-C alkylsulfonyl; or
R5 and R6 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by C C alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by CrC4alkyl or mono-, di- or tri-substituted by 0-C4haloalkyl, C C alkoxy, -CN, -NO2, 0-C4alkylthio, 0-C4alkylsulfinyl or by 0-C4alkylsulfonyl; R8 is hydrogen or CrC8alkyl;
R9 is hydrogen or C Cβalkyl, or is 0-C8alkyl mono-, di- or tri-substituted by -COOH, CrC8alkoxycarbonyl or by -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by CrC4alkyl or mono-, di- or trisubstituted by CrC4haloalkyl, CrC4alkoxy, -CN, -NO , CrC4alkylthio, 0-C4alkylsulfinyl or by C C4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; R10 is hydrogen, 0-C alkyl, C C4haloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, 0-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC4haloalkyl or C3-C6haloalkenyl; R12 is hydrogen, 0-C alkyl, CrC4haloalkyl or C3-C6cycloalkyl; R13 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or R 3 is phenyl or phenyl-CrC6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen or by d-C alkyl or mono-, di- or tri-substituted by C C4halo- alkyl, C C4alkoxy, -CN, -NO2, CrC8alkylthio, CrC8alkylsulfinyl or by CrC8alkylsulfonyl, or R13 is CrC8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, CrC6alkylamino, di(CrC6alkyl)amino or by C C4alkoxy;
R14 is hydrogen, 0-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is CrC8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or by 0-C4alkoxy; R15, R16 and R17 are each independently of the others 0-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by CrC4alkoxy; R18 is hydrogen or 0-C8alkyl;
R19 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by CrC4alkyl or mono-, di- or tri-substituted by CrC haloalkyl, CrC4alkoxy, -CN, -NO2, 0-C4alkylthio, CrC4alkylsulfinyl or by C C4alkylsulfonyl; or
R18 and R19 together are a C -C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R20 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by 0-C alkyl or mono-, di- or tri-substituted by Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, CrC4alkylthio, C C4alkylsulfinyl or by CrC alkylsulfonyl; R21 is hydrogen or C C8alkyl;
R22 is hydrogen or 0-C8alkyl, or is 0-C8alkyl mono-, di- or tri-substituted by -COOH, C C8alkoxycarbonyl or by -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by 0-C4alkyl or mono-, di- or trisubstituted by CrC4haloalkyl, CrC4alkoxy, -CN, -NO2, C C4alkylthio, CrC4alkylsulfinyl or by C C4alkylsulfonyl; or R21 and R22 together are C2-C5alkylene; R23 is hydrogen, Crdalkyl, C C4haloalkyl or C3-C6cycloalkyl; R2 is hydrogen, 0-C4alkyl, CrOhaloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or CrC8alkyl;
R27 is hydrogen or 0-C8alkyl, or is 0-C8alkyl mono-, di- or tri-substituted by -COOH, CrC8- alkoxycarbonyl or by -CN, or R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by C C4alkyl or mono-, di- or trisubstituted by C C4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, 0-C4alkylsulfinyl or by CrC4alkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or 0-C8alkyl;
R29 and R30 are each independently of the other hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by 0-C4alkoxy;
R31 and R32 are each independently of the other 0-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or by d-dalkoxy; m is 0, 1 , 2 or 3; each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -SF5, -NO2, -NR33R3 , -CO2R35, -CONR36R37, -C(R3β)=NOR39, -COR40, -OR41, -SR42, -SOR43, -SOsR*,, -OSO^, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)SO2R57, -N(SO2R58)SO2R59,
Figure imgf000120_0001
-CR62(OR63)OR64, -OC(O)NR65R66> -SC(O)NR67R68, -OC(S)NR69R70 or -N-phthalimide; and/or R2 is a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C haloalkyl, hydroxy-d-dalkyl, d-dalkoxy, CrC4alkoxy-CrC4alkyl, -CN, -NO2, d-C6alkylthio, CrC6alkylsulfinyl or by C C6alkylsulfonyl; R33 is hydrogen or d-C8alkyl; and
R3 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CH3C(O)-, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by O-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, -CN, -NO2, O-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or
R33 and R34 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R35 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by O-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, O-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by CrC4alkylsulfonyl; R36 is hydrogen or d-C8alkyl; R37 is hydrogen or d-C8alkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN, or
R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-Oalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, O-dalkylsulfinyl or by d-dalkylsulfonyl; or R36 and R37 together are C3-C5alkylene; R38 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; R40 is hydrogen, d-dalkyl, d-dhaloalkyl, d-dalkylthio, -C(O)-C(O)Od-C4alkyl or C3-C6- cycloalkyl;
R41 is hydrogen, d-dalkyl, d-dhaloalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C6alkoxy- d-C6alkyl, CrC8alkylcarbonyl, d-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C C6alkoxy- d-C6alkoxycarbonyl, CrC6alkylthio-CrC6alkyl, CrC6alkylsulfinyl-CrC6alkyl or d-C6alkyl- sulfonyl-d-C6alkyl; or
R41 is phenyl or phenyl-Crdalkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2 or by -S(O)2C C8alkyl, or
R41 is Crdalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl, d-dalkylamino, di(d-C6alkyl)amino or by -CN; R42 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or by d-dalkoxy; R^ and R j are each independently of the other Crdalkyl, C3-C8alkenyl or C3-C8alkynyl, or d-dalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or by d-dalkoxy;
R^ is d-dalkyl, d-dalkyl mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by d-C4alkoxy, or is C3-C8alkenyl or C3-C8alkynyl, or R 5 is phenyl, it being possible for the phenyl ring to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by O-dhaloalkyl, d-dalkoxy, -CN, NO2, d-C8alkylthio, C C8alkylsulfinyl or by C C8alkylsulfonyl; R^ is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl or O-dhaloalkyl; R 7 is hydrogen, d-dalkyl, C C4alkoxy, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, d-dalkoxy, d-dalkoxycarbonyl, -NH2, d-dalkylamino, di(Crdalkyl)amino, -NR^COR^, -NRsoSO2R5ι or by -NR52CO2R53, or R47 is phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; p is O or 1 ;
R-18, R 9, R50, R51, Rδ2 and R53 are each independently of the others hydrogen, d-C8alkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono- to penta-substituted by halogen or by C C8alkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, d-dalkylamino, di(CrC4alkyl)amino, -NH2, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
RβΛ and R55 are each independently of the other hydrogen, Crdalkyl, or phenyl which may in turn be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C8alkylthio, d-C8alkylsulfinyl or by d-C8alkylsulfonyl;
Rδβ is hydrogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, it being possible for benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C8alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
R57 is Crdalkyl, d-C4haloalkyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, d-dalkylamino, di(d-C4alkyl)amino, -NH2, -CN, -NO2, Crdalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; R5β and R59 are each independently of the other d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-dalkoxy, C C4alkylamino, di(C C4alkyl)amino, -NH2, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
R60 and R6ι are each independently of the other hydrogen or Crdalkyl; R6 , R63 and R^ are each independently of the others hydrogen or d-dalkyl, or R63 and RM together form a C2-C5alkylene bridge;
Res, Rθ6. R67, Res, Rβ9 and R70 are each independently of the others hydrogen or d-dalkyl, or
R65 and R66, or R67 and R^, or R69 and R70 in each case together form a C2-C5alkylene bridge; and/or each R2 independently is -dalkyl, or is d-dalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -N3, -SCN, -NO2, -OH, -NR71R72, -CO2R73, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79Rβo, -C(C,-C4alky.thio)=NR81, -OR82, -SR^, -SORβ,, -SO2R85, -O(SO2)R86, -N(R87)CO2R88, -N(R89)COR90, -S+(R91)2, -N+(R92)3, -Si(R93)3 or by C3-C6cycloalkyl; and/or each R2 independently is d-dalkyl substituted by a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, hydroxy-d-dalkyl, d-dalkoxy, d-dalkoxy- d-dalkyl, -CN, -NO2, d-dalkylthio, d-C6alkylsulfinyl or by C C6alkylsulfonyl; and/or each R2 independently is C2-C8alkenyl, or is C2-C8alkenyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NO2, -CO2R9 > -CONR95R96, -COR97, -C(R98)=NOR99, -C(S)NR100Rιoι, -C(d-C4alkylthio)=NR102, -ORι03, -Si(R104)3 or by C3-C6- cycloalkyl; and/or each R2 independently is C2-C8alkynyl, or is C2-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -CO2Ri05, -CONR106Rιo7, -CORι08, -C(R109)=NOR110, ^(SJNRmRna, -C(CrC4alkylthio)=NR113, -OR114, -Si(R115)3 or by C3-C6cycloalkyl; and/or each R2 independently is C3-C6cycloalkyl, or is C3-C6cycloalkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -CO2R116, -CONR117R118, -CORu9,
Figure imgf000123_0001
or, when Q is a group Q1 ; Q2, Q3 or Q5, two adjacent R2 substituents together may form a Crdalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; or, when Q is a group Q1 t Q2, Q3 or Q5> two adjacent R2 substituents together may form a 0-C alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; R71 is hydrogen or d-dalkyl;
R72 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by C C4haloalkyl, d-C alkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or
R71 and R72 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom; R7 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta- substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R74 is hydrogen or Crdalkyl;
R75 is hydrogen, d-dalkyl or C3-C7cycloalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl, d-dalkoxy or by -CN; or
R75 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by O-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or
R74 and R75 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R76 is hydrogen, -dalkyl, d-dhaloalkyl or C3-C6cycloalkyl; R-π is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; and
R79 is hydrogen or -dalkyl;
R80 is hydrogen or d-dalkyl, or is C C8alkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
Rβo is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by O-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by Crdalkylsulfonyl; or R79 and R80 together are C2-C5alkylene; R81 is hydrogen or O-dalkyl;
R82 is -Si(d-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl which is mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, d-dalkylamino, di(Cι-C6alkyl)amino or by d-dalkoxy;
R83 is hydrogen, Crdalkyl, C3-C8alkenyl or C3-C8alkynyl, or is O-dalkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, d-dalkylamino, di(CrC6alkyl)amino or by d-dalkoxy;
Rβ4. es and R86 are each independently of the others O-dalkyl, C3-C8alkenyl or C3-C8- alkynyl, or O-dalkyl which is mono- to penta-substituted by halogen or mono-, di- or trisubstituted by -CN or by d-dalkoxy; R87 and R89 are each independently of the other hydrogen, Crdalkyl or d-dalkoxy; R88 is CrC8alkyl; R9o is hydrogen or d-dalkyl; R91 is d-dalkyl;
R92 and R93 are each independently of the other d-dalkyl;
R94 is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C alkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by O-dalkyl or mono-, di- or tri-substituted by d-dhaloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R95 is hydrogen or C C8alkyl;
R96 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by -dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, O-dalkoxy, -CN, -NO2, d-C4alkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or
R95 and R96 together are C2-C5alkylene;
R97 and R98 are each independently of the other hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R99 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl; R100 is hydrogen or Crdalkyl;
R10ι is hydrogen or Crdalkyl, or is Crdalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
R101 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, C C4alkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by CrOalkylsulfonyl; or R100 and R101 together are C2-C5alkylene; R102 is hydrogen or Crdalkyl;
R103 is hydrogen, Crdalkyl, -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; R104 is d-dalkyl;
R105 is hydrogen or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-d- alkyl or mono-, di- or tri-substituted by d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by O-dalkylsulfonyl; R106 is hydrogen or -dalkyl;
R107 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN, or
R107 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, C,-C4alkylthio, d-Oalkylsulfinyl or by d-dalkylsulfonyl; or Rioe and Rι07 together are C2-C5alkylene; R108 is hydrogen, d-dalkyl, O-dhaloalkyl or C3-C6cycloalkyl; R109 is hydrogen, d-dalkyl, O-dhaloalkyl or C3-C6cycloalkyl;
Rno is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; Rm is hydrogen or d-dalkyl;
R112 is hydrogen or Crdalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
R112 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-Oalkylsulfinyl or by d-dalkylsulfonyl; or Rm and R112 together are C2-C5alkylene; R113 is hydrogen or Crdalkyl;
R114 is hydrogen, Crdalkyl, -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; R115 is d-dalkyl;
R116 is hydrogen or is O-dalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by O-Oalkoxy or by phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or tri-substituted by O-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, d-dalkylsulfinyl or by O-dalkylsulfonyl; R117 is hydrogen or d-dalkyl;
R118 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
Rue is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-Oalkylsulfinyl or by d-dalkylsulfonyl; or R117 and R118 together are C2-C5alkylene; Rι19 is hydrogen, d-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl; R120 is hydrogen, -Oalkyl, C C4haloalkyl or C3-C6cycloalkyl;
R121 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C,-C4haloalkyl or C3-C6haloalkenyl; R122 is hydrogen or d-dalkyl;
R123 is hydrogen or Crdalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN; or
Rι23 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen or by d-dalkyl or mono-, di- or trisubstituted by d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by O-dalkylsulfonyl; or
R122 and R123 together are C2-C5alkylene; and R124 is hydrogen or Crdalkyl, or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I.
2. A compound of formula I according to claim 1 , wherein each Rx independently is hydrogen, halogen, -CN, -SCN, -SF5, -NO2, -NR5R6, -CO2R7, -CONR8R9, -C(R10)=NORn, -
COR12, -OR13, -SRι4, -SOR15, -SO2Rι6, -OSO2R17, d-dalkyl, C2-C8alkenyl, C2-C8alkynyl or d-dcycloalkyl; or is d-dalkyl, C2-C8alkenyl or C2-C8alkynyl mono-, di- or tri-substituted by halogen, -CN, -NO2, -NR18R19, -CO2R20, -CONR2ιR22, -COR23, -C(R24)=NOR25, -C(S)NR26R27,
-C(C1-C4alkylthio)=NR28, -OR;*,, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each Rx independently is C3-C6cycloalkyl mono-, di- or tri-substituted by halogen, -CN, -NO2,
-NR18Ri9, -CO2R20, -CONR2ιR22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(CrC4alkyl- thio)=NR28, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each Ri independently is phenyl which may in turn be mono-, di- or tri-substituted by halogen, Crdalkyl, d-dhaloalkyl, -dalkoxy, -CN, -NO2, O-dalkylthio, C dalkylsulfinyl or by d-C alkylsulfonyl; or two adjacent Rx substituents together form a d-Oalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, O-Oalkyl or by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9; or two adjacent Rx substituents together form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, d-dalkyl or by d-dalkoxy, the total number of ring atoms being at least 5 and at most 9;
R3 or R4 are each independently of the other hydrogen, halogen, -CN, O-dalkyl or d-dalkoxy; or
R3 and R together are C2-C5alkylene; R5 is hydrogen or d-dalkyl;
R6 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, d-dalkylsulfinyl or by C C4alkylsulfonyl; or
R5 and R6 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl mono-, di- or tri-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R8 is hydrogen or d-dalkyl;
R9 is hydrogen or Crdalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; R10 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, O-Ohaloalkyl or C3-C6haloalkenyl; R12 is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl; R13 is hydrogen, Crdalkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-Crdalkyl, it being possible for the phenyl ring in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by Crdalkylsulfonyl; or
R13 is d-dalkyl mono-, di- or tri-substituted by halogen, -CN, d-dalkylamino, di(d-O6- alkyl)amino or by d-dalkoxy;
R14 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl mono-, di- or trisubstituted by halogen, -CN or by d-dalkoxy;
R15, R16 and R17 are each independently of the others d-dalkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN or by d-dalkoxy; R18 is hydrogen or d-dalkyl;
R19 is hydrogen, Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-Oalkoxy, -CN, -NO2, O-Oalkylthio, d-dalkylsulfinyl or by C C4alkylsulfonyl; or
R18 and R19 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R20 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; R21 is hydrogen or d-dalkyl;
R22 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, -dalkyl, d-dhaloalkyl, O-Oalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-dalkylsulfonyl; or R21 and R22 together are C2-C5alkylene;
R23 s hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R24 s hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R25 s hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl;
R-« s hydrogen or d-dalkyl;
R27 s hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, O-Oalkoxy, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or d-dalkyl;
R 9 and R30 are each independently of the other hydrogen, Crdalkyl, C3-C8alkenyl or C3-C8alkynyl, or d-dalkyl mono-, di- or tri-substituted by halogen, -CN or by d-C4alkoxy; R31 and R32 are each independently of the other d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl mono-, di- or tri-substituted by halogen, -CN or by d-C4alkoxy; m is 0, 1 , 2 or 3; each R2 independently is hydrogen, halogen, -CN, -SCN, -OCN, -N3, -SF5, -NO2, -NR33R34, -CO2R35, -CONR36R37, -C(R38)=NOR39, -COR-rø, -OR41, -SR42, -SOR43, -SOsR-M, -OSO2R 5, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)SO2R57, -N(SO2R5β)SO2R59, -N=C(OR60)R6ι, -CR62(OR63)OR64, -OC(O)NR65R66, -SC(O)NR67R68> -OC(S)NR69R70 or -N-phthalimide; or R2 is a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono-, di- or trisubstituted by halogen, O-dalkyl, C C haloalkyl, hydroxy-d-dalkyl, d-dalkoxy, O-dalkoxy-d-Oalkyl, -CN, -NO2, d-dalkylthio, d-Oalkylsulfinyl or by d-dalkylsulfonyl; R33 is hydrogen or d-dalkyl; and
R^ is hydrogen, Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, -dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, O-Oalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or
R33 and R34 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R35 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl, C3-C8alkenyl or C3-C8alkynyl mono-, di- or tri-substituted by halogen, d-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by O-dalkylsulfonyl; R36 is hydrogen or d-dalkyl;
R37 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl or by -CN, or
R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C haloalkyl, d-C alkoxy, -CN, -NO2, O-Oalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; or R36 and R37 together are C3-C5alkylene; R3β is hydrogen, -Oalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, d-Oalkyl, d-dalkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; R40 is hydrogen, d-Oalkyl, d-dhaloalkyl, d-dalkylthio, -C(O)-C(O)OCrC4alkyl or C3-C6cycloalkyl;
R41 is hydrogen, d-Oalkyl, d-dhaloalkyl, C3-C8alkenyl, C3-C8alkynyl, 0-C6alkoxy- O-Oalkyl, C C8alkylcarbonyl, Crdalkoxycarbonyl, C3-C8alkenyloxycarbonyl, d-Oalkoxy- CrC6alkoxycarbonyl, O-Oalkylthio-O-Oalkyl, CrC6alkylsulfinyl-CrC6alkyl or C C6alkyl- sulfonyl-d-C6alkyl; or
R41 is phenyl or phenyl-O-dalkyl, it being possible for the phenyl ring in turn to be mono-, di- or tri-substituted by halogen, -dalkyl, d-C4haloalkyl, d-dalkoxy, -CN, -NO2 or by -S(O)2CrC8alkyl, or R4ι is d-C8alkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl, d-dalkylamino, di(0-Oalkyl)amino or by -CN;
R42 is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is Crdalkyl mono-, di- or trisubstituted by halogen, -CN or by d-dalkoxy;
R-J3 and R,M are each independently of the other -dalkyl, C3-C8alkenyl or C3-C8alkynyl, or d-dalkyl mono-, di- or tri-substituted by halogen, -CN or by d-C4alkoxy; R45 is CrC8alkyl, d-dalkyl mono-, di- or tri-substituted by halogen, -CN or by d-C4alkoxy, or is C3-C8alkenyl or C3-C8alkynyl, or
R45 is phenyl, it being possible for the phenyl ring to be mono-, di- or tri-substituted by halogen, Crdalkyl, C C4haloalkyl, d-C4alkoxy, -CN, NO2, d-C8alkylthio, O-Oalkylsulfinyl or by d-dalkylsulfonyl;
R^ is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl or d-dhaloalkyl; R47 is hydrogen, d-dalkyl, d-dalkoxy, C3-C8alkenyl or C3-C8alkynyl, or is O-Oalkyl mono-, di- or tri-substituted by halogen, -CN, d-dalkoxy, d-dalkoxycarbonyl, -NH2, d-dalkylamino, di(Ci-C4alkyl)amino, -NR^COR^, -NR5oSO2R51 or by -NR52CO2R53, or R 7 is phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or trisubstituted by halogen, d-dalkyl, C C4haloalkyl, d-C4alkoxy, -CN, -NO2, O-Oalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; p is 0 or 1 ;
R^, R4g, R50, R51, R5-2 and R53 are each independently of the others hydrogen, d-dalkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C alkoxy, O-dalkylamino, di(d-C4alkyl)amino, -NH2, -CN, -NO2, O-Oalkylthio, O-Oalkylsulfinyl or by O-Oalkylsulfonyl;
RM and R55 are each independently of the other hydrogen, O-Oalkyl, or phenyl which may in turn be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C haloalkyl, d-dalkoxy, -CN, -NO , CrC8alkylthio, Crdalkylsulfinyl or by C,-C8alkylsulfonyl; R56 is hydrogen, d-dalkyl, d-dhaloalkyl, d-C4alkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, it being possible for benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, C,-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-C8alkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl;
R57 is Crdalkyl, d-dhaloalkyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-dalkoxy, O-Oalkylamino, di(C,-C4alkyl)amino, -NH2, -CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by d-dalkylsulfonyl; R58 and R59 are each independently of the other Crdalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, it being possible for the last three aromatic rings to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-C alkoxy, d-dalkylamino, di(C,-C4alkyl)amino, -NH2, -CN, -NO2, O-Oalkylthio, -Oalkylsulfinyl or by O-Oalkyl- sulfonyl;
R60 and R6ι are each independently of the other hydrogen or d-dalkyl; R62, RKJ and R64 are each independently of the others hydrogen or d-dalkyl, or R63 and RM together form a C2-C5alkylene bridge;
Res, Ree, Rβ , Res, Rβ9 and R70 are each independently of the others hydrogen or d-dalkyl, or
R65 and R66, or R67 and R68, or R69 and R70 in each case together form a C2-C5alkylene bridge; or each R2 independently is d-dalkyl, or is Crdalkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -NO2, -NR71R72, -CO2R73, -CONR74R75, -COR76,
Figure imgf000132_0001
-C(S)NR79R80, -C(0-C4alkylthio)=NR8i, -OR82, -SR83, -SORM, -SO2R85, -O(SO2)R86, -N(R87)CO2R88, -N(R89)COR90, -S+(R91)2, -N+(R92)3, -Si(R93)3 or by C3-C6cycloalkyl; or each R2 independently is O-Oalkyl substituted by a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for that heterocyclic ring system in turn to be mono-, di- or tri-substituted by halogen, O- alkyl, O-Ohaloalkyl, hydroxy-d-C4alkyl, d-dalkoxy, d-dalkoxy-d-dalkyl, _CN, -NO2, O- dalkylthio, O-Oalkylsulfinyl or by O-dalkylsulfonyl; or each R2 independently is C2-C8alkenyl, or is C2-C8alkenyl mono-, di- or tri-substituted by -CN, -NO2, -CO2R94, -CONR95R96, -COR97, -C(R98)=NOR99, -C(S)NR100Rιoι, -C(C C4alkyl- thio)=NR102, -OR103, -Si(Rι04)3 or by C3-C6cycloalkyl; or each R2 independently is C2-C8alkynyl, or is C2-C8alkynyl mono-, di- or tri-substituted by halogen, -CN, -CO2R105, -CONR106Rιo7, -COR108, -C(R109)=NOR110, -C(S)NRmR112, -C(C,-C4alkylthio)=NR113, -OR114, -Si(R115)3 or by C3-C6cycloalkyl; or each R2 independently is C3-C6cycloalkyl, or is C3-C6cycloalkyl mono-, di- or tri-substituted by halogen, -CN, -CO2R116, -CONR117Rn8, -COR119, -C(R120)=NOR121, -C(S)NR122R123 or by -C(0-Oalkylthio)=NR124; or, when Q is a group Q^ Q2, Q3 or Q5, two adjacent R2 substituents together may form a d-Oalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, O-Oalkyl or by O-Oalkoxy, the total number of ring atoms being at least 5 and at most 9; or, when Q is a group Qι, Q2, Q3 or Q5, two adjacent R2 substituents together may form a C2-Oalkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be mono-, di- or tri-substituted by halogen, O-Oalkyl or by d-Oalkoxy, the total number of ring atoms being at least 5 and at most 9; R71 is hydrogen or d-dalkyl;
R72 is hydrogen, -dalkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, O-Oalkoxy, -CN, -NO2, 0-C4alkylthio, d-C4alkylsulfinyl or by d-dalkylsulfonyl; or
R7ι and R72 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R73 is hydrogen, O-Oalkyl, C3-C8alkenyl or C3-C8alkynyl, or is -Oalkyl, C3-C8alkenyl or C3-C8alkynyl mono-, di- or tri-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, O- alkoxy, -CN, -NO2, O-Oalkylthio, O- alkylsulfinyl or by O-Oalkylsulfonyl; R7 is hydrogen or O-Oalkyl;
R75 is hydrogen, O-Oalkyl or C3-C7cycloalkyl, or is O-Oalkyl mono-, di- or tri-substituted by -COOH, Crdalkoxycarbonyl, d-C6alkoxy or by -CN; or
R75 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-Oalkyl, O- haloalkyl, O- alkoxy, -CN, -NO2l O- alkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or R74 and R75 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R76 is hydrogen, O-Oalkyl, O- haloalkyl or C3-C6cycloalkyl; Rπ is hydrogen, d-dalkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl; and
R79 is hydrogen or d-dalkyl;
R80 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
Rβo is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-Oalkyl, O-Ohaloalkyl, O-Oalkoxy, -CN, -IMO2, O-Oalkylthio, O-Oalkylsulfinyl or by d-C4alkylsulfonyl; or R79 and Rβo together are C2-C5alkylene; R81 is hydrogen or d-dalkyl; R82 is -Si(CrC6alkyl)3, C3-C8alkenyl or C3-C8alkynyl, or is d-dalkyl which is mono-, di- or trisubstituted by halogen, -CN, -NH2, O-Oalkylamino, di(CrC6alkyl)amino or by d-C4alkoxy; Rrø is hydrogen, d-dalkyl, C3-C8alkenyl or C3-C8alkynyl, or is O-Oalkyl which is mono-, di- or tri-substituted by halogen, -CN, -NH2, O-Oalkylamino, di(CrC6alkyl)amino or by d-dalkoxy;
R&*, Res and R^ are each independently of the others Crdalkyl, C3-C8alkenyl or C3-C8- alkynyl, or 0-C8alkyl which is mono-, di- or tri-substituted by halogen, -CN or by O-Oalkoxy;
R87 and R89 are each independently of the other hydrogen, O-Oalkyl or d-dalkoxy; R88 is d-Cβalkyl; R90 is hydrogen or d-dalkyl; R91 is d-dalkyl;
R92 and R93 are each independently of the other d-dalkyl;
R94 is hydrogen or is O-Oalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono-, di- or tri-substituted by halogen, O- alkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, O-Oalkyl, O-Ohaloalkyl, O-Oalkoxy, -CN, -NO2, O-Oalkylthio, O-Oalkylsulfinyl or by C C4alkylsulfonyl; R95 is hydrogen or O-Oalkyl;
R96 is hydrogen or O-Oalkyl, or is O-Oalkyl mono-, di- or tri-substituted by -COOH, O- alkoxycarbonyl or by -CN; or
R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, O-Oalkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by -dalkylsulfonyl; or R95 and R96 together are C2-C5alkylene;
R97 and R98 are each independently of the other hydrogen, d-dalkyl, d-dhaloalkyl or d-dcycloalkyl;
R99 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R100 is hydrogen or Crdalkyl;
R10ι is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
R10ι is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, O-Ohaloalkyl, d-C4alkoxy, -CN, -NO2, O-Oalkylthio, -Oalkylsulfinyl or by O-Oalkylsulfonyl; or R1∞ and R101 together are C2-C5alkylene; R102 is hydrogen or O-Oalkyl; R103 is hydrogen, O-Oalkyl, -Si(CrOalkyl)3, C3-C8alkenyl or C3-C8alkynyl; R10 is O- alkyl;
R105 is hydrogen or is O-Oalkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono-, di- or tri-substituted by halogen, O-Oalkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, O-Oalkyl, d-C4haloalkyl, O-Oalkoxy, -CN,
-NO2, O- alkylthio, O-Oalkylsulfinyl or by O-Oalkylsulfonyl; 106 is hydrogen or Crdalkyl;
R107 is hydrogen or d-dalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH,
CrOalkoxycarbonyl or by -CN, or
R107 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, O-Oalkyl, O-Ohaloalkyl, O- alkoxy,
-CN, -NO2, O- alkylthio, O- alkylsulfinyl or by O-Oalkylsulfonyl; or
R106 and Rι07 together are C2-C5alkylene;
R108 is hydrogen, O-Oalkyl, O-Ohaloalkyl or C3-C6cycloalkyl;
R109 is hydrogen, O- alkyl, O-Ohaloalkyl or C3-C6cycloalkyl;
R110 is hydrogen, O-Oalkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl;
Rm is hydrogen or -dalkyl;
R112 is hydrogen or Crdalkyl, or is d-dalkyl mono-, di- or tri-substituted by -COOH, d-dalkoxycarbonyl or by -CN; or
Rn2 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy.
-CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by C C4alkylsulfonyl; or
Rm and Rn2 together are C2-C5alkylene;
R113 is hydrogen or O-Oalkyl;
R114 is hydrogen, O-Oalkyl, -Si(0-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
Rns is 0-C6alkyl;
R116 is hydrogen or is O- alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono-, di- or tri-substituted by halogen, d-dalkoxy or by phenyl, it being possible for phenyl in turn to be mono-, di- or tri-substituted by halogen, O-Oalkyl, O-Ohaloalkyl, O-Oalkoxy, -CN,
-NO2, O-Oalkylthio, O-Oalkylsulfinyl or by O-Oalkylsulfonyl;
R117 is hydrogen or O- alkyl;
R118 is hydrogen or O- alkyl, or is O- alkyl mono-, di- or tri-substituted by -COOH,
CrOalkoxycarbonyl or by -CN; or
Rue is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, O- alkyl, O-Ohaloalkyl, O-Oalkoxy,
-CN, -NO2, O-Oalkylthio, O-Oalkylsulfinyl or by O-Oalkylsulfonyl; or
R117 and R118 together are O- alkylene; R119 is hydrogen, O-Oalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R120 is hydrogen, 0-C4alkyl, d-C haloalkyl or C3-C6cycloalkyl;
Ri21 is hydrogen, O-Oalkyl, C3-C8alkenyl, C3-C8alkynyl, 0-C haloalkyl or C3-C6haloalkenyl;
Rι22 is hydrogen or O-Oalkyl;
Ri23 is hydrogen or O-Oalkyl, or is O- alkyl mono-, di- or tri-substituted by -COOH,
CrOalkoxycarbonyl or by -CN; or
R123 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono-, di- or tri-substituted by halogen, O-Oalkyl, O-Ohaloalkyl, O-Oalkoxy,
-CN, -NO2, O-Oalkylthio, O-Oalkylsulfinyl or by d-C4alkylsulfonyl; or
Ri22 and R123 together are C2-C5alkylene; and
Rι2 is hydrogen or O- alkyl.
3. A compound according to claim 2, wherein each Rx independently is halogen, -CN, -NO2, -C(R,o)=NORn, -OR13, -SO2R16, -OSO2Ri7, O-Oalkyl or C2-C8alkenyl, or is O-Oalkyl mono-, di- or tri-substituted by halogen or by -CN; R10 is hydrogen or O-Oalkyl; and Rn is O-Oalkyl.
4. A compound according to claim 2, wherein Q is a group Q^ Q2, Q3 or Q5.
5. A compound according to claim 4, wherein Q is a group Qx, Q2 or Q3.
6. A compound according to claim 2, wherein each R2 independently is hydrogen, halogen, -CN, -SCN, -OCN, -N3, -CONR36R37, -C(R38)=NOR39, -COR-w, -OR41, -OSO2R45, -N([CO]pR46)COR47, -N(R56)SO2R57, -N(SO2R5β)SO2R59, -N=C(OR6o)R6ι or O-Oalkyl. or is O- alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R8o, -OR82, -SOR^, -SO2R85 or by -N(R89)COR9o.
7. A process for the preparation of a compound of formula la
Figure imgf000136_0001
wherein R1 ( R2, R3, R4, Z, m and n are as defined in claim 1 , which comprises reacting a compound of formula II
Figure imgf000137_0001
wherein Ri and n are as defined in claim 1 and X is halogen, with a compound of formula Ilia
Figure imgf000137_0002
wherein R3 and R4 are as defined in claim 1 and M+ is an alkali metal cation, to form a compound of formula
Figure imgf000137_0003
wherein Rx, R3, R4, Z and n are as defined in claim 1 , and then coupling that compound with a compound of formula Va
Figure imgf000137_0004
wherein R2 and m are as defined in claim 1 and A is a leaving group, in the presence of a palladium catalyst and, optionally, oxidising such a compound wherein Z is =N-.
8. A herbicidal and plant-growth-inhibiting composition which comprises, on an inert carrier, a herbicidally effective amount of a compound of formula I.
9. A method of controlling undesired plant growth, which comprises applying a herbicidally effective amount of a compound of formula I or of a composition comprising such a compound to the plants or to the locus thereof.
10. A method of inhibiting plant growth, which comprises applying a herbicidally effective amount of a compound of formula I or of a composition comprising such a compound to the plants or to the locus thereof.
PCT/EP2003/005703 2002-05-31 2003-05-30 Herbicidally active heterocyclylalkynes WO2003104206A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003238179A AU2003238179A1 (en) 2002-05-31 2003-05-30 Herbicidally active heterocyclylalkynes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH920/02 2002-01-04
CH9202002 2002-05-31

Publications (2)

Publication Number Publication Date
WO2003104206A2 true WO2003104206A2 (en) 2003-12-18
WO2003104206A3 WO2003104206A3 (en) 2004-12-09

Family

ID=29721324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/005703 WO2003104206A2 (en) 2002-05-31 2003-05-30 Herbicidally active heterocyclylalkynes

Country Status (3)

Country Link
AR (1) AR040413A1 (en)
AU (1) AU2003238179A1 (en)
WO (1) WO2003104206A2 (en)

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005123703A2 (en) 2004-06-17 2005-12-29 Addex Pharmaceuticals Sa Alkynyl derivatives as modulators of metabotropic glutamate receptors
US7956010B2 (en) 2007-04-27 2011-06-07 Sumitomo Chemical Company, Limited Amide compound and use thereof for controlling plant diseases
US7999136B2 (en) 2007-04-27 2011-08-16 Sumitomo Chemical Company, Limited Amide compound and use thereof
US8003699B2 (en) 2007-04-27 2011-08-23 Sumitomo Chemical Company, Limited Amide compound and use thereof for controlling plant diseases
WO2013039990A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
WO2013040117A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
WO2013040021A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
WO2014151255A1 (en) 2013-03-15 2014-09-25 Monsanto Technology Llc Methods and compositions for weed control
WO2015108982A2 (en) 2014-01-15 2015-07-23 Monsanto Technology Llc Methods and compositions for weed control using epsps polynucleotides
US9121022B2 (en) 2010-03-08 2015-09-01 Monsanto Technology Llc Method for controlling herbicide-resistant plants
US9416363B2 (en) 2011-09-13 2016-08-16 Monsanto Technology Llc Methods and compositions for weed control
US9422558B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9422557B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9540642B2 (en) 2013-11-04 2017-01-10 The United States Of America, As Represented By The Secretary Of Agriculture Compositions and methods for controlling arthropod parasite and pest infestations
US9777288B2 (en) 2013-07-19 2017-10-03 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10041068B2 (en) 2013-01-01 2018-08-07 A. B. Seeds Ltd. Isolated dsRNA molecules and methods of using same for silencing target molecules of interest
US10240162B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10378012B2 (en) 2014-07-29 2019-08-13 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10557138B2 (en) 2013-12-10 2020-02-11 Beeologics, Inc. Compositions and methods for virus control in Varroa mite and bees
US10609930B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10612019B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10655136B2 (en) 2015-06-03 2020-05-19 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
US10801028B2 (en) 2009-10-14 2020-10-13 Beeologics Inc. Compositions for controlling Varroa mites in bees
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10808249B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
US10883103B2 (en) 2015-06-02 2021-01-05 Monsanto Technology Llc Compositions and methods for delivery of a polynucleotide into a plant
US10888579B2 (en) 2007-11-07 2021-01-12 Beeologics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4971982A (en) * 1987-07-06 1990-11-20 Hoffmann-La Roche Inc. Benzopyran derivatives
WO2001055066A2 (en) * 2000-01-25 2001-08-02 Syngenta Participations Ag 3-phenoxy-1-phenyl acetylene derivatives and their use as herbicides
WO2002028182A1 (en) * 2000-10-03 2002-04-11 Syngenta Participations Ag Phenylpropynyloxypyridine herbicides

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1180131A (en) * 1997-09-01 1999-03-26 Mitsubishi Chem Corp Ethynylpyrimidine derivative
JPH11147866A (en) * 1997-09-09 1999-06-02 Sankyo Co Ltd Aminophenol derivative

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4971982A (en) * 1987-07-06 1990-11-20 Hoffmann-La Roche Inc. Benzopyran derivatives
WO2001055066A2 (en) * 2000-01-25 2001-08-02 Syngenta Participations Ag 3-phenoxy-1-phenyl acetylene derivatives and their use as herbicides
WO2002028182A1 (en) * 2000-10-03 2002-04-11 Syngenta Participations Ag Phenylpropynyloxypyridine herbicides

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHAUDHURI G ET AL.: "A highly regio- and steroselective synthesis of (Z)-3-arylidene-2,3-dihydro-5H-1,4-benzodi oxepin-5-ones and (Z)-3-arylidene-1,2,3,5-tetrahydro-4,1-ben zoxazepin-5-ones through palladium-copper catalysis" JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, 2000, pages 775-779, XP002253289 CHEMICAL SOCIETY. LETCHWORTH., GB ISSN: 0300-922X *
DRAPER T L ET AL: "Synthesis of unsymmetrical 3,6-disubstituted pyridazines. A palladium-catalyzed approach from 3-iodopyridazines" JOURNAL OF ORGANIC CHEMISTRY, vol. 60, no. 3, 1995, pages 748-750, XP002253288 AMERICAN CHEMICAL SOCIETY. EASTON., US ISSN: 0022-3263 *
KUNDU N G ET AL: "PALLADIUM-CATALYZED HETEROANNULATION LEADING TO HETEROCYCLIC STRUCTURES WITH TWO HETEROATOMS: A HIGHLY REGIO- AND STEREOSELECTIVE SYNTHESIS OF (Z)-4-ALKYL-2-ALKYL(ARYL)IDENE-3,4-DIHYDRO -2H-1,4-BENZOX AZINES AND (Z)-3-ALKYL(ARYL)IDENE-4-TOSYL-3,4-DIHYDRO -2H-1,4-BENZOXAZINE" JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 66, 2001, pages 20-29, XP000926729 ISSN: 0022-3263 *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 08, 30 June 1999 (1999-06-30) -& JP 11 080131 A (MITSUBISHI CHEM CORP), 26 March 1999 (1999-03-26) *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 11, 30 September 1999 (1999-09-30) -& JP 11 147866 A (SANKYO CO LTD), 2 June 1999 (1999-06-02) cited in the application *

Cited By (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8674106B2 (en) 2004-06-17 2014-03-18 Addex Pharma Sa Alkynyl derivatives as modulators of metabotropic glutamate receptors
WO2005123703A3 (en) * 2004-06-17 2006-10-12 Addex Pharmaceuticals Sa Alkynyl derivatives as modulators of metabotropic glutamate receptors
JP2008502674A (en) * 2004-06-17 2008-01-31 アデックス ファーマ ソシエテ アノニム Novel alkynyl derivatives as modulators of metabotropic glutamate receptors
EA012206B1 (en) * 2004-06-17 2009-08-28 Аддекс Фарма Са. Alkyl derivatives as modulators metabotropic glatamate receptors
US8883826B2 (en) 2004-06-17 2014-11-11 Addex Pharma Sa Alkynyl derivatives as modulators of metabotropic glutamate receptors
WO2005123703A2 (en) 2004-06-17 2005-12-29 Addex Pharmaceuticals Sa Alkynyl derivatives as modulators of metabotropic glutamate receptors
EP2426115A3 (en) * 2004-06-17 2014-09-03 Addex Pharma SA Alkynyl derivatives as modulators of metabotropic glutamate receptors
US8101637B2 (en) 2004-06-17 2012-01-24 Addex Pharma Sa Alkynyl derivatives as modulators of metatropic glutamate receptors
EP2426115A2 (en) 2004-06-17 2012-03-07 Addex Pharma SA Alkynyl derivatives as modulators of metabotropic glutamate receptors
JP2012051937A (en) * 2004-06-17 2012-03-15 Addex Pharma Sa New alkynyl derivative as modulator of metabotropic glutamic acid receptor
AU2005254808B2 (en) * 2004-06-17 2012-04-19 Addex Pharma Sa Alkynyl derivatives as modulators of metabotropic glutamate receptors
US7956010B2 (en) 2007-04-27 2011-06-07 Sumitomo Chemical Company, Limited Amide compound and use thereof for controlling plant diseases
US8003699B2 (en) 2007-04-27 2011-08-23 Sumitomo Chemical Company, Limited Amide compound and use thereof for controlling plant diseases
US7999136B2 (en) 2007-04-27 2011-08-16 Sumitomo Chemical Company, Limited Amide compound and use thereof
US10888579B2 (en) 2007-11-07 2021-01-12 Beeologics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US10801028B2 (en) 2009-10-14 2020-10-13 Beeologics Inc. Compositions for controlling Varroa mites in bees
US11812738B2 (en) 2010-03-08 2023-11-14 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
US9121022B2 (en) 2010-03-08 2015-09-01 Monsanto Technology Llc Method for controlling herbicide-resistant plants
US9988634B2 (en) 2010-03-08 2018-06-05 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
EP3382027A2 (en) 2011-09-13 2018-10-03 Monsanto Technology LLC Methods and compositions for weed control
US9422558B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9422557B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
WO2013039990A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
US9416363B2 (en) 2011-09-13 2016-08-16 Monsanto Technology Llc Methods and compositions for weed control
WO2013040117A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
EP3296402A2 (en) 2011-09-13 2018-03-21 Monsanto Technology LLC Methods and compositions for weed control
US10808249B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
WO2013040021A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
EP3434780A1 (en) 2011-09-13 2019-01-30 Monsanto Technology LLC Methods and compositions for weed control
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
EP3434779A1 (en) 2011-09-13 2019-01-30 Monsanto Technology LLC Methods and compositions for weed control
US10240162B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10240161B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10934555B2 (en) 2012-05-24 2021-03-02 Monsanto Technology Llc Compositions and methods for silencing gene expression
US10041068B2 (en) 2013-01-01 2018-08-07 A. B. Seeds Ltd. Isolated dsRNA molecules and methods of using same for silencing target molecules of interest
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
US10612019B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10609930B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
WO2014151255A1 (en) 2013-03-15 2014-09-25 Monsanto Technology Llc Methods and compositions for weed control
US10568328B2 (en) 2013-03-15 2020-02-25 Monsanto Technology Llc Methods and compositions for weed control
US10597676B2 (en) 2013-07-19 2020-03-24 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9856495B2 (en) 2013-07-19 2018-01-02 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US11377667B2 (en) 2013-07-19 2022-07-05 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9777288B2 (en) 2013-07-19 2017-10-03 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10100306B2 (en) 2013-11-04 2018-10-16 Monsanto Technology Llc Compositions and methods for controlling arthropod parasite and pest infestations
US9540642B2 (en) 2013-11-04 2017-01-10 The United States Of America, As Represented By The Secretary Of Agriculture Compositions and methods for controlling arthropod parasite and pest infestations
US10927374B2 (en) 2013-11-04 2021-02-23 Monsanto Technology Llc Compositions and methods for controlling arthropod parasite and pest infestations
US10557138B2 (en) 2013-12-10 2020-02-11 Beeologics, Inc. Compositions and methods for virus control in Varroa mite and bees
US10334848B2 (en) 2014-01-15 2019-07-02 Monsanto Technology Llc Methods and compositions for weed control using EPSPS polynucleotides
WO2015108982A2 (en) 2014-01-15 2015-07-23 Monsanto Technology Llc Methods and compositions for weed control using epsps polynucleotides
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression
US11124792B2 (en) 2014-07-29 2021-09-21 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10378012B2 (en) 2014-07-29 2019-08-13 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10883103B2 (en) 2015-06-02 2021-01-05 Monsanto Technology Llc Compositions and methods for delivery of a polynucleotide into a plant
US10655136B2 (en) 2015-06-03 2020-05-19 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants

Also Published As

Publication number Publication date
AU2003238179A1 (en) 2003-12-22
WO2003104206A3 (en) 2004-12-09
AU2003238179A8 (en) 2003-12-22
AR040413A1 (en) 2005-04-06

Similar Documents

Publication Publication Date Title
WO2003104206A2 (en) Herbicidally active heterocyclylalkynes
US20050107437A1 (en) Novel herbicides
US20040248739A1 (en) Pyridylpropynyloxyphenyl derivatives for use as herbicides
US20050202973A1 (en) Aryl-alkyne compounds as herbicides
WO2004002981A2 (en) Herbicidal thienylalkynes
WO2005047233A1 (en) Novel herbicides
US6204221B1 (en) Herbicides
US20040102325A1 (en) Phenylpropynyloxypyridine herbicides
US20040242456A1 (en) Herbicidal n-alkysulfonamino derivatives
AU2002218200A1 (en) Phenylpropynyloxypyridine herbicides
US6274536B1 (en) Pyrazole derivatives as herbicides
WO2004002947A1 (en) Phenoxypropenylphenyl derivatives and their use as herbicides
US20040192910A1 (en) Sulfonylamino derivatives useful as herbicides
ZA200209878B (en) Substituted pyridine herbicides.
JP2002524554A (en) Pyridine ketones useful as herbicides
WO1999052893A1 (en) N-pyridonyl herbicides
KR20010042518A (en) Novel herbicides
AU2003276976B2 (en) Nicotinoyl derivatives as herbicidal compounds
WO2001066522A1 (en) Acylated phenyl or pyridine herbicides
AU2002340810A1 (en) Pyridylpropynyloxyphenyl derivatives for use as herbicides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP